Exercises 3

Thermochemistry and chemical thermodynamics

[The specific heat of water is 4.184 J/(g K), memorize it!]

1. Calculate the amount of heat involved in the formation of 30.0 g of Fe2O3 (s) starting from its constitutive
elements in standard conditions. Write also the relative equation.

2. Calculate the amount of heat involved in the formation of 20.0 g of BaCO3 (s) starting from its constitutive
elements in standard conditions. Write also the relative equation.

3. The variation of standard enthalpy for the combustion of monoclinic sulfur [S(mono)] to SO2(g) is -97.16
kJ/mol, while for the combustion of rhombic sulfur [S(rhomb)] it is -296.83 kJ/mol. Calculate the heat
developed or absorbed (specify!) during the transformation of 1.345 g of sulphur according to the reaction
S(mono) → S(rhomb).

4. Write the combustion reactions for the following substances at 25.0 °C and 1.00 bar (Consider the
water produced in the combustion as a liquid):
a) propane C3H8;
b) acetylene C2H2;
c) octane C8H18 (l);
d) ethanol C2H5OH (l);
e) hydrogen H2;
f) carbon graphite, C.

Which of them produces more heat per gram?

5. Calculate the formation enthalpy of methane at T= 298.0 K and at p=1.00 bar, knowing that ΔcH°(CH4)
= ‐890.31 kJ (Consider the water produced in the combustion as a liquid).

6. The Rossi family consumes 200 L per day of hot water. In the heating system, water enters at 8.00 °C
and is brought to 50.0 °C. Calculate the volume of methane (measured at T=0.00° C and p=1.00 atm)
which is needed every day to supply the plant, if the heating system has 70.0% efficiency. (Consider the
water produced in the combustion as a liquid)

7. A pot contains 5.00 L of water at T=20.0°C. How many litres of methane (p=1.00 atm, T=20.0°C) is it
necessary to burn in order to bring water to boil, supposing that only 40.0% of the heat is transferred to
water? (Consider the water produced in the combustion as a liquid)

8. Write the reactions that correspond to the following ΔH°s :

ΔfH°(CO2 , g) = ‐393,5 kJ/mol
ΔfH°(H2O , g) = ‐241,8 kJ/mol
ΔcH°(CH3OH, l) = ‐638,4 kJ (Consider the water produced in the combustion as a gas)
Starting from the previous data, calculate ΔfH°(CH3OH , l)

9. Determine the heat that is liberated when 1.00 m3 of a mixture of 60.0% of ethanol (C2H5OH) vapours
and 40% of methanol (CH3OH) vapours (measured at T = 20.0 °C e p = 1.00 atm) is burnt. Then calculate,
in the same conditions, how many cubic meters of air are theoretically needed for the combustion and the
volume of carbon dioxide that is released in the process. [Consider the water produced in the combustion
as a liquid]

10. In the high mountains, soaked garments may be very dangerous. If a cold wind vaporizes 1.00 kg of water
from your garments, what is the heat loss that your body must fight? Considering a mean body mass of
70.0 kg and a specific heat of 3.60 J K-1 g-1, what temperature would be potentially reached, starting from
 37.0 °C? How much sugar (sucrose, C12H22O11: ΔfH° = ‐2˙222 kJ/mol) should you consume in order to
recover your energetic balance, supposing to exploit 50.0% of the liberated energy?

11. It is clear that supplies of fossil fuels are dwindling and their prices are rising, at a time when the Earth’s
nations have ever-increasing energy needs. Let’s analyse the debate about replacing gasoline with ethanol
(C2H5OH), with the support of some calculations. For the purposes of this analysis, let us use octane
(C8H18) as a substitute for the complex mixture of hydrocarbons in gasoline.
Other data you will need: δ(C2H5OH, l) = 0.785 g/mL; δ(C8H18, l) = 0.699 g/mL.
a. Calculate ΔcH° for ethanol and octane. Which provides more energy per mole? Which provides
more energy per gram? (Consider the water produced in the combustion as a gas)
b. Which produces more energy for a given volume? (1.00 L, for example)
c. What mass of CO2 (a greenhouse gas) is produced per litre of the two fuels?
d. Now compare the fuels on an energy-equivalent basis. What volume of ethanol would have to be
burned to get the same energy as 1.00 L of octane? When you burn enough ethanol to have the
same energy as a litre of octane, which fuel produces more CO2?
e. On the basis of this analysis and assuming the same price per litre, which fuel will propel your car
further? Which will produce less greenhouse gas?

