CHEM 17: Practice Exercises: Chemical Thermodynamics. Dr. Nuesca’s Class.

Problem Set I. Not to be submitted, For your practice only. Mostly taken from Whitten.
Concepts: Calculation of q or ∆H based on a balanced reaction (stoichiometry calculations).
Hess’s Law: Summation of Heats/ Standard Formation

1. Whitten15.16 MeOH is a fuel with a high octane rating that can be produced from coal and H2.
CH3OH (g) + 3/2 O2 (g)
CO2 (g) + 2H2O(l) ∆H = -764 kJ, T = 298 K
Calculate: (a) Heat evolved when 115.0 g of CH3OH(g) burns in excess oxygen.
(b) The mass of O2 is consumed when 925 kJ of heat is evolved.

2. Whitten15.17 2Na(s) + 2H2O (l)
H2 (g) + 2NaOH (aq) ∆H = -368 kJ;

(a) How much heat is liberated when 0.113 mole of Na reacts with
excess water according to the following equation?
(b) The work (kJ) involved in the reaction for liberation of of 1.00 mol H2.
(c) What volume of H2 gas is evolved if T= 298K and P=1 atm?

3. The thermite reaction used for the welding of iron is

8Al(s) + 3 Fe3O4 (s)
4 Al2O3 (s) + 9Fe(s) ∆Ho = - 3350. kJ/mol-rxn

Because this large amount of heat cannot be rapidly dissipated to the surroundings, the reacting mass may
reach to temperatures near 3000oC. How much heat is released by the reaction of 27.6 g of Al with 69.12 g
of Fe3O4?

4. Whitten15.21 Methylhydrazine, CH6N2, is burned with dinitrogen tetroxide, N2O4, in the attitude-control
engines of the space-shuttles.
CH6N2 (g) + 5/4 N2O4 (l)
3H2O (l) + CO2(g) + 9/4 N2(g)
CH6N2 and N2O4 ignite instantly on contact, producing a flame temperature of 3000K. The energy
liberated per 0.100 g of CH6N2 at constant atmospheric pressure after the products are cooled down back
to 250C is 750 kJ.
(a) Find the ∆H for the reaction.
(b) How many kJ of heat is released when 87.5 g of N2 is produced?

5. Whitten15.15 The combustion of 2.22 x10-1 grams of isooctane vapor (C8H18), at constant pressure rises
the temperature of a calorimeter by 0.400oC. The heat capacity of the calorimeter and water combined is
2.48kJ/oC.
(a) Write the balanced equation for combustion of C8H18.
C8H18 (g) + __O2 (g)
__H2O (l) + 8CO2 (g)
(b) Find the molar heat combustion of gaseous isooctane.
(c) Calculate the number of grams C8H18 (g) that must be burned to obtain a 495kJ of heat energy.

Concept: ∆H˚ Standard Enthalpy of Formation, Hess’s Law (Summation of Heats).

6. Write the balanced equations for the standard molar formation of the following compounds.
(a) Ca(OH)2(s) (b) NaHCO3(s)
(c) benzoic acid, C6H5COOH (s) (d) dinitrogen pentoxide, N2O5(g)
(e) Ozone, O3(g) (f) PbCl2
(g) Phosphine , PH3(g) (h) Atomic sulfur, S(g)
(i) Benzene, C6H6(l) (j) SnI2 (s)

7. Use the data in the table of standard enthalpy values, to find the enthalpy of reaction for the following:
(Note: you have to balance the equations first).
(a) SiO2 (s) + C (graphite)
SiC (s) + CO (g)
(b) HI(g) + F2(g)
HF(g) + I2(s)
(c) SF6 (g) + H2O (l)
HF (g) + SO3 (g)
8. Whitten15.30. We burn 3.47 g of Li(s)(M= 6.941 g mol-1) in excess O2(g) at constant atmospheric
pressure to form Li2O(s). Then we bring the reaction mixture back to 298 K. In this process, 146 kJ of heat
is given off. What is the standard molar enthalpy of formation of Li2O?

9. Whitten15-34. Using the thermochemical equations (i) and (ii)

Determine the enthalpy change for the decomposition reaction: 2SO3 (g)
2SO2 (g) + O2 (g) ∆H = ?
(i)S(s) + O2 (g)
SO2 (g) ∆H = -296.8 kJ/mol-rxn
(ii) S(s) +3/2 O2 (g)
SO3 (g) ∆H = -395.6 kJ/mol-rxn.

