Unit 4.

3 Chemical equilibria II
define the terms partial pressure and concentration
Partial pressure (p) Pressure gas would generate if it alone occupied the volume
Concentration Number of moles in a given volume
Homogenous equilibria All reactants and products are in the same physical state ie all are solutions or gases
Heterogenous equilibria Not all reactants and products are in the same physical state
nA + mB + xC pP + yQ [P]p[Q]y 2SO2(g) + O2(g) 2SO3(g) [SO3]2__
n m x Kc = [SO2]2[O2]
Kc = [A] [B] [C]
Equilibrium constant Kc gives POE at a specific temperature
[ ] mole concentration (moldm-3)
All substances present in the equil mixture must be included in the expression for Kc unless they are solids

Units of Kc depend on actual expression of Kc [moldm-3]2

Kc = [moldm-3]2 x [moldm-3] = [moldm-3] -1 = mol-1dm3
To determine values of Kc by experiment: Set up an equil at a given temp
Determine concs of each constituent Sub these values into the expression for the equil constant

Questions
Calculate Kc 2H2S(g) 2H2 (g) + S2 (g) H = +170 kJ mol1
0.5 mol of gaseous H2S were placed in a flask of volume 20.0 dm3 and heated until equilibrium was reached.
When equilibrium was established, there were 0.35 moles of hydrogen sulphide in the flask

H2S H2 S2
Moles initially 0.5 0 0
Number of moles at equilibrium 0.35 0.15 0.075
Concentration /20 0.0175 0.0075 0.00375

K = [0.0075]2 [0.00375]
c
-4 -3
[0.0175]2 = 6.9 x 10 mol dm

Pressure exerted by the gas/gases depends only on No of moles of gases present when:
Gas occupies a container of fixed vol At a given temp
so.(partial pressure)pressure exerted by the gas No of moles of the gas

= dissociation

Sum of all partial pressures of each gas = total pressure in the container

Partial pressure of a gas = mole fraction x total pressure

mole fraction of gas = moles of gas/total number of moles of gas in system

CaCO3(s) CaO(s) + CO2(g) Kp = p(CO2)

Equilibrium constant Kp gives POE for gaseous systems at a specific temperature

N2(g) + 3H2(g) 2NH3(g) p(NH3)2
Kp = p(H2)3p(N2)

N2O4(g) 2NO2(g) = 0.2

moles initially: 1 0
moles at equil: 1-0.2 2x0.2 Total No of moles of gas at equil: 1-0.2+0.4 = 1.2
PCl5(g) PCl3(g) + Cl2(g), Kp? p(PCl3)p(Cl2)
Kp= p(PCl5)
At temp T, PCl5 is 40% dissociated, Total pressure = 2atm, Kp?
PCl5 PCl3 + Cl2
moles initially: 1 0 0
moles at equil: 1-0.4 0.4 0.4 0.6 + 0.4 + 0.4 = 1.4
0.6 0.4
mol fraction: /1.4 /1.4 0.4/1.4
partial pressures: PCl5 = 0.6/1.4 x 2 =0.857 PCl3 =Cl2 = 0.4 /1.4 x 2 =0.571

p(PCl3)p(Cl2) (0.571)2
Kp= p(PCl5) = 0.857 = 0.381atm(3sf)
Factors affecting POE concentration pressure temp
Effect of change in conc at constant temp
nA + mB + xC pP + yQ
Increasing concentration of a reactant and POE moves to RHS.
Increasing concentration of A means more A will react with B & C giving more P & Q until equilibrium is restored.
Argument applies safely to concentration NOT amount, A + B C + D Adding more A(all gases at atmospheric
pressure)increases total vol, conc of A increases and reduces concentrations of all other species
Effect of change in pressure at constant temp
Only affects gaseous equilibria And only if there is a change in total number of molecules
Increasing pressure pushes POE towards side with smaller number of molecules
Increasing pressure moves POE to RHS in this reaction N2(g) + 3H2(g) 2NH3(g) 4 molecules 2 molecules
Effect of change in temp
When temperature increases, Kp increases
Equilibrium constant changes with a change in temp
Affects reactions which involve a H
If temperature raised in exothermic reaction, POE moves to the left & vice versa
If we were to lower the temperature, the equilibrium would shift in such a way as to produce heat (le chateliers principle -
equilibrium shifts to counter-act the imposed change)