Law of mass action

0 Consider the reaction

A+B C+D 0 A/B reactants C/D products 0 Indicates that the reaction is reversible and can reach equilibrium 0 At constant temperature the rate of a reaction is proportional to the active mass of the reactants (mol/L)

A+B

C+D

0 Therefore we can write an expression for the

equilibrium constant Keq = [products] [reactants] Keq = [C][D] [A][B] 0 Activity of a substance refers to the effective concentration of that substance 0 In dilute solutions activity is considered to be almost equal to concentration hence concentration will be used

0 According to the law of mass action:

At equilibrium the product of the concentrations of the products divided by the product of the concentrations of the reactants is a constant known as the equilibrium constant 0 If the concentration of at least one other component is changed then the concentration of another one also changes 0 This is in order to meet the conditions of the equilibrium as defined by Keq

0 Consider the reaction between ethanoic acid and

ethanol 0 Write the reaction moles CH3COOH + C2H5OH CH3COOC2H5 + H20 Initial a b Change -x -x +x +x Final a-x b-x x x 0 If the total volume of the mixture is V litres then concentration is: CH3COOH = (a-x)/V mol/L C2H5OH = (b-x)/V mol/L CH3COOC2H5 = x/V mol/L H20 = x/V mol/L 0 Substitute into the equilibrium expression

Oswalds Dilution law

0 Provides a relationship between the dissociation

constant and the degree of dissociation for a weak acid 0 Describes the equilibrium for a weak electrolyte using the mass law 0 The degree of dissociation of a weak acid is the fraction of the no. of moles of the acid that are converted into ions

0 Consider the dissociation of 1 mole of the weak

electrolyte HA moles HA Initial 1 Change - Final 1- 0 Concentrations: HA = (1-)/V mol/L H+ = /V mol/L A- = /V mol/L

H+ +

A+

Using the law of mass action to write an expression for the dissociation constant: K = [H+][A-] [HA] K=x (1-)V 0 For weak electrolytes only little dissociation occurs 0 Therefore (1-) becomes approximately equal to 1 K=x = 2 (1-)V 1V = (K.V)

0 Therefore as long as the value of K remains constant

(at constant temperature) then the value of the dissociation constant is proportional to V 0 For the same number of moles, an increase in V implies that the solution is more dilute 0 This law can not be applied to strong electrolytes 0 Strong electrolytes completely ionise in aqueous solutions

0 Example: 0 Calculate the degree of dissociation for a 0.1 M

solution of ethanoic acid given that Ka = 1.7x10-5 M and the total volume is 10 L. 0 Solution: CH3COOH <==> H+ + CH3COOH Mols at equi. 1-x x x Applying Ostwalds dilution law x = (1.7x10-5 x 10) = 0.013 mols 0 Initial number of moles = MV = 0.1 mol/L x 10 L = 1 mol 0 Degree of dissociation = (0.013 / 1) x 100 = 1.3%

0 Example: The concentration of H+ ions in 0.10 M

solution of a weak acid is 1.0 10-5 mol/L. Calculate the dissociation constant of the acid. 0 Solution: HA <==> H+ + AConcentration (mol/L) Initial 0.1 0 0 Equilibrium (0.1-1.010-5) 1.010-5 1.010-5 0 [HA] can be taken as 0.1 M as 1.0 10-5 is very small. 0 Applying law of mass action. 0 K = [H+][A-]/[HA] = (1.010-5) 1.0 10-5/0.10 = 1 10-9

Ion product of water

0 Water is a weak electrolyte and is capable of

dissociating slightly to form H+ and OH- ions 2H2O H3O+ + OHH2O H+ + OH0 Using the second reaction Keq is written as: Keq = [H+][OH-] [H2O] 0 Experimental evidence has shown that Keq at 25C is 1.8x10-16 mol/L

0 Since only a few molecules of water dissociate, the

concentration of H2O is considered as constant 0 Pure water has a concentration of 1000 g/L 0 Therefore in pure H2O [H2O] = (1000 g/L)/ 18 g/mol = 55.5 mol/L Keq = [H+][OH-] [H2O] Keq[H2O] = [H+][OH-] *constant [H2O] Kw = [H+][OH-] Kw = 1.8x10-16 mol/L x 55.5 mol/L = [H+][OH-] Kw = 1x10-14 = [H+][OH-] Kw is the ion product of water

0 Therefore in pure water [H+] and [OH-] can be

calculated using: [H+][OH-] = 1x10-14 x2 = 1x10-14 x = 1x10-7 M 0 Note [H+] and [OH-] are reciprocally related 0 A high concentration of one implies a low concentration of the other

pH
0 Concentrations of [H+] are usually very low 0 Need a convenient way of expressing the [H+] 0 Introduce log10 to simplify the expression

pH = -log [H+] 0 pH is a logarithmic function 0 If pH decreases by 1 unit (i.e from 5 to 4) then the [H+] has increased tenfold (from 10-5 to 10-4) 0 An increase in pH would therefore mean a reduction in the [H+] pH < 7 is acidic pH = 7 is neutral pH > 7 is basic

0 Example:

Calculate the pH of a solution having a [H+] of 6.28x10-6 mol/L. 0 Solution: pH = -log [H+] pH = -log (6.28x10-6) pH = 5.20

0 Recall

[H+][OH-] = 1x10-14 0 Taking log at both sides log[H+] + log[OH-] = log (1x10-14) = -14 0 Then multiply through by -1 -log[H+] (log[OH-]) = 14 This simplifies to pH + pOH = 14

0 Example:

Calculate the pH of a 0.1M solution of NaOH 0 Solution: Complete dissociation NaOH Na+ + OH[OH-] = [NaOH] = 0.1M pOH = -log [OH-] pOH = -log (0.1) = 1 Using H + pOH = 14 pH = 14 pOH pH= 14 -1 = 13