10. Calculate the standard enthalpy of formation of solid Mg(OH)2, given the following data:
2 Mg(s) + O2(g)
2MgO(s) ∆H° = -1204.0 kJ
Mg(OH)2(s)
MgO(s) + H2O(l) ∆H° = +37.10 kJ
2H2(g) + O2(g)
2H2O(l) ∆H° = -572.0 kJ

11. Whitten15.30. Given the following thermochemical equations:

H2(g) + ½ O 2 (g)
H2O(l) ∆H= -285.8 kJ/mol
C3H4(g) + 4O2 (g)
3CO2(g) + 2H2O(l) ∆H= -1937. kJ/mol
C3H8(g) + 5O2 (g)
3CO2(g) + 4H2O(l) ∆H= -2220. kJ/mol
Determine the heat of the hydrogenation reaction:
C3H4(g) + 2H2 (g)
3C3H8(g) ∆H = ???

12. Whitten15.23 Which is more exothermic, the combustionof 1 mol gaseous benzene or the combustion
of 1 mol liquid benzene? (No direct calculations needed).

II. Concept: Determination of ∆H based on Tabulated Bond Energy Values.

Bond Energy Values (the average bond energies (in kJ per mol) of bonds):
C-C: 348 C-H: 414 C=C: 602 C=O:799
Br-Br: 193 Br-C: 285 Br-H: 366 Cl-Cl: 242
H-Cl: 432 O-H: 463 O=O: 498 O-O: 146

13. Use the bond energies data above to estimate the enthalpy of reaction for each of the following gas
phase reactions:
(a) H2C = CH2 + Br2
BrH2C - CH2Br (b) H2O2
H2O + ½ O 2

14. Whitten15.37 Methane undergoes several different exothermic reactions with gaseous chlorine. One
example is the formation of chloroform, CHCl3 (g). Estimate the ∆Ho for the reaction. Compare it with the
experimental value of - 305.2 kJ/mol-rxn. Account for the difference.
CH4(g) + 3Cl2(g)
CHCl3(g) + 3HCl(g).

15. Propane has the structure H3C-CH2-CH3. Using the given bond enthalpies, estimate the change in
enthalpy (∆Horxn) for the combustion of 1 mole of propane.
C3H8 (g) + 5O2 (g)
3CO2(g) + 4H2O (g) ∆Horxn= ?

CONCEPT: Energy/Work/Energy Calculations

16. For each of the following chemical and physical changes carried at constant pressure, indicate whether
the work done is by the system on the surroundings or by the surroundings on the system, or whether the
work is negligible.
(a) C6H6 (l)
C6H6 (g) (b) 2SO2 + O2 (g)
2SO3 (g)
(c) CaCO3 (s)
CaO (s) + CO2(g) (d) CO2 (g) + H2O(l) + CaCO3(s)
Ca+2 (aq) + 2HCO3- (aq).
(e) ½ N 2 (g) + 3/2 H2 (g)
NH3 (g) (f) 2 NO (g)
N2 (g) + O2 (g)
17. A certain system absorbs 0.300 kJ of heat and has 0.700 kJ of work performed on it. What is the
value of the ∆E for change in state. Is the reaction exothermic or endothermic?

18. The reaction CaO(s) + 2HCl(g)  CaCl2(s) + H2O(g) has ∆Ho = -217.1kJ. Calculate the ∆Eo for the
reaction. What does this difference in ∆H and ∆E represent?

19. The reaction 2N2O(g)
2N2 (g) + O2(g) has a ∆Horxn= -163.14kJ. What is the value of the ∆E for the
decomposition of 812 g of N2O at 25oC? If we assume that ∆H doesn’t change appreciably with T, what is
the ∆E for this same reaction at 200oC?

20. A 10.0 L vessel at 20.0 oC contains butane, C4H10(g), at a pressure of 2.00 atm. What is the maximum
work that can be obtained by the combustion of butane if the gas is first brought to a pressure of 1.00 atm
and the temperature is brought to 25.0 oC. Assume that the products and reactants are at the same
temperature and pressure.

21. A 1.00 mol of He (an ideal gas) confined in a closed-container and originally at 1.00 atm pressure and
300. K, has expanded at a constant pressure of 1.00 atm until the temperature of the system has increased
to 450. K.
(a) Using the ideal gas law, calculate the volume of the gas before and after expansion.
(b) Calculate the work of expansion. Is the work done on or by the system?
(c) If instead, the initial gas expanded (against a constant pressure of 1 atm) until its final volume
is twice its original volume, what is the resulting final temperature?

22. Whitten-128. Calculate the q, w and ∆E for the vaporization of 12.5 g of liquid ethanol (C2H5OH) at
1.00 atm and 78oC to form a gaseous ethanol at 1.00 atm and 78oC.
Make the following simplifying assumptions: (i) the density of the liquid ethanol at 78oC is 0.789 g/ml (b) the
gaseous ethanol is an ideal gas. The heat of vaporization of ethanol is 855 J/g.

