UNIT 2: THERMODYNAMICS

NON-IDEALITY: GASES AND SOLUTIONS

1. Estimate the molar volume of CO2 at 500 K and 100 atm by treating it as
a van der Waals gas. (a= 3.610 atm dm6 mol-2) and (b = 4.29 dm3 mol-1)
2. Estimate the molar volume of nitrogen gas at 500K and 100atm
by treating it as a VAN DER WAAL'S Equation?
3. At T= 300 K, 1.00 mol of CO2 occupies a volume of 1.50 L. Calculate
the pressures given by the ideal gas equation and the van der Waals
equation. (a= 3.610 atm dm6 mol-2) and (b = 4.29 dm3 mol-1)
4. The van der Waals constants for N2 are: a= 1.370 L2.atm.mol-2 b=
0.0387 L.mol-1. Consider 0.5 moles of N2(g) is in a vessel of volume
10.0L. Assuming that the temperature is 300 K,

(a) compare the pressures predicted by the ideal gas equation and the
van der Waals equation.
(b) What is the percent error in using the ideal gas equation instead of
van der Waals equation?
5. For the van der Waals gas, show that at critical point molar volume,
temperature and pressure are given by the expressions:

8a a
Vc ,m  3b Tc ,m  Pc ,m 
27 Rb 27b 2
And that the compressibility fact at the critical point has a value of 3/8
6. Carbon dioxide gas (1.00 mole) at 373 K occupies 536 mL at
50.0 atmosphere pressure. What is the calculated value of the
pressure using
(i) Ideal gas equation
(ii) Van der Waals equation?
7. Predict which of the substances,
NH3, N2, CH2Cl2, Cl2, CCl4 has
(i) the smallest van der Waals "a" constant
(ii) the largest "b" constant.
8. (i) Using Van der Waals equation, calculate the temperature of 20.0
mole of helium in a 10.0 litre cylinder at 120 atmosphere pressure.
[Data - Van der Waals constants for helium: a = 0.0341 L2 at mol-2;
b = 0.0237 L mol-1]
(ii) Compare this value with the temperature calculated from the ideal
gas equation.
9. Calculate the pressure exerted by Ar for a molar volue of 1,31
Lmol-1 at 426 K using the van der Waals equation of state. The van
der Waal parameters a and b for Ar are 1,355 bar dm6mol-2 and
0,0320 dm3mol-1, respectively. Is the attractive or repulsive portion
of the potential dominant under these conditions?
10. Use the ideal gas and van der Waals equations to calculate the
pressure when 2,25 mol H2 are confined to a volume of 1,65 L at 298
K. Is the gas in the repulsive or attractive region of the molecule-
molecule potential? The van der Waal parameters a and b for H2 are
0,2452 bar dm6mol-2 and 0,0265 dm3mol-1, respectively.
11. Compare the pressures predicted for 0.8 dm3 of Cl2 weighing 17.5
g at 273.15 K using (a) the ideal gas equation and (b) the van der
Waals equation.
12. A particular mass of N2 occupies a volume of 1.00 L at –50 °C and
800 bar. Determine the volume occupied by the same mass of N2 at
100 °C and 200 bar using the compressibility factor for N2. At –50 °C
and 800 bar it is 1.95; at 100 °C and 200 bar it is 1.10. Compare this
value to that obtained from the ideal gas law.
13. The critical temperature Tc of nitrous oxide (N2O) is 36.5 °C, and its
critical pressure Pc is 71.7 atm. Suppose that 1 mol of N2O is
compressed to 54.0 atm at 356 K. Calculate the reduced temperature
and pressure
14, At what temperature and pressure will H2 be in a corresponding
state with CH4 at 500.0 K and 2.00 bar pressure? Given Tc = 33.2 K for
H2, 190.6 K for CH4; Pc = 13.0 bar for H2, 46.0 bar for CH4.
16. The standard enthalpy of formation of H2O (g) at 298 K is -241.82
k J mol-1. Estimate its value at 100 ˚C given the following values of
the molar heat capacities at constant pressure: H2O (g): 33.58 J K-1
mol-1; H2 (g): 28.82 J K-1 mol-1 ; O2(g): 29.36 J K-1 mol-1 . Assume that
the heat capacities are independent of temperature
17. Is the following statement correct? If not, rewrite it so that it is
correct

Because the enthalpy of formation of elements is zero, Hf0 (O(g))=0

18. If the Hf0 for the chemical compounds involved in a reaction are
available at a given temperature, how can HR0 be calculated at
another temperature

19. Is the following statement correct? If not, rewrite it so that it is

correct

If HR0 for a chemical reaction does not change appreciably with

temperature, the heat capacities for reactants and products must be
small.
20. At 1000 K, HR0 = -123,77kJmol-1 for the reaction

N2 (g) + 3H2 (g) 2NH3 (g)

with CP,m = 3.502R, 3.466R and 4,217R for N2(g), H2(g) and NH3(g),
respectively.

