CHEMISTRY IN ACTION Chapter 5: Heat Effects and Energy Relationships in Chemical Reactions EPISODE 16: ENERGY CONSERVATION OVERVIEW

The previous lessons were about the different forms of matter and the changes of matter undergoes. This episode is the first of four lessons on energy relationships accompanying changes in matter. We will begin with ideas on energy conservation and energy transformation when matter undergoes change. OBJECTIVES At the end of this lesson, the student should be able to: 1. define basic concepts in thermodynamics energy, thermodynamics, system, surroundings; 2. differentiate open, closed and isolated system; 3. explain the concepts of heat and work as energy transferred; 4. state the First Law of Thermodynamics; 5. give the operational definition of internal energy; 6. explain the consequence of heat absorption and performance of work on internal energy; 7. explain the internal energy as a state function; and 8. explain the energy transformations that accompany common life processes. INTEGRATION WITH OTHER LEARNING AREAS When matter undergoes change, it is always accompanied by a change in energy content. In Episode 10, one of the indicators of chemical change is absorption or release of heat. Physical changes described in Episode 7 Phases of Matter are also accompanied by energy changes. Quantitative aspects of energy transformations are important topics in physics and engineering. In our homes, energy is an important issue from the food we eat, the activities we do, the materials that we use all produce or use up energy. SCIENCE AND HEALTH IDEAS
Energy in food and nutrition Mans use of energy

SCIENCE PROCESSES
Observing Experimenting Classifying Inferring

CHEMISTRY IN ACTION
Using mathematical relationships Predicting

VALUES
Responsibility for one's actions

LIFE SKILL
Decision making

IMPORTANT CONCEPTS 1. Thermodynamics is the study of energy changes accompanying physical and chemical changes that matter undergoes. 2. The First Law of Thermodynamics states that energy in the universe is conserved. 3. Energy is the capacity to do work. 4. Heat and work are forms of energy in transit. 5. Heat capacity is the amount of heat that has to be absorbed by the system for its temperature to rise by one degree Celsius. 6. The total energy present in a given sample of matter is called its internal energy. 7. Internal energy is a state function. 8. Energy can be transformed from one form to another. BACKGROUND INFORMATION/EPISODE CONTENT Energy is a word that almost everyone reads or uses frequently, but many of us just have a vague understanding of its meaning. But we know it is important to life, we use it, we produce it, and it can take many forms. What is energy and what forms can it take? Thermodynamics. The study of energy and its transformations is called thermodynamics. This area of study straddles both physics and chemistry. Energy conversions to mechanical forms are important concerns in physics. On the other hand, chemical thermodynamics deals with the energy changes accompanying physical and chemical changes that matter undergoes. The succeeding sections 2

CHEMISTRY IN ACTION introduce us to some important terms and concepts used in describing thermodynamic properties.

System and Surroundings. In order to study how energy changes during physical or chemical change, we have to first divide the universe into two parts: the system and the surroundings. A system is a portion of the universe that we isolate for the purpose of study. It is a definite quantity of matter undergoing a change. The system can be the reactants and products of a reaction, or a piece of ice melting on the tabletop, or our bodies. It is separated from the rest of the universe by a real or imaginary boundary. The beaker or flask where the reaction takes place denotes a real boundary. However, the parts of the melting ice that do not touch the table have an imaginary boundary. Everything outside the system is the surroundings including boundaries. Thus, the beaker where a reaction is happening is part of the surroundings of the reactants and products of the reaction. The relationship between the components of the universe is given by the equation: Universe = System + Surroundings Types of Systems. Systems may be classified according to the nature of its interaction with its surroundings into three types: In an open system, both energy and matter can be exchanged between the system and its surroundings. An example of this is a hot cup of coffee as it cools. It loses heat to the surroundings and loses water vapor (matter) in the form of steam. In a closed system, energy can be exchanged between the system and its surroundings but matter cannot be exchanged. A stoppered glass flask of coffee loses heat to its surroundings but does not lose water vapor to it. In an isolated system, neither energy nor matter can be exchanged between the system and its surroundings. Hot water placed in a thermos bottle approximates an isolated system. It does not readily lose energy to and neither does it lose water to its surroundings. However, the thermos bottle is not a perfect boundary for an isolated system since energy is slowly lost to the surroundings, so that in time, the water inside cools. Energy, Work, and Heat. One of the most important knowledge that we have about energy is that it is conserved. In other words, the energy of the universe is constant. This idea is essentially the First Law of Thermodynamics, or more familiarly, the Law of Conservation of Energy, which states that energy can neither be created nor destroyed, but can be converted from one form to another. Energy is often defined as the capacity to do work. Work, on the other hand, is done when force is exerted over a distance. Whenever we define work, a situation 3

CHEMISTRY IN ACTION showing work is being done is always cited. A crawling baby, a boy climbing a tree, and a carabao plowing the fields all show that work is being done. Moving objects do work when they slow down or increase in speed. Maybe not as easily evident as in the other examples, work is also being done when a gas like helium expands or is made to occupy a larger space, or when it is compressed to a smaller space. These events all show that energy is being used for them to occur. Heat is the energy transferred between a system and its surroundings as a result of a temperature difference. Energy, as heat, passes from a warmer body (with higher temperature) to a colder body (with lower temperature). Like work, heat is energy in transit between the system and its surroundings. It is a form by which energy can be transferred across a boundary between the system and its surroundings. Heat and work are the forms by which energy gets transferred or converted to other forms. They can also be transformed into one another. Heat can be used to do work, such as in steam engines. On the other hand, if you rub your hands together and your hands begin to feel warm, work is being converted to heat. Units of Energy. Both heat and work can be expressed in the same unit of measure, typically the joule, J. One joule, 1 J, is approximately the amount of energy needed to lift a 1 kg object about 4 inches against gravity. The energy required by the average human heart to make one beat is also about one joule. Another unit that is often used to describe heat and work is the calorie, cal. One calorie,1 cal, is the amount of heat needed to raise the temperature of one gram of water by 1oC. One calorie is equal to 4.184 J. In food labels, the energy equivalent of food is expressed in big calories. When calorie is abbreviated with a capital C, it means kilocalories or 1000 calories. The label of a certain butter states that 15 g of that butter has an energy equivalent of 110 Calories or 110,000 calories or 460,240 joules! The amount of work or heat involved in a physical or chemical change can be calculated using some mathematical relationships arising from the definitions of these forms of energy and the first law of thermodynamics. Some simple examples are given in the following sections. Work. Work is often defined as the product of force and the distance through which the force acts as described in the equation below. The equation is useful in solving problems in physics that ask how much work is done when a car moves, or a ball rolls downhill or when we climb the stairs. Work (w) = force (F) x distance (d)

CHEMISTRY IN ACTION But let us use an example which has some chemistry in it, like the expansion or compression of a gas. During gas expansion or compression, the force, F, is equal to the pressure and the area on which this pressure is exerted. The equation becomes: Work (w) = (pressure x area) x distance (d) But (area x distance) is actually the change in volume of the gas or the container during the expansion or compression. Thus, work is measured by the pressure multiplied by the change in volume of the gas. Work (w) = V x P When a gas expands, force is exerted on the surroundings, since the system increases in volume and moves against the external pressure. V is positive (final volume is greater than initial volume) but work here carries a negative sign since work is directed out of the system. On the other hand, when a gas is compressed, force is exerted on the gas, causing its volume to decrease. V is negative, but work is positive. Hence, we refine the equation to: Work (w) = - (V x P) Example: Calculate the work done when a gas expands from 40 liters to 58 liters at a constant external pressure of 10 atm or a gas at constant pressure. w = - (V x P) w = - (18 L x 10 atm) = - 180 L-atm To convert to the energy unit, joule, J, the conversion factor is 1 L-atm = 101 J.

w = - 180 L-atm x 101 J/L-atm = -18180 J or -18.2 kJ

Heat. When two objects are in contact, heat always flows from the object of higher temperature to the one of lower temperature. If a cold metal spoon is placed in a cup of hot coffee, heat will flow from the hot coffee to the metal spoon until their temperatures are the same. How much heat is absorbed by the spoon? How much heat is lost by the hot coffee? Heat is represented by the symbol q. In interactions between a system and its surroundings, the amount of heat gained by the system is the same amount of heat lost by the surroundings and vice-versa. Hence, the sum of the heat absorbed and 5

CHEMISTRY IN ACTION heat evolved is equal to zero. qsystem + qsurr = 0 An increase in the temperature of a system implies that the system has absorbed or gained heat. This is indicated by a positive value of q. When the temperature of the system decreases, it evolves or loses heat to the surroundings and is indicated by a negative value of q. However, the magnitude of temperature change is dependent on the amount of heat absorbed or lost and the heat capacity of the system, a property that is characteristic of the substance or material that makes up the system. Heat Capacity. Heat capacity is the quantity of heat needed to change the temperature of a given object by one degree Celsius. If the system is made of the same material throughout, or of a single substance, a more useful way of expressing heat capacity is the specific heat capacity of the substance. Specific heat capacity is the quantity of heat required to raise the temperature of one gram of the substance by one degree Celsius. Water has a specific heat of 4.184 J/g-oC. The mathematical equation used to determine how much heat has been absorbed or lost by a system is: Q = heat capacity x T or Q = specific heat x mass of system x T Example: How much heat must be absorbed by a 42 g piece of iron, Fe, to raise its temperature from 22oC to 80oC? The specific heat of iron is 0.45 J/g-oC. Q = (0.45 J/g-oC) (42 g) (80oC 22oC) Q = 1096 J The value of heat obtained in the example has a positive sign, indicating that heat flowed into the system which is the piece of iron metal. Can you tell how much heat was lost by the surroundings? In the earlier section, we found that the heat gained by the system is exactly the same quantity lost by the surroundings, such that the sum of these two quantities is zero. Hence, the heat lost by the surroundings is also 1096 J, but this quantity carries a negative sign. qsystem + qsurr = 0 1096 J + (-1096 J) = 0

Internal Energy. Heat and work are the means by which the system exchanges energy with its surroundings and they exist only during a change. A system does not contain energy in the form of heat or work. The energy contained within the system, called internal energy, U, is the total energy, potential and kinetic, in various forms 6

CHEMISTRY IN ACTION within the system. These may be in the form of chemical bonds, in the motion of particles, and in intermolecular forces between larger particles. The internal energy of a system is not measurable, but it can be converted to and increased or decreased through heat and work, according to the following equation: U = q + w where U = change in internal energy q = heat absorbed or lost by the system w = work done by or on the system. If we use the system as the reference point (in engineering, the term surroundings is sometimes used as reference point), then the following may serve as useful guides in determining the sign on q and w: When heat is absorbed by the system, q is positive ( > 0 ). If heat is given off by the system, q is negative ( < 0 ). When work is done by the system on the surroundings, the system loses energy, indicated by a negative value of work ( < 0 ). When work is done by the surroundings on the system, the work is positive ( > 0 ).

A positive value ofU indicates an increase in the internal energy of the syst em, while a negative value of U indicates a decrease in the internal energy of the system. The sign forU depends on the balance between the energy transferred to the system and the energy transferred from the system. When the system absorbs heat (q > 0) and the surroundings perform work on the system (w > 0), theU of the system is positive. When the system evolves heat (q < 0) and it performs work on the surroundings,U theo f th e system is negative. When the system absorbs heat but performs work on the surroundings, the net change in internal energy depends on the balance between the energy gained and the energy lost by the system. When the amount of heat absorbed by the system exceeds the energy used to perform work, the net effect is an increase in internal energy. When the amount of heat lost by the system exceeds the work performed on the system, the net effect is a decrease in internal energy.

Energy is a State Function. The previous section tells us that a given amount of change in energy of a system can be achieved in several ways. It can be just through heat transfer, or by work alone, or many possible combinations of heat and work!

CHEMISTRY IN ACTION A property that is determined by the current state of the system and is not determined by the manner in which the system achieved it is called a state function. Internal energy, therefore, is a state function. This can be illustrated by a person going up a fourstory building. The initial state (state 1) is at the ground level and the final state, state 2, is at the fourth level. The person has an initial internal energy at state 1 and a final internal energy at state 2. How can the person get to the fourth floor and achieve the final internal energy? He can go up the building by taking the elevator or taking the stairs. He can go straight up or take the elevator to the third level, go down to the second level, and climb the stairs to the fourth level. He would have achieved the final internal energy state when he is at the fourth level, in whatever way he reaches it. Energy Transformations. Our main source of energy for our daily activities is the combustion of fuels coal, fossil fuels, alcohol, biomass, to name some. But our need for energy is no longer just for keeping warm or cooking food. Today, most of our energy needs are for machines to do work. The heat generated from the burning of fuels must be converted to other forms of energy. What forms can energy take? Energy can be classified into two general forms: potential and kinetic. The energy possessed by a moving body is called kinetic energy. Potential energy is energy due to a condition, position or composition, and is associated with forces of attraction or repulsion between objects. There are more specific forms that energy can be converted into: chemical, electrical, mechanical, light, and heat. The human body converts the chemical energy from the food we eat to heat, thus keeping our body at the right temperature and into mechanical energy that enables our bodies to move. The video lesson also traces the transformation of chemical energy from fossil fuels into mechanical energy and into electrical energy that is transmitted to homes and industrial plants where it is further converted into various energy forms such as light, sound and heat. Can you describe the transformation of energy when a car moves? If the First Law of Thermodynamics is true, then why do we always hear that our energy resources are running out? What we are really saying here is that there are forms of energy that are more useful than others. Our main sources of energy are the fuels that we burn, converting their internal energy into heat. But aside from cooking our food and keeping homes in temperate countries warm, heat is not a very useful form of energy. It has to be converted to work or to other forms such as mechanical energy to run machines and engines or to electrical energy. Man has not been successful in finding an efficient way to convert most of the heat from burning fuels to more useful forms, so most of the heat is simply used to increase the temperature of the surroundings, which is for us just a waste of energy.

CHEMISTRY IN ACTION VOCABULARY WORDS 1. System part of the universe that is being studied. 2. Surroundings the remaining part of the universe outside of the system. 3. Joule the SI unit for energy, equivalent to the energy needed to raise a 1 kg object 4 inches against gravity. 4. calorie calorie with a small c is a unit of energy equivalent to the amount of energy needed to raise the temperature of 1 g of pure water by one degree Celsius. 5. Calorie calorie with a capital C is the unit of energy used in food labels and 1 Calorie is equivalent to 1000 calories. 6. Specific heat capacity the amount of heat needed to raise the temperature of 1 g of substance by one degree Celsius. 7. Internal energy the total energy of the system which includes attractive forces, energy due to motion, etc. 8. State function a property whose change in value from the initial to the final state is not dependent on how the final state was attained. 9. Kinetic energy a form of energy that is due to the motion of particles. 10. Potential energy a form of energy that is due to composition or relative position.

PREVIEWING ACTIVITIES A. Tell the students to list down some activities they do everyday which involve the use of energy. B. Tell the students what we mean when we say you are wasting energy. Where does the energy go? C. Pose the Guide Questions which the students will answer after viewing the episode. Tell them to focus on finding the answers to the Guide Questions as they watch the video.

CHEMISTRY IN ACTION Guide Questions/Answers 1. What is thermodynamics? Thermodynamics is the study of changes in energy that accompany changes that matter undergoes. 2. Differentiate the system from the surroundings. The system is a small part of the universe an object, a chemical reaction, a sample of gas that is being studied. The remaining part of the universe outside of the system is the surroundings. 3. Describe the three kinds of system mentioned in the video lesson. The three kinds of systems presented are the following: open system one that can exchange matter and energy with the surroundings; closed system one that can exchange energy but not matter, with the surroundings. isolated system one that cannot exchange matter nor energy with the surroundings 4. Differentiate potential from kinetic energy. Potential energy is energy due to the position of the sample relative to other particles that interact with it, while kinetic energy is energy due to the motion of the object. 5. What is heat? What is work? Heat is energy that transfers between two or more bodies due to differences in temperature, while work is the energy transformed when a force applied on a body causes movement or changes in position. 6. When a gas expands, is work being done on the system or on the surroundings? Explain your answer. Work is done on the surroundings when a gas expands. During expansion, the volume of the gas increases and exerts force outward as its boundaries move into the surroundings. 7. State the First Law of Thermodynamics. The First Law of Thermodynamics states that energy cannot be created nor destroyed, and it is conserved, but it can be converted from one form to another. 8. Define heat capacity. Heat capacity is the amount of heat needed to raise the temperature of the system or an object by one degree Celsius.

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CHEMISTRY IN ACTION VIEWING ACTIVITIES Activities that show the use of energy can be viewed at segments 2:30 2:50. The First Law of Thermodynamics is illustrated in segments 14:05 to 15:22.

POSTVIEWING ACTIVITY Discuss the answers to the Guide Questions. TEACHING TIP Discuss with the students how the First Law of Thermodynamics is applied in the various situations viewed in the lesson. ASSESSMENT Quiz. Choose the letter corresponding to the best answer. 1. A solution of BaCl2 is added to a beaker that contains a solution of Na2SO4, the mixture is heated to promote the formation of the precipitate, BaSO4. What kind of system is illustrated in this example? A. Open C. Isolated B. Closed D. Non-ideal 2. Which of the following is correct about no. 1? A. System = BaCl2 solution + beaker B. System = BaCl2 + Na2SO4 solutions + beaker C. System = BaCl2 + Na2SO4 solutions + beaker + burner used for heating D. System = everything involved in the experiment + experimenter 3. In what kind of system is the energy of the system constant? A. Open C. Isolated B. Closed D. Ideal 4. Which of the following is NOT a state property? A. Height C. Temperature B. Velocity D. Mass

5. A gas expands as it absorbs 500 J of heat and performs 200 J of work. What happens to the internal energy of the gas? A. It increases by 300 J. C. It increases by 700 J. B. It decreases by 300 J. D. It decreases by 700 J.

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CHEMISTRY IN ACTION 6. Which of the following is correct about the system in no.5? A. q > 0, w > 0 C. q < 0, w > 0 B. q > 0, w < 0 D. q < 0, w < 0 7. Which of the following processes will ALWAYS lead to an increase in internal energy? A. System absorbs heat and performs work. B. System evolves heat and performs work. C. System absorbs heat and surroundings perform work on the system. D. All of the given. 8. Given their respective specific heat capacities, which of the materials A, B, C, and D, would be useful in keeping objects cold? C. 4.0 J/ g-oC. A. 0.004 J/ g-oC. B. 0.40 J/ g-oC. D. 40 J/ g-oC. 9. Which of the following properties/uses of metals result from their very low specific heat capacities? A. Metals make good cooking utensils. B. Metals can be hammered or molded into different shapes. C. Metals have high melting points. D. Metals are used in electrical wirings. 10. What energy transformation occurs when one uses a cell phone? A. q C. U B. w D. All of the given ANSWER KEY Quiz. 1. 6. A B 2. 7. B C 3. C 8. D 4. B 9. A 5. 10. B C

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CHEMISTRY IN ACTION REFERENCES American Chemical Society. (1997). Chemistry in context. (2nd ed.). USA: McGrawHill, Inc. Brown, T. L., LeMay, H. E. & B. E. Bursten. (2004). Chemistry: the central science. NJ: Prentice Hall International, Inc.

Silberberg, M. S. (2000). Chemistry: the molecular nature of matter and change. NY: McGraw Hill, Inc.

Useful websites http://en.wikipedia.org/wiki/Thermodynamics http://www.shodor.org/unchem/advanced/thermo/

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CHEMISTRY IN ACTION Chapter 5: Heat Effects and Energy Relationships in Chemical Reactions EPISODE 17: ENERGY AND CHANGE OVERVIEW Physical and chemical changes are accompanied by changes in energy content of the system. In many instances, the energy changes are measurable. One way of measuring the change in the heat content that accompanies a process or change is through calorimetry, which is described in this lesson. OBJECTIVES At the end of this lesson, the student should be able to: 1. define enthalpy, and change in enthalpy; 2. describe what standard state means for the different physical states of matter; 3. differentiate exothermic from endothermic change; 4. define calorimetry; 5. describe the determination of enthalpy change through calorimetry; 6. construct and calibrate a coffee cup calorimeter; and 7. determine the heat of reaction in an acid-base neutralization. INTEGRATION WITH OTHER LEARNING AREAS The lessons dealing with thermodynamics are covered in Episodes 16 Energy Conservation, 17 Energy and Change, 18 Thermochemical Equations and the Direction of Change, and 19 The Laws of Disorder. The changes in heat content accompanying processes are expressed in units involving molar and stoichiometric quantities of substances. The lessons in Episodes 11 The Mole and 12 Patterns of Change are particularly useful. The energy changes in reactions also influence the direction of adjustments of equilibrium systems when disturbed as discussed in Episode 22 Changes in Equilibrium System: Le Chateliers Principle. SCIENCE AND HEALTH IDEAS
Energy changes during chemical reactions

SCIENCE PROCESSES
Experimenting Observing Using mathematical relationships Classifying Inferring Predicting

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CHEMISTRY IN ACTION

VALUES
Responsibility for one's actions

LIFE SKILL
Decision making

IMPORTANT CONCEPTS 1. Most chemical reactions absorb or release energy usually in the form of heat. Reactions that release energy are exothermic reactions, while those that require energy are called endothermic reactions. 2. The heat content of a substance is called its enthalpy, H. 3. The change in enthalpy, DH, is the change in heat content accompanying a reaction or a physical change occurring at constant pressure. 4. The change in enthalpy of a reaction is the difference between the sum of the enthalpies of products and the sum of the enthalpies of the reactants. 5. The standard enthalpy of formation of a compound is the heat of reaction for the formation of one mole of the compound from its constituent elements at their standard states. 6. Calorimetry is the science of measuring heat changes accompanying physical and chemical changes. BACKGROUND INFORMATION/EPISODE CONTENT One of the indicators of chemical changes described in Episode 10 Indicators of Chemical Change is the release or absorption of heat. In Episode 9 Condensed Phases of Matter, we learned that energy change is also involved in physical processes such as evaporation. The heat absorbed or evolved during physical or chemical change is usually measurable. Exothermic and Endothermic Reactions. One of the most familiar reactions that involve a release of energy is burning or combustion of fuels. The usefulness of combustion reactions is the large amount of energy they produce. Reactions that produce energy are called exothermic reactions. In exothermic reactions, the total heat content of the products is less than the total heat content of the reactants and the difference is the amount of energy released. On the other hand, reactions that require 15

CHEMISTRY IN ACTION energy in order to happen are endothermic reactions. In endothermic reactions, the total heat content of products is greater than the total heat of reactants. The reactions involved in cooking, such as in the hard boiling of an egg, are endothermic reactions. Processes involving phase changes can be exothermic or endothermic. Evaporation is an endothermic process. Condensation of gases into liquids, the opposite process of evaporation, is exothermic. The formation of solutions can be exothermic or endothermic. When sodium hydroxide is dissolved in water, heat is released and an increase in temperature of the solution is observed. On the other hand, the formation of an ammonium chloride solution is an endothermic process. Internal Energy. In Episode 16 Energy Conservation, internal energy, U, was defined the energy associated with the motion of particles (kinetic energy) and the intermolecular forces of attraction that hold the particles in solids and liquids (potential energy). According to the First Law of Thermodynamics, a change in internal energy, DU, involves heat and work, the two forms by which energy is transferred, and is given by the equation: DU = q + w where DU = change in internal energy q = heat absorbed or lost by the system w = work done by the system on the surroundings during the change, which is also equal to (PDV). Enthalpy. Enthalpy, H, is the heat content of a system. It is defined in thermodynamic terms as: H = U + PV where U is the internal energy of the system and PV is the product of pressure and the volume of the system. The change in enthalpy, DH is: D H = D U + PD V Substitution of the term for internal energy, we get: DH = DU + PDV = (q + w) + PDV = (q PDV) + PDV = q

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CHEMISTRY IN ACTION

This implies that when pressure remains constant and with work limited to pressure volume work only, the change in enthalpy is equal to the change in heat content. DH = q where q is the heat absorbed or lost by the system during the process. Like internal energy, absolute values of heat content of substances are impossible to measure, but changes in heat content during a chemical reaction are measurable. And again like internal energy, enthalpy is a state function, meaning that the change in enthalpy, DH, is the difference between the enthalpies of the final state and the initial state: DH = Hf - Hi where Hf and Hi are enthalpies of the final and initial states, respectively. This implies that: for an exothermic process, where heat is released during the reaction, the products have less heat content than the reactants. Therefore, Hf < Hi, and DH < 0 or a negative value. For an endothermic process, where heat is absorbed during the reaction, the products have higher heat content than the reactants. Therefore, Hf > Hi, and DH > 0 or a positive value. The change in enthalpy of a reaction is also referred to as heat of reaction, or enthalpy of reaction or simply enthalpy change. If the reaction is a combustion process, the enthalpy change is also called heat of combustion or enthalpy of combustion. If the process involves formation of a solution, the terms used maybe heat of solution or enthalpy of solution. Determination of Enthalpy Change. Enthalpy changes accompanying processes can be determined in several ways, and the choice of method depends on its suitability based on the nature of the process. The direct way of measuring heat of reaction is through calorimetry. Indirect ways involve the use of known thermochemical data, such as the enthalpy of formation of substances. The determination of the heat of reaction for the formation of carbon monoxide is described below. The heat of reaction for the formation of carbon monoxide, CO, is 110.88 kJ. 17

CHEMISTRY IN ACTION C(s) + O2(g) CO(g) H = 110.88 kJ The reaction, as indicated by the negative value for H is exothermic and 110.88 kJ of heat is evolved when 1 mole of solid carbon burns in oxygen gas to form 1 mole of carbon monoxide gas. The enthalpy of reaction is defined as the difference between the enthalpies of the final and initial states of the system, DH = Hf - Hi For chemical reactions, the initial state is when reactants have not yet reacted, and the final state is when the products have been formed. Thus, Hf is also the sum of the enthalpies of the products, and Hi is the sum of the enthalpies of the reactants, and DH is the difference between the sum of enthalpies of the products (SHP) and the sum of the enthalpies of the reactants (SHR): H = SHP SHR The enthalpy for each substance is the standard enthalpy of formation (Hf). The standard enthalpy of formation of any substance is the heat of reaction for the formation of one mole of the substance from its constituent elements at their standard states. This definition implies that only compounds can have nonzero values for standard enthalpies of formation. What does standard state of an element mean? The standard state of an element is its most stable form at 1 atm and 25C. Solids and liquids are in their standard states when they are in their pure forms. Gases are in their standard states when their pressure is 1 atm. Solutions are in their standard states when their concentration is 1 M (one molar). As an example, let us calculate the enthalpy of combustion of propane, given the standard enthalpies of formation of the substances involved. Standard enthalpies of formation, Hf: C3H8(g) -103.8 kJ/mol CO2(g) -393.5 kJ/mol H2O(g) -241.8 kJ/mol

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CHEMISTRY IN ACTION 1. Write the balanced equation. The coefficients in the balanced equation are important in the calculation of DH since the amount of energy present in any sample of substance is extensive or dependent of the amount of the substance. C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(g) 2. Set up the equation and calculate for DH: H = SHP SHR = [3(Hof CO2(g)) + 4(Hf H2O(g)] [Hf C3H8(g) + 5(Hf O2(g) )] = [3 (-393.5) + 4 (-241.8)] [ (-103.8) + 5 (0) ] kJ/mol H = 2437.4 kJ/mol C3H8 Calorimetry. Calorimetry is the science of measuring of amounts of heat. Calorimetric methods are suitable for the measurement of heat generated by an exothermic process or heat consumed by an endothermic process or heat simply dissipated by a certain object. The device used in calorimetric procedures is called a calorimeter, which can be as sophisticated as a bomb calorimeter, or as simple as a coffee cup calorimeter. The calorimeter usually consists of a wellinsulated vessel containing a known mass of water and may have a smaller vessel that is submerged in water where the reaction takes place. The calorimetric procedure involves enclosing the reaction in the calorimeter, then initiating and allowing the reaction to proceed and noting the temperature difference before and after the reaction. From all of these, the enthalpy change for the reaction is determined. The calculation requires knowledge of the heat capacity of the calorimeter and of course, that of water. Specific Heat and Heat Capacity. As described in the previous episode, substances differ in the amount of energy that they need to absorb or lose to raise or lower their temperatures. The specific heat, S, is the amount of heat needed to raise the temperature of one gram of a substance by one degree Celsius, S = q/(mDt). On the other hand, the heat capacity, C, is the amount of heat needed to raise the temperature of a given quantity of substance by one degree Celsius. If m is the mass of the substance in grams, the relationship between the two is given by C = mS. The specific heat of water is 4.184 J/g-C. The heat capacity of 100 g of water is therefore determined by C = mS = 100 g x 4.184 J/g-C C = 418.4 J/C If 100 g of water is heated from 25C to 50C, how much heat, q, was absorbed by the water? To calculate the heat absorbed, q, we rearrange the equation that defines specific heat, and we get: 19

CHEMISTRY IN ACTION q = = = q = mSt = mS (tfinal tinitial) (100 g x 4.184 J/g-C)(50C 25C) 10,460 J x 1 kJ/(1000 J) 10.46 kJ

Calibrating the Coffee Cup Calorimeter. In the video lesson, a simplified calorimeter, called the coffee cup calorimeter is constructed using two Styrofoam cups with a cover, a stirrer and a laboratory thermometer. The device is calibrated to determine its heat capacity. The calibration procedure involved the following steps: 1. Equal volumes of cold and hot water, whose temperatures were recorded, are measured. 2. These are mixed in the calorimeter. 3. The equilibrium temperature (the highest temperature) of the mixture is measured. Assuming that the calorimeter is an isolated system, and no heat is exchanged with the surroundings, then the final temperature recorded reflects the heat transfer that occurred from the hot water to the cold water and the calorimeter. The calculation of the heat capacity of the calorimeter was carried out as follows: qsystem = qcalorimeter + qcold water + qhot water = 0 where qcalorimeter, qcold water and qhot water refer to the heat absorbed or released by the calorimeter, cold water and hot water, respectively. Hence, qcalorimeter + qcold water = qhot water HC (tf t c) + mcS (tf t c) = mhS (tf t h) where HC = heat capacity of the calorimeter tf = final temperature of the system tc = initial temperature of the cold water th = initial temperature of the hot water mc = mass of cold water mh = mass of hot water Measuring Heat of Reaction. The calibrated calorimeter was used to measure the heat of reaction of an acidbase reaction. The reaction was the neutralization reaction between hydrochloric acid (HCl) and sodium hydroxide (NaOH). HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq) In the demonstration, equal volumes of 2 M HCl solution and 2 M NaOH solution were used. 20

CHEMISTRY IN ACTION 1. The initial temperatures of the two solutions were measured separately. 2. Twenty five, 25, mL of the NaOH solution was placed in the coffee cup calorimeter, then 25 mL of the HCl solution was added.

3. The calorimeter was covered, the solution was stirred and the equilibrium or final temperature of the mixture was measured. Since dilute solutions of acid and base were used, the specific heat (4.184 J/g-C) and density (1.0 g/mL) were assumed to be the same as that of pure water. It was also assumed that no heat was lost to the surroundings or absorbed from the surroundings. The enthalpy of the reaction was determined as follows: qcalorimeter + qsolution + qrxn = 0 HC (tf t i) + mS (tf t i) + DHrxn = 0 where HC tf ti m S DHrxn = heat capacity of the calorimeter = final temperature of the calorimeter and its contents = initial temperature of the solutions before mixing = total mass of the acid and base solutions = specific heat of the solutions = enthalpy of the reaction

The total mass of the solution is obtained by multiplying the total volume, 50 mL, by the density of the solution, which is assumed to be the same as that of water. m = d x V = (1.0 g/mL x 50 mL) = 50 g The DHrxn obtained is for the actual amounts of reactants used in the acidbase reaction. How much was used in the experiment? Using our knowledge on concentrations of solutions described in Episode 13, the number of moles of HCl and NaOH used are obtained by multiplying the concentration of the solution (2 M) by the volume of the solution (25 mL convert to 0.025 L) of the base or the acid since the concentration and the volumes used were identical. Number of moles of HCl (or NaOH) = M x V = 2 mol /L x 0.025 L = 0.050 mole The enthalpy change calculated is for 0.050 mol of HCl (or NaOH). You may proceed to calculate the molar heat of neutralization of HCl and NaOH by dividing the DHrxn obtained by 0.050 mol. 21

CHEMISTRY IN ACTION VOCABULARY WORDS 1. Enthalpy heat content of a substance. 2. Enthalpy of reaction the change in heat content of a chemical reaction occurring at constant pressure. 3. Enthalpy of formation the heat of reaction for the formation of a compound from its constituent elements at their standard states. 4. Specific heat the amount of heat needed to raise the temperature of one gram of substance by one degree Celsius. 5. Heat capacity the amount of heat needed to raise the temperature of a given quantity of substance or an object by one degree Celsius. 6. Calorimetry the science of measurement of heat changes. 7. Calorimeter device used in measuring heat changes accompanying chemical reactions and physical changes.

PREVIEWING ACTIVITIES A. Ask students to recall reactions that they have observed and classify the reactions as endothermic or exothermic. B. Pose the Guide Questions which the students will answer after viewing the episode. Ask them to focus on finding the answers to the guide questions as they watch the video. Guide Questions/Answers 1. In the construction of the coffee cup calorimeter, why are two styrofoam cups used instead of just one? The second styrofoam cup provides another layer of insulation from the surroundings, creating an isolated system that does not exchange matter and heat to the surroundings. The change in temperature recorded in the calorimeter would be more accurate. 2. What characteristic(s) of styrofoam makes it a good material for the calorimeter? Styrofoam is a light plastic material used to make insulation and packaging materials. It contains very small packets of air that does not allow rapid heat transfer since air is not a good thermal conductor. Heat from the inside of the calorimeter will take longer time to escape to the surroundings. 22

CHEMISTRY IN ACTION 3. What is the difference between specific heat and heat capacity? The specific heat, S, is the amount of heat needed to raise the temperature of one gram of a substance by one degree Celsius. On the other hand, the heat capacity, C, is the amount of heat needed to raise the temperature of a given quantity of substance by one degree Celsius. 4. What does it mean when a substance has a high specific heat? A substance with high specific heat requires a large amount of energy to raise its temperature. The substance will not easily become hot. Water has a relatively high specific heat at 4.184 J/g-oC. In comparison, metals have low specific heat values. Mercury, for instance, has a specific heat of only 0.138 J/g-oC. It will require 30 times more heat to raise the temperature by 1oC of a 1-g sample of water compared to 1 g of mercury. If 5 J of heat is applied to each of 1-g samples of water and mercury, the temperature of the water sample will be higher by 1.19oC but the mercury sample will be hotter by 36.23oC! 5. Why do we need to calibrate the coffee cup calorimeter? During heat transfers, the calorimeter itself will absorb or lose some amount of heat. The calibration is essentially the determination of the heat capacity of the calorimeter, which should be taken into consideration for a more accurate determination of the enthalpy of reactions or processes made to occur in the calorimeter. 6. What are the possible sources of error during the calibration? Possible sources of error include: a. not stirring the mixture well b. not placing the cover tightly c. pulling out the thermometer from the calorimeter when reading the temperature d. excluding the temperature of the calorimeter in the measurement of the initial temperature e. reading the temperature of liquids before measuring the amount needed, using a measuring glassware that has not been equilibrated into the temperature of the liquid VIEWING ACTIVITIES In the absence of materials, two segments cited here would be useful in the understanding of calorimetry: (1) Calibration of the Coffee Cup Calorimeter at 14:28 19:13 and (2) Determination of the Heat of Reaction Between an Acid and a Base at 20:50 - 22:50. 23

CHEMISTRY IN ACTION POSTVIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. B. Discuss the principle involved in calorimetry. C. Let the students to construct and calibrate their own coffee cup calorimeter. D. Discuss the computations involved in Activity C. E. Let the students determine the enthalpy change for an assigned reaction. F. Discuss the computations involved in Activity E. ASSESSMENT A. Quiz. Write the letter corresponding to the best answer. 1. How do you classify a reaction where the total energy of the products is greater than the total energy of the reactants? A. Endothermic C. Spontaneous B. Exothermic D. Nonspontaneous 2. What law is applied in calorimetry? A. Law of Conservation of Mass C. Law of Conservation of Energy B. Law of Definite Composition D. Law of Multiple Proportions 3. Which is in its standard state? A. Br2(l) B. O2(g, 1 atm)

C. NaCl (1 M) D. A, B and C

4. Which is CORRECT about the enthalpy change for a reaction? A. It is dependent on the amount of reactants. B. It is negative if the reactants release energy to the surroundings. C. It is the heat change measured at constant pressure. D. A, B and C. 5. Which of the following can absorb the greatest quantity of heat if equal masses of are heated from 0C to 20C? A. Aluminum (Al) metal, S = 0.900 J/g-C B. Graphite (C), S = 0.720 J/g-C C. Iron (Fe) metal, S = 0.444 J/g-C D. Gold (Au) metal, S = 0.129 J/g-C 24

CHEMISTRY IN ACTION 6. A piece of Cu metal previously heated to 70C is dropped into a calorimeter that contains water at 25C. What will be the final temperature of the system at equilibrium? A. Lower than 25C. C. Higher than 25C but lower than 70C. B. Higher than 70C. D. Cannot be determined. 7. How much heat is absorbed by 10 grams of copper, Cu, when it is heated from 20C to 40C? The specific heat of Cu is 0.385 J/g-C. A. 3.85 J C. 38.5 J B. 7.70 J D. 77.0 J 8. To what temperature must you cool 1 kg of water at its normal boiling point for it to release 83.68 kJ of heat? A. 90C C. 80C B. 85C D. 75C 9. Which of the following must be taken into consideration during the determination of heat of reaction? A. Temperature of the reactants before reaction B. Temperature of the reaction mixture after the reaction has taken place C. Quantity of reactant that has reacted D. A, B and C 10. Which of the following can be done to determine the change in enthalpy of a reaction? A. Measuring the amount of heat absorbed or evolved during reaction of a given quantity of a reactant by calorimetry. B. Calculating the change in enthalpy from the enthalpies of formation of the reactants and products. C. Both A and B. D. Neither A nor B.

B. Problem Solving. 1. Fifty (50) grams of aluminum, Al, previously heated to 60C is dropped into 100 mL of water at 20C. If it is assumed that no heat is lost to the surroundings, what will be the equilibrium temperature? The specific heat of Al is 0.900 J/g-C. 2. The combustion of 1 gram of coal produces 30 kJ of heat. How many grams of coal must be burned to heat 1 kg of water from 25C to the boiling point? Assume no heat is lost to the surroundings. 25

CHEMISTRY IN ACTION ANSWER KEY A. Quiz. 1. 6. A C 2. 7. C D 3. D 8. C 4. D 9. D 5. 10. A C

B. Problem Solving. 1. Since it is assumed that there is no heat lost, heat gained by water + heat lost by aluminum = 0 heat gained by water = heat lost be aluminum mwater x Swater x (tf t i)water = mAl x SAl x (tf t i)Al 100 g x 4.184 J/g-C x (tf 20C) = 50 g x 0.900 J/g-C x (tf 60) tf = 23.9C 2. There is no heat lost, therefore: heat released by coal = heat absorbed by water mcoal x DHcoal = mwater x Swater x (tf,water t i,water) mcoal x 30,000 J/g = 1,000 g x 4.184 J/g-C x (100C 25C) mcoal = 10.5 g REFERENCES Brown, T. L., LeMay, H. E. & B. E. Bursten. (2004). Chemistry: the central science. NJ: Prentice Hall, Inc. Chang, R. (2005). Chemistry. NY: McGraw-Hill, Inc. Silberberg, M. S. (2000). Chemistry: the molecular nature of matter and change. NY: McGraw-Hill, Inc.

