Chemistry A Molecular Approach Canadian 2nd Edition Tro Solutions Manual 1

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1. Solution Manual for Chemistry A Molecular Approach Canadian 2nd

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Edition Chapter 6 Thermochemistry
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6 Thermochemistry
Review Questions
6.1 Thermochemistry is the study of the relationship between chemistry and energy. It is impor-
tant because energy and its uses are critical to our society. It is important to understand how
much energy is required or released in a process.
6.2 Energy is the capacity to do work. Work is the result of a force acting through a distance. Examples
of energy are kinetic energy, heat energy, electrical energy, chemical energy, and light or radiant
energy. Examples of work are moving an object, expansion of a cylinder, and running a marathon.
6.3 Kinetic energy is energy associated with the motion of an object. Potential energy is energy
associated with the position or composition of an object. Examples of kinetic energy are water
at the top of Niagara Falls, gas molecules, and a raging river. Examples of potential energy are
a curling stone sliding down the ice, a compressed spring, and molecules.
6.4 The law of conservation of energy states that energy can neither be created nor destroyed.
Energy can be transferred from one object to another, and it can assume different forms. In an
energy exchange, energy is transferred between the system and the surroundings. If the sys-
tem loses energy, the surroundings gain energy, and vice versa.
6.5 The SI unit of energy is kg m2 s–2, defined as the joule (J), named after the English scientist
James Joule. Other units of energy are the kilojoule (kJ), the calorie (cal), the Calorie (Cal), and
the kilowatt-hour (kWh).
6.6 The first law of thermodynamics is the law of energy conservation, stated as follows: The total
energy of the universe is constant. In other words, because energy is neither created nor destroyed
and the universe does not exchange energy with anything else, its energy content does not change.
The first law has many implications, the most important of which is that with energy you do not
get something for nothing. The best we can do with energy is break even—there is no free lunch.
6.7 According to the first law, a device that would continually produce energy with no energy
input, sometimes known as a perpetual motion machine, cannot exist because the best we can
do with energy is break even.
6.8 A state function is a function whose value depends only on the state of the system, not on how
the system arrived at that state. Examples are pressure, volume, and internal energy.
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6.9 The internal energy (U) of a system is the sum of the kinetic and potential energies of all of
the particles that compose the system. Internal energy is a state function.
6.10 If energy is flowing out of the system it is like a withdrawal from a chequing account, and
200 therefore carries a negative sign. Chapter 6 Thermochemistry
6.11 If the reactants have a lower internal energy than the products, ¢Usys is positive and energy
flows into the system from the surroundings.
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200 Chapter 6 Thermochemistry

6.12 Heat is the flow of thermal energy caused by a temperature difference. Thermal energy is actually a type of
kinetic energy because it arises from the motions of atoms or molecules within a substance. The higher the tem-
perature, the greater the motion of atoms and molecules. Heat is measured in units of energy: joules, calories,
kilowatt-hours, etc., while temperature is measured in units of Kelvins, degrees Celsius, and degrees Fahrenheit.
6.13 The internal energy (U) of a system is the sum of the kinetic and potential energies of all of the particles that
compose the system. The change in the internal energy of the system (¢U) must be the sum of the heat trans-
ferred (q) and the work done (w): ¢U = q + w.
6.14 According to the first law of thermodynamics, the change in the internal energy of the system (¢U) must be
the sum of the heat transferred (q) and the work done (w): ¢U = q + w. The total change in internal energy
(¢U) is the difference between its initial energy and its final energy. The amount of work done and the amount
of heat transferred is dependent on the details of the path. In one path more energy may be transferred
through conversion to heat energy (if, for example, there is more friction). In another path more energy may be
transferred through work. Work and heat are not state functions, but their sum (¢U) is constant.
6.15 The heat capacity of a system is usually defined as the quantity of heat required to change its temperature by
1 °C. Heat capacity (C) is a measure of the system’s ability to hold thermal energy without undergoing a large
change in temperature. The difference between heat capacity (C) and specific heat capacity (Cs) is that the spe-
cific heat capacity is the amount of heat required to raise the temperature of 1 gram of the substance by 1 °C.
6.16 Since water has such a high heat capacity, it can moderate temperature changes. This keeps coastal temper-
atures more constant. Changing the temperature of water absorbs or releases large quantities of energy for
a relatively small change in temperature. This serves to keep the air temperature of coastal areas more con-
stant than the air temperature in inland areas.
6.17 When two objects of different temperatures come in direct contact heat flows from the higher temperature
object to the lower temperature object. The amount of heat lost by the warmer object is equal to the amount
of heat gained by the cooler object. The warmer object’s temperature will drop and the cooler object’s tem-
perature will rise until they reach the same temperature. The magnitude of these temperature changes
depends on the mass and heat capacities of the two objects.
6.18 The work caused by an expansion of volume is simply the negative of the pressure that the volume expands
against multiplied by the change in volume that occurs during the expansion: w = –P ¢V.
6.19 In calorimetry, the thermal energy exchanged between the reaction (defined as the system) and the sur-
roundings is measured by observing the change in temperature of the surroundings. A bomb calorimeter is
used to measure the ¢ rU for combustion reactions. The calorimeter includes a tight fitting, sealed container
that forces the reaction to occur at constant volume. A coffee-cup calorimeter is used to measure ¢ rH for
many aqueous reactions. The calorimeter consists of two Styrofoam® coffee cups, one inserted into the other,
to provide insulation from the laboratory environment. Since the reaction happens under conditions of con-
stant pressure (open to the atmosphere), qr = qp = ¢ rH.
6.20 ¢H is the heat exchanged with the surroundings under conditions of constant pressure. ¢H is equal to qp,
the heat at constant pressure. Conceptually (and often numerically), ¢H and ¢U are similar: They both rep-
resent changes in a state function for the system. However, ¢U is a measure of all of the energy (heat and
work) exchanged with the surroundings. ¢H = ¢U + P ¢V.
6.21 An endothermic reaction has a positive ¢H and absorbs heat from the surroundings. An endothermic reac-
tion feels cold to the touch. An exothermic reaction has a negative ¢H and gives off heat to the surround-
ings. An exothermic reaction feels warm to the touch.
6.22 The internal energy of a chemical system is the sum of its kinetic energy and its potential energy. It is this poten-
tial energy that is the energy source in an exothermic chemical reaction. Under normal circumstances, chemical
potential energy (or simply chemical energy) arises primarily from the electrostatic forces between the protons
and electrons that compose the atoms and molecules within the system. In an exothermic reaction, some bonds
break and new ones form, and the protons and electrons go from an arrangement of higher potential energy to
one of lower potential energy. As they rearrange, their potential energy is converted into kinetic energy, the heat
emitted in the reaction. This increase in kinetic energy is detected as an increase in temperature.
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202 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 201

6.23 The internal energy of a chemical system is the sum of its kinetic energy and its potential energy. It is this
potential energy that absorbs the energy in an endothermic chemical reaction. In an endothermic reaction, as
some bonds break and others form, the protons and electrons go from an arrangement of lower potential
energy to one of higher potential energy, absorbing thermal energy in the process. This absorption of ther-
mal energy reduces the kinetic energy of the system. This is detected as a drop in temperature.
6.24 ¢ rH is an extensive property; therefore it depends on the quantity of reactants undergoing reaction. ¢ rH is
usually reported for a reaction involving stoichiometric amounts of reactants and is dependent on the spe-
cific chemical reaction. For example, a reaction A + 2 B : C, ¢ rH is usually reported as the amount of heat
emitted or absorbed when 1 mole A reacts with 2 mole B to form 1 mole C.
6.25 (a) If a reaction is multiplied by a factor, the ¢H is multiplied by the same factor.
(b) If a reaction is reversed, the sign of ¢H is reversed.
The relationships hold because H is a state function. Twice as much energy is contained in twice the quan-
tity of reactants or products. If the reaction is reversed, the final and initial states have been switched and the
direction of heat flow is reversed.
6.26 Hess’s law states that if a chemical equation can be expressed as the sum of a series of steps, then ¢ rH for
the overall equation is the sum of the heats of reactions for each step. This makes it possible to determine
¢H for a reaction without directly measuring it in the laboratory. If you can find related reactions (with
known ¢H) that sum to the reaction of interest, you can find ¢H for the reaction of interest.
6.27 The standard state is defined as follows: for a gas, the pure gas at a pressure of exactly 1 bar; for a liquid or
solid, the pure substance in its most stable form at a pressure of 1 bar and the temperature of interest (often
taken to be 25 °C); and for a substance in solution, a concentration of exactly 1 mol L–1. The standard
enthalpy change (¢H°) is the change in enthalpy for a process when all reactants and products are in their
standard states. The superscript degree sign indicates standard state.
6.28 The standard enthalpy of formation (¢ fH°) for a pure compound is the change in enthalpy when 1 mole of
the compound forms from its constituent elements in their standard states. For a pure element in its stan-
dard state ¢ fH° = 0.
6.29 To calculate ¢ rH°, subtract the heats of formations of the reactants multiplied by their stoichiometric coeffi-
cients from the heats of formation of the products multiplied by their stoichiometric coefficients. In the form
of an equation:
¢ rH° = a np ¢ fH° - a n ¢ H°
products r f reactants
6.30 Most energy comes from the combustion of fossil fuels, which include petroleum, natural gas, and coal.
6.31 One of the main problems associated with the burning of fossil fuels is that, even though they are abundant
in the Earth’s crust, they are a finite and nonrenewable energy source. The other major problems associated
with fossil fuel use are related to the products of combustion. Three major environmental problems associ-
ated with the emissions of fossil fuel combustion are air pollution, acid rain, and global warming. One of
the main products of fossil fuel combustion is carbon dioxide (CO2), which is a greenhouse gas.
6.32 Renewable energy is energy from natural resources that do not have a limited supply. Some examples of
renewable energy sources are wind, solar, biofuels, wave or tidal, and geothermal.
Problems by Topic
Energy Units
6.33 (a) Given: 534 kWh Find: J
Conceptual Plan: kWh : J
3.60 x 106 J
1 kWh
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3.60 x 106J
Solution: 534 kWh x = 1.92 x 109 J
1 kWh
Check: The units (J) are correct. The magnitude of the answer (109) makes physical sense because a
kWh is much larger than a Joule, so the answer increases.
(b) Given: 215 kJ Find: Cal

Conceptual Plan: kJ : J : Cal
1000 J 1 Cal
1 kJ 4184 J
1000 J 1 Cal
Solution: 215 kJ x x = 51.4 Cal
1 kJ 4184 J
Check: The units (Cal) are correct. The magnitude of the answer (51) makes physical sense because a
Calorie is about 41 of a kJ, so the answer decreases by a factor of about four.
(c) Given: 567 Cal Find: J

Conceptual Plan: Cal : J
4184 J
1 Cal
4184 J
Solution: 567 Cal x = 2.37 x 106 J
1 Cal
Calorie is much larger than a Joule, so the answer increases.
(d) Given: 2.85 x 103 J Find: cal

Conceptual Plan: J : cal
1 cal
4.184 J
3 1 cal
Solution: 2 .85 x 10 J x = 681 cal
4.184 J
Check: The units (cal) are correct. The magnitude of the answer (680) makes physical sense because
a J is about 41 the size of a calorie, so the answer decreases by a factor of about four.
6.34 (a) Given: 231 cal Find: kJ

Conceptual Plan: cal : J : kJ
4.184 J 1 kJ
1cal 1000 J
4.184 J 1 kJ
Solution: 231 cal x x = 0.967 kJ
1 cal 1000 J
Check: The units (kJ) are correct. The magnitude of the answer (1) makes physical sense because a kJ
is much larger than a cal, so the answer decreases.
(b) Given: 132 x 104 kJ Find: kcal

Conceptual Plan: kJ : J : cal : kcal
1000 J 1 cal 1 kcal
1 kJ 4.184 J 1000 cal
1000 J 1 cal 1 kcal

Solution: 132 x 104 kJ x x x = 3.15 x 105 kcal
1 kJ 4.184 J 1000 cal
Check: The units (kcal) are correct. The magnitude of the answer (105) makes physical sense because
a kcal is smaller than a kJ, so the answer increases.
(c) Given: 4.99 x 103 kJ Find: kWh

Conceptual Plan: kJ : J : kWh
1000 J
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1 kJ 1 kWh
3.60 x 106 J
1000 J 1 kWh
202 Chapter
Solution: 4.99 x 103 kJ x
6 Thermochemistry x = 1.39 kWh Chapter 6 Thermochemistry 201
1 kJ 3.60 x 106 J
Check: The units (kWh) are correct. The magnitude of the answer (1) makes physical sense because a
kWh is much smaller than a Joule, so the answer increases.
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(d) Given: 2.88 x 104 J Find: Cal

Conceptual Plan: J : Cal
1 Cal
4184 J
1 Cal
Solution: 2 .88 x 10 4 J x = 6.88 Cal
4184 J
Check: The units (Cal) are correct. The magnitude of the answer (7) makes physical sense because a
J is much smaller than a Cal, so the answer decreases.
6.35 (a) Given: 2387 Cal Find: J

Conceptual Plan: Cal : J
4184 J
1 Cal
4184 J
Solution: 2387 Cal x = 9.987 x 106 J
1 Cal
Calorie is much larger than a Joule, so the answer increases.
(b) Given: 2387 Cal Find: kJ
Conceptual Plan: Cal : J : kJ
4184 J 1 kJ
1 Cal 1000 J
4184 J 1 kJ
Solution: 2387 Cal x x = 9.987 x 103 kJ
1 Cal 1000 J
Check: The units (kJ) are correct. The magnitude of the answer (103) makes physical sense because a
Calorie is larger than a kJ, so the answer increases.
(c) Given: 2387 Cal Find: kWh
Conceptual Plan: Cal : J : kWh
4184 J 1 kWh
1 Cal 3.60 x 106 J
4184 J 1 kWh
Solution: 2387 Cal x x = 2.77 kWh
1 Cal 3.60 x 106 J
Check: The units (kWh) are correct. The magnitude of the answer (3) makes physical sense because a
Calorie is much smaller than a kWh, so the answer decreases.
6.36 (a) Given: 745 kWh Find: J

Conceptual Plan: kWh : J
3.60 x 106 J
1 kWh
3.60 x 106 J
Solution: 745 kWh x = 2.68 x 109 J
1 kWh
(b) Given: 745 kWh Find: kJ
Conceptual Plan: kWh : J : kJ
3.60 x 106 J 1 kJ
1 kWh 1000 J
3.60 x 106 J 1 kJ
Solution: 745 kWh x x = 2.68 x 106 kJ
1 kWh 1000 J
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(c) Given: 745 kWh Find: Cal
Conceptual Plan: kWh : J : Cal Chapter 6 Thermochemistry 203
3.60 x 106 J 1 Cal
1 kWh 4184 J
3.60 x 106 J 1 Cal

Solution: 745 kWh x x = 6.41 x 105 Cal
1 kWh 4184 J
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Check: The units (Cal) are correct. The magnitude of the answer (105) makes physical sense because
a kWh is much larger than a Cal, so the answer increases.
Internal Energy, Heat, and Work

