Physical Chemistry 1

Chapter Four

Chemical Equilibrium

By
Prof. Ehab AlShamaileh

March 2020
 Physical Chemistry I Prof. Ehab AlShamaileh

4.1 Chemical equilibrium involving ideal gases

𝑎𝐴 + 𝑏𝐵 ⇌ 𝑦𝑌 + 𝑧𝑍

Ideal gases

𝑉1 𝑃2
∆𝐺 = 𝑛𝑅𝑇 ln 𝑎𝑛𝑑 ∆𝐺 = 𝑛𝑅𝑇 ln
𝑉2 𝑃1

State 1 State 2

P1 = 1 bar (Standard) P2

Go G
𝑜 + 𝑅𝑇 ln 𝑃
∆𝐺 = 𝑛𝑅𝑇 ln 𝑃2 → 𝐺 − 𝐺° = 𝑛𝑅𝑇 ln 𝑃2 → 𝐺𝑚 = 𝐺𝑚

Molar Gibbs energy is called the chemical potential

𝜇 = 𝜇° + 𝑅𝑇 ln 𝑃
 Physical Chemistry I Prof. Ehab AlShamaileh

For nA mol of A in a mixture of A, B, Y and Z

𝜕𝐺
𝜇𝐴 =
𝜕𝑛𝐴 𝑇,𝑃,𝑛𝐵 ,𝑛𝑟 …

For a chemical reaction

𝑦
𝑃𝑌 𝑃𝑍𝑧
∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝑎 𝑏
𝑃𝐴 𝑃𝐵

At equilibrium ∆𝐺 = 0

∆𝐺° = −𝑅𝑇 ln 𝐾𝑃𝑜

𝐾𝑃𝑜 = 1 → ∆𝐺° = 0

𝐾𝑃𝑜 > 1 → ∆𝐺° < 0

𝐾𝑃𝑜 < 1 → ∆𝐺° > 0

 Physical Chemistry I Prof. Ehab AlShamaileh

Pressure  concentration units

𝑛𝑅𝑇
𝑃𝑉 = 𝑛𝑅𝑇 → 𝑃 = = 𝐶 . 𝑅𝑇
𝑉

𝑦
𝑃𝑌 𝑃𝑍𝑧 𝑌 𝑦
𝑅𝑇 𝑦
𝑍 𝑧
𝑅𝑇 𝑧
𝑌 𝑦
𝑍 𝑧
∑𝜈
𝐾𝑃 = 𝑎 𝑏 = 𝑎 𝑎 𝑏 𝑏
= 𝑎 𝑏
. 𝑅𝑇
𝑃𝐴 𝑃𝐵 𝐴 𝑅𝑇 𝐵 𝑅𝑇 𝐴 𝐵

∑𝜈 = 𝑦 + 𝑧 − 𝑎 + 𝑏
∑𝜈
𝐾𝑃 = 𝐾𝐶 𝑅𝑇

∆𝐺° = −𝑅𝑇 ln 𝐾𝐶𝑜 𝐾𝐶𝑜 : 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝐾𝐶

Also, mole fractions x

∆𝐺° = −𝑅𝑇 ln 𝐾𝑥𝑜

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝐾𝑥

Units of K depend on equation

 Physical Chemistry I Prof. Ehab AlShamaileh

Example 4.1

The Gibbs energies of formation of NO2(g) and N2O4(g) are 51.30 and 102.0 kJ.mol-1,
respectively. (Standard state: 1 bar and 25 oC)

