CM1131 Mid-term AY2017/18

Matric Number: _____________________

CM1131 Mid-term Test AY2017/18

Useful Data and Formulae
Thermodynamic Data
∆vap 𝐻°(N2 , 77 K) 5.6 kJ mol−1

∆f 𝐻°(CH3 COOH(aq), 298 K) −485.76 kJ mol−1

∆f 𝐻°(CH3 COO− (aq), 298 K) −486.01 kJ mol−1

∆f 𝐻°(CH4 (g), 298 K) −74.81 kJ mol−1

𝐶𝑝,𝑚 (C(s), 298 K) 32.17 J K −1 mol−1

𝐶𝑝,𝑚 (H2 (g), 298 K) 28.824 J K −1 mol−1

𝐶𝑝,𝑚 (CH4 (g), 298 K) 35.31 J K −1 mol−1

Constants
𝑅 = 8.314 J K −1 mol−1
0 K = −273.15 ℃

Formulae

2 𝑛𝑅𝑇 𝑎
𝑝𝑉 = 𝐸𝐾 𝑝= − 2 𝐻 ≡ 𝑈 + 𝑝𝑉
3 𝑉 − 𝑛𝑏 𝑉𝑚

𝜕𝑈𝑚 𝜕𝐻𝑚
𝛿𝑤 ≡ −𝑝ex 𝑑𝑉 𝐶𝑉,𝑚 ≡ ( ) 𝐶𝑝,𝑚 ≡ ( )
𝜕𝑇 𝑉 𝜕𝑇 𝑝

Reversible adiabatic expansion or 𝐶𝑝,𝑚

For any perfect gas
compression 𝛾=
𝐶𝑝,𝑚 − 𝐶𝑉,𝑚 = 𝑅 𝐶𝑉,𝑚
𝑝𝑓 𝑉𝑓 𝛾 = 𝑝𝑖 𝑉𝑖 𝛾

Reversible isothermal expansion Reversible isobaric heating or

or compression cooling 𝑇c
𝑉𝑓 𝑇𝑓 𝜂 =1−
𝑇h
∆𝑆 = 𝑛𝑅ln ( ) ∆𝑆 = 𝑛𝐶𝑝,𝑚 ln ( )
𝑉𝑖 𝑇𝑖

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CM1131 Mid-term AY2017/18
Questions
1. Indicate by marking an X in the boxes below, which of the following variables are INTENSIVE.

 Internal energy
 Molar heat capacity at constant volume
 Standard molar enthalpy of formation at 298 K
 Volume
 Mole fraction
 Number of moles
 Pressure
(-2 marks for each wrong answer. Lowest mark for the question is 0) (4 marks)

2. If one mol of liquid water was completely vaporized at 100 °C and 1 bar pressure what volume would
the gas occupy?

T = 373.15 K, p = 105 Pa, n = 1 mol

𝑛𝑅𝑇 1 × 8.314 × 373.15
𝑉= =
𝑝 105
−2 3
= 3.102 × 10 m
= 31.02 L

(4 marks)

3. What is the total translational kinetic energy possessed by 2 moles of gaseous molecules at 25 °C?
2
𝑝𝑉 = 𝐸𝐾 = 𝑛𝑅𝑇
3
3 3
𝐸𝐾 = 𝑛𝑅𝑇 = × 2 × 8.314 × (273.15 + 25)
2 2
= 7436 J

(2 marks)
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CM1131 Mid-term AY2017/18
4. Consider the van der Waals parameters for Ne(g) and NH3(g) and then answer the questions below.

Gas a / atm L2 mol-2 b / mL mol-1

Ne 0.2135 17.09
NH3 4.225 37.1
a. Why is the a parameter for Ne smaller than NH3?

The a parameter is a measure of the degree of intermolecular attraction between the particles that
make up the gas. NH3 is a polar molecule, so the attraction to other NH3 molecules will be greater than
the non-polar Ne atom’s attraction to other Ne atoms. Hence the a parameter for NH3 is expected to be
larger than that of Ne.