6.37 (d) ¢Usys = –¢Usurr. If energy change of the system is negative, energy is being transferred from the sys-
tem to the surroundings, decreasing the energy of the system and increasing the energy of the sur-
roundings. The amount of energy lost by the system must go somewhere, so the amount gained by the
surroundings is equal and opposite to that lost by the system.
6.38 The sign is positive since the energy is being taken in by or deposited into the system.
6.39 (a) The energy exchange is primarily heat since the skin (part of the surroundings) is cooled. There is a
small expansion (work) since water is being converted from a liquid to a gas. The sign of ¢Usys is
positive since the surroundings cool.
(b) The energy exchange is primarily work. The sign of ¢Usys is negative since the system is expanding
(doing work on the surroundings).
(c) The energy exchange is primarily heat. The sign of ¢Usys is positive since the system is being heated
by the flame.
6.40 (a) The energy exchange is primarily work since there is a lot of motion. There is a small amount of heat
transferred since there is some friction as the balls roll. The sign of ¢Usys is negative since the kinetic
energy of the first ball is transferred to the second ball.
(b) The energy exchange is primarily work. The sign of ¢Usys is negative since the potential energy of the
book decreases as it falls.
(c) The energy exchange is primarily work. The sign of ¢Usys is positive since the father is doing work
to move the girl and the swing.
6.41 Given: 622 kJ heat released; 105 kJ work done on surroundings Find: ¢Usys
Conceptual Plan: interpret language to determine the sign of the two terms then q, w : ¢Usys
¢U = q + w
Solution: Since heat is released from the system to the surroundings, q = – 622 kJ; since the system is doing
work on the surroundings, w = –105 kJ. ¢U = q + w = - 622 kJ - 105 kJ = - 727 kJ = - 7.27 x 102 kJ.
Check: The units (kJ) are correct. The magnitude of the answer (–730) makes physical sense because both
terms are negative.
6.42 Given: 196 kJ heat absorbed; surroundings do 117 kJ work Find: ¢Usys
¢U = q + w
Solution: Since heat is absorbed by the system, q = +196 kJ; since the surroundings are doing work on
the system, w = +117 kJ. ¢U = q + w = 196 kJ + 117 J = 313 kJ = 3 .13 x 102 kJ.
Check: The units (kJ) are correct. The magnitude of the answer (+300) makes physical sense because both
terms are positive.
6.43 Given: 655 J heat absorbed; 344 J work done on surroundings Find: ¢Usys
¢U = q + w
Solution: Since heat is absorbed by the system, q = +655 J; since the system is doing work on the
surroundings, w = –344 J. ¢U = q + w = 655 J - 344 J = 311 J.
Check: The units (J) are correct. The magnitude of the answer (+300) makes physical sense because heat
term dominates over the work term.
6.44 Given: 155 J heat absorbed; 77 kJ work done on surroundings Find: ¢Usys
Conceptual Plan: interpret language to determine the sign of the two terms J : kJ then q, w : ¢Usys
1 kJ
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¢U = q + w
1000 J
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Solution: Since heat is absorbed by the system, q = +155 J; since the system is doing work on the
1000 J
surroundings, w = –77 kJ. Thus - 77 kJ x = - 77000 J and
1 kJ
¢U = q + w = 155 J - 77000 J = - 77000 J = - 77 kJ.

Check: The units (kJ) are correct. The magnitude of the answer (–77 kJ) makes physical sense because the
work term dominates over the heat term. In fact the heat term is negligible compared to the work term.
Heat, Heat Capacity, and Work

6.45 Cooler A had more ice after three hours because most of the ice in cooler B was melted in order to cool the
soft drinks that started at room temperature. In cooler A the drinks were already cold and so the ice only
needed to maintain this cool temperature.
6.46 Since the specific heat capacity of water is much larger than the specific heat capacity of aluminum, much
more heat needs to be released by the water than the aluminum for each 1 °C of temperature drop. This
means that more heat is stored in each kg of water than aluminum.
6.47 Given: 1.50 L water, Ti = 25.0 °C, Tf = 100.0 °C, d = 1.0 g mL–1 Find: q
Conceptual Plan: L : mL : g and pull Cs from Table 6.4 and Ti, Tf : ¢T then m, Cs, ¢T : q
1000 mL 1.0 g J
4 .184
g # °C
¢T = Tf - q = mCs ¢T
1L 1.0 mL
Ti
1000 mL 1 .0 g
Solution: 1 .50 L x x = 1500 g and ¢T = Tf - Ti = 100 .0 °C - 25 .0 °C = 75 .0 °C
1L 1 .0 mL
J
then q = mCs ¢T = 1500 g x 4 .184 x 75 .0 °C = 4 .7 x 105 J
g # °C
Check: The units (J) are correct. The magnitude of the answer (106) makes physical sense because there is
such a large mass, a significant temperature change, and a high specific heat capacity material.
6.48 Given: 1.50 kg sand, Ti = 25.0 °C, Tf = 100.0 °C Find: q

Conceptual Plan: kg : g and pull Cs from Table 6.4 and Ti, Tf : ¢T then m, Cs, ¢T : q
1000 g J
0 .84
g # °C
¢T = Tf - q = mCs ¢T
1g
Ti
1000 mL 1 .0 g
Solution: 1 .50 L x x = 1500 g and ¢T = Tf - Ti = 100.0 °C - 25 .0 °C = 75 .0 °C
1L 1 .0 mL
J
then q = mCs ¢T = 1500 g x 0.84 # x 75 .0 °C = 9.5 x 10 4 J
g °C
Check: The units (J) are correct. The magnitude of the answer (~105) makes physical sense because there is
such a large mass and a significant temperature change.
6.49 (a) Given: 25 g gold, Ti = 27.0 °C, q = 2.35 kJ Find: Tf

Conceptual Plan: kJ : J and pull Cs from Table 6.4 then m, Cs, q : ¢T then Ti, ¢T : Tf
1000 J J
0 .128 q = mCs ¢T ¢T = Tf - Ti
1 kJ g # °C
1000 J
Solution: 2 .35 kJ x = 2350 J then q = mCs ¢T. Rearrange to solve for ¢T.
1 kJ
q 2350 J
¢T = = = 734 .375 °C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

mCs J
25 g x 0 .128
g # °C
Tf = ¢T + Ti = 734.375 °C + 27.0 °C = 7.6 x 102 °C
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Check: The units (°C) are correct. The magnitude of the answer (760) makes physical sense because
there is such a large amount of heat absorbed, such a small mass, and specific heat capacity. The tem-
perature change should be very large.
206 (b) Given: 25 g silver, Ti = 27.0 °C, q = 2.35 kJ Find: Tf Chapter 6 Thermochemistry
1000 J J
0 .235 q = mCs ¢T ¢T = Tf - Ti
1 kJ g # °C
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1000 J
1 kJ
q 2350 J
¢T = = = 400 °C finally ¢T = Tf - Ti. Rearrange to solve for Tf.
mCs J
25 g x 0 .235
g # °C
Tf = ¢T + Ti = 400 °C + 27 .0 °C = 4.3 x 102 °C
there is such a large amount of heat absorbed, such a small mass, and specific heat capacity. The tem-
perature change should be very large. The temperature change should be less than that of the gold
because the specific heat capacity is greater.
(c) Given: 25 g aluminum, Ti = 27.0 °C, q = 2.35 kJ Find: Tf

1000 J J
0 .903 q = mCs ¢T ¢T = Tf - Ti
1 kJ g # °C
1000 J
1 kJ
q 2350 J
¢T = = = 104 .10°C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

mCs J
25 g x 0 .903
g # °C
Tf = ¢T + Ti = 104.10 °C + 27 .0 °C = 1.3 x 102 °C
there is such a large amount of heat absorbed and such a small mass. The temperature change should
be less than that of the silver because the specific heat capacity is greater.
(d) Given: 25 g water, Ti = 27.0 °C, q = 2.35 kJ Find: Tf
1000 J J
4 .184 q = mCs ¢T ¢T = Tf - Ti
1 kJ g # °C
1000 J
1 kJ
q 2350 J
¢T = = = 22 .488°C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

mCs J
25 g x 4.184
g # °C
Tf = ¢T + Ti = 22 .488 °C + 27 .0 °C = 49 °C
there is such a large amount of heat absorbed and such a small mass. The temperature change should
be less than that of the aluminum because the specific heat capacity is greater.
6.50 (a) Given: Pyrex glass, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 55.4 °C Find: m
Conceptual Plan: pull Cs from Table 6.4 and Ti, Tf : ¢T then ¢T, Cs, q : m
J
0 .75 ¢T = Tf - q = mCs ¢T
g # °C Ti
Solution: ¢T = Tf - Ti = 55.4 °C - 23 .0 °C = 32.4 °C and q = mCs ¢T. Rearrange to solve for m.

q 1 .95 x 103 J
m = = = 80 g or 8 .0 x 101 g
Cs ¢T J
0 .75 # x 32 .4 °C
g °C
Check: The units (g) are correct. The magnitude of the answer (80) makes physical sense because there is
such a large amount of heat absorbed, a moderate temperature rise, and specific heat capacity.
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(b) Given: sand, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 62.1 °C Find: m

J
206 0 .84
g # °C
¢T = Tf -
Ti
Chapter
q =6
mC Thermochemistry
¢T s
Solution: ¢T = Tf - Ti = 62.1 °C - 23 .0 °C = 39.1 °C then q = mCs ¢T. Rearrange to solve for m.
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q 1 .95 x 103 J
m = = = 59 g
Cs ¢T J
0 .84 # x 39.1 °C
g °C
such a large amount of heat absorbed, a moderate temperature rise, and specific heat capacity.
(c) Given: ethanol, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 44.2 °C Find: m

J
2 .42 ¢T = Tf - q = mCs ¢T
g # °C Ti

q 1 .95 x 103 J
m = = = 38.0 g
Cs ¢T J
2.42 # x 21.2 °C
g °C
Check: The units (g) are correct. The magnitude of the answer (40) makes physical sense because
there is such a large amount of heat absorbed, a small temperature rise, and specific heat capacity.
(d) Given: water, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 32.4 °C Find: m

J
4 .184 ¢T = Tf - q = mCs ¢T
g # °C Ti

q 1 .95 x 103 J
m = = = 50 g or 5 .0 x 101 g
Cs ¢T J
4.184 # x 9.4 °C
g °C
such a large amount of heat absorbed, a small temperature rise, and very specific heat capacity.
6.51 Given: Vi = 0.0 L, Vf = 2.5 L, P = 1.1 bar Find: w (J)

Conceptual Plan: Vi, Vf : ¢V then P, ¢V : w (L bar) : w (J)
100 .0 J
¢V = Vf - Vi w = -P¢V
1 L # bar
Solution: ¢V = Vf - Vi = 2 .5 L - 0 .0 L = 2 .5 L then
100 .0 J
w = - P¢V = - 1 .1 bar x 2 .5 L x = - 2.8 x 102 J
1 L # bar
Check: The units (J) are correct. The magnitude of the answer (–2.8) makes physical sense because this is an
expansion (negative work) and we have ~ atmospheric pressure and a small volume of expansion.
6.52 Given: ¢V = 0.50 L, P = 1.0 bar Find: w (J)

Conceptual Plan: P, ¢V : w (L bar) : w (J)
100 .0 J
w = -P¢V
1 L # bar
100.0 J
Solution: w = - P¢V = - 1 .0 bar x 0.50 L x = - 50 J
1 L # bar
Check: The units (J) are correct. The magnitude of the answer (–50 J) makes physical sense because this is a
small expansion (negative work) and we do not expect breathing to take much energy.
6.53 Given: q = 565 J absorbed, Vi = 0.10 L, Vf = 0.85 L, P = 1.0 bar Find: ¢Usys
Conceptual Plan: Vi, Vf : ¢V and interpret language to determine the sign of the heat
¢V = Vf - Vi q = + 565 J
then P, ¢V : w (L bar) : w (J) finally q, w : ¢Usys
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100 .0 J
w = -P¢V ¢U = q + w
1 L # bar
Solution: ¢V = Vf - Vi = 0.85 L - 0 .10 L = 0.75 L then

208 Chapter 6 Thermochemistry 100.0 J Chapter 6 Thermochemistry 207
w = - P¢V = - 1.0 bar x 0.75 L x = - 75 J ¢U = q + w = +565 J - 75 J = 490 J
1 L # bar
Check: The units (J) are correct. The magnitude of the answer (500) makes physical sense because the heat
absorbed dominated the small expansion work (negative work).
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6.54 Given: q = 124 J released, Vi = 5.55 L, Vf = 1.22 L, P = 1.00 bar Find: ¢Usys
Conceptual Plan: Vi, Vf : ¢V and interpret language to determine the sign of the heat
¢V = Vf - Vi q = –124 J
then P, ¢V : w (L bar) : w (J) finally q, w : ¢Usys

100 .0 J
w = -P¢V ¢U = q + w
1 L # bar
Solution: ¢V = Vf - Vi = 1.22 L - 5.55 L = - 4.33 L then

100.0 J
w = - P¢V = - 1 .00 bar x (- 4.33 L) x = + 433 J then
1 L # bar
¢U = q + w = - 124 J + 433 J = 309 J
Check: The units (J) are correct. The magnitude of the answer (300) makes physical sense because the com-
pression work dominated the small heat released.
6.55 Given: T = 298.15 K Find: work associated with decomposition of hydrogen peroxide.
Conceptual Plan: write balanced equation, then ¢n and then ¢n, R, T : w
¢n = nproduct gases - nreactant w = - ¢nRT
gases
1
Solution: hydrogen peroxide decomposes into oxygen and liquid water, H2O2(l) : 2 O2(g) + H2O(l).
1
¢n = nproduct gases - nreactant gases = 2 - 0 = 12.
w = - ¢nRT = - ( 12 )(8.314 J K - 1 mol - 1)(298.15 K) = - 1239 J mol - 1 = - 1.239 kJ mol - 1

Check: The units (kJ mol–1) are correct and the amount of work done by the system is reasonable considering
that half a mole of gas is produced per mole of reaction.
6.56 Given: T = 298.15 K, balanced equation Find: work associated with decomposition of trinitrotoluene.
Conceptual Plan: find ¢n and then ¢n, R, T : w
¢n = nproduct gases - nreactant gases w = - ¢nRT
3 5
Solution: C7H5N3O6(s) ¡ N2(g) + H (g) + 3 O2(g) + 7 C(s)
2 2 2
5 3
¢n = nproduct gases - nreactant gases = a 3 + + b - 0 = 7 - 0 = 7
2 2
w = - ¢nRT = - (7)(8.314 J K - 1 mol - 1)(298.15 K) = - 1.735 x 103 J mol - 1 = - 17.35 kJ mol - 1
Check: The units (kJ mol–1) are correct. Trinitrotoluene (TNT) is a powerful explosive and 7 moles of
gas are produced for every mole of TNT decomposed. We expect a large amount of work to be done by the
system so the value of 17.35 kJ mol–1 is reasonable.
Enthalpy and Thermochemical Stoichiometry

