CHEY10087 Thermodynamics Workshop and Revision Questions

Answers on Web: http://staff.bath.ac.uk/chsataj

1. A small cylinder of compressed CO2 weighs 1.04 kg when full and 0.74 kg
when empty. If the volume is 250 cm3, calculate the pressure of the gas at 20 °C

2. The density of a gaseous compound was found to be 1.23 g dm-3 at 330 K and 25.5 kPa.
What was the molar mass of the gas?

3. What is the heat capacity of a liquid that rose in temperature from 25 °C to 30.23 °C when
supplied with 124 J of heat?

4. Calculate the work done when a gas is compressed from 250 cm3 to 125 cm3 by an external
pressure of 10 kPa.

5. What is the work done when 10-3 mol of Ar expands reversibly from a pressure of 150 kPa
to a final pressure of 50 kPa at 500 K.

6. A sample of methane of mass 4.5 g occupies 12.7 L at 310 K. Calculate the work done
when the gas expands isothermally against a constant external pressure of 200 torr until its
volume has increased by 3.3 dm3. Calculate the work which would be done if the expansion
were done reversibly.

7. The heat capacity of air at room temperature (20 °C) is approx. 21 J K-1 mol-1. How much
heat is required to raise the temperature of a 5 m x 5 m x 3 m room by 10 °C ? How long
will it take a 1 kW heater to achieve this ?

8. A certain liquid has ∆H°(vaporization) = 26 kJ mol-1. Calculate q, w, ∆H and ∆U when 0.50

mol is vaporized at 250K and 750 torr.

9. The standard enthalpy of formation of ethylbenzene is -12 5 kJ mol-1. Calculate its standard
enthalpy of combustion. (***)

10. The decomposition at constant volume of 1 mol of KrF2 gas at 25 °C evolves 59.4 kJ of
heat. The enthalpy of sublimation of solid KrF2 is 41 kJ mol-1. Calculate ∆H°f, 298 for solid
KrF2.

11. The enthalpy of combustion of gaseous ethane at 298 K is -1558.8 kJ mol-1-. Use mean
heat capacities to find the enthalpy of combustion at 373 K. (***).

12. On May 14th 1978, an undergraduate student measured the heat of combustion of
naphthalene (C10 H8) using a bomb calorimeter with a total heat capacity of 10.254 kJ K-1.
The combustion of 647.5 mg of naphthalene with excess oxygen produced a temperature
rise of 2.525 K.
(a). Calculate the enthalpy change on combustion
(b). Calculate the enthalpy of formation of naphthalene

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13. What will be the sign of the enthalpy change ∆Η and the entropy change, ∆S for the
following processes:
(a). water freezing to form ice at 0 oC.
(b). Water vaporizing to steam at 100 oC
(c). The reaction of hydrogen gas and oxygen gas to form water.

14. The standard enthalpy of combustion of phenol(s) is –3054 kJ mol-1 at 298 K. Its standard
molar entropy is 144.0 J K-1 mol-1. Calculate the standard Gibbs free energy of formation at
298 K.

Useful data
∆H°f CO2 = -393.5 kJ mol-1
∆H°f H2O = -255.5 kJ mol-1

Cp C2H6 = 81.67 J K-1 mol-1

Cp O2 = 29.355 J K-1 mol-1
Cp CO2 = 37.11 J K-1 mol-1
Cp H2O(l) = 75.29 J K-1 mol-1

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Answers

1. CO2 = 44 g mol-1. Mass = 0.3 kg = 6.82 mol.

pV = nRT: p (250 x 10-6 m3) = (6.82 mol)(8.314 J K-1 mol-1)(293.15 K).
p = 6.6 x 107 Pa = 66.5 bar

2. Density = 1.23 g dm-3 = 1.23 x 103 g m-3

pV = nRT: (n/V) = (RT/p) = (25500 Pa / (8.314 J K-1 mol-1)(122 K)) = 9.294 m3 mol-1
1 m3 = 9.294 mol = 1.23 x 103 g. so MR = 1230 g / 9.294 mol = 132.34 g mol-1

3. q = c ∆T: c = 124 J / 5.23 K = 23.71 J K-1

4. w = p ∆V = (10000 Pa) (250 – 125) x 10-6 m3 = 1.25 J

5. wrev = nRT ln(Vfin/ Vinit) = (10-3 mol )( 8.314 J K-1 mol-1)(500 K) ln (3 / 1) = 4.57 J
(volume is inversely proportional to pressure)

6. 4.5 g of CH4 = 4.5 / 16 = 0.2813 mol.

w = p ∆V = (200 x 133.32 Pa) (3.3) x 10-3 m3 = 87.99 J
wrev = nRT ln(Vfin/ Vinit) = (0.2813 mol )( 8.314 J K-1 mol-1)(310 K) ln (16 / 12.7)
= 167.5 J

7. Volume = 5 m x 5 m x 3 m = 75 m3.
From the ideal gas equation (101325 Pa)(75 m3) = n (8.314 J K-1 mol-1)(293.2 K)
n = 3117.5 mol.

