TUTORIALS FOR CHEMICAL THERMODYNAMICS

I-EMPIRICAL PROPERTIES OF GASES

1. The vapour of 0.1525 g of a certain organic substance occupies a volume of 35.05 cm3 at
20°C and a pressure of 730 mmHg. An elementary analysis of the gas gives the following
composition: carbon 22.10%, hydrogen 4.58% and bromine 73.32%. Taking that this gas is
ideal, calculate the molecular mass and determine the formula of the organic substance (C =
12, H = 1, Br = 80). Ans: M = 108.91 g/mol; C2H5Br
2. Given that the coefficient of thermal expansion at constant pressure is expressed by
1  V  1  V 
   and that the coefficient of isothermal compressibility by      ,
V  T  P V  P  T

 P 
obtain an expression for   as a function of  and .
 T  V
3. At 50°C, a thermometer is completely filled with mercury. What is the pressure inside the
thermometer when it is heated to 52°C, knowing that, for mercury  = 1.8×10-4°C-1;  =
43.9×10-6 atm-1.
4. For liquid benzene, the coefficient of isothermal compressibility is 9.30×10-6 atm-1 at 420°C.
Knowing it varies only very slightly with pressure, calculate the pressure variation necessary
to provoke a 20% variation in volume by compression.

5. The equilibrium constant for the reaction N2O4(g) ⇌ 2 NO2(g) at 25°C is K = 0.115. It is

related to the degree of dissociation  and the pressure P (atm) by the expression:
4 2 P
K .
1 2
(i) Calculate V/n at P = 2 atm, 1 atm and 0.5 atm, assuming that the equilibrium mixture
behaves ideally. Compare with the volumes if dissociation did not occur.
PV
(ii) Show that as P tends towards zero, the compressibility factor Z  tends to 2
nRT
instead of the usual value of unity.
  
Vm  b   RT .
a
6. Consider a real gas which obeys the van der Waals equation  P  2
 Vm 
a) Express the constants a and b as functions of the critical coordinates Pc, Vc and Tc.
b) Deduce the critical compressibility factor Zc.
c) Determine the corresponding equation of state in reduced coordinates.
7. Revisit question 6 for a gas that obeys the Berthelot equation of state

 
Vm  b   RT .
a
 P 
 TVm2 

 
Vm  b   RT with a
a
8. A mole of carbon dioxide obeys the van der Waals equation  P  2
 Vm 
= 3.5921 L2 atm mol-2 and b = 0.0432 L mol-1.
i) Express a and b in SI units.
ii) Calculate the molar volume Vm at T = 800°C and P = 1 atm.
- using a convenient approximation,
- without any approximation,
- graphically. Ans: Vm = 88.04 L mol-1
9. The compressibility factor for methane is given by Z = 1 + BP + CP2 + DP3. If P is given in atm,
the values of the constants are as follows:
T (K) B C D
-3 -6
200 -5.74×10 6.86×10 18.0×10-9
-3 -6
1000 0.189×10 0.275×10 0.144×10-9
a) Plot the values of Z as a function of P at those two temperatures in the range from 0 to
1000 atm.
b) The critical coordinates of methane are Pc = 45.8 atm, Vc = 98.7 cm3 mol-1 and Tc = 190.6
K.
i. Deduce the parameters of the van der Waals equation for this gas.
ii. Use these values to establish a value for the compressibility factor.
iii. Sketch on the same graph as in a), the curve Z = f(P) for P in the range 0-1000 atm.
Ans: a =1.34 L2 atm mol-2, b = 0.0329 L mol-1

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10. At high pressures (i.e. for small volumes), the van der Waals equation can be rearranged to
 P  RT  2  P  3
the form Vm  b    b  Vm   Vm . Show that this is the case. If the quadratic
 a  P  a
and cubic terms are dropped, then we obtain V0 = b as a first approximation to the smallest
root of the equation. This would represent the volume of the liquid. Using this approximate
value of Vm, show that the next approximation for the volume of the liquid is
b 2 RT
Vm  b  . From this expression, show that the first approximation for the coefficient
a
bR
of thermal expansion,  of the van der Waals equation is .
a
11. At what temperature does the slope of the Z versus P curve (P = 0) have a maximum value
for the van der Waals gas? What is the value of the maximum slope?
12. The following pressure-density data have been reported for CO2 at 0°C.
P (bar) 1.0000 0.6667 0.5000 0.3333 0.2500 0.1667
 (g L )
-1
1.9509 1.2977 0.9722 0.6474 0.4853 0.3233
a) Draw a graph of /P versus P and deduce a value for the gas constant R (take the exact
relative atomic masses C = 12.011, O = 15.999).
b) If the value of R is taken as 0.083143 L bar K-1 mol-1, what value is obtained for the mass
of 1 mole of CO2? Ans: R = 0.08318 L bar mol-1 mol-1; M = 43.987 g mol-1

