THERMODYNAMICS PROBLEM SET

Topic 6.1 - Endothermic and Exothermic Processes

1. Consider the accompanying energy diagram.

a) Does the diagram represent an increase or decrease in internal energy of the system?

b) What sign is given to ΔE for this process?

c) If there is no work associated with the process, is it exothermic or endothermic?

2. Calculate ΔE and determine whether the process is endothermic or exothermic for each of the following
cases:
a. A balloon is heated by adding 850 J of heat. It expands, doing 382 J of work on the atmosphere.

b. A system absorbs 105 kJ of heat from its surroundings while doing 29 kJ of work on the
surroundings.

c. A chemical reaction releases 6.47 kJ of heat and does no work on the surroundings.
3. The contents of the closed box in each of the following illustrations represent a system, and the arrows
show the changes to the system during some process. The lengths of the arrows show the relative
magnitudes of q and w.

a. Which of these processes is endothermic?

b. For which of these processes, if any, is ΔE < 0?

c. For which process, if any, does the system experience a net gain in internal energy?

4. A fire is started in a fireplace by striking a match and lighting crumpled paper under some logs. Explain
all the energy transfers in this scenario using the terms exothermic, endothermic, system, surroundings,
potential energy, and kinetic energy in the discussion.

5. A sample of an ideal gas at 15.0 atm and 10.0 L is allowed to expand against a constant external
pressure of 2.00 atm at a constant temperature. At the same time, 4.5 kJ of heat are transferred from the
surroundings to the system. Calculate the internal energy, in terms of kJ, for the gas expansion. (Hint:
Boyle’s Law applies)
6. Calculate the kinetic energy in joules of an 850-lb motorcycle moving at 66 mph.

By what factor will the kinetic energy change if the speed of the motorcycle is decreased to 33 mph?

Where does the kinetic energy of the motorcycle go when the rider brakes to a stop?

7. Describe why the dissolution of SrF2 in water is endothermic.

8. Dissolving sugar in water is an endothermic process, but dissolving vinegar in water is exothermic.
Explain this in regards to the relative strengths of intermolecular/interparticle interactions before and
after the dissolution process.
Topic 6.2 - Energy Diagrams
 1. Draw an energy diagram for a reaction (label the axis)
Potential energy of reactants = 350 kJ/mol
Activation energy = 100 kJ/mol
Potential energy of products = 250 kJ/mol

2. Is the reaction you drew for #1 exothermic or endothermic? Explain.

3. How could you lower the activation energy for the reaction in #1?

Topic 6.3 - Heat Transfer and Thermal Equilibrium

1. Objects placed together eventually reach the same temperature. When you go into a cool room and touch
a piece of metal, it feels colder than a piece of plastic in the same room. Explain.

2. Arrows were used to represent the relative velocities of the particles in the following two pure samples
of the same gas.
 a. Is System #1 at a lower or higher temperature than system #2? Justify your answer.

b. Will kinetic energy be transferred from one of these systems to the other? Justify your answer in
terms of molecular collisions.

Topic 6.4 - Heat Capacity and Calorimetry

1. Which substance in the table below requires the smallest amount of energy to increase the temperature
of 50.0 g of the substance by 10 K? Calculate the energy needed for this temperature change.

2. The specific heat capacity of silver is 0.24 J/goC.

a. Calculate the energy to raise the temperature of 150.0 g Ag from 273 K to 298 K.
 b. Calculate the energy required to raise the temperature of 1.0 mole of Ag by 1.0oC.

c. It takes 1.25 kJ of energy to heat a sample of pure silver from 12.0oC to 15.2oC. Calculate the
mass of the sample of silver.

3. Consider the following reaction, which occurs at room temperature and pressure:
2 Cl(g) → Cl2(g) ΔH = -243.4 kJ
Which has the higher enthalpy under these conditions 2Cl(g) or Cl2(g)?