a. Calculate KP (1 bar) and KC (1 atm) for reaction 𝑁2 𝑂4 ⇌ 2𝑁𝑂2

∆𝐺° = 2∆𝐺𝑓𝑜 𝑁𝑂2 − ∆𝐺𝑓𝑜 𝑁2 𝑂4 = 2 × 51.3 − 102 = 0.6 𝑘𝐽. 𝑚𝑜𝑙 −1

∆𝐺° = −𝑅𝑇 ln 𝐾𝑃

−0.6 𝑘𝐽. 𝑚𝑜𝑙 −1

→ ln 𝐾𝑃 = = −0.242 → 𝐾𝑃 = 0.785 𝑏𝑎𝑟
8.3145 𝐽. 𝑚𝑜𝑙 −1 . 𝐾 −1 × 298.15 𝐾

∑𝜈
𝐾𝑃
𝐾𝑃 = 𝐾𝐶 𝑅𝑇 → 𝐾𝐶 = ∑𝜈
= 31.7 𝑚𝑜𝑙. 𝑚−3 = 3.17 × 10−2 𝑚𝑜𝑙. 𝑑𝑚−3 𝑀
𝑅𝑇

b. Calculate KX at 1 bar pressure

𝐾𝑃 = 𝐾𝑋 𝑃∑𝜈 ∑𝜈 = 1 → 𝐾𝑋 = 𝐾𝑃 𝑃−1 = 0.785 × 1 𝑏𝑎𝑟 −1
= 0.785
c. ∆𝐺° ? if standard state is 1 mol.dm-3
∆𝐺° = −𝑅𝑇 ln 𝐾𝐶 = −8.3415 298.15 ln 3.17 × 10−2 = 8.56 𝑘𝐽. 𝑚𝑜𝑙 −1
 Physical Chemistry I Prof. Ehab AlShamaileh

Example 4.2

𝐻2 + 𝐼4 ⇌ 2𝐻𝐼

At 731 K, 22.13 cm3 H2 is mixed with 16.18 cm3 I2. After equilibrium is established, HI of
28.98 cm3 was formed at STP. Calculate the equilibrium constant and the Gibbs energy change.

Solution

𝐻2 + 𝐼4 ⇌ 2𝐻𝐼
𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 22.13 16.18 0
𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 22.13 − 14.49 16.18 − 14.49 28.98

28.98 2
𝐾= = 65
7.64 + 1.69
∆𝐺° = −𝑅𝑇 ln 𝐾 = −8.3145 × 731 × ln 65 = −25.4 𝑘𝐽. 𝑚𝑜𝑙 −1
 Physical Chemistry I Prof. Ehab AlShamaileh

4.2 Chemical equilibrium in non-ideal gaseous systems

∆𝐺° = −𝑅𝑇 ln 𝐾𝑎𝑜

𝑦
𝑜
𝑎𝑋𝑥 𝑎𝑌
𝐾𝑎 = 𝑎 𝑏
𝑎𝐴 𝑎𝐵 𝑒𝑞

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝐾𝑎 = −𝑅𝑇 ln 𝐾𝑎𝑜 + 𝑅𝑇 ln 𝐾𝑎

4.3 Chemical equilibrium in solutions

∆𝐺 = ∆𝐺° + 𝑅𝑇 ln 𝑥1 𝑓1

𝑥1 : 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑓1 : 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡

 Physical Chemistry I Prof. Ehab AlShamaileh
Example 4.3

The equilibrium constant KC is 8.9 x 10-5 M at 25 °C for the reaction

Fructose – 1,6 – diphosphate ⇌ glyceraldehyde – 3 – phosphate + dihydroxyacetone phosphate

𝐹𝐷𝑃 ⇌ 𝐺 − 3 − 𝑃 + 𝐷𝐻𝐴𝑃

and we can assume the behavior to be ideal.

a. Calculate ∆𝐺° for the process (standard state: 1 M).

b. Suppose that we have a mixture that is initially 0.01 M in FDP and 10-5 M in both glyceraldehyde-3-
phosphate and dihydroxyacetone phosphate. What is ∆𝐺 ? In which direction will reaction occur?