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 II-THE LAWS OF THERMODYNAMICS

 
Vm  b   RT in which a = 8×104 N m4 mol-2 and b =
a
1. A real gas obeys the equation  P  2
 Vm 
3×10-5 m3 mol-1. Calculate the work required to compress 0.3 mol of this gas isothermally
from a volume of 5×10-3 m3 to 2×10-5 m3 at 300 K. Ans:
2. One mole of a van der Waals gas at 25°C expands isothermally and reversibly from 10 litres
to 30 litres. Calculate the work produced, given that a = 5.49 L 2 atm mol-2 and b = 0.064 L
mol-1. Ans:
3. In a certain experiment designed to determine the specific heat capacity of copper, 0.1 kg of
the metal at 100°C was immersed in 2×10-4 m3 of water at 15°C which is contained in a
thermally insulated vessel of negligible thermal capacity. After the mixture has reached
equilibrium, the temperature is found to 18.8°C. If the heat capacities of copper and water
are essentially constant over the range of temperature concerned, calculate the specific
heat capacity of copper. Does this experiment measure Cp or Cv? Would there be any
difference between these quantities for copper under the conditions of the experiment?
Ans: CCu = 391.61 J K-1 kg-1
4. Calculate the change in entropy of the universe when a block of copper of mass 400 g and
thermal capacity 150 J K-1 g-1 at 100°C is placed in a lake at 10°C. Ans: 2513 J K-1
5. The high temperature behaviour of iron may be idealised as follows: below 900°C and
above 1400°C, -iron is the stable modification and between these temperatures, -iron is
stable. The specific heat capacities of the phases may be taken as constant: 0.775 kJ K -1 kg-1
for -iron and 0.690 kJ K-1 kg-1 for -iron. What is the latent heat at each transition?
6. Calculate the change in entropy of 1 kg of water when it is heated from 15° to 100°C and
completely vaporised. Does the change in entropy imply any irreversibility in the process?
(the latent heat of vaporisation of water at a pressure of 1 atm is 2.3 x 10 6 J kg-1 and its
standard specific heat is 1 cal g-1; 1 cal = 4.184 J) Ans: 6472 J K-1
7. One mole of H2S is burnt in 1.5 mole of O2(g) with a yield of 80% at 25°C.
i. Calculate the adiabatic flame temperature (consider that the molecules do not
dissociate). The standard heats of formation of the different compounds are: H2O(g) = -

4
 242.7 kJ mol-1 ; SO2(g) = -296.8 kJ mol-1; H2S(g) = -20.08 kJ mol-1. The heat capacities (in J
K-1 mol-1) are: H2O(g) = 30.20 + 9.93 x 10-3 T; SO2(g) = 25.72 + 57.90 x 10-3 T; H2S(g) =
26.71 + 23.87 x 10-3 T; O2(g) 25.50 + 13.61 x 10-3 T. Ans: 2911 K
ii. Repeat the calculations in i) if 1.5 mol of air are taken instead of 1.5 mol of O 2. The heat
capacity of nitrogen is 27.20 + 1.24 x 10-3 T J K-1 mol-1. Ans: 2802 K
8. Three moles of an ideal gas at 27°C expand isothermally and reversibly from 20 L to 60 L.
Calculate w, q U and H. Ans: q = -w = 8220 J, U = H = 0
9. One mole of an ideal gas is compressed adiabatically in a single stage with a constant
opposing pressure of 10 atm. Initially, the gas is at 27°C and 1 atm pressure and the final
pressure is 10 atm. Calculate the final temperature of the gas, w, q, U and H, if the gas
were a) monoatomic, b) diatomic. Ans: (a) T = 753.6 K, q = 0, U = w = 5656.8 J, H = 9427.4
J; (b) T = 579.2 K, q = 0, U = w = 8124.4 J, H = 11895.0 J