4. The specific heat of iron metal is 0.450 J/g-K. How many J of heat are necessary to raise the temperature
of a 1.05 kg block of iron from 25.0oC to 88.5oC?

5. Consider the dissolution of CaCl2:

CaCl2 → Ca2+ + 2 Cl- ΔH = - 81.5 kJ/mol
An 11.0-g sample of CaCl2 is dissolved in 125 g of water, with both substances at 25.0oC. Calculate the
final temperature of the solution assuming no heat loss to the surroundings and assuming the solution
has a specific heat capacity of 2.18 J/goC

6. A 1800-g sample of phenol (C6H5OH) was burned in a bomb calorimeter whose total heat capacity is
11.66 kJ/oC. The temperature of the calorimeter increased from 20.94oC to 26.73oC.
a. Write a balanced chemical equation for the bomb calorimeter reaction.

b. What is the heat of combustion per gram of phenol? Per mol of phenol?
 7. When a 9.55-g sample of solid sodium hydroxide dissolves in 100.0 g of water in a coffee-cup
calorimeter, the temperature rises from 23.6oC to 47.4oC. Calculate ΔH (in kJ/mol NaOH) for the
solution process
NaOH(s) → Na+(aq) + OH-(aq)
Assume that the specific heat of the solution is the same as that of pure water.

8. Under constant-volume conditions the heat of combustion of glucose (C6H12O6) is 15.57 kJ/g. A 2.500-g
sample of glucose is burned in a bomb calorimeter. The temperature of the calorimeter increased from
20.55oC to 23.25oC.
a. What is the total heat capacity of the calorimeter?

b. If the size of the glucose sample had been exactly twice as large, what would the temperature
change of the calorimeter have been?

Topic 6.5 - Energy of Phase Changes

1. What quantity of energy does it take to convert 0.500 kg of ice at -[Link] to steam at [Link]?
● Specific heat capacities: Ice = 2.03 J/goC, Steam = 2.01 J/goC
● ΔHvap = 40.6 kJ/mol; ΔHfus = 6.02 kJ/mol
2. A substance, X, has the following properties:
Thermodynamic Data Specific Heat Capacities

ΔHvap 20. kJ/mol X (s) 3.0 J/goC

ΔHfus 5.0 kJ/mol X (l) 2.5 J/goC

Boiling Point 75oC X (g) 1.0 J/goC

Melting Point -15oC

Sketch a heating curve for the substance starting at -50oC and going to 100oC. Make sure all
lengths of segments are proportional to the relative energy associated with the transitions, and
the slope of the diagonal segments are relative to the specific heat values.

3. The fluorocarbon C2Cl3F3 has a normal boiling point of 47.6oC. The specific heats of C2Cl3F3 (l) and
C2Cl3F3(g) are 0.91 J/g*K and 0.67 J/g*K, respectively. The heat of vaporization for the compound is
27.49 kJ/mol. Calculate the heat required to convert 35.0 g of C2Cl3F3 from a liquid at 10.00oC to a gas
at 105.00oC.

4. An ice cube tray contains enough water at 22.0oC to make 18 ice cubes that each has a mass of 30.0
grams. The tray is placed in a freezer that uses CF2Cl2 as a refrigerant. The heat of vaporization of
CF2Cl2 is 158 J/g. What mass of CF2Cl2 must be vaporized to convert all of the water at 22.0oC to ice at
-5.0oC? The heat capacities for H2O(s) and H2O(l) are 2.03 J/goC and 4.18 J/goC, respectively, and the
heat of fusion of ice is 6.02 kJ/mol.
Topic 6.6 - Introduction to Enthalpy of Reaction

1. Consider the following reaction:

2 H2(g) + O2(g) → 2 H2O(g) ΔH = -572 kJ
a. How much heat is evolved for the production of 1.00 mole of H2O?

b. How much heat is evolved when 4.03 g H2 is reacted with excess oxygen?

c. The total volume of hydrogen gas needed to fill the Hindenburg (a large German airship that
exploded in 1937) was 2.0 x 108 L at 1.0 atm and 25oC. How much heat was evolved when the
Hindenburg exploded, assuming all of the hydrogen exploded?

