School of Chemistry
Chemistry 1A
(CHEM1111)
Tutorial 10 (Week 10): Equilibrium
Model 1: The Equilibrium Constant
Many chemical reactions lead to a mixture of reactants and products. You will end up with a mixture
of both NO2(g) and N2O4(g) whether you start with pure NO2(g) or pure N2O4(g). Such reactions are
said to reach an equilibrium in which the amount of each substance does not change.
Consider a reaction such as that below which has been left long enough to reach equilibrium.
wW(g) + xX(g) yY(g) + zZ(g)
The equilibrium constant in terms of concentrations, Kc, is a constant at a given temperature that
defines how much of each substance there will be at equilibrium:
[Y(g)]𝑦𝑦 [Z(g)]𝑧𝑧
Kc =
[W(g)]𝑤𝑤 [X(g)]𝑥𝑥
If Kc > 1, the mixture will contain more of the substances on the right hand side (Y and Z) of the
equation.
If Kc < 1, the mixture will contain more of the substances on the left hand side (W and Z) of the
equation.
Previously, you studied the thermodynamics of the equilibrium between NO2 and its dimer N2O4.
Starting from NO2, the formation of the dimer can be studied using one of the two equations below:
2NO2(g) N2O4(g) (A)
NO2(g) ½ N2O4(g) (B)
Starting from the dimer, the formation of NO2 can be studied using one of the two equations below:
N2O4(g) 2NO2(g) (C)
½ N2O4(g ) NO2(g) (D)
Critical thinking questions
1. Write down the expression for Kc for reactions A, B, C and D in Model 1.
[N2O4]
[N2O4]^1/2 [NO2]^2 [NO]^2
Kc (A) = Kc (B) = Kc (C) = Kc (D) = [N2O4]^1/2
[NO2] N2O4
[NO2]^2
2. Looking at the equations in Q1, what is the mathematical relationship between the different forms
of Kc?
(a) Kc (A) and Kc (B) (b) Kc (A) and Kc (C)
B is the square root of A. C is the inverse of A.
3. At equilibrium at room temperature, [NO2(g)] = 1.60 M and [N2O4] = 0.20 M. Calculate the
values of Kc(A) and Kc(B) and Kc(C) and hence confirm your analysis in Q2.
Kc(A) =
Model 2: The Reaction Quotient
The reaction quotient, Qc, for a reaction wW(g) + xX(g) yY(g) + zZ(g), is defined as follows:
[Y(g)]𝑦𝑦 [Z(g)]𝑧𝑧
Qc =
[W(g)]𝑤𝑤 [X(g)]𝑥𝑥
It looks similar to the equilibrium constant expression. The difference is that Qc can be calculated at
any time during a reaction or if a reaction is disturbed. It is used to predict the direction in which a
reaction will move.
Critical thinking questions
Consider the reaction 2NO2(g) N2O4(g) to be at equilibrium with [NO2(g)] = 1.60 M, [N2O4] =
0.20 M and Kc = 0.078.
1. Predict qualitatively what will happen to this reaction if more NO2 is added so that [NO2(g)] =
2.00 M?
The equilibrium will shift in favour of the forward reaction to oppose the increase [NO2].
2. Predict qualitatively what will happen to this reaction if instead NO2 is removed so that [NO2(g)] =
1.00 M?
The equilibrium will shift in favour of the reverse reaction to oppose the decrease in [NO2] and restore equilibrium.
3. Calculate the values for Qc for these two experiments.
(a) [NO2(g)] = 2.00 M and [N2O4] = 0.20 M: Qc = 0.05
(b) [NO2(g)] = 1.00 M and [N2O4] = 0.20 M: Qc = 0.2
4. Using your answers to Q1 - 3, what in general happens to a reaction if
(a) Qc < Kc The system shifts in favour of the products.
(b) Qc > Kc The system shifts in favour of the reactants.
Model 3: Equilibrium calculations
Model 2 gives you the tools to predict the direction in which a reaction will move if it is not at
equilibrium. The concentrations that will be obtained when equilibrium is finally reached can be
calculated using an ICE table: initial-change-equilibrium.
Consider the starting mixture in Q1 of Model 2: [NO2(g)] = 2.00 M and [N2O4(g)] = 0.20 M. These are
the initial concentrations and are written in the first row of the reaction table below. You know from
Model 2 that this reaction will shift so that some NO2(g) reacts to make N2O4(g). We do not know how
much will react but we can calculate it:
2NO2(g) N2O4(g)
initial 2.00 0.20
change -2x +x
equilibrium 2-2x 0.20 + x
Critical thinking questions
1. From the chemical equation: every time one N2O4 molecule is formed, two NO2 molecules are
lost. If [N2O4(g)] increases by x to reach equilibrium, what will the change in [NO2(g)] be? Add
this change to the second row of the table. (Hint: is the change positive or negative?).