10. For the reaction C(graphite) + H2O(g) ⇌ CO(g) + H2(g): H o298 =31.38 kcal. The values of

CP(cal K-1 mol-1) are C(graphite) = 2.07, H2O(g) = 8.03, CO(g) = 6.97 and H2(g) = 6.89.
Calculate the value of H° at 125°C. Ans:
11. The heat of atomisation of O2(g) is 118.32 kcal and the heat of sublimation of Fe(s) is 96.68
kcal.
i) If the heat of formation of FeO(s) is -63.7 kcal mol-1, calculate H° at 25°C for the

reaction Fe(g) + O(g) → FeO(s).

ii) Assuming that the gases are ideal, calculate U° for this reaction. Deduce the cohesive
energy of the crystal, given that I(Fe2+/Fe) = 1600 kJ mol-1; A(O2-/O) = 649.4 kJ mol-1. Ans:
12. From the following heats of formation at 25°C, calculate the heat of solution of sulphuric
acid for the various solutions and plot Hsol against mole fraction of water in solution:
H2SO4
(ℓ) (aq) (2 aq) (4 aq) (10 aq) (20 aq) (100 aq) (∞ aq)
solution
H (kcal) -193.91 -200.62 -203.93 -206.88 -209.93 -211.00 -211.59 -216.90

13. Given the following heats of formation (in kcal mol-1) at 25°C:
substance H(g) C(g) CH4(g) C2H6(g) C2H4(g) C2H2(g)
H°f 52.09 171.70 -17.89 -20.24 12.50 54.19

5
 Calculate the bond energy of the following bonds: a) C-C, b) C=C, c) C≡C.

14. Two vessels of same volume at the same temperature are made to communicate such that
their contents (one mole of nitrogen in one and one mole of oxygen in the other) can mix. If
the gases are ideal, calculate the variation of entropy due to mixing. Ans: 11.53 J K-1
15. The following reaction is carried out in a certain concentration cell: H 2(g) + ½ O2(g) at 25°C.
For this reaction, S° = -163.2 J K-1 mol-1 and H° = -285.8 kJ mol-1. Deduce the maximum
quantity of electrical energy that may be expected.
16. To a system (m1 = 30 g of H2O(s) + m2 = 20 g H2O(l)) at thermal equilibrium in an adiabatic
vessel, a mass x of solid aluminium at 180°C is introduced.
a) Calculate the value for x such that when the final equilibrium is attained at P = 1 atm,
50% of the water would have vaporised. Lf = 333.5 J/g; Lvap = 2255.18 J/g; Cp(Al) = 88.0 J
K-1 g-1.
b) Calculate S. Is this process reversible? Justify!
Ans: x = 12.85 g, S = -111.89 J K-1
17. Calculate the maximum flame temperature attained when 2 moles of H2(g) are completely
burnt in the theoretical amount of air (4 N2 for 1 O2) at 100°C and 1 atm. Given: H oR ,100C =

116.012 kcal; Cp(H2O) = 16.44 + 0.30 x 10-3 T + 2.68×10-6 T2 cal K-1; Cp(N2) = 27.04 + 2.42×10-3
T + 0.58×10-6 T2 cal K-1. The experimental temperature obtained is of the order of 1900 K.
Explain the difference.

18. Consider the following equilibrium: AgCl. 3/2 NH3(s) ⇌ AgCl(s) + 3/2 NH3(g). Given the

following thermodynamic data at 298 K:

- pressure of NH3 in equilibrium with the two solid phases, P = 0.276 atm
- Sor = 55 cal K-1 mol-1
- specific heat capacities at constant pressure in cal K-1 mol-1: NH3(g): 8.5; AgCl. 3/2NH3(s):
19.6; AgCl(s): 12.1 (neglect their variations with temperature)
a) Calculate the equilibrium constant Kp, the entropy and the enthalpy change of the
reaction at 298 K.