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CHEMISTRY IN ACTION Chapter 5: Heat Effects and Energy Relationships in Chemical Reactions EPISODE 18: THERMOCHEMICAL EQUATIONS AND THE DIRECTION OF CHANGE OVERVIEW This episode is the second lesson on thermochemistry, the study of heat effects that accompany chemical reactions. Writing thermochemical equations and calculating the energy change that accompanies a process from known thermochemical data are the main topics in this lesson. The relationship of enthalpy changes to other thermodynamic properties that influence the spontaneity of a process is introduced. OBJECTIVES At the end of this lesson, the student should be able to: 1. write thermochemical equations; 2. define standard enthalpy of formation and standard enthalpy of reaction; 3. solve for the standard heat of reaction (DHr) from standard heat of formation (DHf) values; 4. recognize the information about substances and chemical reactions from enthalpy of reaction; 5. calculate the heat of reaction (DHr) using Hess Law; 6. calculate the heat of combustion (DHc) of fuels; and 7. compare spontaneous reactions and nonspontaneous reactions. INTEGRATION WITH OTHER LEARNING AREAS This episode is part of the big chapter on thermodynamics which began with Episode 16 - Energy Conservation and runs up to Episode 19 - The Laws of Disorder. SCIENCE PROCESSES Observing Experimenting Using mathematical relationships VALUES Appreciation for the natural resources Care for the environment 27 Inferring Classifying Predicting

CHEMISTRY IN ACTION LIFE SKILLS Judicious use of energy IMPORTANT CONCEPTS 1. Chemical and physical changes can be exothermic or endothermic. 2. Information about the heat change accompanying a reaction is indicated in a thermochemical equation. 3. The reverse of an exothermic process is endothermic. 4. Enthalpy change can be determined indirectly from known thermochemical data. 5. Enthalpy is a state function, and the value is the same regardless of the steps or route taken to get from the initial to the final state. This is the basis of Hess Law, which states that the enthalpy change for a process is the same as the sum of the enthalpy changes of all steps that comprise the process. 6. Fuel efficiency can be compared from their heats of combustion, or from fuel values. BACKGROUND INFORMATION/EPISODE CONTENT Thermochemistry is the quantitative study and measurement of heat changes that accompany physical and chemical changes. The change in heat content during a chemical reaction is called heat of reaction (qrxn), which is defined as the quantity of heat exchanged between a system and its surroundings when a chemical reaction occurs within a system. The change in enthalpy, DH, is the difference between the enthalpies of the final state, Hf, and the initial state, Hi. DH = Hf - Hi When heat is released during a reaction, the products have less heat content than the reactants, thus Hf < Hi. Hence, DH < 0 or a negative value, and the reaction is exothermic. When heat is absorbed during the reaction, the products have higher heat content than the reactants, thus Hf > Hi. DH > 0 or a positive value, and the reaction is endothermic. 28 Conservation of energy sources

CHEMISTRY IN ACTION Determination of Enthalpy of Reaction. The heat of reaction can be determined in two ways: directly through experimental work based on calorimetry, which was described in the previous episode, Episode 17; and indirectly through the use of known thermochemical data. These thermochemical data, which have been determined experimentally by various groups and published in literature, include standard enthalpies of formation of substances, and heats of reactions for various processes. This second method is described in this lesson. Thermochemical Equations. Each thermochemical information corresponds to a process that happens at specific conditions. The manner of representing a process at some specific condition and the heat change that accompanies it is through a thermochemical equation, which is a chemical equation that shows both the mass and energy relationships in a chemical reaction or process. An example of a thermochemical equation is given below for the reaction of hydrogen and chlorine gas to form hydrogen chloride. H2(g) + Cl2(g) 2HCl(g) Writing Thermochemical Equations. thermochemical equations: DH = 185 kJ

The following guide is useful in writing

1. The reaction must be properly balanced as indicated by the stoichiometric coefficients. H2 + O2 H2O 2. The physical states of all reactants and products must be specified using the symbols (s), (l), (g) or (aq). The enthalpy of one mole of H2O(g) at 25oC is 44 kJ larger than that of one mole of H2O(l), this difference being the heat of vaporization of water. H2(g) + O2(g) H2O(l) 3. The sign of the enthalpy change indicates whether the reaction is endothermic (positive DH) or exothermic (negative DH). H2(g) + O2(g) H2O(l) DH = 285.8 kJ 4. The enthalpy of a substance changes with the conditions of measurement such as temperature and concentration or pressure and therefore, the enthalpy change also changes with conditions of measurement. Hence, the temperature and condition at which the enthalpy change was measured must be indicated. Most enthalpy values are measured at 25C and at standard state. 29

CHEMISTRY IN ACTION The correct way of writing a thermochemical equation is shown below. H2(g) + O2(g) H2O(l) DH25C = 285.8 kJ where the superscript () indicates standard state and the subscript indicates the temperature at which the value was measured. Ordinarily, however, DH values are taken to be at 25oC, unless otherwise specified. Proper Use of Thermochemical Equations. Thermochemical equations can be used effectively by applying the following three basic rules of thermochemistry. 1. The magnitude of DH is directly proportional to the amount of reactant or product. This is something we know from experience, that heat content is an extensive property. The more gasoline we burn, the more energy we get! This rule allows us to find DH for any amount of reactant or product. Consider the equation given as an example earlier: H2(g) + Cl2(g) 2HCl(g) DH = 185 kJ

This equation means that 185 kJ of heat are produced when one mole of H2 reacts completely, or one mole of chlorine gas, Cl2, reacts completely, or two moles of hydrogen chloride are formed from H2 and Cl2 . Suppose only 1 mole of HCl was formed. What will be DH? DH = 1.0 mol HCl x
- 185kJ = -92.5 kJ 2molHCl

2. DH for a reaction is equal in magnitude but opposite in sign to the DH for the reverse reaction. This means that the amount of heat released from the formation of HCl from H2 and Cl2 in the example is the same amount of energy needed to be absorbed to decompose the same amount of HCl. H2(g) + Cl2(g) 2HCl(g) 2HCl(g) H2(g) + Cl2(g) DH = 185 kJ DH = +185 kJ

A qualitative statement of this rule is that if a certain reaction is exothermic, then its reverse is endothermic. In Episode 9 Condensed Phases of Matter, we learned that the process of evaporation of a liquid is an endothermic process. The 30

CHEMISTRY IN ACTION reverse process, condensation of a gas to a liquid, must be exothermic or energy releasing. 3. The value of DH for a reaction is the same whether the process occurs in a single step or a series of steps. This principle is known as Hesss Law, which states that if a reaction occurs in several stages or steps, the enthalpy change for the overall process is the sum of the enthalpy changes for the individual steps. Let us consider the formation of nitrogen tetroxide, N2O4, from N2(g) and O2(g). The reaction occurs through 2 steps: Step 1: Step 2: N2(g) + O2(g) NO2(g) 2 NO2(g) N2O4(g) DH = + 33.85 kJ DH = 58.04 kJ

The overall reaction is obtained by: Step 1 x 2: Step 2: N2(g) + 2 O2(g) 2 NO2(g) 2 NO2(g) N2O4(g) DH = 2 (+33.85) kJ DH = 58.04 kJ

Since the overall reaction is obtained by adding the last 2 equations, the enthalpy change for the overall reaction is obtained by adding the values for the 2 equations. We get: N2(g) + 2 O2(g) N2O4(g) DH DH = (2 x 33.85) 58.04 kJ = + 9.66 kJ

Notice that the use of Hess Law and knowledge of heats of reaction of some chemical reactions is also one way of determining the heat of a reaction. What Information the Heat of Reaction Gives. The sign of DH reveals some information about the process itself. Reactions involve bond breaking, which is energy requiring and bond formation, which is energy releasing. For example, the last equation represent a reaction that is endothermic, in which heat is absorbed during the formation of N2O4(g). The positive value of the overall DH shows that a larger amount of energy is needed to break bonds in the reactants than the amount of energy released to form the bonds in the products. Since the amount of energy needed is greater than the amount of energy released, the deficiency in energy is taken from an external source, in some instances, from the surroundings. The heat of reaction also indicates the relative stability of the products of a chemical 31

CHEMISTRY IN ACTION reaction. The greater the amount of heat evolved during the formation of a compound, the more stable is the compound. This means that exothermic reactions form products that are more stable than the reactants. Aside from predicting the stability of the products, it is also possible to predict the chemical reactivity of related compounds from their heats of reaction. For example, the standard enthalpies of formation of the compounds HF, HCl, HBr, and HI are 271.1, -92.3, -36.4 and +26.5 kJ/mol respectively. Since the value for HF is most exothermic, this indicates that HF is the least reactive and most stable among the compounds, and would require the greatest amount of energy to decompose. Determination of Enthalpies of Reaction. In Episode 16 Energy Conservation, the determination of the heat of reaction between HCl and NaOH through calorimetry was demonstrated. Calorimetry is the experimental and direct way of determining heats of reaction. However, many reactions cannot be carried out in calorimeters and the enthalpy changes for these reactions are determined indirectly from known thermochemical data. One way of calculating heats of reactions is through the application of Hess Law, as shown in the section on the proper use of thermochemical equations. The enthalpy change for reactions that are difficult to carry out, such as the formation of carbon monoxide from the incomplete combustion of carbon, can be calculated using this method. The heats of reaction for the complete combustion of carbon (Equation 1) and the reaction of carbon monoxide with oxygen to produce carbon dioxide (Equation 2) are known and can be used to calculate the heat of formation of carbon monoxide. Equation 1: Equation 2: C(s) + O2(g) CO2(g) CO(g) + O2(g) CO2(g) H = -393.5 kJ H = -283.0 kJ

To calculate H for the reaction: a. reverse equation 2:

C(s) + O2(g) CO(g), H = + 283.0 kJ H = + 283.0 kJ H = - 393.5 kJ H = +283.0 + (-

CO2(g) CO(g) + O2(g)

b. add equation 1 to the reverse of equation 2. CO2(g) CO(g) + O2(g) + C(s) + O2(g) CO2(g) C(s) + O2(g) + CO2(g) CO2(g) + CO(g) + O2(g) 393.5)kJ Net equation: C(s) + O2(g) CO(g) 32

H = -110.5 kJ

CHEMISTRY IN ACTION A second way of calculating enthalpy changes of reactions is to use enthalpies of formation of compounds. The difference between the sum of enthalpies of formation of the products (SHP) and the sum of the enthalpies of formation of the reactants (SHR) is the heat or enthalpy of the reaction: H = SHP SHR An example where the enthalpy of reaction is determined from standard enthalpies of formation of compounds is shown in a succeeding section on heat of combustion and another was presented in Episode 17 Energy and Change. Enthalpies of Formation, DHof. The standard molar enthalpy of formation of a compound is the enthalpy change when one mole of compound is formed from the elements at their standard states. The standard state of any substance is the most stable state of the pure element at 1 atm pressure and at the temperature of interest. As mentioned in an earlier section, the superscript degree in the symbol denotes that the enthalpy change is a standard enthalpy change and the subscript f signifies that the reaction is the formation of a substance from its component elements. There is no process involved in forming an element in its most stable form from itself, and thus, the standard enthalpy of formation of an element in its standard state is zero. Heat of Combustion. Combustion is an example of an exothermic process. The heat of reaction for a combustion reaction is called heat of combustion, DHC, which is the heat evolved when one mole of a substance is burned completely in oxygen to form products in their most stable states at standard conditions. Just like for any other reaction, the heat of combustion of a substance can be calculated from known values of standard enthalpies of formation of all products and reactants. For example, the combustion of ethanol, C2H5OH(l), is given by the equation, C2H5OH(l) + 3 O2(g) 2 CO2(g) + 3 H2O(l) The heat of combustion is calculated by subtracting the sum of the enthalpies of formation of the reactants from the sum of the enthalpies of formation of the products. DHC = [2DHf(CO2) + 3DHf(H2O)] [DHf(C2H5OH) + 3DHf(O2)] Hence, DHC = [2 ( -393.5 kJ ) + 3 ( -285.8 kJ )] [( -277.7 kJ ) + 3 ( 0 )] DHC = - 1366.7 kJ /mol C2H5OH 33

CHEMISTRY IN ACTION

Fuel Value. One of the important uses of thermochemical measurements is in assessing materials as energy sources. Most of these materials are what we call fuels which liberate heat through combustion. One way to compare fuels is through their heats of combustion. In general, fuels with higher heat of combustion are better fuels. Among the fuels listed in the table below, we find octane, the main component of gasoline, to have the highest heat of combustion. Fuels can also be compared through their fuel values. Fuel value is the amount of heat produced per gram instead of per mole of burned fuel. From the list below, hydrogen gas yields the most amount of energy per unit mass. Fuel Hydrogen, H2 Methane, CH4 Methanol, CH3OH Ethanol, C2H5OH Octane, C8H18 Fuel Values DHC, kJ/mole 282 880 726.4 1366.7 4947.6 Fuel value (kJ/g) 141 55 22.7 29.7 43.4

Spontaneous and Nonspontaneous Reactions. Combustion reactions are reactions that, once started, can continue on as long as reactants are still available. Chemical reactions and physical processes that occur without external intervention or application of energy are called spontaneous processes. Examples of these are the diffusion of a colored substance in water, burning a piece of paper, browning of cut potatoes, and rusting of metals. On the other hand, processes that take place only upon the application of heat, such as boiling an egg, are nonspontaneous reactions. What makes a process spontaneous? If we look at some familiar processes that are spontaneous, we notice that these processes tend to go in the direction of lower energy state. A ball will roll downhill spontaneously accompanied by a drop in potential and kinetic energy when it rolls to a stop. Combustion reactions are exothermic reactions. Many exothermic processes occur spontaneously but there are some which are not spontaneous. The freezing of water is also an exothermic process, but water will not freeze unless we place it in a freezer. But in Alaska, water will freeze spontaneously! This tells us that temperature also influences the spontaneity of certain processes.

34

CHEMISTRY IN ACTION There are also endothermic processes that occur spontaneously. One example of a spontaneous process that is endothermic is the dissolution of ammonium chloride. What really drives spontaneous processes to occur? That is the topic of the next lesson. VOCABULARY WORDS 1. Enthalpy the heat content of a substance or a system. 2. Standard heat of reaction change in heat content during a reaction where reactants and products are in their standard states. 3. Standard enthalpy of formation a special case of standard heat of reaction, where the reaction involved is the formation of a compound from its component elements in their standard states. 4. Thermochemistry the quantitative study and measurement of heat changes accompanying chemical processes. 5. Thermochemical equation a chemical equation that includes the change in heat content that accompanies the processes being represented by the equation. 6. Heat of combustion enthalpy change accompanying the combustion of one mole of a substance. 7. Hesss Law law that states that the enthalpy change of the overall process is equal to the sum of the enthalpy changes of all the steps that comprise the process. 8. Fuel value the heat liberated from the combustion of one (1) gram of fuel. 9. Spontaneous process a process that occurs without any intervention once the reactants come together at the right conditions. 10. Nonspontaneous reaction a process that requires a continuous input of energy in order to occur. PRE-VIEWING ACTIVITIES A. As a motivational activity, demonstrate to the students the reaction between water and sodium metal. Place a very small piece of sodium metal in a dish with a small amount of water. (WARNING! This should be done by a capable person 35

CHEMISTRY IN ACTION in a proper venue, using the appropriate equipment and protective gear. The audience should be in a safe distance away.) Ask the students to observe the reaction carefully. The reaction of sodium metal with water is very explosive. This is an example of an exothermic reaction wherein energy is liberated in the form of heat and light. B. Introduce the episode that deals with the concepts of enthalpy and enthalpy changes by asking how energy changes are expressed as part of chemical equations. C. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the guide questions as they watch the video. Guide Questions/Answers 1. What are included in a thermochemical equation? A thermochemical equation includes a balanced equation according to the Law of Conservation of Mass, the physical states of the reactants and products are indicated, the temperature at which the reaction occurs, and the heat of reaction carrying the appropriate sign. 2. What does the heat of reaction tell us? It indicates whether the reaction is endothermic or exothermic; whether energy for bond breaking is greater or less than the energy released from bond formation, and the relative stability of the products formed.

3. How is fuel value calculated? Fuel value is calculated by dividing the molar heat of combustion of a fuel by its molar mass to get a value in kJ/g fuel. 4. How is the enthalpy change of a reaction that takes place in several steps determined according to Hess Law? According to Hess Law, the enthalpy change of a reaction that occurs in several steps can be calculated simply by adding the enthalpy changes for all the steps that comprise the reaction. 5. Why is hydrogen not used as a commercial fuel? Hydrogen may have a very high fuel value but its being a gas with an extremely low critical temperature makes it difficult to store and is less portable compared to other fuels. 36

CHEMISTRY IN ACTION 6. What is the relationship between enthalpy, entropy, and spontaneity of a reaction? The spontaneity of a reaction is influenced by both enthalpy and entropy. Many spontaneous reactions have negative enthalpies (exothermic) and positive entropy changes (going to more disorder). VIEWING ACTIVITIES Let the students view the segments on (1) Writing Thermochemical Equations at 2:30 - 8:30 & 9:00 - 19:00 and (2) Introduction to Entropy at 19:05 - 20:50.

POST VIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. B. Discuss how the First Law of Thermodynamics is applied as per the video clip. TEACHING TIP Concept Mapping. Divide the students into groups and ask them to prepare a concept map using the vocabulary words given previously by providing linking words to relate the concepts. Ask the groups to present their concept maps in class. ASSESSMENT Quiz. Give the required information. 1. What is thermochemistry? 2. Give two ways on how enthalpy of a reaction can be determined. 3. What refers to the degree of disorderliness?

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CHEMISTRY IN ACTION 4. What law gives the relationship between heat, work and change in internal energy? 5. What does the symbol PDV means? 6. The enthalpy of formation of the amino acid leucine, C6H13O2N(s) is -637.3 kJ/mol. Write the thermochemical equation to which this value applies. 7. Calculate the standard heat of formation for the fermentation of glucose: C6H12O6(s) 2C2H5OH(l) + 2CO2(g) 8. Calculate DHo for the synthesis of lime, CaCO3, an important step in the manufacture of cement, from the following thermochemical data: CaCO3(s) CaO(s) + CO2(g) DHof , CaCO3(s) = -1206.9 kJ/mol DHof, CaO(s) DHof CO2(g) ANSWER KEY Quiz. 1. Thermochemistry is the study and measurement of heat changes that take place during chemical reactions. 2. Two ways on how enthalpy of a reaction can be determined: a. through calorimetry. b. from standard enthalpies of formation of substances. 3. Entropy 4. First Law of Thermodynamics 5. Pressure-volume work, i.e. expansion or compression 6. C(s) + 13/2 H2(g) + O2(g) + N2(g) C6H13O2N(s) kJ/mol = -635.1 kJ/mol = -393.5 kJ/mol

DHof = 637.3

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CHEMISTRY IN ACTION 7. C6H12O6(s) 2C2H5OH(l) + 2CO2(g) DH = [2(DHof (CO2)) + 2(DHof (C2H5OH))] [DHof (C6H12O6)] DH = [2(-393.5) + 2(-277.7)] [-1271.0] = -71.4 kJ 8. DH = [DHof (CO2) + DHof (CaO)] [DHof (CaCO3)] = [(-393.5) + (-635.1)] [(-1206.9)] = +178.3 kJ REFERENCES Mapa, A. & T. Rabago. (1999). Chemistry III. QC: SD. Masterton, W. L. & C. N. Hurley. (2001). Chemistry: principles and reactions.( 4th ed.). PA: Harcourt College Publishers. McMurry, J. & R. C. Fay. (1995). Chemistry. NJ: Prentice Hall International, Inc. Petrucci, R. H. & W. Harwood. (1993). applications. NY: MacMillan Publishing, Co. Chemistry, principles and modern

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CHEMISTRY IN ACTION Chapter 5: Heat Effects and Energy Relationships in Chemical Reactions EPISODE 19: THE LAWS OF DISORDER OVERVIEW Things around us change even without human intervention. Iron nails rust, fruits ripen, leaves fall from their branches. But other processes need some help to occur. Food will not cook without heat. Water will decompose to hydrogen and oxygen only if electricity is continuously applied through it. This episode, the fourth in this volume on thermodynamics, is about the thermodynamic property called entropy, which is related to the degree of randomness of a system, and how the change in entropy influences the spontaneity of reactions. OBJECTIVES At the end of this lesson, the student should be able to: 1. describe a spontaneous reaction; 2. give example of spontaneous changes; 3. define entropy in his/her own words; 4. determine when a process results to an increase or a decrease in entropy; 5. explain the Second Law of Thermodynamics; 6. define free energy; 7. explain the Third Law of Thermodynamics; and 8. predict whether changes are spontaneous or not based on the change in free energy (G). INTEGRATION WITH OTHER LEARNING AREAS This episode can be best appreciated after going through with the three previous episodes in the same chapter, namely, Episode 16 Energy Conservation, 17 Energy and Change, and 18 Thermochemical Equations and Direction of Change. SCIENCE PROCESSES
Observing Experimenting Using mathematical relationships Classifying Inferring Predicting

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CHEMISTRY IN ACTION VALUES

Appreciation for order

LIFE SKILLS
Organization Orderliness

IMPORTANT CONCEPTS 1. A spontaneous process is a process that occurs by itself once started and will continue to happen without outside intervention. 2. A non-spontaneous process is an unnatural process that once started, requires a continuous application of energy to proceed. 3. Entropy is a property of a system that is a measure of the randomness or disorder of the system. The greater the degree of randomness or disorder in a system, the greater is its entropy. 4. The Second Law of Thermodynamics states that every spontaneous change produces an increase in the entropy of the universe. 5. The Third Law of Thermodynamics states that the entropy of a perfect crystalline substance at absolute zero temperature is zero. 6. The free energy, G, is the energy available to do work. 7. The enthalpy , H, of a system is the sum of the free energy, G, and the energy used to increase the entropy of either the system or the surroundings, S. 8. The change in free energy accompanying a process, G, is given by the Gibbs free energy equation, G = H TS. 9. If G for a process is negative, the process is spontaneous. If G is positive, the process is nonspontaneous. BACKGROUND INFORMATION/EPISODE CONTENT Spontaneous and Non-spontaneous Processes. Chemical and physical changes can be either spontaneous or non-spontaneous. Spontaneous processes are those that once started continue to happen without any need for outside intervention. A ball rolling downhill is an example of a spontaneous mechanical change. The melting of ice cubes in a glass of water at room temperature is a spontaneous 41

CHEMISTRY IN ACTION physical change. A mixture of hydrogen gas and oxygen gas will explode in the presence of a spark. Nonspontaneous processes are those that do not take place without a continuous outside intervention, driving force being applied on the system. A ball will roll uphill only if energy is used to roll the ball. Water will not decompose into hydrogen and oxygen gases unless electricity is continuously applied. When a process is spontaneous, its reverse is non-spontaneous in the same conditions. A ball will roll spontaneously downhill, but an uphill roll is definitely non-spontaneous. Dry ice or solid carbon dioxide will spontaneously sublime, but solid carbon dioxide will not form unless vigorous conditions of extremely high pressure and very low temperature are created. Many spontaneous processes involve a decrease in energy. Combustion reactions are exothermic and spontaneous. When a ball rolls downhill, its potential energy drops. But what about the melting of ice? Or the dissolution of ammonium chloride, NH4Cl, in water, both of which are endothermic? Besides enthalpy, there is another driving force of spontaneous reactions, the randomness factor or entropy. Entropy. Entropy, symbolized by S, is a property of a system that expresses the degree of randomness or disorderliness of the system. The unit for entropy is J/molK. In general, the more random or disorderly is the distribution of particles in a system, the greater the entropy. All substances possess some degree of randomness since particles are in constant motion and thus have positive entropy values. The Third Law of Thermodynamics. Consider the two allotropes of carbon, diamond and graphite, which have the same composition but have different physical properties. Are their entropy values at the same conditions the same? Is entropy a measurable quantity? The determination of entropy values is made possible through the use of a reference point where the entropy of a substance is zero. This condition is described in the Third Law of Thermodynamics, which states that at absolute zero temperature, 0 K, pure crystals of a substance are in a perfectly ordered state and thus have an entropy value of zero. The lowest possible value for the entropy of a substance is therefore zero, when the temperature is at absolute zero, 0 K. When comparing entropies of substances or evaluating entropy changes accompanying processes, the following conditions serve as useful guide: 1. The entropy of a substance always increases as it changes state from solid to liquid to gas. 2. When a pure solid or liquid dissolves in a solvent, the entropy of the substance increases. 3. When gas molecules escape from a solvent, entropy increases. 42

CHEMISTRY IN ACTION 4. Entropy generally increases with increasing molecular complexity. 5. Reactions that increase the number of moles of particles tend to increase the entropy of the system. 6. An increase in temperature increases entropy. Entropy values of substances may not provide much information, but the change in entropy of a substance or a system during a reaction or a physical change is more important when evaluating whether a process is spontaneous or not. The significance of entropy is that whenever a spontaneous change occurs, there is often a positive entropy change. The Second Law of Thermodynamics. Like enthalpy, entropy is a state property, which means that the entropy change of a system, S, depends on the entropy values of the initial and final states and not the path followed by the system to reach the final state. S = Sfinal - Sinitial or for chemical reactions, S = Sproducts Sreactants

If the system changes from a more orderly to a less orderly arrangement, Sfinal > Sinitial , the entropy change of a system, S, is a positive value. A negative value of S indicates that the process caused the system to become more ordered since Sfinal < Sinitial. The Second Law of Thermodynamics states that all systems tend to reach a state of maximum disorder. Every spontaneous change produces an increase in the entropy of the universe. If you expend energy to arrange a pile of newspapers, the pile becomes more organized but all the carbon dioxide and other metabolism products that you produced as you worked are released into the universe. The disorder that you generated exceeds the order that you made. This results to a net increase in entropy of the universe. The second law, therefore, describes the driving force of spontaneous processes: the tendency towards maximum entropy. However, we find some spontaneous processes that show a negative S. For example, water that condenses as droplets on the outer surface of an icefilled glass, seem like a system with decreasing entropy. What factors then drive a spontaneous process? Gibbs Free Energy. Disorder is not only in the physical arrangement of particles. It also involves the dispersal of energy. The American physicist and chemist J. Willard Gibbs is credited with the mathematics that relate changes in enthalpy and entropy and spontaneity of processes. In simplified terms, Gibbs argued that the total heat change, H, is the sum of energy that can be used to do work, or free energy, G, 43

CHEMISTRY IN ACTION and energy that is no longer usable to do work because it has been used to create more disorder, S. H = G + TS On rearrangement, the equation becomes the Gibbs free energy equation, G = H TS where G = change in free energy, Gfinal - Ginitial H = enthalpy change, Hfinal - Hinitial S = entropy change, Sfinal - Sinitial T = absolute temperature, K. Spontaneous processes have a negative free energy change, G < 0. These processes release energy to the surroundings and the greater and more negative G, the greater is the likelihood of the process occurring. Non-spontaneous processes have a positive free energy change, G > 0. For these processes to occur, the system must take in energy from the surroundings. Without this additional energy, the nonspontaneous process will not take place or will stop if it has started. If G = 0, then the process and its reverse occur simultaneously, and the system is in equilibrium. The following table summarizes the effects of enthalpy changes and entropy changes on spontaneity, based on the Gibbs free energy equation: Enthalpy change Exothermic, H < 0 Exothermic, H < 0 Endothermic, H > 0 Endothermic, H > 0 Entropy change Increase, S > 0 Decrease, S < 0 Increase, S > 0 Decrease, S < 0 Spontaneous? Yes, G < 0 Only at low T, if |TS| < |H| Only at high T, if TS > H No, G > 0 at all temperatures Example Oxidation of glucose in muscle Freezing of water Melting of ice Formation of C2H4 from C and H

VOCABULARY WORDS 1. Entropy the degree of randomness of a system. 2. Second Law of Thermodynamics all processes in the universe tend to proceed to a state of increasing entropy of the universe. 3. Spontaneous process one, which when started, will continue to happen even without external intervention. 4. Non-spontaneous process one, which when started, will require continuous 44

CHEMISTRY IN ACTION input of energy in order to continue happening. 5. Third Law of Thermodynamics states that the entropy of all substances in pure crystalline state at 0 K is zero. 6. Free energy the amount of energy involved in a process that is available to do work. PREVIEWING ACTIVITIES A. Let the students to list down processes or reactions happening around them that are: 1. spontaneous. 2. non-spontaneous. B. Discuss the Second Law of Thermodynamics. C. Discuss the Third Law of thermodynamics. D. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the guide questions as they watch the video. Guide Questions/Answers 1. What is entropy? Entropy is the thermodynamic quantity that refers to the degree of randomness or disorder of a system. 2. Is entropy a measurable quantity? The measurable quantity is the change in entropy or the change in the disorder or randomness of the system when a certain process occurs. However, there are reported values of absolute entropy of substances, whose determination is made possible by setting as a reference point when entropy of all substances is set at zero and this is when substances are in pure crystalline states at absolute zero, according to the Third Law of Thermodynamics. 3. What makes a reaction spontaneous? A reaction or process is spontaneous if there is a net free energy released when it occurs. This is indicated by a negative value for G in the Gibbs Free Energy equation.

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CHEMISTRY IN ACTION VIEWING ACTIVITIES Let the students view the segments on Entropy and the Second and Third Laws of Thermodynamics at 2:30 - 10:30 and 10:40 - 23:20.

POST-VIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. B. Discuss how the Second Law of Thermodynamics is applied as per the viewing activity. C. Discuss how the Third Law of Thermodynamics is applied as per the video clip.

ASSESSMENT Quiz. Choose the letter corresponding to the best answer. For Questions 1-3, consider the hypothetical endothermic reaction: 4A(g) + B2(g) 2A2B(g) 1. The change in entropy of the system is most likely A. negative. C. zero. B. positive. D. cannot be determined. 2. The reaction is A. spontaneous at all temperatures. C. spontaneous only at high temperatures. B. non-spontaneous at any temperature. D. non-spontaneous at low temperatures. 3. The reverse of the above reaction is therefore A. spontaneous and exothermic. C. spontaneous and endothermic. B. non-spontaneous and exothermic. D. non-spontaneous and endothermic. 4. Which of the following results in a decrease in entropy? A. Evaporation of water C. Melting of ice B. Freezing of water D. Sublimation of dry ice

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CHEMISTRY IN ACTION 5. At what temperature would you expect the melting of ice to be non-spontaneous at normal atmospheric pressure? A. -10oC C. 10oC o B. 1 C D. 100oC 6. Which of the following processes is non-spontaneous at 25oC? A. Condensation of water vapor C. Burning of candle B. Ripening of mango D. Rusting of iron 7. An increase in entropy occurs when A. solids form from the freezing of pure liquids. B. the temperature of a substance decreases. C. the number of molecules of gas present in the system increases as a result of a chemical reaction. D. a gas condenses into a liquid. 8. Which of the following is true about free energy? A. It is available or unused energy. C. It is released by the system. B. It is absorbed by the system. D. It is zero at absolute zero temperature. 9. Which of the following statements is false? A. A reaction that is endothermic and involves an increase in entropy can be spontaneous at high temperatures. B. In increase in molecular motion results in an increase in entropy. C. Spontaneity is favored by a decrease in both entropy and enthalpy. D. The entropy of the universe is increased when spontaneous reactions occur. 10. At absolute zero temperature, A. most substances have solidified. B. melting of ice is spontaneous. zero. ANSWER KEY Quiz. 1. 6. A A 2. 7. B C 3. A 8. A 4. B 9. C 5. 10. B C

C. particles are no longer moving. D. the free energy of all processes is

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CHEMISTRY IN ACTION REFERENCES Brown, T. L., LeMay, H. E. & B. E. Bursten. (2004). Chemistry: the central science. NJ: Prentice Hall, Inc. Silberberg, M. S., (2000). Chemistry: the molecular nature of matter and change. NY: McGraw-Hill, Inc.

Useful Website Volland, W. Online introductory chemistry. http://scidiv.bcc.ctc.edu/wv/7/0007003-free _energy.htm

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CHEMISTRY IN ACTION Chapter 6: Rates and Limits of Change EPISODE 20: RATES OF REACTION OVERVIEW Chemical reactions are processes in which one or more substances are converted into other substances. Evidences that indicate the occurrence of chemical changes include change in color, evolution of gas, formation of precipitate or change in temperature of the reacting system. Some of these evidences can be observed immediately after the reactants come together for certain reactions, but for other reactions, the observables are not readily apparent because chemical reactions may occur in a snap of a finger or may require many years to reach completion. This episode introduces us to chemical kinetics, the study of the rates and mechanisms of chemical reactions. The factors affecting rates of reactions are investigated and explained using the Collision Theory. OBJECTIVES At the end of this lesson, the student should be able to: 1. define rate of reaction; 2. identify parameters used to measure rate of reaction; 3. enumerate and explain the factors affecting the rates of chemical reactions; 4. state the Collision Theory of molecules; 5. use the Collision Theory to explain the factors affecting reaction rates; and 6. cite applications of chemical kinetics in everyday processes. INTEGRATION WITH OTHER LEARNING AREAS This video lesson makes use of concepts learned in Episode 10 - Indicators of Chemical Change, 16 - Energy Conservation, and 17 - Energy and Change. SCIENCE PROCESSES
Using space-time relationships Inferring Classifying Interpreting data Predicting Observing Experimenting Measuring Controlling variables Using mathematical relationships

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CHEMISTRY IN ACTION VALUES

Helping out one another Industriousness Appreciation for Gods bountiful creations

LIFE SKILLS
Creative thinking Problem solving Understanding ones emotions Coping with stress

IMPORTANT CONCEPTS 1. Some chemical reactions are extremely fast, while others can be very slow. 2. The rate of a chemical reaction can be measured by the rate of formation of products or the disappearance of reactants. 3. The rate of a reaction can be altered by changes in the concentration of reactants or the reaction temperature. 4. A catalyst can increase the rate of a reaction. 5. The activation energy is the amount of energy that reactants must acquire to be able to undergo reaction. BACKGROUND INFORMATION/EPISODE CONTENT Fast and Slow Reactions. Chemical reactions differ in the rate at which they proceed. Some chemical reactions are fast while others occur slowly. Fast chemical reactions take only a short time to complete and the changes are noticeable at once. Examples of fast reactions are the reactions involved in a magnificent display of fireworks. The fireworks are a rapid succession of reactions between oxygen and compounds of active elements like strontium (Sr), barium (Ba), sodium (Na), aluminum (Al), and magnesium (Mg), all of which happen instantaneously. Slow chemical reactions may take days, months or even years to complete. Common examples of slow reactions are the blooming of flowers, which occur over a few days or the rusting of iron nails. The curing of cement is another example of a slow reaction. One can quickly notice the solidification of cement right after being poured off but the reactions do not stop there and can continue for years to make the concrete strong and hard. Rates of Reactions. The area of chemistry that deals with the speed or rate at which reactions occur is chemical kinetics. Whenever we talk about rates or the speed of any occurrence or event, we express this quantitatively through some measurable 50

CHEMISTRY IN ACTION change that happens in a given time interval. The rate of a chemical reaction is measured in either of two ways: by the decrease in the amount or concentration of a reactant or by the increase in the amount of a product within a given unit of time. Consider the hypothetical chemical reaction: A B (reactant) (product) Rate of reaction = change in the concentration of A per unit interval of time or Rate of reaction = change in the concentration of B per unit interval of time We usually look for a property of a reactant or a product of the reaction that can be monitored qualitatively or quantitatively through the use of some measuring instrument. For example, if a reaction produces a colored product, you may follow the progress of a reaction by monitoring the increase in intensity of the color of the reacting mixture as more product is formed. If the reactant is colored, but none of the products are, the rate of disappearance of color can be used to measure rate. Some reactions produce gaseous products and the rate of gas evolution can be followed. An example of a qualitative determination of how fast a reaction occurs is demonstrated in the video lesson. In the experiment shown, the burning of the wood splinter in air is compared with the burning of another wood splinter inside a test tube containing pure oxygen. The flame produced is much brighter and the burning of the wood is quicker inside the test tube with pure oxygen. It can be inferred from these observations that the rate of reaction inside the test tube is greater than the one occurring in open air. A more quantitative comparison of rates can be done by following the changes in the concentration of the reactants or products in the reaction and plotting the data in the form of decay or growth curves of substances. A decay curve of the reactant indicates the decrease in amount of reactants still remaining as the reaction proceeds as illustrated in the figure at the right.

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CHEMISTRY IN ACTION Factors Affecting Reaction Rates. The rate of a reaction is affected by the following factors: concentration of reactants, temperature, and the presence of catalyst. Concentration of Reactants. The burning of the wood splinter shown in the video lesson is a good demonstration of the effect of concentration of reactant, in this case oxygen, on the rate of the reaction. Burning, or in more technical terms, combustion, is the reaction of substances with oxygen. The flame produced from the burning of the wood splinter in open air, which has only about 20% oxygen, is less bright and the burning is slower compared to that in the tube containing pure oxygen. A second laboratory demonstration on the effect of concentration of reactants that is shown in the video lesson is the reaction between hydrochloric acid, HCl in solution, and zinc, Zn, metal. The equation of the reaction is: HCl(aq) + Zn(s) Zn2+(aq) + 2Cl-(aq) + H2(g) Since one of the products of this reaction is a gas, H2, the determination of the rate of reaction is done by getting the volume of gas produced for a certain period of time. An improvised gas buret is used to measure the volume of the gas formed. In the experiment, a constant amount of Zn is dropped in each of the test tubes containing different concentrations of HCl. The rates of reaction at different concentrations of HCl were compared by measuring the amount of hydrogen gas produced in each test tube for the same length of reaction time. The results of the experiment showed that more hydrogen gas was produced from the reaction mixture with a higher concentration of HCl. Thus, the higher the concentration of the HCl solution, the faster is the chemical reaction. As the concentration of reactants increase, the rate of the reaction also increases. Temperature. The same experimental set-up was used in the video lesson to demonstrate the the effect of temperature on the rate of reaction of HCl and Zn. Three different flasks, each containing the same volume of HCl solution and Zn are subjected to different temperatures: hot water bath (40oC), room temperature (30oC), and ice water bath (10oC). The results showed that the rate of gas evolution is greater at higher temperature. One very familiar application of the effect of temperature on rates of reaction is refrigerating perishable foods such as milk. The bacterial reactions that lead to the spoiling of milk proceed more rapidly at room temperature than at the lower temperature of a refrigerator. The higher the temperature, the faster is the reaction. 52

CHEMISTRY IN ACTION Catalyst. The presence of a catalyst is another factor that influences the rate of a chemical reaction. A catalyst is a substance that speeds up a chemical reaction, but is not consumed in the reaction. Hydrogen peroxide or agua oxigenada undergoes decomposition by itself, especially when exposed to bright light. The decomposition reaction is accompanied by the formation of bubbles as oxygen gas is formed and escapes from the liquid. (slow reaction) H2O2(l) 2H2O(l) + O2(g)

In a dark bottle, the reaction is very slow. But if manganese dioxide is added, vigorous bubbling is observed. MnO2 (fast reaction) H2O2(l) 2H2O(l) + O2(g) Manganese dioxide is not an added reactant to the process but a catalyst and is not consumed in the reaction. An evidence of this is that one can recover the substance from the system. There is no change in its amount after being recovered from the reaction vessel. A catalyst can increase the rate of reaction by providing an alternative path for the reactant molecules. This new path is characterized by a lower activation energy requirement. The activation energy is the minimum energy that reactant molecules must acquire to enable them to undergo bond breaking and electron rearrangements during the reaction. Unless a reactant molecule has enough energy to meet this minimum, it cannot be converted into the product. When a catalyst opens an alternative route that is of lower activation energy for the reactants, then more reactant molecules can meet the energy requirement and react to form the products. The Collision Theory of Molecules. The effects of the aforementioned factors on the rate of reactions are best explained by the Collision Theory. The theory suggests that for a chemical reaction to occur, the reactant molecules must collide. The collision must be effective so that a successful reaction results. How can collisions become effective? The colliding molecules must be properly oriented and that the collisions have sufficient energy to meet the activation energy requirement. According to the Collision Theory, an increase in concentration of reactants results in an increase in reaction rates because the increase in the number of particles in the reaction mixture results in an increase in the frequency of collisions. An increase in the temperature of the reaction increases reaction rate because the reacting particles would have greater kinetic energy and thus would collide with one another more frequently and collide with greater impact. When colliding particles have more energy, the probability of collisions becoming effective is also greater. Catalysts are 53

CHEMISTRY IN ACTION also believed to help in positioning reactants in proper orientation to make collisions more effective. Other Factors Affecting Reaction Rates. Other experimental conditions that influence reaction rates are the following: 1) Nature of the reacting species. Oppositely charged species often react more rapidly than neutral species. Thus, during molecular collision, charged reacting species like ions would produce faster reactions than those that are uncharged. Ionic species that are oppositely charged react faster and those with the same charges will repel each other resulting to no reaction. The strength of bonds that need to be broken during the reaction affects the magnitude of the activation energy that the reacting species must overcome. The stronger the bond(s) that have to be broken, the greater is the minimum energy requirement (activation energy) for the reaction to occur. The size and shape of the reacting species also play a significant role in determining rate of reaction. Larger molecules consisting of more atoms in the structure may serve as a barrier and may block the reactive part of the molecule from interacting with another. This barrier may slow down the rate of reaction. 2) The physical state of the reactants also affects the reaction rates. The three states of matter differ in the arrangement and distance of separation between particles, strength of attractive forces, and motion of the particles. Greater distance between molecules reduce the chances for particle collision. With greater distance, the attractive forces among the reacting species are also decreased. When these happen, the reaction slows down. VOCABULARY WORDS 1. Curing of cement process of drying or aging cement. 2. Inhibitor a substance that slows down or prevents a chemical reaction. 3. Papain an enzyme that catalyzes the breakdown of proteins. 4. Wood splinter a thin, sharp piece of wood made by splitting or breaking.

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CHEMISTRY IN ACTION PRE-VIEWING ACTIVITIES A. Initiate a discussion about the spectacular display of colors in fireworks. Let the students tell their own stories. B. Present pictures of different chemical reactions. Lead the students to note that these chemical reactions differ in terms of rate. C. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the Guide Questions as they watch the video clip. Guide Questions/Answers 1. What is rate? How is the rate of a moving object measured? Rate is a measure of how much change has occurred per unit time. For a moving object, rate expresses how much an object has been moved or has changed position over time. It is measured by getting the distance it has traveled divided by the time. 2. What is the rate of chemical reaction? How is it determined? The rate of a chemical reaction refers to the speed by which a chemical reaction proceeds. Rate of reaction is determined by the decrease in the concentration of a reactant or the increase in the concentration of a product during a given unit of time. 3. Explain how the decay and growth curves may be useful in describing the rate of reaction. The decay and growth curves of substances are useful in quantitatively describing changes in the concentrations of the reactants and products in a reaction. The decay curve indicates how much of the reactants are used up while the growth curve indicates the increase in the amount of the products formed. 4. Name the factors that affect reaction rate. The main factors that affect reaction rate are concentration of substances, temperature, and the presence of a catalyst. 5. How do these factors affect the rate of a chemical reaction? In general, an increase in the concentration of the reactants increases the rate of reaction. As temperature increases, the rate of chemical reaction also increases. A catalyst speeds up a reaction. 6. What is a catalyst? Why cant it be considered as another reactant in a chemical reaction? 55

CHEMISTRY IN ACTION A catalyst is a substance that is present in and speeds up a chemical reaction. It cannot be considered as another reactant in a chemical reaction because normally, a reactant is consumed, slowly disappearing in the reaction while a catalyst is not consumed. It remains unchanged in the course of the reaction. 7. What is explained by the Collision Theory? The Collision Theory states that for a chemical reaction to occur, there must be effective collisions among the reacting molecules. Effective collision means that the molecules are properly oriented during collision and that these molecules must possess the minimum energy of activation. 8. How can you relate the Collision Theory to the factors controlling reaction rate? The Collision Theory explains how an increase in concentration of the reacting specie and the reaction temperature can affect reaction rate. With increased concentration of reactant molecules, the chances for molecular collision consequently increase. The more collisions occurring, the greater are the chances for effective collisions, resulting to faster chemical reaction. The increase in the temperature of the reactants also increases the rate of reaction because the added kinetic energy means more collisions and more reacting molecules with sufficient energy for the reaction to proceed. 9. What is activation energy? What is its significance to the rate of reaction? Activation energy is the minimum energy required to produce a chemical reaction. It can be thought of as an energy hill which the molecules must climb before a reaction can begin.

VIEWING ACTIVITIES Suggested viewing segments are 17:42 - 19:12 and 19:19 - 19:39 on Activation Energy.

POST-VIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. B. Additional Useful Information/Teasers.

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CHEMISTRY IN ACTION If God designed the formation of water from the reaction of H2 and O2 to proceed at a fast rate, will mother Earth survive from drowning? Let the students give and explain their own views. Why do apples discolor when they are peeled? Oxygen turns the peeled fruits like apples brown. However, bananas turn brown even when they are not peeled because their skins are not as strong as apple skins so oxygen seeps in. Why do onions make you cry? The onions strong oils mix with the moisture in the eyes. This forms an acid that irritates the eyes and causes them to shed tears. Other questions that can be asked or may arise during discussions are the following: (1) For future engineers What determines the rate at which steel rusts? Which factors control the rate at which fuel burns in an auto engine? (2) For future dentists How do you design a rapidly setting material for dental fillings? (3) For future doctors of medicine Which biochemical reaction rates determine the contraction and relaxation of smooth muscle in the arteries of the heart? Some misconceptions: On the difference between a catalyst and an inhibitor, remember that a catalyst is defined as any substance that serves as stimulus that increases or hastens the occurrence of a result. Inhibitors do the opposite. Catalysts speed up the rate of a chemical reaction. Inhibitors slow down or prevent them from occurring.

Suggested Activities A. Alternative Laboratory Experiment. (adapted from the RBEC Primer). Objectives: To enumerate the factors affecting rates of chemical reactions and to explain how each factor affects reaction rate. Materials: 4 grams of rock salt, magnesium ribbon,1 gram of refined salt, , ethyl alcohol , hydrogen peroxide, manganese dioxide, MnO2, 3 M HCl solution, 6 M HCl solution, tap water, hot water, graduated cylinder, spatula, small beakers

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CHEMISTRY IN ACTION Procedure: 1. Nature of reactants Measure 0.5 g each of the two kinds of salt using a balance. Stir the salt separately in two beakers containing equal amounts of ethyl alcohol and water. Observe what happens and make some comparisons. 2. Temperature Measure two 1-gram rock salt using a balance. Put each gram of salt in two small beakers containing tap water and hot water. Compare the time it takes for each of the salts in two separate beakers to dissolve. 3. Particle size Measure separately 1 gram each of rock salt and refined salt. Put these in beakers containing 5 mL of water. Observe the time it takes for the two salts to dissolve in tap water. 4. Concentration of reactants Get two 2-cm magnesium ribbons. Add each one of these in beakers containing 3 M and 6 M HCl. Observe the reaction. 5. Catalyst Measure 20 ml of hydrogen peroxide in a small beaker. Put a very small amount of manganese dioxide in a spatula. Using a spoon with a long handle, put a burning magnesium ribbon to the beaker. Describe the reaction.

Analysis of Results: 1. Table salt, NaCl, is an ionic species. It readily dissolves in water since water is a polar compound. Ethyl alcohol does not readily dissolve NaCl because ethyl alcohol is non-polar. This system demonstrates like dissolves like. 2. The rock salt that is added to a beaker containing hot water dissolved faster than the one added to a beaker containing tap water. At higher temperature, particles acquire more kinetic energy. Increased kinetic energy increases the speed of the particles. Increased particle motion means more particle collisions, thus a faster dissolution process. 3. The refined salt dissolves faster than the rock salt because refined salt has smaller particles. Smaller particles are more reactive. They have greater surface area or more reactive area, thus increasing the frequency at which particles collide. 58

CHEMISTRY IN ACTION 4. The magnesium ribbon reacted faster in the beaker containing 6 M HCl, which has higher concentration. Higher concentration of reacting molecules means more molecules participating in the reaction. More molecules mean greater chances for particle collision. 5. There was faster evolution of bubbles in the presence of manganese dioxide, indicating faster production of oxygen gas. Manganese dioxide acted as a catalyst in the decomposition of hydrogen peroxide, producing more oxygen to support the burning of magnesium. B. Sketching Models. Ask the students to sketch a model of the orientation and interaction of hydrogen iodide (HI) and chlorine (Cl) that is most probable for a successful reaction. Give the students a preliminary idea by giving them the equation of the reaction. HI(g) + Cl2(g) HCl(g) + I2(g) C. Dyad Activity. Ask students to work in pairs. Test their reasoning by giving them thoughtprovoking questions such as: Can the following statement ever be true? Heating a reaction mixture increases the rate of a certain reaction but decreases the yield of product from the reaction. Explain why or why not? ASSESSMENT Quiz. Choose the letter corresponding to the correct answer. 1. Which of the following conditions will not speed up a chemical reaction? A. Increased temperature B. Increased pressure C. Nature and concentration of reactants D. Presence of catalyst 2. What is the role of a catalyst in a reaction? A. It is one of the reactants. B. It is one of the products of reaction. C. It speeds up a reaction without being consumed in the reaction. D. It forms spectator ions in solution which provide the condition for faster reaction. 3. Papaya contains papain. It is observed that adding papaya in cooking chicken tenderizes the meat and lessens cooking time. What is the role of papain in cooking chicken? A. A flavoring agent C. A catalyst B. An ingredient D. None of these 59

CHEMISTRY IN ACTION 4. According to the Collision Theory, for a chemical reaction to occur, reacting molecules must A. be properly oriented and have enough activation energy during collision. B. have opposite spins and with a minimum energy of activation. C. be in solution mixtures to have an appropriate medium for the reaction D. be chemically active and similar in chemical nature. 5. Which of the following provides an explanation to how chemical reactions occur successfully? A. Law of Chemical Kinetics B. Law of Conservation of Matter and Energy C. Collision Theory of Molecules D. Law of Action and Interaction 6. The minimum energy required for a reaction to proceed is called A. collision energy. C. molecular energy. B. activation energy. D. bond energy. 7. Which of the following correctly describes the effect of temperature on rate of reaction? A. As temperature increases, the rate of reaction increases. B. As temperature increases, the rate of reaction decreases. C. A change in temperature of the reactants does not change the reaction rate. D. At higher temperature, less molecules participate, thus slowing down the reaction. 8. Molar concentration, M, of substances in solution is also expressed as A. m/L. C. mol/L. B. mL. D. mass/L. 9. In the example of burning steel wool in air which contains 20% oxygen, but bursts into a brilliant white flame in pure oxygen, what factor affects the reaction rate? A. Concentration of reactants C. Addition of catalyst B. Temperature D. None of the above 10. The physiology of most living species depends crucially on enzymes which are protein molecules that increase the rate of selected biochemical reactions. As a catalyst, how do they affect reaction rate? A. Catalysts provide the needed energy for the reaction. B. Catalysts release energy during reaction. C. Catalysts absorb energy during reaction. D. Catalysts provide a new path of lower energy for the reaction to occur. 60

CHEMISTRY IN ACTION ANSWER KEY Quiz. 1. 6. B B 2. 7. C A 3. C 8. C 4. A 9. A 5. 10. C D

REFERENCES Brown, T., LeMay H. E., & B. E. Bursten. (1994). Chemistry the central science. NJ: Prentice Hall International, Inc. Caret, R. (1997). Principles and applications of inorganic, organic and biological chemistry. MA: McGraw-Hill, Inc. Goldberg, D. (1998). Fundamentals of chemistry. MA: McGraw-Hill, Inc.