6.57 Given: 1 mol fuel, 3452 kJ heat produced; 11 kJ work done on surroundings Find: ¢Usys , ¢H
Conceptual Plan: interpret language to determine the sign of the two terms
then q : ¢H and q, w : ¢Usys
¢H = qp ¢U = q + w
Solution: Since heat is produced by the system to the surroundings, q = –3452 kJ; since the system is
doing work on the surroundings, w = –11 kJ. ¢H = qp = - 3452 kJ and
¢U = q + w = - 3452 kJ - 11 kJ = - 3463 kJ
Check: The units (kJ) are correct. The magnitude of the answer (–3500) makes physical sense because both
terms are negative. We expect significant amounts of energy from fuels.
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6.58 Given: 1 mol octane, P = 1.0 bar, ¢Usys = –5084.3 kJ; ¢H = –5074.1 kJ Find: w
Conceptual Plan: interpret language to determine the sign of the two terms then q : ¢H and q, ¢Usys : w
¢U = –5084.3 kJ; ¢ H = –5074.1 kJ
sys
Chapter 6 Thermochemistry
¢H = q p ¢U = q + w
207
Solution: Since heat is produced by the system to the surroundings, ¢H = qp = - 5074 .1 kJ;
¢Usys = –5084.3 kJ ¢U = q + w. Rearrange to solve for w.
w = ¢U - q = - 5084.3 kJ - 5074.1 kJ = - 10.2 kJ
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Check: The units (kJ) are correct. The magnitude of the answer (–10) makes physical sense because the work
should be negative in an expansion. We expect more heat than work in an engine.
6.59 (a) Combustion is an exothermic process; ¢H is negative.
(b) Evaporation requires an input of energy, so it is endothermic; ¢H is positive.
(c) Condensation is the reverse of evaporation, so it is exothermic; ¢H is negative.
6.60 (a) Sublimation requires an input of energy, so it is endothermic; ¢H is positive.
(b) Combustion is an exothermic process; ¢H is negative.
(c) Since the temperature drops, this is an endothermic process; ¢H is positive.
6.61 Given: 177 mL acetone (C3H6O), ¢ rH° = – 1790 kJ; d = 0.788 g mL–1 Find: q
Conceptual Plan: mL acetone : g acetone : mol acetone : q
0 .788 g 1 mol -1790 kJ
1 mL 58 .08 g 1 mol
0.788 g 1 mol - 1790 kJ
Solution: 177 mL x x x = - 4.30 x 103 kJ or 4.30 x 103 kJ released
1 mL 58.08 g 1 mol
Check: The units (kJ) are correct. The magnitude of the answer (–103) makes physical sense because the enthalpy
change is negative and we have more than a mole of acetone. We expect more than 1790 kJ to be released.
6.62 Given: natural gas (CH4), ¢ rH° = –802.3 kJ; q = 267 kJ Find: m
Conceptual Plan: q : mol natural gas : g natural gas
1 mol 16 .04 g
-802.3 kJ 1 mol
1 mol 16.04 g
Solution: - 267 kJ x x = 5.34 g
- 802.3 kJ 1 mol
Check: The units (g) are correct. The magnitude of the answer (5) makes physical sense because the enthalpy
change per mole is so large and we need to burn less than a mole.
6.63 Given: pork roast, ¢ rH° = –2217 kJ; q needed = 1.6 x 103 kJ, 10% efficiency Find: m(CO2)
Conceptual Plan: q used : q generated : mol CO2 : g CO2
100 kJ generated 3 mol 44 .01 g

10 kJ used 2217 kJ 1 mol
100 kJ generated 3 mol CO2 44.01 g CO2
Solution: 1 .6 x 103 kJ x x x = 9.5 x 102 g CO2
10 kJ used 2217 kJ 1 mol CO2
Check: The units (g) are correct. The magnitude of the answer (~1000) makes physical sense because the
process is not very efficient and a lot of energy is needed.
6.64 Given: carbon, ¢ rH° = –393.5 kJ; q needed = 5.00 x 102 kJ Find: m(CO2)
Conceptual Plan: q needed : mol CO2 : g CO2
1 mol 44 .01 g
393.5 kJ 1 mol
1 mol CO2 44.01 g CO2

Solution: 5 .00 x 102 kJ x x = 55.9 g CO 2
393.5 kJ 1 mol CO2
Check: The units (g) are correct. The magnitude of the answer (~60) makes physical sense as there is a 1:1 mol
ratio between the carbon burned and the carbon dioxide produced.
Thermal Energy Transfer
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6.65 Given: silver block, TAgi = 58.5 °C, 100.0 g water, TH2Oi = 24.8 °C, Tf = 26.2 °C Find: mass of silver block
Conceptual Plan: pull Cs values from Table 6.4 then H2O: m, Cs, Ti , Tf : q Ag: Cs, Ti, Tf : m
J J Chapter 6 Thermochemistry 209
Ag: 0 .235 H2O: 4.184 q = mCs(Tf - Ti) then set qAg = –qH2O
g # °C g # °C
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Solution: q = mCs(Tf - Ti) substitute in values and set qAg = –qH2O.
J
qAg = mAgCAg(Tf - TAgi) = mAg x 0 .235 # x (26.2 °C - 58.5 °C) =
g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 100.0 g x 4 .184 # x (26.2 °C - 24 .8 °C)
g °C
Rearrange to solve for mAg.
J - 585.7 J
mAg x a - 7.5905 b = - 585.7 J : mAg = = 77.1622 g Ag = 77 g Ag
g J
- 7.5905
g
Check: The units (g) are correct. The magnitude of the answer (77 g) makes physical sense because the heat
capacity of water is much greater than the heat capacity of silver.
6.66 Given: 32.5 g iron rod, TFei = 22.7 °C, TH2Oi = 63.2 °C, Tf = 59.5 °C Find: mass of water
Conceptual Plan: pull Cs values from Table 6.4 then Fe: m, Cs, Ti , Tf : q H2O: Cs, Ti, Tf : m
J J
Fe: 0 .449 H2O: 4 .184 q = mCs(Tf - Ti) then set qFe = –qH2O
g # °C g # °C
Solution: q = mCs(Tf - Ti) substitute in values and set qFe = –qH2O.

J
qFe = mFeCFe(Tf - TFei) = 32.5 g x 0.449 # x (59.5°C - 22.7 °C) =
g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - mH2O x 4 .184 # x (59.5 °C - 63.2 °C)
g °C
Rearrange to solve for mH2O.
J 537.004 J
537.004 J = - mH2O x a 15 .481 b : mH2O = = 34.68794 g H2O = 34.7 g H2O
g J
15.481
g
Check: The units (g) are correct. The magnitude of the answer (35 g) makes physical sense because the heat
capacity of water is much greater than the heat capacity of iron.
6.67 Given: 31.1 g gold, TAui = 69.3 °C, 64.2 g water, TH2Oi = 27.8 °C Find: Tf
Conceptual Plan: pull Cs values from Table 6.4 then m, Cs, Ti : Tf
J J
Au: 0 .128 H2O: 4 .184 q = mCs(Tf - Ti) then set qAu = – qH2O
g # °C g # °C
Solution: q = mCs(Tf - Ti) substitute in values and set qAu = – qH2O.

J
qAu = mAuCAu(Tf - TAui) = 31.1 g x 0 .128 # x (Tf - 69 .3 °C) =
g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 64.2 g x 4 .184 # x (Tf - 27 .8 °C)
g °C
Rearrange to solve for Tf.
J J
3.9808 x (Tf - 69 .3 °C) = - 268.613 x (Tf - 27 .8 °C) :
°C °C
J J
3 .9808 Tf - 275 .8694 J = - 268.613 Tf + 7467 .4358 J :
°C °C
J J J
268.613 Tf + 3 .9808 Tf = 275 .8694 J + 7467 .4358 J : 272 .5938 Tf = 7743 .3052 J :
°C °C °C
7743 .3052 J
Tf = = 28 .4 °C
J
272.5938
°C
Check: The units (°C) are correct. The magnitude of the answer (28) makes physical sense because the heat
transfer is dominated by the water (larger mass and larger specific heat capacity). The final temperature
should be closer to the initial temperature of water than of gold.
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6.68 Given: 2.85 g lead, TPbi = 10.3 °C, 7.55 g water, TH2Oi = 52.3 °C, Find: Tf
J J
Pb: 0 .128 H2O:4 .184 q = mCs(Tf - Ti) then set qPb = – qH2O
g # °C g # °C
Solution: q = mCs(Tf - Ti) substitute in values and set qPb = – qH2O.

J
qPb = mPbCPb(Tf - TPbi) = 2.85 g x 0 .128 # x (Tf - 10.3 °C) =
g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 7.55 g x 4 .184 # x (Tf - 52.3 °C)
g °C
J J
0.3648 x (Tf - 10.3 °C) = - 31.589 x (Tf - 52.3 °C) :
°C °C
J J
0 .3648 Tf - 3.75744 J = - 31.589 Tf + 1652 .1047 J :
°C °C
J J J
0 .3648 Tf + 31 .589 Tf = 3.75744 J + 1652 .1047 J : 31 .9538 Tf = 1655.8621 J :

°C °C °C
1655 .8621 J
Tf = = 51.8 °C
J
31 .9538
°C
should be closer to the initial temperature of water than of lead.
6.69 Given: 6.15 g substance A, TAi = 20.5 °C, 25.2 g substance B, TBi = 52.7 °C, Cs = 1.17 J g–1 °C–1, Tf = 46.7 °C
Find: specific heat capacity of substance A
Conceptual Plan: A: m, Ti , Tf : q B: m, Cs, Ti, Tf : q and solve for C
q = mCs(Tf - Ti ) then set qA = –qB
Solution: q = mCs(Tf - Ti) substitute in values and set qA = –qB.

qA = mACA(Tf - TAi) = 6.15 g x CA x (46.7 °C - 20.5 °C) =
J
- qB = - mBCB(Tf - TBi) = - 25.2 g x 1.17 # x (46.7 °C - 52.7 °C)
g °C
Rearrange to solve for CA.
176.904 J J J
CA x (161.13g # °C) = 176.904 J : CA = = 1.097896 # = 1.10 #
161.13g # °C g °C g °C
Check: The units (J g–1 °C–1) are correct. The magnitude of the answer (1 J g–1 °C–1) makes physical sense
because the mass of substance B is greater than the mass of substance A by a factor of ~4.1, and the temper-
ature change for substance A is greater than the temperature change of substance B by a factor of ~4.4, so
the heat capacity of substance A will be a little smaller.
6.70 Given: 2.74 g substance that may be gold, TAu?i = 72.1 °C, 15.2 g water, TH2Oi = 24.7 °C, Tf = 26.3 °C
Find: heat capacity of substance that may be gold, and could it be gold
Conceptual Plan: pull Cs values from Table 6.4 substance: m, Ti , Tf : q H2O: m, Cs, Ti, Tf : q
J J
Au: 0 .128 q = mCs(Tf - then set qAu? = –qH2O.
g # °C
H2O: 4 .184
g # °C
Ti )
and solve for C
Solution: q = mCs(Tf - Ti) substitute in values and set qAu? = –qH2O.
qAu? = mAu?CAu?(Tf - TAu?i) = 2.74g x CAu? x (26.3 °C - 72.1°C) =
J
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- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 15.2 g x 4.184 x (26.3 °C - 24.7 °C)

g # °C
Rearrange to solve for CAu?.
- 101.7549 J J J
212 Chapter
CAu? (- 125.492 g # °C) = - 101.7549 J
6 x Thermochemistry : CAu? = Chapter
# 6 Thermochemistry
= 0.8108477 # = 0.81 # 211
- 125.492 g °C g °C g °C
Since the specific heat capacity of gold is 0.128 J g–1 °C–1, this substance is not gold.
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Check: The units (J g–1 °C–1) are correct. The magnitude of the answer (1 J g–1 °C–1) makes physical sense
because the mass of the substance is much less than the mass of the water by a factor of ~5.5, and the
temperature change for the substance is greater than the temperature change of the water by a factor of
~29, so the heat capacity of the unknown substance will be a factor of ~5.2 smaller than the water, but
not as low as 0.128 J g–1 °C–1.
Calorimetry
6.71 ¢ rH = qp and ¢ rU = qV = ¢H - P¢V. Since combustions always involve expansions, expansions do
work and therefore have a negative value. Combustions are always exothermic and therefore have a nega-
tive value. This means that ¢ rU is more negative than ¢ rH and so A (–25.9 kJ) is the constant volume process
and B (–23.3 kJ) is the constant pressure process.
6.72 Constant volume conditions should be used. Since ¢U = q + w and w = –P ¢V, this means that at
constant V, w = 0 and all of the energy is released as heat (¢ rU = qV). At constant P, ¢ rH = qp and
¢ rU = qp = ¢H - P¢V. Since combustions always involve expansions; expansions do work and so have
a negative value. Combustions are always exothermic and so have a negative value. This means that ¢ rU is
more negative than ¢ rH and so more heat will be generated in a constant V process.
6.73 Given: 0.5141 g biphenyl (C12H10), bomb calorimeter, Ti = 25.823 °C, Tf = 29.419 °C, Ccal = 5.861 kJ °C–1
Find: ¢ rU and ¢ rH
Conceptual Plan: Ti, Tf : ¢T then ¢T, Ccal : qcal : qr then g C12H10 : mol C12H10
1 mol
¢T = Tf - Ti qcal = Ccal ¢T qcal = -qr
154.21 g
then qr, mol C12H10 : ¢ rU

qr
¢ rU =
mol C12 H10
Write balanced equation, find ¢n and then ¢n, R, T, ¢ rU : ¢ rH
¢n = nproduct gases - nreactant gases ¢ rH = ¢ rU + ¢nRT
Solution: ¢T = Tf - Ti = 29.419 °C - 25.823 °C = 3.596 °C then

qcal = Ccal ¢T = 5 .861 kJ °C - 1 x 3 .596 °C = 21.076 kJ.
1 mol
qr = - qcal = - 21.076 kJ and mol C12H10 = 0 .5141 g x = 3 .33377 x 10 - 3 mol C12H10 then
154.21 g
qr -21 .076 kJ 3 -1
¢ rU = = = - 6 .322 x 10 kJ mol
mol C12H10 3 .33376 x 10 - 3 mol
The balanced equation is C12H10 (s) + 29/2 O2(g) : 12 CO2(g) + 5 H2O(l) and ¢n = 12 – 14.5 = –2.5
1 kJ
¢ rH = ¢ rU + ¢nRT = - 6322 kJ mol - 1 + (- 2.5)(8.314 J K - 1 mol - 1)a b (298 K)
1000 J
= - 6322 kJ mol - 1 - 6.194 kJ mol - 1 = - 6328 kJ mol - 1
Check: The units (kJ mol–1) are correct. ¢ rH is more negative than ¢ rU because work is done on the system
as it contracts because there is less moles of gas on the product side. Using ¢U = q + w, the internal energy
change must be more positive than the enthalpy change.
6.74 Given: 1.025 g napthalene (C10H8), bomb calorimeter, Ti = 24.259 °C, Tf = 32.338 °C, Ccal = 5.112 kJ °C–1
Find: ¢ rU and ¢ rH
Conceptual Plan: Ti, Tf : ¢T then ¢T, Ccal : : qr then g C12H10 : mol C12H10
qcal 1 mol
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¢T = Tf - Ti qcal = Ccal ¢T qcal = -qr 128.164 g
then qr, mol C10H8 : ¢ rU

q
212 Chapter 6 Thermochemistry r
Chapter 6 Thermochemistry 211
¢ rU =
mol C10 H8
Write balanced equation, find ¢n and then ¢n, R, T, ¢ rU : ¢ rH
¢n = nproduct gases - nreactant gases ¢ rH = ¢ rU + ¢nRT
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Solution: ¢T = Tf - Ti = 32.338 °C - 24.259 °C = 8.079 °C then
qcal = Ccal ¢T = 5.112 kJ °C - 1 x 8.079 °C = 41.2998 kJ.
1 mol
qr = - qcal = - 41.2998 kJ and mol C10H8 = 1.025 g * = 7.9976 * 10 - 3 mol C10H8 then
128.164 g
qr -41.2998 kJ 3 -1
¢ rU = = = - 5.164 x 10 kJ mol
mol C10H8 7.9976 * 10 - 3 mol
The balanced equation is C10H8 (s) + 12 O2 (g) : 10 CO2 (g) + 4 H2O (l) and ¢n = 10 – 12 = –2.
1 kJ
¢ rH = ¢ rU + ¢nRT = - 5164 kJ mol - 1 + (- 2)(8.314 J K - 1 mol - 1)a b (298.15 K)
1000 J
= - 6328 kJ mol - 1 - 4.958 kJ mol - 1 = - 5169 kJ mol - 1
Check: The units (kJ mol–1) are correct. ¢ rH is more negative than ¢ rU because work is done on the system
as it contracts because there is less moles of gas on the product side. Using ¢U = q + w, the internal energy
change must be more positive than the enthalpy change.
6.75 Given: 0.103 g zinc, coffee-cup calorimeter, Ti = 22.5 °C, Tf = 23.7 °C, 50.0 mL solution, d (solution) = 1.00 g mL–1,
Csoln = 4.184 kJ g–1 °C–1 Find: ¢ rH
Conceptual Plan: Ti, Tf : ¢T and mL soln : g soln then ¢T, Ccal : : qr then
1 .0 g
qcal
¢T = Tf - Ti qcal = m Csoln ¢T qsoln = -qr

