Physical Chemistry

Chapter 5: Physical Transformations of Pure Substances

Professor: Dr. Hassan Farrokhzad
By: Amirali Masoumi

December 2024
1. The difference in chemical potential between two regions of a system
is −8.3 kJ.mol−1. By how much does the Gibbs energy change when
0.15 mmol of a substance is transferred from one region to the other?

Solution:

For pure substances, the chemical potential is the molar Gibbs energy:
𝑑𝐺 = 𝜇2 − 𝜇1 𝑑𝑛 → ∆𝐺 = 𝜇2 − 𝜇1 𝑛

𝑘𝐽
= −8.3 0.15 × 10−3 𝑚𝑜𝑙 = −1.2 × 10−3 𝑘𝐽 = −1.2 𝐽
𝑚𝑜𝑙

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2. What is the maximum number of phases that can be in mutual
equilibrium in a four-component system?

Solution:
𝐹 =𝐶−𝑃+2→𝑃 =𝐶−𝐹+2=4−𝐹+2=6−𝐹 ≤6

The maximum number phases in equilibrium occurs when the number

of degrees of freedom is at a minimum, namely zero; that number is six.

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3. Iron is heated from 100°C to 1000°C. By how much does its chemical
potential change? Take S°m = 53 J.K−1.mol−1 for the entire range (its average
value).
Solution:

𝜕𝜇
Eqn 4.2: 𝑑𝜇 = 𝑑𝑇 = −𝑆𝑚 𝑑𝑇 → ∆𝜇 = − ‫ = 𝑇𝑑 𝑚𝑆 ׬‬−𝑆𝑚 ∆𝑇
𝜕𝑇 𝑝
𝐽 4 𝐽 𝑘𝐽
= −53 × 1000 − 100 𝐾 = 4.8 × 10 = 48
𝑚𝑜𝑙.𝐾 𝑚𝑜𝑙 𝑚𝑜𝑙

Note: As the problem stated, we assumed that the entropy is constant over the
temperature range.

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4. The temperature dependence of the vapor pressure of solid sulfur
dioxide can be approximately represented by the relation log(p/Torr) =
10.5916 − 1871.2/(T/K) and that of liquid sulfur dioxide by log(p/Torr)
= 8.3186 − 1425.7/(T/K). Estimate the temperature and pressure of the
triple point of sulfur dioxide.

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Solution:

At the triple point, 𝑇3 , the vapor pressures of liquid and solid are equal:

1871.2 𝐾 1425.7 𝐾
10.5916 − = 8.3186 − → 𝑇3 = 196.0 𝐾
𝑇3 𝑇3

1871.2 𝐾
log 𝑝3 Τ𝑇𝑜𝑟𝑟 = − + 10.5916 = 1.0447 → 𝑝3 = 11.1 𝑇𝑜𝑟𝑟
196.0 𝐾

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5. The enthalpy of vaporization of a certain liquid is found to be 14.4
kJ.mol−1 at 180 K, its normal boiling point. The molar volumes of the
liquid and the vapor at the boiling point are 1.15 cm3.mol−1 and 14.5
dm3.mol−1, respectively. (a) Estimate dp/dT from the Clapeyron
equation and (b) the percentage error in its value if the Clausius–
Clapeyron equation is used instead.

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 Clapeyron equation for vaporization
Solution:

𝑑𝑝 ∆𝑡𝑟𝑠 𝑆 ∆𝑣𝑎𝑝 𝐻 𝑑𝑝 ∆𝑣𝑎𝑝 𝐻

Clapeyron equation: = → For vaporization: ∆𝑣𝑎𝑝 𝑆 = → =
𝑑𝑇 ∆𝑡𝑟𝑠 𝑉 𝑇 𝑑𝑇 𝑇∆𝑣𝑎𝑝 𝑉

𝐽
𝑑𝑝 ∆𝑣𝑎𝑝 𝐻 14.4×103 𝑚𝑜𝑙 𝑘𝑃𝑎
(a) = = 𝑚3
= +5.56
𝑑𝑇 𝑇𝑏 ∆𝑣𝑎𝑝 𝑉 −3 −4
(180 𝐾)×(14.5×10 −1.15×10 )𝑚𝑜𝑙 𝐾

Clausius–Clapeyron equation
𝐽
𝑑𝑝 ∆𝑣𝑎𝑝 𝐻 𝑑𝑙𝑛𝑝 ∆𝑣𝑎𝑝 𝐻 𝑑𝑝 ∆𝑣𝑎𝑝 𝐻 14.4×103 𝑚𝑜𝑙 ×(101325 𝑃𝑎)
(b) = 𝑅𝑇 → = → = ×𝑝 = 𝐽
𝑑𝑇 𝑇 𝑑𝑇 𝑅𝑇 2 𝑑𝑇 𝑅𝑇 2 8.3145𝑚𝑜𝑙.𝐾 ×(180 𝐾)2
𝑝

