CHEMICAL EQUILIBRIA

Compiled by
Dr. L. Coo

When a chemical reaction takes place in a container which prevents the entry or escape of any of the substances involved in the reaction, the quantities of these components change as some are consumed and others are formed. Eventually this change will come to an end, after which the composition will remain unchanged as long as the system remains undisturbed. The system is then said to be in its equilibrium state, or more simply, "at equilibrium".

In a chemical process, chemical equilibrium is the state in which the chemical activities or concentrations of the reactants and products have no net change over time. Usually, this would be the state that results when the forward chemical process proceeds at the same rate as their reverse reaction. The reaction rates of the forward and reverse reactions are generally not zero but, being equal, there are no net changes in any of the reactant or product concentrations. This process is called dynamic equilibrium.

In principle, all chemical reactions are reversible,

If the equilibrium state is one in which significant quantities of both reactants and products are present (as in the hydrogen iodide example given in the previous slide), then the reaction is said to be reversible.

Guldberg and Waage showed that the rate of the reaction in either direction is proportional to what they called the "active masses" of the various components: in which the proportionality constants k are called rate constants and the quantities in square brackets represent concentrations. If we combine the two reactants A and B, the forward reaction starts immediately; then, as the products C and D begin to build up, the reverse process gets underway. As the reaction proceeds, the rate of the forward reaction diminishes while that of the reverse reaction increases. Eventually the two processes are proceeding at the same rate, and the reaction is at equilibrium: If we now change the composition of the system by adding some C or withdrawing some A (thus changing their "active masses"), the reverse rate will exceed the forward rate and a change in composition will occur until a new equilibrium composition is achieved. The Law of Mass Action is thus essentially the statement that the equilibrium composition of a reaction mixture can vary according to the quantities of components that are present. This of course is just what Berthollet observed in his Egyptian salt ponds, but we now understand it to be a consequence of the dynamic nature of chemical equilibrium.

 How do we know when a reaction is at equilibrium?

According to the Law of Mass Action, for a reversible reaction at equilibrium and at constant temperature, a certain ratio of reactant and product concentrations (when each term raised to the power of its coefficient in the equilibrium reaction) has a constant value, K.

Kc = equilibrium constant, unitless [A], [B], [C], [P], [Q], [R] = equilibrium molar conc

K, equilibrium constant
The value of which at any temp does not depend on the initial concentration of the reactant and products The value varies with temperature

Homogeneous equilibrium

Homogeneous equilibrium
Reversible rxns wherein all reacting species are in the same phase.

Kp

2SO3 2SO2 O2

1. PCl5(g)

PCl3(g) + Cl2(g) COCl2(g) 2NH3(g) 2HI(g)

Kc = [PCl3][Cl2] [PCl5] Kc = [COCl] [CO][Cl2] [NH3]2 [N2][H2]3 [HI]2 [H2][I2]

2. CO(g) + Cl2(g) 3. N2(g) + 3H2(g) 4. H2(g) + I2(g) 5. H3PO4(aq)

Kc =

Kc =

3H+(aq) + PO3-4(aq)

Kc = [H+]3[PO43-] [H3PO4]

Kp = Kc(RT)

n = moles of gaseous products moles of gaseous reactants R = gas constant, 0.0821 L-atm/mol-K T= absolute temp, Kelvin

Express the equilib constant in terms of Kp, in terms of Kc of the following equilibria.
1. 2. 3. 4. N2(g) + 3H2(g) CO(g) + Cl2(g) PCl5(g) 2NH3(g) COCl2(g)

PCl3(g) + Cl2(g) 2HI(g)

H2(g) + I2(g)

Heterogeneous equilibria

Heterogeneous equilibria
Reversible rxns involving reactants and products that are in different phases. Ex: CaO(s) + CO(2)(g) 1. CaCO3(s) 2. P4(s) + 6Cl2(g) 4PCl3(l)

Neither solids nor liquids are significantly affected by changes in pressure. For any pure solid or pure liquid, the activity (concentration) is taken as 1 so that terms for these species do not appear in the K expressions for heterogeneous equilibria.

P4(s) + 6Cl2(g) 4PCl3(l) Kc = 1 [Cl2]6

2H2O(l) H3O+(aq) + OH-(aq) Kc = [H3O+][OH-]

Multiple Equilibria
A chemical system in which the product molecules in one equilibrium system are involved in a second equilibrium process. A+B C+D C+D E+F

If a rxn can be expressed as the sum of two or more rxns, the equilib constant for the overall rxn is given by the product of the equilib constants of the individual rxns. A+B C+D A+B C+D E+F E+F Kc Kc Kc

overall rxn :

Kc = Kc x Kc

K and the equilibrium eqn

1. when the eqn for a reversible rxn is written in the opposite direction, the equilib constant,K becomes the reciprocal of the original K. 2NH3 K = 54 3H2 + N2 K = 1 = 1 = 0.19 2NH3 3H2 + N2 K 54

2. The value of K depends on how the equilib equation is balanced. 3H2 + N2 6H2 + 2N2 3/2H2 + 1/2N2 2NH3 K

4NH3 K = K2 NH3 K = K1/2

Magnitude of Equilib constants

K values vary from very large to very small Sometimes, knowing only the magnitude of the equilibrium constant, it is possible to decide on the feasibility of a rxn. Magnitude of Kc = a measure of the extent to which reactions occurs.