2. Complete the third row of the table.
3. Substitute the equilibrium concentrations from the third row into your expression for Kc(A) from
Q1 in Model 1.
Kc = [N2O4]/[NO2]^2 = (0.20+x)/(2.0-2x)^2
4. You now have a mathematical expression to solve for x. Using Kc = 0.078. solve for x and
hence work out the equilibrium values of [NO2(g)] and [N2O4(g)].
(0.20+x)/(2.0-2x)^2=0.078
0.20 + x = 0.078(4 - 8x + 4x^2)
0.312x^2 -1.624x + 0.112 = 0
x = 5.135... or x = 0.0699...
x<2
Therefore x = 0.070molL-1
[NO2] = 1.9 molL-1
[N2O4] = 0.27 molL-1
Example exam question:
Marks
• Consider the following reaction. 4
N2O4(g) 2NO2(g)
An equilibrium mixture in a 1.00 L container is found to contain [N2O4] = 1.00 M and [NO2] =
0.46 M. The vessel is then compressed to half its original volume while the temperature is
kept constant. Calculate the concentration [N2O4] when the compressed system has come
to equilibrium. Show all working.
Kp = [NO2]^2/[N2O4] = (0.46)^2/1 = 0.212
After compression:
Qp = [NO2]^2/[N2O4]
Qp = (0.92)^2/2
Qp = 0.423 > Kp, therefore equilibrium shifts in favour of reactants
N2O4 NO2
I 2.00 0.92
C 2.00 + x 0.92 - 2x
E
Kc = [NO2]^2/[N2O4] = 0.212
(0.92 - 2x)^2/(2 + x) = 0.212
4x^2 -3.68x + 0.8464 = 0.212x + 0.424
4x^2 - 3.892x + 0.4224 = 0
x = 0.849 or x = 0.124
2x < 0.92
Therefore x = 0.124
Therefore [N2O4] = 2.124 molL-1
Model 4: Enthalpy (ΔrxnH) and Entropy (ΔrxnS) of Reaction
In Model 3 in week 9, you developed a way of working out the value of enthalpy change for any
reaction from the values of the enthalpies of formation of the reactants and products:
ΔrxnH° = ΔfH° (products) – ΔfH° (reactants) (1)
The change in entropy in a reaction can similarly be calculated as the difference in the entropies of
the reactants and products:
ΔrxnS° = S° (products) – S° (reactants) (2)
Critical thinking questions
1. Using the data below, calculate ΔrxnH° and ΔrxnS° for reaction A in Model 1.
ΔfH°: NO2(g), 33 kJ mol-1, N2O4(g) 9 kJ mol-1. S°: NO2(g), 240 J K-1 mol-1, N2O4(g) 304 J K-1
mol-1
ΔrxnH = 9 - 33x2 ΔrxnS = 304 - 240 x 2
= -57 kJmol-1 = -176 JK-1mol-1
2. Explain in words the origin of the sign of ΔrxnH° and ΔrxnS° in terms of the chemical changes in
the reaction.
ΔH<0, denoting a decrease in enthalpy as a result of the reaction. As such, the reaction is an exothermic process
which leads to a loss of enthalpy in the system. Conversely, the negative ΔS implies a decrease in entropy, due
to the two molecules of NO2 reacting to form one molecule of N2O4, decreasing the net disorder of the system.
3. Calculate ΔrxnH° and ΔrxnS° for reaction B in Model 1. How are these values related to your
answer to Q1?
ΔrxnH = 0.5 x 9 - 33 ΔrxnS = 0.5 x 304 - 240
= -28.5 kJmol-1 = -88 JK-1mol-1
(half of value from question 1) (half of value from question 1)
4. Calculate ΔrxnH° and ΔrxnS° for reaction C in Model 1and explain in words the origin of the sign
of ΔrxnH° and ΔrxnS° in terms of the chemical changes in the reaction.
ΔrxnH = 2 x 33 - 9 There is a net increase in enthalpy in the reaction as it is an endothermic process.
= 57 kJmol-1 In addition, there is an increase in entropy during the reaction as one N2O4 molecule
reacts to form two NO2 molecules.
ΔrxnS = 240 x 2 - 304
= 176 JK-1mol-1
5. What are the values of ΔrxnH° and ΔrxnS° for reaction D in Model 1?
ΔH = 33 - 0.5 x 9
= 28.5 kJmol-1
ΔS = 240 - 0.5 x 304
= 88 JK-1mol-1