(2 marks)

b. Why is the b parameter for Ne smaller than NH3?

The b parameter is measure of the physical size of the particles that make up the gas. NH3 is larger in
physical size the Ne, so it’s b parameter should be larger.

(2 marks)

5. A piston was designed not to allow heat to enter or leave it. It was also sealed so that the gas inside
could not escape. This system possess walls with the following properties. One wall is nonrigid, while
the rest of them are rigid. All the walls are impermeable to matter and they are adiabatic. This type
of systems is characterized as closed. The blanks each should contain one of the following words:
open, permeable, adiabatic, nonrigid, closed, nonadiabatic, impermeable, isolated, rigid, diabatic.

(2 marks)

6. Estimate the value of 𝑈𝑚 − 𝑈𝑚 (0) at −195.8 ℃ and 1 bar in kJ mol-1 for…

a. N2(g)

3 5
𝑈𝑚 − 𝑈𝑚 (0) = 𝑅𝑇 + 𝑅𝑇 = 𝑅𝑇 = 1608 J mol−1
2 2

(1 mark)

b. N2(l)

∆vap 𝐻 = ∆vap 𝑈 + ∆(𝑝𝑉), ∆vap 𝑈 = ∆vap 𝐻 − ∆(𝑝𝑉) = ∆vap 𝐻 − ∆(𝑛𝑅𝑇) = ∆vap 𝐻 − 𝑅𝑇∆𝑛
= 5600 − 8.314 × (273.15 − 195.8) × 1 = 4957 J
𝑈𝑚 − 𝑈𝑚 (0) = 2.5𝑅𝑇 − ∆vap 𝑈 = −3349 J (3 marks)

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CM1131 Mid-term AY2017/18
7. Ar(g) at 1 bar is rapidly compressed irreversibly and isothermally from 10 L under a constant external
pressure of 5 bar.
a. How much work was performed on the gas?

𝛿𝑤 ≡ −𝑝ex 𝑑𝑉
𝑤 = −𝑝ex ∆𝑉
= −5 × 105 × (2 − 10) × 10−3 J
= 4 kJ

(3 marks)

b. How much heat was added to the gas?

Isothermal process and a perfect gas, so ∆𝑈 = 0, and from the first law, ∆𝑈 = 𝑞 + 𝑤 we find that 𝑞 =
−𝑤. Therefore 𝑞 = −4 kJ.

(1 mark)

8. Ar(g) at 1 bar is compressed reversibly and isothermally from 10 L to 2 L.

a. How much work was performed on the gas?

𝛿𝑤 ≡ −𝑝ex 𝑑𝑉
𝑉𝑓 𝑉𝑓 𝑉𝑓 𝑉𝑓
𝑑𝑉
𝑤 = − ∫ 𝑝𝑑𝑉 = −𝑛𝑅𝑇 ∫ = −𝑛𝑅𝑇 ln ( ) = −𝑝𝑖 𝑉𝑖 ln ( )
𝑉𝑖 𝑉𝑖 𝑉 𝑉𝑖 𝑉𝑖
1
= −105 × 10 × 10−3 × ln ( ) = 1.609 kJ
5

(3 marks)

b. How much heat was added to the gas?

As before, (Q7b), 𝑞 = −𝑤 = −1.609 kJ

(1 mark)
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CM1131 Mid-term AY2017/18
9. Estimate the numerical value for the molar heat capacity of Xe(g) at room temperature under…
a. …constant volume conditions.

3
𝐶𝑉,𝑚 [Xe(g)] = 𝑅 = 12.47 J K −1 mol−1
2

(2 marks)

b. …constant pressure conditions.

𝐶𝑝,𝑚 = 𝐶𝑉,𝑚 + 𝑅
5
𝐶𝑝,𝑚 [Xe(g)] = 𝑅 = 20.79 J K −1 mol−1
2

(2 marks)

c. Is there a difference between your answers in (a) and (b)? If so why?