2. Portable hot packs are available for skiers and people engaged in other outdoor activities in a cold
climate. The air-permeable paper packet contains a mixture of powdered iron, sodium chloride, and
other components, all moistened by a little water. The exothermic reaction that produces the heat is a
very common one - the rusting of iron:
4 Fe(s) + 3 O2(g) → 2 Fe2O3(s) ΔH = -1644.4 kJ/mol
When the outside plastic envelope is removed, O2 molecules begin to penetrate the paper, causing the
reaction to begin. A typical packet contains 250 g of iron to warm your hands or feet for up to 4 hours.
How much heat (in kJ) is produced by this reaction?

3. Consider the following reaction:

2 CH3OH (g) → 2 CH4(g) + O2(g) ΔH = + 252.8 kJ
a. Calculate the amount of heat transferred when 24.0 g of CH3OH(g) is decomposed by this
reaction at constant pressure.
 b. For a given sample of CH3OH, the enthalpy change during the reaction is 82.1 kJ. How many
grams of methane gas are produced?

c. How many kilojoules of heat are released when 28.5 g of CH4(g) react with 14.0 g of O2(g) at
constant pressure?

4. A quantity of 2.00 x 102 mL of 0.862 M HCl is mixed with an equal volume of 0.431 M Ba(OH)2 in a
constant-pressure calorimeter of negligible heat capacity. The initial temperature of the HCl and
Ba(OH)2 solutions is the same at 20.48oC. What is the final temperature of the mixed solutions
corresponding to the following equation:
H+(aq) + OH-(aq) → H2O(l) ΔH = -56.2 kJ/mol

5. Meals-ready-to-eat (MREs) are military meals that can be heated on a flameless heater. The heat is
produced by the following reaction:
Mg(s) + 2 H2O(l) → Mg(OH)2(s) + H2(g) ΔH = -355 kJ
Calculate the number of grams of Mg needed for this reaction to release enough energy to increase the
temperature of 75 mL of water from 21oC to 79oC
Topic 6.7 - Bond Enthalpies
1. The bond energy for a C -- H bond is about 413 kJ/mol in CH4 but 380 kJ/mol in CHBr3. Although these
values are relatively close in magnitude, they are different. Explain why they are different on the basis
of electronegativity.

2. Acetic acid is responsible for the sour taste of vinegar. It can be manufactured using the following
reaction:

Use tabulated values of bond energies to estimate ΔH for this reaction.

3. Consider the following reaction:

ΔH = -549 kJ/mol
Estimate the carbon-fluorine bond energy given that the C-C bond energy is 347 kJ/mol, the C=C bond
energy is 614 kJ/mol, and the F-F bond energy is 154 kJ/mol.

4. Answer the following questions regarding bond enthalpies for reactions of carbon and fluorine:
a. Using average bond enthalpies, determine which of the following reactions will be most
exothermic:
i. C(g) + 2 F2(g) → CF4(g)

ii. CO(g) + 3 F2(g) → CF4(g) + OF2(g)

 iii. CO2(g) + 4 F2(g) → CF4(g) + 2 OF2(g)

b. Explain the trend, if any, that exists between reaction exothermicity and the extent to which the
carbon atom is bonded to oxygen.

5. Two compounds are isomers if they have the same chemical formula but a different arrangement of
atoms. Use a bond energy table to estimate ΔH for each of the following gas-phase isomerization
reactions, and indicate which isomer has the lower enthalpy:
Topic 6.8 - Enthalpy of Formation

1. For each of the following compounds, write a balanced thermochemical equation depicting the
formation of one mole of the compound from its elements in their standard states and use the appendix
to obtain the value of ΔHfo.
a. NO2(g) b. SO3(g) c. NaBr(s) d. Pb(NO3)2(s)

2. The ΔHfo values of the two allotropes of oxygen, O2 and O3, are 0 and 142.2 kJ/mol, respectively, at
25oC. Which is the more stable form at this temperature? Why?