12. Calculate ΔrH° for the reaction P4O10 (s) + 6 PCl5 (g) → 10 POCl3 (g) given the following ΔrH°s:
P4 (s) + 6 Cl2 (g) → 4 PCl3 (g) ΔrH° = -1˙225.6 kJ/mol
P4 (s) + 5 O2 (g) → P4O10 (s) ΔrH° = -2˙967.3 kJ/mol
PCl3 (g) + Cl2 (g) → PCl5 (g) ΔrH° = -84.2 kJ/mol
PCl3 (g) + ½ O2 (g) → POCl3 (g) ΔrH° = -285.7 kJ/mol

13. Calculate ΔfH° of tungsten carbide (WC), given the following combustion enthalpies:
2 W (s) + 3 O2 (g) → 2 WO3 (g) ΔcH°(W) = -1˙680.6 kJ/mol
C (graph) + O2 (g) → CO2 (g) ΔcH° (C) = -393.5 kJ/mol
2 WC (s) + 5 O2 (g) → 2 WO3 (s) + 2 CO2 (g) ΔcH° (WC) = -2˙391.6 kJ/mol

14. Without using the Tables, put the following substances in ascending order of standard molar entropy S°:
Hg (l), Ne (g); CO2 (g), Zn (s). Motivate the order. For each of them, indicate if the ΔfΗ° is zero, higher
or lower than zero at a temperature of 20 °C and at a pressure of 1.0 bar.

15. Dinitrogen tetraoxide (N2O4) decomposes to nitrogen dioxide (NO2). Establish the temperature interval
where such reaction is spontaneous.

16. Just by observing the chemical equations (no tables), predict the sign of the entropy variations associated
with each of the following processes:
a) H2(g) + Cl2(g) → 2 HCl(g) b) 2 NO2(g) → N2O4(g)
c) 2 NH3(g) → N2(g) + 3 H2(g) d) NaCl(s) → NaCl(l)

17. Calculate the variation of standard enthalpy for the following reaction:
2 C(s) + O2 (g) → 2 CO (g)

18. Using the data provided in the Tables, calculate the boiling point of benzene (C6H6) in °C at p = 1.00
bar.

19. Using the data provided in the Tables, calculate the boiling point of carbon disulfide (CS2) in °C at p =
1.00 bar.
20. The molar enthalpy of fusion of solid ammonia is 5.65 kJ/mol, and its molar entropy of fusion is 28.9
J/K mol.
a) Calculate the variation of Gibbs energy for the fusion of 1.00 mol of NH3 at 170 K.
b) Calculate the variation of Gibbs energy for the conversion of 3.60 mol of solid ammonia to liquid
ammonia at 170 K.
c) Does ammonia spontaneously melt at 170 K?

21. Calculate ΔrH°, ΔrS°, ΔrG° for the reaction: CO(g) + ½ O2(g) → CO2(g) at T = 25.0 °C and T = 50.0 °C.

22. The standard Gibbs energy for the combustion of diamond is -397.3 kJ/mol and for graphite is -394.4
kJ/mol. Without using the table, calculate ΔrG° for the reaction C(diamond) → C(graphite). Which of the
two forms of carbon is more thermodynamically stable in standard conditions?

23. Benzene can be prepared from acetylene: 3 C2H2 (g) → C6H6 (l)
Is it more convenient to run the reaction at room temperature (25°C) or at 850°C?