6
 b) Establish a relation between the pressure of NH3(g) in equilibrium with the two solid
phases and temperature. Calculate this pressure at 50°C.
c) 0.02 mol of AgCl(s) are introduced into a vessel of 5 L maintained at 298 K. What is the
minimum amount of NH3 that must be added into the vessel for the complete
conversion of AgCl(s) into AgCl. 3/2NH3(s)?
Ans: Kp = 0.145, Sor = 230.12 J K-1 mol-1, H or = 73360 J mol-1; 0.32 atm; 0.076 mol

19. Consider the gas-phase reaction: N2O4 ⇌ 2 NO2. It is known that the fraction of N2O4

dissociated is 0.20 at 27°C and 0.89 at 100°C.

a) Calculate the values of Kp at these two temperatures when P = 1 atm.
b) Calculate the density of the mixture at equilibrium at 27°C.
c) Calculate the enthalpy of dissociation (H°diss) if is considered constant in the
interval 27-100°C.
Ans: 0.167, 15.240;  = 3.114 g L-1; (H°diss = 57.524 kJ mol-1)

20. For the equilibrium CO(g) + H2O(g) ⇌ CO2(g) + H2(g), the following thermodynamic data are
given:
Substance CO(g) H2O(g) CO2(g) H2(g)
H°f,298 K (kJ mol )
-1
110.35 -241.60 -393.13 0
S°298 K (J K mol )
-1 -1
197.71 188.64 213.60 130.46
-1 -1 -3 -3 -3 -3
C°p (J K mol ) 26.51 + 1.84×10 T 29.30 + 12.6×10 T 30.54 + 20.0×10 T 27.28 + 3.26×10 T

a) Calculate the temperature at which Kp = 1 (neglect the influence of C°p)

b) Calculate Kp at 1073 K and 873 K. Are these results coherent with Le Chatelier’s
principle?
21. The endothermic dissociation equilibrium of hydrogen chloride is under consideration: 2
HCl(g) ⇌ H2(g) + Cl2(g). The initial state is HCl(g) at a pressure P and a temperature T.
a. What are the effects on the equilibrium position of i) a variation of pressure, ii) of a
variation of temperature?
b. Calculate the variance of the system. What is the significance of the numerical result
obtained?
c. Write down the expression of Kp as a function of the partial pressures and as a function
of the fraction  of HCl dissociated.

7
 d.  is measured at different temperatures and the following results are obtained:
TK 800 1200
-7
 8.60×10 9.35×10-6
Calculate the different values of Kp by carrying out any legitimate approximations.
e. From the above result, draw the graph lnKp = f(1/T) and deduce the enthalpy of the
reaction, H or supposed to be constant in the temperature range considered.
22. Consider the heterogeneous equilibrium: 2 CuO(s) ⇌ Cu2O(s) + ½ O2(g). At 298 K, the
standard enthalpy change and the standard entropy change of the reaction are respectively
H or = 143.1 kJ and Sor = 111.1 J K-1. The difference between the specific heats at constant
pressure of (Cu2O + ½ O2) and (CuO) is Cp = (-14.64×10-3 T) J K-1.
a) Derive the equation by which Kp can be calculate at various temperatures.
b) Calculate the temperature at which CuO would transform into Cu2O under a pressure of 10-5
atm.

8
 III-THERMODYNAMIC EQUILIBRIUM APPLIED TO PURE SUBSTANCES
 x   y   z 
1. If z is a function of two variables x and y, show that        1 .
 y  z  z  x  x  y
2. Verify the cyclic rule for the ideal equation of state.
RT
3. Verify the cyclic rule for the truncated virial equation of state P  where B is a
Vm  B

function of T.

2
4. i) Show that the difference in heat capacities CP and CV can be written as C P  C V  TV

where  is the coefficient of thermal expansion and  is the coefficient of isothermal
compressibility.
ii) Apply this to lead at 750 K given  = 32  10-6 K-1, -1 = 45.8 MN m-2 and V = 18.4 L mol-1.
Comment on the nature of this gas.
Ans: Cp-Cv = 0.65 J mol-1 K-1

 V   2a Vm  b 2 
5. For a van der Waals gas, T m   Vm  b 1   . From this, derive the
 T  P
3
 RTVm 
expression for difference in heat capacities.
 P   S 
6. Show that      (Maxwell’s relation) and hence, derive an expression for the
 T  V  V  T
change in entropy of (i) an ideal gas at constant temperature, (ii) a van der Waals gas at
constant temperature.
7. From the van der Waals constants, calculate the temperature below which helium may be
liquefied (use the Joule-Thomson effect). Ans: T = 35.5 K
8. Find the variance of a system consisting of solid sucrose in equilibrium with an aqueous
solution of sucrose.
9. a) Find the variance of a system consisting of CaCO3(s), CaO(s) and CO2(g) when all the
CaO(s) and CO2(g) come from the dissociation of the carbonate. b) What is the maximum
number of phases that can co-exist in a quaternary system? c) What must be true about a
number of independent components in a system with ten liquid phases in equilibrium?

