September 22, 2008

CHEM 2820: Physical Chemistry

Problem Set #1 (Corrected Number Sequence)

PART 1. EXERCISES

Assume all gases are perfect unless stated otherwise. Unless otherwise stated, thermochemical
data are for 298.15 K.

Chapter 1

1.1(b) (a) Could 25 g of argon gas in a vessel of volume 1.5 dm3 exert a pressure of 2.0 bar at
30°C if it behaved as a perfect gas? If not, what pressure would it exert? (b) What pressure
would it exert if it behaved as a van der Waals gas?

1.2(b) A perfect gas undergoes isothermal compression, which reduces its volume by 1.80 dm3.
The final pressure and volume of the gas are 1.97 bar and 2.14 dm3, respectively. Calculate the
original pressure of the gas in (a) bar, (b) Torr.

1.3(b) A sample of hydrogen gas was found to have a pressure of 125 kPa when the temperature
was 23°C. What can its pressure be expected to be when the temperature is 11°C?

1.4(b) A homeowner uses 4.00 × 103 m3 of natural gas in a year to heat a home. Assume that
natural gas is all methane, CH4, and that methane is a perfect gas for the conditions of this
problem, which are 1.00 atm and 20°C. What is the mass of gas used?

1.5(b) What pressure difference must be generated across the length of a 15 cm vertical drinking
straw in order to drink a water-like liquid of density 1.0 g cm–3?

1.6(b) A manometer like that described in Exercise 1.6a contained mercury in place of water.
Suppose the external pressure is 760 Torr, and the open side is 10.0 cm higher than the side
connected to the apparatus. What is the pressure in the apparatus? (The density of mercury at
25°C is g cm–3.)

1.13 (b) Calculate the pressure exerted by 1.0 mol H2S behaving as (a) a perfect gas, (b) a van
der Waals gas when it is confined under the following conditions: (i) at 273.15 K in 22.414 dm3,
(ii) at 500 K in 150 cm3. Use the data in Table 1.5.

1.15 (b) A gas at 350 K and 12 atm has a molar volume 12 per cent larger than that calculated
from the perfect gas law. Calculate (a) the compression factor under these conditions and (b) the
molar volume of the gas. Which are dominating in the sample, the attractive or the repulsive
forces?

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Chapter 2

2.2 (b) A chemical reaction takes place in a container of cross-sectional area 50.0 cm2. As a
result of the reaction, a piston is pushed out through 15 cm against an external pressure of 121
kPa. Calculate the work done by the system.

2.3 (b) A sample consisting of 2.00 mol He is expanded isothermally at 22°C from 22.8 dm3 to
31.7 dm3 (a) reversibly, (b) against a constant external pressure equal to the final pressure of the
gas, and (c) freely (against zero external pressure). For the three processes calculate q, w, ΔU,
and ΔH.

2.4(b) A sample consisting of 2.00 mol of perfect gas molecules, for which CV,m = 5/2R, initially
at p1 = 111 kPa and T1 = 277 K, is heated reversibly to 356 K at constant volume. Calculate the
final pressure, ΔU, q, and w.

2.5 (b) A sample of argon of mass 6.56 g occupies 18.5 dm3 at 305 K. (a) Calculate the work
done when the gas expands isothermally against a constant external pressure of 7.7 kPa until its
volume has increased by 2.5 dm3. (b) Calculate the work that would be done if the same
expansion occurred reversibly.

2.6 (b) A sample of 2.00 mol CH3OH(g) is condensed isothermally and reversibly to liquid at
64°C. The standard enthalpy of vaporization of methanol at 64°C is 35.3 kJ mol–1. Find w, q, ΔU,
and ΔH for this process.

2.7(b) A piece of zinc of mass 5.0 g is dropped into a beaker of dilute hydrochloric acid.
Calculate the work done by the system as a result of the reaction. The atmospheric pressure is 1.1
atm and the temperature 23°C.