3. Gasoline is composed primarily of hydrocarbons, including many with eight carbon atoms called
octanes. One of the cleanest-burning octanes is a compound called 2,3,4-trimethylpentane, which has the
structural formula:

The complete combustion of one mole of this compound to CO2(g) and H2O(g) leads to a
ΔH = -5064.9 kJ/mol.
a. Write a balanced chemical equation for the combustion of 1 mol of C8H18.

b. Write a balanced equation for the formation of C8H18 from its elements.

c. By using the information in this problem and appendix data, calculate the ΔHfo for 2,3,4-
trimethylpentane.
4. Using appendix values, calculate the value of ΔHfo for each of the following reactions:
a. 2 SO2(g) + O2(g) → 2 SO3(g)

b. Mg(OH)2(s) → MgO(s) + H2O(l)

c. N2O4(g) + 4 H2(g) → N2(g) + 4 H2O(g)

d. SiCl4(l) + 2 H2O(l) → SiO2(s) + 4 HCl(g)

5. Use the values of ΔHfo in the appendix to calculate ΔHo for the following reactions:

a.

b.
 c.

6. Pentaborane-9, B5H9, is a colorless, highly reactive liquid that will burst into flame when exposed to
oxygen. The reaction is:
2 B5H9(l) + 12 O2(g) → 5 B2O3(s) + 9 H2O(l) ΔHfo = -8890.2 kJ/mol
Calculate the heat of formation of B5H9 and the kilojoules of heat released per gram of the compound
reacted with oxygen.

7. The Ostwald process for the commercial production of nitric acid from ammonia and oxygen involves
the following steps:
4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g)
2 NO(g) + O2(g) → 2 NO2(g)
3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g)
a. Use the values of ΔHfo to calculate the value of ΔH for each of the three reactions.
Reaction 1:

Reaction 2:

Reaction 3:

b. The overall reaction is NH3 + 2 O2 → HNO3 + H2O. Use Hess’ Law to determine the
overall enthalpy released in the Ostwald process.
Topic 6.9 - Hess’s Law

1. Calculate the ΔHrxn of N2(g) + 2 O2(g) → 2 NO2(g) based on the following reactions:
A) N2 (g) + O2 (g) → 2 NO (g) ΔH = +180 kJ
B) 2 NO (g) + O2 (g) → 2 NO2 (g) ΔH = -112 kJ

2. Calculate the ΔHrxn of C(graphite) → C(diamond) based on the following reactions:

A) C(graphite) + O2 (g) → CO2 (g) ΔH =-394 kJ
B) C(diamond) + O2 (g) → CO2 (g) ΔH =-396 kJ

3. Find the ΔH for the reaction below given the following reactions and subsequent ΔH values:
½ H2 (g) + ½ Cl2 (g) → HCl (g)

A) COCl2 (g) + H2O (l) → CH2Cl2 (l) + O2 (g) ΔH = + 47.5 kJ

B) 2 HCl (g) + ½ O2 (g) → H2O (l) + Cl2 (g) ΔH = +105 kJ
C) CH2Cl2 (l) + H2 (g) + 3/2 O2 (g) → COCl2 (g) + 2 H2O (l) ΔH = -402.5 kJ

4. Calculate the ΔHrxn of 2 C2H6(g) + 7 O2(g) → 4 CO2(g) + 6 H2O(g) based on the following
reactions:
A) 2 C (s) + 3H2 (g) → C2H6 (g) ΔH = -84.7 kJ
B) C (s) + O2 (g) → CO2 (g) ΔH = -393.5 kJ
C) H2 (g) + ½ O2 (g) → H2O (g) ΔH = -242 kJ
5. Calculate the ΔHrxn of NH4Cl → NH3 + HCl based on the following reactions:
A) N2 + 3 H2 → 2 NH3 ΔH = -91.2 kJ
B) H2 + Cl2 → 2 HCl ΔH = -184.6 kJ
C) N2 + 4 H2 + Cl2 → 2 NH4Cl ΔH = -618.8 kJ