Q = n cp ∆T = (3117.5 mol)( 21 J K-1 mol-1)(10 K) = 654.67 kJ.

1 kW = 1 kJ s-1. Hence heater needs 654.7 s or 10.9 min.

8. ∆H°(vaporization) = qp = 26 kJ mol-1 = 13 kJ for 0.5 mol.

V per mol at these conditions (from Ideal gas equation) = 0.02051m3.

w = p ∆V = (750 torr x 133 32 Pa torr-1) (0.5 mol x 0.02051 m3 mol-1)
= 1025.4 J

∆H = ∆U + ∆n RT . Hence, ∆U = 11.974 kJ.

9. C6H5C2H5 + 10.5 O2 → 8 CO2 + 5 H2O

∆H°(comb.) = Σ ∆H°f (products) - Σ ∆H°f (reactants)

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 = [ (8 x –393.5) + (5 x –285.5)]-[(-12.5) + (0)] = 4564.5 kJ mol-1

10. (a) KrF2(g) → Kr(g) + F2(g) ∆U = -59.4 kJ mol-1 (CONSTANT VOLUME)

(b) KrF2(s) → KrF2(g) ∆H = +41 kJ mol-1

From (a), ∆H = ∆U + ∆n RT = -59400 + (1)(8.314)(298) = -56.9 kJ mol-1

∆H°f is the enthalpy change when 1 mol of a compound is formed from its elements in their
standard states.

-(a) – (b): Kr(g) + F2(g) → KrF2(s) ∆H°f = +56.9 – 41 = 15.9 kJ mol-1

11. ∆H°298 = -1558.8 kJ mol-1. ∆H°373 = ∆H°298 + ∆cp (373 – 298)

Kirchoff eqn.

C2H6 + 3.5 O2 → 2 CO2 + 3 H2O: ∆cp = 144.76 J K-1 mol-1

∆H°373 = -1558800 J mol-1 + (144.76 J K-1 mol-1) (373 – 298) K = -1547.9 kJ mol-1.

12. Bomb calorimeter is at constant volume so that the heat change is ∆U directly.

(a). Energy released = (10.254 kJ K-1) (2.525 K) = -25.892 kJ. This is for 0.6475 g so ∆U =
(25.892 kJ) (128.1 g mol-1) / (0.6475 g) = -5122.4 kJ mol-1. [Negative since heat is released]

∆H = ∆U + ∆ngasRT. C10 H8 (s) + 12 O2(g) = 10 CO2(g) + 4 H2O(l). Hence, ∆ngas = -2

∆H = -5122400 J mol-1 + (-2)(8.314 J K-1 mol-1)(298 K) = -5127.4 kJ mol-1.

(b) ∆H°(reaction) = Σ ∆H°f(products) - Σ ∆H°f(reactants)

-5127.4 = [10(-393.5) + 4(-285.8)]-[ ∆H°f (Naphth.) + 0]

∆H°f (Naphth.) = 49.2 kJ mol-1.

13. (a). ∆H negative - heat released; ∆S negative - ice is more ordered than water.
(b). ∆H positive - heat needed so added to the water; ∆S positive - gas is more
disordered than liquid.
(c). ∆H negative - heat released in an exothermic reaction; ∆S negative - liquids are more
ordered than gases. Also, 3 molecules react to form 2. HOWEVER, this is just for the system.
As I showed in lectures, ∆S for the Universe increases. Illustrates the point about being careful to
carefully define what we are thinking about.

(b) will be much bigger than (a). It takes more heat to evaporate since molecules have to be
moved further apart and gases have greater degrees of molecular motion. The difference in order
between a liquid and a gas is much greater than that between a solid and a liquid.

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14. ∆G° = ∆H° - TS° - but all need to refer to the formation reaction.

C6H5OH + 7½ O2 → 6CO2 + 3H2O ∆H°= Σ ∆H°f(prod.) - Σ ∆H°f(react)

-3054 = [6(-393.5) + 3(-285.8)]-[ ∆H°f (phenol) + 0]

∆H°f (phenol) = -164.4 kJ mol-1. S° = 144.0 J K-1 mol-1

∆G° = ∆H° - TS° = (-164.4 x 103 J mol-1) – (298.15)( 144.0 J K-1 mol-1)
= 207.34