Solution

a) ∆𝐺° = −𝑅𝑇 ln 𝐾° = −8.3145 × 298.15 × ln 8.9 × 10−5 = 23.12 𝑘𝐽. 𝑚𝑜𝑙−1

𝐺−3−𝑃 𝐷𝐻𝐴𝑃 10−5 ×10−5
b) ∆𝐺 = ∆𝐺° + 𝑅𝑇 ln = 23.12 + 8.3145 × 298.15 ln 10−2 = −22.54 𝑘𝐽. 𝑚𝑜𝑙 −1
𝐹𝐷𝑃

∆𝐺 < 0 rxn will go from left to right (spontaneously) (→)

10−5 ×10−5
Proof: = = 10−8 < 𝐾°
10−2
 Physical Chemistry I Prof. Ehab AlShamaileh

4.4 Heterogeneous equilibrium

Different phases

𝐶𝑎𝐶𝑂3 𝑠 ⇌ 𝐶𝑎𝑂 𝑠 + 𝐶𝑂2 𝑔

𝐶𝑎𝑂 𝐶𝑂2
𝐾𝑐∗ = = 𝐶𝑂2
𝐶𝑎𝐶𝑂3

More exactly: 𝐾𝑐 = 𝑎𝐶𝑂2

Example 4.4

The solubility of silver chloride in pure water at 25 °C is 1.265 x 10-5 mol.dm-3. Calculate the
solubility product and ∆𝐺° for the process.

𝐴𝑔𝐶𝑙 𝑠 ⇌ 𝐴𝑔+ 𝑎𝑞 + 𝐶𝑙 − 𝑎𝑞

Solution

𝐾𝑠𝑝 = 𝐴𝑔+ 𝐶𝑙 − = 𝑆 2 = 1.265 × 10−5 2 = 1.599 × 10−10

∆𝐺° = −𝑅𝑇 ln 𝐾° = 55.9 𝑘𝐽. 𝑚𝑜𝑙 −1

 Physical Chemistry I Prof. Ehab AlShamaileh

4.5 Tests for Chemical Equilibrium

2𝐻2 + 𝑂2 ⇌ 2𝐻2 𝑂 Is a slow reaction
→ Catalysts speed up reactions

4.6 Shifts of Equilibrium at Constant Temperature

Le Chatelier principle

“If there is a change in the condition of a system in equilibrium, the system will adjust
itself in such a way as to counteract, as far as possible, the effect of that change”.

Example 4.5

𝐶𝑙2 ⇌ 2𝐶𝑙 𝐾𝑃 = 0.57𝑏𝑎𝑟 𝑎𝑡 2000 𝐾

If 0.1 mol Cl2 in 5 L at 2000 K. What will be the degree of dissociation? If the volume is
expanded to 20 L, what is it?
 Physical Chemistry I Prof. Ehab AlShamaileh
Solution

0.1 mol in 5 L is concentration not P.

𝐾𝑃 = 𝐾𝐶 𝑅𝑇 ∑𝜈 ∑𝜈 = 1

−1
1 −3
→ 𝐾𝐶 = 𝐾𝑃 𝑅𝑇 = 0.57 𝑏𝑎𝑟 = 3.43 × 10 𝑀
8.3145 𝐽. 𝐾 −1 . 𝑚𝑜𝑙 −1 × 2000 𝐾

−3 𝑚3
10 105 𝑃𝑎
𝑁𝑜𝑡𝑒: 𝐽 ≡ 𝑃𝑎. 𝑚3 →
1 𝑑𝑚3 1 𝑏𝑎𝑟

𝐶𝑙2 ⇌ 2𝐶𝑙
𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 0.1 𝑚𝑜𝑙 0 𝑚𝑜𝑙
𝑎𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 0.1 − 0.1𝛼 𝑚𝑜𝑙 +0.2𝛼 𝑚𝑜𝑙
0.2𝛼 2
𝐶𝑙 2 5
𝐾𝐶 = = = 3.43 × 10−3
𝐶𝑙2 0.1 − 0.1𝛼
5
H.W.: 𝛼 = 0.187 H.W.: If 𝑉 = 20 𝐿 → 𝛼 = 0.339

As volume increases, more dissociation occurs.

