28  1  The properties of gases

FOCUS 1  The properties of gases

TOPIC 1A  The perfect gas

Discussion questions
D1A.1 Explain how the perfect gas equation of state arises by combination of D1A.2 Explain the term ‘partial pressure’ and explain why Dalton’s law is a
Boyle’s law, Charles’s law, and Avogadro’s principle. limiting law.

Exercises
E1A.1(a) Express (i) 108 kPa in torr and (ii) 0.975 bar in atmospheres. E1A.7(a) Calculate the mass of water vapour present in a room of volume
E1A.1(b) Express (i) 22.5 kPa in atmospheres and (ii) 770 Torr in pascals. 400 m3 that contains air at 27 °C on a day when the relative humidity is 60 per
3 cent. Hint: Relative humidity is the prevailing partial pressure of water vapour
E1A.2(a) Could 131 g of xenon gas in a vessel of volume 1.0 dm exert a
expressed as a percentage of the vapour pressure of water vapour at the same
pressure of 20 atm at 25 °C if it behaved as a perfect gas? If not, what pressure
temperature (in this case, 35.6 mbar).
would it exert?
3 E1A.7(b) Calculate the mass of water vapour present in a room of volume
E1A.2(b) Could 25 g of argon gas in a vessel of volume 1.5 dm exert a pressure
250 m3 that contains air at 23 °C on a day when the relative humidity is
of 2.0 bar at 30 °C if it behaved as a perfect gas? If not, what pressure would it
53 per cent (in this case, 28.1 mbar).
exert?
E1A.8(a) Given that the mass density of air at 0.987 bar and 27 °C is 1.146 kg
E1A.3(a) A perfect gas undergoes isothermal compression, which reduces its
3 m−3, calculate the mole fraction and partial pressure of nitrogen and oxygen
volume by 2.20 dm . The final pressure and volume of the gas are 5.04 bar
assuming that (i) air consists only of these two gases, (ii) air also contains
and 4.65 dm3, respectively. Calculate the original pressure of the gas in (i) bar,
1.0 mole per cent Ar.
(ii) atm.
E1A.8(b) A gas mixture consists of 320 mg of methane, 175 mg of argon, and
E1A.3(b) A perfect gas undergoes isothermal compression, which reduces its
225 mg of neon. The partial pressure of neon at 300 K is 8.87 kPa. Calculate
volume by 1.80 dm3. The final pressure and volume of the gas are 1.97 bar
(i) the volume and (ii) the total pressure of the mixture.
and 2.14 dm3, respectively. Calculate the original pressure of the gas in (i) bar,
−3
(ii) torr. E1A.9(a) The mass density of a gaseous compound was found to be 1.23 kg m
−2 at 330 K and 20 kPa. What is the molar mass of the compound?
E1A.4(a) A car tyre (an automobile tire) was inflated to a pressure of 24 lb in 3
E1A.9(b) In an experiment to measure the molar mass of a gas, 250 cm of the
(1.00 atm = 14.7 lb in−2) on a winter’s day when the temperature was −5 °C.
gas was confined in a glass vessel. The pressure was 152 Torr at 298 K, and
What pressure will be found, assuming no leaks have occurred and that the
after correcting for buoyancy effects, the mass of the gas was 33.5 mg. What is
volume is constant, on a subsequent summer’s day when the temperature is
the molar mass of the gas?
35 °C? What complications should be taken into account in practice?
−3
E1A.4(b) A sample of hydrogen gas was found to have a pressure of 125 kPa E1A.10(a) The densities of air at −85 °C, 0 °C, and 100 °C are 1.877 g dm ,
−3 −3
when the temperature was 23 °C. What can its pressure be expected to be 1.294 g dm , and 0.946 g dm , respectively. From these data, and assuming
when the temperature is 11 °C? that air obeys Charles’ law, determine a value for the absolute zero of
3 temperature in degrees Celsius.
E1A.5(a) A sample of 255 mg of neon occupies 3.00 dm at 122 K. Use the 3
E1A.10(b) A certain sample of a gas has a volume of 20.00 dm at 0 °C and
perfect gas law to calculate the pressure of the gas.
3 3 1.000 atm. A plot of the experimental data of its volume against the Celsius
E1A.5(b) A homeowner uses 4.00 × 10  m of natural gas in a year to heat a
temperature, θ, at constant p, gives a straight line of slope 0.0741 dm3 °C−1.
home. Assume that natural gas is all methane, CH4, and that methane is a
From these data alone (without making use of the perfect gas law), determine
perfect gas for the conditions of this problem, which are 1.00 atm and 20 °C.
the absolute zero of temperature in degrees Celsius.
What is the mass of gas used?
3
E1A.11(a) A vessel of volume 22.4 dm contains 2.0 mol H2(g) and 1.0 mol
E1A.6(a) At 500 °C and 93.2 kPa, the mass density of sulfur vapour is 3.710 kg
N2(g) at 273.15 K. Calculate (i) the mole fractions of each component,
m−3. What is the molecular formula of sulfur under these conditions?
(ii) their partial pressures, and (iii) their total pressure.
E1A.6(b) At 100 °C and 16.0 kPa, the mass density of phosphorus vapour is 3
E1A.11(b) A vessel of volume 22.4 dm contains 1.5 mol H2(g) and 2.5 mol
0.6388 kg m−3. What is the molecular formula of phosphorus under these
N2(g) at 273.15 K. Calculate (i) the mole fractions of each component,
conditions?
(ii) their partial pressures, and (iii) their total pressure.

