CHEM 120 / 2013 Physical Chemistry Tutorial 5 Solutions

School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus

Chemical Reactivity - CHEM120R - 2013

TUTORIAL 5 - SOLUTIONS

ENTROPY & GIBBS FREE ENERGY

1. For each compound below, write a balanced equation depicting the formation of one mole
of the compound from its elements.

a) Al2O3(s) b) TiCl4(l) c) Mg(OH)2(s) d) NH4NO3(s)

a) 2Al(s) + 1O2(g) Al2O3(s)

b) Ti(s) + 2Cl2(g) TiCl4(l)
c) Mg(s) + O2(g) + H2(g) Mg(OH)2(s)
d) N2(g) + 2H2(g) + 1O2(g) NH4NO3(s)

2. Calculate the enthalpy change, Hfo for the formation of one mole of strontium carbonate
(the material that gives the red colour in fireworks) from its elements. (-1120 kJ mol 1)
Sr(s) + O2(g) SrO(s) H1o = -592 kJ
SrO(s) + CO2(g) SrCO3(s) H2o = -234 kJ
C(graphite) + O2(g) CO2(g) H3o = -394 kJ

Hesss law:
Sr(s) + O2(g) SrO(s) H1o = -592 kJ
SrO(s) + CO2(g) SrCO3(s) H2o = -234 kJ
C(graphite) + O2(g) CO2(g) H3o = -394 kJ
Sr(s) + C(graphite) + 1O2(g) SrCO3(s) HRXN

HRXN = H1o + H2o + H3o = (-592) + (-234) + (-394) = -1220 kJ

3. Does the entropy increase, decrease or remain the same when the following processes or
reactions occur?
a) 2 NO(g) + O2(g) 2 NO2(g) b) CaCO3(s) CaO(s) + CO2(g)

a) decrease b) increase

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CHEM 120 / 2013 Physical Chemistry Tutorial 5 Solutions

4. Urea reacts slowly with water to form ammonia and carbon dioxide. Using the given data,
calculate the standard entropy change at 25 C for the reaction:
CO(NH2)2(aq) + H2O(l) CO2(g) + 2 NH3(g)
Compound CO(NH2)2(aq) H2O(l) CO2(g) NH3(g)
S (J K-1 mol-1) 173.8 69.96 213.6 192.5
1
(354.8 J K mol 1)

S = So(Products) - So(Reactants)
= [(213.6) + 2(192.5)] [173.8 + 69.96]
= 598.6 243.8
= 354.8 J K-1

5. Calculate the entropy change for the vaporization of water at 100.0 C. The enthalpy of
vaporization is 45.0 kJ mol-1. (121 J K 1 mol 1)

G = H TS = 0 at phase transition

H 45.0 x 103 J mol-1

S = = = 121 J K-1 mol-1
T 373.2 K

6. Urea can be synthesized by the reaction of phosgene, COCl2, with ammonia. Use the
thermodynamic data given to calculate G for this reaction at 25.0 C.
COCl2(g) + 4 NH3(g) CO(NH2)2(s) + 2 NH4Cl(s)
Compound COCl2(g) NH3(g) CO(NH2)2(s) NH4Cl(s)
-1
Hf (kJ mol ) -218.8 -46.11 -319.2 -314.4
S (J K-1 mol-1) 283.5 192.5 173.8 94.6
(-338.9 kJ)

H = Hfo(Products) - Hfo(Reactants)
= [(-319.2) + 2(-314.4)] [(-218.8) + 4(-46.11)]
= [-319.2 628.8] [-218.8 184.4]
= -948.0 + 403.2
= -544.8 kJ

S = So(Products) - So(Reactants)
= [(173.8) + 2(94.6)] [283.5 + 4(192.5)]
= [173.8 + 189] [283.5 + 770.0]
= 363 1053.5
= -691 J K-1 = -0.691 kJ K-1

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CHEM 120 / 2013 Physical Chemistry Tutorial 5 Solutions

G = H - TS
= -544.8 (298.2)(-0.691)
= -544.8 + 206
= -338.7
= 339 kJ

7. Calculate G (kJ mol-1) for the combustion of ethane, C2H6, in the presence of oxygen,
given that:
Compound C2H6(g) O2(g) CO2(g) H2O(l)
Gf (kJ mol-1) - 32.82 0 - 394.4 - 237.1
(-1467.3 kJ mol 1)