9
10. Ethanol has a normal boiling point of 78.4°C and at this temperature, H ovap = 9.26 kcal mol-
1
; to what value must P be reduced in order to boil ethanol at 25°C in a vacuum distillation?
Ans: 0.093 atm
11. Methyl mercaptan (CH3SH) has vapour pressures P° = 100 torr at -34.8°C and P° = 400 torr at
-7.9°C. i) Calculate its heat of vaporisation. ii) Estimate its normal boiling point. Ans: Hvap =
6466 cal K-1 mol-1; T° = 279.7 K
12. Given that for CS2, the normal boiling point is 319.4 K, a) use Trouton’s rule to estimate
H ovap and S ovap at the normal boiling point, b) use the Trouton-Hildebrand-Everett rule.

Ans: 6707.4 cal mol-1; 6516 cal mol-1

13. From the boiling point Tb of a liquid and the assumption that the liquid follows Trouton’s
rule, calculate the value of the vapour pressure at any temperature T. The normal boiling
point of diethyl ether is 34.6°C, calculate its vapour pressure at 25°C. Ans: 0.76 atm
14. Use Trouton’s rule to show that the change T in normal boiling point Tb due a small change
Tb P
P in pressure, is roughly T  
11.5 atm

15. The heat of fusion of mercury is 2.82 cal g-1 at its normal boiling point -38.9°C. The densities
of Hg(s) and Hg(l) at -38.9°C and 1 atm are 14.193 and 13.690 g cm-3 respectively. Find the
melting point of Hg at a) 100 atm; b) 800 atm. Comment on the results. Ans: 234.6 K; 238.2
K

16. In the liquid phase, allocimen (A) gives the dimer (D) by the reversible reaction: 2 A ⇌ D. The

normal enthalpy of vaporisation of A is 9656 cal/mol; its normal boiling is 177.0°C and that
of D is 189.5 °C. The mixture A + D constitutes an ideal solution. The density is constant and
equal to 0.694 g/cm3. Molar mass of A is 136 g/mol. Liquid allocimen is put in a flask and
after removing all air, the flask is sealed and heated to 189.5°C. When equilibrium is
attained, 89% of A has dimerised. Calculate:
(i) the mole fraction xA of the monomer in equilibrium at 189.5°C.
(ii) the normal enthalpy of vaporisation of the dimer D, supposing that Trouton’s rule is
valid.

10
 (iii) the vapour pressure of pure A at 189.5°C, using the Clausius-Clapeyron equation.
(iv) the pressure inside the sealed flask at equilibrium at 189.5°C.
Ans: xA = 0.198; H°vap = 9.713 kcal mol-1; P = 1.34 atm; P = 1.064 atm
17. The vapour pressures of liquid sodium are
P (mmHg) 1 10 100
T (°C) 439 549 701
By plotting these data appropriately, determine the normal boiling point of liquid sodium,
the heat of vaporisation and the entropy of vaporisation at the boiling point.