1 .0 mL
g Zn : mol Zn then qr, mol Zn : ¢ rH
1 mol qp
¢ rH =
65.37 g mol Zn
1 .00 g
Solution: ¢T = Tf - Ti = 23.7 °C - 22 .5°C = 1.2°C and 50 .0 mL x = 50 .0 g then
1 .00 mL
J
qsoln = m Csoln ¢T = 50 .0 g x 4.184 x 1.2 °C = 251 .0 J then qsoln = - qr = - 251.0 J and
g # °C
1 mol Zn
0 .103 g Zn x = 0 .00157565 mol Zn then
65 .37 g Zn
qp -251 .0 J 5 -1 2 -1
¢ rH = = = - 1.6 x 10 J mol = - 1.6 x 10 kJ mol
mol Zn 0.00157565 mol Zn
Check: The units (kJ mol–1) are correct. The magnitude of the answer (–160) makes physical sense because
there is such a large heat generated from a very small amount of zinc.
6.76 Given: 1.25 g NH4NO3, coffee-cup calorimeter, Ti = 25.8 °C, Tf = 21.9 °C, 25.0 mL solution, d (solution) = 1.00 g mL–1,
Csoln = 4.184 kJ g–1 °C–1 Find: ¢ rH
Conceptual Plan: Ti, Tf : ¢T and mL soln : g soln then ¢T, Ccal : : qr then
qcal
1 .0 g
¢T = Tf - Ti qcal = m Csoln ¢T qsoln = -qr
1 .0 mL
g NH4NO3 : mol NH4NO3 then qr, mol NH4NO3 : ¢ rH
1 mol qp
¢ rH =
80.05 g mol NH NO
4 3
1 .00 g
Solution: ¢T = Tf - Ti = 21.9 °C - 25 .8 °C = - 3.9 °C and 25 .0 mL x
J 1 .00 mL
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= 25 .0 g then
qsoln = mCsoln ¢T = 25 .0 g x 4.184 x (- 3.9 °C) = - 407 .94 J then qsoln = - qr = 407 .94 J and
g # °C
1 .25 g NH NO x
1 mol NH4NO3
= 0 .0156152 mol NH4NO3 then
213
4 3
80 .05 g NH4NO3
qP 407 .94 J
¢ rH = = = 2.6 x 104 J mol - 1 = 26 kJ mol - 1
mol NH NO 0 .0156152 mol NH NO
4 3 4 3
–1
Check: The units (kJ mol ) are correct. The magnitude of the answer (26) makes physical sense because
there is such a small amount of heat absorbed.
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Quantitative Relationships Involving ¢ rH and Hess’s Law

6.77 (a) Since A + B : 2 C has ¢H1 then 2 C : A + B will have a ¢H2 = – ¢H1. When the reaction direction
is reversed, it changes from exothermic to endothermic (or vice versa), so the sign of ¢H changes.
(b) Since A + 12 B : C has ¢H1 then 2 A + B : 2 C will have a ¢H2 = 2 ¢H1. When the reaction amount
doubles, the amount of heat (or ¢H) doubles.
(c) Since A : B + 2 C has ¢H1 then 12 A : 12 B + C will have a ¢H1’ = 12 ¢H1. When the reaction amount is
cut in half, the amount of heat (or ¢H) is cut in half. Then 21 B + C : 21 A will have a ¢H2 = –¢H1’ = – 21
¢H1. When the reaction direction is reversed, it changes from exothermic to endothermic (or vice versa),
so the sign of ¢H changes.
6.78 (a) Since A + 2 B : C + 3 D has ¢H = 155 kJ mol–1 then 3A + 6 B : 3 C + 9 D will have a ¢H’ = 3
¢H = 3 (155 kJ mol–1) = 465 kJ mol–1. When the reaction amount triples, the amount of heat (or ¢H) triples.
(b) Since A + 2 B : C + 3 D has ¢H = 155 kJ mol–1 then C + 3 D : 3A + 6 B will have a ¢H’ = –¢H
= –155 kJ mol–1. When the reaction direction is reversed, it changes from endothermic to
exothermic, so the sign of ¢ H changes.
(c) Since A + 2 B : C + 3 D has ¢H = 155 kJ mol–1 then 12 A + B : 1

2 C + 3/2 D will have a ¢H’ = 1
2 ¢H = 1
2
(155 kJ mol–1) = 77.5 kJ mol–1. When the reaction amount is cut in half, the amount of heat (or ¢H) is
cut in half. Then 21 C + 3/2 D : 12 A + B will have a ¢H’’ = –¢H’ = –77.5 kJ mol–1. When the reaction
direction is reversed, the sign of it changes from endothermic to exothermic, so the sign of ¢H
changes.
6.79 Since the first reaction has Fe2O3 as a product and the reaction of interest has it as a reactant, we need to
reverse the first reaction. When the reaction direction is reversed, ¢H changes.
Fe2O3 (s) : 2 Fe (s) + 3/2 O2 (g) ¢H = + 824 .2 kJ mol - 1
Since the second reaction has 1 mole CO as a reactant and the reaction of interest has 3 moles of CO as a
reactant, we need to multiply the second reaction and the ¢H by 3.
3[CO (g) + 1/2 O2 (g) : CO2 (g)] ¢H = 3(- 282 .7 kJ mol - 1) = - 848 .1 kJ mol - 1
Hess’s Law states the ¢H of the net reaction is the sum of the ¢H of the steps.
The rewritten reactions are as follows:
Fe2 O3 (s) : 2 Fe (s) + 3/2 O2 (g) ¢H = + 824 .2 kJ mol - 1
3 CO (g) + 3/2 O2 (g) : 3 CO2 (g) ¢H = - 848 .1 kJ mol - 1
Fe2 O3 (s) + 3 CO (g) : 2 Fe (s) + 3 CO2 (g) ¢ rH = - 23 .9 kJ mol - 1
6.80 Since the first reaction has CaCO3 as a product and the reaction of interest has it as a product, we simply
write the first reaction and the ¢H unchanged.
Ca (s) + CO2 (g) + 1>2 O2 (g) : CaCO3 (s) ¢H = - 812 .8 kJ mol - 1
Since the second reaction has 2 moles CaO as a product and the reaction of interest has 1 mole of CaO as a
reactant, we need to reverse the direction of the reaction of the second reaction and multiply it by 21 . The sign
of the ¢H in the second reaction is changed and is multiplied by 21 .
1/2[2 CaO (s) : 2 Ca (s) + O2 (g)] ¢H = - 1>2(- 1269 .8 kJ mol - 1) = + 634.9 kJ mol - 1
Ca (s) + CO2 (g) + 1>2 O2 (g) : CaCO3 (s) ¢H = - 812 .8 kJ mol - 1
CaO (s) : Ca (s) + 1>2 O2 (g) ¢H = + 634.9 kJ mol - 1
CaO (s) + CO2 (g) : CaCO3 (s) ¢ rH = - 177.9 kJ mol - 1
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6.81 Since the first reaction has C5H12 as a reactant and the reaction of interest has it as a product, we need to
Chapter
5 CO2 (g) + 66 HThermochemistry
2O (g) : C5H12 (l) + 8 O2 (g) ¢H = + 3505.8 kJ mol - 1 213
Since the second reaction has 1 mole C as a reactant and the reaction of interest has 5 moles of C as a reac-
tant, we need to multiply the second reaction and the ¢H by 5.
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5[C (s) + O2 (g) : CO2 (g)] ¢H = 5(- 393.5 kJ mol - 1) = - 1967.5 kJ mol - 1
Since the third reaction has 2 moles H2 as a reactant and the reaction of interest has 6 moles of H2 as a reac-
tant, we need to multiply the third reaction and the ¢H by 3.
3[2 H2 (g) + O2 (g) : 2 H2O (g)] ¢H = 3(- 483.5 kJ mol - 1) = - 1450.5 kJ mol - 1
5 CO2 (g) + 6 H2O (g) : C5H12 (l) + 8 O2 (g) ¢H = + 3505.8 kJ mol - 1
5 C (s) + 5 O2 (g) : 5 CO2 (g) ¢H = - 1967.5 kJ mol - 1
6 H2 (g) + 3 O2 (g) : 6 H2O (g) ¢H = - 1450.5 kJ mol - 1
5 C (s) + 6 H2 (g) : C5H12 (l) ¢ rH = + 87.8 kJ mol - 1
6.82 Since the first reaction has CH4 as a product and the reaction of interest has it as a reactant, we need to
CH4 (g) : C (s) + 2 H2 (g) ¢H = + 74.6 kJ mol - 1
Since the first reaction has CCl4 as a product and the reaction of interest has it as a product, we simply write
the first reaction and the ¢H unchanged.
C (s) + 2 Cl2 (g) : CCl4 (g) ¢H = - 95.7 kJ mol - 1
Since the third reaction has 2 moles HCl as a product and the reaction of interest has 4 moles of HCl as a
product, we need to multiply the third reaction and the ¢H by 2.
2[H2 (g) + Cl2 (g) : 2 HCl (g)] ¢H = 2(- 92.3 kJ mol - 1) = - 184.6 kJ mol - 1
CH4 (g) : C (s) + 2 H2 (g) ¢H = + 74.6 kJ mol - 1
C (s) + 2 Cl2 (g) : CCl4 (g) ¢H = - 95.7 kJ mol - 1
2 H2 (g) + 2 Cl2 (g) : 4 HCl (g) ¢H = - 184.6 kJ mol - 1
CH4 (g) + 4 Cl2 (g) : CCl4 (g) + 4HCl (g) ¢ rH = - 205.7 kJ mol - 1
1 3
6.83 (a) N (g) + H2 (g) : NH3 (g) ¢ fH° = - 45.9 kJ mol - 1
2 2 2
(b) C (s, graphite) + O2 (g) : CO2 (g) ¢ fH° = - 393.5 kJ mol - 1
3
(c) 2 Fe (s) + O (g) : Fe2O3 (s) ¢ fH° = - 824.2 kJ mol - 1
2 2
(d) C (s, graphite) + 2 H2 (g) : CH4 (g) ¢ fH° = - 74.6 kJ mol - 1
1
6.84 (a) N (g) + O2 (g) : NO2 (g) ¢ fH° = 33.2 kJ mol - 1
2 2
3
(b) Mg (s) + C (s, graphite) + O2 (g) : MgCO3 (s) ¢ fH° = - 1095.8 kJ mol - 1
2
(c) 2 C (s, graphite) + 2 H2 (g) : C2H4 (g) ¢ fH° = 52.4 kJ mol - 1
1
(d) C (s, graphite) + 2 H2 (g) + 2 O2 (g) : CH3OH (l) ¢ fH° = - 238.6 kJ mol - 1
6.85 Given: N2H4 (l) + N2O4 (g) :
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2 N2O (g) + 2 H2O (g) Find: ¢ rH°

Conceptual Plan: ¢ rH° = a np ¢ fH° - a n ¢ H°
Solution: Chapter 6 Thermochemistry 215
Reactant/Product ¢fH°(kJ mol -1 from Appendix IIB)
N2H4 (l) 50.6
N2O4 (g) 11.1
N2O (g) 81.6
H2O (g) - 241.8
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Be sure to pull data for the correct formula and phase.
¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH°(N2O (g))) + 2(¢ fH°(H2O (g)))] - [1(¢ fH°(N2H4 (l))) + 1(¢ fH°(N2O4 (g)))]
= [2(81.6 kJ mol - 1) + 2(- 241.8 kJ mol - 1)] - [1(50.6 kJ mol - 1) + 1(11.1 kJ mol - 1)]
= [- 320.4 kJ mol - 1] - [61.7 kJ mol - 1]
= - 382.1 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is negative, which means that the reaction is exother-
mic. The answer is dominated by the negative heat of formation of water.
6.86 Given: C5H12 (l) + 8 O2 (g) : 5 CO2 (g) + 6 H2O (g) Find: ¢ rH°

Solution:
Reactant/Product ¢ fH°(kJ mol -1 from Appendix IIB)
C5H12 (l) - 146.8
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [5(¢ fH°(CO2 (g))) + 6(¢ fH°(H2O (g)))] - [1(¢ fH°(C5H12 (l))) + 8(¢ fH°(O2 (g)))]
= [5( - 393.5 kJ mol - 1) + 6(- 241.8 kJ mol - 1)] - [1( - 146.8 kJ mol - 1) + 8(0.0 kJ mol - 1)]
= [- 3418.3 kJ mol - 1] - [ - 146.8 kJ mol - 1]
= - 3271.5 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is negative, which means that the reaction is exothermic,
which is typical for combustion reactions.
6.87 (a) Given: C2H4 (g) + H2 (g) : C2H6 (g) Find: ¢ rH°

Solution:
C2H4 (g) 52.4
H2 (g) 0.0
C2H6 (g) - 84.68

¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(C2H6 (g)))] - [1(¢ fH°(C2H4 (g))) + 1(¢ fH°(H2 (g)))]

= [1( - 84.68 kJ mol - 1)] - [1(52.4 kJ mol - 1) + 1(0.0 kJ mol - 1)]
= [- 84.68 kJ mol - 1] - [52.4 kJ mol - 1]
= - 137.1 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is negative, which means that the reaction is
exothermic. Both hydrocarbon terms are negative, so the final answer is negative.
(b) Given: CO (g) + H2O (g) : H2 (g) + CO2 (g) Find: ¢ rH°

Solution:
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CO (g) - 110.5
216 Chapter 6
H2O (g) Thermochemistry - 241.8 Chapter 6 Thermochemistry 215
H2 (g) 0.0
CO2 (g) - 393.5

¢ rH° = a np ¢ fH° - a n ¢ H°
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= [1(¢ fH°(H2 (g))) + 1(¢ fH°(CO2 (g)))] - [1(¢ fH°(CO (g))) + 1(¢ fH°(H2O (g)))]
= [1(0.0 kJ mol - 1) + 1(- 393.5 kJ mol - 1)] - [1( - 110.5 kJ mol - 1) + 1(- 241.8 kJ mol - 1)]
= [- 393.5 kJ mol - 1] - [ - 352.3 kJ mol - 1]
= - 41.2 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is negative, which means that the reaction is exothermic.
(c) Given: 3 NO2 (g) + H2O (l) : 2 HNO3 (aq) + NO (g) Find: ¢ rH°