Problems
P1A.1 A manometer consists of a U-shaped tube containing a liquid. One side external pressure is 760 Torr, and the open side is 10.0 cm higher than the side
is connected to the apparatus and the other is open to the atmosphere. The connected to the apparatus. What is the pressure in the apparatus? The mass
pressure p inside the apparatus is given p = pex + ρgh, where pex is the external density of mercury at 25 °C is 13.55 g cm−3. (ii) In an attempt to determine an
pressure, ρ is the mass density of the liquid in the tube, g = 9.806 m s−2 is the accurate value of the gas constant, R, a student heated a container of volume
acceleration of free fall, and h is the difference in heights of the liquid in the 20.000 dm3 filled with 0.251 32 g of helium gas to 500 °C and measured the
two sides of the tube. (The quantity ρgh is the hydrostatic pressure exerted by pressure as 206.402 cm in a manometer filled with water at 25 °C. Calculate the
a column of liquid.) (i) Suppose the liquid in a manometer is mercury, the value of R from these data. The mass density of water at 25 °C is 0.997 07 g cm−3.
 Exercises and problems  29

P1A.2 Recent communication with the inhabitants of Neptune have revealed of atmosphere with a cross-sectional area of 1.00 dm2 if the abundance is
that they have a Celsius-type temperature scale, but based on the melting 250 Dobson units (a typical midlatitude value)? In the seasonal Antarctic
point (0 °N) and boiling point (100 °N) of their most common substance, ozone hole, the column abundance drops below 100 Dobson units; how
hydrogen. Further communications have revealed that the Neptunians know many moles of O3 are found in such a column of air above a 1.00 dm2 area?
about perfect gas behaviour and they find that in the limit of zero pressure, Most atmospheric ozone is found between 10 and 50 km above the surface
the value of pV is 28 dm3 atm at 0 °N and 40 dm3 atm at 100 °N. What is the of the Earth. If that ozone is spread uniformly through this portion of the
value of the absolute zero of temperature on their temperature scale? atmosphere, what is the average molar concentration corresponding to (a)
250 Dobson units, (b) 100 Dobson units?
P1A.3 The following data have been obtained for oxygen gas at 273.15K. From
the data, calculate the best value of the gas constant R. P1A.11‡ In a commonly used model of the atmosphere, the atmospheric
pressure varies with altitude, h, according to the barometric formula:
p/atm 0.750 000 0.500 000 0.250 000
Vm/(dm3 mol−1) 29.8649 44.8090 89.6384 p = p0e–h/H

