Chapter 12: Phase Changes and Equilibrium Grade Level Indicator Describe how a physical, chemical, or ecological system

in equilibrium may return to the same state of equilibrium if the disturbances it experiences are small. Large disturbances may cause it to escape equilibrium and eventually settle into some other state of equilibrium. Essential Question How do various factors combine to cause a substance to be a given phase of matter? I can... list and define all phase changes (boiling, freezing, etc.) relate phase changes to energy transfers and attractive forces explain how the concept of dynamic equilibrium relates to phase changes discuss the relationship between temperature, vapor pressure, and the boiling point of a substance analyze heating and cooling curves and use them to determine the amount of energy associated with phase change compare molar heat of fusion and molar heat of vaporization, and explain the difference in their magnitudes analyze and interpret phase diagrams Key Words equilibrium phase evaporation freezing deposition vapor pressure nonvolatile boiling point molar heat of fusion triple point critical temperature dynamic equilibrium condensation boiling sublimation Le Chateliers principle volatile freezing point molar heat of vaporization phase diagram critical point critical pressure

Chapters 12: Phase Changes and Equilibrium

Section 1: Mathematics of Phase Changes Different phases exist because of the relationship between a substances temperature, pressure, and intermolecular forces Every phase change is accompanied by a change in energy Energy is either released in the process(exothermic), or absorbed in the process(endothermic) The energy change associate with these processes can be thought of in both the qualitative and quantitative sense Qualitatively, this can be determined by applying a little logic SAMPLE EXERCISE: For each of the following processes, determine if the process is endothermic or exothermic

a) H2O(s) H2O(l)

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b) H2O(g) H2O(l)

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c) CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) _________________________ Quantitatively, the energy change associated with a phase change is found using the molar heat of fusion and the molar heat of vaporization The molar heat of fusion is the amount of heat energy(in kJ) that must be absorbed to melt 1 mole of a substance, or the amount of heat released when 1 mole of a substance freezes The molar heat of vaporization is the amount of heat energy(in kJ) that must be absorbed to vaporize(evaporate) 1 mole of a substance, or the amount of heat released when 1 mole of a substance condenses The three important points to remember with molar heats of fusion and vaporization are:

1) Heat of fusion is used with melting and freezing; heat of vaporization is used with evaporating and condensing 2) Each substance has its own heat of fusion and heat of vaporization The heat of fusion of water is different than the heat of fusion of pudding 3) The heats of fusion and vaporization and fusion are the number of kJ for every one mole of the substance: if there is more or less than 1 mole, this must be taken into account Substance Water, H2O Butane, C6H6 Ethanol, C2H5OH Oxygen, O2 Heat of Fusion 6.02 kJ/mol 5.0 kJ/mol 5.02 kJ/mol 0.22 kJ/mol Heat of Vaporization 40.7 kJ/mol 24.0 kJ/mol 38.56 kJ/mol 3.41 kJ/mol

SAMPLE EXERCISE 1: What quantity of energy is needed to melt 500.0 grams of ice, H2O(l)?

SAMPLE EXERCISE 2: How much heat is given off when 37.0 g of C6H6(g) is converted to C6H6(l)?

Chapters 12: Phase Changes and Equilibrium

Section 2: Phase Changes The phase of a sample of matter(solid, liquid, gas) depends in part on the relationship between kinetic energy

What happens to a sample of H2O when the temperature reaches 0C(at a pressure of 1 atm)?

What happens to a sample of H2O when the temperature reaches 100C(at a pressure of 1 atm)?

From this, it is seen that at the temperature of the phase change, the two phases exist in dynamic equilibrium Dynamic equilibrium exists when two opposite processes occur at identical rates At a constant temperature(and pressure of 1 atm)) of 0C, H2O is melting and freezing at the same rate

H2O(s) + heat energy H2O(l) H2O(l) H2O(l) + heat energy So while ice is constantly melting, and water is constantly freezing, the amount of each remains constant H2O(s) + heat energy H2O(l) At a constant temperature(and pressure of 1 atm) of 100C, H2O is evaporating and condensing at the same rate

H2O(l) + heat energy H2O(g) H2O(g) H2O(l) + heat energy

So while water is constantly evaporating, and steam is constantly condensing, the amount of each remains constant H2O(l) + heat energy H2O(g)

