Tutorial
Questions and answers
1. Explain the term ‘partial pressure’ and explain why Dalton’s law is a limiting law.
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2. What is the significance of the critical constants?
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3. Explain how the van der Waals equation accounts for critical behaviour.
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4. (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?
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5. 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.
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6. 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?
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7. 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?
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8. 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?
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9. 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 13.55 g cm−3.)
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10. The following data have been obtained for oxygen gas at 273.15 K. Calculate the best value
of the gas constant R from them and the best value of the molar mass of O2.
ρ/atm 0.70000 0.500000 0.250000
Vm/dm3. mol-1 29.9649 44.8090 89.6384
ρ/g/dm3 0.914110 0.714110 0.356975
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11. At 100°C and 1.60 kPa, the mass density of phosphorus vapour is 0.6388 kg m−3. What is
the molecular formula of phosphorus under these conditions?
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12. Calculate the mass of water vapour present in a room of volume 250 m3 that contains air at
23°C on a day when the relative humidity is 53 per cent.
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13. A gas mixture consists of 320 mg of methane, 175 mg of argon, and 225 mg of neon. The
partial pressure of neon at 300 K is 8.87 kPa. Calculate (a) the volume and (b) the total
pressure of the mixture.
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14. In an experiment to measure the molar mass of a gas, 250 cm3 of the gas was confined in a
glass vessel. The pressure was 152 Torr at 298 K and, after correcting for buoyancy effects,
the mass of the gas was 33.5 mg. What is the molar mass of the gas?
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15. A certain sample of a gas has a volume of 20.00 dm3 at 0°C and 1.000 atm. A plot of the
experimental data of its volume against the Celsius temperature, θ, at constant p, gives a
straight line of slope 0.0741 dm3 (°C)−1. From these data alone (without making use of the
perfect gas law), determine the absolute zero of temperature in degrees Celsius.
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16. Express the van der Waals parameters a = 1.32 atm dm6 mol−2 and b =0.0436 dm3 mol−1
in SI base units.
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17. 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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18. Cylinders of compressed gas are typically filled to a pressure of 200 bar. For oxygen, what
would be the molar volume at this pressure and 25°C based on (a) the perfect gas equation,
(b) the van der Waals equation. For oxygen, a = 1.364 dm6 atm mol−2, b = 3.19 × 10−2 dm3
mol−1.
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19. At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate (a) the volume
occupied by 8.2 mmol of the gas under these conditions and (b) an approximate value of the
second virial coefficient B at 300 K.
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20. A vessel of volume 22.4 dm3 contains 1.5 mol H2 and 2.5 mol N2 at 273.15 K. Calculate (a)
the mole fractions of each component, (b) their partial pressures, and (c) their total pressure.
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21. The critical constants of ethane are pc = 48.20 atm, Vc = 148 cm3 mol−1, and Tc=305.4 K.
Calculate the van der Waals parameters of the gas and estimate the radius of the molecules.
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22. Use the van der Waals parameters for hydrogen sulfide to calculate approximate values of
(a) the Boyle temperature of the gas and
(b) the radius of a H2S molecule regarded as a sphere (a = 4.484 dm6atm mol−2, b =0.0434
dm3 mol−1).
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23. Suggest the pressure and temperature at which 1.0 mol of (a) H2S, (b) CO2, (c) Ar will be in
states that correspond to 1.0 mol N2 at 1.0 atm and 25°C.
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24. A certain gas obeys the van der Waals equation with a = 0.76 m6 Pa mol−2. Its volume is
found to be 4.00 × 10−4 m3 mol−1 at 288 K and 4.0 MPa. From this information calculate
the van der Waals constant b. What is the compression factor for this gas at the prevailing
temperature and pressure?
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25. 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.
Answer
26. Show that the van der Waals equation leads to values of Z < 1 and Z > 1, and identify the
conditions for which these values are obtained.
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27. Derive an expression for the compression factor of a gas that obeys the equation of state p(V–
nb) = nRT, where b and R are constants. If the pressure and temperature are such that Vm =
10b, what is the numerical value of the compression factor?
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