where p0 is the pressure at sea level and H is a constant approximately equal

P1A.4 Charles’s law is sometimes expressed in the form V = V0(1 + αθ),
to 8 km. More specifically, H = RT/Mg, where M is the average molar mass
where θ is the Celsius temperature, α is a constant, and V0 is the volume of
of air and T is the temperature at the altitude h. This formula represents the
the sample at 0 °C. The following values for have been reported for nitrogen
outcome of the competition between the potential energy of the molecules
at 0 °C:
in the gravitational field of the Earth and the stirring effects of thermal
motion. Derive this relation by showing that the change in pressure dp
p/Torr 749.7 599.6 333.1 98.6
for an infinitesimal change in altitude dh where the mass density is ρ is
3
10 α/°C –1
3.6717 3.6697 3.6665 3.6643 dp = −ρgdh. Remember that ρ depends on the pressure. Evaluate (a) the
pressure difference between the top and bottom of a laboratory vessel
For these data estimate the absolute zero of temperature on the Celsius scale. of height 15 cm, and (b) the external atmospheric pressure at a typical
cruising altitude of an aircraft (11 km) when the pressure at ground level
P1A.5 Deduce the relation between the pressure and mass density, ρ, of a
is 1.0 atm.
perfect gas of molar mass M. Confirm graphically, using the following data on
methoxymethane (dimethyl ether) at 25 °C, that perfect behaviour is reached P1A.12‡ Balloons are still used to deploy sensors that monitor meteorological
at low pressures and find the molar mass of the gas. phenomena and the chemistry of the atmosphere. It is possible to investigate
some of the technicalities of ballooning by using the perfect gas law. Suppose
p/kPa 12.223 25.20 36.97 60.37 85.23 101.3 your balloon has a radius of 3.0 m and that it is spherical. (a) What amount of
ρ/(kg m )–3
0.225 0.456 0.664 1.062 1.468 1.734 H2 (in moles) is needed to inflate it to 1.0 atm in an ambient temperature of
25 °C at sea level? (b) What mass can the balloon lift (the payload) at sea level,
where the mass density of air is 1.22 kg m−3? (c) What would be the payload if
P1A.6 The molar mass of a newly synthesized fluorocarbon was measured
He were used instead of H2?
in a gas microbalance. This device consists of a glass bulb forming one
end of a beam, the whole surrounded by a closed container. The beam is P1A.13‡ Chlorofluorocarbons such as CCl3F and CCl2F2 have been linked to
pivoted, and the balance point is attained by raising the pressure of gas ozone depletion in Antarctica. In 1994, these gases were found in quantities
in the container, so increasing the buoyancy of the enclosed bulb. In one of 261 and 509 parts per trillion by volume (World Resources Institute,
experiment, the balance point was reached when the fluorocarbon pressure World resources 1996–97). Compute the molar concentration of these gases
was 327.10 Torr; for the same setting of the pivot, a balance was reached under conditions typical of (a) the mid-latitude troposphere (10 °C and
when CHF3 (M = 70.014 g mol−1) was introduced at 423.22 Torr. A repeat of 1.0 atm) and (b) the Antarctic stratosphere (200 K and 0.050 atm). Hint:
the experiment with a different setting of the pivot required a pressure of The composition of a mixture of gases can be described by imagining that
293.22 Torr of the fluorocarbon and 427.22 Torr of the CHF3. What is the the gases are separated from one another in such a way that each exerts the
molar mass of the fluorocarbon? Suggest a molecular formula. same pressure. If one gas is present at very low levels it is common to
express its concentration as, for example, ‘x parts per trillion by volume’.
P1A.7 A constant-volume perfect gas thermometer indicates a pressure of
Then the volume of the separated gas at a certain pressure is x × 10−12 of
6.69 kPa at the triple point temperature of water (273.16 K). (a) What change
the original volume of the gas mixture at the same pressure. For a mixture
of pressure indicates a change of 1.00 K at this temperature? (b) What pressure
of perfect gases, the volume of each separated gas is proportional to its
indicates a temperature of 100.00 °C? (c) What change of pressure indicates a
partial pressure in the mixture and hence to the amount in moles of the gas
change of 1.00 K at the latter temperature?
molecules present in the mixture.
3
P1A.8 A vessel of volume 22.4 dm contains 2.0 mol H2(g) and 1.0 mol N2(g)
P1A.14 At sea level the composition of the atmosphere is approximately
at 273.15 K initially. All the H2 then reacts with sufficient N2 to form NH3.
80 per cent nitrogen and 20 per cent oxygen by mass. At what height above
Calculate the partial pressures of the gases in the final mixture and the total
the surface of the Earth would the atmosphere become 90 per cent nitrogen
pressure.
and 10 per cent oxygen by mass? Assume that the temperature of the
P1A.9 Atmospheric pollution is a problem that has received much attention. atmosphere is constant at 25 °C. What is the pressure of the atmosphere at
Not all pollution, however, is from industrial sources. Volcanic eruptions can that height? Hint: Use a barometric formula, see Problem P1A.11, for each
be a significant source of air pollution. The Kilauea volcano in Hawaii emits partial pressure.
200−300 t (1 t = 103 kg) of SO2 each day. If this gas is emitted at 800 °C and
1.0 atm, what volume of gas is emitted?
P1A.10 Ozone is a trace atmospheric gas which plays an important role in
screening the Earth from harmful ultraviolet radiation, and the abundance
of ozone is commonly reported in Dobson units. Imagine a column passing
up through the atmosphere. The total amount of O3 in the column divided
by its cross-sectional area is reported in Dobson units with 1 Du =
0.4462 mmol m−2. What amount of O3 (in moles) is found in a column ‡
  These problems were supplied by Charles Trapp and Carmen Giunta.
30  1  The properties of gases