𝐶𝑝,𝑚 is larger than 𝐶𝑉,𝑚 because gases under constant pressure conditions are able to perform work
when heat is added to them. Some of the heat energy added to gases under constant pressure
conditions is converted into work as the gas expands. Thus gases under constant pressure conditions
require more heat for a given temperature increase compared to gases under constant volume
conditions. This is because some of the heat energy is used to do work, rather than heat the gas, under
constant pressure conditions.

(4 marks)

d. Do you expect there to be any significant difference between 𝐶𝑉,𝑚 and 𝐶𝑝,𝑚 for liquid Xe?
Why?
No. A liquid, when heated, does not significantly change its volume, and therefore does not do any
significant work. As a liquid, virtually all of the heat energy goes into heating up the liquid under constant
pressure conditions, due to an insignificant amount of heat energy being used to do work. Thus 𝐶𝑝,𝑚 −
𝐶𝑉,𝑚 ≈ 0 for liquids, as well as solids.

(4 marks)
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CM1131 Mid-term AY2017/18
10. Write a balance chemical reaction at 25 °C for the combustion of urea (CH4N2O). State any
assumptions you make.

CH4N2O(s) + 3/2 O2(g)  CO2(g) + 2H2O(l) + N2(g)

Assume N2(g) as the only product containing nitrogen. In fact there will be various NOx(g) species present
in the real combustion depending on the availability of O2(g).

(3 marks)

11. What is the enthalpy of reaction for the following reaction? CH3COOH(aq) ⇌ CH3COO-(aq) + H+(aq)

∆𝑟 𝐻 = ∆𝑓 𝐻[H + (aq)] + ∆𝑓 𝐻[CH3 COO− (aq)] − ∆𝑓 𝐻[CH3 COOH(aq)]

= 0 − 486.01 + 485.76 = −0.25 kJ mol−1

(2 marks)

12. 0.1 mol of Ar(g) at 1 bar is compressed reversibly and adiabatically from 10 L to 2 L.
a. How much work was performed on the gas?

∆𝑈 = 𝑞 + 𝑤, 𝑞 = 0, ∴ ∆𝑈 = 𝑤 = 𝑛𝐶𝑉,𝑚 ∆𝑇, so we need the final temperature of the gas. This can be
obtained from the equation of state, once we have pf.

𝑝𝑓 𝑉𝑓 𝛾 = 𝑝𝑖 𝑉𝑖 𝛾
𝛾
𝑉𝑖
𝑝𝑓 = 𝑝𝑖 ( ) = 1 × 5𝛾
𝑉𝑓
5
𝐶𝑝,𝑚 2 𝑅 5
𝛾= = =
𝐶𝑉,𝑚 3 𝑅 3
2
𝑝𝑓 = 14.62 bar
𝑝𝑓 𝑉𝑓 14.62 × 105 × 2 × 10−3
𝑇𝑓 = = = 3517 K
𝑛𝑅 0.1 × 8.314
𝑝𝑖 𝑉𝑖 1 × 105 × 10 × 10−3
𝑇𝑖 = = = 1203 K
𝑛𝑅 0.1 × 8.314
𝑤 = 𝑛𝐶𝑉,𝑚 ∆𝑇 = 0.1 × 1.5 × 8.314 × (3517 − 1203) = 2.886 kJ

(4 marks)

b. How much heat was added to the gas?

Adiabatic process, q = 0.

(1 mark)
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CM1131 Mid-term AY2017/18
13. Calculate the enthalpy of reaction at 500 K for the following reaction: C(s) + 2H2(g)  CH4(g)

C(s) + 2H2(g)  CH4(g) is the formation reaction for CH4(g), therefore ∆𝑟 𝐻 = ∆𝑓 𝐻[CH4 (g)] =
𝜕𝐻𝑚
−74.81 kJ mol−1 at 298 K. At 500 K we need 𝐶𝑝,𝑚 ≡ ( ) .
𝜕𝑇 𝑝