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CHEMISTRY IN ACTION Chapter 6: Rates and Limits of Change EPISODE 21: CHEMICAL EQUILIBRIUM THE LIMITS OF CHANGE OVERVIEW Chemical reactions take place at different rates. Some occur almost instantaneously while others take many years to form substantial amounts of products. The rate of a chemical reaction is affected by changes in the concentration of reactants, and in temperature, and the presence of catalysts. In most of the earlier discussions on chemical reactions, it has always been considered that they proceed to completion. That is, all the reacting materials are assumed to be completely used up, and that only the products remain at the end of the reaction. However, this is not true for many chemical reactions. This episode looks into processes that do not go to completion but instead reach equilibrium. OBJECTIVES At the end of this lesson, the student should be able to: 1. define the state of equilibrium; 2. distinguish between reversible and irreversible reactions; 3. write equilibrium constant expressions for chemical reactions; 4. state what the magnitude of the equilibrium constant indicates about a reaction; and 5. use the equilibrium constant to determine the concentrations of reactants and products in a system at equilibrium. INTEGRATION WITH OTHER LEARNING AREAS The episodes that deal with concepts that are important to the understanding of chemical equilibrium include the following: Episode 12 - Patterns of Change, 17 Energy and Change, 18 - Thermochemical Equations and the Direction of Change, and 20 - Rates of Reaction. SCIENCE PROCESSES Experimenting Observing Measuring Using mathematical relationships Controlling variables Interpreting data Classifying Inferring Predicting 62

CHEMISTRY IN ACTION VALUES Ecological balance awareness Balancing of all aspects of ones life LIFE SKILLS Creative thinking Critical thinking Decision making IMPORTANT CONCEPTS 1. Reversible reactions are reactions that can proceed in both forward and reverse directions at a given set of conditions at the same time and in the same reaction vessel. 2. Chemical equilibrium is a condition wherein the forward and reverse directions of a reversible reaction or process occur at equal rates. 3. Law of mass action states that the ratio of products of concentrations of products to reactants, each raised to their stoichiometric coefficients, is equal to a constant. 4. Equilibrium constant is the value of the reaction quotient at equilibrium. BACKGROUND INFORMATION/EPISODE CONTENT Reversible Processes. The evaporation of water from the liquid and its reverse process, the condensation of water vapor, can occur simultaneously at room conditions. When they do, they are called a reversible process. H2O (l) H2O (g) H2O (l) H2O (g) A reversible process is one that can proceed in either direction, forward or backward. Many physical processes are reversible at certain conditions. The melting of ice into liquid and freezing back into ice at the melting point of water is also a reversible process. Many chemical reactions are reversible and can proceed in either direction: the reactants can produce the products and the products formed are capable of reforming back the reactants. On the other hand, some reactions are irreversible 63 Problem solving Understanding ones emotions Coping with stress Ability to make balanced judgment

CHEMISTRY IN ACTION and the backward reaction does not take place under the same conditions as the forward reaction. Reactions involving formation of precipitate and evolution of gas are usually irreversible. To represent the reversibility of a process, both the forward and backward directions are combined in one equation, using a double arrow to denoting that the reaction goes in both directions: A + B The evaporation-condensation process for water is thus written as: H2O (l) H2O (g) When a reversible process is represented in this manner, the process that is read from left to right is the forward process and that from right to left is the backward process. The reactant(s) of the forward process is on the left of the arrow and the products are on the right. For the backward process, the reactants are on the right (yes, they are the products of the forward process!) and the products are on the left. Equilibrium. When two exactly opposite or reversible processes taking place in the same vessel or container at the same time occur at exactly the same rate, then the system is said to be in a state of equilibrium. The most important characteristic of a reversible process in equilibrium is that the rate of the forward process is exactly the same as the rate of the backward process. When the rates of the two directions become unequal, the system is no longer in equilibrium. Chemical Equilibrium. Equilibrium that exists in chemical systems is referred to as chemical equilibrium. This is a state at which the conversion of reactants into products and the conversion of products back into reactants occur simultaneously at the same rate and under the same conditions of temperature and pressure. When the rates of the forward and the backward reactions are equal, then the concentrations of all substances involved in the equilibrium, as well as other measurable properties such as intensities of colors, remain the same over time. As long as equilibrium is maintained, no further change in all these properties is observed. The characteristics of a chemical system in equilibrium are as follows: 1. Equilibrium is a dynamic condition. Although concentrations of reactants and products reach a constant value, the processes by which they are formed and used up, the forward and backward processes continue to occur. 2. Equilibrium is reached when the rates of forward and reverse reactions are equal. It is NOT when the concentrations of reactants and products are equal that indicate that equilibrium has been reached. In fact, 64 AB

CHEMISTRY IN ACTION a system reaching equilibrium when the concentrations of reactants and products are equal may be quite uncommon. 3. A mathematical relationship exists among the concentrations of the substances involved when the equilibrium exists. The Law of Mass Action. In 1864, the Norwegian chemists Guldberg and Waage recognized that a quantitative relationship exists among the concentrations of reactants and products of a reaction at equilibrium. They called this relationship the Law of Mass Action or Law of Equilibrium, which states that the ratio of the product of the concentrations of the products to the product of the concentrations of the reactants is equal to a constant, provided that the concentrations of products and reactants are each raised to a power numerically equal to their respective coefficients in the balanced equation. This mouthful may be symbolically expressed as follows for a general reaction: nA + mB pC + qD the ratio described above is equal to a constant, Keq, the equilibrium constant.
[C ] p [ D] q [ A ] n [B] m = K eq

The ratio of the concentrations of products to reactants is called the mass action expression, the reaction quotient or the equilibrium constant expression. Equilibrium Constant Expression. The equilibrium constant expression can be written only after a correct, balanced chemical equation that describes the equilibrium system has been developed. By convention, the expression is written for the forward process, with the concentrations in the numerator being those of the substances on the right side of the chemical equation, and those in the denominator for the substances on the left side. The coefficients in the balanced equation become the exponents of the concentrations in the equilibrium constant expression. The concentrations used in the mass action expression are in units of mole per liter or molarity, M. By convention, a substance enclosed in square brackets represents the molar concentration of that substance. Owing to the different values of the exponents to which concentration terms are raised, the equilibrium constant Keq is considered a dimensionless quantity and does not carry any units. The following are examples of the equilibrium constant expression for the given reaction: Equation 1: 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g) 65

CHEMISTRY IN ACTION Equilibrium constant expression:

K eq = [NO] 4 [H 2 O] 6 [NH 3 ] 4 [O 2 ]5

Equation 2:

2SO2(g) + O2(g)

2SO3(g)

Equilibrium constant expression:

K eq = [SO 3 ] 2 [SO 2 ] 2 [O 2 ]

Expressions for Heterogeneous Equilibria. Some reactions involve a heterogeneous system wherein one or more of the substances involved is a pure liquid or solid, but the other substances are gases. When writing the equilibrium constant expression for heterogeneous systems, it is no longer necessary to include terms for the pure liquids and solids because their concentrations are based on their densities and do not change appreciably. An example is given below: Equation 3. CoO(s) + H2(g) Co(s) + H2O(g)
K eq = [H 2 O] [H 2 ]

Equilibrium constant expression:

Equilibrium Constant, Keq. When two opposing processes are in equilibrium at a certain temperature, the value of the mass action expression or reaction quotient is equal to a constant, the equilibrium constant, Keq. The value of this constant is specific for a reaction, its stoichiometry, and the temperature. The equilibrium constants of reactions can be very small or extremely large. The formation of gaseous hydrogen fluoride, HF, from hydrogen and fluorine gases has an equilibrium constant of 1.15 x 102 at a certain temperature. On the other hand, the formation of ammonia, NH3, from hydrogen and nitrogen has an equilibrium constant of 5.1 x 10-2. What do these values mean? The magnitude of the equilibrium constant indicates the extent to which the reaction proceeds before it reaches equilibrium. A large Keq means that there will be greater amounts of products (the substances in the numerator of the reaction quotient) compared to reactants (substances in the denominator of the reaction quotient) in the mixture when equilibrium is reached. On the other hand, only a small amount of products compared to reactants would be present at equilibrium for systems with small Keq. 66

CHEMISTRY IN ACTION In general, if Keq is between 10 -4 to 10+4, reactants and products are present at equilibrium. If Keq is very large, that is Keq > 10+5, the forward reaction is favored. In this case, the equilibrium mixture consists mainly of products and there are only small amounts of reactants present. If Keq is less than 10-4, the backward reaction is favored. The equilibrium mixture contains mostly reactants and very small amounts of the products. The magnitude of Keq provides important information especially in the manufacture of commercial or industrial products. It is likewise important to those who study the effect of equilibrium reactions on environmental systems and living organisms. Determining Equilibrium Constants. The value of the equilibrium constant for a given reaction at a given temperature can be calculated from the concentrations of the substances present at equilibrium. If these concentrations are known, then the equilibrium constant can be easily calculated based on the Law of Mass Action. For example, if for the system: CH4(g) + H2O(g) CO(g) + 3H2(g) it was determined that at 1400 K, the equilibrium concentrations of methane, steam, carbon monoxide, and hydrogen gases are 0.150 M, 0.233 M, 0,513 M and 0.259 M, respectively, The equilibrium constant for the reaction at 1400 K is calculated as:
[CO] [H 2 ]3 [CH 4 ] [H 2 O]

Keq = =

(0.513)(0.259) 3 (0.150)(0.233) Keq = 0.255

According to the Law of Mass Action, a system is in equilibrium only if the reaction quotient or equilibrium constant expression is equal to the equilibrium constant. Any combination of concentrations of reactants and products which when substituted into the equilibrium constant expression does not result to the equilibrium constant is not an equilibrium mixture.

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CHEMISTRY IN ACTION VOCABULARY WORDS 1. Equilibrium constant expression the ratio of the product of the concentrations of products to the product of the concentrations of reactants, where the concentrations are each raised to the power equal to the stoichiometric coefficients in the balanced equation. When the system is in equilibrium, this ratio is equal to a constant. 2. Reaction quotient another term used to refer to the equilibrium constant expression. 3. Homogeneous equilibria an equilibrium system where the components of the reversible process are of the same phase. 4. Heterogeneous equilibria an equilibrium system where the components of the reversible process are of two or more phases. PRE-VIEWING ACTIVITIES A. For motivational activities, ask the students to recall physical systems at equilibrium. Using as an initial example the freezing of water into ice and the melting of ice at 0oC, ask them to cite specific situations that will show various kinds of equilibrium. R Tell the students to recall what they have learned about saturated solution, evaporation, and osmosis. B. Differentiate reversible and irreversible reactions either through a laboratory demonstration in class or by actual experiments. C. Introduce the concept of the equilibrium constant and its derivation from a given chemical equilibrium system. Knowing the value of equilibrium constant Keq, let the students predict if a reaction will go to completion or not. The students should be able to determine the direction of a reaction. D. Give illustrative problems to show how equilibrium constant expression are calculated. Cite practical applications of Keq in industrial proesses. E. Pose the Guide Questions that the students will answer after viewing the episode. Tell them to focus on finding the answers to the guide questions as they watch the video.

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CHEMISTRY IN ACTION Guide Questions/Answers 1. Describe the state of equilibrium. Equilibrium is the condition when the rates of occurrence of two opposing forces are exactly equal such that it appears that no change is happening in the system. 2. Why is a system in equilibrium described to be dynamic? The system in equilibrium is dynamic because the two opposing processes continue to take place. 3. Differentiate reversible and irreversible reactions. A reversible reaction is one in which the forward and the backward reactions occur simultaneously in the same place. The reactants are capable of forming the products, while the products can form back the reactants. In an irreversible reaction, the products are not capable of forming the reactants such that the backward reaction is unable to take place under the same conditions as the forward reactions. 4. What are the instances when a chemical reaction cannot be reversed? Chemical reactions in which a precipitate is formed and removed, or an evolved gas is allowed to escape, cannot be reversed. Reactions involving the production of these types of substances on the product side cannot force back the backward reaction to take place. 5. How can the reaction of a system in equilibrium be represented in the chemical equation? The substances involved in the equilibrium can be represented using neutral species or ionic species. Often the ionic equation is favored because it simplifies the reaction. An ionic equation only includes the ionic species transformed in the course of the reaction. A system in equilibrium is also represented by using the double arrow ( or ) which serves as an indicator of a reversible process and it is a reminder that a dynamic nature exists in the process. 6. Describe chemical equilibrium. A chemical equilibrium is a dynamic system where the forward and backward reactions proceed at equal rates under the same given conditions of temperature and pressure. No observable changes in measurable properties are detected as time goes by and the concentrations of the reactants and products remain constant over time.

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CHEMISTRY IN ACTION 7. What is the equilibrium constant? How is it written or expressed? The equilibrium constant, symbolized by Keq, is the ratio of the equilibrium concentrations of the products to those of the reactants, where each concentration is raised to a power equal to the coefficient in the balanced chemical equation. 8. What is the importance of knowing the equilibrium constant of a system? The value of the equilibrium constant will tell us how far a chemical reaction reaches its completion. 9. How can the equilibrium constant be used to determine the limits of a chemical reaction? If the value of Keq is between 10-4 to 10+4, reactants and products are present at equilibrium. If the value is below 10-4, the backward reaction is favored and more reactants are present than products. If the Keq value is very large or >10+5, then the system mixture consists mostly of products and small amounts of reactants. Thus, the forward reaction is favored. 10. What are the experimental conditions that will affect the value of the equilibrium constant? For a given reversible reaction, Keq is constant for all equilibrium mixtures at a given temperature. Any change in temperature will affect the value of Keq. However, changes in pressure, volume or concentrations of substances do not affect the value of the Keq of a system. In addition, the presence of a catalyst has no effect on the Keq. VIEWING ACTIVITIES Suggested video clips are: (1) Comparison of Irreversible & Reversible Reactions at 2:30 - 10:10 and (2) Factors Affecting Chemical Equilibrium & The Significance of Equilibrium Constant at 10:20 - 19:35.

POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions.

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CHEMISTRY IN ACTION TEACHING TIPS A. Teaser. How did Napoleon Bonaparte help discover reversible reactions? The concept of reaction reversibility in Chemistry was developed by the eminent French Chemist Claude Louis Berthollet, who was Napoleons scientific advisor, from his observations of various places where he was brought by Napoleon. In the expedition into Egypt in 1798, Berthollet noticed deposits of sodium carbonate around the edges of some salt lakes found there. He immediately realized that the Na2CO3 whose dissolution in water was believed to proceed to completion must have been formed by the reverse of the process due to the very high concentration of salt in the slowly-evaporating waters. This observation led Berthollet to question the belief then that a reaction could only proceed in a single direction. His speculations on chemical affinity and his discovery that an excess of the product of a reaction could drive it in the reverse reaction were presented in his textbook Essai de statique chimique. B. Misconceptions. 1. The following misconceptions concerning chemical equilibrium are common: The original substance vanishes completely and forever in a chemical reaction. Equilibrium means equal concentrations. Once equilibrium is achieved, the system becomes static and nothing happens in the equilibrium mixture. Students may believe that no reactions are occurring at equilibrium because the net reaction is zero. However, reactions continue to occur both forward and backward reactions at the same rate, and no net change is observed. Reactions that proceed more rapidly also proceed further or more completely. This shows a discrepancy between the concepts of speed and completeness. A reaction can reach equilibrium before it has been completed, regardless of how fast the reaction proceeds. Chemical reactions will continue until all the reactants are exhausted. Reactions can reach equilibrium before the reactants are exhausted as explained by equilibrium constants and Le Chateliers Principle. To resolve these misconceptions, you can try the inquiry activity using a water analogy and make the students to continue swapping water once equilibrium is reached. Refer to the activity shown in this episode or show the said video clip. Let the students answer the following questions: 71

CHEMISTRY IN ACTION a. What happens to the volume of liquids contained in both cylinders after continued transfer? b. What does this indicate about the system? 2. More misconceptions: a. The rate of the forward reaction increases with time from the mixing of the reactant until equilibrium is established. b. A simple arithmetical relationship exists between the concentration of reactants and products at equilibrium. c. When a system is at equilibrium and a change is made in the conditions, the rate of the forward reaction increases but the rate of the other reaction decreases. d. Students prior experience of reactions that proceed to completion appears to have influenced their conception of equilibrium reactions; many students failed to discriminate clearly between the characteristics of completion reactions and reversible reactions. e. An increase in temperature always increases the value of the equilibrium constant. The reason for the widespread misconception may lie in the so-called kinetic proof of the law of chemical equation where one equates at equilibrium the rates of the forward and backward reaction. But from chemical kinetics, students know that an increase in temperature always results in an increase of the reaction rate. f. Increasing temperature increases the amount of products. g. The position of equilibrium does not change if equal numbers of moles of a reactant and a product are added to a system which is at equilibrium. B. Suggested Activity. Problem-Solving Exercises. Let the students do some practice exercises on writing equilibrium constant expressions. Consider the following problems: 1. Write the equilibrium constant expression for the reaction of nitrogen and hydrogen to form ammonia at 500oC. Balanced equation: Answer: 3H2(g) + N2(g) [NH3]2 Keq = [H2]3 [N2] 2NH3(g)

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CHEMISTRY IN ACTION 2. Write the equilibrium constant expression for the following reaction at 500oC: Balanced equation: Answer: 2NO(g) Keq = N2(g) + O2(g)

[N2] [O2] [NO]2

3. Write the chemical equations corresponding to the following equilibrium constant expressions, assuming the reactions are homogeneous: [CO] [Cl2] Reaction quotient: Keq = [COCl2] Answer: Reaction quotient: COCl2 CO + Cl2 [O2]9 [C3H6]2 Keq= [CO2]6 [H2O]6 6CO2 + 6H2O 9O2 + 2C3H6

Answer:

4. Hydrogen iodide is placed in a sealed container and allowed to come to equilibrium. Find the equilibrium constant given the equilibrium reaction and equilibrium concentrations as follows: 2HI(g) [HI] = [H2] = [I2] = H2(g) + I2(g) 0.54 M 1.72 M 1.72 M

Solution: First, write the equilibrium constant expression: [H2] [I2] Keq = [HI]2 Then, substitute the equilibrium concentrations of the products and reactants in the equilibrium constant expression: (1.72) (1.72) Keq = (0.54)2 73 2.96 = -----0.29

CHEMISTRY IN ACTION D. Research Work. Ask the students to do research on examples of chemical equilibrium in biological systems. ASSESSMENT A. Quiz. 1. In a chemical reaction, the word 'reversible' as represented by the symbol means A. the products and reactants of a reaction are in equal amounts. B. only half of the reactants are converted to products. C. products can be readily converted back to reactants. D. heat is alternately given out and taken in as the reaction proceeds. 2. CuSO45H2O(s) CuSO4(s) + 5H2O(g) The above equation shows the dehydration of blue hydrated copper(II) sulfate salt to the white anhydrous salt when heated. Which statement is TRUE about this reversible reaction? A. The dry CuSO4 can be used as a dehydrating agent. B. The reaction is not reversible. C. The forward reaction is exothermic. D. When water is added, the solids present changes color from blue to white. 3. The following statements are true for a dynamic equilibrium EXCEPT A. The concentration of reactants and products are equal. B. The forward and reverse reactions occur at the same rate. C. The concentrations of reactants and products remain constant over time. D. Reactants and products are present in the equilibrium mixture. 74

CHEMISTRY IN ACTION 4. Potatoes cook more quickly in boiling vegetable oil than in boiling water. This is because oil A. boils at a higher temperature than water. B. catalyses the cooking process. C. replaces the water in the potatoes. D. contains water. 5. Two statements are incorrect here, please mark them. A. At equilibrium, the reaction stops; no more reactants are transformed into products. B. A large equilibrium constant indicates that the reaction favors the formation of products. C. At equilibrium, there are equal amounts of reactants and products. D. An understanding of the factors that affect rates of reactions leads to knowing chemical equilibrium. B. True or False. 1. A large numerical value of the equilibrium constant indicates that mostly reactants are present in the reaction mixture. 2. When the reaction of hydrogen and nitrogen in the production of ammonia is at equilibrium, the rate of depletion of hydrogen and nitrogen is equal to the rate of depletion of ammonia. 3. A balanced chemical equation is essential in describing equilibrium system since the coefficients in the equation become the exponents of the concentrations in the equilibrium constant expression. 4. A complete reaction is one in which all reactants have been converted to products. 5. The amounts of substances present in an equilibrium mixture are of the same proportions as the coefficients of the balanced equation.

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CHEMISTRY IN ACTION ANSWER KEY A. Quiz. 1. 2. 3. 4. 5. Products can be readily converted back to reactants. The dry CuSO4 can be used as a dehydrating agent. The concentration of reactants and products are equal. Boils at a higher temperature than water. At equilibrium, the reaction stops; no more reactants are transformed into products. At equilibrium, there are equal amounts of reactants and products.

B. True or False. 1. False 2. True 3. True 4. True 5. False

REFERENCES Goldberg, D. (1998). Fundamentals of chemistry. MA: McGraw-Hill, Inc. Mortimer, C. (1990). Chemistry. ( 6th ed.). CA: Wadsworth. Robinson, H. (1990). College chemistry with qualitative analysis. MA: D.C. Heath.

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CHEMISTRY IN ACTION Chapter 6: Rates and Limits of Change EPISODE 22: CHANGES IN EQUILIBRIUM SYSTEM: LE CHATELIERS PRINCIPLE OVERVIEW A reversible process is in equilibrium when the forward and backward directions occur simultaneously and at the same rate. As a consequence, a mixture of products and reactants exists in the reaction vessel, and the composition of the mixture remains constant until the experimental conditions are changed. What happens when the conditions of a system that is in equilibrium are changed? In this episode, we look into the effect of changes in conditions or stresses on an equilibrium system. These stresses on systems in equilibrium include changes in temperature and concentration of the substances, changes in pressure and volume of gaseous systems, and the addition of a catalyst. The response of a system in equilibrium to disturbances is predictable, according to the Le Chateliers Principle. This episode presents how this principle can be utilized favorably to cause reversible reactions that are used in the manufacture of industrial products to shift towards formation of products by introducing disturbances when the reacting system reaches equilibrium. OBJECTIVES At the end of this lesson, the student should be able to: 1. understand and explain Le Chateliers Principle; 2. predict the effects of the various stresses on a system at equilibrium; 3. use vant Hoffs equation in explaining the effect of changing temperature on a chemical equilibrium; 4. explain how Le Chateliers principle was applied in ammonia production using the Habers process; and 5. apply the concept of equilibrium and Le Chateliers Principle to everyday life. INTEGRATION WITH OTHER LEARNING AREAS The episodes that are related to the topics discussed in this episode are: Episode 12 Patterns of Change, with emphasis on balancing chemical equations and stoichiometry, Episode 17 - Energy and Change, specifically energy changes accompanying chemical reactions, Episode 20 - Rates of Reaction, particularly that on the collision theory and activation energy of a reaction, and Episode 21 77

CHEMISTRY IN ACTION Chemical Equilibrium: The Limits of Change, such as reversible and irreversible reactions, properties of systems in equilibrium and factors that affect the value of equilibrium constants. SCIENCE PROCESSES Observing Experimenting Controlling variables Measuring Using mathematical relationships VALUES Problems as stresses disturbing the balance of life LIFE SKILLS Creative thinking Critical thinking Problem-solving Decision-making IMPORTANT CONCEPTS 1. According to the Le Chateliers Principle, a system in equilibrium when disturbed will make adjustments to absorb the disturbance and return to equilibrium. 2. When a stress is applied to a system in equilibrium such that the condition of equilibrium is lost, the system will favor the direction that removes part of the disturbance introduced. BACKGROUND INFORMATION/EPISODE CONTENT Le Chateliers Principle. Chemical systems that reach equilibrium remain in equilibrium until conditions that cause changes in the rates of the reversible processes are introduced. When a system at equilibrium is disturbed by some external stress, the system adjusts itself to absorb the change and enables it to return to equilibrium. This is essentially Le Chateliers Principle. 78 Interpersonal skills Coping with stress Understanding ones emotions Making adjustments in life Interpreting data. Classifying Inferring Predicting

CHEMISTRY IN ACTION What conditions or stresses will disturb the equilibrium? Any change applied to the system that can cause the rate of one direction to be slower or faster than the opposite direction will destroy the equilibrium. The stresses identified here are changes in the concentration of the substances, temperature, pressure, and volume of gaseous reaction mixtures. The addition of a catalyst on systems in equilibrium is also considered as an external stress on the system. Changes in the Concentrations of Substances. When additional quantities of substances are added to a system that is in equilibrium, the chemical system may be shifted out of equilibrium because of an increase in the rate of either the forward or the reverse reaction. As an example, consider the chromate-dichromate system shown in the video, which is initially in equilibrium: 2CrO4-2 + 2H+ Cr2O7-2 + H2O The addition of an acid causes an increase in the hydrogen ion, H+, concentration and the system responds by an increase rate of its reaction of chromate ions, CrO4-2, as is expected based on what was learned in Episode 20 - Rates of Reaction. This results in the rate of the forward reaction becoming faster than the backward reaction and the system is no longer in equilibrium. As a result of the sudden increase in the rate of the forward reaction after the addition of the acid, more of the products will be formed and the concentrations of the dichromate, Cr2O7-2, and hydroxide, OH-, will begin to increase since these are products of the forward reaction! The increase in concentration of products will now cause the reverse reaction to increase in rate. As more of the added acid is used up, the rate of the forward reaction starts to decline again. The forward reaction initially surged when acid was added and now it is slowing down. On the other hand, the backward reaction is increasing in rate because of the increase in the amount of products present. Eventually, the rates of the forward and reverse reactions become equal again and equilibrium is established again. In this new state of equilibrium, the new concentrations of the reacting substances are different from those in the original equilibrium condition. There is an increase in the concentration of the dichromate ion, Cr2O7-2, as evidenced by the increase in the intensity of orange color of the solution. In the same system of chromate-dichromate ions, the addition of sodium hydroxide will cause the reverse reaction to occur faster than the forward reaction. The OH - ion is a reactant of the reverse reaction and an increase in OH- concentration will favor this direction. The resulting increase in the concentrations of CrO4-2 and H+ ions will cause the rate of the forward reaction to slowly increase. In time, the rates of the two reactions become equal and a new equilibrium is reached. 79

CHEMISTRY IN ACTION Although the concentrations of the substances in this system have changed and a new state of equilibrium is reached, the equilibrium constant, Keq, remains equal to its original value. Hence, when the new concentrations of the ions are substituted in the equilibrium constant expression, the same value of Keq would be obtained. For a given reaction, changing the concentrations of reactants or products while keeping the temperature constant does not change the value of Keq. For gaseous systems like the NO2 N2O4 system whose equation for the dimerization process is shown below, changes in concentration of NO 2 or N2O4 will have the same effect as described above for the chromate-dichromate system. 2NO2(g) N2O4(g) Adding more NO2 shifts the reaction forward causing more N2O4 to be formed. The formation of more N2O4, on the other hand, causes an increase in the rate of the reverse reaction, until the rates of the opposite processes are equal and equilibrium is once more achieved. The effect of removing one of the substances in the equilibrium is the same as decreasing the concentration of the said component and the effect on the system is opposite that of an increase in concentration. Removing NO2 slows down the forward process, making the reverse reaction occur faster. The NO2 formed will increase the rate of the forward reaction again. In all these cases, the value of Keq remains the same provided the temperature of the system does not change. An easy way to identify the direction of shift of the system to reestablish equilibrium when concentrations of substances are changed is as follows: when a substance is added, equilibrium will shift in the direction where the added substance is used up. when a substance is removed, the equilibrium shift is in the direction that will produce more of the substance removed. Changes in Volume and Pressure. Other factors affecting gaseous systems in equilibrium are changes in pressure and volume of the system. While changes in volume of reaction vessels do not have much effect on solids and liquids since these physical states have fixed volumes, such change would result in a change in the concentrations of gases whose volume is the volume of its container. When volume of the reaction vessel increases, the net result is a decrease in concentration of the gaseous components while an opposite effect on concentrations is expected when volume is decreased. Consider again the NO2-N2O4 system. If one such system in a 100 mL syringe barrel is in equilibrium state and the volume is decreased to 50 mL by pushing in the syringe barrel, the concentrations of both NO2 and N2O4 would double. It is easy to 80

CHEMISTRY IN ACTION argue that since the change in concentrations is the same for the gaseous components. But a check on the equilibrium constant expression should show that the change has different effects on the two gases. 2NO2(g)
K eq =

N2O4(g)

[N 2 O 4 ] [NO 2 ] 2

Notice that in the equilibrium constant expression, the molar concentration of NO2 is squared. Hence, when the volume was decreased, resulting in the doubling of the concentrations of NO2 and N2O4, the system is no longer in equilibrium and would only return to equilibrium if some of the NO2 would be used up and more N2O4 is present in the system. This is manifested by a decrease in brown color attributed to NO2. The effect of changing the volume of a gaseous system in equilibrium is different for the reaction of sulfur and oxygen to produce sulfur dioxide. S(s) + O2(g) SO2(g)
K eq = [SO 2 ] [O 2 ]

If a similar doubling of concentration as in the NO2-N2O4 system happened to this system, this system remains in equilibrium! The ratio of [SO2] to [O2] will still be equal to Keq. Changes in volumes in gaseous systems actually translate to changes in concentrations and we recognize that changes in concentrations affect rates of reactions and can disturb equilibrium. However, in gaseous systems, the change in volume affects the concentrations of all gases in the system in the same proportion and an evaluation of the effect of the change on the equilibrium constant expression is necessary to determine the shift in equilibrium. An easier way to identify the direction of shift of the system to reestablish equilibrium when the volume of a gaseous system is changed is as follows: when the volume is decreased, equilibrium will shift in the direction where there are fewer gaseous particles in the equation. when the volume is increased, the equilibrium shift is in the direction that will produce more gaseous particles.

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CHEMISTRY IN ACTION To try this guide and predict the shift in equilibrium when the volume of the container of this system in equilibrium is increased: N2(g) + 3H2(g) 2NH3(g) The answer is in the backward direction. Why? Count the molecules in the two sides of the equation! In the equation, there are 4 molecules in the reactant side (1 molecule of N2 and 3 molecules of H2) while the product side has 2 (2 molecules of NH3). An increase in volume favors the direction that has more gaseous particles. Therefore, the system shifts towards the backward direction. Changes in pressure affect systems in equilibrium only when there is a resulting change in the rates of either direction of the reversible chemical reaction. Such change in pressure, therefore, must be one that results in a change in the concentration of one or more substances involved in the equilibrium and is achieved by the addition or removal of gaseous substances or by a change in volume. The change in volume described earlier for the NO2 and N2O4 system also resulted in a change in pressure. An increase in pressure due to a decrease in volume favors the forward reaction and this can be noted when the gas mixture loses its color initially as some NO2 molecules combine forming more N2O4. On the other hand, if the pressure is decreased by an increase in volume, the reaction forming more gas molecules which is the backward reaction in this case is favored. The gas mixture becomes darker as more NO2 is formed. When the pressure of a gaseous system in equilibrium is changed by a change in volume, the system behaves as follows: when the pressure is decreased, equilibrium will shift in the direction where there are more gaseous particles in the equation. when the pressure is increased, the equilibrium shifts in the direction that will reduce the number of gaseous particles. Gas pressure in an equilibrium system can also be changed by the addition or removal of gaseous substances. If the substance removed or added is a reactant or product in the equilibrium system, the effect is essentially that of increasing or decreasing concentrations of substances on the rates of reaction and consequently on the system in equilibrium. However, if the substance added is not a part of the equilibrium system, such as neon gas, Ne, added to the NO2-N2O4 system, we can easily predict that the added neon gas has no effect on the equilibrium although its presence increases the total pressure of the system. Ne is not part of the reversible process so it cannot affect the rates of either the forward or backward process nor would it change the value of the equilibrium constant expression. 82

CHEMISTRY IN ACTION Changes in Temperature. A change in temperature has a more complex effect on systems in equilibrium, gaseous or otherwise, and often results to a change in the value of the equilibrium constant as well. An increase in temperature indicates an increase in kinetic energies of particles. This will result in an increase in rates of both forward and backward directions. However, the increase in rates cannot be equal for both directions, according to the vant Hoffs Law which states that in every system in equilibrium, an increase in temperature favors the endothermic process while a decrease in temperature favors the exothermic process. All chemical reactions involve either the release (exothermic) or the absorption (endothermic) of energy. In a reversible process in equilibrium, exothermic and endothermic reactions are taking place simultaneously. The formation of N2O4 is exothermic while the formation of NO2 is endothermic. The changes in enthalpy of the two processes are as follows: 2NO2 N2O4 N2O4 2NO2 H = -57.3 kJ/mole of N2O4 (exothermic) H = +57.3 kJ/mole of NO2 (endothermic)

When temperature is increased, the endothermic reaction is favored. The system shifts to the direction that absorbs energy. At higher temperature, the system turns brown as more NO2 is formed. On the other hand, placing the system in an ice bath will cause the brown color lose its intensity. When the temperature of a gaseous system in equilibrium is changed, the system behaves as follows: when the temperature is increased, equilibrium will shift in the direction where heat will be used up. when the temperature is decreased, the equilibrium shifts in the direction that will produce heat. Presence of a Catalyst. A catalyst has no effect on the value of the equilibrium constant Keq on systems in equilibrium. It merely increases the rate of both the forward and the reverse reactions to the same extent so that equilibrium is reached more rapidly. In other words, the addition of catalyst causes a system to achieve equilibrium faster but does not alter the position of equilibrium. An Example: The Haber Process. The factors affecting equilibrium such as changes in concentration of substances, pressure, volume, and temperature, are used in the industrial production of ammonia, NH3. Ammonia is an important industrial product and is prepared from the reaction of hydrogen and nitrogen gases, an exothermic process. The equation for the reaction is: N2(g) + 3H2(g) 83 2NH3(g)

CHEMISTRY IN ACTION The equilibrium constant for the process is reasonably large and product-favored at room temperature. The problem is that the reaction is way too slow for appreciable amounts of product to be collected, particularly during the war when fixed nitrogen was needed for making ammunitions. It was the German chemist Fritz Haber who determined the necessary conditions for the successful production of this commercially important product. According to Le Chateliers principle, to favor the production of ammonia, large concentrations of nitrogen and hydrogen gases must be maintained and the produced ammonia must continuously be removed from the reaction vessel. The removal of ammonia from the system increases the rate of the forward reaction forming more ammonia. High pressures also favor the formation of ammonia since there are fewer particles in the product side of the equation. In the Haber process, typical pressures are between 200 to 600 atm and the reaction temperature is 450 to 600oC. At these conditions, ammonia is formed at reasonable rates and yields. Summary of the effects of the stresses on the Haber process: Temperature change: Increasing the temperature will make the reaction occur faster. However, since the reaction is exothermic, increasing the temperature would cause the equilibrium to shift to the left and produce more reactants in order to absorb some of the heat that is added. Concentration change: Adding N2 or H2 will shift the position of the equilibrium to the right which in turn yields more product. Likewise removal of NH3 will cause the equilibrium to shift right to make more NH3. Pressure change: In the equation N2(g) + 3H2(g) 2NH3(g) there are 4 moles of gaseous reactants and 2 moles of products. Increasing the pressure will cause the equilibrium to shift to the side having fewer moles of gas to partially offset the added pressure. Consequently, adding pressure to the system at equilibrium will produce a shift toward making more products. This increase in pressure is brought about by compressing the gases or reducing the volume the reaction mixture occupies. The effect of this change in pressure is essentially that of increasing the concentrations of the gases. Adding a catalyst: The Haber process uses as catalyst finely divided iron containing molybdenum or aluminum oxide. The catalyst lowers the activation energy required to initiate the reaction and speeds up the rate of reaction. Equilibrium will be reached more quickly but will have no effect on the equilibrium position.

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CHEMISTRY IN ACTION VOCABULARY WORDS 1. Synthesis the formation of a more complex compound by the combination of two or more simpler compounds, elements or radicals. 2. Subzero temperature temperature below zero degree. 3. Photochromic the ability certain materials, such as glass or films, to change color or turn dark when exposed to light and return to its normal transparency with the removal of light. 4. Thermochromic the ability of certain materials to change color when heated. PRE-VIEWING ACTIVITIES A. Introduce the episode that investigates Le Chateliers Principle as it is applied to systems in equilibrium. Relate this episode to previous episodes concerning rates of chemical reactions and chemical equilibrium. B. Instruct the students to take note of the following terms as they view the episode: 1. Chemical equilibrium is the situation in which two opposing processes occur simultaneously and at the same rate. 2. Shift is a net reaction of reactants to form products or of products to form reactants. 3. Stress is any change in the conditions affecting a system at equilibrium. 4. Reactions shifting to the right means that the substances on the left (reactant side) undergo reaction to produce those on the right (product side). 5. Reactions shifting to the left means that the substances on the right (product side) undergo reaction to produce those on the left (reactant side). 6. Forward reaction is the reaction that proceeds from left to right of the equation and favors the formation of more products. 7. Reverse reaction is the reaction that proceeds from right to left of the equation and favors the formation of more reactants. C. Pose the following Guide Questions that the students will answer after viewing the episode. Tell them to focus on finding the answers to these questions as they watch the video. Guide Questions/Answers 1. State Le Chateliers Principle and describe its significance. Le Chateliers Principle states that if a stress is applied to a system at equilibrium, the system will shift in the direction that would relieve the stress. This principle describes the response of a system initially at 85

CHEMISTRY IN ACTION equilibrium to a stress placed upon it, but it only indicates the direction of an equilibrium shift but not the extent. This principle can be used to set conditions that would increase or decrease yields of products of reactions. 2. How is Le Chateliers Principle illustrated in the video? The Le Chateliers Principle is presented and explained through a laboratory demonstration of adding stress to some chemical systems in equilibrium. The chromate-dichromate system was used to illustrate the effect of changing concentrations of substances involved in the equilibrium. Another chemical system shown is the NO2-N2O4 gaseous system which illustrated the effect of volume, pressure, and temperature changes. 3. What are the stresses described in the video that may disturb a system in equilibrium? The stresses which can disturb a system in equilibrium include changes in the concentrations of the components of the system, pressure, volume, and temperature. The presence of a catalyst may appear to be a disturbance, but generally would not affect a system that is already in a state of equilibrium. 4. Explain how these stresses affect systems in equilibrium. The chemical system will respond to these applied stresses by shifting the equilibrium towards the direction that will reduce the stress. For example, equilibrium will shift in the direction that would decrease the concentration of a substance that has been added to the system or that would use up heat when temperature is raised or that would decrease the number of moles of gas per unit volume when pressure is increased. Although the addition of a catalyst causes no shift in the equilibrium, its presence in the system will make the reaction reach equilibrium more rapidly. 5. How is the effect of pressure changes on equilibrium explained in the video? A recall of Boyles Law in gases was first presented to explain the relationship between pressure and volume of gases. Recalling that at constant temperature, pressure is inversely proportional to volume, that decreasing the volume of the container increases the pressure of the gas since the gas molecules are compressed crowding the molecules. When such disturbance is applied on a system in equilibrium, the reaction that forms fewer molecules is favored. The NO2-N2O4 system was used to support the explanation of the effect of pressure changes on equilibrium, 6. How does Vant Hoffs Law relate to chemical equilibrium? This law states that when the temperature of a system in equilibrium is raised, the equilibrium is displaced in such a way that heat is absorbed, favoring the endothermic direction. 86

CHEMISTRY IN ACTION 7. What are the chemical systems used in the video that explain the effect of temperature changes on the equilibrium constant? To explain the effect of temperature changes on equilibrium, the NO2-N2O4 system was used. This system was exposed to different temperature conditions. Since the colors of the two gases are different, the effect of a change in temperature was very apparent. 8. What is the Haber process? The Haber process is a process of producing ammonia from nitrogen and hydrogen gases at conditions that favor better yield and faster production. The German scientist Fritz Haber determined the necessary conditions for the successful synthesis of ammonia by utilizing Le Chateliers Principle. 9. How is ammonia synthesized in the laboratory? Ammonia is produced from the reaction of hydrogen and nitrogen gases. Because the reaction is very slow at room temperature, the best conditions for the reaction to successfully produce ammonia are at pressures between 200 to 600 atm and a temperature between 450-600oC. 10. What examples of equilibrium systems encountered in daily life were presented in the video? Examples of equilibrium systems shown in the video are those on CO2(aq)CO2(g) in carbonated drinks, solid-liquid equilibrium in the ice-water system and ice skating. VIEWING ACTIVITIES The video shows the effect of pressure and temperature changes on specific equilibrium systems at segments 2:15 18:20. Play, pause, and play of video clips. Insert a discussion or an activity about pushing and pulling in equilibrium systems. Another way of looking at a system in equilibrium is in terms of pushing and pulling the equation. Whenever one adds something to a system at equilibrium, it will have the effect of pushing the equation to the other side. If something is removed, it will pull the equation back toward the same side. POST-VIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. 87

CHEMISTRY IN ACTION B. Demonstration. An activity on Photochromic and Thermochromic Reactions (Adapted from Goldberg, 1998.) Introduction: Many chemical reactions are photochromic and thermochromic.These are reactions that produce a change in color (-chromic) that is driven by light (photo) or heat (thermo). Some of the most dramatic of these reactions involve the equilibria of different metal salts. Silver salts have long been used in photographic plates. There are also many organic compounds that change color when illuminated or heated. Since many of these chemical reactions are reversible, you will be able to demonstrate Le Chateliers Principle using light and heat. Materials: 1 teaspoon of cornstarch, drops of tincture of iodine or Betadine solution, 1 vitamin C tablet, 1 small glass or vial, a pan of boiling water Procedure: Fill the vial half full of water. Mix in a pinch of cornstarch and 6 to 10 drops of iodine, enough to give the solution a deep blue-black color. Using a test tube holder, heat the vial by holding it in the boiling water. After several seconds, the heat should cause the color to disappear. Removing the vial from the heat should cause the color to shift back to the blue-black color. This can be repeated several times, although you may have to add some more iodine occasionally. The addition of vitamin C will irreversibly remove the color. Guide Results of the Activity: The mixture of starch and iodine forms a loose complex that absorbs light. Heating disrupts this complex and therefore causes the solution to become clear. Recooling drives the equilibrium back in favor of the light absorbing complex. The appearance and disappearance of color can be repeated as long as some iodine is still present in solution. Some of the iodine is removed by the slow oxidation of starch. By adding Vitamin C or ascorbic acid, the iodine is completely reduced to iodide so the equilibrium involving iodine and starch no longer exists. C. Group Dynamics. Divide the class into 5 groups. Give each group a problem situation to solve. After giving them enough time, ask each group to report their work in the class for checking and discussion of the following Problem Situations.
1.