TOPIC 1B  The kinetic model

Discussion questions
D1B.1 Specify and analyse critically the assumptions that underlie the kinetic D1B.3 Use the kinetic model of gases to explain why light gases, such as He,
model of gases. are rare in the Earth’s atmosphere but heavier gases, such as O2, CO2, and N2,
once formed remain abundant.
D1B.2 Provide molecular interpretations for the dependencies of the mean free
path on the temperature, pressure, and size of gas molecules.

Exercises
E1B.1(a) Determine the ratios of (i) the mean speeds, (ii) the mean E1B.6(a) Evaluate the collision frequency of H2 molecules in a gas at 1.00 atm
translational kinetic energies of H2 molecules and Hg atoms at 20 °C. and 25 °C.
E1B.1(b) Determine the ratios of (i) the mean speeds, (ii) the mean E1B.6(b) Evaluate the collision frequency of O2 molecules in a gas at 1.00 atm
translational kinetic energies of He atoms and Hg atoms at 25 °C. and 25 °C.
E1B.2(a) Calculate the root-mean-square speeds of H2 and O2 molecules at E1B.7(a) Assume that air consists of N2 molecules with a collision diameter of
20 °C. 395 pm. Calculate (i) the mean speed of the molecules, (ii) the mean free path,
E1B.2(b) Calculate the root-mean-square speeds of CO2 molecules and He (iii) the collision frequency in air at 1.0 atm and 25 °C.
atoms at 20 °C. E1B.7(b) The best laboratory vacuum pump can generate a vacuum of about
1 nTorr. At 25 °C and assuming that air consists of N2 molecules with a
E1B.3(a) Use the Maxwell–Boltzmann distribution of speeds to estimate the
collision diameter of 395 pm, calculate at this pressure (i) the mean speed of
fraction of N2 molecules at 400 K that have speeds in the range 200–210 m s−1.
the molecules, (ii) the mean free path, (iii) the collision frequency in the gas.
Hint: The fraction of molecules with speeds in the range v to v + dv is equal to
f(v)dv, where f(v) is given by eqn 1B.4. E1B.8(a) At what pressure does the mean free path of argon at 20 °C become
E1B.3(b) Use the Maxwell–Boltzmann distribution of speeds to estimate comparable to the diameter of a 100 cm3 vessel that contains it? Take
the fraction of CO2 molecules at 400 K that have speeds in the range σ = 0.36 nm2.
400–405 m s−1. See the hint in Exercise E1B.3(a). E1B.8(b) At what pressure does the mean free path of argon at 20 °C become
comparable to 10 times the diameters of the atoms themselves? Take
E1B.4(a) What is the relative mean speed of N2 and H2 molecules in a gas at
σ = 0.36 nm2.
25 °C?
E1B.4(b) What is the relative mean speed of O2 and N2 molecules in a gas at E1B.9(a) At an altitude of 20 km the temperature is 217 K and the pressure is
25 °C? 0.050 atm. What is the mean free path of N2 molecules? (σ = 0.43 nm2).
E1B.9(b) At an altitude of 15 km the temperature is 217 K and the pressure is
E1B.5(a) Calculate the most probable speed, the mean speed, and the mean
12.1 kPa. What is the mean free path of N2 molecules? (σ = 0.43 nm2).
relative speed of CO2 molecules at 20 °C.
E1B.5(b) Calculate the most probable speed, the mean speed, and the mean
relative speed of H2 molecules at 20 °C.

