CHEM 3411, Fall 2016

Thermodynamics, Kinetics, and Statistical Mechanics

Midterm Exam #1

September 19th, 2016

1. Given the list below, determine if the variable is extensive or intensive.

a. (2 pts) Temperature
b. (2 pts) Pressure
c. (2 pts) Chemical potential
d. (2 pts) Heat capacity
e. (2 pts) Friction

2. (6 pts) Determine if the expression below is an exact or inexact differential. Clearly show your
work for full credit.

𝑑𝑓 = 𝑥 2 𝑦 𝑑𝑥 + 2𝑥 𝑑𝑦

3. A sample of 4.50 g of methane occupies 12.7 L at 310 K. The molar mass of methane is 16 g/mol.

a. (7 pts) Calculate the work done (in Joules) when the gas expands isothermally against a
constant external pressure of 0.263 atm until its volume has increased by 3.3 L.

b. (7 pts) Calculate the work done (in Joules) if the same expansion occurred reversibly.

4. For the following processes, state whether each of the thermodynamic quantities q, w, and ΔE is
greater than, equal to, or less than zero for the system specified. Explain your answers briefly.

a. (4 pts) An ideal gas expands freely while heated.

b. (4 pts) An ideal gas is compressed isothermally under constant pressure.

CHEM 3411, Fall 2016
Thermodynamics, Kinetics, and Statistical Mechanics

c. (4 pts) The piston directly above an ideal gas-containing cylinder which undergoes
adiabatic expansion.

5. Suppose that a sample of neon gas at 298 K, 3.85 atm, and 7.45 L is allowed to expand into a
volume of 14.45 L.

a. (10 pts) What is the total entropy change under an isothermal reversible expansion
against Pex=0. Show your work for full credit.

b. (4 pts) What is the entropy change of the system under an isothermal irreversible
expansion against Pex=0. Explain your answer briefly.

c. (4 pts) What is the entropy change of the system under an adiabatic reversible
expansion? Explain your answer briefly.

6. (10 pts) Starting with the total differential of the Helmholtz free energy (dA) as a function of
volume (V) and temperature (T), derive 𝑑𝐴 = −𝑃 𝑑𝑉 − 𝑆 𝑑𝑇. Show detailed work for full credit.
CHEM 3411, Fall 2016
Thermodynamics, Kinetics, and Statistical Mechanics

7. (15 pts) Considering the change in ∆𝐺 as a function of T (Hint: should equal -∆𝑆), derive the
van’t Hoff equation:
𝐾𝑓 ∆𝐻 1 1
𝑙𝑛 ( ) = − ( − )
𝐾𝑖 𝑅 𝑇𝑓 𝑇𝑖
Show detailed work for full credit.
CHEM 3411, Fall 2016
Thermodynamics, Kinetics, and Statistical Mechanics

8. (15 pts) Using the data in Table 1, calculate the standard Gibbs energy and the equilibrium
constant at (a) 298 K and (b) 400 K for the reaction PbO(s) + CO(g) ⇌ Pb(s) + CO2(g). Assume the
reaction enthalpy is independent of temperature.

Table 1. Thermodynamic data for problem 9

Compound ∆𝒇 𝑮𝒐 (kJmol-1) ∆𝒇 𝑯𝒐 (kJmol-1)

CO2(g) -394.36 -393.51
CO(g) -137.17 -110.53
PbO(s) -188.93 -218.99
CHEM 3411, Fall 2016
Thermodynamics, Kinetics, and Statistical Mechanics

List of equations

𝑃𝑉 = 𝑛𝑅𝑇 ∆𝐺𝑚 (𝑃𝑓 ) = ∆𝐺𝑚 (𝑃𝑖 ) + 𝑉𝑚 (𝑃𝑓 − 𝑃𝑖 )

𝑃
𝐶𝑃 − 𝐶𝑉 = 𝑛𝑅 ∆𝐺𝑚 (𝑃𝑓 ) = ∆𝐺𝑚 (𝑃𝑖 ) + 𝑅𝑇𝑙𝑛 ( 𝑃𝑓 )
𝑖

∆𝐸 = 𝑤 + 𝑞
𝐺 = 𝐻 − 𝑇𝑆
𝐴 = 𝐸 − 𝑇𝑆
𝐻 = 𝐸 + 𝑃𝑉
𝑑𝑤 = −𝑃𝑑𝑉
𝑤 = −𝑃𝑒𝑥𝑡 ∆𝑉
𝑤 = −𝐶𝑉 ∆𝑇
𝑉𝑓
𝑤 = −𝑛𝑅𝑇𝑙𝑛 ( )
𝑉𝑖
𝑑𝑞
𝑑𝑠 =
𝑇
𝑇𝑓
∆𝑆 = 𝐶𝑉 𝑙𝑛 ( )
𝑇𝑖
𝑉𝑓
∆𝑆 = 𝑛𝑅𝑙𝑛 ( )
𝑉𝑖
∆𝐺 𝑜 = −𝑅𝑇𝑙𝑛𝐾
∆𝑆𝑡𝑜𝑡𝑎𝑙 = ∆𝑆𝑆𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑆𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠

𝐾𝑓 ∆𝐻 1 1
𝑙𝑛 ( )=− ( − )
𝐾𝑖 𝑅 𝑇𝑓 𝑇𝑖

Constants

R = 8.134 J mol-1 K-1

R = 0.08206 L atm mol-1 K-1

R = 0.08314 L bar mol-1 K-1