 Physical Chemistry I Prof. Ehab AlShamaileh

4.7 Coupling of reactions

𝐴+𝐵 ⇌𝑋+𝑌 𝑠ℎ𝑖𝑓𝑡 → … 1

Also

𝑋⇌𝑍 𝑖𝑠𝑜𝑚𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 … 2

𝑋 𝑌 𝑍
𝐾1 = 𝐾2 =
𝐴 𝐵 𝑋
∆𝐺1𝑜 = −𝑅𝑇 ln 𝐾1 ∆𝐺2𝑜 = −𝑅𝑇 ln 𝐾2

Add

→𝐴+𝐵 ⇌𝑌+𝑍 … 3

𝑌 𝑍
𝐾3 = = 𝐾1 . 𝐾2
𝐴 𝐵

Also

∆𝐺3𝑜 = −𝑅𝑇 ln 𝐾3 = ∆𝐺1𝑜 + ∆𝐺2𝑜 𝐻𝑒𝑠𝑠 ′ 𝑠 𝐿𝑎𝑤

 Physical Chemistry I Prof. Ehab AlShamaileh

Example 4.6

𝛼 − 𝑘𝑒𝑡𝑜𝑔𝑙𝑢𝑡𝑎𝑟𝑎𝑡𝑒 + 𝑎𝑙𝑎𝑛𝑖𝑛𝑒 ⇌ 𝑔𝑙𝑢𝑡𝑎𝑚𝑖𝑛𝑒 + 𝑝𝑦𝑟𝑢𝑣𝑎𝑡𝑒

At 25 °C the ∆𝐺° for this reaction is 251 J.mol-1

Calculate the equilibrium constant for the process. Suppose that the pyruvate formed is
oxidized in a process for which ∆𝐺° is -258.6 kJ mol-1; what effect does this have on the
transamination process?

Solution
∆𝐺° 251
− 𝑅𝑇 −8.3145×298.15
∆𝐺° = −𝑅𝑇 ln 𝐾𝐶 → 𝐾𝐶 = 𝑒 =𝑒 = 0.9

If reaction is coupled

∆𝐺° = ∆𝐺° + ∆𝐺° = 251 + −258600 = −258349 𝐽. 𝑚𝑜𝑙 −1

∆𝐺° −258349
− 𝑅𝑇 −8.3145×298.15
𝐾𝐶 = 𝑒 = 𝑒 = 1.8 × 1045 𝑣𝑒𝑟𝑦 ℎ𝑖𝑔ℎ, 𝑠ℎ𝑖𝑓𝑡 →, 𝑐𝑜𝑚𝑝𝑙𝑒𝑡𝑒
 Physical Chemistry I Prof. Ehab AlShamaileh

4.8 Temperature dependence of K

The Gibbs – Helmholtz equation
𝜕 ∆𝐺° ∆𝐻°
=− ∆𝐺° = −𝑅𝑇 ln 𝐾𝑃𝑜
𝜕𝑇 𝑇 𝑃
𝑇2
𝜕 ∆𝐻° 𝜕 ln 𝐾𝑃𝑜 ∆𝐻°
−𝑅 ln 𝐾𝑃𝑜 =− 2 → =
𝜕𝑇 𝑃
𝑇 𝜕𝑇 𝑃
𝑅𝑇 2
P effect is little:
𝑑 ln 𝐾𝑃𝑜 ∆𝐻°
= 𝑣𝑎𝑛′ 𝑡𝐻𝑜𝑓𝑓 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛
𝑑𝑇 𝑅𝑇 2
Also
𝑑 ln 𝐾𝑃𝑜 ∆𝐻°
=−
1 𝑅
𝑑 𝑇
1 ∆𝐻°
Plot ln 𝐾𝑃𝑜 vs. 𝑇 → 𝑠𝑙𝑜𝑝𝑒 = − 𝑅
∆𝐻° 1
𝑑 ln 𝐾𝑃𝑜 = − 𝑑
𝑅 𝑇
 Physical Chemistry I Prof. Ehab AlShamaileh

∆𝐻° ∆𝐺°
ln 𝐾𝑃𝑜 = − + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ∆𝐺° = −𝑅𝑇 ln 𝐾𝑃𝑜 → ln 𝐾𝑃𝑜 = −
𝑅𝑇 𝑅𝑇
∆𝐺° ∆𝐻°
=− →−+ 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑅𝑇 𝑅𝑇
∆𝐺 ∆𝐻 ∆𝑆 ∆𝑆°
∆𝐺 = ∆𝐻 − 𝑇∆𝑆 → − =− + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 =
𝑅𝑇 𝑅𝑇 𝑅 𝑅