Solution:
NO2 (g) 33.2
H2O (l) - 285.8
HNO3 (aq) - 207
NO (g) 91.3

¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH (HNO3 (aq))) + 1(¢ fH°(NO (g)))] - [3(¢ fH°(NO2 (g))) + 1(¢ fH°(H2O (l)))]
°
= [2( - 207 kJ mol - 1) + 1(91.3 kJ mol - 1)] - [3(33.2 kJ mol - 1) + 1(- 285.8 kJ mol - 1)]
= [- 322.7 kJ mol - 1] - [ - 186.2 kJ mol - 1]
= - 137 kJ mol - 1
(d) Given: Cr2O3 (s) + 3 CO (g) : 2 Cr (s) + 3 CO2 (g) Find: ¢ rH°

Solution:
Cr2O3 (s) - 1139.7
CO (g) - 110.5
Cr (s) 0.0
CO2 (g) - 393.5

¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH°(Cr (s))) + 3(¢ fH°(CO2 (g)))] - [1(¢ fH°(Cr2O3 (s))) + 3(¢ fH°(CO (g)))]
= [2(0.0 kJ mol - 1) + 3(- 393.5 kJ mol - 1)] - [1( - 1139.7 kJ mol - 1) + 3(- 110.5 kJ mol - 1)]
= [- 1180.5 kJ mol - 1] - [ - 1471.2 kJ mol - 1]
= 290.7 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is positive, which means that the reaction is endothermic.
6.88 (a) Given: 2 H2S (g) + 3 O2 (g) : 2 H2O (l) + 2 SO2 (g) Find: ¢ rH°

Solution:
H2S (g) H2O (l) SO2 (g)
O2 (g)
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- 20.6 - 285.8
0.0 - 296.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH (H2O (l))) + 2(¢ fH (SO2 (g)))] - [2(¢ fH°(H2S (g))) + 3(¢ fH°(O2 (g)))]
° °
= [- 1165.2 kJ mol - 1] - [ - 41.2 kJ mol - 1]
= - 1124.0 kJ mol - 1
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(b) Given: SO2 (g) + 1/2 O2 (g) : SO3 (g) Find: ¢ rH°

Solution:
SO2 (g) - 296.8
O2 (g) 0.0
SO3 (g) - 395.7

¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(SO3 (g)))] - [1(¢ fH°(SO2 (g))) + 1>2(¢ fH°(O2 (g)))]

= [1( - 395.7 kJ mol - 1)] - [1( - 296.8 kJ mol - 1) + 1>2(0.0 kJ mol - 1)]
= [- 395.7 kJ mol - 1] - [ - 296.8 kJ mol - 1]
= - 98.9 kJ mol - 1
mic. The SO3 has a more negative heat of formation than SO2, so we expect an exothermic reaction.
(c) Given: C (s) + H2O (g) : CO (g) + H2 (g) Find: ¢ rH°

Solution:
C (s) 0.0
H2O (g) - 241.8
CO (g) - 110.5
H2 (g) 0.0

¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(CO (g))) + 1(¢ fH°(H2 (g)))] - [1(¢ fH°(C (s))) + 1(¢ fH°(H2O (g)))]
= [1( - 110.5 kJ mol - 1) + 1(0.0 kJ mol - 1)] - [1(0.0 kJ mol - 1) + 1(- 241.8 kJ mol - 1)]
= [- 110.5 kJ mol - 1] - [ - 241.8 kJ mol - 1]
= 131.3 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is positive, which means that the reaction is endother-
mic. The CO has a smaller (less negative) heat of formation than H2O, so we expect an endothermic reaction.
(d) Given: N2O4 (g) + 4 H2 (g) : N2 (g) + 4 H2O (g) Find: ¢ rH°

Solution:
N2O4 (g) 11.1
H2 (g) 0.0
N2 (g) 0.0
H2O (g) - 241.8

¢ rH° = a np ¢ fH° - a n ¢ H°
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= [1(¢ fH°(N2 (g))) + 4(¢ fH°(H2O (g)))] - [1(¢ fH°(N2O4 (g))) + 4(¢ fH°(H2 (g)))]
= [1(0.0 kJ mol - 1) + 4(- 241.8 kJ mol - 1)] - [1(11.1 kJ mol - 1) + 4(0.0 kJ mol - 1)]
218 Chapter [- 967.2 kJ mol - 1] - [11.1 kJ mol - 1]
6 =Thermochemistry Chapter 6 Thermochemistry 217
= - 978.3 kJ mol - 1
mic. The H2O has a more negative heat of formation than N2O4, so we expect an exothermic reaction.
6.89 Given: form glucose (C6H12O6) and oxygen from sunlight, carbon dioxide, and water Find: ¢ rH°
Conceptual Plan: write balanced reaction then ¢ rH° = a np ¢ fH° - a n ¢ H°
Solution: 6 CO2 (g) + 6 H2O (l) : C6H12O6 (s) + 6 O2 (g)
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Reactant/Product ¢ fH°(kJ mol - 1 from Appendix IIB)
CO2 (g) - 393.5
H2O (l) - 285.8
C6H12O (s) - 1273.3
O2 (g) 0.0

¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(C6H12O (s))) + 6(¢ fH°(O2 (g)))] - [6(¢ fH°(CO2 (g))) + 6(¢ fH°(H2O (l)))]
= [1( - 1273.3 kJ mol - 1) + 6(0.0 kJ mol - 1)] - [6( - 393.5 kJ mol - 1) + 6(- 285.8 kJ mol - 1)]
= [- 1273.3 kJ mol - 1] - [ - 4075.6 kJ mol - 1]
= + 2802.5 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is positive, which means that the reaction is endother-
mic. The reaction requires the input of light energy, so we expect that this will be an endothermic reaction.
6.90 Given: ethanol (C2H5OH) combustion Find: ¢ rH°

Solution: Combustion is the combination with oxygen to form carbon dioxide and water. Water is a liquid
at standard state.
C2H5OH (l) + 3 O2 (g) : 2 CO2 (g) + 3 H2O (l)

C2H5OH (l) - 277.6
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 285.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH°(CO2 (g))) + 3(¢ fH°(H2O (l)))] - [1(¢ fH°(C2H5OH (l))) + 3(¢ fH°(O2 (g)))]
= [- 1644.4 kJ mol - 1] - [ - 277.6 kJ mol - 1]
= - 1366.8 kJ mol - 1
mic; this is typical for combustion reactions.
6.91 Given: 2 CH3NO2 (l) + 3/2 O2 (g) : 2 CO2 (g) + 3 H2O (l) + N2 (g) and ¢ rH° = –709.2 kJ mol–1
Find: ¢ fH° (CH3NO2 (l))
Conceptual Plan: fill known values into ¢ rH° = a np ¢ fH° - a n ¢ H° and rearrange to solve
°
for ¢ fH (CH3NO2 (l))
Solution:

O2 (g) 0.0
CO2 (g) - 393.5
H2O (l) - 285.8
N2 (g) 0.0
¢ rH° = a np ¢ fH° - a n ¢ H°
= [2(¢ fH°(CO2 (g))) + 3(¢ fH°(H2O (l))) + 1(¢ fH°(N2 (g)))] - [2(¢ fH°(CH3NO2 (l))) + 3>2(¢ fH°(O2 (g)))]
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2(- 709.2 kJ mol - 1) = [2( - 393.5 kJ mol - 1) + 3(- 285.8 kJ mol - 1) + 1(0.0 kJ mol - 1)]
- [2(¢ fH°(CH3NO2(l)) + 3>2(0.0 kJ mol - 1)]
- 1418.4 kJ mol - 1 = [- 1644.4 kJ mol - 1] Chapter
- [2(¢ fH°(CH3NO2(l))] 6 Thermochemistry 219
° -1
¢ fH (CH3NO2(l)) = - 113 kJ mol
Check: The units (kJ mol–1) are correct. The answer is negative (but not as negative as water and carbon
dioxide), which is consistent with an exothermic combustion reaction.
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6.92 Given: 4 C3H5N3O9 (l) : 12 CO2 (g) + 10 H2O (g) + 6 N2 (g) + O2 (g) and ¢ rH° = –5678 kJ mol–1
Find: ¢ fH° (C3H5N3O9 (l))

Conceptual Plan: fill known values into ¢ rH° = a np ¢ fH° - a n ¢ H° and rearrange to solve
for ¢ fH° (C3H5N3O9 (l))
Solution:

CO2 (g) - 393.5
H2O (g) - 241.8
N2 (g) 0.0
O2 (g) 0.0
¢ rH° = a np ¢ fH° - a n ¢ H°
= [12(¢ fH°(CO2 (g))) + 10(¢ fH°(H2O (g))) + 6(¢ fH°(N2 (g))) + 1(¢ fH°(O2 (g)))]
- [4(¢ fH°(C3H5N3O9(l)))]
[4( - 5678 kJ mol - 1) = [12( - 393.5 kJ mol - 1) + 10(- 241.8 kJ mol - 1) + 6(0.0 kJ mol - 1) + 1(0.0 kJ mol - 1)]
- [4(¢ fH°(C3H5N3O9 (l)))]; - 22712 kJ mol - 1 = [- 7140. kJ mol - 1] - [4(¢ fH°(C3H5N3O9 (l))]
¢ fH°(CH3NO2(l)) = 3893 kJ mol - 1
Check: The units (kJ mol–1) are correct. The answer is positive, which is not surprising since this is a com-
plex molecule with very high potential energy.
Energy Use and the Environment

6.93 (a) Given: methane, ¢ rH° = –802.3 kJ; q = 1.00 x 102 kJ Find: m(CO2)
Conceptual Plan: q : mol CO2 : g CO2
1 mol 44 .01 g
-802.3 kJ 1 mol
1 mol CO2 44.01 g CO2

Solution: - 1 .00 x 102 kJ x x = 5.49 g CO 2
- 802.3 kJ 1 mol CO2
Check: The units (g) are correct. The magnitude of the answer (~5) makes physical sense because less
than a mole of fuel is used.
(b) Given: propane, ¢ rH° = –2217 kJ; q = 1.00 x 102 kJ Find: m(CO2)
3 mol 44 .01 g
-2217 kJ 1 mol
3 mol CO2 44.01 g CO2

Solution: - 1 .00 x 102 kJ x x = 5.96 g CO 2
- 2217 kJ 1 mol CO2
(c) Given: octane, ¢ rH° = –5074.1 kJ; q = 1.00 x 102 kJ Find: m(CO2)
8 mol 44 .01 g
-5074.1 kJ 1 mol
8 mol CO2 44.01 g CO2

Solution: - 1 .00 x 102 kJ x x = 6.94 g CO2
- 5074.1 kJ 1 mol CO2
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The methane generated the least carbon dioxide for the givenChapter 6 Thermochemistry
amount of heat, while the octane gen- 219
erated the most carbon dioxide for the given amount of heat.
6.94 Given: methanol (CH3OH) combustion Find: ¢ rH°, m(CO2)/kJ for methane and octane (using Problem 93)
then q : mol CO2 : g CO2 then for octane m(CO2)/ 1.00 x 102 kJ : m(CO2)/ kJ
1 mol 44 .01 g
, 100
°
¢ rH (kJ) 1 mol
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Solution: Combustion is the combination with oxygen to form carbon dioxide and water:
CH3OH (l) + 3/2 O2 (g) : CO2 (g) + 2 H2O (g)

CH3OH (l) - 238.6
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(CO2 (g)) + 2(¢ fH°(H2O (g))] - [1(¢ fH°(CH3OH (l)) + 3>2(¢ fH°(O2(g))]
= [1( - 393.5 kJ mol - 1) + 2(- 241.8 kJ mol - 1)] - [1( - 238.6 kJ mol - 1) + 3>2(0.0 kJ mol - 1)]
= [- 877.1 kJ mol - 1] - [ - 238.6 kJ mol - 1]
= - 638.5 kJ mol - 1
1 mol CO2 44.01 g CO2
- 1 kJ x x = 0.06893 g CO2 for methanol and
- 638.5 kJ 1 mol CO2
6 .94 g CO2
x - 1 kJ = 0.0694 g CO2 for octane
- 1 .00 x 102 kJ
Methanol contributes less CO2/kJ than octane, contributing less to global warming.
Check: The units (g) are correct. The magnitude of the answer makes physical sense because less than a
mole of fuel is used.
6.95 Given: 7 x 1012 kg/yr octane (C8H18), ¢ rH° = –5074.1 kJ (using Problem 93), 2 x 1017 kg CO2 in the atmosphere
Find: m(CO2) in kg and time to double atmospheric CO2
Conceptual Plan: use reaction from Problem 93 C8H18 (l) + 25/2 O2 (g) : 8 CO2 (g) + 9 H2O (g)
kg (C8H18) : g (C8H18) : mol (C8H18) : mol CO2 : g CO2 : kg CO2 produced
1000 g 1 mol C8H18 8 mol CO2 44 .01 g 1 kg

1 kg 114.22 g 1 mol C8H18 1 mol 1000 g
then kg CO2 : yr
2 x 1017 kg CO2
kg CO2 produced
a b
yr
Solution:
1000 g 44.01 g CO2 1 kg
1 mol C8H18 8 mol CO2
7 x 1012 kg x x x x x = 2 .158 x 1013 kg CO
2
1 kg 114.22 g 1 mol C8H18 1 mol CO2 1000 g
= 2 x 1013 kg CO2 per year

2 x 1017 kg CO2
= 9268 yr = 9000 yr
2.158 x 1013 kg CO2 produced
a b
yr
Check: The units (kg and yr) are correct. The magnitude of the answer (1013 kg) makes physical sense because
the mass of CO2 is larger than the hydrocarbon mass in a combustion (since O is much heavier than H).
6.96 Given: sunlight power density = 1 kW m–2, solar cell efficiency = 15%, home usage = 385 kWh month–1
Find: m2 solar cells needed
Conceptual Plan:
power density available : power density generated : kWh m–2 # 24 hr : kWh m–2 day–1
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15 kW generated 8 hr power generation 24 hr

100 kW available 24 hr 1 day
222 Chapter 6 kWh

then m–2 day–1 : kWh m–2 month–1 generated thenChapter
Thermochemistry 6 Thermochemistry
power needed/month : m2 needed 221
30 days
, kWh m–2 month generated
1 month
Solution:
1 kW available 15 kW generated 8 hr power generation 24 hr 30 day kWh generated

x x x x = 36
1m 2 100 kW available 24 hr 1 day 1 month m2 month
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kWh needed
385
month
= 10 .694 m2 = 1 x 101 m2
kWh generated
a 36 b
m2 month
Check: The units (m2) are correct. The magnitude of the answer (10) makes physical sense because this could
fit on the roof of a house.
Cumulative Problems
6.97 Given: billiard ballA = system: mA = 0.17 kg, vA1 = 4.5 m s–1 slows to vA2 = 3.8 m s–1 and vA3 = 0; ballB: mB =
0.17 kg, vB1 = 0 and vB2 = 3.8 m s–1, and KE = 21 mv2 Find: w, q, ¢Usys
Conceptual Plan: m, v : KE then KEA3, KEA1 : ¢Usys and KEA2, KEA1 : q and KEB2, KEB1 : wB
1 2
KE = mv ¢Usys = KEA3 - KEA1 q = KEA2 - wB = KEB2 - KEB1

2
KEA1
¢Usys , q : wA verify that wA = – wB so that no heat is transferred to ballB
¢U = q + w
1
Solution: KE = mv2 since m is in kg and v is in m s–1, KE will be in kg · m2/s2, which is joule.
2
1 m 2 kg #m2
KEA1 = (0 .17 kg) a 4 .5 b = 1 .7213 = 1.7213 J,
2 s s2
1 m 2 kg #m2
KEA2 = 2 (0 .17 kg) a 3 .8 s b = 1 .2274 = 1.2274 J,
s2
1 m 2 kg #m 2
1 m 2 kg #m 2
KEA3 = (0 .17 kg) a 0 b = 0 = 0 J, KEB1 = (0 .17 kg) a 0 b = 0 = 0 J and
2 s s2 2 s s2
1 m 2 kg #m2
KEB2 = (0 .17 kg) a 3 .8 b = 1 .2274 = 1.2274 J.