2.8 (b) The constant-pressure heat capacity of a sample of a perfect gas was found to vary with
temperature according to the expression Cp/(J K–1) = 20.17 + 0.4001(T/K). Calculate q, w, ΔU,
and ΔH when the temperature is raised from 0°C to 100°C (a) at constant pressure, (b) at
constant volume.

2.9(b) Calculate the final temperature of a sample of carbon dioxide of mass 16.0 g that is
expanded reversibly and adiabatically from 500 cm3 at 298.15 K to 2.00 dm3.

2.10(b) A sample of nitrogen of mass 3.12 g at 23.0°C is allowed to expand reversibly and
adiabatically from 400 cm3 to 2.00 dm3. What is the work done by the gas?

2.11(b) Calculate the final pressure of a sample of water vapour that expands reversibly and
adiabatically from 87.3 Torr and 500 cm3 to a final volume of 3.0 dm3. Take γ = 1.3.

2.12(b) When 178 J of energy is supplied as heat to 1.9 mol of gas molecules, the temperature of
the sample increases by 1.78 K. Calculate the molar heat capacities at constant volume and
constant pressure of the gas.

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2.16 (b) A certain liquid has ΔvapH° = 32.0 kJ mol–1. Calculate q, w, ΔH, and ΔU when 0.75 mol
is vaporized at 260 K and 765 Torr.

2.17 (a) The standard enthalpy of formation of ethylbenzene is –12.5 kJ mol–1. Calculate its
standard enthalpy of combustion.
OR
2.17 (b) The standard enthalpy of formation of phenol is –165.0 kJ mol–1. Calculate its standard
enthalpy of combustion.

2.19(b) When 2.25 mg of anthracene, C14H10(s), was burned in a bomb calorimeter the
temperature rose by 1.35 K. Calculate the calorimeter constant. By how much will the
temperature rise when 135 mg of phenol, C6H5OH(s), is burned in the calorimeter under the
same conditions? (ΔcH_(C14H10, s) = –7061 kJ mol–1.)

2.22 (b)Given the reactions (1) and (2) below, determine (a) ΔrH° and ΔrU° for reaction (3), (b)
ΔfH° for both HCl(g) and H2O(g) all at 298 K.
(1) H2(g) + I2(s) → 2 HI(g) ΔrH° = +52.96 kJ mol–1
(2) 2 H2(g) + O2(g) → 2 H2O(g) ΔrH° = –483.64 kJ mol–1
(3) 4 HI(g) + O2(g) → 2 I2(s) + 2 H2O(g)

2.25 (b) Use the information in Table 2.5 to predict the standard reaction enthalpy of 2 H2(g) +
O2(g) → 2 H2O(l) at 100°C from its value at 25°C.

PART 2. PROBLEMS

1.8 At 273 K measurements on argon gave B = –21.7 cm3 mol–1 and C = 1200 cm6 mol–2, where
B and C are the second and third virial coefficients in the expansion of Z in powers of 1/Vm.
Assuming that the perfect gas law holds sufficiently well for the estimation of the second and
third terms of the expansion, calculate the compression factor of argon at 100 atm and 273 K.
From your result, estimate the molar volume of argon under these conditions.

1.14 Express the van der Waals equation of state as a virial expansion in powers of 1/Vm and
obtain expressions for B and C in terms of the parameters a and b. The expansion you will need
is (1 – x)–1 = 1 + x + x2 +…. Measurements on argon gave B = –21.7 cm3 mol–1 and C = 1200 cm6
mol–2 for the virial coefficients at 273 K. What are the values of a and b in the corresponding van
der Waals equation of state?

2.20 Show that the following functions have exact differentials: (a) x2y + 3y2, (b) x cos xy, (c)
x3y2, (d) t(t + es) + s.

2.24 Start from the expression Cp – CV = T(∂p/∂T)V(∂V/∂T)p, use the appropriate relations
between partial derivatives to show that:
Cp – CV = T(∂V/∂T)p2/(∂V/∂T)T,
Evaluate Cp – CV for a perfect gas.