𝑑𝐻𝑚 = 𝐶𝑝,𝑚 𝑑𝑇
𝑑∆𝑟 𝐻 = ∆𝑟 𝐶𝑝,𝑚 𝑑𝑇
∆𝑟 𝐻[500 K] − ∆𝑟 𝐻[298 K] = ∆𝑟 𝐶𝑝,𝑚 ∆𝑇
∆𝑟 𝐻[500 K] = ∆𝑟 𝐻[298 K] + (35.31 − 32.17 − 2 × 28.824) × (500 − 298)
= −74.81 × 103 − 54.508 × 202
= −74810 − 11011
= −85.82 kJ mol−1

(8 marks)

14. 0.1 mol of Ar(g) at 1 bar is rapidly compressed irreversibly and isothermally from 10 L under a
constant external pressure of 5 bar.
a. What is the change in entropy of the system?

𝑉𝑓
∆𝑆 = 𝑛𝑅ln ( )
𝑉𝑖
2
= 0.1 × 8.314 × ln ( )
10
= −1.338 J K −1

(4 marks)

15. A gas expands reversibly and isothermally. Indicate whether the following are positive, negative or
zero.

a. ∆𝑆 >0

b. ∆𝑆𝑠𝑢𝑟 <0

c. ∆𝑆𝑢𝑛𝑖 0

(3 marks)
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CM1131 Mid-term AY2017/18
16. Indicate by marking an X in the boxes below, which of the following processes are spontaneous.

 Ice melting at 0 °C under 1 atm pressure

 Liquid water freezing at -5 °C under 1 atm pressure
 Free expansion
 Isenthalpic adiabatic expansion
 Reversible adiabatic expansion
 Two miscible liquid mixing
 Perfect Carnot heat engine
(-2 marks for each wrong answer. Lowest mark for the question is 0) (4 marks)
17. A typical car engine operates between 30 °C and 500 °C. The standard molar enthalpy of combustion
of octane is -5471 kJ mol-1. If octane was used as a fuel, how many kJ of useful work could be
performed by the car engine per mole of octane when combusted assuming that the car engine was
the most efficient ever built.

𝑇c (273.15 + 30)
𝜂 =1− =1− = 0.6079
𝑇h (273.15 + 500)
𝑞 = 𝜂∆𝑟 𝐻 = 0.6079 × −5471 = −3326 kJ mol−1

Thus 3326 kJ mol-1 of octane burnt can be used to do useful work on the surroundings.

(4 marks)

18. One mole of O2(g) initially at 25 °C and 1 bar pressure underwent some process. At the end of that
process the mole of O2(g) was at 500 °C and 10 bar pressure. What is the change in the entropy of
O2(g)?

Make up a reversible path to get from (𝑇𝑖 , 𝑝𝑖 ) to (𝑇𝑓 , 𝑝𝑓 ). First perform a reversible isobaric heating from
(𝑇𝑖 , 𝑝𝑖 ) to (𝑇𝑓 , 𝑝𝑖 ) then perform a reversible isothermal compression from (𝑇𝑓 , 𝑝𝑖 ) to (𝑇𝑓 , 𝑝𝑓 ).

Step 1 (𝑇𝑖 , 𝑝𝑖 ) to (𝑇𝑓 , 𝑝𝑖 )

𝑇𝑓 7 500 + 273.15
∆𝑆 = 𝑛𝐶𝑝,𝑚 ln ( ) = 1 × 𝑅ln ( ) = 27.73 J K −1
𝑇𝑖 2 25 + 273.15
Step 2 (𝑇𝑓 , 𝑝𝑖 ) to (𝑇𝑓 , 𝑝𝑓 )
𝑉𝑓 𝑝𝑖 1
∆𝑆 = 𝑛𝑅ln ( ) = 𝑛𝑅ln ( ) = 1 × 𝑅ln ( ) = −19.14 J K −1
𝑉𝑖 𝑝𝑓 10

Total change in S is:

∆𝑆 = 27.73 − 19.14 = 8.58 J K −1

(7 marks)