What will be the effect of adding more ammonia to this system at equilibrium? Explain. 2NH3(g) 3H2(g) + N2(g) 88

CHEMISTRY IN ACTION 2. What will be the effect of removing ammonia from the same chemical system as above at equilibrium? 3. What will be the effect of adding heat to this system at equilibrium? 2NH3(g) + heat 3H2(g) + N2(g)

4. Predict how reducing the volume of the reaction vessel affects the state of equilibrium on the reaction: N2(g) + O2(g) 2NO(g) 5. Silver ion reacts with chloride ion to form the precipitate silver chloride in the reaction: Ag+ (aq) + Cl- (aq) AgCl(s) After the reaction has reached equilibrium, the chemist filtered 99% of the solid silver chloride from the solution, hoping to shift the equilibrium to the right to form more products. Comment on the chemists experiment. D. Graphical Presentation of a System. The following graphs can be used in explaining to the students what really happens to a system at equilibrium if it is disturbed by the addition or removal of substances: 1. The effect of adding some reactant A on the rates of the forward and reverse reactions for A + B C + D initially at equilibrium.
R A T E O F R E A C T I O N Addition of more A Rate 1 for A + B Rate 1 = Rate 2

System at new equilibrium Rate1=Rate 2 Rate 2 for C + D System at initial equilibrium

T IME

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CHEMISTRY IN ACTION 2. The effect of removing some reactant A on the rates of the forward and reverse reactions for A + B C + D when the system is initially at equilibrium.
R A T E O F R E A C T I O N

Rate 1 = Rate 2 Rate 2 for C + D Rate 1 = Rate 2

Removal of some A
Rate 1 for A + B

System at new equilibrium

TIME

E. Additional Useful Information. Misconception: Physical changes are reversible while chemical changes are not. Chemical changes are also reversible. Consider equilibrium reactions in which forward and backward reactions are both occurring at the same time such as in the formation of ammonia, NH3, from nitrogen gas, N2, and hydrogen gas, H2. On the other hand, some physical changes are hard to reverse such as crushing a rock. Information 1. The Le Chateliers Principle in hemoglobin and oxygen transport. Many of the chemical reactions that occur in living organisms are governed by Le Chateliers Principle. One of these relates to aerobic respiration particularly in the transport of oxygen to the cells. The partial pressure of O2 in the air and approximately so in the lungs is 0.2 atm, sufficient to allow these molecules to be taken up by hemoglobin (the red pigment of blood) in which it becomes bound in a complex known as oxyhemoglobin as blood passes through the vessels in the lungs: hemoglobin + O2 oxyhemoglobin

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CHEMISTRY IN ACTION In the tissues, the oxygen concentration is reduced by about 50% owing to its consumption by the cells, shifting the equilibrium to the left, releasing the oxygen so it can diffuse into the cells. Hemoglobin picks up oxygen molecules again when it returns to the oxygen-rich place, the lungs. 2. The dissolution and removal of carbon dioxide, CO2 , in our the body involves two equilibria. Carbon dioxide produced from metabolism reacts with water to form the weak acid H2CO3 (Equation 1), which would cause the blood acidity to become dangerously high when it dissociates to produce hydrogen ions and bicarbonate ions (Equation 2). Equation 1: Equation 2: CO2(aq) + H2O H2CO3(aq) H2CO3(aq) H+ (aq) + HCO3- (aq)

These two equilibria pull or push one another through the carbonic acid, H2CO3, at the center. Two organs of the body work to prevent very large changes in blood pH. When the blood becomes too basic, or pH is high, the kidney removes excess HCO3 - ions and cause more H2CO3 to dissociate and produce more H+, which will lower the pH. When the blood is too acidic, or its pH is too low, the lungs allow CO2 to escape from the body, pulling the equilibria to the left. ASSESSMENT A. True or False. Write T if the statement is true and write F if the statement is false. 1. A reaction is at equilibrium when no reactants remain. 2. Decreasing the volume of the container increases the pressure of a system. 3. A reaction continues to occur at equilibrium. 4. Changing the concentration of one of the components of a reaction alters the equilibrium composition of the system. 5. A catalyst has no effect on the equilibrium composition. B. Complete the Table. Fill up the table below by predicting the effect of the following changes on the chemical system initially at equilibrium. Give the shift in equilibrium and the expected color change, if there would be any.

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CHEMISTRY IN ACTION Chemical System at Equilibrium H2 + I2 2HI(g) DH =(+)

colorless violet colorless

Change Applied to the System Lower the temperature of the system Volume of the container is decreased More base is added to the mixture More Fe+3 is added to the mixture

Effect on the Chemical System

2NO2(g)

N2O4(g)

H2O

brown colorless -2 + 2CrO4 + 2H Cr2O7-2 + yellow orange

brown

Fe+3 + 6SCN- Fe(SCN)6+3

colorless red

C. Predicting Equilibrium Shifts. Given the reaction below, predict the direction of equilibrium shift ( to the left, L or to the right, R) for each of the following changes: 4NO2 (g) + 6H2O(g)
1. increasing the temperature 2. adding water 3. removing NO2

7O2 (g) + 4NH3(g) (endothermic)

4. adding ammonia 5. adding a catalyst

ANSWERS KEY (Under Post-Viewing Activities) C. Group Dynamics. 1. The addition of more ammonia is a stress causing an increase in the concentration of ammonia as well as the partial pressure of ammonia. The equilibrium will shift to the right to use up some of the added ammonia. After the shift, more nitrogen and hydrogen gases and less ammonia would be present in time. The system reestablishes a new equilibrium because the two opposing reactions eventually become equal. 2. The removal of ammonia is considered a stress causing a decrease in the concentration of ammonia. The equilibrium will shift to the left to replace some of the ammonia removed. 3. The addition of heat will cause the equilibrium to shift to the right to use up some of the added heat. 4. The reduction in the volume of the reaction vessel means an increase in the total pressure of the system. A change in pressure of a system at equilibrium favors the direction that will yield less number of gas molecules. Since there are two moles of gas on both sides of the equation, neither a shift to the left 92

CHEMISTRY IN ACTION or to the right will change the total pressure. The reduction in the volume of the container causes an increase in pressure but will not shift the equilibrium. 5. When the dissolution and precipitation of AgCl reaches equilibrium, the equilibrium concentration of the ions in solution are not affected by the removal of the solid AgCl. Hence, even if the AgCl is removed, the ions in the filtrate remain in equilibrium. (Under Assessment) A. True or False. 1. F 2. T 3. T 4. T 5. T

B. Complete the Table. 1. The equilibrium shifts to the left and the mixture becomes more violet. 2. The equilibrium shifts to the right and the mixture becomes colorless. 3. The equilibrium shifts to the left and the mixture becomes more yellow. 4. The equilibrium shifts to the right and the mixture becomes red. D. Predicting Equilibrium Shifts. 1. R 2. R 3. L

4. L

5.

No change

REFERENCES Caret, R. (1997). Principles and applications of inorganic, organic, and biological chemistry. MA: McGraw-Hill, Inc. Goldberg, D. (1998). Fundamentals of chemistry. MA: McGraw-Hill, Inc.

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CHEMISTRY IN ACTION Chapter 6: Rates and Limits of Change EPISODE 23: PLEASE PASS THE PROTONS: ACIDS AND BASES OVERVIEW Acids and bases are two classes of compounds that are widely used and encountered in everyday life. These compounds are present in our foods and fruits. The manufacture of some important commercial and industrial products makes use of acids and bases. Acids and bases are vital to life processes. Concepts of acids and bases are likewise useful in understanding other areas of concern such as soil productivity, food preservation, health maintenance, and some of the most pressing environmental problems. Chemists have studied the distinguishing properties of acids and bases over the past century, thereby contributing to a better understanding of the chemistry behind these compounds. This episode focuses on the properties of acids and bases as well as their reactions and uses. It explains how acidity and basicity/alkalinity are expressed, determined, and quantified. It also includes a discussion on how pH and pOH scales are used to determine the strengths of acids and bases. Furthermore, this episode explains the different types of neutralization reactions involving acids and bases. OBJECTIVES At the end of this lesson, the student should be able to: 1. give operational definitions for acids and bases; 2. differentiate among the Arrhenius, Bronsted-Lowry and Lewis theories of acids and bases; 3. relate the pH value to acidity or basicity of a solution; 4. explain how the pH of a solution is determined experimentally by using indicators; 5. explain the strength of acids and bases based on the degree of ionization; 6. describe a neutralization reaction; 7. prepare acid-base indicators from plant extracts; 8. calculate the pH of a solution given the [H3O+] 9. appreciate and value the uses of acids and bases in everyday life; and 10. develop concern for the protection of the environment by discussing the damage caused by acids in the atmosphere. INTEGRATION WITH OTHER LEARNING AREAS Many chemical compounds that are produced as industrial wastes and discarded into the air and water are acids or bases. Understanding the physical and chemical 94

CHEMISTRY IN ACTION properties of these substances (i.e. pH, acidity or alkalinity) allows the development of simple detection methods for their presence. This episode is thus related to Episode 6 - Substances We Use as well as to Episode 10 and 12 - Indicators of Chemical Change and Patterns of Change, respectively. Prior to this episode, students should have had an understanding of molecular and structural formulas, atomic and molecular weights, the mole, and concentration, specifically in terms of molarity, stoichiometry, and equilibrium. Acid-base properties of substances that we use are important to issues and topics concerning medical or clinical findings as well as environmental concerns such as global warming, acid rain formation, air and water pollution, waste disposal and the like. SCIENCE AND HEALTH IDEAS Concentrated acids (having a pH of 2 or less) and bases (having a pH of 12.5 or greater) are corrosive. Products with these properties are threats to human health and the environment and should be handled with extreme care. SCIENCE PROCESSES Observing Measuring Collecting data Analyzing data Organizing data VALUES Honesty and integrity Scientific orientation Creativity Environmental care Compassion LIFE SKILLS Active listening Giving and receiving feedbacks Cooperation Teamwork Problem solving 95 Decision making Goals setting Critical thinking Personal discipline Building self-esteem and self awareness Holistic health Promotion of the common good Cooperation and teamwork Reverence and respect for life Inferring Hypothesizing Predicting Science modeling Communicating

CHEMISTRY IN ACTION IMPORTANT CONCEPTS 1. Definitions can be of two types: operational and conceptual. The operational definition of acids and bases is based on the observable and experimental observations of these substances. The conceptual definition is based on the molecular behavior of the substances.

2. The general properties of acids and bases are as follows: Acids taste sour change blue litmus paper to red react with certain metals producing H2 gas Bases taste bitter change red litmus paper to blue slippery or soapy feel

3. Three concepts regarding acids and bases are: Theories Arrhenius Bronsted-Lowry Lewis Acids form H ions in aqueous solution proton donor electron pair acceptor
+

Bases form OH ions in aqueous solution proton acceptor electron pair donor

4. A strong acid or base is one that ionizes completely in water. A weak acid or base is not completely ionized since ions recombine and form their molecules again in solution. 5. In solutions of weak acids and weak bases, the ions formed by the ionization of the acid or the base reach equilibrium with their unionized forms. 6. The values of the ionization constant can be used to compare strengths of different acids and bases. An acid with the higher ionization constant is stronger than one with a lower Ka. The same is true with bases. 7. Water undergoes self-ionization to produce small concentrations of hydronium ions and hydroxide ions: H2O(l) + H2O(l) H3O+(aq) + OH(aq) 8. One way of expressing the acidity or basicity of a dilute solution of a substance is by its pH. pH is defined as the negative of the logarithm of the molar concentration of hydrogen ions in solution. pH = log [H+] or pH = log ( 1/[H+] ), where [H+] is the concentration of the hydrogen ions in mol/liter. The pH of 96

CHEMISTRY IN ACTION solutions or substances maybe determined using a pH meter or estimated using indicators. 9. Indicators are usually organic acids that change color when protons are either added to or removed from their structure. 10. Neutralization is the reaction between an acid and a base to produce water and salt. In a neutralization reaction, the solution of the salt obtained may be acidic, basic or neutral depending on the kind of acids and bases involved in the reaction. BACKGROUND INFORMATION/EPISODE CONTENT Acids and bases are defined in terms of the general properties that they exhibit. Acids are substances that change blue litmus paper to red, taste sour, and react with certain metals to produce hydrogen gas. Bases are substances that change red litmus paper to blue, taste bitter, and are slippery or soapy to touch. To understand the behavior of acids and bases better, let us go beyond these operational definitions and look at the characteristics of these groups of substances at the molecular level. Three Theories of Acids and Bases. There are three theories of acids and bases that are most commonly-used the Arrhenius, Bronsted-Lowry, and Lewis theories. In 1884, Svante August Arrhenius defined acids as substances that release hydrogen ions, H+, when dissolved in water, and bases as substances that yield hydroxide ions, OH, when dissolved in water. The Arrhenius theory was limited to acids and bases in aqueous medium. Examples of Arrhenius acids are hydrochloric acid, HCl, and nitric acid, HNO3. Examples of Arrhenius bases are sodium hydroxide, NaOH, and barium hydroxide, Ba(OH)2. The BronstedLowry theory of acids and bases is an extension of the Arrhenius concept. This theory defined acids and bases in terms of their ability to donate or accept hydrogen ions, H+ or protons. Acids are defined as proton donors and bases as proton acceptors. While the definition seems different from that of Arrhenius, it still involved the acidic hydrogen and all Arrhenius acids and bases are also Bronsted-Lowry acids and bases. In this theory, water is not just a solvent or a medium for an acid-base reaction but has acid and base properties, too. Thus, the dissolution process of HCl in water is just the formation of an acid solution for Arrhenius, but for Bronsted and Lowry, it is already an acid-base reaction. HCl + H2O H3O+ + proton donor proton acceptor Cl-

This theory further recognizes that after losing or accepting a proton, the resulting species can also behave as acid or base. When an acid loses a proton, what remains of the former structure is called the conjugate base because this can pick up a 97

CHEMISTRY IN ACTION proton and form the acid back. When nitric acid, HNO3, donates its proton to some acceptor molecule Y, what will remain of the nitric acid is the nitrate ion, NO3-. HNO3 acid + Y YH+ + NO3conjugate base

The nitrate ion, which is nitric acid minus its proton, is the conjugate base of nitric acid. When the nitrate ion accepts a proton (see, it is a base!), it becomes nitric acid again. When a base accepts a proton from an acid, it forms its conjugate acid which can subsequently give up a proton and reform the base. Ammonia, NH3, is a base. When it accepts a proton from some acid HA, it becomes the ammonium ion, NH4+. + ANH3 + HA NH4+ base conjugate acid The ammonium ion, which is ammonia plus a proton, is the conjugate acid of ammonia. Can you show how the ammonium ion can reform ammonia back? Thus, according to the Bronsted-Lowry theory, an acid has a conjugate base and a base has a conjugate acid. A conjugate acid-base pair may be: (1) an acid and its conjugate base or (2) a base and its conjugate acid. (1) Acid: HClO Conjugate base: ClO(2) Base: CH3NH2 Conjugate acid: CH3NH3+ Some substances can behave both as Bronsted-Lowry acid and base, that is, they can donate as well as accept protons. These substances, many of which are ions, are called amphiprotic substances. The bicarbonate ion, HCO3-, is amphiprotic. Water is also amphiprotic as shown in the table below. Amphiprotic Type of substance behavior HCO3H2O acid base acid base Reaction ( HA and Y are any appropriate acid and base, respectively) HCO3 + Y HY+ + CO32HCO3- + HA A- + H2CO3 H2O + Y HY+ + OHH2O + HA H3O+ + A-

Gilbert N. Lewis expanded further the definition of acids and bases. According to the Lewis theory, an acid is a substance that accepts a pair of electrons and a base is a substance that donates a pair of electrons. Interestingly, Bronsted-Lowry acids and bases are also Lewis acids and bases. But there are other substances that do not donate or accept hydrogens but fall under the Lewis models. 98

CHEMISTRY IN ACTION An example of a reaction involving a Lewis acid and a Lewis base is given below. BF3 + :NH3 F3B:NH3 The electron pair donor is ammonia, NH3, specifically the N atom. The electron pair acceptor is boron trifluoride, BF3, specifically the B atom. The process of electron pair donation and acceptance between N and B results in the formation of a covalent bond between N and B. While proton transfer processes are also Lewis acid-base reactions, the Lewis concept is most useful in describing situations that do not involve proton transfers, such as reactions involving gases and solids and complex ion formation. Most of the succeeding topics in this lesson refer to acids and bases in the Bronsted-Lowry model, that is, proton donors and proton acceptors. The Hydronium Ion. The proton donated by a Bronsted-Lowry acid is also referred to as hydrogen ion or hydronium ion Are they all the same? The hydrogen ion and the proton are one and the same. The hydrogen atom, H, is made up of one proton in its nucleus and one electron moving around this nucleus. When the electron of the hydrogen atom is removed, it becomes the hydrogen ion, H+, which is essentially, just a proton! A proton is a very tiny positively-charged particle and one with such an extremely high charge density cannot exist unattached in the presence of atoms with electrons around them. Hence, in water, this proton is believed to attach itself to a water molecule, specifically, at one of the unshared pairs of oxygen, forming the hydronium ion, H3O+. However, for ease of representation, the hydronium ion may be represented as H+ and simply referred to as a hydrogen ion. pH. The acidity and basicity of dilute solutions can be expressed in terms of pH or the power of hydrogen ions. The pH is defined mathematically as the negative of the logarithm of the hydrogen ion concentration (or the logarithm of the reciprocal of the hydrogen ion concentration.). pH = log [H+] or pH = log ( 1/[H+] ) where the brackets [ ] mean concentration of H+ in moles per liter of solution. For example, a solution with a hydrogen ion concentration of 1.00 101 mol/liter, has a pH of 1.00. pH = log [H+] = log (1.00 101) = (1.00) = 1.00

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CHEMISTRY IN ACTION The pH scale has a range of values from 0 to 14. Solutions may be classified as acids or bases according to their pH. A neutral solution has a pH value equal to 7. A solution with a pH value lower than 7 is acidic while a pH value higher than 7 is basic. The pH scale below, Table 1, describes solutions with different pH values. The pH of Water. Pure water undergoes autoprotolysis or self-ionization to a limited extent to produce 0.00000010 mole of hydronium ions, H3O+, per liter or 1.0 107 M and an equal concentration of hydroxide ion, OH1, 1.0 107 M. The pH of pure water is calculated as: pH = log (1.0 x 10-7) = 7.0 In any sample of pure water or aqueous solution at 25oC, an equilibrium exists between the ions of water. The product of the molar concentrations of hydronium and hydroxide ions is equal to the equilibrium constant for the ionization of water, also known as the ion-product of water, Kw, which has a value of 1.0 1014 at 25oC. This equilibrium expression for the reaction H2O(l) + H2O(l) H3O+ (aq) + OH (aq) is given as follows: Kw = [H3O+] [OH] = (1.0 107 M) (1.0 107 M) = 1.0 1014 Table 1. Solutions with different pHvalues. pH 0.0
Inc A C I D I T Y

Aqueous System 1 M HCl (0.0) 0.1M HCl (1.0) Gastric juice (1.6 1.8) Lemon juice (2.3), vinegar (2.4 3.4) Soda water (3.8), tomato juice(4.2) Black coffee (5.0) Milk (6.3 6.6), urine (5.5 -7.0) Pure water (7.0), saliva (6.2 7.4) Blood (7.35 7.45), bile (7.8 8.6) Sodium bicarbonate (8.4), seawater (8.4) Milk of magnesia (10.5) Household ammonia (11.5) Washing soda (12.0) 0.1 M NaOH (13.0) 1 M NaOH (14.0)

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0

Neutral
Inc B A S I C I T Y

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CHEMISTRY IN ACTION Since Kw is a constant, then there exists an inverse relationship between the concentrations of hydronium and hydroxide ions. Thus, if an acid is introduced to water and the [H3O+] increases, there would be an accompanying decrease in the [OH-] and vice versa. The acidity of solutions with hydrogen ion concentration greater than 1 M are usually not expressed in pH anymore since the pH scale was developed as a convenient way to express very small values of hydronium ion concentrations of dilute solutions. Indicators. The pH of solutions can be estimated using indicators. Indicators are usually organic acids that exhibit a change in color when they donate or accept protons. Some common acid-base indicators include the universal indicator, litmus paper, methyl red, phenolphthalein, phenol red, and methylene blue. These indicators change color in acidic and basic conditions. Litmus paper is one of the common laboratory acid-base indicators which uses a pigment obtained from certain lichens. Another common indicator is phenolphthalein which is colorless in acidic conditions but turns pink in basic conditions. The pH can be measured more accurately using an electrical device called a pH meter. Strength of Acids and Bases. The strength of acids and bases depends on the degree of their ionization. Strong acids and bases are 100% ionized. There are six commonly encountered strong acids and these are hydrochloric acid, HCl, hydrobromic acid, HBr, hydroiodic acid, HI, nitric acid, HNO3, perchloric acid, HClO4, and sulfuric acid, H2SO4. In a HCl solution, all the HCl would have donated their protons or H+ to water and there would be no whole HCl that can be detected. The strong bases are metal hydroxides like sodium hydroxide, NaOH, and potassium hydroxide, KOH. Weak acids and weak bases ionize slightly in aqueous solutions. An example of a weak acid is acetic acid, CH3COOH. In a solution of acetic acid, only a small number of acetic acid donate protons to water. Most are unionized and remain in molecular form. The ions formed by weak acids and weak bases in solution reach equilibrium with their corresponding unionized or undissociated forms. The equations for the reactions of weak acids and weak bases with water and the corresponding equilibrium constant expressions are given in the following table. The equilibrium constants are called the acid dissociation constant, Ka, and the base dissociation constant, Kb, for the weak acid and the weak base, respectively.

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CHEMISTRY IN ACTION Reaction Acid: Base:

(aq)

HX(aq) H+(aq) + X(aq) YOH(aq) Y+(aq) + OH

Equilibrium Constant Expression [ H + ][ X - ] Ka = [ HX ]

[OH - ][Y + ] Kb = [YOH ]

Neutralization Reactions. The reaction between an acid and a base is called a neutralization reaction. When an equivalent amount of acid and base undergo neutralization, water and salt are produced. Salt is a general term used to refer to an ionic compound. (When we want to refer to sodium chloride, NaCl, we say table salt.) In a neutralization reaction, the resulting solution of the salt may be acidic, basic or neutral depending on the whether the acid and base involved are strong or weak. VOCABULARY WORDS 1. Amphiprotic substance a substance that can behave both as BronstedLowry acid and base because it can donate as well as accept protons. 2. Indicator - an organic acid that exhibits a change in color when it donates or accepts protons. 3. Neutralization - the reaction between an acid and a base forming water and salt. 4. pH a way of expressing the acidity and basicity of dilute solutions in terms of the power of hydrogen ions; it is defined mathematically as the negative of the logarithm of the hydrogen ion concentration or the logarithm of the reciprocal of the hydrogen ion concentration. PRE-VIEWING ACTIVITIES A. Before a thorough discussion of acids and bases in this episode, students may be involved in games that can be sourced from the following web pages: sciencespot.net; www.brainpop.com; pbskids.org; and www.quia.com, to mention some. B. Introduce the video clip that deals with common examples of acids and bases found at home.

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CHEMISTRY IN ACTION C. Pose the Guide Questions that the students will answer after viewing the video clips in the episode. Remind them from time to time to focus on finding the answers to the guide questions as they watch the video clips. Guide Questions/Answers 1. What are the different characteristic properties of acids and bases? Acids are substances that taste sour, change blue litmus paper to red, and react actively with certain metals to liberate hydrogen gas. Bases are substances that taste bitter, are slippery to touch, and change red litmus paper to blue. 2. What are the three commonly used acid-base theories? How are the acids and bases differentiated according to these three concepts? Theories Arrhenius BronstedLowry Lewis Acids form H ions in aqueous solution proton donor
+

Bases form OH ions in aqueous solution proton acceptor

electron pair acceptor

electron pair donor

3. Explain what happens to water as it ionizes. In pure water, small number of water molecules dissociate or break up in a reversible reaction to hydrogen ions, H+, and hydroxide ions, OH. This reaction produces equal amounts of the two ions. 4. How is acidity or basicity of a solution is measured? The acidity or basicity of a solution is measured through the hydrogen ion concentration of the solution. For dilute solutions, this hydrogen ion concentration is expressed in terms of pH. 5. How is pH related to acidity? A pH between 0 to less than 7 means that there are more hydrogen ions than hydroxide ions present in the solution, thus the solution is acidic. A pH of more than 7 to 14 means that there are less hydrogen ions present in the in the solution. Instead, more hydroxide ions are present, thus the solution is basic. A pH of 7 means there are equal amounts of hydrogen ions and hydroxide ions and the solution is neutral. 6. Differentiate strong from weak acids and bases. Strong acids and strong bases in aqueous solutions are 100% ionized. No equilibrium exists in the system and the ionization reaction is complete and 103

CHEMISTRY IN ACTION irreversible. Weak acids and weak bases are only partly ionized and most are unionized or in molecular form. Thus, the backward reaction occurs and equilibrium exists between the ions and the molecular forms. 7. What happens when an Arrhenius acid reacts with an Arrhenius base? When an Arrhenius acid reacts with an Arrhenius base, salt and water are produced in the process called neutralization. 8. In this episode, some uses and applications of acids and bases in everyday life were shown. Name a few. Many common household chemicals are acids or bases. These chemicals are very useful in cleaning glass windows (ammonia), cleaning stubborn kitchen stains (muriatic acid or hydrochloric acid), clearing clogged drainage (lye or sodium hydroxide), and as sources of vitamins (ascorbic acid). VIEWING ACTIVITIES Let the students them view the clips on: (1) Acids and Bases: Operational and Conceptual Definitions at 2:31 8:44, (2) Determining H3O+ Concentration at 9:06 11:02, (3) Using of Indicators at 11:10 12:36, (4) Relative Strengths of Acids and Bases at 12:39 15:42, and (5) Types of Neutralization Reactions at 15:43 18:40.

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CHEMISTRY ACTION Video clip IN tracks 7:38 to 8:24 in this episode can best be discussed and presented by considering the annotations below: As published and cited in the digital library of Journal of Chemical Education, G. N. Lewis developed a theory of acids and bases that is based upon the sharing of electron pairs. A Lewis acid is a substance that can accept a pair of electrons from another atom to form a new bond. A Lewis base, on the other hand, is a substance that can donate a pair of electrons to another atom to form a new bond. A simple example is the formation of the hydronium ion from a hydrogen ion, H+, which is just a proton (no electrons), and water (has electron pairs to donate):
+

H2 O

H3 O

The product is called the addition product or the adduct. When all the electrons that are being shared come from only one of the atoms forming the bond, the bond is called a coordinate covalent bond. In this example, H+ is the Lewis acid and H2O is the Lewis base.

POST-VIEWING ACTIVITIES A. Discuss the answers to the Guide Questions. B. Suggested Laboratory Experiments. 1. Recognizing Acids and Bases. Materials: small amount of the following household materials: vinegar, AlkaSeltzer, antacid tablet, garden fertilizer, softdrinks, milk of magnesia, detergent, cuticle remover, shampoo, calamansi juice, muriatic acid, toothpaste, ammonia, aspirin, soap, baking powder and aluminum foil, red and blue litmus paper, 15 clean, dry plastic bottle caps, medicine droppers, water *The teacher is advised to demonstrate the tests with muriatic acid and ammonia.

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CHEMISTRY IN ACTION Procedure: a. Place 35 drops of each of the 15 household sample materials in the clean dry bottle caps. For solid substances, add a small quantity of water to dissolve the solid. Observe and record the physical properties of sample materials as to color and odor. WARNING: Taste only those samples which the teacher deems safe to taste. b. Test the reaction of the samples with litmus paper. Place a drop of the sample on a small piece of red litmus paper. Record your observations. Repeat the test using blue litmus paper. c. Then, to each of these samples, add small piece of aluminum foil. Enter all observations in a table similar to the one found below. Data and Observations: Materials Vinegar Alka-Seltzer Antacid tablet Fertilizer Softdrinks Milk of magnesia Detergent Cuticle remover Shampoo Calamansi juice Muriatic acid Toothpaste Ammonia Etc. Discussion Questions: a. What color did the each piece of red litmus paper turn to when a drop of the different samples was tested with it? Blue litmus paper? b. Which of the materials are acids? Which are bases? How were you able to classify? 106 N/A N/A N/A N/A N/A N/A Odor Color Taste Reaction with litmus paper aluminum foil

CHEMISTRY IN ACTION c. What did you observe when aluminum foil came in contact with an acid? with a base? d. List all the properties of acids and bases that you have observed. 2. Preparing Natural Indicators. Extracts from local plants can be used to indicate the approximate pH values of sample solutions based on the sharp color changes in acids and bases. Ask the students to prepare acid-base indicators from local plants extracts. Plants that may be used are colored vegetables like carrots, brightly colored flowers, and leaves. The procedure below is for eggplant peel. Materials: one small eggplant, 75 mL ethyl alcohol, 75 mL water, 3 mL of 0.1 M NaOH, 3 mL of 0.1 M HCl, filter paper, knife and chopping board, alcohol lamp, 3 medicine droppers, 6 vials, graduated cylinder, beaker Procedure: a. Peel the skin of the eggplant thinly. Chop the skin peelings into small pieces. Put about 5 grams of the chopped material into 50 mL solution containing one part alcohol and one part water. b. Heat gently over an alcohol lamp until the liquid in the mixture yields a violet blue color. c. Allow the mixture to cool for a few minutes. Then immerse a piece of filter paper into the mixture and allow the paper to absorb the liquid. Remove the filter paper and air-dry. Cut the paper into strips. This may be used in acid-base testing similar to litmus paper. d. Dip a strip of the eggplant indicator paper in the HCl and another strip in the base. Note the color change in the indicator paper for each case. Data and Observations: Extract Color of Extract Eggplant 3. Neutralization Reaction. Materials: about 10 mL 0.1 M NaOH solution, about 10 mL 0.1 M HCl solution, phenolphthalein indicator (or an appropriate plant extract), 10 mL graduated cylinder, evaporating dish, two medicine droppers Procedure: a. Put 5 mL of 0.1 M NaOH solution in an evaporating dish. Add a drop of phenolphthalein. Record your observation. 107 Color in 0.1 M HCl Color in 0.1 M NaOH

CHEMISTRY IN ACTION b. Place exactly 10 mL of the 0.1 M HCl solution in the graduated cylinder. c. Use a dropper to add carefully drop-by-drop 0.1 M HCl solution into the evaporating dish with constant swirling until the color of the solution in the evaporating dish fades. (NOTE: if too much acid has been added, measure out 1 mL of the NaOH solution and add to the evaporating dish. The color should reappear. Then add HCl again until the color just disappears.) d. How many milliliters of HCl remain in the graduated cylinder? How many milliliters of HCl solution were used? Compare the volumes of NaOH solution and HCl solution used. e. Heat the solution in the evaporating dish to dryness. Do not overheat. What did you observe? f. Describe the solid that remained in the evaporating dish. What is the identity of this solid? (DO NOT TASTE! The residue still contains phenolphthalein indicator and possibly excess NaOH!) Discussion Questions: a. Write a chemical equation for the reaction between HCl and NaOH. b. How is water formed in the neutralization reaction, i.e. where do the atoms that form water come from? c. At what pH does phenolphthalein change color? Why is it appropriate to use this indicator in the neutralization reaction that you observed? 4. Acid Rain. Background Information: Rain is naturally slightly acidic because of the carbon dioxide in the atmosphere that dissolves in the water as rain forms and falls. Gases produced by industry and motor vehicles, including some oxides of nonmetals such as those of sulfur and nitrogen, also dissolve in the water vapor in the air making rain more acidic. This phenomenon is known as acid rain. Pollutant Source power plant automobile automobile, people and animals Pollutant Gas SO2, SO3 sulfur oxides NO, NO2, NO3 nitrogen oxides CO2 carbon dioxide Acid(s) Formed H2SO3, sulfurous acid H2SO4sulfuric acid HNO2, nitrous acid HNO3, nitric acid H2CO3 carbonic acid

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CHEMISTRY IN ACTION Purpose: To compare the acidity of carbon dioxide, CO2, in exhaled breath to that produced by pieces of alka-seltzer in water. Materials: one Alka-Seltzer tablet broken into pieces, bromothymol blue indicator in dropper bottle, two 250-mL beakers, several drinking straws Procedure: a. Fill each of the beakers one-half full with water. b. Add 2 drops of bromothymol blue indicator to each beaker stirring until the solution is decidedly blue in color. c. Use a drinking straw to bubble your breath through the blue indicator solution in one of the beakers. Hold the straw slightly above the bottom of the beaker and use only small puffs of breath to keep the blue solution from splattering. Continue to do this until a definite color change in the solution is observed. This is Beaker A. d. Add of an Alka-Seltzer table to the bromothymol blue solution in the second beaker, Beaker B. Observe any color change. e. Record final colors and complete the table below. Initial color of indicator solution Beaker A Beaker B Acidic , neutral, or basic?* Final color after CO2 dissolves Acidic, neutral, or basic?

*While pure water is neutral, a few drops of the indicator should make the water in the beaker basic since bromothymol blue solution is in basic medium. Discussion Questions/Explorations: a. What is the effect of bubbling carbon dioxide on the acidity of water? b. Is there a difference in the acidity of water containing carbon dioxide from your breath compared to that with carbon dioxide from AlkaSeltzer? Suggest an explanation for any observed difference. c. What product is formed when carbon dioxide dissolves in water? Try to work out the chemical equation for the reaction of water and carbon dioxide.

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CHEMISTRY IN ACTION d. Acid rain is associated with industrial and motor vehicle pollutants. Show using equations how oxides of sulfur and nitrogen can make rain acidic. e. What effect would acid rain have on plants and animals? f. What could be done to reduce acid rain? TEACHING TIPS Suggested Activities A. Brainstorming. Divide the students into groups and assign each group some questions to answer. The questions may be environmental issues or problems encountered in daily life that involve acids and bases. The following are some suggested questions: 1. What is acid rain? What causes rain to be acidic? 2. Acid rain has been described as a regional problem, while the greenhouse effect is a global problem. Do you agree with this statement? Why or why not? 3. How is the concept of acids and bases utilized in the manufacture of toothpaste and in the maintenance of healthy teeth? 4. Many foods can be acidic or basic. How does the human body keep its own acid-base balance? B. Plant Visit. Plan a visit to any of the following places: 1. Soap industry 3. Metallurgy plant 2. Electroplating plant 4. Bottling company Make a report or listing of the acids and bases used in their production or operation. C. Natural Acids and Bases. Ask the students to list down acids and bases in the food we eat. D. Research Report. Ask the students to select an important acid or base used at home or in industry and make a research report on it. The report should include how the substance is prepared and its uses.

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CHEMISTRY IN ACTION E. Soap Making. Soap is the salt formed from the reaction of a fatty acid and a strong base like NaOH. Ask the students to collect ashes from different kind of woods or palms. Let them make their own soap with the collected ash and coconut oil. Provide the students with a simple procedure on soap making. ASSESSMENT Quiz. Select the letter corresponding to the best answer. 1. Acetic acid is a weak acid because it is A. a proton donor. C. slightly ionized in solution. B. sour. D. an electron pair acceptor. 2. When an acid has reacted completely with a base, A. an acid is formed. C. only salt is formed. B. a base is formed. D. salt and water are formed. 3. Which of the following will NOT give a visible reaction to litmus paper? A. Lye solution C. Muriatic acid B. Milk of magnesia D. Table salt solution 4. Which of the following is an Arrhenius base? A. H2O C. NaOH B. H2SO4 D. NH3 5. A solution that has a pH of 6.50 is A. slightly basic. B. slightly acidic. C. very acidic. D. very basic.

6. Which of the following is NOT a strong acid? A. H2SO4 C. HCl B. HC2H3O2 D. HNO3 7. Which of the following best describes Bronsted-Lowry acid and base? A. An acid forms H+ in solution while a base forms OH in the solution. B. An acid is an electron pair acceptor while a base is an electron pair donor. C. An acid is a proton donor while base is a proton acceptor. D. An acid is sour while base is generally bitter in taste.

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CHEMISTRY IN ACTION 8. Which of the following about the pH of a solution is INCORRECT? A. A solution has a high pH if the concentration of H+ is also high. B. As the pH of solution increases, acidity decreases. C. Indicators can give an estimate of the pH of solutions. D. The pH of a 0.10 M HCl solution is 1.0. 9. Pineapple juice is both sour and sweet. The pH of pineapple juice must be A. equal to 7.0. C. higher than 14.0. B. higher than 7.0. D. lower than 7.0. 10. A colorless solution turned pink when 2 drops of phenolphthalein indicator were added. The solution must be A. acidic. C. neutral. B. basic. D. cannot be determined. ANSWER KEY Quiz. 1. 6. C B 2. 7. D C 3. D 8. A 4. C 9. D 5. 10. B B

REFERENCES Goldberg, D. (1998). Fundamentals of chemistry. CA: McGraw-Hill, Inc. Nueva Espaa, R. et al. (1990). Science and technology III. QC: Abiva. Magno, M. et al. (1991). Science and technology III SEDP Series. QC: Book Media Press. Scott, W. H. (1996). Chemistry basic facts. Great Britain: HarperCollins.

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CHEMISTRY IN ACTION Useful Websites _____. Acid-Base in the Human Body. Accessed 14 September 2007. National Kidney and Urologic Diseases Information Clearinghouse Web Page. (http://kidney.niddk.nih.gov/ kudiseases/pubs/tubularacidosis/index.htm) _____. Acid-base Reaction. Accessed 14 September 2007. Journal of Chemical Education Web Page. (http://www.jce.divched.org/JCEDLib/ChemInfo) _____. Dancing Raisins and Popcorn Kernels: Fun With CO2 Gas in Water. Accessed 14 September 2007. (http://chemsrvr2.fullerton.edu/HES/introduction/contents.htm) _____. Fascinating Facts. Accessed 14 September 2007. Mrs. Jenkins Biology and Chemistry Home Page. (http://home.att.net/~jenkinsg524/index.htm) _____. Trivia About Acids and Bases. Accessed 13 September 2007. Fun Trivia.Com Webpage. (http://www.funtrivia.com/en/SciTech/Acids-and-Bases6848.html) _____. Where Do Acids Come From? What is Acid Rain? Accessed 14 September 2007. (http://chemsrvr2.fullerton.edu/HES/introduction/contents.htm)

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 24: THE ATOM: A VIEW FROM WITHIN OVERVIEW In the previous episodes, chemical reactions were discussed in terms of various combinations of atoms and molecules. This is a view from the outside; it does not tell us what molecules and atoms look like on the inside. The structure of the atom has long intrigued and engaged minds of people. During the 20th century, the power of the atom was harnessed in making atomic bombs and in generating electricity. It became possible for the atom to be split into even smaller pieces called subatomic particles. This episode takes a closer look inside an atom. We will see how various scientists answered questions like What is an atom? What is it made of? What does it look like? The fascinating story of how discoveries in various fields of science resulted in the current view of the atom is presented. The episode will show the historical development of atomic structure by presenting models from the time of Democritus up to how it is conceived today. OBJECTIVES At the end of this lesson, the student should be able to: 1. name and describe the subatomic particles; 2. perform simple calculations involving atomic number and mass number; 3. describe Rutherfords alpha-scattering experiment; 4. explain the observations obtained from Rutherfords experiment that suggested the existence of the nucleus; 5. describe and compare the different models of the atom the atom as conceived by the Greeks, John Dalton, Joseph J. Thomson, Ernest Rutherford, Niels Bohr, Arnold Sommerfeld, Erwin Schroedinger, and Max Born; 6. summarize the development of the atomic theory; and 7. appreciate contributions of scientists in the development of the atomic theory; and demonstrate creative thinking, critical thinking and problem solving skills.

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CHEMISTRY IN ACTION INTEGRATION WITH OTHER LEARNING AREAS This episode focuses mainly on the subatomic particles and the different atomic models. Other details about the atom, particularly how the electrons are arranged in an atom, will be the subject of the succeeding episodes. SCIENCE PROCESSES Observing Interpreting and organizing data Making inferences VALUES Knowledge builds up from simple to complex Investigating and researching needs patience Endless quest for knowledge and truth Unlimited possibilities to contribute to progress Predicting Formulating hypotheses

LIFE SKILLS Designing strategies Endless quest for knowledge and truth Unlimited possibilities to contribute to progress IMPORTANT CONCEPTS 1. The word atom came from the Greek word, atomos, which meant indivisible or indestructible. 2. The atom consists of three fundamental subatomic particles: proton, electron, and neutron. 3. The atomic number is the number of protons in the nucleus of an atom. It is equal to the number of electrons in a neutral atom. 4. The mass number is the total number of protons and neutrons in the nucleus of an atom. Problem-solving Interpersonal relationship Collaboration Effective communication

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CHEMISTRY IN ACTION 5. John Dalton adopted Democritus concept of the atom as the smallest particle of matter. He believed that atoms of a specific substance were small spheres of identical size. 6. Joseph J. Thomson proposed the plum pudding model of the atom. His atom was a uniform mass of positive charge in which negatively charged electrons (which he first called corpuscles) were embedded. 7. Ernest Rutherford performed the alpha particle scattering experiment that led him to conclude that: (a) the atom was mostly empty space, (b) there was a small, massive, and positively-charged particle which he called the nucleus at the center of the atom, and (c) the electrons moved in the space around the nucleus. This model was called the nuclear model. 8. In his attempt to explain the atomic spectrum of hydrogen, Niels Bohr suggested that electrons traveled around the nucleus in circular orbits. The energy of the electrons increased with the radius of their orbits. Later Arnold Sommerfeld proposed that orbits were elliptical. 9. Following developments in Quantum Theory, Erwin Schroedinger proposed a mathematical description of the atom and described electrons in terms of wave functions. Max Born interpreted the square of the wave function as the probability of finding the electron in a given volume of space outside the nucleus. BACKGROUND INFORMATION/EPISODE CONTENT What is matter made of? This question has baffled people since the ancient times. Some say that matter is composed of particles. The fact that some forms of matter can spread into other substances or materials supports the idea that matter is made up of small pieces that can separate from one another. The demonstration in the video lesson showing potassium permanganate diffusing slowly throughout the water as indicated by the spread of its color proves this point. That we are able to smell perfumes or fuel gas or the scent of flowers even if we are at a distance from their sources likewise supports this belief. Early Atomic Theories. The idea that matter is made up of atoms and molecules is not a simple conclusion that anyone could make from observing things. But in about 400 B.C., this was the belief of the Greek philosophers Leucippus and Democritus when they suggested that one can subdivide a sample of matter only up to a certain point where it could no longer be further subdivided. They called that smallest piece of indivisible part of 116

CHEMISTRY IN ACTION matter the atom. For Democritus, atoms of water were smooth and atoms of fire have sharp edges. The ideas of Democritus and Leucippus ran contrary to those of Aristotles who believed that matter is continuous and can be subdivided indefinitely. Being the more revered philosopher of his time, Aristotles ideas prevailed. Daltons Atomic Theory. More than 2,000 years after Democritus, John Dalton revived the concept of atoms. He proposed an atomic theory to explain the Law of Conservation of Mass and Law of Definite Proportions that were earlier established by Antoine Lavoisier and Joseph Proust, respectively. The Atomic Theory of John Dalton was described in a series of papers published from 1803 to 1810 and it suggested that the two laws on chemical combination can best be explained if matter is thought of as being composed of atoms. The postulates of Daltons atomic theory were as follows: 1. Matter is made of atoms. 2. All atoms of an element are the same. 3. Atoms of different elements are different (size, properties). 4. Atoms of different elements can combine to form compounds. 5. In chemical reactions, atoms are not made, destroyed or changed. 6. In any compound the numbers and kinds of atoms remain the same. Daltons atomic theory formed the groundwork for chemistry. Dalton envisioned atoms as indestructible tiny spheres, as the Greek philosophers did, but with hooks on them. With these hooks, one atom could combine with another in definite proportions. But some elements could combine to make two or more different compounds (e.g., hydrogen and oxygen could make water or hydrogen peroxide). Dalton was not certain about the numbers of each atom in the molecules of specific substances. Did water have one oxygen atom combined with one hydrogen atom or with two hydrogen atoms? These uncertainties were later resolved when chemists figured out how to weigh atoms. Thomsons Plum Pudding Model. In 1897, Joseph J. Thomson, through experiments with cathode ray tubes, CRT), showed that electrons were produced in the CRT regardless of the metal used as electrodes. He concluded that these negatively charged particles were fundamental constituents of matter. He has discovered the first subatomic particle which he called corpuscles and later renamed the electron. In 1904, Thomson proposed the plum pudding model of the atom. In this model, the atom is a uniform mass of positive charge where small negatively-charged particles, the electrons, are embedded. Plum pudding is a 117

CHEMISTRY IN ACTION dessert familiar to the British, but not to many of us Filipinos, so tapioca pudding was shown in the video lesson instead. In this local pudding, raisins, which are likened to electrons, are dispersed in the filling which in turn is compared to the positively charged mass. Another local material that can be used as analogy to Thomsons model is the raisin bread. In the hundred years between Dalton and Thomson, the idea of the atom changed from a simple particle without parts to a more complex one with parts. Rutherfords Experiment. Ernest Rutherfords investigations on the nature of radiation produced by radioactive materials led to his alpha, , particle scattering experiment that probed the inner structure of the atom. His experimental setup included a source of high-energy alpha particles, a stationary gold foil, and a detector to track down the alpha particles as in Figure 1. Alpha particles emanating from the radioactive source were directed towards a very thin piece of gold foil and Rutherford noted where the alpha particles scattered after hitting the gold foil.