23. A 2.00-gram liquid CCl4 sample (Molar mass = 154.0 g/mol) is vaporized to form gaseous CCl4 at 1.00
atm and its boiling point of 77.0°C. The density of the liquid CCl4 is 1.60 g/ml and the gaseous CCl4 is
adequately described by the ideal gas equation. The heat of vaporization of CCl4 is 213.0 J/g.
For the vaporization process described above, calculate:
(a) q (in J) (b) w (in J) (c) ∆E (in J)

BOMB CALORIMETRY
24. A 100.0-gram propane, C3H8 (M=44.0g/mol), a gas used for cooking, was placed in a bomb calorimeter
with excess oxygen and then ignited. The initial T of the calorimeter was 25.000oC and its total heat
capacity was 97.1 kJ per oC. The reaction raised the temperature of the calorimeter to 27.282oC.
(a) Write the balanced reaction. (b) Calculate the energy liberated.
(c) What is the molar heat of combustion of propane (in kJ/mol).

25. Whitten15.70 A 6.620-gram sample of decane, C10H22 (liquid) (M=142 g/mol) was burned in a bomb
calorimeter whose heat capacity had been determined to be 2.45 kJ/ oC. The temperature of 1250.0 g of
water rose from 24.6 oC to 26.4oC. Calculate the ∆E for the reaction in J/g decane and kJ/g decane.
The specific heat of water is 4.184 J/g oC.
2010 Chem 17 Practice Exercises 1. Dr. Nuesca’s Class.

Concepts: 2nd and 3rd law of thermodynamics, ∆S and ∆G calculations, Spontaneity of Reactions.

1. Indicate whether the following processes are accompanied by an increase or a decrease in entropy of
the system:
(a) dry ice sublimes at -78oC amd then the resulting CO2 (g) is warmed to 0oC.
(b) Water vapor forms snowflakes.
(c) Silver sulfate precipitates from an aqueous solution containing silver and sulfate ions.
(d) Solid NaCl is dissolved in water at room temperature.
(e) CCl4 evaporates.
(f) The reaction PCl3 (g) + Cl2 (g)
PCl5 (g) occurs.

2. Whitten15.97. For each of the following pair, tell which would have the greater absolute entropy per
mole at the same temperature. Give the reasor for your choice.
(a) NaCl(s) or CaO(s) (b) Cl2(g) or Kr(g)
(c) AsH3(g) or Kr(g) (d) NH4NO3(s) or NH4NO3(aq)
(e) Ga(s) or Ga(l). (f) NaF(s) or MgO (s)
(g) Au(s) or Hg(l) (h) H2O(g) or H2S (g)
+ -
(i) CH3OH(l) or C2H5OH(l) (j) AgCl(s) or (Ag , Cl )(aq)

3. Without doing Entropy calculations based on tabulated absolute entropy values, predict whether the
following reactions are marked by a decrease or increase in entropy.
(a) C6H6 (l)
C6H6 (g) (b) 2SO2 + O2 (g)
2SO3 (g)
(c) CaCO3 (s)
CaO (s) + CO2(g) (d) N2 (g) + 3H2 (g)
2NH3 (g)
(e) 2NO (g)
N2 (g) + O2 (g) (f) Mg(s) + ½ O 2(g)  MgO(s)

4. Whitten15.108 Calculate the ∆G0 (at 298K) for the reaction: 2 NO2 (g)  N2O4 (g)
given that ∆Horxn = -57.20 kJ./mol and ∆Sorxn =-175.83 J/mol K. Is the reaction spontaneous? What is
the driving force for spontaneity?

5. Using standard enthalpy and entropy values, calculate the ∆H0, ∆S0 , ∆G0 for the reaction:
H2O2 (l)  2H2O(l) + O2 (g). Is there any temperature at which H2O2 is stable at 1.00 atm?
∆H0 ∆S0
H2O2 (l)
H2O(l)
O2 (g)

6. The heat of vaporization of ammonia is 21.7 kJ/mol. and the boiling point of ammonia is -33.3oC.
Estimate the entropy change for the vaporization of liquid ammonia.

7. The heat of vaporization of Hg is 60.7 kJ/mol. The S0 = 76.1 J/mol K and for S0 = 175 J/mol K.
Estimate the normal boiling point of Hg(l) (in K and Celsius).

8. For the melting point of aluminum, Al(s)
Al (l), ∆H0 = 10.0 kJ/mol and ∆S0 = 9.50 J/mol K.
Calculate the melting point of Al. Account for the difference between this value and actual value of 660oC.

9. Calculate ∆G0 for the reduction of the oxides of iron and copper by carbon at 650K. The equations are:
(a) 2Fe2O3 (s) + 3C (graphite)
4Fe (s) + 3CO2 (g)
(b) 2CuO (s) + C (graphite)
2Cu (s) + CO2 (g)
∆G0f at 650K are -92kJ/mol for CuO(s); -632 kJ/mol for Fe2O3 (s) and -395kJ/mol for CO2(g).
Which oxide can be reduced using carbon in a wood fire (assuming standard state conditions)?