2 s s2
¢Usys = KEA3 - KEA1 = 0 J - 1 .7213 J = - 1.7213 J = - 1 .7 J, q

= KEA2 - KEA1 = 1 .2274 J - 1 .7213 J = - 0.4939 J = - 0.5 J, wB
= KEB2 - KEB1 = 1 .2274 J - 0 J = 1 .2274 J and
w = ¢U - q = - 1 .7213 J - - 0 .4939 J = - 1 .2274 J = - 1 .2 J.
Since wA = – wB no heat is transferred to ballB.
Check: The units (J) are correct. Since the ball is initially moving and is stopped at the end, it has lost energy
(negative ¢Usys). As the ball slows due to friction, it is releasing heat (negative q). The kinetic energy is trans-
ferred to a second ball, so it does work (w negative).
6.98 Given: 100-W lightbulb in a piston; bulb on for 0.015 hr, Vi = 0.85 L, Vf = 5.88 L, P = 1.0 bar
Find: w, q, ¢Usys
Conceptual Plan: bulb wattage, time : ¢Usys(Wh) : ¢Usys(Wh) : ¢Usys(J) and Vi, Vf : ¢V then
1 kW 3.60 x 106 J
¢U = (wattage)(time) ¢V = Vf - Vi
1000 W 1 kWh
P, ¢V : w (L bar) : w (J) finally ¢Usys, w : q
100 .0 J
w = -P¢V ¢U = q + w
1 L bar
1 kW 3 .60 x 106 J
Solution: ¢U = (wattage)(time) = (100W)(0 .015 hr) = 1.5 Wh x x = 5400 J and
1000 W 1 kWh
¢V = Vf - Vi = 5 .88 L - 0.85 L = 5.03 L then
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100 .0 J
w = - P¢V = - 1.0 bar x 5.03 L x = - 509.539 J = - 5 .1 x 10 2 J ¢U = q + w
1 L bar
3
222 Chapter 6 solve
Rearrange to for q. q = ¢Usys
Thermochemistry - w = + 5400 J - ( - 509 .539 J) = 5.9 x 10
Chapter 6 JThermochemistry 221
Check: The units (J) are correct. Electricity is added so energy is added (positive ¢Usys). The piston expands
and so does work (negative work). In order for the lightbulb to generate light, it must be heated or it must
absorb energy (positive q).
6.99 Given: H2O (l) : H2O (g) ¢ rH° = +44.01 kJ/mol; ¢Tbody = – 0.50 °C, mbody = 95 kg, Cbody = 4.0 J g–1 °C–1
Find: mH2O
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Conceptual Plan: kg : g then mbody, ¢T, Cbody : : qr (J) : qr (kJ) : mol H2O : g H2O
qbody
1000 g 1 kJ 1 mol 18.01 g

qbody = qr = -qbody
1 kg 1000 J 44.01 kJ 1 mol
mbodyCbody ¢Tbody
1000 g
Solution: 95 kg x
1 kg = 95000 g then
J
qbody = mbodyCbody ¢Tbody = 95000 g x 4.0 x (- 0.50°C) = - 190000 J then
g # °C
1 kJ 1 mol 18 .01 g
qr = - qbody = 190000 J x x x = 78 g H2O
1000 J 44 .01 kJ 1 mol
Check: The units (g) are correct. The magnitude of the answer (78) makes physical sense because a person
can sweat this much on a hot day.
6.100 Given: propane gas combustion, ¢ rH° = –2044 kJ; 1.5 L water, TH2Oi = 25.0 °C, TH2Of = 100.0 °C,
15% efficiency Find: mpropane gas
Conceptual Plan: L : mL : g and Ti, Tf : ¢T then mH2O, ¢TH2O, CH2O : qH2O : qr
1000 mL 1 .0 g
¢T = Tf - qH2O = qr = -qH2O
1L 1 .0 mL
Ti mH2OCH2O ¢TH2O
then qr needed : qr generated (J) : qr (kJ) : mol propane gas : g propane gas
100 J generated 1 kJ 1 mol 44.09 g

15 J needed 1000 J -2044 kJ 1 mol
1000 mL 1 .0 g
Solution: 1 .5 L x x = 1500 g and ¢T = Tf - Ti = 100 .0 °C - 25 .0 °C = 75 .0 °C then
1L 1 .0 mL
J
qH2O = mH2OCH2O ¢TH2O = 1500 g x 4.184 x (75 .0 °C) = 470700 J then
g # °C
100 J generated 1 kJ 1 mol 44 .09 g
qr = - qH2O = - 470700 J needed x x x x = 68 g propane gas

15 J needed 1000 J - 2044 kJ 1 mol
Check: The units (g) are correct. The magnitude of the answer (68) makes physical sense because a tank of
propane gas contains many orders of magnitude more than this amount.
6.101 Given: H2O (s) : H2O (l) ¢ fH° (H2O (s)) = –291.8 kJ/mol; 355 mL beverage TBevi = 25.0 °C, TBevf = 0.0 °C,
CBev = 4.184 J g–1 °C–1, dBev = 1.0 g mL–1 Find: ¢ rH° (ice melting) and mice
Conceptual Plan: ¢ rH° = a np ¢ fH° - a n ¢ H° mL : g and Ti, Tf : ¢T then
1 .0 g
¢T = Tf - Ti
1 .0 mL
mH2O, ¢TH2O, CH2O : qH2O : qr (J) : qr (kJ) : mol ice : g ice
1 kJ 1 mol 18.01 g
qBev = mBevCBev ¢TBev qr = -qBev
1000 J ¢ r H° 1 mol
Solution:

H2O (s) - 291.8
H2O (l) - 285.8
¢ rH° = a np ¢ fH° - a n ¢ H°
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= [1(¢ fH (H2O (l)))] - [1(¢ fH°(H2O (s)))]

°
224 = [1( - 285.8 kJ mol - 1)] - [1( - 291.8 kJ mol - 1)]

Chapter 6 Thermochemistry Chapter 6 Thermochemistry 223
= + 6.0 kJ mol - 1
1 .0 g
355 mL x = 355 g and ¢T = Tf - Ti = 0 .0 °C - 25 .0 °C = - 25 .0 °C then
1 .0 mL
J
qBev = mBevCBev ¢TBev = 355 g x 4 .184 # x (- 25 .0 °C) = - 37133 J then
g °C
1 kJ 1 mol 18 .01 g 2
qr = - qBev = - 37133 J x x x = 1.1 x 10 g ice

1000 J - 6 .0 kJ 1 mol
Check: The units (kJ and g) are correct. The answer is positive, which means that the reaction is endother-
mic. We expect an endothermic reaction because we know that heat must be added to melt ice. The magni-
tude of the answer (110 g) makes physical sense because it is much smaller than the weight of the beverage
and it would fit in a glass with the beverage.
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6.102 Given: CO2 (s) : CO2 (g) ¢ fH° (CO2 (s)) = –427.4 kJ mol–1; 15.0 L water TH Oi = 85 °C, TH Of = 25 °C
2 2
Find: ¢ rH° (dry ice sublimation) and mdry ice
Conceptual Plan: ¢ rH° = a np ¢ fH° - a n ¢ H° L : mL : g and Ti, Tf : ¢T then
1000 mL 1 .00 g
¢T = Tf - Ti
1L 1 .00 mL
mH2O, ¢TH2O, CH2O : qH2O : qr (J) : qr (kJ) : mol ice : g ice
1 kJ 1 mol 44.01 g
qH2O = mH2OCH2O ¢TH2O qr = -
qH2O
1000 J ¢ rH° 1 mol
Solution:

CO2 (s) - 427.4
CO2 (g) - 393.5
¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(CO2 (g)))] - [1(¢ fH°(CO2 (s)))]

= [1( - 393.5 kJ mol - 1)] - [1( - 427.4 kJ mol - 1)]
= + 33.9 kJ mol - 1
1000 mL 1 .00 g
15 .0 L x x = 15000 g and ¢T = Tf - Ti = 25 °C - 85 °C = - 60 . °C then
1L 1 .00 mL
J
qH2O = mH2OCH2O ¢TH2O = 15000 g x 4 .184 x (- 60 . °C) = - 3765600 J then
g # °C
1 kJ 1 mol 44 .01 g 3
qr = - qH2O = 3765600 J x x x = 4.9 x 10 g dry ice

1000 J 33.9 kJ 1 mol
Check: The units (kJ and g) are correct. The answer is positive, which means that the reaction is endother-
mic. We expect an endothermic reaction because we know that heat must be added to sublime dry ice. The
magnitude of the answer (4900 g) makes physical sense because the temperature change of the water is
fairly large, and the volume of water is large. It is a reasonable amount to put in a cooler.
6.103 Given: 25.5 g aluminum, TAli = 65.4 °C, 55.2 g water, TH2Oi = 22.2 °C Find: Tf
J J
Al: 0 .903 H2O: 4.184 q = mCs(Tf - Ti) then set qAl = –qH2O
g # °C g # °C
Solution: q = mCs(Tf - Ti) substitute in values and set qAl = –qH2O.

J
qAl = mAlCAl(Tf - TAli) = 25 .5 g x 0.903 # x (Tf - 65 .4 °C) =
g °C
J
g °C
J J
23.0265 x (Tf - 65 .4 °C) = - 230.957 x (Tf - 22 .2 °C) :
°C °C
J J
23 .0265 Tf - 1505 .93 J = - 230 .957 Tf + 5127 .25 J :
°C °C
J J J
- 5127 .25 J - 1505 .93 J = - 230 .957 Tf - 23 .0265 Tf : 6633 .18 J = 253.9835 Tf :
°C °C °C
6633 .18 J
Tf =
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J = 26 .1° C
253.9835
°C
224 Chapter
Check: The 6 (°C) are correct. The magnitude of the answer (26) Chapter
Thermochemistry
units 6 sense
makes physical Thermochemistry
because the heat 223
should be closer to the initial temperature of water than of aluminum.
6.104 Given: ethanol: 50.0 mL; d = 0.789 g mL–1, TEtOHi = 7.0 °C, water: 50.0 mL; d = 1.00 g mL–1 TH 2Oi = 28.4 °C Find: Tf
Conceptual Plan: pull Cs values from Table 6.4 mL : g then m, Cs, Ti : Tf
J J 0 .789 g 1 .0 g
EtOH: 2 .440 H2O: 4 .184 EtOH: H2O: q = mCs(Tf - Ti) then set qEtOH = –qH2O
g # °C g # °C 1 .0 mL 1 .0 mL
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0 .789 g 1 .00 g
Solution: 50 .0 mL x = 39.45 g EtOH and 50 .0 mL x = 50.0 g H2O then
1 .0 mL 1 .00 mL
q = mCs(Tf - Ti) substitute in values and set qEtOH = –qH2O.

J
qEtOH = mEtOHCEtOH(Tf - TEtOHi) = 39.45 g x 2.440 # x (Tf - 7.0 °C) =
g °C
J
g °C
J J
96.258 x (Tf - 7.0 °C) = - 209.2 x (Tf - 28 .4 °C) :
°C °C
J J
96 .258 Tf - 673 .806 J = - 209 .2 Tf + 5941 .3 J :
°C °C
J J J
- 673 .806 J - 5941 .3 J = - 209 .2 Tf - 96.258 Tf : 6615 .106 J = 305 .458 Tf :

°C °C °C
6615 .106 J
Tf = = 21 .7 °C
J
305.458
°C
should be closer to the initial temperature of water than of ethanol.
6.105 Given: palmitic acid (C16H32O2) combustion ¢ fH° (C16H32O2 (s)) = –208 kJ mol–1; sucrose (C12H22O11) com-
bustion ¢ fH° (C12H22O11 (s)) = –2226.1 kJ mol–1 Find: ¢ rH° in kJ mol–1 and Cal g–1
Conceptual Plan: write balanced reaction then ¢ rH° = a np ¢ fH° - a n ¢ H° then
kJ mol–1 : J mol–1 : Cal mol–1 : Cal g–1
1000 J 1 Cal 1 mol 1 mol

PA: S:
1 kJ 4184 J 256.42 g 342 .30 g
Solution: Combustion is the combination with oxygen to form carbon dioxide and water (l):
C16H32O2 (s) + 23 O2 (g) : 16 CO2 (g) + 16 H2O (l)

C16H32O2 (s) - 208
O2 (g) 0.0
CO2 (g) - 393.5
H2O (l) - 285.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [16(¢ fH°(CO2 (g))) + 16(¢ fH°(H2O (l)))] - [1(¢ fH°(C16H32O2 (s))) + 23(¢ fH°(O2 (g)))]
= [16( - 393.5 kJ mol - 1) + 16(- 285.8 kJ mol - 1)] - [1( - 208 kJ mol - 1) + 23(0.0 kJ mol - 1)]
= [- 10868.8 kJ mol - 1] - [ - 208 kJ mol - 1]
= - 10660.8 kJ mol - 1
kJ 1000 J 1 Cal 1 mol -1
- 10660.8 x x x = - 9.9368 Cal g

mol 1 kJ 4184 J 256.42 g
C12H22O11 (s) + 12 O2 (g) : 12 CO2 (g) + 11 H2O (l)
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C12H22O11 (s) - 2226.1

O2 (g) 0.0
CO (g) - 393.5
226 Chapter 62 Thermochemistry Chapter
- 285.8
6 Thermochemistry 225
H2O (l)
¢ rH° = a np ¢ fH° - a n ¢ H°
= [12(¢ fH°(CO2 (g))) + 11(¢ fH°(H2O (l)))] - [1(¢ fH°(C12H22O11 (s))) + 12(¢ fH°(O2 (g)))]
= [- 7865.8 kJ mol - 1] - [ - 2226.1 kJ mol - 1]
= - 5639.7 kJ mol - 1
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kJ 1000 J 1 Cal 1 mol -1
- 5639.7 x x x = - 3.938 Cal g

mol 1 kJ 4184 J 342.30 g
Check: The units (kJ mol–1 and Cal g–1) are correct. The magnitudes of the answers are consistent with the
food labels we see every day. Palmitic acid gives more Cal g–1 than sucrose.
6.106 Given: hydrogen, methanol (CH3OH), and octane combustion Find: q released in kJ kg–1
then kJ mol–1 : kJ g–1 : kJ kg–1
1 mol 1 mol 1 mol 1000 g

H2: MeOH: O:
2.016 g 32.04 g 114 .22 g 1 kg
1
H2 (g) + O2 (g) : H2O (g). This reaction is the heat of formation of gaseous water, so
2
¢ rH° = - 241.8 kJ mol - 1.

kJ 1 mol 1000 g 5 -1
- 241 .8 x x = - 1.199 x 10 kJ g H2 and
mol 2 .016 g 1 kg
CH3OH (l) + 3/2 O2 (g) : CO2 (g) + 2 H2O (g)

CH3OH (l) - 238.6
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [1(¢ fH°(CO2 (g))) + 2(¢ fH°(H2O (g)))] - [1(¢ fH°(CH3OH (l))) + 3>2(¢ fH°(O2 (g)))]
= [1( - 393.5 kJ mol - 1) + 2(- 241.8 kJ mol - 1)] - [1( - 238.6 kJ mol - 1) + 3>2(0.0 kJ mol - 1)]
= [- 877.1 kJ mol - 1] - [ - 238.6 kJ mol - 1]
= - 638.5 kJ mol - 1
kJ 1 mol 1000 g 4 -1
- 638 .5 x x = - 1.993 x 10 kJ kg CH3OH and
mol 32.04 g 1 kg
kJ 1 mol 1000 g 4 -1
- 5074.1 x x = - 4.4424 x 10 kJ kg C8H18 This result is from Problem 93.