Problems
P1B.1 A rotating slotted-disc apparatus consists of five coaxial 5.0 cm diameter square speed? (iii) What are the proportions having speeds greater and smaller
discs separated by 1.0 cm, the radial slots being displaced by 2.0° between than the mean speed? Hint: Use mathematical software to evaluate the integrals.
neighbours. The relative intensities, I, of the detected beam of Kr atoms for
P1B.5 Calculate the fractions of molecules in a gas that have a speed in a range
two different temperatures and at a series of rotation rates were as follows:
Δv at the speed nvmp relative to those in the same range at vmp itself. This
calculation can be used to estimate the fraction of very energetic molecules
ν/Hz 20 40 80 100 120 (which is important for reactions). Evaluate the ratio for n = 3 and n = 4.
I (40 K) 0.846 0.513 0.069 0.015 0.002 n 1/n
P1B.6 Derive an expression for 〈v 〉 from the Maxwell–Boltzmann
I (100 K) 0.592 0.485 0.217 0.119 0.057 distribution of speeds. Hint: You will need the integrals given in the Resource
section, or use mathematical software.
Find the distributions of molecular velocities, f(vx), at these temperatures, and P1B.7 Calculate the escape velocity (the minimum initial velocity that will
check that they conform to the theoretical prediction for a one-dimensional take an object to infinity) from the surface of a planet of radius R. What is the
system for this low-pressure, collision-free system. value for (i) the Earth, R = 6.37 × 106 m, g = 9.81 m s−2, (ii) Mars, R = 3.38 ×
106 m, mMars/mEarth = 0.108. At what temperatures do H2, He, and O2 molecules
P1B.2 Consider molecules that are confined to move in a plane (a two-
have mean speeds equal to their escape speeds? What proportion of the
dimensional gas). Calculate the distribution of speeds and determine the
molecules have enough speed to escape when the temperature is (i) 240 K,
mean speed of the molecules at a temperature T.
(ii) 1500 K? Calculations of this kind are very important in considering the
P1B.3 A specially constructed velocity-selector accepts a beam of molecules composition of planetary atmospheres.
from an oven at a temperature T but blocks the passage of molecules with a
P1B.8 Plot different Maxwell–Boltzmann speed distributions by keeping the
speed greater than the mean. What is the mean speed of the emerging beam,
molar mass constant at 100 g mol−1 and varying the temperature of the sample
relative to the initial value? Treat the system as one-dimensional.
between 200 K and 2000 K.
P1B.4 What, according to the Maxwell–Boltzmann distribution, is the
P1B.9 Evaluate numerically the fraction of O2 molecules with speeds in the
proportion of gas molecules having (i) more than, (ii) less than the root mean
range 100 m s−1 to 200 m s−1 in a gas at 300 K and 1000 K.
 Exercises and problems  31

P1B.10 The maximum in the Maxwell–Boltzmann distribution occurs when P1B.11 A methane, CH4, molecule may be considered as spherical, with a
df(v)/dv = 0. Find, by differentiation, an expression for the most probable radius of 0.38 nm. How many collisions does a single methane molecule make
speed of molecules of molar mass M at a temperature T. if 0.10 mol CH4(g) is held at 25 °C in a vessel of volume 1.0 dm3?