24. Predict the behaviour of ΔrG° as a function of T for the following exothermic reaction (do not use tables):
N2(g) + 3 H2(g) → 2 NH3(g)

25. Hydrogenation, the addition of hydrogen to an organic compound, is an industrially relevant reaction.
Predict the interval of temperature where the hydrogenation of acetylene (C2H4) to ethane (C2H6) is
spontaneous.
Solutions

1. ΔrH = 155 kJ

2. ΔrH = 124 kJ

3. 8.40 kJ

4.
a. C3H8 + 5 O2 → 3 CO2 + 4 H2O qm = 50.3 kJ/g
b. C2H2 + 5/2 O2 → 2 CO2 + H2O qm = 50.1 kJ/g
c. C8H18 + 27/2 O2 → 8 CO2 + 9 H2O qm = 47.4 kJ/g
d. C2H5OH + 3 O2 → 2 CO2 + 3 H2O qm = 30.0 kJ/g
e. H2 + ½ O2 → H2O qm = 143 kJ/g
f. C + O2 → CO2 qm = 32.8 kJ/g

5. -74.8 kJ mol-1

6. 1˙260 L

7. 113 L

8. C (s) + O2 (g) → CO2 (g)

H2 (g) + ½ O2 (g) → H2O (g)
CH3OH (l) + 3/2 O2 (g) → CO2 (g) + 2 H2O (g)
ΔfH° (CH3OH) = -238.7 kJ mol-1

9. 47.8 MJ; 12.0 m3; 1.60 m3

10. qloss = 2˙450 kJ; Tfin = 27.3 °C; m(C12H22O11) = 297 g

11. Answers:
a. ΔcH°(C2H5OH, l) = -1˙230 kJ/mol; qm(C2H5OH, l) = -26.7 kJ/g
ΔcH°(C8H18, l) = -5˙070 kJ/mol; qm(C8H18, l) = -44.5 kJ/g
Octane provides more energy both per mole and per gram.
b. qV(C2H5OH, l) = -21˙000 kJ/L
qV(C8H18, l) = -31˙100 kJ/L
Octane produces almost 50% more energy per litre of fuel
c. m(CO2 per L of ethanol) = 1.50 kg/L
m(CO2 per L of octane) = 2.16 kg/L
d. Veq(C2H5OH) = 1.48 L (energetically equivalent to 1.00 L octane)
meq(CO2) = 2.22 kg (burning 1.48 L of ethanol)
Since 2.22 kg > 2.16 kg, to obtain the same amount of energy, slightly more carbon dioxide
is produced by the combustion of ethanol.
e. Your car will travel about 50% farther on a litre of octane, and it will produce slightly less
CO2 emissions, than if you burned 1.0 L of ethanol.
12. ΔrH° = -610.1 kJ/mol

13. ΔrH° = -38.0 kJ/mol

14. Increasing S°: Zn(s) < Hg(l) < Ne (g) monoatomic gas < CO2(g) triatomic molecule
ΔfH° is zero for Hg(l), Ne (g), Zn(s) because are elements in their standard state. For CO2 it is negative
because it corresponds to ΔcH°(CO2), and combustions are always exothermic.
15. The reaction is spontaneous above 326 K.
16. a) ΔS ≈ 0 (no variation in gas moles) b) ΔS < 0 (gas moles decrease) c) ΔS > 0 (gas moles
increase) d) ΔS > 0 (from solid to liquid)
17. ΔrS° = 179.4 J/K mol
18. 352 K = 79 °C
19. 323 K = 50°C
20. a) 0.74 kJ/mol b) 2.66 kJ c) ΔG>0, the process is not spontaneous
21. ΔrH° (298 K) = ΔfH° (CO2) - ΔfH° (CO) = -283.0 kJ/ mol
ΔrS° (298 K) = S°(CO2) - S°(CO) – ½ S°(O2) = - 86.9 J/K mol
ΔrG° (298 K) = ΔrH° - TΔrS° = -257.1 kJ/ mol
ΔrG° (323 K) = ΔrH° - TΔrS° = -254.9 kJ/ mol.
22. Since the products from the two combustions are the same (CO2), it is convenient to apply the Hess’s
law:

ΔrH° = -2.90 kJ/mol. The transformation of diamond (less stable) into graphite (more stable) is
thermodynamically spontaneous.
23. The graph is (T0 = 1˙520°C):

So, it is more convenient to run the reaction at room temperature

24. Since the reaction is exothermic, ΔrH° < 0. Moreover, the moles of gaseous products decrease during the
reaction, hence ΔS° < 0. Therefore, the graph is:
25. Strategy: write the balanced reaction, then calculate the reaction enthalpy and entropy, and evaluate,
using, ΔrG°(T) = ΔrH° - TΔrS°, the interval where ΔrG°<0: T<1˙140 K