Also
𝑑 ln 𝐾𝐶𝑜 ∆𝑈°
=
𝑑𝑇 𝑅𝑇 2
Or
𝑑 ln 𝐾𝐶𝑜 ∆𝑈°
=−
1 𝑅
𝑑 𝑇
 Physical Chemistry I Prof. Ehab AlShamaileh

Example 4.8

𝐴 + 𝐵 ⇌ 𝐴𝐵

𝑘 = 1.8 × 103 𝑑𝑚3 . 𝑚𝑜𝑙 −1 𝑎𝑡 25℃ and 3.45 × 103 𝑑𝑚3 . 𝑚𝑜𝑙 −1 𝑎𝑡 40℃

Assume ∆𝐻° is independent of T, calculate ∆𝐻° and ∆𝑆°

Solution

∆𝐻° ∆𝑆° ∆𝐻° ∆𝑆°

ln 𝐾1𝑜 = − + − ln 𝐾2𝑜 = − +
𝑅𝑇1 𝑅 𝑅𝑇2 𝑅

𝐾1𝑜 ∆𝐻° 1.8 × 103 ∆𝐻° 1 1

ln 𝑜 = − → ln =− −
𝐾2 𝑅 3.45 × 103 8.3145 298.15 313.15

∆𝐻° = 33.67 𝑘𝐽. 𝑚𝑜𝑙 −1 𝑡ℎ𝑒𝑛 ∆𝑆° = 175.2 𝐽𝐾 −1 . 𝑚𝑜𝑙 −1

 Physical Chemistry I Prof. Ehab AlShamaileh

4.9 Pressure dependence of K

∆𝑉°
ln 𝐾° = − 𝑃 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑅𝑇

Example 4.9
2𝑁𝑂2 ⇌ 𝑁2 𝑂4
At 22 oC, K increases by a factor of 3.77 when the pressure is increased from 1 bar to 1500 bar.
Calculate ∆𝑉°.
Solution
−1.32711499 𝑏𝑎𝑟 −1 × 8.3145 × 293.15 𝐽. 𝑚𝑜𝑙 −1
∆𝑉° =
1 × 105 𝑃𝑎. 𝑏𝑎𝑟 −1
= −2.16 × 10−5 𝑚3 . 𝑚𝑜𝑙 −1 = −21.6 𝑐𝑚3 . 𝑚𝑜𝑙 −1
 Q21 The equilibrium constant for a reaction
(4.2)
is 0.1 What amount of A must be mixed with 3 mol of B to yield, at
equilibrium, 2 mol of Y?
Solution
 Q22 The equilibrium constant for the reaction
(4.3)
6 –2 3
is 0.25 dm mol . In a volume of 5 dm , what amount of A must be mixed
with 4 mol of B to yield 1 mol of Z at equilibrium?

Solution
 Q23 At 3000 K the equilibrium partial pressures of CO , CO, and O are 0.6, 0.4,
2 2

(4.17) and 0.2 atm, respectively. Calculate ΔG° at 3000 K for the reaction

Solution
 Q24 A gas reaction:
(4.25)

is endothermic and its equilibrium constant K is 1 bar at 25 °C.

P

a. What is ΔG° at 25 °C (standard state: 1 bar)?

b. Is ΔS°, with the same standard state, positive or negative?
c. For the standard state of 1 M, what are K and ΔG°?
c

d. Will K at 40 °C be greater than or less than 1 bar?

P

e. Will ΔG° at 40 °C (standard state: 1 bar) be positive or negative?

Solution

b.

c.
c.

d.

e.
 Q25 At 1 bar pressure liquid bromine boils at 58.2 °C, and at 9.3 °C its vapor
(4.46) pressure is 0.1334 bar. Assuming ΔH° and ΔS° to be temperature
independent, calculate their values, and calculate the vapor pressure and
ΔG° at 25 °C.
Solution