TOPIC 1C  Real gases

Discussion questions
D1C.1 Explain how the compression factor varies with pressure and D1C.3 Describe the formulation of the van der Waals equation and suggest a
temperature and describe how it reveals information about intermolecular rationale for one other equation of state in Table 1C.4.
interactions in real gases.
D1C.4 Explain how the van der Waals equation accounts for critical behaviour.
D1C.2 What is the significance of the critical constants?

Exercises
E1C.1(a) Calculate the pressure exerted by 1.0 mol C2H6 behaving as a van der van der Waals equations of state. Calculate the compression factor based on
Waals gas when it is confined under the following conditions: (i) at 273.15 K these calculations. For ethane, a = 5.507 dm6 atm mol−2, b = 0.0651 dm3 mol−1.
in 22.414 dm3, (ii) at 1000 K in 100 cm3. Use the data in Table 1C.3 of the E1C.5(b) At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate
Resource section. (i) the volume occupied by 8.2 mmol of the gas molecules under these conditions
E1C.1(b) Calculate the pressure exerted by 1.0 mol H2S behaving as a van der and (ii) an approximate value of the second virial coefficient B at 300 K.
Waals gas when it is confined under the following conditions: (i) at 273.15 K
E1C.6(a) The critical constants of methane are pc = 45.6 atm, Vc =
in 22.414 dm3, (ii) at 500 K in 150 cm3. Use the data in Table 1C.3 of the
98.7 cm3 mol−1, and Tc = 190.6 K. Calculate the van der Waals parameters of
Resource section.
the gas and estimate the radius of the molecules.
6 −2 3 −1
E1C.2(a) Express the van der Waals parameters a = 0.751 atm dm  mol and E1C.6(b) The critical constants of ethane are pc = 48.20 atm, Vc = 148 cm  mol ,
b = 0.0226 dm3 mol−1 in SI base units (kg, m, s, and mol). and Tc = 305.4 K. Calculate the van der Waals parameters of the gas and
6 −2
E1C.2(b) Express the van der Waals parameters a = 1.32 atm dm  mol and estimate the radius of the molecules.
b = 0.0436 dm3 mol−1 in SI base units (kg, m, s, and mol).
E1C.7(a) Use the van der Waals parameters for chlorine in Table 1C.3 of the
E1C.3(a) A gas at 250 K and 15 atm has a molar volume 12 per cent smaller Resource section to calculate approximate values of (i) the Boyle temperature
than that calculated from the perfect gas law. Calculate (i) the compression of chlorine from TB = a/Rb and (ii) the radius of a Cl2 molecule regarded as a
factor under these conditions and (ii) the molar volume of the gas. Which are sphere.
dominating in the sample, the attractive or the repulsive forces? E1C.7(b) Use the van der Waals parameters for hydrogen sulfide in Table
E1C.3(b) A gas at 350 K and 12 atm has a molar volume 12 per cent larger 1C.3 of the Resource section to calculate approximate values of (i) the Boyle
than that calculated from the perfect gas law. Calculate (i) the compression temperature of the gas from TB = a/Rb and (ii) the radius of an H2S molecule
factor under these conditions and (ii) the molar volume of the gas. Which are regarded as a sphere.
dominating in the sample, the attractive or the repulsive forces?
E1C.8(a) Suggest the pressure and temperature at which 1.0 mol of (i) NH3, (ii) Xe,
E1C.4(a) In an industrial process, nitrogen is heated to 500 K at a constant (iii) He will be in states that correspond to 1.0 mol H2 at 1.0 atm and 25 °C.
volume of 1.000 m3. The mass of the gas is 92.4 kg. Use the van der E1C.8(b) Suggest the pressure and temperature at which 1.0 mol of (i) H2O (ii) CO2,
Waals equation to determine the approximate pressure of the gas at its (iii) Ar will be in states that correspond to 1.0 mol N2 at 1.0 atm and 25 °C.
working temperature of 500 K. For nitrogen, a = 1.352 dm6 atm mol−2, b = 6
E1C.9(a) A certain gas obeys the van der Waals equation with a = 0.50 m
0.0387 dm3 mol−1. −2 –4 3 −1
Pa mol . Its molar volume is found to be 5.00 × 10  m  mol at 273 K and
E1C.4(b) Cylinders of compressed gas are typically filled to a pressure of
3.0 MPa. From this information calculate the van der Waals constant b. What is
200 bar. For oxygen, what would be the molar volume at this pressure and
the compression factor for this gas at the prevailing temperature and pressure?
25 °C based on (i) the perfect gas equation, (ii) the van der Waals equation? 6
E1C.9(b) A certain gas obeys the van der Waals equation with a = 0.76 m
For oxygen, a = 1.364 dm6 atm mol−2, b = 3.19 × 10–2 dm3 mol−1. −2 –4 3 −1
Pa mol . Its molar volume is found to be 4.00 × 10  m  mol at 288 K and
3
E1C.5(a) Suppose that 10.0 mol C2H6(g) is confined to 4.860 dm at 27 °C. 4.0 MPa. From this information calculate the van der Waals constant b. What is
Predict the pressure exerted by the ethane from (i) the perfect gas and (ii) the the compression factor for this gas at the prevailing temperature and pressure?

