TUTOTIAL 1 – THERMODYNAMICS

1. The density of liquid water at 100°C 0.9168 g cm -3 and that of steam at the same
temperature is 0.000596 g cm-3. If the enthalpy of evaporation of water at atmospheric
pressure is 40.63 kJ mol-1, calculate ∆U. Calculate the work done by the system during
the evaporation process.

2. A sample of liquid acetone weighing 0.700 g was burned in a bomb calorimeter for which
the heat capacity (including the sample) is 6937 J K -1. The observed temperature risel
was from 25.00°C to 26.69°C.
a. Calculate ∆U for the combustion of 1 mol of acetone.
b. Calculate ∆H for the combustion of 1 mol of acetone.

3. An average man weighs about 70 kg and produces 10 460 kJ of heat per day.
a. Suppose that a man were an isolated system and that his heat capacity were 4.18 J K -
1
; if his temperature were 37°C at a given time, calculate his temperature 24 hours
later.
b. A man is in fact an open system, and the main mechanism for maintaining his
temperature constant is evaporation of water. If the enthalpy of vaporization of water
at 37°C is 43.4 kJ mol-1, calculate the amount of water that needs to be evaporated
per day to keep the temperature constant.

4. In an open beaker at 25°C and 1 atm pressure, 100 g of zinc is caused to react with
dilute sulfuric acid. Calculate the work done by the liberated hydrogen gas, assuming it
behaves ideally. Calculate the work that would be done if the reaction took place in a
sealed vessel.

5. A balloon is 0.5 m in diameter and contains air at 25°C and 1 bar pressure. It is then
filled with air isothermally and reversibly until the pressure reaches 5 bar. Assume that
the pressure is proportional to the diameter of the balloon and calculate (a) the final
diameter of the balloon and (b) the work done in the process.

6. Two moles of oxygen gas, which can be regarded as ideal with CP,m = 29.4 J K-1 mol-1
(independent of temperature) are maintained at 273 K in a volume of 11.35 dm 3.

a. Calculate the pressure of the gas.

b. Calculate PV.
c. Calculate CV,m.

7. Supposed that the gas in Problem 6 is reversibly compressed to half its initial volume at
constant temperature (273 K).
a. Calculate the change in U.
b. Calculate the final pressure.
c. Calculate the work done on the system.
d. Calculate the amount of heat that flows out of the system.
 e. Calculate the change in H.

8. Suppose that the gas in Problem 6 is heated reversibly to 373 K at constant volume:
a. Calculate the work done on the system.
b. Calculate the increase in internal energy.
c. Calculate the amount of heat added to the system.
d. Calculate the final pressure.
e. Calculate the final value of PV.
f. Calculate the increase in enthalpy, ∆H.

9. Initially 0.1 mol of methane is at 1 bar pressure and 80°C. The gas behaves ideally and
the value of CP,m/CV,m is 1.31. the gas is allowed to expand reversibly and adiabatically to
a pressure of 0.1 bar.
a. Calculate the initial and final volumes of the gas.
b. Calculate the final temperature.
c. Calculate ∆U and ∆H for the process.

10. A gas that behaves ideally was allowed to expand reversibly and adiabatically to twice its
initial volume. Its initial temperature was 25°C, and C V,m = (5/2)R. Calculate ∆Um and
∆Hm for the expansion process.

11. The accompanying diagram represents a reversible Carnot cycle for an ideal gas:
 a. Calculate the thermodynamic efficiency of the engine.
b. Calculate the amount of heat that is rejected at the lower temperature, 200 K, during
the isothermal compression,
c. Calculate the entropy increase during the isothermal expansion at 1000 K.
d. Calculate the entropy decrease during the isothermal compression at 200 K.
e. Calculate the overall entropy change for the entire cycle.

12. An engine operates between 125°C and 40°C. Calculate the minimum amount of heat
that must be withdrawn from the reservoir to obtain 1500 J of work.

13. Suppose that a reversible Carnot engine operates between 300 K and a higher
temperature Th. If the engine produces 10 kJ of work per cycle and the entropy change
in the isothermal expansion at Th is 100 J K-1, calculate qh, qc, and Th.

14. The following diagram represents a reversible Carnot cycle for an ideal gas:

a. Calculate the thermodynamic efficiency of the engine.

b. Calculate the amount of heat that is absorbed at 400 K.
c. Calculate the amount of heat that is rejected at 300 K.
d. Calculate the entropy change in the process A → B.
e. Calculate the entropy change in the entire cycle.
f. Calculate the amount of heat that must be absorbed in order for the engine to
perform 2 kJ of work.
15. Initially 1 mol of O2 is contained in a 1-litre vessel, and 5 mol of N 2 are in a 2-litre vessel;
the two vessels are connected by a tube with a stopcock. If the stopcock is opened and
the gases mix, calculate the entropy change.

16. Calculate the entropy of mixing per mole of air, taking the composition by volume to be
79% N2, 20% O2, and 1% Argon.
a. One mole of an ideal gas at 25°C is allowed to expand reversibly and isothermally
from 1 dm3 to 10 dm3. Calculate ∆S for the gas and ∆S for the surroundings.
b. The same gas is expanded adiabatically and irreversibly from 1 dm 3 to 10 dm3 with
no work done. Calculate the final temperature of the gas. Calculate ∆S for the gas,
and ∆S for the surroundings. The calculate the net ∆S.

17. One mole of liquid water at 0.0°C and 1 atm pressure is turned into steam at 100.0°C
and 1 atm pressure by the following two paths:
a. Heated at constant pressure to 100.0°C and allowed to boil into steam ( ∆vapH° =
40.67 J mol-1 at this temperature).
b. Pressure lowered to 0.00602 atm so that water evaporates to steam at 0°C ( ∆vapH° =
44.92 J mol-1 at this temperature), heated at the constant pressure of 0.00602 atm
to 100°C, and compressed at 100.0°C to 1 atm pressure.

Calculate the entropy change along each path and verify that they are the same,
thus proving that ∆S° is a state function/property. The CP,m for liquid water and
water vapour are 75.48 and 30.54 J K -1 mol-1, respectively.

18. Initially 5 mol of an ideal gas, with CV,m = 12.5 J K-1 mol-1, are at a volume of 5 dm3 and a
temperature of 300 K. If the gas is heated to 373 K and the volume increases to 10
dm3, calculate the entropy change.

19. At 0°C 20 g of ice are added to 50 g of water at 30°C in a vessel that has a water
equivalent of 20 g. Calculate the entropy changes in the system and in the
surroundings. The heat of fusion of ice at 0°C is 6.02 kJ mol-1, and the specific heat
capacities of water and ice may be taken as constant at 4.184 and 2.094 J K -1 g-1
respectively, and independent of temperature.

20. One mole of liquid water at 0°C is placed in a freezer having a temperature of -12°C.
The water freezes and the ice cools to -12°C. Calculate the change in entropy in the
system and its surrounding (Freezer) and the net entropy change.

CP,m (water) = 75.3 J K-1 mol-1

CP,m (ice) = 37.7 J K-1 mol-1
∆fH(ice → water) = 6.02 kJ mol-1 at 0°C