C2H6(g) + 3O2(g) 2CO2(g) + 3H2O(l)

G = Gfo(Products) - Gfo(Reactants)
= [2(-394.4) + 3(-237.1)] [(-32.82) + 3(0)]
= -788.8 711.3 + 32.82
= -1467.3 kJ mol-1

8. Given that GRxn = 474.4 kJ, calculate the equilibrium constant for the following
equilibrium at 25.0 C.
2 H2O(l) H2(g) + O2(g)
(8.307 x 10 84)

G = -R x T x ln K
-G -474.4 x 103 J
ln K = = = -191.3
RT 8.314 x 298.2 K

K = anti-ln(-191.3) = 8.307 x 10-84

Additional Problems

1. The vapour pressure of ethanol (C2H5OH) and 1-propanol (C3H7OH) at 35C are 100 mmHg
and 37.6 mmHg, respectively. Assume ideal behaviour and calculate the partial pressures
of ethanol and 1-propanol at 35C, over a solution of ethanol in 1-propanol. The mole
fraction of ethanol is 0.300.

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CHEM 120 / 2013 Physical Chemistry Tutorial 5 Solutions

Pethanol = xPethanol = (0.300)(100 mmHg) = 30.0

P1-propanol = xP1-propanol = (0.700)(37.6 mmHg) = 26.3

2. As solution is prepared by dissolving 35.0 g of haemoglobin (Hb) in enough water to make

up 1 L in volume. If the osmotic pressure of the solution is found to be 10.0 mmHg at
25C, calculate the molar mass of haemoglobin.

= MRT
M = /RT = 10.0 mmHg x 1 atm/760 mmHg
0.0821 L atm K-1 mol-1 (298 K)
= 5.38 x 10-4 M

or = (n/V)RT
n = V/ RT = 10.0 mmHg x 1 atm/760 mmHg(1 L)
[0.0821 L atm K-1 mol-1 (298 K)]
= 5.38 x 10-4 moles

The volume of solution is 1 L, so it must contain 5.38 x 10-4 mol of Hb.

Molar mass of Hb = mass of Hb/ moles of Hb

= 35.0 g/ 5.38 x 10-4 mol
= 6.51 x 104 g mol-1

3. Calculate the standard entropy changes for the combustion of 1 mol of propane vapour at
25oC
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
[So(J K-1 mol-1): C3H8(g) = 269.9, O2(g) = 205.1, CO2(g) = 213.7 and H2O(l) = 69.90].
So = So(products) - So(reactants)
= {3So[CO2(g)] + 4So[H2O(l)]} {So[C3H8(g)] + 5So[O2(g)]}
= {3(213.7 J K-1 mol-1) + 4(69.90 J K-1 mol-1)} {269.9 J K-1 mol-1) +
5(205.1J K-1 mol-1)} = -374.7 J K-1

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CHEM 120 / 2013 Physical Chemistry Tutorial 5 Solutions

4. (a) Potassium chlorate, a common oxidizing agent in fireworks and match-heads,

undergoes a solid state disproportionation reaction when heated.
4KClO3(s) 3KClO4(s) + KCl(s)
Calculate the standard free energy change, Go, for the reaction at 25oC:

4KClO3(s) 3KClO4(s) KCl

o -1
H (kJ mol )
f -397.7 -432.8 -436.7
So (J K-1 mol-1) +143.1 +151.0 +82.6

Horxn = {3Hof [KClO4(s)] + Hof [KCl(s)]} - 4Hof [KClO3(s)]

= [(3)(-432.8 kJ mol-1) + (-436.7 kJ mol-1)] - (4)(-397.7 kJ mol-1)
= -144 kJ

Sorxn = [3(151.0 J K-1 mol-1) + 82.6 J K-1 mol-1] - 4(143.1 J K-1 mol-1)]
= -36.8 J K-1

Gorxn = Horxn -TSorxn = -144 kJ [(298 K)( -36.8 10-3 kJ K-1)] = -133 kJ

(b) Is the reverse reaction which is the formation of KClO3 spontaneous or non-
spontaneous?
Non-spontaneous, Gorxn > 0

(c) What is the standard free energy change for 1 mole of KClO4 formed?
Gof = -133 kJ/3 = -44.3 kJ

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