Problems
P1C.1 What pressure would 4.56 g of nitrogen gas in a vessel of volume in the expansion of Z in powers of 1/Vm. Assuming that the perfect gas law
2.25 dm3 exert at 273 K if it obeyed the virial equation of state up to and holds sufficiently well for the estimation of the molar volume, calculate the
including the first two terms? compression factor of argon at 100 atm and 273 K. From your result, estimate
the molar volume of argon under these conditions.
P1C.2 Calculate the molar volume of chlorine gas at 350 K and 2.30 atm using
(a) the perfect gas law and (b) the van der Waals equation. Use the answer to P1C.4 Calculate the volume occupied by 1.00 mol N2 using the van der
(a) to calculate a first approximation to the correction term for attraction and Waals equation expanded into the form of a virial expansion at (a) its
then use successive approximations to obtain a numerical answer for part (b). critical temperature, (b) its Boyle temperature. Assume that the pressure is
3 −1 10 atm throughout. At what temperature is the behaviour of the gas closest
P1C.3 At 273 K measurements on argon gave B = −21.7 cm  mol and
6 −2 to that of a perfect gas? Use the following data: Tc = 126.3 K, TB = 327.2 K,
C = 1200 cm  mol , where B and C are the second and third virial coefficients
a = 1.390 dm6 atm mol−2, b = 0.0391 dm3 mol−1.
32  1  The properties of gases