Gold foil

Figure 1. Setup for Rutherfords alpha particle scattering experiment. He observed that most of the alpha particles went through the gold foil undeflected. However, about one in eight thousand were scattered usually at small angles. Most unexpectedly, a tiny fraction of the alpha particles did not pass through and were deflected back. The video episode shows a simulation of the experiment at the atomic level to help one visualize Rutherfords results. The beam of alpha particles hitting the gold foil can be likened to firing bullets at an iron grill fence. Most of the bullets pass through the fence without encountering any barrier that could stop or deflect them from their path. Occasionally, a bullet hits an iron bar and gets deflected.

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CHEMISTRY IN ACTION The Nuclear Model of the Atom. The observations obtained in the alpha particle scattering experiment led Rutherford to make the following conclusions about the atom which were not consistent with the plum pudding model proposed by Thomson. Rutherfords model, known as the nuclear model of the atom, that embodies his findings is illustrated in Figure 2. 1. The atom is mostly empty space. 2. There is small and heavy mass with positive charge at the center of the atom. 3. The electrons move around in the space outside the nucleus.

Figure 2. Illustration of how Rutherford explained his observations. The nuclear model of the atom proposed by Rutherford presented an atom that was mostly empty space but with a tiny, positive, massive center which he called the nucleus. What is the nucleus made of? Rutherford deduced in 1919 that the nucleus contained positively charged particles that were also fundamental components of atoms and called them protons. Further experiments and calculations showed that a proton is about 2000 times heavier than an electron and that its charge is exactly of the same magnitude but opposite in sign as that of an electron. In 1932, Rutherfords student, James Chadwick, established the existence of another particle in the nucleus, the neutron. The neutron has no electrical charge and does not contribute to the charge of the nucleus but has a mass that is almost equal to the proton which explains the additional mass observed in the nuclei of most atoms. Protons and neutrons make up the nucleus and account for almost all of the mass of the atom. The Subatomic Particles. The following table summarizes the properties of the subatomic particles. Table 1. Summary of properties of the subatomic particles. Mass Particle (Discoverer) Amu Gram 119 Charge Assigned value Coulomb

CHEMISTRY IN ACTION Electron 0.00054897 (Thomson) Proton (Rutherford) Neutron (Chadwick) 1.00727663 1.0086654

9.1091 x 1028

-1 +1 0

-1.60 x 10-19 +1.60 x 1019

1.67232 x 10-24 1.67482 x 10-24

Atomic Notations: Atomic Number and Mass Number. The atomic number, Z, is the number of protons in the nucleus of an atom. The number of protons in the nucleus of an atom gives the identity of the atom. It is also equal to the number of electrons in a neutral atom and numerically equal to the charge of the nucleus. The mass number, A, is the total number of protons and neutrons in the nucleus of an atom. The atomic number and mass number are always whole numbers. The composition of the nucleus of an atom can be symbolically represented by its isotopic symbol whose general form is: where X is the symbol of the element A A is the mass number and Z Z is the atomic number.

For example, the nucleus of the sodium atom contains 11 protons and 12 neutrons. Its isotopic symbol is:
23 11

Na

The atomic number, Z, of Na is 11 and since it has 12 neutrons, then its mass number, A, is 11 + 12 or 23. Electron Orbits: Bohr and Sommerfeld Models. One phenomenon that has remained unexplained in the late 1800s was the discontinuous or line spectrum obtained when light emitted by hydrogen gas was passed through a prism. In 1900, Max Planck proposed his revolutionary Quantum Theory and suggested that light has a dual nature wave and particulate. In 1913, Niels Bohr used Plancks theory to explain the line spectrum of hydrogen and proposed a new model of the atom! Niels Bohr described the electrons in an atom as moving around the nucleus in circular orbits in much the same way that planets orbit the sun. The crosssectional representation of the Bohr model is shown in Figure 3. In an atom, there are only certain orbits that are allowed. Electrons could move from one orbit to another by absorbing or emitting energy but they could not stay in 120

CHEMISTRY IN ACTION between allowed orbits. The orbits, being three-dimensional, are also called shells.

Figure 3. The Bohr model of the atom.

(Source: http://www.britannica.com/nobel/cap/oatoms0001a4.html)

The Bohr model successfully explained the line spectrum of hydrogen but his equations did not work with atoms containing more than one electron. In 1916, Arnold Sommerfeld suggested that some orbits were elliptical in shape. However, the elliptical orbits were not any better in explaining the more complex spectra of other elements. Orbitals: The Quantum Mechanical Model of the Atom. The model of the atom that replaced the Bohr model is the currently accepted quantum mechanical model or the wave model. The model is highly mathematical and the equations developed by Erwin Schroedinger were successful in describing the energy states of atoms of the elements. Instead of treating the electron as a particle moving in orbits, Schrodinger described it in terms of a mathematical formula called the wave function. Max Born, another physicist, interpreted the square of the wave function as the probability of finding the electron in a given volume of space outside the nucleus. In the wave model, the allowed energy states of an electron are referred to as orbitals which defined by four quantum numbers. The orbital may also refer to a region in space in an atom where the probability of finding the electron is very high. Orbitals are often represented as boundary surfaces that enclose the region in space where electrons can be found more than 95% of the time. These are the familiar shapes that we know: spherical for s orbitals and dumbbell-shaped for the p orbitals. It is in this model of the atom that the distribution of electrons in atoms that is consistent with the physical and chemical behavior of the elements is described. A more detailed discussion of the wave model and the electronic 121

CHEMISTRY IN ACTION structure of the atom is described in the next episode, Episode 25 Electronic Structure of an Atom. VOCABULARY WORDS 1. Alpha particles radioactive particles bearing positive charge with a mass equal to helium. 2. Atom - the smallest indivisible piece of matter . 3. Electron - the negatively charged particle of matter. 4. Proton the positively charged particle that is a fundamental component of atoms and is found in the nucleus. 5. Neutron - another particle in the nucleus but has no electrical charge; it has a mass that is almost equal to the proton. 6. Nucleus a small yet heavy mass with positive charge at the center of the atom. 7. Atomic number - the number of protons in the nucleus of an atom; it is also equal to the number of electrons in a neutral atom. 8. Mass number - total number of protons and neutrons in the nucleus of an atom. 9. Orbit circular paths where the electrons are thought of as moving around the nucleus; later believed to being three-dimensional and were then also called shells. PRE-VIEWING ACTIVITIES A. Ask the class: What is matter made of? Some might answer matter is composed of particles. Others might say matter is made up of atoms and molecules. Let the students share their ideas on matter before and after discussing this lesson on atomic structure. B. Use this episode as introduction to a detailed discussion of the structure of the atom. C. Pose the Guide Questions to the students before viewing the episode. Ask them to find the answers to the guide questions in the video. 122

CHEMISTRY IN ACTION Guide Questions/Answers 1. What is Democritus idea of matter? Democritus believed that matter is composed of small indivisible particles he called atoms. 2. What is meant by the Greek word atomos? Atomos is a Greek word that means uncuttable or indivisible. 3. How did Democritus describe the atoms of water and of fire? For Democritus, atoms of water were smooth and atoms of fire has sharp edges. 4. What was the first subatomic particle to be discovered? Who discovered it? The first subatomic particle to be discovered was the electron. Joseph J. Thomson discovered it in 1897. 5. What are the other subatomic particles? Give a short description of each. The subatomic particles are the electron, proton, and neutron. The electron is a negatively charged particle that moves around the nucleus. The proton is a positively charged particle found in the nucleus. The neutron is a particle that has no electrical charge and can also be found in the nucleus. 6. What properties did Dalton propose that atoms of an element have in common? John Dalton proposed that atoms of a specific substance/element were small, indivisible spheres of identical size and mass. 7. According to Dalton, what did atoms have that enable them to combine and form compounds? According to Dalton, atoms have hooks that made them combine to form other compounds. 8. Why was Thomsons model called the plum pudding model? Thomsons model was called the plum pudding model because it resembled a plum pudding, where the plums represent the embedded electrons and the filling represents the positively charged sphere of the atom.

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CHEMISTRY IN ACTION 9. What were the conclusions arrived at by Rutherford in his alpha particle scattering experiment? Based on the results of Ernest Rutherfords alpha particle scattering experiment, he was able to formulate the following conclusions: a. The atom is mostly empty space. b. There is small and heavy mass with positive charge at the center of the atom, the nucleus. c. The electrons move around in the space outside the nucleus. 10. What is the difference between the atomic models of Bohr and Sommerfeld? In Niels Bohrs atomic model, electrons travel around the nucleus in circular orbits, while in Arnold Sommerfelds model, the orbits are elliptical in shape. 11. How does the energy of the electrons change with the radius of its orbit? As the radius of each orbit increases, the energy of the electrons in that orbit also increases. 12. Who discovered the neutron? Why is its presence important in the atom? James Chadwick discovered the neutron in 1932. Neutrons account for the additional mass observed in the nucleus that is not accounted for by the protons present. 13. How did Schroedinger and Born describe the electron? Erwin Schrodinger described the electron in terms of the wave function because an electron behaves like a wave. The square of wave function, according to Max Born, is the probability of finding the electron in a given volume outside the nucleus. 14. What is the difference between atomic number and mass number? The atomic number is the number of protons in the nucleus of an atom. It is also the number of electrons in a neutral atom. On the other hand, mass number is the total number of protons and neutrons in the nucleus of an atom. VIEWING ACTIVITIES Focus on segments 7:12 - 11:55 for Rutherfords Alpha Scattering Experiment. 124

CHEMISTRY IN ACTION POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions. TEACHING TIPS Suggested Activities A. Paper Clip Demonstration. From the ancient Greeks up to today, man has pondered over what ordinary matter is made of. (Snyder, 3rd ed.) Procedure: 1. Take a pile of paper clips, all the same in size and in color. 2. Divide them into two equal piles. 3. Divide each of the smaller piles into two equal piles. 4. Repeat step (3) until you are down to a pile containing only one paper clip. That one paper clip does the job of a paper clip (i.e. hold loose papers together). 5. Now take a pair of scissors/cutter and cut one paper clip in half. Can half of the paper clip do the same job as the single paper clip? Discussion: If one does the same with any element, ultimately one will reach an indivisible part that retains the properties of the element like the single paper clip. This indivisible part is the atom. Recall the statements in Daltons atomic theory and explain each one in terms of what was observed with the paper clip. 1. Every element is made of atoms (each pile of paper clips represent an element). 2. All atoms of an element are the same (all the paper clips in a pile are the same in size and in color). 3. Atoms of different elements differ in properties. (a pile may be composed of paper clips of different size and color as those in another pile). 4. Atoms of different elements can combine to form compounds (one can link different sizes and colors of paper clips to make new structures). 5. In chemical reactions, atoms are not made, destroyed or changed (no new paper clips appear, no paper clips are lost, and no paper clips change in size when linked up with one another). 6. In any compound, the numbers and kinds of atoms remain the same (a compound is represented by a set of paper clips with the same number, kind, and arrangements of paper clips). 125

CHEMISTRY IN ACTION B. Simulation Game. Here is a group activity for the students to simulate Rutherfords alpha scattering experiment. Objective: To estimate the size and location of an object without actually seeing it by simulating Rutherfords experiment. Discussion: Rutherford suggested that an atom is mostly empty space. The positive charges, as well as the mass of the atom, are concentrated in a very small portion of the atom. He called this the nucleus. He estimated the size of the nucleus by observing the number of alpha particles deflected. Tips: 1. Use a heavy stone so that it will not move when hit by marbles. 2. Choose a dark colored plant extract, like that from alugbate seeds, if blue or black dye is not available. Any dark colored ink may also be used. 3. Do not use ruled paper. This is already lined and the lines made by the marble would not be very visible. (Note: Using ruled paper might seem advantageous if it will make the preparation shorter. Procedure: 1. Paste two sheets of unruled paper together along their lengths. Using a pencil, make light lines from one end of the paper to the other end with a 2-cm distance between lines. See Figure 4.

Figure 4. How to prepare the set up for the activity. 2. Fold two sides of a cardboard to a height slightly higher than a stone to be hidden under it, but not too high that the stone can be easily 126

CHEMISTRY IN ACTION seen. The cardboard should be shorter than the length of the paper such that when placed over the paper, about half an inch of the paper extends on each side. The lines of the paper should run perpendicular to the open ends of the cardboard. 3. Place a heavy stone somewhere on the ruled paper without letting anybody see where it was put. Immediately cover the stone on the ruled paper with the folded cardboard. See Figures 5 and 6.

Figure 5. Side view of the set up, open end of cardboard.

4. 5. 6. 7. 8. 9.

Figure 6. Top view of the set up. Dip a marble in the plant extract/ink. Roll the marble under the cardboard, between the edge and first line of the paper. Apply sufficient force on the marble so it will come out of the other side. Wet the marble again then roll it along the next column on the paper (between first and second lines). Mark the columns where a sound is heard as the marble hits the stone. When you have rolled the marble in all columns on the paper, repeat the rolling of the marble along the columns at the opposite end (this means you will roll the marble from both open ends). Remove the cardboard and the stone. From the markings left by the marble on the paper estimate the size and location of the stone.

Discussions/ Questions: Below are some questions that may be asked the students. 1. In what way(s) is/are the activity similar to Rutherfords alpha scattering experiment? 2. What did the stone represent? What did the marble represent? 127

CHEMISTRY IN ACTION 3. Describe the path of the marble. What observation suggests that the atom is mostly empty space? 4. What observations imply that a massive portion of the atom was hit? 5. How can one estimate the size of the stone even if it cannot be seen? 6. How was Rutherford able to estimate the size of the nucleus? C. Models in a Timeline. Ask the students to construct the different atomic models (e.g. plum pudding, nuclear model, and Bohr model) and present these in a timeline. To link this lesson with the other subjects like Social Studies and Mathematics, ask the students to incorporate important events in history or milestones in mathematics that happened on the same dates as the ones on the time line. Here are questions about the atomic models the students can answer: 1. In what ways is your model like a real atom? 2. In what ways is your model unlike a real atom? D. Reflection. Ask the students the following questions: 1. Which model of the atom would best describe you? Why? 2. What subatomic particle would you want to be and why? 3. Why is it important to learn and understand the concept of the atom? E. Who Are They? Unscramble each of the clue words. Copy the letters in the numbered cells to other cells with the same number. Then you will know who they are.

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CHEMISTRY IN ACTION

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CHEMISTRY IN ACTION F. Concept Map. Ask the students to complete the concept map on changing an atom.

ATOM

add or remove a proton

?A

add or remove an electron

add or remove a neutron ?B add to/join with another atom Select from the following: 1. A new element 2. Nucleus 3. Ion 4. Isotope 5. Molecule

?D ?C

ASSESSMENT A. Quiz. Choose the letter corresponding to the correct answer. 1. Who first said that the atom was the smallest indivisible piece of matter? A. Niels Bohr C. Arnold Sommerfeld B. Democritus D. Joseph J. Thomson 2. Who discovered the electron? A. John Dalton B. James Chadwick 3. Who discovered the neutron? A. James Chadwick B. Ernest Rutherford 130 C. Erwin Schrdinger D. Joseph J. Thomson C. Erwin Schrdinger D. Joseph J. Thomson

CHEMISTRY IN ACTION 4. Who proposed that atoms have hooks on them that made them combine to form compounds? A. Niels Bohr C. Erwin Schrdinger B. John Dalton D. Joseph J. Thomson 5. What is the atomic model of Thomson called? A. Nuclear model C. Plum pudding model B. Planetary model D. Quantum mechanical model 6. What is the atomic model of Rutherford known? A. Nuclear model C. Plum pudding model B. Planetary model D. Quantum mechanical model 7. Who stated that the atom has a massive, positive center? A. Niels Bohr C. Ernest Rutherford B. John Dalton D. Joseph J. Thomson 8. Who proposed that electrons move in circular orbits? A. Niels Bohr C. John Dalton B. James Chadwick D. Arnold Sommerfeld 9. Who said that some orbits were elliptical in shape? A. Max Born C. Arnold Sommerfeld B. Democritus D. Joseph J. Thomson 10. Who described the electron in terms of the wave function? A. Niels Bohr C. Ernest Rutherford B. James Chadwick D. Erwin Schrdinger B. Protons and Neutrons. Label each of the following phrases as applicable to a neutron, a proton, both of these or neither of these. 1. Found in the nucleus of an atom. 2. Has a negative charge. 3. Has no electrical charge. 4. Has a positive electrical charge. 5. Moves around the nucleus. C. Atomic Number and Mass Number. Consider the following atoms and answer the following questions. 131

CHEMISTRY IN ACTION 1. Which atoms have the same mass numbers? 2. Which atom(s) has (have) the atomic number 7? 3. Which are isotopes of the same element? A 6 6 6 B 6 7 6 Atoms C D 6 7 8 6 7 7 E 8 6 8 F 7 8 7

Number of electrons Number of neutrons Number of protons

D. Complete the Table. One would need a periodic table for the symbols of the elements. Atomic number 5 Mass number 11 Mo 118 ANSWER KEY (Under Teaching Tips, Suggested Activities) E. Who are they? Democritus Dalton Thomson Rutherford Bohr Sommerfeld Schrodinger Born 50 54 Symbol of the element Number of protons Number of neutrons

They are responsible for the development of the atomic structure. F. Concept Map. A. New element B. Molecule (Under Assessment) A. Quiz. 132 C. Isotope D. Ion

CHEMISTRY IN ACTION 1. 6. B A 2. D 7. C 3. A 8. A 4. B 9. C 5. 10. C D

B. Protons and Neutrons. 1. Both of these. 2. Neither of these. 3. Neutron 4. Proton 5. Neither of these.

C. Atomic Number and Mass Number. 1. Atoms C, D, and E. 2. Atoms D and F. 3. Atoms A, B, and C. Atoms D and F.

D. Complete the Table. Atomic number 5 42 50 REFERENCES Masterton, W. L. & C. N. Hurley. (2005). Chemistry: principles and reactions. (4th ed.). FL: Saunders College Publishing. Morris, H. (1990). Foundations of college chemistry. CA: Wadsworth. Snyder, C. (1998) .The extraordinary chemistry of ordinary things. (3rd ed.). NY: John Wiley & Sons, Inc. The Columbia Electronic Encyclopedia. (2000). Columbia University Press. Zumdahl, S. S. (2010). Chemistry. CA: D.C. Heath & Co. Mass number 11 96 118 Symbol of the element B Mo Sn Number of protons 5 42 50 Number of neutrons 6 54 68

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CHEMISTRY IN ACTION Useful Websites http://school.discovery.com http://www.howstuffworks.com/atoms http://www.galaxy.net/~k12/matter

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 25: ELECTRONIC STRUCTURE OF AN ATOM OVERVIEW The present day idea of the atom evolved from the development of the different atomic models. From an indestructible and indivisible particle, the atom has been shown to consist of subatomic particles: electrons, protons, and neutrons. In this episode, the focus will be on the distribution of electrons in atoms based on the findings of Niels Bohr and other scientists in their study of the nature of light and of the line spectrum of hydrogen. This episode is presented in two segments. The first segment is about the line spectrum and the Bohr atomic model. The second segment presents the current model of the atom, the quantum mechanical model, and the distribution of electrons in the atom. OBJECTIVES At the end of this lesson, the student should be able to: 1. state the relationship between wavelength and energy of light; 2. explain the use of the flame test in analyses of some samples of matter; 3. explain the use of the light emission spectrum in analyses of elements; 4. describe Bohrs model of the atom and use it to explain the emission spectrum of hydrogen; 5. determine the set of quantum numbers for a given electron in an atom and state the significance of each number; 6. arrange the atomic orbitals according to increasing energy; 7. apply the Aufbau principle, Hunds rule of maximum multiplicity, and Paulis exclusion principle in electron distribution; 8. demonstrate logical reasoning, open-mindedness and ability to follow rules; and 9. appreciate the convenience and logic in following a set of rules INTEGRATION WITH OTHER LEARNING AREAS In order to get a better appreciation of how mans understanding of atomic structure developed, it is suggested that Episode 25 be viewed soon after Episode 24 The Atom: A View from Within. SCIENCE PROCESSES Observing Predicting 135

CHEMISTRY IN ACTION Interpreting and organizing data Making inferences VALUES Conformity with rules LIFE SKILLS Sharing of ideas Understanding the nature of things Open mindedness IMPORTANT CONCEPTS

Formulating hypotheses

Order in a system

Teamwork Valuing others work

1. When passed through a prism, white light separates into a continuous spectrum of colors. Each color corresponds to a wavelength that has an equivalent energy. 2. The energy of a given color of light is inversely proportional to its wavelength. 3. The light given off by vaporized atoms shows colors that are characteristic of each element. 4. In an emission spectrum, the color, number, and position of the lines are distinct for each element and can be used to identify the element. 5. When energy is applied to an atom, the electrons get excited and absorb just enough energy to enable them to jump to available higher energy levels. Excited electrons eventually go back to lower levels and in doing so, emit exactly the amount of energy equal to the difference between the two levels. 6. Bohrs model of the atom consists of a nucleus surrounded by electrons moving in certain allowed orbits. The energy of an electron is constant as long as it stays in the same orbit. 7. The quantum mechanical model explains the line spectra of the other elements in addition to that of hydrogen. 8. An atomic orbital is an energy state. It is also a region in space where an electron is most likely to be found. A definite energy, shape, and orientation in space characterize each orbital. 9. The energy and most probable location of an electron can be described by four (4) quantum numbers: n, the principal quantum number l, the azimuthal or the orbital angular momentum quantum number ml, the magnetic quantum number 136

CHEMISTRY IN ACTION ms, the spin angular momentum quantum number. 10. The principal quantum number, n, designates the main energy level or the principal shell of an electron. This quantum number can have only integral values starting from 1; hence n=1, 2, 3. The energy of an electron increases with n. The higher the value of n for an electron, the farther it is from the nucleus. 11. Each main energy level consists of sublevels with one or more atomic orbitals. The number of sublevels in a main energy level is equal to the value of n. Sublevels are designated by l, the azimuthal quantum number, whose allowed values are from 0 to (n-1). Thus, for n = 2, there are two sublevels, designated by l = 0 and l = 1. The sublevels may also be identified by letter designations corresponding to the values of l. The sublevel designations s, p, d, f, and g correspond to sublevels of l = 0, 1, 2, 3 and 4, respectively. 12. How electrons will occupy the orbitals in an atom at its ground state is described by the Aufbau building-up principle, which states that electrons occupy the orbitals in order of increasing energy. The orbitals may be arranged in increasing energy using the (n + l) rule. 13. Hunds rule of maximum multiplicity states that when electrons enter a sublevel with degenerate orbitals, the electrons occupy the orbitals singly first, with parallel spins, before pairing up. 14. Paired electrons occupying the same orbital must have opposite spins. This is in accordance with Paulis exclusion principle, which states that no two electrons in the same atom can have the same set of four quantum numbers. BACKGROUND INFORMATION/EPISODE CONTENT When light is passed through a prism, the light separates into a continuous spectrum of colors. Scientists have shown that each color corresponds to a particular wavelength and frequency and a definite energy. The relationship between frequency and energy of light is given by the equation: E = h or E = hc/ where h = Plancks constant (6.63 x 10-34 J s) = frequency of radiation c = velocity of light = wavelength. Among the colors of the rainbow, also the visible spectrum of light, violet has the shortest wavelength and the greatest energy while red has the longest wavelength and the lowest energy. 137

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Figure 1. Continuous spectrum of color. When certain elements or compounds are heated, the vaporized atoms emit light of characteristic colors. Sodium compounds give off yellow light, compounds of strontium give off red light, and those of copper give off blue light. When the light given off by elements is passed through a prism, the spectrum obtained consists of lines of certain colors rather than a continuous band of colors. Every element has its own distinct line spectrum. The spectrum for hydrogen is given in Figure 2. This spectrum is called a line emission spectrum.

Figure 2. A line emission spectrum. The Bohr Model of the Atom and the Line Spectrum of Hydrogen. Niels Bohr explained the line spectrum of hydrogen with a new model of the atom. This model of the atom has new features that were based on the quantum theory of light proposed by Max Planck that states that light may also be viewed as a stream of particles of energy. In the Bohr model, the electrons move in orbits around the nucleus but there are only certain orbits that are allowed. Each orbit is designated by the principal quantum number, n, that can have values 1, 2, 3, and so on. The orbit n = 1 is the orbit closest to the nucleus and as the value of n increases, the radius of the orbit increases, and the farther from the nucleus the electron is that occupies this orbit.

Figure 3. The Bohr model of the atom.

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CHEMISTRY IN ACTION The greater the value of n, the greater the energy associated with that orbit. An electron in orbit n= 1 has the lowest energy and an electron in the next higher energy orbit (n = 2) will have a higher energy. When an electron is in a given orbit, its energy does not change and no energy is absorbed nor emitted by the electron even though it is moving around the nucleus. However, an electron can move to another allowed orbit by absorption or emission of a photon of light with energy that is exactly the amount needed for the transfer or transition to happen. This implies that an electron can only have certain values of energy, corresponding to the orbit where it is located. In other words, the energy of the electron is quantized. If energy is applied or added to an atom, the energy absorbed causes the electron to jump from its original orbit to an orbit of higher energy farther from the nucleus. When this happens, the electron is said to be in an excited state. As the electron returns from an orbit of higher energy to a lower one, it emits the energy it previously absorbed. The energy is given off as light and shows up as a line in the emission spectrum. In the spectrum of the hydrogen atom shown in Figure 2, the red line is emitted when an electron goes from orbit n = 3 to n = 2, while the green line is due to the transition from n = 4 to n = 2. The line spectrum of hydrogen is not limited to just the visible region of the electromagnetic spectrum. There are electron transitions that require energy in the UV region and others that need smaller amounts corresponding to the infrared region. Unfortunately, the Bohr model was unable to explain the more complex spectra of elements whose atoms contain more than one electron. The model of the atom needed some changes to satisfactorily explain the observed spectra of hydrogen as well as the other elements. The Quantum Mechanical Model of the Atom. The present model of the atom is a mathematical model based on concepts of quantum mechanics that suggest that electrons could exhibit wave properties and that for particles as small as an electron. But one cannot measure simultaneously both its location and energy with certainty. This is in contrast with Bohrs model that allowed the calculation of both energy and location of the electron but worked only for hydrogen. The quantum mechanical model calculates for the energy of an electron in any atom, not just of hydrogen, and makes an estimate of the location of the electron in terms of the probability of finding the electron in a certain region of space about the nucleus. Because electrons are treated as waves, this model is also called the wave model of the atom. Energy Sublevels and Atomic Orbitals. The complexity of the spectra of elements with more than one electron reveals the presence of energy sublevels within a main energy level, meaning there are more allowed energy levels in the atom than what was detected in the hydrogen atom. An electron, therefore, has many allowed energy 139

CHEMISTRY IN ACTION levels to move into by absorption or emission of energy. Each line in the spectrum of any element is an energy difference between these allowed energy states. In the wave model, the allowed energy levels of electrons in the atom are designated not by one, but three quantum numbers: n, the principal quantum number, l, the azimuthal quantum number, and ml, the magnetic quantum number. A set of these three quantum numbers (e.g. n = 2, l = 1, ml = -1) describes an orbital. An electron can be described completely by these three quantum numbers, plus a fourth one, ms, the spin quantum number. An orbital, therefore, represents an energy level. An orbital may also be defined as a mathematical description of a three-dimensional region in space where there is some probability of finding an electron. Quantum Numbers. The restrictions in the allowed values of the quantum numbers result in the quantization of energy of electrons: only certain values are allowed. The allowed values of the first quantum number, the principal quantum number n, is n = 1, 2, 3 . . . This quantum number gives the main energy level of the electron. The higher the value of n, the higher the energy of the electron, and the farther from the nucleus is its most probable location. The second quantum number, known as the azimuthal quantum number, l, can have integral values from 0 to (n-1). Thus, at n= 2, there are two allowed values of l: 0 and 1. Each value of l corresponds to an energy sublevel, each with a letter designation: Value of l: Letter designation: 0 s 1 p 2 d 3 f 4 g

There are two sublevels in n = 2, the 2s and 2p sublevels (corresponding to l = 0 and l = 1, respectively). The second quantum number also describes the shape of the orbital. The orbital in the s sublevel or the s orbital is spherical in shape. The only electron of hydrogen is most likely located in this type of orbital, the 1s orbital. The 1s orbital and all other s orbitals are spherically symmetrical around the nucleus, but a 2s orbital has a greater radius than the 1s. In the p sublevel, the orbitals are dumbbell shaped while the orbitals found in l = 2, the d sublevel are four-lobed.

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Figure 4. The shapes of s, p, and d orbitals. Each sublevel contains one or more orbitals of the same energy. The number of orbitals is determined by the number of allowed values for the third quantum number, the magnetic quantum number, ml. For each value of l, ml can be any integer from l to +l. Thus, in the p sublevel, l = 1, there are three values for ml: -1, 0, and +1. Thus, there are three orbitals in any p sublevel, which are in oriented in different directions about the nucleus: p x, py, and pz orbitals. See Figure 5. There are five types of d orbitals as shown in Figure 6.

Figure 5. Three types of p orbitals.

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Figure 6. Shapes of d orbitals. Table 1 gives a summary of the different orbitals in an atom. The number of sublevels in a main energy level is equal to n. Thus, in n = 3, there are three sublevels: s, p, and d. There are n2 orbitals in a main energy level. There are 32 or 9 orbitals in the 3rd main energy level, n= 3. The orbitals belonging to the same sublevel have the same energy and are termed degenerate. The three p orbitals are degenerate; the same is true of the 5 orbitals in the d sublevel. Table 1. Orbitals in the first three main energy levels. n main energy level 1 0 0 2 1 0 3 1 2 l sublevel 1s 2s 2p 3s 3p 3d 0 1s 0 2s -1 2px 0 3s -1 3px -2 3dxy ml orbitals

0 2py

+1 2pz

0 +1 3py 3pz -1 0 +1 +2 2 3dxz 3dyz 3dz 3dx2-y2

Energy of Atomic Orbitals. The atomic spectra of elements show that these orbitals differ in energy. While we know that orbitals in lower values of n are lower in energy than those in higher values of n, what about the sublevels within a main energy level? 142

CHEMISTRY IN ACTION One can arrange these orbitals in increasing energy by following the (n+l) rule. Within a given n, the energy of the orbitals increases in the order of s < p < d < f . As shown in Figure 7. However, notice that some orbitals of one main energy level may overlap in energy with orbitals of another main energy level. A useful mnemonic guide to use in the sequencing of the orbitals in increasing energy is shown in Figure 8.

Figure 7. Energy sublevels in an atom.

Figure 8. Mnemonic device in arranging orbitals in increasing energy. The Distribution of Electrons in Orbitals. There are many ways of distributing electrons in an atom but there is only one arrangement of lowest energy. This arrangement is called the ground state distribution of electrons in the atom. To arrive at this arrangement, the following rules are applied: 143

CHEMISTRY IN ACTION 1. Aufbau principle: Atomic orbitals are successively filled starting with the orbitals of lowest energy. 2. Paulis exclusion principle: No two electrons can have exactly the same set of four quantum numbers. This means that even if two electrons have the same first three quantum numbers and would occupy the same orbital, they cannot be exactly the same. Otherwise, they would repel each other because they are both negatively charged. If they differ in their spins, part of the repulsions is relieved. Since there are only two possible spin directions, clockwise and counterclockwise, an orbital can accommodate only two electrons. Easier way to state this rule: Each orbital can accommodate only two electrons which would have opposite spins. (This rule also implies that since only two electrons can be assigned to one orbital, then the total number of electrons that can be accommodated in one energy level is equal to 2n2.) 3. Hunds rule of maximum multiplicity: For sublevels containing more than one orbital (e.g. the p or d sublevel), each of the degenerate orbitals is filled singly with electrons of the same spins or parallel spins first and only when the sublevel is half-filled do electrons pair up. The Electron Configuration of Atoms. spin Electron configuration is a shorthand way of s writing the distribution of electrons in an atom. The spdf notation indicates (1) main energy level n as a no. 1, 2, 3; (2) sublevel l as s, p, d, 2p 2 main level orbital f; (3) orbital ml as subscript like in px, py, pz; x n 2 ml and (4) spin s as superscript like in 3s (if 1 paired) and 3px (if unpaired). Thus, the four (4) quantum numbers are all represented in the sublevel l electron configuration. In the configuration: 1s2 2s2 2px2 2py2 2pz2 3s2 3px1 3py1. There are 14 electrons in the atom, two of which are in the 1s sublevel, two in the 2s sublevel, six in the 2p sublevel, another two in the 3s sublevel and two in the 3p sublevel. This configuration may also be represented in an even shorter way using the noble gas core configuration. In this type of notation, we can abbreviate configuration corresponding to a noble gas with its symbol in square brackets. Since 1s2 2s2 2p6 is the ground state configuration for Ne then the above spdf notation can also be written as: [Ne] 3s2 3p2 or [Ne] 3s2 3px1 3py1 . 144

CHEMISTRY IN ACTION Another way to show the spins of electrons is to use an orbital diagram representation. In this notation, orbitals are represented as boxes, and the electrons are shown as arrows that point either up or down. Electrons in the same orbital are shown with paired or opposite spins. Unpaired electrons in degenerate orbitals are shown with parallel spins. 1s 2s 2px2 2py2 2pz2 3s2 1 3px 3py1 3pz0

When writing electron configurations, it is important to ascertain that all electrons are accounted for. Let the viewing focus on segments 3:36 17:00 on Electron Configurations.

VOCABULARY WORDS 1. Ground state - when an electron is occupying an original orbit according to the minimum allowable energy it can possess to stay in that level. 2. Excited state when an electron absorbs energy and causes it to jump from its original orbit to an orbit of higher energy farther from the nucleus. 3. Quantized it implies that an electron can only have certain values or quantity of energy. 4. Continuous spectrum obtained when ordinary light is passed through a prism and the light separates into different colors characteristic of a rainbow. 5. Line absorption spectrum the kind of spectrum obtained when certain elements or compounds are heated and the light given off is passed through a prism; the spectrum obtained consists of lines of certain colors distinct for every element. 6. Principal quantum number the first quantum number; this gives the main energy level occupied by an electron. 7. Azimuthal quantum number the second quantum number; it corresponds to an energy sublevel. 8. Magnetic quantum number the third quantum number; identifies the orbital occupied by an electron.

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CHEMISTRY IN ACTION 9. Spin quantum number the fourth quantum number; identifies the spin of an electron. 10. Degenerate orbitals belonging to the same sublevel and have the same energy. 11. Orbital a three-dimensional region in space where an electron is most likely to be found. 12. Electron configuration - a shorthand way of writing the distribution of electrons in an atom. PRE-VIEWING ACTIVITIES A. Ask questions to review the previous episode. Focus on two atomic models: the Bohr and the quantum mechanical models. B. Emphasize that the last episode is related to the new concepts that will be discussed in this episode, namely, emission spectra, energy levels, atomic orbitals and electron configuration. C. Pose the Guide Questions to be answered after viewing the episode. Guide Questions/Answers 1. What is the relationship between the wavelength and energy of light? Wavelength and energy are inversely proportional to each other. 2. Which color in the visible spectrum has the shortest wavelength? Violet has the shortest wavelength and yet the greatest energy. 3. What color do strontium compounds give off in a flame test? Strontium compounds give off red light. 4. What instrument is used to see the line emission spectrum? The spectroscope is used to view the emission spectrum of a sample. 5. What is the relationship of the energy of an electron to the radius of its orbit? The energy of an electron increases with the radius of its orbit. 6. What the formula gives the maximum number of electrons that can fill each orbit? The formula that gives the maximum number of electrons that can fill each orbit is 2n2. 7. How many bright lines are seen in the line spectrum of hydrogen? Four bright lines are observed in the spectrum of hydrogen: red, green, blue and violet. 146

CHEMISTRY IN ACTION 8. What is the shape of an s orbital? A p orbital? The s orbital is spherical while the p orbital is dumbbell shaped. 9. How many types of p, d, and f orbitals are there? There are three types of p orbitals, five types of d orbitals and seven types of f orbitals. 10. What do you call orbitals of equal energy? Orbitals of equal energy are called degenerate orbitals. 11. Describe the spin of two electrons in the same orbital. Two electrons in the same orbital must have opposite spins. VIEWING ACTIVITIES Focus on segments 3:36 17:00 for a discussion of Electron Configuration.

POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions. TEACHING TIPS Suggested Activities A. Model-Making. Ask the students to make models of the s, p, and d orbitals using recyclable materials at home like newspapers and plastic products. What is important in this activity is that they visualize the shapes and orientation of the orbitals. B. Research. Assign your students to research on fireworks. In this activity, they will see how the Bohr model of the atom is able to explain the colors in a firework display. C. Laboratory Activity: Flame Test. In the following activity, the students will be able to conduct a flame test similar to the one they saw in this episode. They will be able to verify for themselves the experimental results. Objectives: At the end of this activity, the student should be able to identify selected elements by the color they emit when burned and relate the emission of the colored light to the electronic structure of the atom. 147

CHEMISTRY IN ACTION Introduction: Fireworks are spectacular sights during New Year and other grand celebrations. Fireworks or pyrotechnic materials are made of different elements including sodium, barium, potassium, and copper. Different elements emit light of different colors Which of these elements give the spectacular and varied colors in fireworks? Materials: sticks, denatured alcohol, Bunsen burner or alcohol lamp, mixture of each of the following compounds with ammonium chloride: sodium chloride, barium chloride, strontium chloride, potassium chloride, antimony chloride, copper chloride, and calcium chloride Safety Tips/Hints: 1. Denatured alcohol is poisonous. Wash off any alcohol that drops on the skin. Avoid inhaling its vapor. 2. Have ready a wet cloth in case of fire. 3. Ammonium chloride gives off a white smoke when burned. When mixed with the substances under test, the smoke could serve as a background for the colors emitted by the tested elements. Better visual effect is obtained. 4. The sticks are dipped in denatured alcohol. When the compound is burned, its vapors go with the alcohol. The color emitted will be observed soon as the compound starts to burn. Do not use rubbing alcohol; it contains too much water. 5. Test the compounds one at a time. 6. Throw all used sticks in the wastebasket. Procedure: 1. Prepare a mixture of each of the following compounds with ammonium chloride: (a) sodium chloride, (b) barium chloride, (c) strontium chloride, (d) potassium chloride (e) antimony chloride, (f) copper chloride, and (g) calcium chloride. Use equal parts of ammonium chloride and the compound to be tested. 2. Dip in denatured alcohol as many sticks as there are compounds to be tested. 3. Then dip the wet end of the stick into the ammonium chloride mixture of a sample. 4. Ignite the sample on the stick. Note the color of the flame. 5. Repeat 3 and 4 using the other samples. Data and Observations: (Prepare a table with the following columns: Compound, Color of light, Element responsible.)

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CHEMISTRY IN ACTION Questions: 1. Does the presence of ammonium chloride or denatured alcohol affect the color produced by each element? Why? Why not? 2. How can the flame test be used to determine the presence of elements in soils, foods, and other samples? 3. Why do elements emit light of characteristic colors when vaporized? D. Reflection. For reflection, ask your students these questions: 1. In what places are there sets of rules to follow? 2. What are some of these rules? 3. Why is it important to follow a set of rules? E. Word Hunt. Answer the following items. The answers to these items are found in the word maze given below. Search for these words. The words may be spelled horizontally, vertically, diagonally or backwards. element that gives off yellow light color in the visible spectrum that has the greatest energy quantum number designated by n maximum number of electrons in the second orbit term used to describe that an electron in a given orbit has a fixed amount of energy 6. state when an electron jumps to a higher energy orbit 7. element with four bright lines in its spectrum 8. term used to describe orbitals that have equal energies 9. principle that states that an orbital must be filled before the next higher energy orbital is filled up 10. a shorthand notation for writing the distribution of electrons in an atom 11. it determines the color and energy of light 12. region in space where the electron is most likely to be found 13. spins of electrons in degenerate orbitals that are singly occupied 14. maximum number electrons that can occupy the sublevel 15. shape of the p orbital 1. 2. 3. 4. 5.

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CHEMISTRY IN ACTION Word Maze L I C H U N O R B I T A L H H T O H L J O A M M D L J Y H K T X Z R U I U L U F T D U L F G K Q I E T T A J I R W E L O X I F F J A P B B O D L R L U Q J N K A R G R G F L O E E R N H Q W E U D E I A U X S B T Z C Q A J G N E R N C A T B E X T K W V I Y A Z I C H Q M E T R Z I Q F P Q T I G I R U N E R T K K N W E G I T C P D M L A F S O O D K E L S N C A H O Y D D X C Q L X L C E A Y L I Q E T A R E N E G E D X U N V Q H T G N E L E V A W Y G Q

ASSESSMENT

Quiz. Choose the letter corresponding to the best answer. 1. What happens to the energy of light when the wavelength increases? A. Decreases C. Increases or decreases B. Increases D. Does not change 2. What is the color of the light that sodium compounds give off? A. Green C. Violet B. Red D. Yellow 3. How many orbitals are there in the d sublevel? A. 1 C. 5 B. 3 D. 7 4. What sublevels are found in the third energy level? A. s C. p, d, f B. s, p, d D. s, p d, f

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CHEMISTRY IN ACTION 5. What is the maximum number of electrons that can fill the third main energy level? A. 2 C. 18 B. 8 D. 32 6. Which of the following orbitals have a dumbbell shape? A. s C. d B. p D. f 7. What term is used to describe orbitals that have equal energy? A. Degenerate C. Ground B. Excited D. Quantized 8. What is the maximum number of electrons that can occupy the f sublevel? A. 2 C. 10 B. 6 D. 14 9. What rule states that each orbital can have a maximum of only two electrons and with opposite spins? A. Aufbau principle C. Paulis exclusion principle B. Hund rule of maximum D. Schroedingers theory multiplicity 10. What rule states that lower energy orbitals must be filled first before higher energy orbitals are filled up? A. Aufbau principle C. Paulis exclusion principle B. Hund rule of maximum D. Schroedingers theory multiplicity ANSWER KEY (Under Teaching Tips, Suggested Activities) C. Laboratory Activity: Flame Test. Data and Observations: Compound 1. sodium chloride 2. barium chloride 3. strontium chloride 4. potassium chloride 5. antimony chloride 6. copper chloride 7. calcium chloride Color of Light yellow green red violet white blue orange 151 Element Responsible sodium barium strontium potassium antimony copper calcium

CHEMISTRY IN ACTION Answers to Questions: 1. Does the presence of ammonium chloride or denatured alcohol affect the color of the flame produced by an element? Why? Why not? No, they do not affect the color of the flame produced by an element. Ammonium chloride gives off a white smoke when burned. When mixed with another substance, the smoke serves as a background for whatever color may be emitted by the tested element giving a better visual effect. The sticks are dipped in denatured alcohol. When the compound is burned, its vapors go with the alcohol. The color emitted will be observed soon as the compound starts to burn. 2. How can the flame test be used to determine the presence of elements in soils and in foods? Some elements impart characteristic color to the flame. Compare the color of any sample subjected to such test with the standards for identification of possible element(s) that may be present. 3. Why do elements emit light of characteristic colors when vaporized? Elements emit light of characteristic colors when vaporized. This is because when an atom is subjected to heat, its electrons absorb energy in discrete amounts. The electrons become excited and jump from lower to higher energy orbits. When the electrons return to the lower energy orbit, they release the energy previously absorbed in the form of light. The color of the light emitted depends on the energy difference between the lower and the higher orbits.

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CHEMISTRY IN ACTION E. Word Hunt. Word Maze + + + + + N O R B I T A L H + + + + + + O + M + + + + Y + + + + + + + I U + U + + D + L F + + + + + T + A + I R + E L O + + + + + A P + B O D L + L U + + + + + R + R G F L O E E R + + + + + U D E I A U X S B T + + + + + G N E R N C A T B E + + + + + I + A Z I C H + M E T + + + + F P + T I G I + U N E + + + + N + E + I T + P D + L + + + + O D + E + + N + A + O + + + + C + + + + + + A + L I + E T A R E N E G E D + U + V + H T G N E L E V A W + + Q

1. 2. 3. 4. 5. 6. 7. 8.