Equilibrium is a part of all virtually every chemical process; at some point in a reaction, a dynamic equilibrium is reached in which the rate of the forward process equals the rate of the reverse reaction

Chapters 12: Phase Changes and Equilibrium

Section 3: Mathematics of Phase Changes II This gives a way to calculate the amount of energy involved in, for example, the melting of 25.00 g of ice, H2O(s) But think about what would need to happen if this sample of ice is initially at a temperature of -10.00C Would the energy initially added to the ice cause the ice to melt? Therefore, to calculate the energy needed to melt 25.00 grams of ice that had an initial temperature of -10.00C, it is also necessary to calculate the amount of energy needed to get the ice to its melting point at 0.00C Unless told otherwise, it is always assumed that the temperature for a phase change is the normal(at 1 atm) temperature for that phase change To help organize and plan the work for these questions, heating curves and cooling curves are very helpful

 To see how this works, consider the amount of energy needed to take 25.00 grams of ice, H2O(s) and melt it all. That is, convert it all to H2O(l). H2O(s) <---> H2O(l)

Heat of Vaporization, H2O: 40.67 kJ/mol Heat of Fusion, H2O Specific Heat, H2O(s) Specific Heat, H2O(l) Specific Heat, H2O(g) : 6.008 kJ/mol : 2.092 J/gK : 4.184 J/gK : 1.841 J/gK

Note the specific heat(c) also depends on the phase of a substance SAMPLE EXERCISE 1: Calculate the enthalpy change upon converting 18.02 grams of ice at -25.0C to water vapor(steam) at 125C under a constant pressure of 1 atm.

56.0 kJ or 56,000 J

SAMPLE EXERCISE 2 : What is the energy change during the process in which 100.0 g of water at 50.0C is cooled to ice at -30.0C? Is this an endothermic or exothermic process?

60.6 kJ or 60,600 J

Chapters 12: Phase Changes and Equilibrium

Section 4: Vapor Pressure and Vapor Pressure Diagrams Imagine, if you will, a sealed bottle of water: what are the H2O(l) molecules at the surface of the liquid constantly doing? How will this cause the pressure inside the bottle do change?

When this dynamic equilibrium has been reached, the constant pressure inside the bottle is known as the equilibrium vapor pressure, although it is more commonly just called vapor pressure Vapor pressure is normally defined as the pressure exerted by a vapor in equilibrium with its liquid or solid phase

 In the chart above, the curves represent the vapor pressures of various liquids-------------------------------------------------------------------------------------------------------------------------------------------------------------------------- Answer the following questions based on the vapor pressure diagram above: 1) What is the relationship between temperature and vapor pressure?

2) What is the relationship between atmospheric pressure and the vapor pressure of the liquid at the liquids boiling point?

3) What is the normal boiling point(boiling point at 1 atm) for diethyl ether? For ethyl alcohol?

4) Which of these three substances has the strongest intermolecular forces? Which has the weakest? Middle?

Chapters 12: Phase Changes and Equilibrium

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Section 5: Phase Diagrams

Shown above is the phase diagram for water; this shows the characteristic appearance of a phase diagram All phase diagrams have essentially the same appearance, with only a few small differences In looking at the graph, what conditions determine the phase(solid, liquid, or gas) of a substance?

So when it is said water boils at 100C, is this always true?

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 Notice the diagram is separated into three regions; each of these regions represents one of the phases of matter Which region goes with which phase?

The same phase goes with the same region in every single phase diagram you will ever see Water at 0.5 atm and -20C would be at what phase?

Water at 0.5 atm and 50C would be at what phase?

So water at 0.5 atm and -20C would undergo what phase change when the pressure remains unchanged and the temperature increases to 50C? The lines between the phases regions show the pressure and temperature conditions at which a given phase change will occur 12

 At any set of temperature and pressure data that are a point along a line, this is where a phase change occurs, and the two phases exist in equilibrium What happens where all three of these line segments come together? The other point to be aware of is the critical point: this point represents the critical temperature and the critical pressure Beyond the critical point, the liquid and the gas phases are indistinguishable Critical temperature is the highest possible temperature at which a substance can still be a liquid The critical pressure is the pressure at the critical temperature

SAMPLE EXERCISE: Describe any changes in the phases present when H2O is kept at 1000C while the pressure is increased from 6.0 x 10-3 atm to 10 atm.

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