11
 IV-SOLUTION THERMODYNAMICS
1. The Henry’s law constant for argon in water is 2.17×104 atm at 0°C and 3.97×104 atm at
30°C. Calculate the standard heat of solution of argon in water in kcal mol-1.
2. The normal freezing point depression constant of benzene is 5.07 K kg mol -1. A 0.45%
solution of monoclinic sulphur in benzene freezes 0.088 K below the freezing point of pure
benzene. Find the molecular formula of sulphur in benzene.
3. Find the osmotic pressure at 25°C and 1 atm of a solution of 1.8016 g of glucose (C6H12O6) in
1000 g of water. The molecular masses of glucose and water are 180.160 and 18.015 g/mol
respectively and the density of water at 25°C and 1 atm is 0.99704 g/cm3.
4. The saturation vapour pressure of water varies with temperature according to the following
table:
T (°C) 10 20 30 50 70 90
S
P (atm) 0.012 0.023 0.043 0.122 0.308 0.692
a) Calculate the standard enthalpy of vaporisation, supposing that the molar volume of
liquid water is negligible and that water vapour behaves like an ideal gas.
b) What happens if the water vapour is known to behave like a real gas obeying the van
der Waals equation of state?
c) 2.5 g of NaCl are added to 100 g of water. Calculate the new boiling point of the
solution, given that the ebullioscopic constant for water is 0.51.
5. Raoult found out that when 4.94 g of ethyl benzoate were dissolved in 200 g of benzene,
the vapour pressure of benzene reduced, at 80°C, from 751.9 mmHg to 742.6 mmHg.
Calculate the molecular mass M2 of this compound (given Mbenzene = 78).
6. Benzene and octane are mixed at 20°C and it is found that the enthalpy of mixing is zero. At
equilibrium, and in the liquid phase, there are one mole of octane and four moles of
benzene.
a) Calculate the total pressure of the pressure.
b) What is the composition of the vapour? You are given that the saturation vapour
pressure are P°(octane) = 20 mmHg and P°(benzene) = 100 mmHg.
7. The composition of vapour over an ideal binary solution is determined by the composition
of the liquid. If x1 and y1 are the mole fractions of (1) in the liquid and vapour respectively,

12
 find the value of x1 for which (y1-x1) has a maximum. What is the value of the total pressure
at this composition?
8. The specific gravity of water-methanol solution is 0.915. If the mole fraction of methanol is
0.4, calculate the partial molar volume of water, given that that of methanol is 39 mL. The
density of water is 1 g/mL. What is the contraction of the mixture (the molar volume of
methanol is 40.5 mL and that of water is 18.07 mL?
9. An ideal solution of benzene (1) in toluene (2) is in equilibrium with the vapour at 27°C.
a) What are the total pressure and the composition of the gaseous phase for a solution
containing one mole of benzene and one mole of toluene?
b) Calculate the latent heats of vaporisation of the two substances.
c) Calculate the heat of mixing of this solution. You are given: at 27°C, the saturation
vapour pressures are P1o = 103 mmHg, P2o = 32.06 mmHg; the normal boiling points are

T1o = 80.1°C and T2o = 110.6°C.

10. A reservoir with two compartments (1) and (2) contains two ideal gases in the following
conditions:
- compartment (1): n1 = 3 mol H2, P1 = 1 atm, T1 = 25°C
- compartment (2): n2 = 1 mol H2, P2 = 3 atm, T2 = 25°C
a) Find an expression for the free enthalpy of the system as a function of the standard
chemibal potentials of the gases and the parameters of thE system.
b) A communication is created between the two compartments; calculate the equilibrium
pressure and deduce a new expression for the free enthalpy.
c) Calculate the free enthalpy of mixture of this transformation; deduce from this, the
change in entropy. What comment can you make of these two properties calculated?
11. The partial molar volume of potassium chloride varies as A function of molality m as v1 =
26.32 + 3.615 m (mL).
a) Knowing that the molar volume of pure water is 18.07 mL, calculate the partial molar
volume of water (v2) as a function of m. Calculate the density of a 0.2 molal solution of
KCl at 25°C (MKCl = 74.5 g/mol).
b) What is the mixing volume Vm?

13
12. A regular binary solution is defined by the equation i = °i + RT ln xi + w(1-xi)2 where w is a
constant.
a) Express ln i in terms of w.
b) At 25°C, w = 77.5 cal/mol for mixtures of benzene and carbon tetrachloride. Calculate 
for CCl4 in solutions with x CCl4 = 0.25, 0.50, 0.75, 1.0.

13. The activity coefficient of aluminium in liquid solutions of aluminium (1) and zinc (2) at 873
K (with reference to pure aluminium) may be expressed as ln 1  1.007 x12 .

a) Give the expression for 2 as a function of x1 and calculate its value for x1 = 0.25, 0.50
and 0.75.
b) Calculate the excess enthalpy of aluminium in this alloy at 653 K.
14. Consider a binary solution (1) and (2) in which the activity coefficients are given by