SODIUM (7, 13, NW) VIOLET (15, 1, W) PRINCIPAL (5, 7, SE) EIGHT(12, 9, SW) QUANTIZED (15, 15, NW) EXCITED (6, 13, NE) HYDROGEN (1, 14, NE) DEGENERATE (14, 12, N)

9. AUFBAU (8, 12, NW) 10. CONFIGURATION (13, 6, W) 11. WAVELENGTH (15, 12, N) 12. ORBITAL (1, 7, S) 13. PARALLEL (10, 7, SW) 14. FOURTEEN (3, 15, E) 15. DUMBBELL (11, 14, W)

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CHEMISTRY IN ACTION (Under Assessment) Quiz. 1. 6. A B 2. 7. D A 3. C 8. D 4. B 9. C 5. 10. C A

REFERENCES Mendoza, E. and T. Religioso. (1995). You and the natural world series: chemistry. QC: Phoenix Publishing. Morris, H. (1990). Foundations of college chemistry. CA: Wadsworth. Useful Website http://school.discovery.com

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 26: THE PERIODIC TABLE OF ELEMENTS OVERVIEW In Episode 25 Electronic Structure of an Atom, it was discussed how atomic orbitals can be arranged according to increasing energy and how to write ground state electronic configurations of atoms of various elements using simple rules as guides. In this episode, we will find that the electronic structure of the elements is the explanation to the arrangement of the elements in the periodic table developed by Mendeleev in 1869. The organization of the elements, the trends and periodicity in their properties that are seen from their arrangement are all related to their electronic structures. The first segment of this episode features how the periodic table developed from the ideas of scientists in the 19th century and its evolution to the present form. The second segment relates electron configurations with the chemical properties of elements. OBJECTIVES At the end of this lesson, the student should be able to: 1. describe the organization of the periodic table; 2. show the different ways elements are grouped in the periodic table: a. groups and periods, b. representative and transition elements, c. metals, metalloids, and non metals; 3. use the periodic table to predict the chemical behavior of an element; 4. relate the number of valence electrons of an element to its group number in the periodic table; 5. relate the highest energy level of an atom to its period number in the periodic table; 6. give the relationship between the valence shell electronic configurations and the properties of elements; and 7. demonstrate logical thinking and problem-solving skills. INTEGRATION WITH OTHER LEARNING AREAS The periodic table is the most important tool in chemistry. An understanding of the basis of the arrangement of elements in the table enables the chemist as well as students in chemistry a wealth of information that can be used to explain and make 155

CHEMISTRY IN ACTION predictions of behavior of elements and their compounds. This episode is, therefore, important in almost all of the episodes that follow and would be useful when one looks back at the past episodes. SCIENCE AND HEALTH IDEAS Orderliness in nature SCIENCE PROCESSES Observing Classifying VALUES Being systematic Organized LIFE SKILLS Critical thinking Effective communication IMPORTANT CONCEPTS 1. The periodic law on which the modern periodic table is based is that periodicity of properties is a function of the atomic numbers. In contrast, the periodic table developed in 1869 by Russian chemist Dmitri Mendeleev was based on increasing atomic weights. 2. Each element in the periodic table is identified by its chemical symbol and atomic number. 3. The atomic number is the number of protons in the nucleus of an atom and is the distinguishing characteristic of an element. 4. The mass number is the sum of the number of protons and number of neutrons in the nucleus of an atom. 5. In the periodic table: a. Elements are arranged in the order of increasing atomic number. b. Each horizontal row is called a period and is identified by an Arabic numeral. c. Each vertical column is called a group or family and is identified by an Arabic numeral from 1 to 18, as recommended by the International Union of Pure and Applied Chemistry (IUPAC). 156 Decision making Orderliness Inferring Predicting

CHEMISTRY IN ACTION d. The elements of groups 1-2 and 13-18 are called main group or representative elements. e. The elements of group 18 are called noble gases. f. The elements in groups 3 to 12 are called transition elements. g. Elements found in two bottom rows are called the inner transition elements (the lanthanoid and actinoid series). h. Between the metallic elements and the nonmetallic elements is a diagonal group of elements called the metalloids. i. The metals are found on the left of the metalloids (except hydrogen) and the nonmetals on the right side. 6. The electrons in the outermost shell or main energy level are called valence electrons. For the representative elements, the digit unit of their group number gives the number of valence electrons of the elements in the group. 7. The highest energy level occupied by electrons in the ground state electron configuration gives the period to which the element belongs. 8. Elements can be grouped according to the type of orbitals being filled up by valence electrons. Hence, groups 1 and 2 compose the s block, groups 13 to 18 are the p block, groups 3 to 12 comprise the d block, and the two rows of elements below the main body of the periodic table are the f block. 9. In general: a. The reactivity of metals within a group increases from top to bottom while that of the nonmetals decreases from top to bottom. b. Valence electrons are responsible for the chemical properties of an element. c. Elements in the same group have similar characteristics because they have the same number and type of valence electrons. 10. Elements with completely filled outer orbitals, ns2 np6, are said to be of noble gas configurations. They are very stable and unreactive. BACKGROUND INFORMATION/EPISODE CONTENT History of the Periodic Table. By the early part of the 19th century, there were more than 80 elements that have been discovered. Chemists already had adequate knowledge of their properties and were beginning to notice similarities and trends in properties. Dobereiners Triads. J. Dobereiner observed the existence of triads of elements that behaved similarly. He noticed that in these triads, the atomic weight of the middle element was approximately the average of the two other elements. He also noted that many other properties of the central element were approximately the average of the other two elements. Table 1 below shows two sets of Dobereiners triads and their relative atomic weights and densities. 157

CHEMISTRY IN ACTION Table 1. Properties of some of Dobereiners triads. Triads Chlorine Bromine Iodine Average of chlorine and iodine Calcium Strontium Barium Average of calcium and barium Atomic Weight 35.5 79.9 126.9 81.2 40.1 87.6 137.3 88.8 Density (g/ml at 4OC) 1.56 3.12 4.95 3.26 1.55 2.6 3.5 2.52

Newlands Octaves. In 1864, J. Newlands proposed his Law of Octaves. Newlands observed that when elements are arranged in order of increasing atomic weights, every eighth element had similar properties. It is important to note that at this time, the noble gases have not yet been discovered. However, his theory was ridiculed by his contemporaries in the Royal Chemistry Society and was refused to be published. But many years later, Newlands was awarded the highest honor of the society for introducing the concept of periodicity, a very important contribution to the development of the periodic table. Mendeleevs Periodic Table. In 1869, Dmitri Mendeleev published an arrangement of elements based on increasing atomic weights that illustrated a periodicity in the properties of the elements at certain regular intervals. His version of the table was the first to accommodate all the known elements and successfully predicted the existence of several elements that have not yet been discovered. His table actually had blank spaces for these elements that were yet to be discovered. The Modern Periodic Table. The inconsistencies that Mendeleev observed in his periodic table were resolved when the suggestion that the periodicity in properties of the elements was due to factors other than atomic weight was put to test by Henry Moseley, an English physicist, in 1913. He found that there is in the atom a fundamental quantity which increases by regular steps as one passes from an element to the next..., and referred to the atomic number or the number of protons in the nucleus of atoms. The periodic law that serves as basis for the arrangement of elements in the modern periodic table reads as follows: The properties of the elements vary periodically with their atomic numbers. The Elements in the Periodic Table. How many known elements are there today? Theoretically, the number of elements is limitless. As of 2008, 117 have been reported known or observed, but of these only 92 occur naturally on earth and the rest are artificially prepared. With the exception of technetium and promethium (elements 43 and 61, respectively), elements from 1 to 83 have stable isotopes. Elements 84 to 94, although naturally formed in the universe either by stellar nucleosynthesis or as shortlived products 158

CHEMISTRY IN ACTION of nuclear reactions, have unstable isotopes and undergo nuclear decay. All elements of atomic number higher than 94 are artificially prepared. The last element that has been officially given a name is element 112, copernicium, Cn. Reports of the successful preparation of element 118 came out in a 2006 news bulletin of the American Institute of Physics but this has still to be confirmed by other laboratories. The arrangement of the elements in the periodic table is in the order of increasing atomic numbers, but there are horizontal, vertical, and even diagonal relationships in the properties or trends in properties of the elements. Figure 1 shows how elements are arranged in rows and columns, with each element having its own place in the periodic table.

Figure 1. Arrangement of the Elements in the Modern Periodic Table In the standard periodic table, each element is identified by its symbol, atomic number and average atomic mass. A common way of presenting this information is shown below for nitrogen, N.

N
14.00674

Atomic number symbol for nitrogen

average atomic mass

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CHEMISTRY IN ACTION The atomic number is the number of protons in the nucleus of an atom. It is also equal to the charge of the nucleus and the number of electrons in the neutral atom. The average atomic mass is a weighted average of the relative masses of the isotopes and the weight is based on the relative abundances of the isotopes. Periods and Groups. Each horizontal row of the periodic table is called a period. The first period contains only two members, hydrogen and helium. The periods are numbered from top to bottom. Each vertical column is called a group or family. The present table is composed of 18 vertical columns or groups and the periodicity in properties is observed from one horizontal row to the next. See Figure 2. The current numbering system for the groups as recommended by the International Union of Pure and Applied Chemistry, IUPAC, makes use of Arabic numerals from 1 to 18. This numbering system should have superseded the two older numbering systems, one of European and the other of American usage, that both make use of Roman numerals followed by either letter A or B, although these can still be seen in some periodic tables today. period number
1 1 2 3 4 5 6 7 3 4 5 6 7 8 9 10 11 12 2 13 14 15 16

group number
18 17

Figure 2. Period and group numbers shown in periodic table. Elements belonging to Groups 1 and 2,and 13-18 are called the main group or representative elements. Elements of Groups 3 to 12 are the transition elements. The elements in the two rows at the bottom of the main body of the table are the inner transition elements, also called the lanthanides (or lanthanoids) and the actinides (or actinoids). 160

CHEMISTRY IN ACTION Some of the main groups are known by special names and a few are listed below: Group 1, with the exception of H Alkali Metals Group 2 Alkaline Earth Metals Group 17 Halogens or Salt-formers Group 18 Noble Gases Chemical Properties of Elements. The arrangement of the elements in the periodic table is such that elements in a horizontal row or period, show a trend or pattern in their properties that repeats in the next period. On the other hand, members of each vertical group display similarities in chemical properties. Alkali Metals. Group 1 elements, except H, are called the alkali metals and they all exhibit metallic properties. They are good electrical and thermal conductors, malleable, and lustrous. They also react vigorously with water. The video episode shows the reaction of potassium and sodium with water to form their respective metallic hydroxides and hydrogen gas. 2 Na + 2 H2O 2 NaOH + H2 2 K + 2 H2O 2 KOH + H2 Both reactions are highly exothermic with the reaction of potassium and water being more violent, showing that potassium is more reactive than sodium. In general, the reactivity of metals in a group increases from top to bottom. It can be predicted that lithium would be the least reactive of the group while francium, if it can be isolated and observed for a reasonable period of time, should be the most reactive. Alkaline Earth Metals. The reactivity of alkaline earth metals or Group 2 elements magnesium and calcium with water, as indicated by the production of bubbles, was shown in the video episode . Magnesium does not show visible reaction with water at room temperature although a reaction is readily observed at 100oC. Calcium, on the other hand, reacts slowly with water at room temperature. Calcium is more reactive than magnesium, consistent with the trend. Mg + 2H2O Ca + 2H2O Mg (OH)2 + H2 Ca (OH)2 + H2

Halogens. The elements of Group 17 are called the halogens: fluorine, chlorine, bromine, and iodine. Fluorine and chlorine are gases at room temperature. Chlorine, a yellowish gas, can displace bromine in sodium bromide and cause bromine to return to the elemental state, Br2, as manifested by the release of the red-brown gas. This indicates that sodium will preferentially react with chlorine than bromine, if both elements are present, or that chlorine is more reactive towards sodium than bromine. Bromine, on the other hand, can displace iodine in sodium iodide, but not 161

CHEMISTRY IN ACTION chlorine in sodium chloride. The reactivity of the Group 17 elements can be ranked as follows: F > Cl > Br > I, fluorine being the most reactive. The reactivities of nonmetals are observed to decrease from top to bottom of the group. Cl2 Cl2 Br2 Br2 + + + + 2NaBr 2NaI 2NaI 2NaCl 2NaCl + Br2 2NaCl + I2 2NaBr + I2 no reaction

Noble Gases. The noble gases, Group18, are considered special elements. They are generally unreactive and require extremely vigorous conditions for the heavier noble gases to react. So far, helium, neon, and argon have remained inert. Electronic Configuration and the Periodic Table. It is not an accident that elements in a group exhibit similar properties and elements in a period show a trend in properties that repeat in the following period. The explanation for the observed trends in properties lies in the electronic configurations of the elements. If the ground state electronic configurations of elements in a group are compared, one will notice a similarity at the end of the configurations. Consider the ground state electronic configurations of the alkali metals, the elements of Group 1, and notice the last terms which are encircled: Li3 Na11 1s2 1s2 K19 2s1 2s2 1s2 2p6 2s2 3s1 2p6

3s2

3p6

4s1

These electrons lie in the highest occupied main energy levels of each element and are called outermost electrons or more appropriately, valence electrons. Being at the outermost part of the atom, valence electrons are the ones that participate in chemical reactions. Since the atoms of the Group 1 elements have the same number, only 1 electron in this case in their respective outermost main energy level. They have the same type of valence electron and this electron is an s orbital electron, so we can expect these elements to react with other atoms in a similar manner. The same observation is seen with the Group 2 elements. They have the same valence shell electronic configuration, ns2, where n is the outermost main energy level. Be4 1s2 12 Mg 1s2 Ca20 2s2 2s2 1s2 2p6 2s2 3s2 2p6

3s2

3p6

4s2

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CHEMISTRY IN ACTION Notice that the highest main energy level occupied by electrons in the atom also gives the period number of the element. The element that follows calcium in the group is strontium. What is the valence shell electronic configuration of strontium? If you said 5s2, you are correct. The valence electrons of elements in Group 17 are the ns2 np5 type. The elements fluorine, chlorine, bromine, iodine and astatine have seven valence electrons. On the other hand, the noble gases or Group 18 have completely filled s and p orbitals, ns2 np6, with the exception of helium which has a filled shell with a 1s2 configuration. This must be the reason why noble gases are so unreactive. They all have filled s and p sublevels. The other main block elements tend to lose, gain or share electrons so that their outermost shell will have 8 electrons and resemble the valence shell of the noble gases. This last statement is essentially the Octet Rule. He2 Ar18 1s2 Ne10 1s2 Kr36 1s2 2s2 1s2 2s2 2p6 2s2 2p6 3s2 2p6

3p6 3s2

3p6

3d10

4s2

4p6

The valence shell electron configurations of all the groups in the main block are given in the table below. Do you notice any relationship between the number of valence electrons and the group number? Table 2. Valence shell electron configurations of the main block elements. Grp 1 ns1 Grp 2 ns2 Grp 13 ns2 np1 Grp 14 ns2 np2 Grp 15 ns2 np3 Grp 16 ns2 np4 Grp 17 ns2 np5 Grp 18 ns2 np6

Group Number Valence Shell Electronic Configuration Number of Valence Electrons

The number of valence electrons of the representative elements is equal to the unit digit of their group number. The outermost electrons of the transition elements, Groups 3 12, are of the ns 2 (n1)dx type. These elements fill up the s sublevel of a new main energy level, then fill up the d sublevel of the preceding main energy level, in accordance with the rules on electron distribution described in Episode 25. Thus, when we write the electronic 163

CHEMISTRY IN ACTION configuration of scandium, Sc, the 19th and 20th electrons go to the 4s orbital, but its 21st electron goes to one of the 3d orbitals. Sc21 1s2 2s2 2p6 3s2 3p6 4s2 3d1 Scandium has three valence electrons: 4s2 3d1. Other examples of electronic configurations of transition elements are those of copper and zinc, which have 11 and 12 valence electrons, respectively. Notice that in copper, instead of a ground state valence configuration of 4s2 3d9, one of the 4s electrons moved to the remaining vacant slot in the 3d sublevel since the 4s and 3d sublevels are actually very close in energy and a completely filled sublevel, such as a 3d 10, gives some special stability to the atom. Cu29 1s2 2s2 2p6 3s2 3p6 4s1 3d10 Zn30 1s2 2s2 2p6 3s2 3p6 4s2 3d10 Table 3 gives the valence shell electron configuration of the elements in the first transition series. Notice that the valence electrons of chromium deviates from the expected arrangement of 4s2 3d4 to give 4s1 3d5, resulting in an exactly half-filled d sublevel, which also has some special stability. The number of valence electrons of transition elements is equal to their group number. Table 3. Valence shell configuration of the elements of the first transition series. Group No. 3 4 Ti 4s2 3d2 5 V 4s2 3d3 6 Cr 4s1 3d5 7 Mn 4s2 3d5 8 Fe 4s2 3d6 9 Co 4s2 3d7 10 Ni 4s2 3d8 11 Cu 4s1 3d9 12 Zn 4s2 3d10

Valence Shell Sc Electronic Configuration 4s2 of 1st 3d1 transition elements Number of Valence Electrons 3

10

11

12

164

CHEMISTRY IN ACTION Groupings of the Elements. Elements in the periodic table may be divided into sections according to the types of orbitals that their valence electrons are filling up as illustrated in Figure 3. The elements of Groups 1and 2 are called the s-block elements since their Figure 3. valence electrons are in Groupings in the periodic table s orbitals. The elements according to orbitals being filled. of Groups 13 to 18 are p-block elements, while transition elements of Groups 3 12 are d-block elements. The lanthanides and actinides are f-block elements. The s- and pblock elements are collectively called main block or representative elements. Metals and Nonmetals. Another way of grouping the elements in the periodic table according to properties is by grouping them into metals and nonmetals. A group of elements, called the metalloids or semimetals, are in a diagonal arrangement across the p block and separates the metals from the nonmetals. The elements to the left of this diagonal group are metals, except for hydrogen, and those to the right are nonmetals as shown in Figure 4.

Figure 4. Periodic Table showing the metals, nonmetals, and metalloids. 165

CHEMISTRY IN ACTION There are less than twenty (20) elements that fall into the nonmetallic group and seven (7) elements are metalloids. The rest are all metals. Metals exhibit the following physical properties: 1. most are solids at ordinary temperatures; 2. opaque, except in extremely thin films; 3. good electrical and thermal conductors; 4. lustrous or shiny; 5. have a crystalline structure when in the solid state; 6. malleable and ductile; 7. most are hard, with high tensile strength, and exhibit fatigue resistance; 8. high density and high melting temperature. Metals can be combined with other elements to form alloys, materials that retain the general metallic properties but may differ in properties like strength or melting point from the pure metal. Brass is an alloy with a bright golden color formed from copper, which is reddish, and zinc which is silver in color. Stainless steel is formed from iron, chromium, and nickel and the alloy is harder and more corrosion resistant compared to pure iron. Solder is an alloy of lead and tin that melts at a temperature very much lower than that of lead. Nonmetals differ in properties from metals. They are characterized by the following properties: 1. gas, liquid or solid at room conditions; 2. low density; 3. low melting temperature; 4. poor conductors, if not nonconductors, of electricity and heat; 5. solids are brittle; 6. dull (not shiny). Familiar examples of nonmetallic elements sulfur, oxygen, and carbon. Metalloids. Along the diagonal or zigzag group that separates the metals from the nonmetals are seven (7) elements that exhibit some properties of metals and some of nonmetals. These elements are the metalloids: boron, silicon, germanium, arsenic, antimony, tellurium, and polonium. Metalloids are like metals because they are lustrous. On the other hand, they are like nonmetals because they do not form positively charged ions during reactions. Their ability to conduct electricity is intermediate those of metals and nonmetals and hence are called semiconductors. The most familiar semiconductors are silicon and germanium which are used in radios, computers, and solar batteries.

166

CHEMISTRY IN ACTION VOCABULARY WORDS 1. Periodic law- basis for the arrangement of the elements in the periodic table. The modern periodic law states that the properties of the elements are periodic functions of their atomic numbers. 2. Atomic number the number of protons in the nucleus of an atom. 3. Mass number the total number of protons and neutrons in the nucleus of an atom. 4. Group or Family a vertical column of elements in the periodic table and is identified by an Arabic numeral (or a Roman number plus letter A or B). 5. Period- a horizontal row of elements in the periodic table and is identified by an Arabic numeral. 6. Representative elements - elements belonging to groups 1and 2, 13-18; the s and p block elements. 7. Transition elements- elements of groups 3 to 12; the d block elements. 8. Valence electrons- electrons in the outermost orbital of an atom. 9. Hardness the resistance to surface deformation or abrasion. 10. Tensile strength the resistance to breakage. 11. Elasticity the ability to return to the original shape after deformation. 12. Malleability the ability to be shaped by hammering. 13. Ductility the ability to be shaped into wire or thread. 14. Fatigue resistance the ability to resist repeated stress. PRE-VIEWING ACTIVITIES A. Divide the class into two groups and have them play Pictionary. A representative of each group alternately draws on the board the words written on the pieces of paper that the teacher gives them. These words are things like ring, frying pan, coin, etc. that are made from elements like gold, aluminum, and copper, respectively. The other members of the group are to guess the word. This activity is used as springboard to view the episode which is about the periodic table of elements. Use the elements to introduce the periodic table. 167

CHEMISTRY IN ACTION B. Ask the students questions to review what has been viewed in the previous episode putting emphasis on the electron configuration. C. Introduce the episode that focuses on the parts that make up the periodic table. D. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the guide questions as they watch the video. Guide Questions/Answers 1. What ways can be used to refer to an element? An element may be identified by its chemical symbol, name, and atomic number. 2. What do you call the horizontal rows of elements in the periodic table? The horizontal rows are called periods. 3. What do you call the vertical columns of elements in the periodic table? The vertical columns are called groups. 4. To what family or group do the representative elements belong? Representative elements belong to families/groups 1 and 2, 13 to 18. 5. What do you call elements of groups 3 to 12? These elements are called transition elements. 6. What special name is given to the elements of group18? Group 18 elements are known as noble gases. 7. What two groups does zigzag line in the periodic table divide? The zigzag line divides the periodic table into metals and nonmetals. 8. What are valence electrons? Valence electrons are electrons in the outermost main energy level. 9. How do you determine the number of valence electrons of an element? The number of valence electrons is equal to the digit unit of the group number of a representative element; and is equal to the group number of a transition element.

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CHEMISTRY IN ACTION 10. How do you determine the period to which an element belongs? The highest value of n in the ground state electronic configuration is also the period to which an element belongs. 11. What two alkali metals were used in the experiment shown in the video episode? Which one is more reactive and why? Sodium and potassium were used to react with water. Potassium is more reactive than sodium since its reaction with water is more vigorous and more exothermic. 12. Based on the results of the demonstration, arrange the following elements according to increasing reactivity: bromine, chlorine, and iodine. What is the basis of your answer? F > Cl > Br > I. This arrangement is based on the rule that in general, the reactivity of nonmetals within a group decreases from top to bottom. VIEWING ACTIVITIES Let the students view the segments on Periodic Table - Family and Period and Importance of Atomic Number and Mass Number at 2:10 - 5:00.

POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions. TEACHING TIPS Suggested Activities A. Elemental Dice. Show your students how to construct some element dice. Each die or cube has six faces. Let your students draw lots to know what element will be assigned to them. Ask them to construct the elemental dice from an old cardboard or carton. Assign them to put the following information on the six faces of the cube: Chemical symbol Atomic number and mass number Physical properties Chemical properties Uses Trivia about the element 169

CHEMISTRY IN ACTION You can devise a number of games or question and answer sessions using the dice. B. Research. Assign your students to research on the usefulness of metals in homes and in industries to enable them to see the importance of metals. C. Reading Assignment. Ask your students to read on: 1. Metallurgy how metals are produced from their ores. 2. New Materials. 3. Toxicity of Some Elements. D. Reflection. Ask your students these questions: 1. Why are elements important? In what ways are they important? 2. How is the electron configuration of elements important in determining how elements behave at certain conditions? 3. How can you help conserve mineral resources in the country? ASSESSMENT A. Multiple Choice. Choose the letter corresponding to the correct answer. Write your answers on your answer sheet. 1. Which of the following refers to the number of protons in the nucleus of an atom? A. Atomic number C. Mass number B. Period number D. Group number 2. Which of the following gives the mass number of an element? A. Number of electrons C. Number of protons B. Number of neutrons D. Total number of protons and neutrons 3. What do you call the Group 17 elements? A. Alkali metals C. Halogens B. Alkaline earth metals D. Noble gases 4. Aluminum belongs to Group 13 and period 3. What is its electron configuration? A. 1s22s22p63s2 C. 1s22s22p63s23p2 2 2 6 2 1 B. 1s 2s 2p 3s 3p D. 1s22s22p63s23p3

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CHEMISTRY IN ACTION 5. The electronic configuration of neon is 1s2 2s2 2p6. To what group and period does neon belong? A. Group 2, Period 2 C. Group 18, Period 2 B. Group 16, Period 6 D. Group 2, Period 8 6. The electron configuration of manganese is 1s22s22p63s23p64s23d5. To what block does manganese belong? A. s C. d B. p D. f 7. How many valence electrons does calcium (atomic no = 20) have? A. 2 C. 6 B. 4 D. 20 8. Which of the following alkali metals is the most reactive? A. Sodium (atomic number = 11) C. Rubidium (atomic number = 37) B. Potassium (atomic number = 19) D. Cesium (atomic number = 55) 9. Which of the following halogens is the most reactive? A. F (atomic number = 9) C. Br (atomic number = 35) B. Cl (atomic number = 17) D. I (atomic number = 53) 10. The noble gases are stable and inert because they have completely-filled A. s orbital C. s and p sublevels B. p orbital D. s, p, d and f sublevels B. Representative Elements. Determine the group number and the period number of the representative elements with the following electron configurations. Then refer to the periodic table to identify these elements. 1. 1s22s22p5 2. 1s22s22p63s1 3. 1s22s22p63s23p64s23d104p3 C. Identifying Elements. Use the periodic table to identify the elements belonging to the following groups and periods: 1. Group 2, period 5 3. Group 18, period 2 2. Group 4, period 4 4. Group 2, period 3 Which of these four elements have similar chemical properties? D. Electronic Configurations. Write the electronic configuration of the following elements and determine the period and family. 1. Sodium (atomic no. 11) 4. Calcium (atomic no. 20) 2. Phosphorus (atomic no. 15) 5. Bromine (atomic no. 35) 3. Argon (atomic no. 18) 171

CHEMISTRY IN ACTION ANSWER KEY A. Multiple Choice. 1. 6. A C 2. 7. D A 3. C 8. D 4. B 9. A 5. 10. C C

B. Representative Elements. 1. Group 17, Period 2: fluorine 2. Group 1, Period 3: sodium 3. Group 15, Period 4: arsenic C. Identifying Elements. 1. Sr 2. Ti 3. F 4. Mg Sr and Mg are in the same group so they have similar chemical properties. D. Electronic Configurations. 1. Sodium (atomic no. 11), 1s2 2s2 2p6 3s1 , Period 3, Group 1 2. Phosphorus (atomic no. 15), 1s2 2s2 2p6 3s2 3p3, Period 3, Group 15 3. Argon (atomic no. 18), 1s2 2s 22p6 3s2 3p6 , Period 3, Group 18 4. Calcium (atomic no. 20), 1s2 2s2 2p 63s2 3p6 4s2, Period 4, Group 2 5. Bromine (atomic no. 35), 1s2 2s2 2p6 3s2 3p6 4s2 3d10 4p5, Period 4, Group 17

REFERENCES Bloomfield, M. M. & L. J. Stephens. (1996). Chemistry and the living organism. Singapore: John Wiley & Sons, Inc. Mendoza, E. & T. Religioso. (1995). You and the natural world series: Chemistry. QC: Phoenix. Morris, H. (1990). Foundations of College Chemistry. CA: Wadsworth. Metals, Microsoft Encarta Online Encyclopedia (2002). The 1999 Grolier multimedia encyclopedia.

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CHEMISTRY IN ACTION Useful Websites http://encarta.msn.com. http://usinfo.state.gov/xarchives/display.html?p=washfileenglish&y=2006&m=October&x=20061019095701lcnirellep0.4545099 http://school.discovery.com http://www.encyclopedia.com/doc/1G1-141092422.html

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 27: PERIODIC PROPERTIES OF ELEMENTS OVERVIEW Episode 26 The Periodic Table of Elements related the electron configuration of the atom of an element to its position in the periodic table and also discussed the trends of reactivity within elements of the same group. This episode shall focus on the study of the different atomic properties of the elements and will examine the variation of these properties within the same group and period. OBJECTIVES At the end of this lesson, the student should be able to: 1. define or illustrate the following terms: atomic size, ionization energy, electron affinity, and electronegativity; 2. describe the trends in atomic size, ionization energy, electron affinity and electronegativity across a period and down a group of elements in the periodic table; 3. explain these trends in terms of the atomic structure or electron configuration of the elements; 4. discuss further the chemistry of alkali metals, alkaline earth metals, and halogen: and their compounds 5. interpret graphs, tables, and charts of ionization energy, electronegativity and atomic size; 6. appreciate the order in nature in general and among the elements in particular; 7. correlate atomic structure and the physical and chemical properties of an element to the position of the element on the periodic table; 8. use the periodic table to correlate the number of protons, neutrons, and electrons in an atom; 9. identify similarities in chemical behavior of elements within a group; 10. generalize trends in reactivity of elements within a group to trends in other groups; and 11. compare properties of elements e.g., metal, nonmetallic, metalloid based on their positions in the periodic table.

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CHEMISTRY IN ACTION INTEGRATION WITH OTHER LEARNING AREAS Episodes 25 Electronic Structure of the Atom and 26 The Periodic Table of Elements would provide good background materials for a better understanding of this episode. SCIENCE PROCESSES Observing Inferring Recognizing patterns and trends VALUES Orderliness in life LIFE SKILLS Critical thinking Logical thinking IMPORTANT CONCEPTS 1. The radius of the atom is the approximate distance between the nucleus and the valence electron of an atom. 2. Atomic size of elements within the same group increases from top to bottom of the periodic table. 3. Within the same period, atomic size decreases from left to right. The trend includes the noble gases. 4. Ionization energy is the energy required to remove an electron from a gaseous atom or ion. The lower the ionization energy of an atom, the greater is its tendency to form a positive ion or a cation. 5. Successive removal of electrons from an atom requires an increasing amount of ionization energy. In all cases, the second ionization energy is greater than the first, and the third ionization energy is greater than the second, i.e. IE1 < IE2 < IE3 < . and so on. 6. The first ionization energies of elements belonging in the same group decreases from top to bottom in the group. In contrast, the first ionization energy increases from left to right across a period. 175 Decision making Effective communication Classifying Predicting

Appreciation of the similarities and differences among Gods creation

CHEMISTRY IN ACTION 7. Electron affinity is the energy involved when a gaseous atom or ion gains an electron. The greater is the tendency of an atom to accept an electron, the more negative the value of electron affinity. 8. The more exothermic the process and the more negative the electron affinity of an element, the greater is its tendency to form negative ions or anions. 9. In general, atoms with large effective nuclear charges have greater affinity for electrons. 10. Electron affinity decreases from top to bottom in a group but increases from left to right in a period. The noble gases are excluded from this trend as they exhibit very low affinity for electrons. 11. Electronegativity is the tendency of an atom to attract shared electrons to itself as it forms bonds with other atoms and is exhibited by elements only in the bonded state. 12. Electronegativity decreases from top to bottom within the same group of elements and increases from left to right within the same period. The noble gases are excluded from this trend. 13. Metallic character of an atom is contributed by a large radius, a low ionization energy, and a less negative electron affinity. 14. The metallic character of elements decreases across a period of elements. 15. Alkali metals have low ionization energies, easily lose their s1 valence electron, and form positively charged (+1) ions with ns2 np6 noble gas configuration. 16. Alkaline earth metals, compared to alkali metals, have slightly higher ionization energies. Hence they are less reactive, lose their s2 valence electrons, and form positively charged (+2) ions with ns2 np6 noble gas configuration. 17. Halogens are reactive nonmetals with high ionization energies and so do not readily lose electrons. They readily gain electrons instead to complete their ns2 np5 configuration and become negatively charged (-1) ions. BACKGROUND INFORMATION/EPISODE CONTENT The episode begins with a review of previous Episode 26 concentrating on the properties of elements belonging in the same group. A concept map is shown to illustrate what has been discussed. This map will be referred to again in the course 176

CHEMISTRY IN ACTION of this episode and would be explained to include the new concept to be discussed in this episode. The two concept maps for Episode 26 and 27 are shown in the succeeding two pages. ELEMENT arranged in PERIODIC TABLE consists of

GROUPS designated by

PERIODS designated by

GROUP NUMBERS unit digit is equal to number VALENCE ELECTRONS determined from ELECTRONIC STRUCTURE

PERIOD NUMBERS corresponds to ENERGY LEVELS occupy outermost

Figure 1. Concept map for Episode 26. PERIODIC TABLE

illustrates the trends and periodicity of 177

CHEMISTRY IN ACTION ATOMIC PROPERTIES include

ATOMIC SIZE

IONIZATION ENERGY

ELECTRONEGATIVITY

Figure 2. Concept map for Episode 27. The Modern Periodic Law. The elements are arranged in increasing atomic number according to the modern periodic law: The properties of the elements are a periodic function of their atomic numbers. The arrangement results in elements exhibiting similar properties fall in the same group. The previous episode showed that the similarity in properties of such elements is due to their similar valence configurations. For example, members of Group 1(or IA), except hydrogen, are all metals and react readily with water. They all have ns1 valence shell electronic configurations. A demonstration of the explosive reactions of alkali metals with water can be seen in the video episode. The reaction of the alkali metals with water becomes more reactive when going from lithium down the group because in moving down the group, the valence electrons of these elements are found farther and farther away from the nucleus of the atom. The attraction between valence electrons and the nucleus correspondingly decreases and can thus participate in reactions more readily. Li3 1s2 Na11 2s1 1s2 K19 2s2 1s2 2p6 2s2 3s1 2p6

3s2

3p6

4s1

Periodic Properties of Elements. The arrangement of the elements in the periodic table shows that chemical properties repeat themselves at regular intervals of 2, 8, 18 or 32 elements. These chemical properties are influenced by many atomic properties which themselves follow certain patterns among elements as arranged in the periodic table. These atomic properties include atomic size, ionization energy, electron affinity, and electronegativity. The periodic trends of these properties are the main topics of this episode. An examination of these properties allows a better 178

CHEMISTRY IN ACTION understanding of the similarities and differences in the physical chemical properties of each group of elements. Trends in Atomic Size. The size of an atom is difficult to define, but can be approximated by x-ray diffraction measurements of the internuclear distances of bonded atoms. The assumptions in this measurements are that atoms are spherical and are just touching each other in the bonded state. The atomic radius is determined by taking half the distance between the nuclei of adjacent atoms. For example, the distance between the nuclei of the two chlorine atoms in Cl2 is measured to be 1.988 (1 = 10-8 cm). The atomic radius of chlorine is one-half of the internuclear distance or 0.994 .

Figure 3. Atomic radius of Cl. The atomic sizes of the main group elements are shown in Figure 4. In general, atomic radius of elements (a) increases from top to bottom within the same group and (b) decreases from left to right in a period. atomic size decreases

s i z e i n c r e a s e

Figure 4. Relative atomic sizes of selected elements.

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CHEMISTRY IN ACTION Since the radius of the atom is essentially the distance of the outermost electron from the nucleus, the increase in size from Li to Cs can be explained using the electronic configurations of these elements. Their valence electrons are in successively farther locations as seen from the increasing values of n of the outermost shell. The elements within the same period, on the other hand, show a decreasing trend from left to right. We note that even if the number of protons and electrons also increase from one atom to the next in a period, just like for elements in a group, the electrons added go into the same main energy level where the valence electrons of previous elements are located. You can see this from the electronic configurations given below for elements in the third period. Table 1. Electronic configuration of the eight elements in period 3.

Elem ent Na Mg Al Si P S Cl Ar

Nuclear Charge 11 12 13 14 15 16 17 18

Electron Configuration 1s 2 2s 2 2p 6 3s 1 1s 2 2s 2 2p 6 3s 2 1s 2 2s 2 2p 6 3s 2 3p 1 1s 2 2s 2 2p 6 3s 2 3p 2 1s 2 2s 2 2p 6 3s 2 3p 3 1s 2 2s 2 2p 6 3s 2 3p 4 1s 2 2s 2 2p 6 3s 2 3p 5 1s 2 2s 2 2p 6 3s 2 3p 6

The way to explain the trend in atomic radius across a period is in terms of the effective nuclear charge experienced by the valence electrons. The effective nuclear charge, Zeff, is the actual charge or attraction felt by an electron from the nucleus. Electrons do not actually feel the total positive charge present in the nucleus because as they move around the nucleus, they tend to cover or shield the nucleus from each other. Electrons in lower main energy levels tend to shield the nucleus from outer electrons to a large extent. On the other hand, electrons that occupy the same orbital or the same main energy level shield the nucleus from each other to a smaller extent. From left to right in a period, there is a one proton and one electron increase from one element to the next and results in a successive increase in nuclear charge, but the electron that comes in enters the same main energy level as the other valence electrons. In other words, n remains the same. Since the shielding contribution of the entering electron to the rest of the valence electrons is small, the electrons feel a successively increasing charge from the nucleus, or an increasing effective nuclear charge. The larger the attraction of the nucleus for the electrons, the closer the electrons are to the nucleus, and consequently, the smaller the atom. This is known as atomic shrinkage. 180

CHEMISTRY IN ACTION Two important factors that affect atomic size are: 1. n of the outermost electron(s), an increase of which results in an increase in size of the atom; 2. Zeff felt by the outermost electron(s), an increase of which results in a decrease in size of the atom. In a group, n of the outermost electrons increases, hence the sizes of the atoms of the elements increase. On the other hand, n of the outermost electrons across a period remains the same but the effective nuclear charge increases, hence sizes of atoms decrease from left to right. Ionic Radii. When an atom loses or gains an electron and forms an ion, the size of the atom changes. The positive ion or cation formed when one or more electrons are lost has a smaller ionic radius compared to the neutral atom. In a cation, there are more protons than electrons and the nucleus is able to attract the electrons closer to itself. This attraction is easy to see with the element sodium, Na, which loses one electron to form a +1 cation when it reacts with other elements. Na 1s22s22p63s1 11 protons, 11 electrons radius: 0.186 nm Na+ 1s22s22p6 11 protons, 10 electrons radius: 0.095 nm

The loss of the lone valence electron of sodium yields a cation with only 10 electrons and whose outer electrons were formerly the inner core electrons. The cation has one less main energy level occupied and its radius is just a little more than half of the neutral sodium atom. On the contrary, adding one or more electrons to a neutral atom to form an anion causes the radius to increase compared to the neutral atomic radius. This increase happens because there are more electrons than protons in the particle resulting in greater electron-electron repulsions. Consider the neutral fluorine and the fluoride ion. F 1s 2s22p5 9 protons, 9 electrons radius: 0.064 nm
2

F1s 2s22p6 9 protons, 10 electrons radius: 0.136 nm

2

The sodium ion and the fluoride ion both have 10 electrons and have the same ground state electronic configurations and are therefore isoelectronic. Even if they have the same number of electrons, they are not of the same sizes. Both O2- and Fnow have the same number of valence electrons but the valence electrons in O 2experience a lower effective nuclear charge compared to the valence electrons in F 181

CHEMISTRY IN ACTION since O2- has only 8 protons in its nucleus while F- has 9 protons. Therefore O2- is larger than F-. Trends in Ionization Energy. For an atom to lose electrons, it has to absorb sufficient energy to break the attractive force between the nucleus and the electron. This amount of energy that is required to remove an electron from a gaseous atom or ion is called ionization energy. A polyelectronic atom would have many ionization energies. The energy needed to remove the outermost electron from a neutral atom is the first ionization energy. Na(g) Na+(g) + eDH = IE1 (first ionization energy) Ionization energy is a measure of the difficulty to remove an electron from an atom. The more strongly held the electron, the more difficult it is to remove that electron and the larger is the ionization energy. The plot of the first ionization energies of the elements is shown in Figure 5. The general trend in the first ionization energies is decreasing from top to bottom in a group and increasing from left to right in a period including the noble gases. These trends are opposite that for atomic sizes indicating that the smaller the atom the stronger would be the attractive force between nucleus and electrons, the more difficult it is to remove electrons and thus the higher the ionization energy.

Figure 5. Plot of ionization energies of the elements vs atomic number. The general trend is for the ionization energy to increase across a period. Among the elements, the noble gases have the highest ionization energies while alkali metals have the lowest. Metals generally have lower ionization energies than nonmetals so that it is easier to remove a valence electron from a metal than from a nonmetal. 182

CHEMISTRY IN ACTION The ionization energy of elements belonging to the same group decreases as the atomic number increases. In Group 1or formerly IA, lithium has the highest ionization energy while cesium has the lowest. Compared to other elements in the same group, the 2s electron of lithium experiences the greatest nuclear attractive force, greater energy therefore is required to remove it from the neutral atom. Cesium, on the other hand, has the lowest ionization energy because its valence electron is in the 6s orbital and farthest from the nucleus. See Figure 6.

Li

Na Figure 6. Bohr atoms of Li, Na, and Cs.

Cs

Trends in Electron Affinity. Another important element property that influences reactivity and exhibits some trends in the periodic table is electron affinity. Electron affinity is a measure of the ability of an atom to accept an electron and is defined as the energy change that occurs when an electron is added to a gaseous atom. X(g) + eX- (g) DH = EA (electron affinity)

Table 2 shows the electron affinity values of some elements. A plot of electron affinity of the elements of the second period is shown in Figure 7. For many elements, electron affinity is a negative value, indicating that the electron gain process results in the formation of a net attraction between the nucleus and the entering electron. When the net attraction between the nucleus and the electron is strong, the electron affinity is highly exothermic and has a large negative value. The more negative the electron affinity, the greater tendency of the atom to accept an electron.

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CHEMISTRY IN ACTION Table 2. Electron affinities (kJ/mole) of representative elements.

H -77 Li -58 Na -53 K -48 Rb -47 Cs -45 He (21) Ne (29) Ar (35) Kr (39) Xe (40) Rn ?

Be (241) Mg (230) Ca (154) Sr (120) Ba (52)

B C N O F -23 -123 0 -142 -333 Al Si P S Cl -44 -120 -74 -200 -348 Ga Ge As Se Br (-35) -118 -77 -195 -324 In Sn Sb Te I -34 -121 -101 -190 -295 Ti Pb Bi Po At -48 -101 -100 ? ? *Note: The values in parenthesis are estimates.

Figure 7. Electron affinity of elements of the second period. It is not easy to give a general trend of electron affinities since there are groups that show marked deviations. However, it is apparent that smaller atoms tend to have greater tendencies to accept an electron as indicated by their highly negative electron affinity values. Below are some observations on the electron affinities of the main group elements. In general: across a period, from left to right, the affinity for electron increases - the values become more negative. This general trend excludes the noble gases. the values within a group vary very little. 184

CHEMISTRY IN ACTION metals have lower or less negative electron affinities than nonmetals within a group. group 2 or IIA elements, the alkaline earths, have low electron affinity values. These elements are relatively stable because they have filled subshells. group 17 or VIIA elements, the halogens, have high electron affinities because the addition of an electron to an atom results in a completely filled shell. group 18 or VIIIA elements, the noble gases, have electron affinities near zero, since each atom possesses a stable octet and will not accept an electron readily. elements of other groups have low electron affinities. Elements with highly exothermic electron affinities are those that easily form negative ions or anions. The values given in Table 2 show that the halogens are the best anion formers. Figure 8 gives a summary of the trends in atomic properties of the elements in the periodic table.

Decreasing radius Increasing ionization energy Increasing affinity for electrons Increasing size Decreasing ionization energy Decreasing affinity for electrons

Figure 8. Summary of trends in atomic properties.

Trends in Electronegativity. Electronegativity is the tendency of an atom to attract electrons to itself as it forms bonds with other atoms. Unlike size, ionization energy and electron affinity which are atomic properties, electronegativity is a property exhibited by an element only when it is bonded to another atom. Between two elements, the more electronegative one has the greater attraction for the electrons shared with the atom of the other element. Table 3 gives electronegativity values of the main group elements. Notice that the column for noble gases is missing. Noble gases do not usually form bonds and since this property is exhibited when the element is bonded to another, then there are no values for the noble gases. 185

CHEMISTRY IN ACTION
1 (IA ) Li 1 .0 Na 0 .9 K 0 .8 Rb 0 .8 Cs 0 .7 Fr 0 .7 2 (IIA) Be 1 .5 Mg 1 .2 Ca 1 .0 Sr 1 .0 Ba 0 .9 13 (IIIA ) B 2 .0 Al 1 .5 Ga 1 .6 In 1 .7 Ti 1 .8 14 ( I VA ) C 2 .5 Si 1 .8 Ge 1 .8 Sn 1 .8 Pb 1 .8 15 (VA ) N 3 .0 P 2 .1 As 2 .0 Sb 1 .9 Bi 1 .8 16 (VIA ) O 3 .5 S 2 .5 Se 2 .4 Te 2 .1 Po 2 .0
17 (V IIA )

F 4 .0 Cl 3 .0 Br 2 .8 I 2 .5 At 2 .2

Table 3. Electronegativities of representative elements.