Calculate Hf0 of NH3 (g) at 450 K from this information, Assume

that the heat capacities are independent of temperature.
21. Calculate Hf0 of NO (g) at 975 K, assuming the heat capacities of
reactants and products are constant over the temperature interval at
their values at 298,15 K
22. At 298 K, HR0 =131,28kJ mol-1 for the reaction

C(graphite) + H2O (g)  CO(g) + H2 (g), with CP,m = 8,53, 33,58,

39,12 and 28,82 J K-1 mol-1 for graphite, H2O (g), CO(g) and H2 (g),
respectively. Calculate HR0 at 240 C from this information, Assume
that the heat capacities are independent of temperature
23
Given that p* (H2O) = 0.02308 atm and p (H2O) = 0.02239 atm in a solution in
which 0.122 kg of a non-volatile solute (M = 241 g.mol-1) is dissolved in 0.920 kg
water at 293 K, calculate the activity and activity coefficient of water in the
solution.
23. Beckmann and Faust [Z. Physik. Chemie, 89, 235(1915)] found
that a solution of chloroform in acetone in which the mole fraction of
the latter is 0.713 has a total vapor pressure of 220.5 Torr at 28.15 °C.
The mole fraction of acetone in the vapor is 0.818. The vapor
pressure of pure chloroform at this temperature is 221.8 Torr.
Assuming that the vapor behaves ideally, calculate the activity and
the activity coefficient of chloroform
24. When 12.5 g of A, a nonvolatile compound, is dissolved in 520.8 g
of ethanol, the vapor pressure of the pure solvent, 56.18 Torr, is
reduced to 55.24 Torr. Calculate the molar mass of compound A.
25. The vapor pressure of pure ethylene dibromide is 172 Torr and
that of pure propylene dibromide is 128 Torr both at 358 K and 1 atm
pressure. If these two components follow Raoult’s law, estimate the
total vapor pressure and the vapor composition in equilibrium with a
solution that is 0.600 mol fraction propylene dibromide.
26. In a molar mass determination, 18.04 g of the sugar mannitol
was dissolved in 100.0 g of water. The vapor pressure of the
solution at 298 K was 2.291 kPa, having been lowered by 0.0410
kPa from the value for pure water. Calculate the molar mass of
mannitol.
27.

A liquid has a vapor pressure of 40.00 kPa at 298.15 K. When 0.080 kg

of an involatile solute is dissolved in 1 mol of the liquid, the new vapor
pressure is 26.66 kPa. What is the molar mass of the solute? Assume
that the solution is ideal.
28. Components 1 and 2 form an ideal solution. The pressure of pure
component 1 is 13.3 kPa at 298 K, and the corresponding vapor
pressure of component 2 is approximately zero. If the addition of 1.00
g of component 2 to 10.00 g of component 1 reduces the total vapor
pressure to 12.6 kPa, find the ratio of the molar mass of component 2
to that of component 1.
29. Calculate the activity and activity coefficients for 0.330 mol
fraction toluene in benzene. The vapor pressure of pure benzene is
9.657 kPa at 298 K. P2* = 3.572 kPa for toluene. The vapor pressure
for benzene above the solution is P1 = 6.677 kPa and for toluene P2 =
1.214 kPa.
30. Calculate the mole fraction, activity, and activity coefficients for
water when 11.5 g NaCl are dissolved in 100 g water at 298 K. The
vapor pressure is 95.325 kPa.
31. The mole fraction of a nonvolatile solute dissolved in water is
0.010. If the vapor pressure of pure water at 293 K is 2.339 kPa and
that of the solution is 2.269 kPa, calculate the activity and activity
coefficient of water.
32. Calculate the ionic strengths of 0.1 M solutions of KNO3, K2SO4,
ZnSO4, ZnCl2, and K4Fe(CN)6; assume complete dissociation and
neglect hydrolysis.
33. Calculate the mean activity coefficient γ± for the Ba2+ and SO42−
ions in a saturated solution of BaSO4 (Ksp = 9.2 × 10–11 mol2 dm–6 ) in
0.2 M K2SO4, assuming the Debye-Hückel limiting law to apply.
34. The solubility of AgCl in water at 25 °C is 1.274 × 10–5 mol dm–3 .
On the assumption that the Debye-Hückel limiting law applies,

a. Calculate ΔG° for the process AgCl(s) → Ag+ (aq) + Cl– (aq).

b. Calculate the solubility of AgCl in an 0.005 M solution of K2SO4.

35. What concentrations of the following have the same ionic strength as 0.1 M
NaCl?

CuSO4, Ni(NO3)2, Al2(SO4)3, Na3PO4

Assume complete dissociation and neglect hydrolysis.

36. The solubility product of PbF2 at 25.0 °C is 4.0 × 10–9 mol3 dm–9 .
Assuming the Debye-Hückel limiting law to apply, calculate the
solubility of PbF2 in

(a) pure water and

(b) (b) 0.01 M NaF.

37. Calculate the solubility of silver acetate in water at 25 °C,
assuming the Debye-Hückel limiting law to apply; the solubility
product is 4.0 × 10–3 mol2 dm–6 .
38. If the solubility product of barium sulfate is 9.2 × 10–11 mol2 dm–6 ,
calculate the solubility of BaSO4 in a solution that is 0.10 M in NaNO3
and 0.20 M in Zn(NO3)2; assume the Debye-Hückel limiting law to
apply
39. Silver chloride, AgCl, is found to have a solubility of 1.561 × 10–5 M
in a solution that is 0.01 M in K2SO4. Assume the Debye-Hückel limiting
law to apply and calculate the solubility in pure water.
40. Make use of the Debye-Hückel limiting law to estimate the activity
coefficients of the ions in an aqueous 0.004 M solution of sodium
sulfate at 298 K. Estimate also the mean activity coefficient.
41. Calculate the ionic strength and the mean activity coefficient ()
of 2.0m mol kg-1 Ca(NO3)2 at 25 oC.
42. The mean activity coefficient () in a 0.100 mol kg-1 MnCl2(aq)
solution is 0.47 at 25oC. What is the percentage error in the value
predicted by the Debye-Huckel limiting law?
43. The mean activity coefficient () of NaCl in a diluted aqueous
solution at 25oC is 0.907 (at 10.0 mmol kg-1). Estimate the value of B
in the extended Debye-Huckel law.
44. Calculate the ionic strength and the mean activity coefficient ()
of 5.0×10-3 mol kg-1 KCl(aq) and 1.00 mmol kg-1 CaCl2 (aq) at 25°C.