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CHEMICAL EQUILIBRIUM

System. Types of systems. Reversible and irreversible processes.


System is the part of the universe being studied, while the surroundings is everything outside of the systems boundaries i.e. the rest of the universe that interacts with the system. In chemistry, the system is usually a reaction mixture in a flask (left figure) or a test tube with the content in it (right figure). In thermodynamics, systems are classified as isolated, closed and open, based on the possible transfer of matter and energy across the systems boundaries. An isolated system can exchange neither matter nor energy with its surroundings (vacuum flask). A closed system can exchange energy, but not mater with its surroundings. An example is a battery. An open system can exchange both matter and energy with the surroundings. Examples are automobile engine, the human body and an open flask in which some reaction takes place. Most chemical reactions take place in closed or open systems.

Isolated system

Closed system

Open system

As you learned in the preceding chapter, chemical processes can be irreversible and reversible. Processes in which the reaction products cannot interact to give back the initial reactants are irreversible. The amount of the reactants if are taken in stoichiometric ratio would be so small, so we may consider that reactants are consumed almost completely. The amount of the reactants is not measurable on the scale (balance). However, if one of the reactants is in excess, the other reactant will consumed completely so the amount of the reactant consumed would not be measurable quantity. When an alcohol burns in the air, liberates CO2 and H2O. C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O(g)

When the entire amount of alcohol will burn out, the process stops since there is no measurable quantity of alcohol. The reverse reaction; combination of CO2 and H2O to obtain the initial substances, does not take place globally. Actually, the reverse process takes place but insignificant number of product particles interacts to produce reactants. Anywise, most of the reactions are reversible so that we will pay more attention on the reversible reactions.

Chemical reactions, in which the reaction products interact to give back the initial reactants, are termed reversible. E.g. At 20 C two molecules of a reddish-brown gas NO2 react with each other to form one molecule of N2O4, a colorless gas. Its dimmer is not very stable and at 20 C dissociates into two molecules of NO2. 2NO2(g) N2O4(g) In every reversible reaction, two opposite processes take place at same time, written in one equation. Two opposite half arrows placed between the left and right side of the equation, express the reversibility of this reaction. The reaction, which proceeds from left to right, is termed forward while the opposite back (backward) or reverse reaction. In case of reversible reaction, there are measurable quantities of all participants present in the reaction system. Their amount can be measured on the scale.

Chemical equilibria.

During some chemical process the concentrations of present participants change over time. So that, three major questions impose (appear). How long will this change in concentration of participants last? When does the reaction finish? How do we know that the reaction is completed? The answer is - until chemical equilibrium is established. All chemical systems tend toward equilibrium, so the study of the equilibrium state naturally is one of the central topics in chemistry. Every reaction has a point in which equilibrium is established. To be in equilibrium is to be in a state of balance. Two types of equilibrium exist: physical (mechanical) and chemical. Physical equilibria: If both panes of a balance have equal masses, equilibrium is established. This equilibrium is static because both panes are at rest. Actually, no processes take place after the system reaches equilibrium. In static equilibria, an object is at rest and no processes take place after reaching equilibrium. This type of equilibrium studies the part of physics called mechanics. Chemical equilibria: For irreversible reactions, it occurs at the point when essentially all reactants are converted to products and as it usually say, reaction has gone to completion. But for reversible reactions, equilibrium occurs when only part of the reactants is converted into products. When a chemical reaction takes place, it proceeds for a period of time and then seems to stop before all the reactants are consumed. Nevertheless, the reaction does not actually stop. Instead, the reaction reaches a point of chemical equilibrium in which the reverse reaction is converting products into reactants as fast as products are formed in the forward reaction. To understand this better, let us consider the following reversible reaction. Synthesis of ammonia is described by the following equation: N2(g) + 3H2(g) 2NH3(g) Hydrogen and nitrogen vapors are mixed in a closed container at 500 C. The initial rate, f, of the reaction is high. As time passes, the reactants concentration decreases over time although the forward reaction slows down. The rate of the reverse process, r, at the beginning of the process is zero because there is no ammonia in the mixture. When the first molecules of ammonia are formed, they decomposed immediately to H2 and N2. Increasing the concentration of ammonia accelerates the reversed reaction. At a certain moment, the rate of forward and reverse reaction becomes equal. This means, as many ammonia molecules are formed in the system per unit of time, as are decomposed. Therefore, the concentrations of H2, N2 and NH3 remain constant and no longer change. It is said that the system is at equilibrium (chemical).

Frequently used definitions for equilibria: The term equilibrium represents an ultimate result occurring one chemical reaction. Chemical equilibrium is a condition in which a chemical reaction is occurring at equal rates in its forward and reverse directions, so that the concentrations of the reacting substances do not change with time. Chemical equilibrium differs from mechanical by its character. It has dynamic character. At equilibrium, when both the forward and reverse reactions take place equally fast, the concentration of every specie no longer change. The equilibrium composition remains constant over time, but this doesnt mean that H2, N2 and NH3 particles stop reacting. A contrary, synthesis and decomposition continuously occur on a microscopic level. The reaction may seem finished, but both reactions; forward and reverse occur with the same rate. This is dynamic equilibrium.
To understand the concept of static equilibrium, let us consider two children sitting on a seesaw. At balance point (i.e. equilibrium) no movements of children on the seesaw occur - static equilibrium. In case of reversible reaction, however a static equilibrium is not being established. In case of ammonia synthesis, using deuterium, D (an isotope of hydrogen) it has been proved that even at equilibrium, decomposition of ammonia into hydrogen and nitrogen and combination of hydrogen and nitrogen into ammonia continues. This equilibrium is dynamic in nature and is therefore called dynamic equilibrium. A dynamic steady state can be compared with the equilibrium of water in a reservoir, which is being simultaneously filled and discharged. If the rate of water flowing in is equal to the rate of water flowing out, the quantity of water in the reservoir will remain unchanged like the quantities of all substances in the point of chemical equilibrium. Hence, water level does not change.