𝑘𝑃𝑎 5.42−5.56
= +5.42 → 𝑒𝑟𝑟 = × 100 = 2.58%
𝐾 5.42

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6. The vapor pressure of nitric acid varies with temperature as follows:

T/°C 0 20 40 50 70 80 90 100
p/kPa 1.92 6.38 17.7 27.7 62.3 89.3 124.9 170.9

What are (a) the normal boiling point and (b) the enthalpy of
vaporization of nitric acid?

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Solution:

𝑑𝑙𝑛𝑝 ∆𝑣𝑎𝑝 𝐻
The Clausius–Clapeyron equation: =
𝑑𝑇 𝑅𝑇 2

𝑙𝑛 𝑝
∆𝑣𝑎𝑝 𝐻 𝑇 𝑑𝑇 ∆𝑣𝑎𝑝 𝐻 1 1 ∆𝑣𝑎𝑝 𝐻
→ න 𝑑𝑙𝑛𝑝 = න 2 =− − ∗ → 𝑙𝑛 𝑝 = 𝑐𝑡𝑒 −
𝑙𝑛 𝑝∗ 𝑅 𝑇∗ 𝑇 𝑅 𝑇 𝑇 𝑅𝑇

1 ∆𝑣𝑎𝑝 𝐻
Plot 𝑙𝑛 𝑝 against and identify − as the slope of the graph:
𝑇 𝑅

T/K 273 293 313 323 343 353 363 373

p/kPa 1.92 6.38 17.7 27.7 62.3 89.3 124.9 170.9
ln p 0.65 1.85 2.87 3.32 4.13 4.49 4.83 5.14
1000 K/T 3.66 3.41 3.19 3.10 2.92 2.83 2.75 2.68
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 ∆𝑣𝑎𝑝 𝐻
𝑚=− = −4575.7 𝐾
𝑅
Solution: → ∆𝑣𝑎𝑝 𝐻 = 38
𝑘𝐽
𝑚𝑜𝑙
5.5
5
4.5
4
3.5 Normal boiling point occurs at 𝑝 = 1 𝑎𝑡𝑚
ln(p/kPa)

3 = 101.325 𝑘𝑃𝑎, or 𝑙𝑛 𝑝Τ𝑘𝑃𝑎 = 4.618

2.5 y = -4.5757x + 17.446
From interpolation: 𝑇𝑏 = 356.76 ≈ 84℃
2
1.5
1
0.5
2.6 2.8 3 3.2 3.4 3.6 3.8
(103/T) K

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7. The change in enthalpy is given by dH = CpdT + Vdp. The Clapeyron
equation relates dp and dT at equilibrium, and so in combination the two
equations can be used to find how the enthalpy changes along a phase
boundary as the temperature changes and the two phases remain in
equilibrium. Show that d(ΔH/T) = ΔCpd ln T.

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Solution:
𝑑𝐻 = 𝐶𝑝 𝑑𝑇 + 𝑉𝑑𝑝 → 𝑑∆𝐻 = ∆𝐶𝑝 𝑑𝑇 + ∆𝑉𝑑𝑝 Note: ∆ signifies a difference between phases

𝑑𝑝 ∆𝐻
Phase boundary 𝑑𝑝 and 𝑑𝑇 are related by: =
𝑑𝑇 𝑇∆𝑉

∆𝐻 ∆𝐻 𝑑∆𝐻 ∆𝐻
→ 𝑑∆𝐻 = ∆𝐶𝑝 + ∆𝑉 × 𝑑𝑇 = ∆𝐶𝑝 + 𝑑𝑇 → = ∆𝐶𝑝 + (I)
𝑇∆𝑉 𝑇 𝑑𝑇 𝑇

𝑑 ∆𝐻 1 𝑑∆𝐻 ∆𝐻 1 𝑑∆𝐻 ∆𝐻
= − = − (II)
𝑑𝑇 𝑇 𝑇 𝑑𝑇 𝑇2 𝑇 𝑑𝑇 𝑇

𝑑 ∆𝐻 ∆𝐶𝑝 ∆𝐻 ∆𝐶𝑝 𝑑𝑇
From I and II: = →𝑑 = = ∆𝐶𝑝 𝑑𝑙𝑛𝑇
𝑑𝑇 𝑇 𝑇 𝑇 𝑇

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