NH3(g) + H2O(l) Au+(aq) + 2CN-(aq) Cl2(g) PbC2O4(s)

-

NH4+(aq) + OH-(aq) [Au(CN)2]-(aq)

Kc = 1.8 x 10-5 Kc = 2.0 x 1038 Kp = 5.6 x 10-7 Kc = 1.0 x 10-18 Kc = 1.0 x 107 Kc 1.0 x 10-25

2Cl(g) Pb2+(aq) + C2O42-(aq) H2S(aq) 3Ca2+(aq) + 2PO43-(aq)

HS-(aq) + H+(aq) Ca3(PO4)2(s)

Possible method of fixing atmospheric N2 (converting it to a cpd) N2(g) + O2(g) 2 NO(g) K = 2NO = 1.1 x 10-30, 25oC N2O2 N2(g) + 3H2(g) 2NH3(g) K = 2NH3 = 6.0 x 105, 25oC N23H2

Other characteristics of K
Temperature dependent __________________
2NO2(g)
[N2O4]i [NO2]i 1 2 3 4 0 0 0.1178 0.2009 0.1200 0.1300 0.1351 0

N2O4(g)
[N2O4]eq [NO2]eq 0.00140 0.00280 0.00312 0.00452 0.0814 0.1152 0.1216 0.1463 Kc 0.211 0.211 0.211 0.212

Prodn of NH3 by Haber process (% NH3)

TempoC 200 atm 400 450 500 600 38.7 27.4 18.9 88 300 atm 47.8 35.9 26.0 12.9 400 atm 54.9 42.9 32.2 16.9 500 atm 60.6 48.8 37.8 20.8

10

Factors affecting Equilibrium

Le Chateliers Principle:
If a system at equilib is disturbed by a change in temperature, pressure or the concentration of one of the components, the system will shift its equilibrium position so as to counteract the effect of the disturbance.

1. Change in reactant or product concentrations

If a substance (either a reactant or product) is added, the rxn will shift to the direction so as to reestablish equilib by consuming part of the added substance. Conversely, removal of a substance will result in the reaction moving in the direction that forms more of the substance

3H2(g) + N2(g)

2NH3(g)

Addition of H2 into the system Removal of N2 Addition of NH3

11

2. Change of Pressure (volume)

(Decrease in volume = Increase in pressure)

Reducing the volume of a gaseous equilibrium mixture causes the system to shift in the direction that reduces the number of moles of gas. Conversely, increasing the volume causes a shift in the direction that produces more gas molecules.
A system can reduce its pressure by reducing the total number of gas molecules

3H2(g) + N2(g)
Increase pressure Increase volume

2NH3(g)

3. Change in Temperature
Treat heat as if it were a chemical reagent

products Endothermic: Reactants + heat Exothermic: Reactants products + heat When heat is added to the system, the equilibrium shifts in the direction that absorbs (or use up) heat.

12

Cooling equilib system:

Has opposite effects of heating.

4. Addition of catalyst
A catalyst increases the rate at which equilibrium is achieved, but it does not change the composition of the equilibrium mixture.

The reaction between hydrogen and iodine at 700K is described by the equilibrium: H2(g) + I2(g) 2HI(g)

In a certain experiment at 700 K, the various concentrations at equilibrium were found to be [H2] = 1.84 x 10-3 mol/L [I2] = 3.13 x 10-3 mol/L [HI] = 17.7 x 10-3 mol/L Calculate Kc for this equilibrium at 700K.

13

Calculating Equilibrium constants

1. Tabulate the known initial and equilibrium concentrations of all species involve in the equilibrium reaction. 2. For those species for which both and initial equilib conc are known, calculate the change in conc that occurs as the system reaches equilib. 3. Use the stoichiometry of the rxn to calculate the changes in conc for all the other species in the equilib rxn. 4. From the initial conc and the changes in conc, calculate the equilib conc. These are used to evaluate the equilib constant.

Given the rxn: CO(g) + H2O(g)

CO2(g) + H2(g)

The system starts with 6.0 mol of CO and 7.0 mol of H2O in a 1.00L vessel. When equilib is attained, 4.5 mol of CO2 is formed. Calculate the value of Kc.

A sealed 2.00 L tube initially contains 9.84 x 10-4 mol H2 and 1.38 x 10-3 mol I2. It is kept at 350oC until the rxn; 2HI(g) H2(g) + I2(g) comes to equilibrium. At equilib, 4.73 x 10-4 mol I2 is present. Calculate Kc.

14

Given A(g) + B(g) C(g) + 2D(g) 1.00 mol of A and 0.500 mol of B are placed in a 400.0 mL container. After equilibrium has been established, 0.200 mol of C is present in the container. Calculate Kc for the rxn.

Answer

I2 (3.0 x 10-2 moles) and H2 (2.0 x 10-2 moles) were mixed in a closed 1.00 L container and heated to 700K. The equilibrium constant Kc for the reaction is 55. How many moles of HI, I2 and H2 will be present at equilibrium?

15

Solving quadratic equations: For a general quadratic equation y = x2 + bx + c, x2 + bx + c = 0 the roots of the equation (i.e., the values of x when the equation is zero, y = 0), are given by

Application of Equilibrium constant

Recall: Magnitude of K indicates the extent to which a reaction proceeds Appln: 1. Can predict the direction of the rxn to reach equilibrium. 2. Can calculate the conc of reactant and products at equilibrium.

Predict the direction in which the reaction will proceed to reach equilibrium. 2CO(g) + O2(g) 2CO2(g) K = [CO2]2 = 5.0 x 103 [CO]2[O2] [CO2]i = 0.25 M [CO]i = 0.50 M [O2]i = 0.50 M at 950K

16

2CO + O2

2CO2

Kc = 5.0x103

Using initial conc: Q = rxn quotient = (0.25)2 = 0.50 Q = [CO2]2i 2 [O ] 2(0.50) [CO] i 2 I (0.50) Q < Kc

To achieve equilib Q must equal Kc

Effect of relative value of Q and K to the direction of rxn Q > Kc rxn proceeds to the left Q < Kc rxn proceeds to the right Q = Kc rxn at equilibrium

17