In general, electronegativity decreases from top to bottom within the same group of elements. In Group 16 or VIA, oxygen has the highest electronegativity while polonium has the lowest because as atomic size increases from top to bottom the attraction of the nucleus for the outer electrons decreases. Unlike ionization energy, electronegativity cannot be measured directly. Electronegativities are based on a relative scale with values the highest of which is 4.0 for fluorine, the most electronegative of the elements. Note that metals have low electronegativities. Electronegativity and electron affinity are both measures of how an atom attracts electrons, but how do they differ? In electron affinity, the electron is completely acquired by the atom, giving the atom a full negative charge. In electronegativity, how well an atom pulls towards itself but not completely accepting the electrons it shares with another atom is measured. Density. The densities of elements increase from left up to the middle part of the period then decreases up to the noble gases. The metals have the highest densities while the nonmetals existing as gases at normal conditions have the lowest densities because the atoms are arranged in the condensed state. Past episodes showed that metals that are generally solid have the highest densities. Similar trends are observed for elements in other periods except for the transition and inner transition metals. Properties of Group 1 (IA) Elements. Alkali metals have low ionization energies and easily lose their valence electrons during chemical reactions and form positive ions which have ns2np6 noble gas configuration. Because they are so reactive, alkali 186

CHEMISTRY IN ACTION metals are not usually found in their elemental state. They occur only as salts, such as sodium chloride, NaCl, potassium chloride, KCl, and potassium carbonate, K2CO3. Cesium easily releases the valence electrons on mere exposure to light. This lightinduced emission of electrons is called the photoelectric effect. Cesium is used in photocells which convert light signals into electrical signals. Properties of Group 2 (IIa) elements. The alkaline earth metals all tend to form +2 or bivalent metal ions. As with the monovalent ions of the Group 1 elements, these bivalent ions are isoelectronic with the noble gases before them in the periodic table. They have slightly higher ionization energies than the alkali metals so that on the whole, they are less reactive than the Group1 metals. Still, they exist in nature as minerals not as free elements. Beryl is a mineral of beryllium which contains oxygen, aluminum, and silicon. Magnesium occurs in talc as magnesium silicate, a solid white rock, and calcium as calcite, a heptangular almost clear crystal of calcium carbonate. Calcium is also found in the gypsum or hydrated calcium sulfate. Barium occurs as barite or barium sulfate. Properties of Group 17 (VIIA) Elements. Halogens have high ionization energies. They do not readily lose their electrons but readily gain them creating a negative ion, which has a noble gas configuration of ns2p6. This negative ion contributes to their great reactivity, thus they do not occur as free elements but are found as negative ions (anions) in salts and minerals such as sodium chloride and the chloride, bromide, and iodide of potassium. Sodium fluoride when added to drinking water or toothpaste, can reduce the incidence of dental cavities. Chlorine is used to purify water including swimming pool water. Tincture of iodine used as an antiseptic is a solution of iodine in alcohol. Sea salt or iodized salt provides the necessary iodine to prevent disorders of the thyroid gland. Iodine is an essential constituent of the thyroid gland specifically the thyroid hormone, thyroxine. VOCABULARY WORDS 1. Periodic law - states that the properties of the elements are periodic functions of their atomic numbers. 2. Atomic size - the distance from the nucleus to the valence electron of an atom. 3. Ionization energy - the energy required to remove an outer electron from gaseous atom in a ground state or its lowest energy state. 4. Electron affinity - the energy released when an electron is added to a gaseous atom. 5. Electronegativity - the tendency of an atom to attract electrons to itself as it forms bonds with other atoms. 187

CHEMISTRY IN ACTION PRE-VIEWING ACTIVITIES A. Present this illustration to the class.

Ask the students what is missing in the illustration. The students should be able to answer right away that the lightning is missing. Why? They are able to predict because of the pattern or trend in the illustration. With this simple activity, the lesson can be introduced that like the illustration, the elements in the periodic table also show patterns or trends in their properties. B. Introduce the episode that features the trends in the chemical properties of elements as illustrated in the periodic table. C. Post the Guide Questions which the students will answer after viewing the episode. Ask them to focus on finding the answers to the Guide Questions as they watch the video.

Guide Questions/Answers 1. What are the three periodic properties discussed in this episode? Atomic size, ionization energy, and electronegativity. 2. Define each property. Atomic size is determined by the radius of the atom or the approximate distance between the nucleus and the valence electron of the atom. Ionization energy is the energy required to remove an outer electron from gaseous atom in a ground or lowest energy state. Electronegativity is the tendency of an atom to attract electrons to itself as it forms bonds with other atoms. 3. What is the trend of atomic size within a group and across a period? Atomic size within the same group increases from top to bottom, the higher the principal quantum number of the valence electron, the larger the atom. Within the same period, atomic size decreases from left to right, from Group 1 (IA) to Group 17(VIIA).

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CHEMISTRY IN ACTION 4. What is the trend of ionization energy within a group and across a period? The ionization energy of the same group decreases as the atomic number increases. Ionization energy increases from left to right as one goes across a period. 5. What is the trend of electronegativity within a group and across a period? Electronegativity decreases from top to bottom within the same group of elements. It increases from left to right within the same period. 6. Which is the most reactive metal in Group 1(IA)? Francium. 7. Which has the largest atomic size among the Group 2(IIA) elements? Radium. 8. Which is the least metallic of the Group 13(IIIA) elements? Boron. Metallic character increases from top to bottom in a group of elements. 9. Cite three examples of the practical uses of halogens as discussed in this episode. Sodium fluoride, when added to drinking water or toothpaste, can reduce the incidence of dental cavities. Chlorine is used to purify water including swimming pool water. Tincture of iodine is an antiseptic; a solution of iodine may be used to prevent disorders of the thyroid gland. Iodine is an essential constituent of the thyroid hormone, thyroxine. 10. What group of elements has low ionization energy, easily loses valence electrons during chemical reactions and forms positive ions and whose ions are isoelectronic with the noble gases? Name at least three examples of these elements. These are the alkali metals. Examples are lithium, sodium, potassium, rubidium, cesium, and francium. VIEWING ACTIVITIES
Let the students view the parts on (1) The Periodic Properties which includes Atomic Radius, Ionization Energy and Electronegativity at 2:28 - 8:80 and Discuss the answers to the Guide Questions. (2) General Properties and Uses of Elements within a Family at 9:45 17:13.

POST-VIEWING ACTIVITIES

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CHEMISTRY IN ACTION TEACHING TIPS Suggested Activities A. Summary of Trends. After viewing the episode and discussing the periodic properties of elements, it will be helpful to summarize the trends. Moving left right within a PERIOD Metallic property decreases Atomic size decreases Ionization energy increases Electronegativity increases Moving top bottom within a GROUP Metallic property increases Atomic size increases Ionization energy decreases Electronegativity decreases

B. Research. For enrichment, you can ask your students to research on the importance of some alkali metals and alkaline earth metals in the human body. Ask them to prepare a chart of the human body and indicate in what parts the said metals are important, e.g. calcium is important for the bones. With this activity, the students will appreciate the importance of metals and they will be able to see the relationship of chemistry to other subjects like biology. C. Reflection. Ask your students: 1. why the study of the periodic trends is important in chemistry. 2. to give examples where they can find order in nature.

ASSESSMENT A. Quiz. Multiple Choice. Select the letter that best answers the question or statement. 1. Which of the following atoms has the smallest atomic radius? A. Boron, B C. Gallium,Ga B. Aluminum, Al D. Indium, In 2. Which of the following atoms has the largest atomic size? A. Tin, Sn C. Tellerium, Te B. Antimony, Sb D. Strontium, Sr 3. Which of the following atoms is the most electronegative? A. Potassium, K C. Gallium,Ga B. Calcium, Ca D. Germanium, Ge

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CHEMISTRY IN ACTION 4. Which of the following atoms is the least electronegative? A. Nitrogen, N C. Arsenic, As B. Phosphorus, P D. Antimony, Sb 5. Which of the following atoms is most nonmetallic? A. Nitrogen, N C. Arsenic, As B. Phosphorus, P D. Antimony, Sb 6. Which of the following atoms is the most metallic? A. Barium, Ba C. Calcium, Ca B. Strontium, Sr D. Magnesium, Mg 7, Which of the following atoms is a metalloid? A. Nitrogen, N C. Germanium, Ge B. Phosphorus, P D. Iodine, I 8. Which of the following atoms has the least tendency to give up electrons? A. Lithium, Li C. Fluorine, F B. Nitrogen, N D. Iron, Fe 9. Which of the following statements is true? A. Metals have high ionization energies. B. Metals have tendency to lose electrons and become anions. C. Metals have higher densities than nonmetals. D. Metallic properties increase from left to right. 10. Which of the following statements is true of the periodic table? A. There are more nonmetallic elements than metallic elements. B. Metallic character of the elements decrease from top to bottom in a family of elements. C. Elements with high ionization energies tend to have very metallic properties. D. In general, within a group or family, electronegativity increases as atomic size increases. B. Relative Positions of Elements. For nos. 1 and 2, refer to the periodic table to see the relative positions of the elements. 1. Arrange each of the following groups of atoms in order of decreasing atomic size A. B, Al, Ga D. As, P, Cl B. Sn, Sb, Te E. O, F, Cl
C. Cd, Si, Ga

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CHEMISTRY IN ACTION 2. For each of the following pairs, predict which element has (1) the larger radius and (2) the larger ionization energy. A. Na and Cl E. Ne and Xe B. C and O F. N and Sb C. Li and Rb G. Sr and Si D. As and F H. Fe and Br 3. Why is the 19th electron of a potassium atom located in the fourth energy level rather than in the third energy level.

4. Use the skeleton periodic table below to answer the following questions. Assume that the fictitious elements A-P have electron configurations consistent with their positions in the periodic table.

1 D G

2 E

5 A

6 B

7 C F

H J M O P K N

I L

A. Give the letters for those elements (A-P) that are (i) alkaline earth metals, (ii) halogens, and (iii) noble gases. B. Arrange the following four elements according to the radii of their atoms, from smallest to largest: D, E, F, G. C. Arrange the following four elements according to increasing electronegativity: H, I, J, K. D. Arrange the following four elements according to decreasing metallic properties: C,A, H, M. E. Which element has the valence electron configuration 2s22p3? F. What is the electron configuration of element I? 5. Explain why the atomic radius of a phosphorus atom is smaller than the atomic radius of a magnesium atom.

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CHEMISTRY IN ACTION 6. Explain why the atomic radius of a sodium atom is smaller than the atomic radius of cesium atom. ANSWER KEY A. Quiz. 1. 6. A A 2. 7. D C 3. D 8. C 4. D 9. C 5. 10. A B

B. Relative Positions of Elements. 1. A. Ga, Al, B B. Sn, Sb, Te C. Cd, Ga, Si D. As, P, Cl E. Cl, O, F

2. A. (1) Na, (2) Cl B. (1) C, (2) O C. (1) Rb, (2) Li D. (1) As, (2) F

E. (1) Xe, (2) Ne F. (1) Sb, (2) N G. (1) Sr, (2) Si H. (1) Fe, (2) Br

3. According to the (n+ l) rule, the 4s sublevel is lower in energy than the 3d sublevel. According to the Aufbau Principle, lower energy orbitals are filled first before the higher energy orbitals. The 19th electron of K goes to the 4s orbital. 4. A. (i) Elements E and J are alkaline earth metals. (ii) Elements C and F are halogens (iii) Elements I and L are noble gases. B. F < E < D < G C. I < J < K < H D. M > H > A > C E. Element A F. 1s2 2s2 3s2 3p6 4s2 3d10 4p6

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CHEMISTRY IN ACTION REFERENCES Bloomfield, M. M. & L. J. Stephens. (1996). Chemistry and the living organism. Singapore: John Wiley & Sons, Inc. Mendoza, E. & T. Religioso. (1995). You and the natural world series: Chemistry. QC: Phoenix. Zumdahl, S.S. (1993). Introductory chemistry, a foundation. (2nd ed.). CA: D.C. Heath & Co. Useful Websites http://www.colorado.edu/physics/2000/periodic_table/periodic_properties http://intro.chem.okstate.edu/1314F00/Lecture/Chapter7/Lec111300.html http:www.chem.uncc.edu/faculty/murphy.htm

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 28: PUTTING ATOMS TOGETHER OVERVIEW This episode concentrates on the atom, the nature of the chemical forces binding atoms together in a substance, and how these bonds are responsible for the states of the elements or substances. OBJECTIVES At the end of this lesson, the student should be able to:
1. illustrate the formation of ionic, covalent and metallic bonds; 2. relate the type of bond formed between elements to their electron configurations and locations in the periodic table; 3. compare and contrast polar and non-polar covalent bonds; 4. discuss the role of electrons in chemical bonding; 5. use the concept of bonding to explain some of the properties of substances; 6. predict the uses of substances based on their chemical bonds; 7. demonstrate creativity and logical thinking skill; and 8. appreciate the importance of order and of following a set of rules.

INTEGRATION WITH OTHER LEARNING AREAS One important lesson that can be viewed prior to tackling this one would be Episode 25 Electronic Structure of An Atom, although running through the next two episodes namely 26 The Periodic Table of Elements and 27 Periodic Properties of Elements would likewise be very helpful. SCIENCE PROCESSES Observing Classifying VALUES Sharing LIFE SKILLS Critical thinking Logical thinking Decision-making Effective communication 195 Appreciation of the similarities and differences of Gods creation Inferring Predicting

CHEMISTRY IN ACTION IMPORTANT CONCEPTS 1. A chemical bond is the net electrical attraction between atoms or group of atoms that hold them together and allow them to behave as a unit. 2. Bond energy is the energy required to separate two bonded atoms; it is a measure of the strength of the chemical bond. The larger the bond energy the stronger the bond. 3. An electrolyte is a substance that dissociates or forms ions in solution resulting in a solution that can conduct electricity. A non-electrolyte is a substance that does not form ions in solution and whose solution is a nonconductor of electricity. 4. A metallic bond is the cohesive force resulting from the attraction between the mobile sea of electrons and the positive ions that make up the crystal lattice of a metal. 5. An ionic bond is the attraction between positive and negative ions in an ionic solid. 6. A binary ionic compound is formed from the combination of a metallic element with a nonmetallic element. The metallic element loses electrons to the nonmetal forming cations and anions, respectively. 7. In an ionic solid, the positive and negative ions are arranged in an orderly and repeating pattern called the crystal lattice. 8. A covalent bond is the attractive force that exists between the nuclei and the electrons shared between two atoms. Two or more atoms held together as one unit by one or more covalent bonds is called a molecule. 9. A polar bond is formed when atoms with different electronegativities form a covalent bond. 10. A non-polar bond is a covalent bond between two like atoms or two atoms of similar electronegativities, resulting in a uniform distribution of electron density because of equal attraction of both nuclei for the shared electrons.

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CHEMISTRY IN ACTION BACKGROUND INFORMATION/EPISODE CONTENT Chemical Bonds. A chemical bond is the attractive interaction between atoms. This may be an intramolecular force between atoms and molecules or this be an intermolecular force between molecules in a substance. Solubility Test. The episode begins by showing three common hard materials such as stone, sand, and iron nail do not change when heated in an ordinary flame. What keeps these solid materials unchanged by heating? Another experiment is conducted to show the solubility of some sample materials such as table salt, sugar, stone, sand, and iron nail. These materials are mixed with 10 mL of water. The following are the results of the experiment: Table 1. Solubility of sample materials in water. Material table salt sugar stone sand iron nail Dissolves in Water Yes Yes No No No

The salt and sugar solutions are then heated. The sugar first becomes syrupy, turns to brown, and then chars to a black mass. On the other hand, salt is recovered from salt solution when the water evaporates. Iron, sand, and stone melt at higher temperatures, as shown in Table 2. Molten sodium chloride is used in the industrial manufacture of sodium metal and chlorine gas. Molten iron is produced in smelters. Molten silica is used to make wax. Table 2. Melting points of sample materials. Material Sodium chloride (NaCl) Iron (Fe) Silicon dioxide (SiO2) Melting Point 800.4oC 1535 oC 1435 oC

Conductivity Test. Another experiment is conducted on salt, sugar, sand, stone, and iron to test their electrical conductivities by using a current detector. The current detector consist of a dry cell as power source, which is connected to continuous coil of copper wire and a magnetic compass securely placed under the coil. The compass needle is aligned with the coil. When electrical current flows through the wires, the 197

CHEMISTRY IN ACTION compass needle is deflected. For comparison and for control of the experiment, the conductivity of pure water is also tested. Table 3 gives the results of the experiment. Table 3. Electrical conductivity of sample materials.
Material sodium chloride (solid) sugar (solid) sodium chloride solution sugar solution iron nail stone sand pure water Electrically Conductive? no no yes no yes no no no

Metallic Bonds. Of the materials tested, only iron conducts electricity in its solid state. In metals like iron, electrons can move freely within the metal when an electric potential is applied, as shown in Figure 1. No such free electrons are present in table salt, sugar, and sand. In electronic or solid conductors, the electric current consists of moving electrons. Figure 1. Nature of electric current. In a conducting solution, the electric current is carried by ions moving toward the electrode with the opposite charge as in Figure 2. Figure 2. Migration of ions toward electrodes. The atoms in the solid metal are usually in a close-packed arrangement consistent with the high density of most metals. Close-packed structures are arrangements of atoms that make efficient use of space. However, some metals do not exhibit close-packing structures, iron being one of them and which crystallizes in a bodycentered cubic lattice as in Figure 3.

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Figure 3. Structure of solid iron. The spheres represent iron atoms arranged in a body-centered cubic crystal lattice.

Figure 4. Sea of electron model of metallic bonding.

In the structure of metals, all atoms can easily give up electrons but none would have the tendency to accept electrons. Hence, the atoms give up their valence electrons to the crystal lattice of positively charged ions in a sea of electrons. The valence electrons are delocalized since they no longer stay with one specific atom but move throughout the crystal. The attraction between sea of electrons and the cations making up the crystal lattice provides the cohesive force that keeps the crystal together. The metallic bond is therefore the totality of the attractive forces provided by the sea of electrons and the positive ions in the metal. Because of the motion of these delocalized electrons, metals are good electrical conductors and an applied electric potential will push the electrons to move in one direction towards the positive end. Silver and copper have been found to be excellent metal conductors. Both have an s1d10 valence configuration. Cu: Ag: 4s1 3d10 5s1 4d10

The sea of electron model of metallic bonding also explains the malleability and ductility properties of metals. Metals do not break or shatter when hammered or drawn into wires. When atoms slide past one another, the sea of electrons follows the movement of the atoms and hence the metallic bond is not broken. 199

CHEMISTRY IN ACTION Before distortion

+ + + + + + + + + + + + + + + + + + + + + + + +

After distortion

+ +

+ + +

+ +

Ionic Bonds. Ionic compounds like sodium chloride, NaCl, do not conduct electricity in the solid state because there are no moving electrons nor other charged particles in the NaCl crystal. Between a pair of sodium and chloride ions, electrostatic attraction exists. The ionic bond is the electrostatic attraction between two oppositely charged ions. An ionic compound is a compound formed from the interaction of oppositely charged ions. In the crystal structure of NaCl, each sodium ion, Na +, has six chloride ions, Cl -1, as neighbors and each chloride ion has six sodium ion neighbors, as shown in Figure 5. Hence, each ion in the crystal experiences attractive forces from all its neighbors, such that to break the crystal, a large number of attractive forces need to be broken. This is the reason why good crystals of NaCl are very hard.

Figure 5. Structure of NaCl crystal. Bond Energy is the energy required to separate two bonded atoms. It is the measure of the strength of the chemical bond. A higher the bond energy means the stronger the bond. The high melting point of sodium chloride suggests that ionic bonds are very strong. Every pair of ions in a sodium chloride crystal is held together by an ionic bond. But no single pair of ions is independent of the others so as to be called a molecule. Since there are a large number of attractive forces that hold the crystal together, an equally large amount of energy is needed to melt or break the ionic crystal. 200

CHEMISTRY IN ACTION Conducting Solutions. The conductivity experiment seen in the video showed that the aqueous solution of sodium chloride is an electrical conductor. Substances whose solutions conduct electricity are called electrolytes. Pure water is a nonconductor and is a non-electrolyte. The experiment showed that in the NaCl solution, there are freely moving ions or charged particles that carry electric current. When sodium chloride is dissolved in water, the ionic bond between sodium and chloride ions is weakened as each ion becomes attracted to water molecules. In solutions, ions move independently of each other. When an electric potential is applied, the positive sodium ions move toward the negative electrode or cathode. The negative chloride ions move toward the positive electrode called the anode. This migration of ion towards the oppositely-charged electrodes produces the electric current as in Figure 6. Formation of an Ionic Compound. The simplest ionic compounds are the binary compounds which are composed of only two elements: one element that easily forms cations and another element that readily forms anions. The resulting combination is a metal (the cation former) and a nonmetal (the anion former). Examples of binary ionic compounds are NaCl, CaCl2, MgO, and Al2O3. In the formation of a binary ionic compound from the constituent elements, electron transfer happens: atoms of the metallic element lose their electrons and form cations and the electrons are gained by Figure 6. Migration of ions. atoms of the nonmetal and become anions. The number of electrons lost or gained depends on how many electrons the atoms have in excess or lack to attain a noble gas configuration, an ns2 np6 valence configuration. The number of ions that combine to form the compound depends on the charges of the ions such that a neutral compound is formed. Tables 4 and 5 show how sodium and chlorine and aluminum and oxygen combine to achieve more stable noble gas configuration by forming ionic compounds.

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CHEMISTRY IN ACTION Table 4. Formation of sodium chloride. Before electron transfer Na [Ne] 3s1 11p+ 11eCl [Ne] 3s2 3p5 17p+ 17eAfter electron transfer Na+ [He] 2s2 2p6 11p + 10e (isoelectronic with neon) Cl- [Ne] 3s2 3p6 17p+ 18e- (isoelectronic with argon)

Formula of compound: NaCl Table 5. Formation of aluminum oxide. Before electron transfer Al [Ne] 3s2 3p1 13p+ 13eO [He] 2s2 2p4 8p+ 8eAfter electron transfer Al3+ [He] 2s2 2p6 13p + 10e (isoelectronic with neon) O2- [He] 2s2 2p6 8p+ 10e- (isoelectronic with neon)

Formula of compound: Al2O3 Many ionic compounds are more complex in formula and contain more than two elements. Ionic solids are a major part of the rocks, hills, and mountains of the landscape. These solids are kept rigid by the strength of ionic bonds. Covalent Bonds. In the experiments conducted earlier, water behaved differently from metals and ionic compounds. Water did not conduct electricity in the solid or liquid state indicating the absence of moving charged particles. What kind of bonding then is present in water? The valence electron configurations of hydrogen and oxygen can be represented by using simple electron dot symbols or Lewis formula. Hydrogen has 1 valence electron in the 1s level. This valence electron is represented by a single dot. Oxygen has 6 valence electrons in the second energy level represented by 6 dots.

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CHEMISTRY IN ACTION Lewis dot formulas of: Hydrogen Oxygen To attain a noble gas configuration, H needs to gain one electron to become isoelectronic with helium. Being a nonmetal, oxygen also needs to gain electrons, two electrons in fact, to become isoelectronic with neon.

When H and O combine to make water, two atoms of H bond with one atom of O. Electrons are shared by the H and O atoms to complete their noble gas configurations. No electron transfer occurs because nonmetals have high ionization energies and would not easily give up electrons. Hence, electrons are shared, instead of being completely lost to or gained by another atom.

As a result, attractive forces form between the electron of the hydrogen and the nucleus of the oxygen and between the electrons of oxygen and the nucleus of hydrogen. The attraction between two atoms and shared electrons is called a covalent bond. In the Lewis formula, a solid line or a pair of dots between two atoms represents a pair of shared electrons equivalent to a covalent bond. Unshared or lone pairs of electrons are shown as dots.

Atoms in a covalent bond can share up to 3 pairs of electrons.

carbon monoxide ammonia

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CHEMISTRY IN ACTION Covalent bonds exist among atoms in a molecule. When H and Cl form a bond by sharing electrons, the hydrogen chloride, HCl, molecule is formed. In sucrose or table sugar all bonds are covalent. See Figure 7. Sugar molecules do not break up into ions when dissolved in water. This is why sugar solution is a poor electrical conductor. Sugar like water is a non-electrolyte. When a sugar solution is heated, the water evaporates and the sugar crystals are recovered. Further heating eventually decomposes the HOH2C sugar as it caramelizes and finally chars.
H H OH HO H HO O HOH2C O H H HO CH2OH O H H

C12H22O11 (s)

12C (s) + 11H2O (l)

Figure 7. Table sugar or sucrose, C12H22O11.

Polar and Nonpolar Bonds. A covalent bond between two like atoms results in a uniform distribution of HO H electron density around the two atoms because of the equal attraction of the two nuclei for the shared electrons. This covalent bond is described as nonpolar. A nonpolar bond is electrically symmetrical since the electron pair is shared equally by the bonding atoms. Simple diatomic molecules like H2 and Cl2 are nonpolar.

hydrogen chlorine oxygen nitrogen

On the other hand, when a covalent bond exists between two atoms with different electronegativities the bond formed is polar. In hydrogen chloride, HCl, Cl is more electronegative than H. Cl attracts the shared electron to a greater extent and acquires a partial negative charge. Electron density is pulled away from H and as a result, H assumes a partial 204

Figure 8. Hydrogen chloride

CHEMISTRY IN ACTION positive charge as shown in Figure 8. A polar bond is electrically unsymmetrical. One end is more negative, the other end is more positive. Network Substances. Some nonmetallic elements form covalently-bonded structures that are extremely hard, with very high melting points and are not conductors of electricity in the solid or molten states. Examples are sand (silicon dioxide or silica), and diamond. These substances are called network covalent substances, and are characterized by a continuous array of covalently bonded atoms in a structure that appears to be just one big, big molecule. In silicon dioxide, SiO2, each silicon atom is covalently bound to four oxygen atoms. Each oxygen atom is covalently bound to two silicon atoms shown in Figure 9. oxygen atom silicon atom

repeating unit Figure 9. Structure of silica. In diamond, each carbon atom is covalently bonded to 4 other carbon atoms and each of these four atoms are in turn bonded to four other carbon atoms and makes the structure extremely strong and hard. See Figure 10. Diamond is, in fact, the hardest known naturally occurring substance. All valence electrons of each carbon atom in the diamond structure are involved in covalent bonding and there are no free electrons to carry electric current. Hence, diamond does not conduct electricity. Graphite, on the other hand, has an interesting structure that makes it an exception to the general properties of network solids. Each carbon atom is bonded to 3 other carbon atoms forming a two-dimensional planar arrangement of interconnected hexagons as shown in Figure 11. The fourth valence electron of every atom is free and is delocalized throughout the structure. Because of these free electrons, graphite is able to conduct electricity. The carbon rod that serves as the cathode in a flashlight battery or dry cell is made of graphite. The planar structures in graphite are connected by weak forces of attraction called van der Waals forces, that allow the planes to slide over one another making graphite soft.

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CHEMISTRY IN ACTION

Figure 10. Structure of diamond.

Figure11. Structure of graphite.

Coordinate Covalent Bonds. Atoms share electrons to form a covalent bond. Each of the two atoms furnishes an electron to make the pair that is shared between them. A covalent bond may also be formed when two atoms share electrons that both originate from just one of the atoms. This bond is called coordinate covalent bond, or semi-polar bond. When formed, a coordinate covalent bond is no different from any other covalent bond because it is simply a pair of electrons shared between two atoms. The electron-dot structures of sulfurous and sulfuric acids in Figure 12 each show a coordinate covalent bond between the sulfur and the oxygen atoms that are not bonded to hydrogen atoms. The boxed pairs are the electrons of the sulfur atom that shares with oxygen. Covalent bonds Coordinate covalent bonds Covalent bonds

Sulfurous acid Sulfuric acid Figure 12. Coordinate covalent bonds in sulfurous and sulfuric acid.

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CHEMISTRY IN ACTION Writing Lewis Dot Structures. A Lewis or electron-dot structure is a convenient way of showing the covalent bonds in many molecules or ions of the representative elements. There were many Lewis structures in the previous discussions where a pair of dots or a dash placed between two atoms indicated a bonding pair of electrons. This section gives some guidelines in writing Lewis structures of simple molecules or ions. Get the total number of electrons to be distributed in the structure by adding the valence electrons in all of the atoms in the molecule or ion. In writing the structure of an ion, add one electron for each negative charge or subtract one electron for each positive charge on the ion. Recall that the number of valence electrons elements is related to their group number in the periodic table. Place the atoms in the molecule in a skeletal arrangement and connect adjacent atoms with a single covalent bond as either two dots or one dash. Usually, the central atom is the less electronegative atom. Hydrogen, which has only one electron, can form only one covalent bond and is always a terminal atom. Fluorine is also often in a terminal position. Oxygen atoms are not normally bonded to each other except in compounds known to be peroxides and in elemental oxygen. Oxygen atoms can have a maximum of two covalent bonds which can be two (2) single bonds or one (1) double bond. Place pairs of electrons or dots around each atom to give each atom a total of eight electrons around it as required by the Octet Rule, excluding hydrogen, for which a pair would suffice. If there are too few pairs to give each atom eight electrons, shifting unbonded pairs of electrons between atoms to make double bond or triple bonds until the number of electrons distributed is equal to the sum calculated in Step 1. Examples: Write the Lewis structure for formaldehyde, H2CO. Step 1. Determine the total number of valence electrons to be distributed. H 1 valence e- x 2 atoms = 2 C 4 valence e- x 1 atom = 4 O 6 valence e- x 1 atom = 6 Total 12 e- to be distributed

Step 2. Arrange the atoms in a skeletal structure. Excluding H, which is always terminal, C is the less electronegative atom and is the central atom. Connect the atoms with a pair of dots or a line. 207

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H C H O

Step 3. Complete the octets of C and O and the duets of the two H atoms. Then count the electrons!

H Notice that including the electron pairs used for bonding, we have distributed a total of 14 electrons, 2 electrons in excess of the total number of valence electrons that the atoms in the molecule have.
Step 4. Shift a pair of electrons to make a double bond between C and O. Let us shift a pair from oxygen. This allows us to remove a pair of electrons from
carbon so that it will have only an octet.

C H

Now, there is correct number of electrons the Lewis structure for formaldehyde, H2CO. C O H VOCABULARY WORDS

1. Covalent bond forms when each of the two atoms furnishes an electron to make the pair that is shared between them. 2. Coordinate covalent bond - a covalent bond formed when two atoms share electrons that both originate from just one of the atoms. 3. Metallic bond - the totality of the attractive forces provided by the sea of electrons and the positive ions in the metal. PRE-VIEWING ACTIVITIES A. Ask your students to predict what will happen to the following materials when each is placed in 10 mL of water: table salt, sugar, stone, sand, and an iron nail. Ask them if the materials will dissolve or not. Then, tell them to observe the 208

CHEMISTRY IN ACTION experiment shown in the episode for them to verify if their predictions are correct. B. Introduce the episode that deals with the different types of bonds that can be found in substances. C. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the Guide Questions as they watch the video. Guide Questions/Answers 1. What substances were tested for electrical conductivity in the experiment? Which among these materials are electrically conductive? Why? Solid sodium chloride, solid sugar, sodium chloride solution, sugar solution, iron nail, stone, sand, and pure water were tested for electrical conductivity. Only the NaCl solution and the iron nail are electrically conductive. In the NaCl solution, there are ions that can move freely towards the oppositely charged electrodes producing electric current. The iron nail is a metal. In metals, electrons can move freely when electric potential is applied. 2. Define metallic bond, ionic bond, and covalent bond. Metallic bond is the cohesive force provided by the attraction between the positive ions in the crystal lattice and the sea of electrons in a metal. Ionic bond is the electrostatic attraction between oppositely charged ions forming a compound. Covalent bond is the attraction between the nuclei and the shared electrons of two atoms. 3. What subatomic particles are involved when atoms form a bond? Only the outermost electrons are involved. When atoms combine, only their outermost parts come in contact with one another. 4. Name two properties of metals that could be explained by the sea of electron model of metallic bond. Any two of these: high melting point, heat and electrical conductivity, malleability, ductility. 5. What is bond energy? Bond energy is the energy required to separate two bonded atoms. 6. What kind of bond is produced when an element from Group 1 (IA) combines with an element from Group 17 (VIIA)? Ionic bond. 209

CHEMISTRY IN ACTION 7. What do you call positive ions and negative ions? Positive ions are called cations. Negative ions are called anions. 8. Give three examples of ionic compounds mentioned in this episode. Lithium fluoride, potassium bromide, cesium chloride, rubidium oxide, strontium sulfide, magnesium iodide, sodium chloride. 9. What is the difference between an electrolyte and a non-electrolyte? An electrolyte is substance whose aqueous solution conducts electricity. A non-electrolyte is a substance whose solution does not conduct electricity. 10. What is the difference between a polar and a non-polar bond? A polar bond is formed when a covalent bond exists between two atoms with different electronegativities. It is electrically unsymmetrical and has a partially positive and a partially negative ends. A non-polar bond is a covalent bond between two atoms of the similar electronegativities. The electrons are equally shared resulting in a uniform distribution of electron density. It is electrically symmetrical. VIEWING ACTIVITIES Let the students view the segments on
Types of bonds: metallic, ionic, and covalent as well as polar and nonpolar bonds at 4:25 - 19:00.

POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions. TEACHING TIPS Suggested Activities A. Importance of Ions. For enrichment, ask your students to do research on the importance of some ions (e.g. Na+, Ca+2, K+, etc.) in the human body. Ask them to prepare a collage of the human body and indicate in what parts certain ions are important, e.g. calcium ions are important in the blood clotting mechanism. Have the students show in their collage the following: 1. Important ions in the body. 2. Uses of these ions. 3. Result of too little or too much of the ions in the body. 4. Sources of the ions (e.g. fruits, vegetables, milk). 210

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With this activity, the students will get to appreciate the importance of ions and they will be able to see the relationship of chemistry to other subjects like biology and art. B. Comic Strip/Puppet Show. Ask your students to prepare a comic strip or a puppet show that will present the different characteristics of an ionic bond and a metallic bond. In this way, the students can show their creativity and artistry, as well as their understanding of the concepts. C. Reflection. For reflection, ask your students: 1. In this episode, what set of rules are presented? 2. In your home, what are some of the rules you have to follow? D. Word Maze. Answer the items listed below, then search for these words in the word maze. The words may be spelled horizontally, vertically, diagonally or backwards. When you find all the words, a hidden message will be revealed. The letters in the message are hidden between the words you have found. 1. Type of bond that binds atoms in a metal 2. A property of metals that allow them to be hammered into sheets without breaking 3. Type of bond between two oppositely-charged ions 4. Positive ion 5. Negative ion 6. A solution that conducts electricity 7. Negative electrode 8. Positive electrode 9. Formula used to represent the valence electron configuration of elements where dots are used to represent electrons 10. Bond formed between two atoms sharing electrons 11. Bond where three pairs of electrons are shared 12. Bond that is electrically symmetrical 13. Bond that has a partially positive end and a partially negative end 14. A electrically neutral group of covalently bonded atoms behaving as a unit 15. Repeating pattern in a crystal structure

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CHEMISTRY IN ACTION M O G Z S B Y K M T M K P R K E A G P T D X B F N D B Y A D C L L K G C D C O E O P N L R H N E L X J A I G L S Z R O T E D F C E Q T T U A P A G P N M I S C T A E P H V L B C N U I N Q G C R B D X O Q B G O O C G H R Q R O I P C D N S N Y L A T T I C E L L A O E P T C M E T A L L I C Y I O S M V M A V C I N O I P N T T N Y U M E D O N A W C A G E E Y C W G T R I P L E M O L E C U L E H L G V S U P A N K H H T F P X B E Y S I W E L U J J L L N P

The hidden message is: ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ___ ASSESSMENT A. Multiple Choice. Choose the letter corresponding to the correct answer. 1. What cohesive force binds the atoms in a gold bar? A. Ionic bond C. Non-polar bond B. Metallic bond D. Polar covalent bond 2. Which of the following is an electrolyte? A. Pure water C. Starch in water B. Salt solution D. Sugar solution 3. Magnesium belongs to Group 2 (IIA) while bromine belongs to Group 17 (VIIA). What bond is formed when Mg and Br combine? A. Ionic bond C. Non-polar covalent bond B. Metallic bond D. Polar covalent bond 4. What bond is formed when two nonmetals combine? A. Covalent bond C. Metallic bond B. Ionic bond D. Nonmetallic bond

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CHEMISTRY IN ACTION 5. What bond is formed between C and H in CH4 ? A. Ionic bond C. Non-polar covalent bond B. Metallic bond D. Polar covalent bond 6. When magnesium (atomic no. 12) loses its two valence electrons in electron transfer, it will become isoelectronic with A. oxygen (atomic no. 8) C. silicon ( atomic no. 14) B. neon (atomic no. 10) D. sulfur (atomic no.16) 7. Which of the following statements will NOT be true when fluorine (atomic no. 9) atom gains one electron? A. It will become a cation. B. It will have a -1 charge. C. It will be isoelectronic with neon (atomic no. 10.) D. It will have 10 electrons and 9 protons. 8. Which of the following has non-polar covalent bond? A. H2 C. NaBr B. HCl D. CCl4 9. Potassium (atomic no. 19) will tend to A. gain electrons. C. gain protons. B. lose electrons. D. lose protons 10. What is the maximum number of electron pairs that atoms in a covalent bond can share? A. 1 C. 3 B. 2 D. 4 B. Skeleton Periodic Table. Use the skeleton periodic table to answer the following questions. Assume that the fictitious elements A-P have electron configurations consistent with their positions in the periodic table. 1 2 13 14 15 A D G E H J M O 213 P K N 16 B 17 C F I L 18

CHEMISTRY IN ACTION 1. Give the cation formed from element: (a) D. (b) H. 2. Give the anion formed from element: (a) N. (b) F. 3. Write the formula of the chemical compounds expected to form between elements (a) E and B. (b) J and C. (c) F and N. C. Lewis Formula. Identify the type of chemical bond (ionic or covalent) used to form the following compounds. If the compound is covalent, draw its Lewis formula. 1. CCl4 2. Na2S D. Questions. Answer the following questions: 1. State the difference between a single, double, and triple covalent bond. Give an example of each. 2. Is it possible for a molecule to be non-polar even though it contains polar bonds? Explain. 3. Predict whether the following molecules are polar or non-polar: (a) Oxygen diflouride, OF2 (b) Fluorine, F2 (c) Hydrogen iodide, HI (d) Methane, CH4 (e) Chloromethane, CH3Cl 4. Calcium chloride is often used instead of sodium chloride for thawing icy streets and sidewalks. Write the formula for this compound. Is this compound ionic or covalent? What particles make up a crystal of this substance? ANSWER KEY (Under Teaching Tips, Suggested Activities) D. Word Maze. 1. 2. 3. 4. 5. 6. 7. 8. METALLIC MALLEABILITY IONIC CATION ANION ELECTROLYTE CATHODE ANODE 9. LEWIS 10. COVALENT 11. TRIPLE 12. NON-POLAR 13. POLAR 14. MOLECULE 15. LATTICE The hidden message is: CHEMICAL BONDING. 214

CHEMISTRY IN ACTION (Under Assessment) A. Multiple Choice. 1. 6. B B 2. 7. B A 3. A 8. A 4. A 9. B 5. 10. D C

B. Skeleton Periodic Table. 1. (a) D+ 2. (a) N-2 3. (a) EB C. Lewis Formula. 1. CCl4 covalent bond

(b) H+3 (b) F(b) JC2

(c) F2N 2. Na2S ionic bond

D. Questions. 1. A single bond is a covalent bond in which two electrons are shared between two atoms. For example, H:H. A double bond is a covalent bond in which four electrons are shared between two atoms. For example, O::C::O. A triple bond is a covalent bond in which six electrons are shared between two atoms. For example, N:::N. 2. Yes. A compound can be non-polar if its polar bonds are arranged symmetrically in space so that the center of positive charge coincides with the center of negative charge for the molecule. 3. (a) polar (d) non-polar (b) non-polar (e) polar (c) polar 4. CaCl2. Ionic. A crystal of this substance consists of Ca2+ and Cl- ions.

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CHEMISTRY IN ACTION REFERENCES Bloomfield, M. M. & L. J. Stephens. (1996). Chemistry and the living organism. Singapore: John Wiley & Sons, Inc. Bucat, R. B. (ed). (1983). Elements of Chemistry. Vol.1. Canberra A.C.T., Australia: Australian Academy of Science Publication. Masterton, W.L. & C.N. Hurley. (2001). Chemistry: principles and reactions. (4th ed.). FL: Harcourt Brace College Publishers. Morris, H. (1984). Foundations of college chemistry. CA: Wadsworth. The 1999 Grolier multimedia encyclopedia.

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 29: BINDING AMONG MOLECULES OVERVIEW Episode 28 Putting Atoms Together discusses the forces that hold particles together and the two types of covalently bound substances: the molecular and the network substances. This episode shall discuss the chemical structures of specific molecules to enable us to understand the interactions and binding among them. It also deals with the different intermolecular attractions such as London dispersion forces, dipole-dipole forces and hydrogen-bonding. It then shows how these forces influence certain properties of common molecular substances such as water, ammonia, and gasoline. OBJECTIVES At the end of this lesson, the student should be able to: 1. define intermolecular forces of attraction; 2. list and differentiate the types of intermolecular forces of attractions; 3. relate some physical properties of substances with the type and strength of intermolecular forces; and 4. demonstrate critical, logical, and visual-spatial skills. INTEGRATION WITH OTHER LEARNING AREAS This episode is better understood after going over the two previous ones namely, Episode 27 Periodic Properties of Elements and Episode 28 Putting Atoms Together. SCIENCE PROCESSES Observing Classifying VALUES Sharing Inferring Predicting

Appreciation of the similarities and differences of Gods creation

LIFE SKILLS Critical thinking Logical thinking Decision making Effective communication 217

CHEMISTRY IN ACTION IMPORTANT CONCEPTS 1. A molecule assumes the most stable shape when electrostatic repulsions between electron clouds surrounding a central atom is at a minimum. 2. The most stable shape of a molecule can be predicted using the Valence Shell Electron Pair Repulsion (VSEPR) theory. 3. There are five (5) basic shapes of molecules depending on the number of groups bonded to a central atom. These are linear, trigonal planar, tetrahedral, trigonal bipyramidal, and octahedral. These shapes are modified if there are nonbonded electrons or lone pairs connected to the key atom. 4. Attractive forces hold molecules together in definite arrangements in the solid state and in the liquid state. These are called intermolecular forces of attraction or van der Waals forces. 5. There are three (3) kinds of van der Waals forces, namely: London dispersion forces, dipole-dipole forces, and hydrogen-bonding. BACKGROUND INFORMATION/EPISODE CONTENT Geometry of Molecules. The geometry or shape of a molecule is the arrangement of the atoms of the molecule relative to one another in space. For example, carbon dioxide, CO2, has all three atoms in a straight line while the atoms of water, H2O, are in a V-shaped arrangement. This small difference in spatial arrangement of atoms in these two compounds makes a big difference in many of their physical properties. CO2 is a gas at room temperature while water is a liquid at room conditions. We have seen all three states of water: solid, liquid, and gas, but none of us have seen or handled carbon dioxide in the liquid state at ordinary conditions. And this is largely because carbon dioxide is a linear molecule. What dictates the positions that atoms in a molecule take relative to one another? A simple model that describes and explains the shapes assumed by small molecules is given by the Valence Shell Electron Pair Repulsion (VSEPR) Theory. The VSEPR Theory is based on the premise that electrons repel one another and valence electron pairs around an atom will orient themselves as far apart as possible to minimize repulsion. Thus, the positions of atoms bonded to a central atom are determined by the positions of electron pairs used for bonding by this central atom. Working out geometries of molecules is best done using actual models that can be held and rotated and viewed at different angles. In the absence of such models, the 218

CHEMISTRY IN ACTION video lesson may be useful in helping us visualize the arrangement of atoms in molecules. Let us then look at the different shapes that molecules assume using the VSEPR Theory. The Basic Arrangements. The VSEPR Theory suggests that there are basic or ideal arrangements of electron pairs in the valence shell of an atom that result in minimum repulsion. Consider, for example, an atom with two pairs of electrons in its outermost shell. How would these two electron pairs position themselves such that repulsion between them is at a minimum? The farthest that they can go is at the opposite ends of the central atom or at 180o.
X X X X

If these two pairs of electrons are used for bonding, such as in BeF2, what will be the shape of the molecule? Let us say the middle or central atom X is beryllium, Be.