6. Find the ΔH for the reaction below, given the following reactions and subsequent ΔH values:
2CO2(g) + H2O(g) → C 2H2(g) + 5/2O2(g)
a. C2H2(g) + 2H2(g) → C2H6(g) ΔH =-94.5 kJ
b. H2O(g) → H2(g) + 1/2O2 (g) ΔH =+71.2 kJ
c. C2H6(g) + 7/2O2(g) → 2CO2(g) + 3H2O(g) ΔH =-283 kJ

7. Calculate the ΔHrxn of C(s) + H2O(g) → CO(g) + H2(g) based on the following reactions:
A.) C (S) + ½ O2 (g) → CO (g) ΔH = -110.5 kJ
B.) C (s) + O2 (g) → CO2 (g) ΔH = -393.5 kJ
C.) CO (g) + ½ O2 (g) → CO2 (g) ΔH = -283.0 kJ
D.) H2 (g) + ½ O2 (g) → H2O (g) ΔH = -242.0 kJ

8. Find the ΔH for the reaction below, given the following reactions and subsequent ΔH values:
NO (g) + O (g) → NO2 (g)
A.) 2 O3 (g) → 3 O2 (g) ΔH = - 427 kJ
B.) O2 (g) → 2 O (g) ΔH = + 495 kJ
C.) NO (g) + O3 (g) → NO2 (g) + O2 (g) ΔH = - 199 kJ
9. Find the ΔH for the reaction below, given the following reactions and subsequent ΔH values:
CO2 (g) → C (s) + O2 (g)

A.) H2O (l) → H2 (g) + ½ O2 (g) ΔH = + 286 kJ

B.) C2H6 (g) → 2 C (s) + 3 H 2 (g) ΔH = - 190.6 kJ
C.) 2 CO2 (g) + 3 H2O (l) → C 2H6 (g) + 7/2 O2(g) ΔH = + 3511.1 kJ

10. Find the ΔH for the reaction below, given the following reactions and subsequent ΔH values:
P4O10 (s) + 6 PCl5 (g) → 10 Cl3PO (g)
A.) P4 (s) + 6 Cl2 (g) → 4 PCl3 (g) ΔH = - 1225.6 kJ
B.) P4 (s) + 5 O2 (g) → P4O10 (s) ΔH = - 2967.3 kJ
C.) PCl3 (g) + Cl2 (g) → PCl5 (g) ΔH = - 84.2 kJ
D.) PCl3 (g) + ½ O2 (g) → Cl3PO (g) ΔH = - 285.7 kJ

11. Calculate the ΔHrxn of Fe3O4(s) + CO(g) → 3 FeO(s) + CO2(g) based on the following reactions:
A.) 2 Fe (s) + 3 CO2 (g) → Fe2O3 (s) + 3 CO (g) ΔH = - 23 kJ
B.) 2 Fe3O4 (s) + CO2 (g) → 3 Fe2O3 (s) + CO (g) ΔH = - 39 kJ
C.) FeO (s) + CO (g) → Fe (s) + CO2 (g) ΔH = + 18 kJ

12. Find the ΔH for the reaction below, given the following reactions and subsequent ΔH values:
N2H4 (g) + O2 (g) → N2 (g) + 2 H2O (l)

A.) 2 NH3 (g) + 3 N2O (g) → 4 N2 (g) + 3 H2O (l) ΔH = - 1010 kJ

B.) N2O (g) + 3 H2 (g) → N2H4 (l) + H2O (l) ΔH = - 317 kJ
C.) 2 NH3 (g) + ½ O2 (g) → N2H4 (l) + H2O (l) ΔH = - 143 kJ
D.) H2 (g) + ½ O2 (g) → H2O (l) ΔH = - 286 kJ