bx 22 bx 2
ln 1  and ln  2  1 where b is neither a function of temperature nor of
RT RT
composition. Show that the molar enthalpy of mixing is bx1x2.
15. The propanol-water mixture is studied at 25°C. The partial pressures of the two constituents
are given below, as a function of the mole fraction of the alcohol in water in the liquid
phase.
xprop 0 0.02 0.05 0.10 0.20 0.40 0.60 0.80 0.90 0.95 1.00
Pprop 0 5.05 10.8 12.7 13.6 14.2 15.5 17.8 19.4 20.8 21.8
Pwate 23.8 23.5 23.2 22.7 21.8 21.7 19.9 13.4 8.1 4.2 0
a) Deduce the Henry’s constant for propanol in a dilute aqueous solution; verify that in this
case, water obeys Raoult’s law.
b) Calculate the activity coefficients prop and water for xprop = 0.2 with reference to pure
liquid at 25°C.
16. The total molar specific enthalpy of mixing of the binary (1), (2) solution is represented by
expression hm = x1x2(Ax1 + Bx2) where A = -446 J/mol and B = 1322 J/mol are constants
independent of T in a large domain around 25°C.
i) What is the molar heat capacity of mixing of this binary solution?
ii) Deduce the expressions of the partial molar mixing enthalpies h 1m and h2m.

14
 iii) If the solution is known to be regular (in the sense of Hildebrand), determine the
activities of the two components in an equimolar solution at 25°C.
17. At 35°C, the partial pressure of CS2 in the vapour in equilibrium with its solution in acetone
varies as follows:
x CS2 0.0050 0.0100 0.1800 0.5000 1.0000
PCS2 (torr) 10.0 19.8 258 404 512

Calclulate 2, taking as reference state:

a) the pure substance,
b) the infinitely dilute solution.

15
 V-THERMODYNAMICS OF PHASE DIAGRAMS
1. Dissociation of CaCO3(s)
c) Find the variance of the system consisting of CaCO3(s), CaO(s) and CO2(g) where all the
CaO and CO2 come from the dissociation of the carbonate.
d) What must be true about the number of independent components in a system with ten
liquid phases in equilibrium?
e) What is the maximum number of phases that can coexist in a quaternary system?
2. The solid-liquid phase diagram of water-nitric acid shows the formation of two congruently
melting compounds: HNO3.3H2O at -18°C and HNO3.H2O at -38°C. The melting point of HNO3
is -41°C. Going across the diagram from H2O to HNO3, the eutectic temperatures are -43, -42
and -66°C. Sketch the solid-liquid diagram. Label all areas. Sketch the cooling curves for
solutions of compositions x(HNO3) = 0.2 and 0.5.
3. Given the following melting points and heats of fusion: benzene: 5.5°C, 30.4 cal/g;
cyclohexane: 6.6°C; 7.47 cal/g. Plot the T-x diagram for these two compounds and find the
eutectic temperature and the eutectic composition. Assume that the liquid solutions are
ideal and that no solid solutions are formed. Neglect the temperature-dependence of
H°fus. Compare your values with the experimental eutectic values: -42.5°C and 0.735
cyclohexane.
4. Bi and Te form the solid compound Bi2Te3 which melts congruently at about 600°C. Bi and
Te melt at 300 and 450°C respectively. Solid Bi2Te3 is partially miscible at all temperatures
with solid Bi and is also partially miscible with solid Te at all temperatures. Sketch the Bi-Te
T-x solid-liquid phase diagram and label all regions.
5. Use the following facts to sketch the H2O-NaCl -wt solid-liquid phase diagram up to 100°C
(wt is the weight percent of NaCl). Label all the phases present.
a) The components form the compound NaCl.2H2O which melts incongruently at the
peritectic temperature of -0.1°C. The melting point of ice is 0.0°C. The eutectic
temperature for liquid+ice+ NaCl.2H2O is -21°C and occurs at 23% wt NaCl. The
freezing point for 13% wt NaCl aqueous solution is -9°C. The solubility of NaCl in water
is 26 g NaCl per 74 g H2O and increases to 28 g NaCl per 72 g H2O at 100°C.