P1C.5‡ The second virial coefficient of methane can be approximated by the P1C.14 Equations 1C.3a and 1C.3b are expansions in p and 1/Vm, respectively.
2
empirical equation B(T) = a + e − c/T , where a = −0.1993 bar−1, b = 0.2002 bar−1, Find the relation between B, C and B′, C′.
and c = 1131 K2 with 300 K < T < 600 K. What is the Boyle temperature of
P1C.15 The second virial coefficient B′ can be obtained from measurements of
methane?
the mass density ρ of a gas at a series of pressures. Show that the graph of p/ρ
P1C.6 How well does argon gas at 400 K and 3 atm approximate a perfect gas? against p should be a straight line with slope proportional to B′. Use the data
Assess the approximation by reporting the difference between the molar on methoxymethane in Problem P1A.5 to find the values of B′ and B at 25 °C.
volumes as a percentage of the perfect gas molar volume.
P1C.16 The equation of state of a certain gas is given by p = RT/Vm + (a + bT)/
P1C.7 The mass density of water vapour at 327.6 atm and 776.4 K Vm2, where a and b are constants. Find (∂Vm/∂T)p.
is 133.2 kg m−3. Given that for water a = 5.464 dm6 atm mol−2, b =
P1C.17 Under what conditions can liquid nitrogen be formed by the
0.03049 dm3 mol−1, and M = 18.02 g mol−1, calculate (a) the molar volume. Then
application of pressure alone?
calculate the compression factor (b) from the data, and (c) from the virial
expansion of the van der Waals equation. P1C.18 The following equations of state are occasionally used for approximate
calculations on gases: (gas A) pVm = RT(1 + b/Vm), (gas B) p(Vm − b) = RT.
P1C.8 The critical volume and critical pressure of a certain gas are
3 −1 Assuming that there were gases that actually obeyed these equations of state,
160 cm  mol and 40 atm, respectively. Estimate the critical temperature by
would it be possible to liquefy either gas A or B? Would they have a critical
assuming that the gas obeys the Berthelot equation of state. Estimate the radii
temperature? Explain your answer.
of the gas molecules on the assumption that they are spheres.
P1C.19 Derive an expression for the compression factor of a gas that obeys the
P1C.9 Estimate the coefficients a and b in the Dieterici equation of state from
equation of state p(V − nb) = nRT, where b and R are constants. If the pressure
the critical constants of xenon. Calculate the pressure exerted by 1.0 mol Xe
and temperature are such that Vm = 10b, what is the numerical value of the
when it is confined to 1.0 dm3 at 25 °C.
compression factor?
P1C.10 For a van der Waals gas with given values of a and b, identify the
P1C.20 What would be the corresponding state of ammonia, for the conditions
conditions for which Z < 1 and Z > 1.
described for argon in Brief illustration 1C.5?
P1C.11 Express the van der Waals equation of state as a virial expansion
P1C.21‡ Stewart and Jacobsen have published a review of thermodynamic
in powers of 1/Vm and obtain expressions for B and C in terms of the
properties of argon (R.B. Stewart and R.T. Jacobsen, J. Phys. Chem. Ref. Data
parameters a and b. The expansion you will need is (1 − x)−1 = 1 + x + x2 + … .
18, 639 (1989)) which included the following 300 K isotherm.
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? p/MPa 0.4000 0.5000 0.6000 0.8000 1.000
Vm/(dm3 mol−1) 6.2208 4.9736 4.1423 3.1031 2.4795
P1C.12 The critical constants of a van der Waals gas can be found by setting
the following derivatives equal to zero at the critical point: p/MPa 1.500 2.000 2.500 3.000 4.000
Vm/(dm3 mol−1) 1.6483 1.2328 0.98 357 0.81 746 0.60 998
dp RT 2a
=− + =0
dVm (Vm − b)2 Vm3
(a) Compute the second virial coefficient, B, at this temperature. (b) Use non-
d2 p 2 RT 6a linear curve-fitting software to compute the third virial coefficient, C, at this
2 = 3 − =0
  dVm (Vm − b ) Vm4 temperature.
Solve this system of equations and then use eqn 1C.5b to show that pc, Vc, and P1C.22 Use the van der Waals equation of state and mathematical software
Tc are given by eqn 1C.6. or a spreadsheet to plot the pressure of 1.5 mol CO2(g) against volume as it
is compressed from 30 dm3 to 15 dm3 at (a) 273 K, (b) 373 K. (c) Redraw the
P1C.13 A scientist proposed the following equation of state:
graphs as plots of p against 1/V.
RT B C P1C.23 Calculate the molar volume of chlorine on the basis of the van der
p= = −
  Vm Vm2 Vm3 Waals equation of state at 250 K and 150 kPa and calculate the percentage
difference from the value predicted by the perfect gas equation.
Show that the equation leads to critical behaviour. Find the critical constants
of the gas in terms of B and C and an expression for the critical compression P1C.24 Is there a set of conditions at which the compression factor of a van der
factor. Waals gas passes through a minimum? If so, how does the location and value
of the minimum value of Z depend on the coefficients a and b?

FOCUS 1  The properties of gases

Integrated activities
I1.1 Start from the Maxwell–Boltzmann distribution and derive an expression kinetic energy density of the atmosphere is 0.15 J cm−3, what is the total kinetic
for the most probable speed of a gas of molecules at a temperature T. Go on energy density, including rotation?
to demonstrate the validity of the equipartition conclusion that the average
I1.3 Methane molecules, CH4, may be considered as spherical, with a collision
translational kinetic energy of molecules free to move in three dimensions is 32  kT.
cross-section of σ = 0.46 nm2. Estimate the value of the van der Waals
I1.2 The principal components of the atmosphere of the Earth are diatomic parameter b by calculating the molar volume excluded by methane molecules.
molecules, which can rotate as well as translate. Given that the translational