Be

F Be F

Be

The molecule would be linear. It is true that there are other electron pairs around the fluorine atoms, but they do not determine where the fluorine atoms would be positioned. The positions of the fluorine atoms are determined only by the positions of the bonding electrons shared by F with Be as the central atom! The basic arrangements for two, three, four, five, and six pairs of electrons around a central atom are given in Table 1. Table 1. Basic arrangements of three, four, five, and six pairs of electrons and their modifications.

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To show the geometry of some simple molecules, balloons may be used to represent electron pairs. To start with, a molecule with six electron pairs around the key atom was shown. An example of this is sulfur hexafluoride illustrated in Figure 1 below.

Figure 1. Octahedral shape of Sulfur hexafluoride, SF6. Six balloons tied together or the equivalent plastic stick model could represent this molecule. At its center is a sulfur atom. The balloons are farthest away from each other when they are oriented along the x, y, and z axes of an octahedron. Because all bonds are identical and oriented symmetrically in space, the molecule has a uniform electrical charge distribution. Each S-F bond is polar. But since each bond is directed in the opposite direction as another bond, then their dipoles cancel out each other and the molecule as a whole is non-polar. 220

CHEMISTRY IN ACTION If atoms bonded to the key atom in a molecule are not identical, the molecule may be polar. We say that a dipole exists. A dipole exists when there is a separation of charges in a molecule due to unequal attraction of electrons by the bonded atoms. The sulfur chloropentafluoride, SF5Cl, in Figure 2 is polar as a result of an unequal attraction of chlorine and fluorine atoms for electron pairs.
F F F S F Cl F

Figure 2. Sulfur chloropentafluoride, SClF5, octahedral.

A molecule with five bonding electron pairs and one nonbonding electron pair such as in IF5, the position of the nonbonding pair will be vacant when we consider the final shape of the molecule. The six balloons still take an octahedral geometry but the five electron pairs bonded to fluorine atoms take a square pyramid geometry as iodine atom positions itself at the center of the square base, as shown in Figure 3. There is a lone pair below the base of the square pyramid. All the five fluorine atoms are on one side of the molecule making the molecule slightly polar.
F F F I F F

Figure 3. Iodine pentafluoride, IF5, square pyramidal.

When there are five pairs of electrons around the central atom in a molecule and when all the electron pairs are used in bonding, the molecule takes a trigonal bipyramidal shape. An example of a molecule of this shape is phosphorus pentachloride, PCl5 shown in Figure 4. Figure 4. Phosphorous pentachloride, PCl5, trigonal bipyramidal. The shape is that of two pyramids joined at the base with the key atom, P, at the center of the triangular base. Even if each P-Cl bond is polar, PCl5 is non-polar because the dipoles of the bonds cancel out. The molecule tellurium tetrachloride, TeCl4, has five pairs of electrons around Te, but only four of these are bonding pairs and one is nonbonding or a lone electron pair. While the five electron pairs still form a trigonal bipyramid, since the lone pair belongs to the central atom and it would appear to be an empty side. 221

CHEMISTRY IN ACTION Nonbonding pairs tend to repel other electron pairs strongly and would usually be situated at positions with the least number of 90o neighbors. In the trigonal bipyramidal structure, these positions would be any of the three positions in the middle or equatorial plane. Thus, for TeCl4, the shape of the molecule would be a see-saw. The shape is more clearly seen if the molecule is rotated 90o counterclockwise shown as the second drawing in Figure 5. Can you tell if TeCl4 is polar or not?
Cl Cl Cl Te Cl Cl Te Cl Cl Cl

Figure 5. Tellurium tetrachloride, TeCl4, see-saw.

A tetrahedral shape is observed with molecules whose central atom has four electron pairs around it where all four are used for bonding with other atoms. An example of this is methane, CH4, in Figure 6.

H H C H H

Figure 6. Methane, CH4, tetrahedral.

The shapes of the molecules ammonia and water originate from the general tetrahedron structure with one or two positions being occupied by nonbonding electron pairs. Ammonia has three bonding pairs and a lone pair and exhibits a pyramidal shape, while water has two bonding pairs and two lone pairs and is Vshaped as in Figure 7. While methane is non-polar, ammonia and water are both polar molecules. Figure 7. O H N H Ammonia, NH3, pyramidal and H water, H2O, bent or V-shaped. H

The CH bonds in methane are equidistant from one another at 109o. However, the observed bond angle between the NH bonds in ammonia is 107 o and not the tetrahedral bond angle 109o. This decrease in bond angle is due to the strong repulsion exerted by the nonbonding electron pair. Repulsion is actually strongest between two nonbonded electron pairs, such as that in water, causing the two unshared pairs of the oxygen atom to occupy a larger space on the surface. The bonding pairs are forced to come even closer in water at 104.5o. 222

CHEMISTRY IN ACTION Repulsion between electron clouds decreases in the order: lone pair-lone pair >lone pair-bonded pair > bonded pair-bonded pair. Compounds of boron, B, would usually have a triangular planar arrangement of atoms around boron. This is when boron does not complete an octet of electrons and have only three pairs in its outermost shell. An example of a boron compound where boron has only three pairs of electrons in its valence shell is boron trifluoride, BF3. Boron trifluoride is a triangular planar or trigonal planar molecule. The BF bonds are identical and are 120o away from each other. See Figure 8. While the B F bond is polar, the bond dipoles cancel out each other in the trigonal planar arrangement making the molecule non-polar.

Figure 8. Boron trifluoride, BF3, triangular planar/trigonal planar.

What shape would be exhibited by molecules whose central atoms have only two pairs of electrons in their outermost shell? If you recall the first example that was used in this section, BeF2, it is said the molecule would be linear since the farthest that two groups of electrons can go to minimize repulsions is at 180o as seen in Figure 9. Figure 9. Beryllium fluoride, BeF2, F Be F linear. BeF2 is a non-polar molecule because the dipoles of the two BeF bonds are exactly opposite in directions and would cancel each other out. Not all linear molecules are non-polar. Simple diatomic molecules are also linear and can be polar or non-polar depending on the electronegativities of the atoms which make up the molecule. Examples of non-polar diatomic molecules are the following: H2, O2, N2, and F2. The molecules of hydrogen fluoride, HF, nitric oxide, NO, and carbon monoxide, CO, are linear molecules that are polar. Intermolecular Attractions. Atoms that make up molecules are held together by covalent bonds. But what keeps the molecules of sugar, iodine, and carbon dioxide in dry ice, together in solid crystals and water and butane in the liquid state? The attractive forces that hold molecules together in definite arrangements in the solid state or in more condensed aggregates in the liquid state are called intermolecular forces of attraction. These are also called van der Waals forces. Intermolecular forces are weak forces of attraction compared to covalent bonds. The amount of energy needed to break or form these intermolecular forces and allow a molecular substance to undergo change in state is very much less compared to breaking or forming covalent bonds. Thus, when we heat water to boiling, the energy we provide is enough to separate the molecules of water but 223

CHEMISTRY IN ACTION not to break the covalent bonds that hold the oxygen and hydrogen atoms in the water molecules. There are several types of intermolecular or van der Waals forces. They are all electrical in nature. Some substances have only one kind, but most others have two or more intermolecular forces operating between their molecules. London dispersion forces. London dispersion forces are the most common type of intermolecular forces present not only between molecules but between atoms as well. They exist between/among instantaneous dipoles that arise from the motion of electrons in atoms.

Figure 10. Formation of instantaneous dipoles. In an atom, the electrons are not always uniformly distributed as in Figure 10a. There will be instances when one side of the atom has more electrons than the other side due to the movement of electrons. The atom will then have one side partially negative and the electron-deficient side partially positive - a dipole! See Figure 10b. The dipole formed from the motion of electrons in one atom will cause a shift in the electron distribution of the next atom as in Figure 10c. These dipoles, although formed instantaneously, are also very temporary or momentary in nature because the electrons keep on moving. These dipoles will continuously keep on forming and disappearing all the time, hence, London dispersion forces by that nature are very weak. Because London dispersion forces are very weak, the forces become significant only when the molecules are close together. This is the only type of intermolecular forces that exist between molecules of non-polar substances like iodine and carbon dioxide. These substances sublime easily indicating that a very small amount of energy is needed to convert the solid to the gaseous state. The noble gases helium, argon, xenon, and krypton exist as free uncombined atoms. They condense at extremely low temperatures. What holds these atoms together in the liquid phase?

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CHEMISTRY IN ACTION Table 2. Melting points and boiling points of noble gases. Element He Ne Ar Kr Xe Rn Melting Point, oC -272.2 -248.7 -189.2 -156.6 -111.9 -71.0 Boiling Point, oC -268.9 -246.0 -185.7 -152.3 -107.1 -61.8

Notice a few things about the melting and boiling points of noble gases in Table 2. First, they are all extremely low! We have to cool the noble gas to very low temperatures before it condenses to a liquid or freeze to a solid. Second, it takes only a little energy to boil off the liquid. Neon melts at -248.7oC, but at less than two degrees higher, it will boil! The third feature is that the heavier or the larger the atoms of the noble gas are, the higher is the melting point or boiling point. London dispersion forces tend to increase in strength as the molar mass of atoms become bigger. Compounds made up of mostly carbon and hydrogen are usually non-polar. Methane, CH4, the simplest hydrocarbon, is a gas at room temperature. Hexane, C6H14, is a liquid at room conditions. But hydrocarbons with 20 or more carbon atoms, such as eicosane,C20H42, are solids. Since the only intermolecular forces in these compounds are London dispersion forces, we can also say that for similar molecules like the hydrocarbons, the strength of London dispersion forces increases with increasing number of atoms in the molecule. This is not surprising, since the more atoms present in the molecule, there would be more electrons involved in the creation of the instantaneous dipoles. Butter and margarine are mixtures of chemically similar molecules. They do not pack well because of their irregular shape. This makes them soft and easy to spread on biscuits or bread. The motion of the butter knife breaks the weak London forces that hold the solid together. Dipolar forces. Polar substances like chloroform and acetone exhibit higher melting and boiling points compared to non-polar substances of similar molar masses. This is because in addition to London dispersion forces, there exists another type of intermolecular force between their molecules. This intermolecular force, called dipolar force, arises from the permanent dipole that exists in the molecules. Dipolar forces are stronger attractive forces than London dispersion forces. Tables 3 and 4 show that polar molecules exhibit higher melting points and boiling points compared to non-polar molecules of similar molar mass. 225

CHEMISTRY IN ACTION Table 3. Melting points and boiling points of some non-polar molecules. Substance N2 SiH4 GeH4 Br2 Molar Mass, g/mol 28 32 77 160 Melting Point, o C -210 -185 -165 -160 Boiling Point, o C -196 -112 -90 59

Table 4. Melting points and boiling points of some polar molecules. Substance CO PH3 AsH3 ICl Molar Mass, g/mol 28 34 78 162 Melting Point, o C -199 -133 -116 14 Boiling Point, o C -192 -88 -55 97

Hydrogen Bond. A special kind of dipole-dipole attraction exists between molecules where there are hydrogen atoms that are bonded directly to highly electronegative atoms like fluorine, oxygen or nitrogen. The lone electron of hydrogen which it shares with the electronegative atom gets pulled away, almost exposing the nucleus of hydrogen. This makes hydrogen become highly positive and becomes very attractive to other electron-rich electronegative atoms. See Figure 11. Figure 11. Hydrogen bonding between molecules. X is the electronegative atom.

hydrogen bond

The hydrogen bond is the strongest of all intermolecular forces. Hence, substances whose molecules are held by hydrogen bonding exhibit unusually high melting points and boiling points. The graph of Figure 12 shows how exceptionally high the boiling points of substances that exhibit hydrogen bonding like H2O, HF, and NH3, and how they deviate from the trends in boiling points of analogous compounds even if their molecular weights are very low. Hydrogen bonds are very important intermolecular forces in biological systems. They are responsible for the helical and pleated structures of proteins and for the helical structure of DNA. 226

CHEMISTRY IN ACTION Figure 12. Boiling points of some binary hydrides.

The Properties of Water. We use water everyday and find this clear colorless liquid quite ordinary. But there is nothing ordinary about water. Compared to most other substances on earth, water is pretty special, unusual, and unique. In addition to the high melting point and boiling point of water, some of its other unusual properties include high surface tension, high heat of vaporization and heat of fusion, and lower density of solid that is less dense than its liquid state. All these properties are due to the extensive hydrogen bonding in water. This hydrogen bonding in water gives it an unusually high boiling point, keeps water liquid at room conditions, and allows us to use it for drinking or cleaning at comfortable temperatures. Hydrogen bonds likewise keep the water molecules in regular hexagonal pattern in ice in Figure 13. Figure 13. Hydrogen bonding in ice. The polarity of water makes it a very good solvent and it is often called the universal solvent because it can dissolve a wide range of substances. Ordinary dipole-dipole interaction explains the solubility of polar substances in water. On the other hand, in a solution of sodium chloride and water, ion-dipole attractions exist between the ions and the polar water molecules. The water molecules surround each sodium ion, with the negative ends of water molecules oriented toward the positively-charged sodium ion. The chloride ion attracts the positive ends of the surrounding water molecules as can be seen in Figure 14. What will explain the miscibility of some alcohols in water? Alcohols are substances with hydroxyl groups. Alcohols with low molar mass like methanol and ethanol can form extensive hydrogen bonding with water which accounts for their complete miscibility in water.

227

CHEMISTRY IN ACTION

Figure 14. Dissolution of sodium chloride in water.

Sucrose is soluble in water despite its high molecular mass of 342. The hydroxyl groups of sucrose form hydrogen bonds with water. Compared to the eight hydroxyl groups of sucrose, 1-butanol has only one hydroxyl group that is available for hydrogen bonding with water. The remaining part of the molecule is a non-polar four carbon chain.. The solubility of 1-butanolin water is limited indicating that the effect of the non-polar chain outweighs the effect of the hydrogen bonding. Hydrocarbons such as gasoline and kerosene are mixtures of non-polar molecules. All hydrogen atoms in both molecules are bonded to carbon atoms whose electronegativity is very close to that of hydrogen. These non-polar substances do not mix with polar water molecules. The London dispersion forces that may form between hydrocarbon and water molecules are too weak to provide enough energy to overcome the intermolecular forces to separate water molecules from one another. Butane is another non-polar molecule. Liquid butane is used as lighter fluid. When the lighter is flicked, the butane vaporizes. Friction of the flint provides the spark needed to ignite the vapors of butane. The similarities in the energy involved in breaking and forming attractive forces between particles of substances that dissolve in each other is the basis of the observation that like dissolves like.

228

CHEMISTRY IN ACTION VOCABULARY WORDS 1. Geometry of molecules refers to shapes of molecules. 2. Linear the shape exhibited by a molecule whose central atom has only two pairs of electrons in its outermost shell. 3. Trigonal planar the geometry of a molecule when there are three pairs of electrons in its valence shell. 4. Tetrahedral the shape of a molecule whose central atom has four electron pairs around it and where all four are used for bonding with other atoms. 5. Trigonal bipyramidal the shape taken by a molecule when there are five pairs of electrons around the central atom and all the electron pairs are used in bonding. 6. Octahedral the configuration assumed by a molecule with six electron pairs around the key atom. 7. Non-polar covalent bond - a bond wherein the electric charges are evenly distributed between the bonded atoms. 8. Polar covalent bond - a bond wherein the electric charges are not evenly distributed between the bonded atoms. 9. Dipole a molecule that exhibits separation of charges due to unequal attraction of electrons by the bonded atoms. 10. van der Waals forces - collective term for all kinds of intermolecular attractive forces. 11. London dispersion forces also called hydrophobic forces; the attraction between rapidly fluctuating temporary/induced/momentary dipoles. 12. Dipolar force also called dipole-dipole interaction; intermolecular force arising from molecules that behave as the permanent dipoles. 13. Hydrogen bond - the attractive interaction between a molecule with an electronegative atom and that which contains hydrogen atom(s) bonded directly to highly electronegative atoms like F, O, N.

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CHEMISTRY IN ACTION PRE-VIEWING ACTIVITIES A. Ask the students the following questions and let them write their answers on a piece of paper: 1. Why do water and oil not mix? 2. Why do mothballs or naphthalene placed inside a cabinet disappear? They will go back to their answers after viewing the episode. Let them judge for themselves if their answers are correct or at least approximate the correct answers. B. Introduce the episode that describes the different geometries of molecules, the different intermolecular forces, and how these forces affect the physical properties of substances. C. Pose the Guide Questions that the students will answer after viewing the episode. Ask them to focus on finding the answers to the Guide Questions as they watch the video. Guide Questions/Answers 1. What is the most stable shape of a molecule? The most stable shape of a molecule is that where the electrostatic repulsions of electron clouds is at a minimum. 2. What causes the deviation in the bond angles of ammonia from that of methane? The bond angles of ammonia are smaller than the tetrahedral bond angle in methane because the repulsion between bonding and non-bonding pairs is stronger compared to those between two bonding pairs. 3. What holds the free uncombined atoms of noble gases together in the liquid phase? Induced dipole attractions hold free uncombined atoms of noble gases to condense or liquefy the gas but only when temperatures very low and the atoms are very close to one another. 4. Why is water called the universal solvent? Water is called the universal solvent because it can dissolve a wide range of substances. 5. Explain the miscibility of low molecular weight alcohols in water. Alcohols with low molecular weights like methanol and ethanol form extensive hydrogen bonding with water. This is responsible for their complete miscibility. 230

CHEMISTRY IN ACTION 6. Why do water and gasoline not mix? Hydrocarbons such as gasoline and kerosene are mixtures of non-polar molecules. Water, on the other hand, is polar. The intermolecular forces that can exist between non-polar and polar substances are only London dispersion forces and the formation of these weak forces is not enough to break the strong dipolar forces and H-bonding in water. 7. What keeps the molecules of iodine, dry ice, and butane together in their solid crystals? The weak London forces keep the molecules of iodine, dry ice, and butane together in the solid state. These substances easily sublime or vaporize because London dispersion forces are very weak intermolecular forces.

VIEWING ACTIVITIES Let the students view the following segments on: (1) Molecular Geometry at 2:20 - 10:35, (2) Intermolecular Forces of Attraction and Relation to Properties of Substances (Solubility, Melting Point, Boiling Point) at 11:00 - 19:40.

POST-VIEWING ACTIVITIES Discuss the answers to the Guide Questions. TEACHING TIPS A. Review. It is suggested to review the students about the characteristic properties of the three states of matter solid, liquid, and gas. Emphasize that a change in physical state essentially involves formation or breaking of intermolecular forces. B. Intramolecular and Intermolecular Forces. Illustrate the difference between bonding in atoms or ions and bonding between molecules. For example, the five fluorine atoms and the chlorine atom in sulfur chloropentafluoride SF5Cl, are strongly bonded to the central atom S with covalent bonds (intramolecular). However, among SF5Cl molecules intermolecular forces of attraction also exist. Since SF5Cl is polar, dipole231

CHEMISTRY IN ACTION dipole attractions in addition to London dispersion forces are present among SF5Cl molecules. C. Role Play. To visualize tip # 2, ask for 14 volunteers from the class to role play. Divide the volunteers into two groups. Each group will represent one molecule of SF5Cl. Each member of the group represents an atom. Ask each member to bond covalently with each other to form a molecule. This will show bonding between atoms. Then ask the two groups to come close to each other to show intermolecular attraction.

AVN RED ASLAW

12

NOAROPNL
1 3

ROPLA
5

DEOILP-DEILPO
2 2

2 1 7

NOLNDO OINSPESRID
24 18 2

NYGDHROE GOINNDB
4

RERHTALTAED
16 3 1 9 14 8

RAELIN
1 23 1 7

HAEDARLTCO
10

NALGIRTO RIALADYPM
20 1 5 1 1
1 0 1 1 1 2 1 3

SUQRAE PARNLA
9

1 4

15

1 6

2 7

1 8

1 9

2 0

2 1

2 2

2 3

2 4

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CHEMISTRY IN ACTION Puzzle. Unscramble each of the clue words. Copy the letters in the numbered cells to other cells with the same number to reveal the hidden phrase. ASSESSMENT A. Multiple Choice. Choose the letter corresponding to the correct answer. 1. Which of the following intermolecular forces exists between molecules of N2? A. Dipole-dipole C. Hydrogen bonding B. Dipole-induce dipole D. London dispersion 2. For which of the following molecules will dipole-dipole interactions be important? A. CH4 C. CH2Cl2 B. C6H6 D. CCl4 3. Which of the following will NOT form hydrogen bonds with water? A. HF C. NH3 B. CH4 D. HCOOH 4. Which of the following is TRUE about a polar bond? In a polar bond, there is A. electron transfer. B. equal distribution of electrons between bonded atoms. C. unequal distribution of electrons between bonded atoms. D. no sharing of electrons. For items 5 to 7, refer to the following choices: A. Dipole-dipole only B. London dispersion only C. Dipole-dipole and London dispersion D. Dipole-induced dipole and London dispersion What type(s) of intermolecular forces exist between the following pairs? 5. HF and H2S 6. I2 and CBr4 7. NH3 and CH4 For items 8 to 10, refer to the following choices: A. See-saw B. Linear C. Tetrahedral D. Trigonal bipyramid 233

CHEMISTRY IN ACTION 8. What is the shape of BeCl2 ? 9. What is the shape of SF4 ? 10. Chat is the shape of SiCl4 ?

B. Boiling Point. Which substance in each pair is likely to have the higher boiling point? Why? 1. HCl and NaCl 2. HF and HCl 3. H2O and CH3OH ANSWER KEY (Under Teaching Tips) D. Puzzle. The clue words are: van der Waals Nonpolar Polar Dipole-dipole London dispersion Hydrogen bonding Tetrahedral Linear Octahedral Trigonal pyramidal Square planar

The hidden phrase is: Intermolecular Attractions (Under Assessment) A. Multiple Choice. 1. 6. D B 2. 7. C D 3. B 8. B 4. C 9. A 5. 10. C C

B. Boiling Point 1. NaCl, because ion-ion forces are stronger than dipole-dipole forces. 2. HF, because hydrogen bonding is present in HF but not significantly in HCl. 3. H2O, because it has more extensive hydrogen bonding.

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CHEMISTRY IN ACTION REFERENCES Atkins, P. & L. Jones. (1988) Chemical principles: the quest for insight. NY: W.H. Freeman. Chang, R. (1988). Chemistry (3rd ed.). NY: Random House. Hein, M. & S. Arena. (2000). Foundations of chemistry. (10th ed.) CA: Brooks/Cole. Mendoza E. & T. Religioso. (1990). You and the natural world series: chemistry. QC: Phoenix. http://school.discovery.com/

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CHEMISTRY IN ACTION Chapter 7: Structure of Matter and Chemical Bonding EPISODE 30: ELECTRICITY AND CHEMICAL CHANGE OVERVIEW This episode is about electrochemistry, its principles and applications. The chemical reactions that occur during corrosion are illustrated with an experiment. Different types of electrochemical cells are introduced with corresponding diagrams to show the sites of chemical reaction. Simple applications of electrochemistry are also shown particularly those of the dry cell and the lead storage battery. OBJECTIVES At the end of this lesson, the student should be able to: 1. explain the electrochemical nature of the corrosion of metal and illustrate this with appropriate chemical equations; 2. differentiate the following terms: oxidation from reduction, oxidizing agent from reducing agent, and anode from cathode; 3. explain how a voltaic cell works and how oxidation and reduction reactions produce electricity; 4. predict which reactant will undergo oxidation or reduction in a voltaic cell; 5. write half-cell reactions; 6. differentiate oxidation potential from reduction potential; 7. calculate the total cell potential of an electrochemical cell; 8. predict if a reaction is spontaneous or non-spontaneous; 9. explain the process of electrolysis and appreciate its practical applications; 10. differentiate between a voltaic cell and an electrolytic cell; and 11. explain how a dry cell functions INTEGRATION WITH OTHER LEARNING AREAS The episode can stand on its own. However, a review of Episode 28 Putting Atoms Together could prove helpful especially in predicting the changes in oxidation states of some elements. SCIENCE PROCESSES Observing Experimenting Interpreting the data

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CHEMISTRY IN ACTION VALUES Proper disposal LIFE SKILLS Creative thinking Critical thinking IMPORTANT CONCEPTS

Recycling of batteries.

Designing electrochemical cells from materials at home

1. Corrosion is a process generally associated with the degradation of metals; almost always, it is an oxidation-reduction reaction. 2. Oxidation-reduction reaction is also called redox reaction and is a reaction that involves transfer of electron(s) from one substance to another. 3. An electrochemical cell is a set-up where oxidation and reduction do not take place at the same site and requires a conducting medium to allow the movement of electrons and an electrolyte to allow the movement of ions to keep the charges neutral at all times. An electrochemical cell may be (1) a voltaic/galvanic cell or (2) an electrolytic cell. BACKGROUND INFORMATION/EPISODE CONTENT Corrosion. Corrosion is commonly associated with the degradation of metals. The main driving force for corrosion is the lowering of Gibbs Free energy. Metals have the tendency to go to their native low energy state which is the oxide form. Figure 1. Corrosion of iron. This process is inevitable but the use of barriers or corrosion control materials can slow down the progress of corrosion. From a chemists point of view, corrosion involves the chemical reaction of a metal with oxygen. This reaction is termed as oxidation reaction. Consider the rusting of iron when exposed to moisture in the air. The oxidation reaction of iron is an electrochemical process as illustrated in Figure 1. 237

CHEMISTRY IN ACTION
http://images.google.com.ph/imgres?imgurl=http://hyperphysics.phyastr.gsu.edu/hbase/chemical/ imgche/corrosion.gif&imgrefurl=http://hyperphys

Through a series of chemical reactions, iron transforms from its metallic state into rust or hydrated ferric oxide, Fe2O3.H2O. The overall reaction for the corrosion of iron is given in equation 4.
(1) (2) (3) (4) Fe (s) Fe
2+

(aq) + 2 e
-

O 2 (g) + 2 H 2O( l ) + 4 e Fe (aq) + OH- (aq) Fe(OH)2 (s) + O2 (g)

2+

4 OH ( aq ) Fe(OH)2 (s) Fe2 O3 .H2 O (s) + H2 O (l)

Corrosion of metals is not only due to reaction with water and oxygen. Other factors that can cause corrosion includes acids, bases, salts, oils, and other chemicals. Reduction- Oxidation Reaction (Redox Reaction). The corrosion of metallic iron is an example of an oxidation-reduction or redox reaction. A redox reaction is a type of reaction that involves a transfer of electrons. We can follow the transfer of electrons from one substance to another through a bookkeeping process of monitoring changes in the oxidation states of the substances. The oxidation state or number of an atom refers to the actual or apparent charge that an atom has when bonded to other atoms. There is a set of rules to follow when assigning oxidation numbers. If the oxidation states of atoms change in a reaction, the reaction must be a redox reaction. The oxidation and reduction processes always take place simultaneously, never one without the other. Hence they are sometimes called half-reactions: the oxidation half-reaction and the reduction half-reaction. To illustrate a redox reaction, consider the reactions involved in the corrosion of iron: Oxidation: Reduction: Fe(s) Fe2+ (aq) (0) (+2) O2(g) + H2O(l) (0) OH(aq) (-2)

The oxidation number of iron changed from zero to +2 indicating that iron lost two electrons. Substances that lose electrons undergo oxidation and their oxidation number becomes more positive. When a substance loses electrons, electrons do not just vanish. Another substance must accept these electrons. In other words, if a substance undergoes oxidation, another substance has to undergo 238

CHEMISTRY IN ACTION a complementary reaction called reduction. A reduction reaction is a reaction in which a substance gains electrons. In a reduction reaction, the oxidation number of a substance decreases or becomes less positive. The oxidation number of oxygen in the above reaction changed from zero to -2. Table 1 gives a summary of the important terminology associated with redox reactions. Table 1. Some terms associated with redox reactions. Substance undergoes ... Oxidation Reduction Characteristics An atom loses electrons An atom gains electrons Oxidation number of atom becomes more positive Oxidation number of atom becomes more negative Atom is oxidized Atom is reduced Substance is the reducing agent Substance is the oxidizing agent

Balancing Redox Equations. Consider again the chemical reaction for the corrosion of iron. The complete reaction involved is: Fe + O2 + H2O Fe+2 + OH In balancing redox reactions, the reaction can be broken down into two halfreactions, one showing the oxidation reaction and the other showing the reduction reaction: Oxidation half-reaction: Reduction half-reaction: Fe(s) Fe2+ (aq) O2(g) + H2O(l) OH(aq)

Equations showing the redox reaction must be balanced just like any chemical reaction. The number of atoms and the charges must be balanced. Add the appropriate number of electrons to the more positive side of the equation to balance the charges. For the oxidation reaction: Fe Fe2+ + 2eThe reduction reaction is balanced as: O2 + 2H2O + 4e- 4 OH

The final requirement in balancing a redox reaction is that the number of electrons lost in the oxidation half reaction must equal the number of electrons gained in the reduction half-reaction. Hence, we multiply the whole equation for the oxidation of Fe by 2 to make the number of electrons lost equal to 4. The overall reaction is obtained by adding the two half-reactions. As such the two half reaction becomes: 2Fe 2Fe+2 + 4e239

CHEMISTRY IN ACTION O2 + 2H2O + 4e- 4 OH Adding the two half equations results to the overall equation: 2Fe + O2 + 2H2O 2Fe+2 + 4 OH Notice that similar terms on both sides of the arrow cancel out. Therefore two atoms of iron plus one molecule of oxygen plus two molecules of water give two ferrous ions and four hydroxide ions. Iron is oxidized and is called a reducing agent; it caused the reduction of oxygen. The substance reduced, oxygen, O2, is called an oxidizing agent; it causes the oxidation of iron. Sites of Oxidation and Reduction. Redox reactions involve a transfer of electrons. In the reaction involved in the corrosion of iron, it is easy to imagine that when iron atoms come in contact with oxygen, they give up electrons to oxygen. Thus, iron is oxidized and oxygen is reduced. But the experiment illustrating the corrosion of iron shown in the video lesson tells us that there is more to it than simply passing electrons from one atom to another! Let us take a look at the results of the experiment. Blue and pink patches were observed on different parts of the nail after an hour or two. What has happened? As the metal in the iron nail is oxidized, the ions dissolve in the aqueous agar matrix. The oxidation reaction is: Fe Fe+2 + 2e-. The ferrous ions produced from the oxidation of iron react with potassium ferricyanide to form a blue complex. Fe+2 + K3[Fe(CN)5] KFe[Fe(CN)5] + 2K+ blue On the other hand, the phenolphthalein indicator turns pink due to the hydroxide ions produced by the reduction reaction: O2 + 2H2O + 4e- 4 OH. In the experiment on corrosion the patches of different colors identify the sites where the reactions occur: blue for the site of oxidation, pink for the site of reduction of oxygen. The site where oxidation happens is called the anode, while the site of reduction is called the cathode. The experiment tells us that when the iron nail corrodes, these two sites are not at the same part of the nail! One part of the nail acts as the anode (blue), another part of the nail acts as the cathode (pink). Discoloration of the Nail Pink Blue Cathode Anode Reduction Oxidation + 2H2O + 4e- 4 OH Fe Fe+2 + 2e240

O2

CHEMISTRY IN ACTION 2Fe(OH)3(s) Surface water film corrosion spot 2Fe2O3.2H2O(s) + H2O(l) (rust) corrosion spot

O2(g) + 2H2O(l) + 4e- 4OH- (aq) anode Fe Fe2+ + 2ecathode anode Fe Fe2+ +

2e-

Figure 2. Sites of oxidation and reduction during corrosion of iron. During electron transfer, the electrons move along the nail from the site they were given up (anode) to the site where they would be accepted by oxygen (cathode). An electrolyte is important since it serves as conducting medium for ions to keep all areas on the nail neutral. In this experiment, the electrolyte is the aqueous agar matrix to which NaCl is added in order to increase its conductivity. Electrochemical cells. The corroding iron nail described above is an example of an electrochemical cell. It is a set-up where oxidation and reduction do not take place at the same site. It requires (1) a conducting medium to allow the movement of electrons and (2) an electrolyte to allow movement of ions to keep electrical neutrality of the set up. The following set up in Figure 3 is a typical electrochemical cell.

Figure 3. An electrochemical cell.

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CHEMISTRY IN ACTION An electrochemical cell consists of two electrodes: the anode and the cathode. Oxidation takes place at the anode and reduction takes place at the cathode. Electrochemical cells can be of two types: one, the voltaic or galvanic cell, which makes use of spontaneous redox reactions; and two, the electrolytic cell, which forces a non-spontaneous redox reaction to happen by passing electricity through the reactants. The important product of each type of cell is apparent. A voltaic cell can produce electricity, while we use an electrolytic cell for the chemical products formed. Voltaic Cells. Two experiments are presented to illustrate how voltaic cells work. In the first experiment, the zinc metal was immersed in copper (II) sulfate solution. After sometime the zinc metal was coated with metallic copper. A displacement reaction has occurred showing that zinc, a more reactive metal than copper, displaced copper from its salt. The reaction can be written in the ionic form and includes only the species that have changed in the course of the reaction. The net ionic equation is: Zn + CuSO4 ZnSO4 + Cu Zn + Cu+2 Zn+2 + Cu (net ionic equation) The above reaction clearly shows a redox reaction. Zinc was oxidized and lost two electrons in the process: Zn Zn+2 + 2e- (anode). On the other hand, the copper ions gained electrons. Copper metal was deposited on the zinc strip upon reduction: Cu+2 + 2e- Cu (cathode). When the site of oxidation is physically separated from the site of reduction and the circuit is completed between electrodes, the cell is then called a voltaic cell. See Figure 4. In the voltaic cell, the metals are the electrodes and the flow of electrons is from the anode to the cathode. A voltaic cell converts chemical energy into electrical energy.

Figure 4. A voltaic cell.

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CHEMISTRY IN ACTION In the second experiment, the metal plates serve as the electrodes and the solution is the electrolyte. The cellophane separates the two solutions but allows the migration of water and ions through its pores. To complete the circuit, a small motor is inserted and connected in series with a metal electrode. The motor runs, proof that the cell generates enough electrical energy to run it. The zinc plate is the anode and the copper plate is the cathode. Electrons from the zinc plate flow to the outside circuit through the motor and back to the cell via the copper plate. Here the electrons are taken up by the copper ions in solution and deposit as metallic copper. The zinc ions dissolving in the solution must migrate through the cellophane towards the cathode to keep the solution electrically neutral. Likewise, sulfate and other negative ions must migrate through the cellophane in the opposite direction. Otherwise, the current will stop flowing. Cell Potential. As zinc ions are produced and go into solution, electrons accumulate on the zinc plate. An electric potential develops on the surface of the zinc. This potential is known as the oxidation potential of zinc, denoted by the symbol Eo. Each oxidation reaction has its unique oxidation potential. The value depends on the type of metal as well as the temperature and concentration of ions in the solution. The oxidation potential of zinc metal immersed in a 1M solution of zinc ions at 25oC is +0.76 volts. The positive sign indicates that Zn is preferentially oxidized compared to the standard H2 gas. If this reaction is written in reverse, the reaction is reduction and the value of Eo, called the reduction potential of zinc, is 0.76 volts. The depletion of copper ions in the voltaic cell occurs at the cathode and produces a corresponding electrical potential. The reduction potential of copper immersed in a 1M solution of Cu+2 ions at 25oC is +0.34v. The positive reduction potential indicates that Cu2+ will preferentially be reduced compared to H+ in 1M solution. The sum of the oxidation potential of zinc and the reduction potential of copper gives the total cell potential. The cell potential is denoted by the symbol E ocell. It is also known as the cell electromotive force or EMF. A positive total cell potential indicates that the reaction is spontaneous; a negative cell potential means the reaction is nonspontaneous. For the Cu Zn voltaic cell, the cell potential is equal to +1.10 eV and the reaction is spontaneous. Cell reaction: Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s) Eo cell = Eoox(Zn) + Eored(Cu) = +0.76 v + 0.34 v = +1.10 v 243

CHEMISTRY IN ACTION For the reverse reaction: Cu (s) + Zn2+ (aq) Zn (s) + Cu2+(aq) Eocell = -1.10 v The negative sign means the reaction is not spontaneous and the cell reactions will not occur. That is when a copper strip is immersed in a zinc sulfate solution, no reaction will occur and the cell will not produce electricity. We say that copper is a less reactive metal than zinc.

Figure 5. A dry cell.

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Some familiar examples of voltaic cells are the ordinary dry cell shown in Figure 5 and the lead storage battery in cars illustrated in Figure 6. In the dry cell, the zinc casing acts as the anode; a graphite rod in the center serves as the cathode. The electrolyte is a mixture of zinc chloride, ammonium chloride, and manganese dioxide in paste form. The reaction that occurs in the anode is: Zn Zn2+ + 2e-. At the cathode, the reduction reaction is: NH4+ + 2e- NH3 + H2. When excess hydrogen gas from the cathode reaction accumulates on the surface of the graphite, an increase in the cell resistance occurs and the actual cell voltage drops. Upon standing, a weak dry cell peaks up. The hydrogen gas is removed by the reaction with manganese dioxide. H2 + 2MnO2 Mn2O3 + H2O The lead storage battery, on the other hand, is a type of voltaic cell that is used in automobiles. It consists of six two-volt cells connected in series. Each component cell is composed of several negative pure spongy lead (anode) and positive lead oxide (cathode) electrodes. The electrodes are immersed in a dilute solution of sulfuric acid.

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CHEMISTRY IN ACTION Figure 6. A lead storage battery.

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The reactions involved when the lead storage battery is used and discharging electricity include: Pb plate (anode): Pb + SO42- PbSO4 + 2ePbO2 plate (cathode): PbO2 + 4H+ + SO42- + 2e- PbSO4 + 2H2O Overall reaction: Pb + PbO2 + 4H+ + 2SO42- 2PbSO4 + 2H2O Lead storage battery can be recharged by applying a direct current to the reverse reaction. 2PbSO4 + 2H2O Pb + PbO2 + 4H+ + 2SO42Electrolytic Cells. The recharging of a car battery makes use of electricity to make a non-spontaneous redox reaction to occur. In effect, the car battery becomes an electrolytic cell on recharging! A negative cell potential for a redox reaction means that it is a non-spontaneous reaction. For the reaction to occur, an outside source of power is needed to drive the reaction. This process is called electrolysis. Figure 7 shows a diagram of an electrolytic cell.

Figure 7. An electrolytic cell.

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CHEMISTRY IN ACTION Some applications of electrochemistry, more specifically electrolysis, include the chrome finishing of car bumpers, refrigerator door handles, and other metal objects. The chrome finish consists of layers of copper, nickel, and chromium electroplated on base metals such as iron and zinc. The finish makes the metal surface more resistant to corrosion. The top layer of bluish chromium gives it an attractive appearance. Additional Useful Information 1. In an electrolyte solution, the flow of electric current is due to the movement of ions and not electrons towards the oppositely-charged electrode to maintain the charge balance in the electrochemical cell. 2. Water is a poor conductor of electricity because of its very small ionization constant. The conductivity of water is due to dissolved ions and not due to water itself. 3. Electrochemical cells include both voltaic/galvanic and electrolytic cells. 4. A 12-volt car battery contains six (6) cathode/anode pairs each producing two (2) volts. 5. Wood or glass fiber spacers are used in lead storage battery to prevent the electrodes from touching. 6. Electroplating is used to prevent corrosion. VOCABULARY WORDS 1. Corrosion a process commonly associated with the degradation of metals; it involves the reaction of a metal with oxygen. 2. Anode site of oxidation in an electrochemical cell. 3. Cathode site of reduction in an electrochemical cell. 4. Reducing agent a substance that induces another to be reduced and in the process it undergoes oxidation. 5. Oxidizing agent a substance that brings about oxidation of another and in the process, it is reduced. 6. Electrochemical cell - a set-up where oxidation and reduction do not take place at the same site; it requires a conducting medium to allow the 246

CHEMISTRY IN ACTION movement of electrons and an electrolyte to allow movement of ions to keep the charges balanced. 7. Voltaic cell also called a galvanic cell; it makes use of spontaneous redox reactions to produce electricity. 8. Electrolytic cell one that makes use of electricity to make a nonspontaneous redox reaction to occur. PRE-VIEWING ACTIVITIES A. The teacher may show pictures of materials containing some metal. B. The same materials may again be shown but this time rusting is evident. C. The teacher may ask the students what the causes of corrosion are. D. The teacher may also provide or prepare cut-outs of nails used in the video clip, blue and pink crayons, strips of cartolina paper each showing an individual reaction and a term such as anode, cathode, reducing agent, oxidizing agent, oxidation, and reduction as presented in the video. VIEWING ACTIVITIES Show the video clip on the experiment for Corrosion of Nail at 7:44 - 10:29 for set induction purposes.

POST-VIEWING ACTIVITIES A. Place the nail cut-out prepared on the board and asks students to do the following: 1. Color the designated areas with blue and pink crayons. 2. Identify where the oxidation and reduction occurs. 3. Label the anode and the cathode. 4. Identify the oxidizing agent and the reducing agent. B. Use the experiment and the activity to start the discussion on corrosion of metals. ASSESSMENT A. Quiz. Choose the letter corresponding to the correct answer, 247

CHEMISTRY IN ACTION 1. The oxidation number of S in Na2SO4 is A. +2. B. +4. C. +6. D. +8. +

2. What happens to Cu in the given reaction? CuO + H2 Cu H2O A. Copper gains one electron. C. Copper gains two electrons. B. Copper loses one electron. D. Copper loses two electrons. 3. The oxidizing agent in the reaction A. C. B. PbO. C + PbO CO + Pb is C. CO. D. Pb.

4. The substance reduced in the reaction H2 is A. Zn. B. HCl.

Zn + 2HCl ZnCl2 + C. ZnCl2. D. H2.

5. In the reaction Zn + CuSO4 ZnSO4 + Cu, the element that undergoes reduction is A. Zn. B. Cu. C. S. D. O. 6. What term describes the chemical reaction of a metal with oxygen? A. Corrosion C. Oxygenation B. Electrolysis D. Reduction 7. Where does oxidation take place in an electrochemical cell? A. Anode C. Electrolyte B. Cathode D. Salt Bridge 8. In a voltaic cell, the cathode is A. the negative electrode. B. the positive electrode. C. where oxidation takes place. D. where electrons come from.

9. A positive cell potential value indicates that redox reaction A. is spontaneous. C. takes place at the anode. B. is non-spontaneous. D. takes place without reduction. 10. What is the substance reduced called? A. Electrolyte C. Reducing agent B. Oxidizing agent D. Salt bridge

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CHEMISTRY IN ACTION B. Crossword Puzzle. Use the following clues to answer the crossword puzzle.
1 2 3

4 6 10 7 9 8

11

13

12 14

Across 2. Half-reaction in which a substance gains electrons 10. Conducting solution like copper sulfate 11. Reaction in which a substance combines with oxygen and loses electrons 13 Electrode where reduction takes place 14. Two words: substance that undergoes oxidation Down 1. A process by which electricity is used to make a chemical reaction occur 3. Two words: the substance reduced 4. Two words: the substance oxidized 5. A type of electrochemical cell consisting of two half-cells separated by a semi-permeable membrane 6. Type of cell that converts electrical energy to chemical energy 7. Involves a chemical reaction of a metal with oxygen 8. Two words: charge assigned to an atom on losing or gaining electrons 249

CHEMISTRY IN ACTION 9. Also reduction-oxidation reactions; can produce electricity or can be brought about by electricity 10. Process by plating out an object with a metal using electricity 12. Is due to the reaction of iron with oxygen and water ANSWER KEY A. Quiz. 1. 6. C A 2. 7. C A 3. B 8. B 4. B 9. A 5. 10. B B

B. Crossword Puzzle.

10

E L E C T R O L Y S I S

E L L E C T C T R O L Y T I C
14

C O R R O S I O N

E L E C T R O L Y S I S A
12

E
4

D U O X I D D A T I O N N U M B G E R
8

Y T

R E D 11 O X

13

H O

R E D U C I N G A G E N T A

O X 5 V I O D L I T Z A I I O N C G A G E N T

R U S T I N G

N T

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CHEMISTRY IN ACTION REFERENCES Atkins, P. & L. Jones. (1999). Chemical principles: the quest for insight. NY: W.H. Freeman. Chang, R. (1998). Chemistry. (3rd ed.). NY: Random House. Encyclopedia Britannica Standard cd (2000). Hein, M. & S. Arena. (2000). Foundations of chemistry. (10th ed.). Pacific Grove: Brooks/Cole.

Useful Websites http://school.discovery.com/ http://www.montgomery.college.edu/Departments/scilcgt/v-cell.pdf http://www.electrochem.org/dl/interface/spr/spr06/spr06_p24-26.pdf http://www.corrosion-doctors.org/Principles/Theory.htm http://intro.chem.okstate.edu/ChemSource/electrochem/electrochem9.htm

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