The Equilibrium Constant. At equilibrium, rates of forward and reverse reaction


are equal. For the synthesis of ammonia the forward and reverse rate expressions are:
f r

= kf c(N2) c (H2) = kr c2(NH3)

for synthesis of ammonia for decomposition of ammonia

At equilibrium,

r,

so mathematically the right sides in both equations are also equal: kf c(N2) c3(H2) = kr c2(NH3)

After few math rearrangements, the rate constants appear on the left side of the equation while the concentrations of the product and reactants appear on the right side:

kf kr

c 2 ( NH3 ) c3 (H2 ) c( N2 )

Since kf and kr are constant at given temperature, their ratio is also a constant. It is called equilibrium constant in terms of concentration and denotes by Kc.

Kc

c 2 (NH3 ) c3 (H2 ) c( N2 )

Here from, equilibrium constant is defined by the ratio of products and reactants concentrations, each of them raised to its coefficient (acting as exponents).

Kc

c(product/s ) c(reactant/s)

Notice that the ratio is always written with the products over the reactants. Each concentration must be raised to the power of its stoichiometric coefficient in the equation. Because NH3 has a coefficient of 2 in above equation, its concentration must be squared in the preceding expression. Similar, the coefficient for hydrogen is 3 and it appears as an exponent. It is important to remember that only gases and aqueous phases are included in the equilibrium expression because concentrations of liquids and solids are constant. E.g. C(s) + CO2(g) 2CO(g) The equilibrium constant expression for the mentioned reaction is:

Kc
For a generalized reaction written:

c 2 (CO) c(CO2 )

Notice that the concentration of the solid carbon is not included in the Kc equation since it is a constant

aA + bB pP + rR the Kc, at constant temperature and pressure is given by:

Kc

c ( P) p c ( R ) r c(A)a c(B)b

where a, b, p, r are the stoichiometric coefficients indicating the number of moles of the reacting species whereas c(A), c(B), c(P), c(R) are the equilibrium molar concentrations of represented participants. It is important to say that the equilibrium constant expression is valid only when the reaction system reaches equilibrium. Therefore, the concentrations that appear in the Kc expression must be those found in equilibrium. From the above said, two questions are imposed; What happen if the concentration of one or more of the reactant/s is/are changed? Did the equilibrium constant change its value? Before we answered to these questions, look at the table bellow! Table shows the results of four experiments of synthesis of ammonia in a closed container at 500 C. In examine table, we can see that the initial molar concentrations of both; hydrogen, H2 and nitrogen, N2 are different. The equilibrium concentrations of both reactants at equilibrium differ as well. But if we use equilibrium concentrations to calculate Kc, we can conclude that the equilibrium constant, Kc at 500 C has the same value, regardless of the equilibrium concentrations of the reactants. In other words, the value of Kc remains constant. This means, if we add or remove some quantity of either reactant or product, the Kc shouldnt changed. Here from it follows that changing the concentration of a particular participant does not affect on the equilibrium constant, Kc. Initial Concentrations c(H2) 0,168 0,630 1,97 4,33 c(N2) 0,756 1,04 1,36 2,48 c(NH3) 0 0 0 0 Equilibrium Concentrations c(H2) 0,150 0,500 1,35 2,43 c(N2) 0,750 1,00 1,15 1,85 c(NH3) 1,23 10-2 8,66 10-2 4,12 10-1 1,27 Average Kc

c( NH3 ) 2 c( H 2 ) 3 c( N 2 )
5,98 6,00 6,00 6,08 6,00 10-2 10-2 10-2 10-2 10-2

Exercises:
Write expressions for equilibrium constant in terms of concentration (Kc), for the reactions given by these equations: a) 2PCl(g) + O2(g) 2POCl3(g) b) 2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g) c) 2NO2(g) N2O4(g) d) 2ClO (aq) Cl (aq) + ClO2 (aq) e) 2NO(g) + O2(g) 2NO2(g) Give the units for Kc. (To determine theirs units assume that the equilibrium molar concentrations of each substance is 1 mol/dm3) Solution: We compose the equilibrium constant expression by raising the molar equilibrium concentrations of each substance to a power equal to its coefficient in the balanced equation. Following the usual convention, the product appears in the numerator and the reactants in the denominator. The second reaction is an example of heterogeneous equilibrium. In this reaction, we have an equilibrium involving two gases, CO2 and H2O, and two solid phases, NaHCO3 and Na2CO3. The concentrations of the last two do not appear in the equilibrium expression, so the Kc is going to be determined by the product of carbon dioxides concentration and the concentration of the water steam. It can be notice from the examples above that Kc has different units for each reaction. It is understandable considering that for each reaction there is s different set of coefficients in the balanced equations.

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