mol 114 .22 g 1 kg
Hydrogen delivers the most energy per weight of fuel. This is not surprising since hydrogen is so light.
Octane delivers more energy per gram than methanol.
Check: The units (kJ kg–1 fuel) are correct. The magnitude of the answers (104 - 105) makes physical sense
because there are many moles of fuel in a kg and the heat of reactions are high.
6.107 At constant P ¢ rH = qP and at constant V ¢ rU = qV = ¢ rH - P¢V. PV = nRT at constant P, and a con-
stant number of moles of gas, as we change the T the only variable that can change is V, so P¢V = nR¢T.
Substituting into the equation for ¢ rU we get ¢ rU = ¢ rH - nR¢T or ¢ rH = ¢ rU + nR¢T.
Find: ¢ rH(SO2 (g))
6.108 Given: SO2 (g) + 1/2 O2 (g)
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: SO3 (g), ¢ rH= +89.5 kJ mol–1, and ¢ fH (SO3 (g)) = – 204.2 kJ mol–1
Conceptual Plan: fill known values into ¢ rH = a np ¢ fHproducts - a nr ¢ fHreactants and rearrange to solve
226 Chapter
for ¢ fH (SO62 (g))
Thermochemistry Chapter 6 Thermochemistry 225
Solution:
Reactant/Product ¢ fH(kJ mol -1)
O2 (g) 0.0
SO3 (g) - 204.2
¢ rH = a np ¢ fHproducts - a nr ¢ fHreactants
= [1(¢ fH (SO3 (g)))] - [1(¢ fH (SO2 (g))) + 1>2(¢ fH (O2 (g)))]

= [1( - 204.2 kJ mol - 1)] - [1(¢ fH (SO2 (g))) + 1>2(0.0 kJ mol - 1)]
+ 89 .5 kJ mol - 1 = [- 204.2 kJ mol - 1] - [¢ fH(SO2 (g)]
¢ fH (SO2(g)) = - 293.7 kJ mol - 1
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Check: The units (kJ mol–1) are correct. The answer is more negative than ¢ fH (SO3 (g)), which makes sense
since the reaction is endothermic.
6.109 Given: 16 g peanut butter, bomb calorimeter, Ti = 22.2 °C, Tf = 25.4 °C, Ccal = 120.0 kJ °C–1
Find: calories in peanut butter
Conceptual Plan: Ti, Tf : ¢T then ¢T, Ccal : qcal : qr (kJ) : qr (kJ) : qr (Cal)
1000 J 1 Cal
¢T = Tf - qcal = -Ccal ¢T qr = -qcal
1 kJ 4184 J
then qr (Cal) Ti
: Cal g–1
, 16 g peanut butter
kJ
Solution: ¢T = Tf - Ti = 25.4 °C - 22 .2 °C = 3.2 °C then qcal = Ccal ¢T = 120.0 x 3 .2 °C = 384 kJ
°C
1000 J 1 Cal 91 .778 Cal
then qr = - qcal = - 384 kJ x x = 91 .778 Cal then = 5 .7 Cal g - 1
1 kJ 4184 J 16 g
Check: The units (Cal g–1) are correct. The magnitude of the answer (6) makes physical sense because there
is a significant percentage of fat and sugar in peanut butter. The answer is in line with the answers in Problem
105.
6.110 Given: 2.0 mol H2 (g) + 1.0 mol O2 (g) at 25 °C Find: temperature of water
then kJ mol–1 : q(kJ) : q(J) then 2.0 mol H2 + 1.0 mol O2 : mol H2O : g H2O then
1000 J 1 mol H2O 18 .01 g

x mol of limiting reagent
1 kJ 1 mol H2 1 mol
qr : qH2O then pull Cs for H2O (l) then q, m, Cs, Ti : Tf

J
qr = -qH2O 4 .184 q = mCs(Tf - Ti)
g # °C
Solution: Combustion is the combination with oxygen to form water; choose liquid water because T = 25 °C.
1
H2 (g) + O2 (g) : H2O (l). This reaction is the heat of formation of gaseous water, so
2
¢ rH° = - 285.8 kJ mol - 1. The two reactants are in the stoichiometric ratio, so either amount can be used.
kJ 1000 J
- 285 .8 x 2 .0 mol H2 x = - 571600 J and qH2O = - qr = 571600 J
1 mol H2 1 kJ
1 mol H2O 18 .01 g
2 .0 mol H2 x x = 36 .02 g H2O then q = mCs(Tf - Ti). Rearrange to solve for Tf.
1 mol H2 1mol H2O
J
(36 .02 g x 4 .184 x 25 °C) + 571600 J
mCsTi + q g # °C
Tf = = = 3818 °C. This is much higher than the
mC
s J
36 .02 g x 4 .184
g # °C
boiling point of water. The heat needed to raise the water to 100 °C is
J
q = mCs(Tf - Ti) = 36 .02 g x 4 .184 # x (100 °C - 25 °C) = 11303 J so 571600 J - 11303 J = 560297 J
g °C
is still available. 2.0 moles H2O utilizes 88,000 J (= 44 kJ mol–1) so 472297 J (=560297 J – 88000 J) is
available to heat steam. Note: Cs (steam) = 2.04 J/g # °C.
mCsTi + q mC (36 .02 g x 2.04 J
= g # °C
Using equation from above Tf =
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x 100. °C) + 472297 J

= 6.5 x 103
228 Chapter 6 Thermochemistry °C Chapter 6 Thermochemistry 227
s J
36 .02 g x 2.04
g # °C
Check: The units (°C) are correct. The temperature is extremely high. A large amount of heat is liberated and
only a relatively small amount of mass absorbs it.
6.111 Given: V1 = 20.0 L at P1 = 3.0 bar; P2 = 1.5 bar let expand at constant T Find: w, q, ¢Usys
Conceptual Plan: V1, P1, P2 : V2 then V1, V2 : ¢V then P, ¢V : w (L bar) : w (J)
100 .0 J
P1V1 = P2V2 ¢V = V2 - V1 w = -P¢V
1 L # bar
for an ideal gas ¢Usys a T, so since this is a constant temperature process ¢Usys = 0 finally ¢Usys, w : q
¢U = q + w
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P1 3 .0 bar
Solution: P1V1 = P2V2. Rearrange to solve for V2. V2 = V1 = (20 .0 L) x = 40 .L and
P2 1 .5 bar
¢V = V2 - V1 = 40. L - 20.0 L = 20. L then
100 .0 J 3
w = - P¢V = - 1.5 bar x 20. L x = - 3000 J = - 3.0 x 10 J ¢U = q + w
1 L # bar
Rearrange to solve for q. q = ¢Usys - w = + 0 J - ( - 3000 J) = 3.0 x 103 J

Check: The units (J) are correct. Since there is no temperature change, we expect no energy change
(¢Usys = 0). The piston expands and so does work (negative work) and so heat is absorbed (positive q).
6.112 Given: 10.00 g P4 (s) + O2 (g) to form P4O10(s); q released heats 2950 g water from Ti = 18.0 °C to Tf = 38.0 °C
Find: ¢ fH° (P4O10 (s))
Conceptual Plan: write balanced reaction then ¢ rH° = a np ¢ fH° - a n ¢ H° then
m, Cs, Ti, Tf : qH2O : qr (J) : q(kJ) then g (P4) : mol (P4) finally
1 kJ 123 .90 g
q = mCs(Tf - Ti) qr = -qH2O
1000 J 1 mol
q(kJ), mol (P4) : ¢ fH° (P4O10 (s))

q
¢ f H°(P4O10 (s)) =
mol P4
Solution: P4 (s) + 5 O2 (g) : P4O10 (s). This reaction is the heat of formation of P4O10 (s), so
J
¢ rH° = ¢ fH°(P4O10 (s)) then q = mCs(Tf - Ti) = 2950 g x 4.184 x (38 .0 °C - 18 .0 °C) = 246856 J
g # °C
1 kJ 1 mol P4
qr = - qH2O = - 246856 J x = - 246.856 kJ then 10 .00 g P4 x = 0.080710 mol P4
1000 J 123.90 g P4
q - 246.856 kJ
then ¢ fH°(P4O10 (s)) = = = - 3.06 x 103 kJ mol - 1
mol P4 0.080710 mol
Check: The units (kJ mol–1) are correct. The negative sign is consistent with the fact that there was heat
released to heat a large amount of water. The magnitude (3000) is not surprising since a small amount of
phosphorous heated a lot of water (a high heat capacity material).
6.113 The oxidation of S (g) to SO3 can be written as follows:

S (g) + 3/2 O2 (g) : SO3 (g) ¢H = - 204 kJ mol - 1
The oxidation of SO2 (g) to SO3 can be written as follows:

SO2 (g) + 1/2 O2 (g) : SO3 (g) ¢H = + 89.5 kJ mol - 1
The enthalpy of formation reaction for SO2 (g) under these conditions can be written as follows:
S (g) + O2 (g) : SO2 (g) ¢H = ??
Since the second reaction has 1 mole SO2 as a reactant and the reaction of interest has 1 mole of SO2 as a
product, we need to reverse the second reaction. When the reaction direction is reversed, ¢H changes sign.
SO3 (g) : SO2 (g) + 1/2 O2 (g) ¢H = - 89.5 kJ mol - 1
S (g) + 3/2 O2 (g) : SO3 (g) ¢H = - 204 kJ mol - 1
SO3 (g) : SO2 (g) + 1/2 O2 (g) ¢H = - 89.5 kJ mol - 1
S (g) + O2 (g) : SO2 (g) ¢H = - 294 kJ mol - 1 = ¢ fH
Note that this is not under standard conditions, since S is not a solid.
6.114 The heat of formation of TiI3 (s) can be written as follows:
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Ti (s) + 3/2 I2 (s) : TiI3 (s) ¢H° = - 328 kJ mol - 1
The reaction of Ti (s) with I (g) can be written as follows:

228 Chapter
2 Ti (s) + 3 6
I2 (g)
2
Thermochemistry
: 2 TiI3 (s) Chapter
¢H° = - 839 kJ mol - 1
6 Thermochemistry 227
The sublimation of I2 (s) can be written as follows:
I2 (s) : I2 (g) ¢H° = ??
Since the first reaction has 3/2 moles I2 (s) as a reactant and the reaction of interest has 1 mole of I2 (s) as a
reactant, we need to multiply it by 2/3.
2/3 Ti (s) + I2 (s) : 2>3 TiI3 ¢H° = (2>3)( - 328 kJ mol - 1) = - 218.667 kJ mol - 1
(s)
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Since the second reaction has 3 moles I2 (g) as a reactant and the reaction of interest has 1 mole of I2 (g) as a
product, we need to reverse the second reaction and divide it by 3. When the reaction direction is reversed,
¢H changes sign.
2>3 TiI3 (s) : 2/3 Ti (s) + I2 (g) ¢H° = (- 1>3)( - 839 kJ mol - 1) = + 279 .667 kJ mol - 1
Hess’s Law states that the ¢H of the net reaction is the sum of the ¢H of the steps.
2/3 Ti (s) + I2 (s) : 2>3 TiI3 (s) ¢H° = (2>3)( - 328 kJ mol - 1) = - 218.667 kJ mol - 1
2>3 TiI3 (s) : 2/3 Ti (s) + I2 (g) ¢H° = (- 1>3)( - 839 kJ mol - 1) = + 279 .667 kJ mol - 1
I2 (s) : I2 (g) ¢H° = + 61 .0 kJ mol - 1 = ¢ rH°
Note that this is endothermic, as expected.
6.115 Given: 25.3% methane (CH4), 38.2% ethane (C2H6), and the rest propane (C3H8) by volume; V = 1.55 L tank,
P = 755 torr, and T = 298 K Find: heat for combustion
Conceptual Plan: percent composition : torr : bar then P, V, T : n then
1 bar
Dalton’s Law of Partial Pressures PV = nRT

750.064 torr
use data in Problem 93 for methane, and calculate heat of combustion for ethane and propane
¢ H° (CH4) = –802.3 kJ; ¢ H° (C3H8) = –2217 kJ write balanced reaction then ¢ rH° = a np ¢ fH° - a n ¢ H°
r r product r f reactants
s
then n, ¢H : q
25 .3 torr CH4 1 bar CH4
Solution: PCH4 = x 755 torr gas x = 0.2546649 bar CH4,
100 torr gas 750.064 torr
38 .2 torr C2H6 1 bar C2H6
PC2H6 = x 755 torr gas x = 0.3845139 bar C2H6,
100 - (25 .3 + 38 .2) torr 1 bar C3H8
C3H8
PC3H8 = x 755 torr gas x = 0.3674020 bar C3H8
PV = nRT Rearrange to solve for n.
PV 0.2546649 bar CH4 x 1.55 L
nCH4 = = = 0.01593215 mol CH4,
RT L #bar
0 .08314 x 298 K
mol # K
PV 0.3845139 bar C2H6 x 1.55 L

nC2H6 = = = 0.02405567 mol C2H6
RT L #bar
0 .08314 x 298 K
mol # K
PV 0.3674020 bar C3H8 x 1.55 L

nC2H6 = = = 0.02298513 mol C3H8
RT L #bar
0 .08314 x 298 K
mol # K
C2H6 (g) + 7/2 O2 (g) : 2 CO2 (g) + 3 H2O (g)

C2H6 (g) - 84.68
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
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= [2(¢ fH°(CO2 (g))) + 3(¢ fH°(H2O (g)))] - [1(¢ fH°(C2H6 (g))) + 7>2(¢ fH°(O2 (g)))]
= [2( - 393.5 kJ mol - 1) + 3(- 241.8 kJ mol - 1)] - [1(Chapter 6- 1Thermochemistry
- 84.68 kJ mol ) + 7>2(0.0 kJ mol - 1)] 229
= [- 1512.4 kJ mol - 1] - [ - 84.68 kJ mol - 1]
= - 1427.7 kJ mol - 1
C3H8 (g) + 5 O2 (g) : 3 CO2 (g) + 4 H2O (g)

C3H8 (g) - 103.85
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
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¢ rH° = a np ¢ fH° - a n ¢ H°
[3(¢ fH (CO2 (g))) + 4(¢ fH (H2O (g)))] - [1(¢ fH°(C3H8 (g))) + 5(¢ fH°(O2 (g)))]
= ° °
[3( - 393.5 kJ mol - 1) + 4(- 241.8 kJ mol - 1)] - [1( - 103.85 kJ mol - 1) + 5(0.0 kJ mol - 1)]
=
[- 2147.7 kJ mol - 1] - [ - 103.85 kJ mol - 1]
=
- 2043.9 kJ mol - 1
=
- 802 .3 kJ
0.01593215 mol CH4 x = - 12.782364 kJ,
1 mol CH4
- 1427.7 kJ
0.02405567 mol C2H6 x = - 34.344280 kJ, and
1 mol C H
2 6
- 2043.9 kJ
0.02298513 mol C3H8 x = - 46.979307 kJ
1 mol C H
3 8
The total heat is –12.782364 – 34.344280 – 46.979307 = –94.105951 = –94.1

Check: The units (kJ) are correct. The magnitude of the answer (–100 kJ) makes sense because heats of com-
bustion are typically large and negative.
6.116 Given: methane (CH4) + propane (C3H8); V = 11.7 L, P = 745 torr, and T = 298 K, 769 kJ released
Find: mole fraction of methane in mixture
Conceptual Plan: let x = mole fraction methane : torr : bar then P, V, T : n then
1 bar
Dalton’s Law of Partial Pressures PV = nRT

