GAS NYATA

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
E1C.2(a) Express the van der Waals parameters a = 0.751 atm dm mol and 3 −1
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
P1C.2 Calculate the molar volume of chlorine gas at 350 K and 2.30 atm using the molar volume of argon under these conditions.
(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
P1C.3 At 273 K measurements on argon gave B = −21.7 cm mol and
−1 10 atm throughout. At what temperature is the behaviour of the gas closest
C = 1200 cm6 mol−2, where B and C are the second and third virial coefficients to that of a perfect gas? Use the following data: Tc = 126.3 K, TB = 327.2 K,
a = 1.390 dm6 atm mol−2, b = 0.0391 dm3 mol−1.
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′.
2
and c = 1131 K 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
= − =0
dVm2 (Vm − b)3 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?