16
 b) If an aqueous solution of NaCl is evaporated to dryness at 20°C, what solid(s) is(are)
obtained?
c) Describe what happens when a system at 20°C with all overall composition of 80% wt
NaCl is slowly cooled to -10°C. Is any ice present at -10°C?
6. Thermal analysis of the two-component system A-B (metals melting at 1200°C and 600°C
respectively) shows that the two solid phases of composition 40%B and 60%B respectively
are in equilibrium at 800°C with liquid of composition 80%B. Construct the simplest melting
point diagram consistent with this information and label all phase regions. Sketch the
cooling curves for solutions of composition 20%B and 70%B; and fully label what happens at
each break and halt.
7. Na and K melt at 98°C and 65°C respectively; they form one solid compound, NaK which
decomposes at 10°C to give a solid and a melt containing 60 mol% K. There is a eutectic at -
5°C. Sketch the simplest phase diagram consistent with the above data and label the phase
regions. Draw cooling curves for melts containing 40% K, 55% K and 90% K. Indicate the
phases appearing or disappearing at each break and halt.
8. The following data concern the isobaric isothermal system H2O-Na2SO4-NaCl at 25°C and 1
atm:
saturated solution (in wt%) in equilibrium with solid phases
1. 80% H2O, 0% Na2SO4 NaCl
2. 80% H2O, 0% NaCl Na2SO4.10H2O
3. 75% H2O, 10% Na2SO4 NaCl + Na2SO4
4. 75% H2O, 15% Na2SO4 Na2SO4 + Na2SO4.10H2O
Sketch a reasonable phase diagram consistent with these data and label all the regions.
Describe the sequence of events on evaporating a solution containing 5% NaCl, 5% Na2SO4
and 90% H2O.
9. The mole fraction solubility for the system CHCl3-CH3COOH-H2O is shown below, with some
representative tie lines. What phase(s) and of what composition(s) will be present if one
mole of CHCl3 is added to a system consisting of 0.6 mol of water and 0.4 mol of acetic acid?
If more than one phase is present, give the relative amounts of each.

17
 CH3COOH

a s b

CHCl3 H2O

18
 VI-ELECTROCHEMISTRY
1. The silver electrode
a) Calculate the potential of the Ag+, Ag electrode, V° = 0.80 V for activities of Ag+ = 1, 0.1,
0.01 and 0.001.
b) For AgI, Ksp = 10-16; what will be the potential of the Ag+/Ag electrode in a saturated
solution of AgI?
c) Calculate the standard potential of the AgI/Ag/I- electrode.
2. H.S. Harned and W.J. Hamer [J. Amer. Chem. Soc. 57, 33 (1935)] present values for the emf
of the cell: Pb/PbSO4//H2SO4(a)/PbSO4/PbO2/Pt over a wide range of temperature and
concentration of H2SO4. In a 1-molal solution of H2SO4, they found between 0° and 60°C
that:
E = (1.917 + 56.1×10-6  + 108.0×10-8 2)V
where  is the Celsius temperature.
a) Calculate G, H and S for the cell reaction at 0°C, then at 60°C.
b) For the following half cells at 25°C, calculate the mean ionic activity coefficient in 1-m
(molal) H2SO4. Assume that the activity of water is unity.

PbO2(s) + SO42- + 4 H+ 2 e ⇌ PbSO4(s) + 2 H2O: V° = 1.68 V

PbSO4(s) + 2 e ⇌ Pb(s) + SO42-: V° = -0.35 V

3. Consider the cell: Zn/Zn(NO3)2(0.100 M)//AgNO3(0.100 M)/Ag.

a) Write the equation of the global cell reaction.
b) Calculate the cell emf.
c) Calculate the residual concentrations of Zn2+ and Ag+; given that

Ag+ + e ⇌ Ag: E° = 0.80 V at 25°C

Zn2+ + 2 e ⇌ Zn: E° = -0.76 V at 25°C.

4. Calculate the equilibrium constants for the reactions:

Cu(s) + Cu2+ ⇌ 2 Cu+

and Cu(s) + Cu2+ 2 Cl- ⇌ 2 CuCl(s) at 25°C;

19
 given that E°(Cu2+/Cu) = 0.34 V; E°(Cu2+/Cu+) = 0.15 V; Ksp(CuCl) = 3.2×10-7
5. The equivalent conductivities at infinite dilution are: sodium benzoate: 82.4; hydrochloric
acid: 426.2; sodium chloride: 126.5. Calculate ° for benzoic acid.
6. The equivalent conductivity of acetic acid at different concentrations is:
 49.50 35.67 25.60
c (eq L-1) 9.88×10-4 19.76×10-4 39.52×10-4
a) Calculate the degree of dissociation at each concentration.
b) Calculate the value of the dissociation constant.
(the ion conductances at infinite dilution at 25°C: °+(H+) = 349.8, °-(COOH-) = 40.9.
7.

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