Chemical equilibrium..

GENERAL CONCEPTS OF EQUILIBRIUM

The state in which both reactants and products are present at conc. which have no further tendency to change with time.

Progress of a chemical reaction

The rate of the forward reaction diminishes with time, while that of the backward reaction increases, until they are equal. A large K means the reaction lies far to the right at equilibrium. A + B <=> C + D

Standard State

The concentrations of solutes should expressed as moles per liter. The concentrations of gases should be expressed in atmospheres. The concentrations of pure solids, pure liquids, and solvents are omitted because they are unity.

Chemical Equilibrium
At equilibrium, Concentration of components do not change. Temperature and pressure do not change. Rate of forward rxn. = rate of backward rxn. Reactions happen on microscopic scale.
5

Chemical Equilibrium

Basic concept: aA + bB
k1 k1

Cc

+ Dd

At equilibrium;
K = k1

k1 [A]a [B]b = k1 [C]c [D]d

= [C]c [D]d [A]a [B]b
6

k1

2013/2014

Manipulating Equilibrium Constants

HA H+ + AK1 = [H+ ] [A-] [HA]

Stepwise Dissociation
A2B + 2B A + AB K1 = [A] [AB]2 [A2B] K2 = [A] [B] [AB]

AB A + B

H+ + A- HA
K1 = [HA] [H+ ] [A-] K'1 = 1/K1
7

OVERALL: A2B 2A + B Keq = [A]2 [B] = K1 x K2 = [A] [AB]2 x [A] [B] [A2B] [A2B] [AB]
8

Types of Equilibria
Equilibrium Acid-base dissociation Solubility Complex formation Reductionoxidation Phase distribution Reaction HA + H2O = H3O+ + AMX = Mn+ + XnMn+ + aLb- = MLa(n-ab)+ Ared + Box = Aox + Bred Equilibrium Constant Ka, acidity constant Ksp, solubility product Kf, formation constant Keq, reaction equilibrium constant KD, distribution coefficient

Equilibrium constants
Acid-base Equilibrium
2H2O H3O+ + OHK = [H3O+] [OH-] [H2O] KW = [H3O+] [OH-] , [H2O] 1
Kw = Ion solubility constant
9 10

AH20 = Aorganic

Cont
Weak Acid
CH3COOH + H2O

Cont
Weak base
NH3 + H2O NH4+ + OHK = [OH-] [NH4+] [NH3] [H2O] Kb = [OH-] [NH4+] [NH3]

Precipitate Equilibrium
BaSO4(p) Ba2+ (ak) + SO42-(ak) Ksp = [Ba 2+ ] [SO42- ] [BaSO4 ]

H3O + CH3COO-

K = [H3O+] [CH3COO-] [CH3COOH] [H2O] Ka = [H3O+] [CH3COO-] [CH3COOH]

[AB2 ] 1

Ka= Acid dissociation constant Kb=Base dissociation constant

11

Ksp= Solubility product

12

2013/2014

Cont
Complexometri Equilibrium
Cu2+ + 4NH3 Kf = Cu(NH3)4 2+

Cont
Redox Equilibrium
5 Fe2+ + MnO4- + 8H3O+ K eq = 5 Fe3+ + Mn2+ + 12H2O

[Cu(NH3)4 2+] [Cu2+] [NH3]4

[Fe3+ ]5 [Mn2+ ] [Fe2+ ] 5 [MnO4-] [H3O+ ]8

, [H2O] 1

Kf = Complex formation constant

Keq= redox reaction equilibrium constant

13

14

Example :

Cont

Calculate the equilibrium constant for the reaction : 2A + B C + 3D the following information is given : R1: A+BD K1 = 0.40 R2: A + E C + D + F K2 = 0.10 R3: C+EB K3 = 2.0 R4: F+CD+B K4 = 5.0
15

R1 + R2 R3 + R4 R3 is reversed R5 B C + E K5 = 1/K3 = 0.50 The overall reaction is R1 + R2 + R5 + R4 and Keq = K1 x K2 x K5 x K4 = 0.10

16

Le Chteliers Principle

Calculation Using Equilibrium Constants

Equilibrium concentration of reactants & products can be altered by applying stress to the system. The effect of such changes can be predicted from Le Chteliers Principle. Stress : ~ temperature (heat increases endothermic to right) ~ pressure (pressure increases reduction in volume) ~ concentration (do not affect equilibrium constant) ~ catalyst (do not affect equilibrium constant) For quantitative analysis, equilibria should be at least 99.9% to the right for precise measurements.
17

Example : A+B C+D , K = 0.30 Assume 0.20 mol of A and 0.50 mol B are dissolved in 1.00 L, and the reaction proceeds. Calculate the [ ] of reactants and product at equilibrium. Answer : [A] initial = 0.20M [B] initial = 0.50M K = [C][D] / [A-x][B-x] 0.30= (x)(x) / (0.20-x)(0.50-x) x2 = (0.30)(0.10-0.20x-0.50x+ x2) x2 = 0.030-0.21x+0.30 x2 0 = 0.70 x2 +0.21x-0.030 0 = ax2 + bx c ~Quadratic equation

18

18

2013/2014

Cont
0 = x = = = ax2 + bx c ~Quadratic equation -b (b2 4ac) 2a -0.21 {0.21-4(0.70)(-0.030)} 2(0.70) 0.11M

Cont
In most reactions of analytical interest, the K are large and the equilibrium lies far to the right. If K is very large, the concentration of reactants are very small compared to product concentration. Example with large K : A+B C+D , K = 2.0 x 1016 Assume 0.20 mol of A and 0.50 mol B are dissolved in 1.00 L, and the reaction proceeds. Calculate the concentration of reactants and product at equilibrium.
20

At equilibrium, [A] = 0.20 0.11 = 0.09M [B] = 0.50 0.11 = 0.39M [C] = [D] = 0.11M
19

19

20

Cont
Answer : B is added in excess, at equilibrium, the concentration of A will be the smallest among the reactants and products. Assume that at equilibrium, the [A] = x At equilibrium, [A] = [B] = [C] = [D] =

Cont
At equilibrium, all of A is converted to a like amount of C & D, except for a small amount of x. x will be very small compared to 0.20 & 0.30 and can be neglected, so [A] = x [B] = 0.30 M [C] = 0.20 M [D] = 0.20 M K = (0.20)(0.20) / (x)(0.30) 2.0 x 1016 = 0.04 / 0.30x x = 6.7 x 10-18 M
21

x 0.30 + x 0.20 x 0.20 x

21

22

Cont

Cont
Answer : At equilibrium, [AB] = [A] = [B] = K = 3.0 x 10-6 = x = 0.10 x x x (x)(x) / 0.10 x2 / 0.10 5.5 x 10-4 M 0.10

If K is very small, the concentration of products are very small compared to reactants concentration at equilibrium which is not desired in analytical reaction. Example with small K : AB A+B , K = 3.0 x 10-6 Calculate the equilibrium concentrations of A and B in a 0.10M solution of a weak electrolyte AB

Thus, [A] = [B] = 5.5 x 10-4 M

23 24

23

2013/2014

25

2013/2014