750.064 torr
use data in Problem 115 for methane and propane, then q, ¢H : x

¢ rH° (CH4) = –802.3 kJ; ¢ rH° (C3H8) = –2043.9 kJ
Solution: Let x = mole fraction methane, then

1 bar CH4
PCH4 = xCH4PTotal = x x 745 torr gas x = x(0.99324858) bar CH4,
750.064 torr
1 bar C3H8
PC3H8 = xC3H8PTotal = (1 - x) x 745 torr gas x = (0.99324858 - 0.99324858x) bar C3H8
750.064 torr
PV = nRT. Rearrange to solve for n.
PV x(0.99324858) bar CH4 x 11.7 L
nCH4 = = = x(0.46900855) mol CH4 ,
RT L #bar
0 .08314 x 298 K
mol # K
PV (0.99324858 - 0.99324858x) bar C3H8 x 11.7 L

nC2H6 = = = (0.46904826 - 0.46904826x) mol C3H8
RT L #bar
0 .08314 x 298 K
mol # K
The total heat is the sum of the combustion of the two components.
- 802 .3 kJ - 2043.9 kJ
¢H = - 769 kJ = x(0.46904826) mol CH4 x + (0.46904826 - 0.46904826x) mol C3H8 x

1 mol CH 1 mol C H
4 3 8
Solve for x. - 769 kJ = x(- 376.3174) kJ + (- 958.6877 kJ) + x(958.6877 kJ) :
+ 189.6877 kJ
+ 189.6877 kJ = x(+ 582.3703 kJ) : x = = 0.325717 = 0.326 mole fraction methane
+ 582.3703 kJ
Check: The units (none) are correct. The magnitude of the answer (0.3) makes sense because if the mixture
were all methane the amount of heat would have been –376 kJ, and if the mixture were all propane the
amount of heat would have been –1040 kJ. Since the heat released is closer to the all-propane amount, the
mixture must be mostly propane.
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6.117 Given: 1.55 cm copper cube and 1.62 cm aluminum cube, TMetalsi = 55.0 °C, 100.0 mL water, TH2Oi = 22.2 °C
Other: density (water) = 0.998 g mL–1 Find: Tf
Conceptual Plan: pull d values from Table 1.4 then edge length : V : m then
-1 -1 3
Cu: 8 .96 g mL Al: 2 .70 g mL V=l d = m/V
pull Cs values from Table 6.4 then m, Cs, Ti :
Tf
J J J
Cu: 0 .385 Al: 0.903 # H O: 4.184 # q = mCs(Tf - Ti) then set qCu + qAl = –qH2O
g # °C g °C 2 g °C
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Solution: VCu = l3 = (1.55 cm)3 = 3.723875 cm3 = 3.723875 mL and

VAl = l 3 = (1.62 cm)3 = 4.251528 cm3 = 4.251528 mL then d = m/V. Rearange to solve for m. m = dV
g
mCu = 8.96 x 3.723875 mL = 33.36592 g Cu,
mL
g g
mAl = 2.70 x 4.251528 mL = 11.4791256 g Al and mH2O = 0.998 x 100.0 mL = 99.8 g H2O
mL mL
q = mCs(Tf - Ti) substitute in values and set qCu + qAl = –qH2O.
qCu + qAl = mCuCCu(Tf - TCui) + mAlCAl(Tf - TAli) =
J J
33.36592 g x 0.385 # x (Tf - 55 .0 °C) + 11.4791256 g x 0 .903 # x (Tf - 55 .0 °C) =
g °C g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 99.8 g x 4 .184 x (Tf - 22 .2 °C)
g # °C
J J J
12.84588 x (Tf - 55 .0 °C) + 10.36565 x (Tf - 55 .0 °C) = - 417 .563 x (Tf - 22 .2 °C) :
°C °C °C
J J J
12.84588 Tf - 706.5234 J + 10.36565 Tf - 570 .1108 J = - 417 .563 Tf + 9269 .899 J :
°C °C °C
J J J
12.84588 Tf + 10.36565 Tf + 417 .563 Tf = + 706 .5234 J + 570 .1108 J + 9269 .899 J :
°C °C °C
J 10546 .533 J
440.7745 Tf = 10546 .533 J : Tf = = 23.92726 °C = 23.9 °C
°C J
440.7745
°C
should be closer to the initial temperature of water than of copper and aluminum.
6.118 Given: mass (gold + silver) = 14.9 g, TMetalsi = 62.0 °C, 15.0 mL water, TH2Oi = 23.5 °C, Tf = 25.0 °C
Other: density (water) = 0.998 g mL–1 Find: mass of each ring
Conceptual Plan: V : m then pull Cs values from Table 6.4 then
d = m/V
pull Cs values from Table 6.4, then let x = mass of gold ring, and then m, Cs, Ti, Tf : m
J J J
Au: 0 .128 # Ag: 0 .235 # H O: 4 .184 # q = mCs(Tf - Ti) then set qAu + qAg = –qH2O
g °C g °C 2 g °C
g
Solution: d = m/V. Rearange to solve for m. m = dV so mH2O = 0.998 x 15.0 mL = 14.97g H2O
mL
Let x = mass of the gold ring. q = mCs(Tf - Ti) substitute in values and set qAu + qAg = –qH2O.
qAu + qAg = mAuCAu(Tf - TAui) + mAgCAg(Tf - TAgi) =
J J
x x 0 .128 # x (25 .0 °C - 62.0 °C) + (14.9 g - x) x 0 .235 # x (25 .0 °C - 62.0 °C) =
g °C g °C
J
- qH2O = - mH2OCH2O(Tf - TH2Oi) = - 14.97 g x 4 .184 x (25 .0 °C - 23 .5 °C)
g # °C
Rearrange to solve for mass of Au.
J J
x a - 4.736 b - 129.5555 J + x a - 8.695 b = - 93.9517 J :
g g
J J J
x a - 4.736 b + x a - 8.695 b = + 129.5555 J - 93.9517 J : xa - 13.431 b = - 35.6038 J :
g g g
- 35.6038 J
x = = 2.6509 g Au = 2.7 g Au and 14.9 g - 2.7 g = 12.2 g Ag

J
- 13.431
g
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Check: The units (g) are correct. The magnitude of the answer (12 g and 3 g) makes physical sense because
the heat transfer is dominated by the larger specific heat capacity of water. The mass is mostly silver: the
temperature change of the metals is large compared to the temperature change of the water, indicating a low
metal specific heat.
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6.119 Given: mice = 2.0 kg, Ti = –15 °C, Tf = 15 °C, ¢Hfus for ice = 6.01 kJ mol–1, Cice = 2.108 J g–1 °C–1, ¢Hcomb
for methane = –891 kJ mol-1 Find: volume of methane at STP required to convert ice to water at required
temperature.
Conceptual Plan: determine total heat required by summing the heat required to raise temperature of ice
from –15 °C to 0 °C, the heat required to melt the ice, and the heat required to raise the temperature of
water from 0 °C to 15 °C.
1 mol
4.184 J g–1 °C–1 q = mCs ¢T q = n¢Hfus qtotal = q1 + q2 + q3 ....
18.02 g
Relate the heat required to melt the ice and warm the water to the number moles of methane required
to generate that much heat.
qice>water = - qmethane = - n¢Hcomb
then use the ideal gas law to find the volume.
bar L
PV = nRT 0.08314
mol K
Solution: qice = mCs ¢T = (2.0 x 10 -3 g) (2.108 J g–1 °C–1)(0 – (–15)) = 6.324 x 104 J
2.0 x 103 g
qmelt = 6.01 kJ mol–1 x = 6.67037 x 102 kJ = 6.67037 x 105 J
18.02 g mol-1
qwater = mCs ¢T= (2.0 x 103g) (4.184 J g–1 °C–1)(15 – 0) = 1.2552 x 105 J
qtotal = 6.324 x 104 J + 6.67037 x 105 J + 1.2552 x 105 J = 8.55797 x 105 J = 8.55797 x 102 kJ
1 mol
nmethane = x 8.55797 x 102 kJ = 0.96049 mol CH4
891 kJ
bar L
(0.96049 mol) a 0.08314 b (273.15 K)
nRT mol K
V = = = 21.812 L = 22 L
P 1 bar
Check: The volume of one mole of an ideal gas at STP is 22.7 L. Since a little less than one mole of methane
is required, the answer of 22 L is reasonable.
6.120 Given: mmethane + mpropane = 4.00 g, mwater = 125 g, for water: Ti = 0.0 °C, Tf = 100.0 °C, 25% of heat pro-
duced by mixture used to raise temperature of water Find: mass of propane and methane.
Conceptual Plan: determine the amount of heat required to raise the temperature of the water,
100 J
4.184 J g–1 °C–1 q = mCs ¢T
25 J
The heat required to raise the temperature of the water plus lost heat is related to the heat released by
the methane and propane. Use tabulated enthalpy of combustion values for methane and propane to
determine the number of moles of propane and methane required.
- 882 kJ - 2202 kJ
qtotal = – (qmethane + qpropane ) q = n¢Hcomb for methane: ¢Hcomb = for propane: ¢Hcomb =
1 mol 1 mol
Substitute moles with mass and molar mass and define one of the masses in terms of the other.
g
n = mpropane = mtotal - mmethane
g mol-1
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Solution: qwater = mCs ¢T = (125 g)(4.184 J g–1 °C–1)(100.0 °C – 0.0 °C) = 5.23 x 104 J
100 J
qtotal = 5.23 x 104 J x = 2.092 x 104 J = 209.2 kJ
25 J
qtotal = – (qmethane + qpropane ) = 209.2 kJ = – (nmethane x ¢Hcomb + npropane x ¢Hcomb)
- 882 kJ - 2202 kJ
209.2 kJ = – nmethane x – npropane x
1 mol 1 mol
mmethane -882 kJ mpropane -2202 kJ

209.2 kJ = – x – x
16.042 g mol-1 1 mol 44.094 g mol-1 1 mol
mmethane -882 kJ 4.00 - -2202 kJ
mmethane
209.2 kJ = – x – x
16.042 g mol-1 1 mol 44.094 g mol-1 1 mol
209.2 kJ = 54.98068 mmethane + 199.7551 – 49.93877 mmethane

5.04191mmethane = 9.4449 mmethane = 1.8733 = 1.87 g mpropane = 4.00 – 1.8733 = 2.13 g
1.87g 882 kJ 2.13 g 2202 kJ

Check: qmethane + qpropane = -1
x + -1
x = 102.81 + 106.36 = 209.17 kJ.
16.042 g mol 1 mol 44.094 g mol 1 mol
This is equal to the total heat required.
6.121 Given: for dissolution of NH4NO3 ¢ rH = 28.1 kJ mol–1, Cbeer = 1.5 kJ °C–1, 250 g H2O, Ti = 20 °C, Tf = 9 °C,
35% cooling efficiency Find: mass of NH4NO3 required for cooling.
Conceptual Plan: determine the amount of heat lost to cool the beer and water and then factor in the
cooling efficiency to determine the total amount of heat absorbed by the NH4NO3.
1.5 kJ 4.184 J 100 J
qbeer = Cbeer ¢T ° qwater = mCs ¢T °
1 C 1g C 35 J
Use the heat absorbed by the NH4NO3 and the enthalpy of dissolution to determine the moles of
NH4NO3. Convert moles to mass of NH4NO3.
g 80.052 g
q = ¢ rH x n n = -1
g mol 1 mol
Solution:
qbeer = Cbeer ¢T = (1.5 kJ °C–1 )(9 – 20) = –16.5 kJ = –1.65 x 104 J
qwater = mCs ¢T = (250 g)(4.184 J g–1 °C–1)(9 – 20) = –1.1506 x 104 J
100 J 100 J
qtotal = (qbeer + qwater) a b = (–1.65 x 104 J + –1.1506 x 104 J) a b = –8.0017 x 10 4 J = –8.0017 x 101 kJ
35 J 35 J
1 mol
qNH NO = –qtotal = 8.0017 x 101 kJ nNH NO = (8.0017 x 101 kJ) a b = 2.84759 mol
4 3 4 3
28.1 kJ
80.052 g
mNH NO = (2.84759 mol) a b = 227.955 g = 2.3 x 102 g
4 3
1 mol
Check: Given the mass of water and beer to cool, plus considering the 35% “cooling power” efficiency of
the cold pack, a mass of 230 g of ammonium nitrate is reasonable.
Challenge Problems
6.122 Given: 655 kWh yr–1, coal is 3.2 % S, remainder is C, S emitted as SO2 (g) and gets converted to H2SO4 when
reacting with water Find: m (H2SO4) yr–1
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(since the form of sulfur is not given, assume all heat is from combustion of only carbon) then
kWh : J : kJ : mol (C) : g (C) : g (S) : mol (H2SO4) : mol (H2SO4) : g (H2SO4)
6 98 .09 g
3.60 x 10 J 1 kJ mol C 12 .01 g 3 .2 g S 1 mol 1 mol H2 SO4
1 kWh 1000 J ¢ f H°(CO2 (g)) 1 mol (100 .0 - 3 .2) g C 32 .06 1 mol S 1 mol
g
Solution: C (s) + O2 (g) : CO2 (g). This reaction is the heat of formation of CO2 (g), so
¢ rH° = ¢ fH°(CO2 (g)) = - 393 .5 kJ mol - 1 then
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3 .60 x 106 J 1 kJ mol C 12 .01 g C 3 .2 g S 1 mol S
655 kWh x x x x x x x
1 kWh 1000 J 393.5 kJ 1 mol C (100 .0 - 3 .2) g 32 .07 g S
C
1 mol H2SO4 98 .09 g H2SO4

x x = 7.3 x 103 g H2SO4
1 mol S 1 mol H2SO4
Check: The units (g) are correct. The magnitude (7300) is reasonable, considering this is just one home.
6.123 Given: 2.5 x 103 kg SUV, v1 = 0.0 mph, v2 = 65.0 mph, octane combustion, 30% efficiency Find: m (CO2)
Conceptual Plan: mi hr–1 : m hr–1 : m min–1 : m s–1 then m, v : KE then
1000 m 1 hr 1 min 1 2
KE = mv
0 .6214 mi 60 min 60 sec 2
KE1, KE2 : ¢U used : ¢U generated
100 J generated
¢Usys = KE2 - KE1
30 J used
use reaction from Problem 93 C8H18 (l) + 25/2 O2 (g) : 8 CO2 (g) + 9 H2O (g)
with ¢ rH° = –5074.1 kJ
¢U generated (J) : kJ : mol (C8H18) : mol CO2 : g CO2
1 kJ 1 mol C8H18 8 mol CO2 44 .01 g

1000 J 5074.1 kJ 1 mol C8H18 1 mol
1000 m 1 hr 1 min 1
Solution: v1 = 0.0 m s–1, 65 .0 mi hr - 1 x x x = 29 .0563 m s - 1 then KE = mv2
0 .6214 mi 60 min 60 sec 2
1
KE1 = (2 .5 x 103 kg)(0)2 = 0
2
1 3 m 2
6
kg m2 6
KE2 = (2 .5 x 10 kg) a 29 .0563 b = 1.05533 x 10 = 1.05533 x 10 J
2 s s2
100 J generated
¢Usys = KE2 - KE1 = 1 .05533 x 106 J - 0 J = 1 .05533 x 106 J used x =
30 J used
= 3.51777 x 106 J generated
1 kJ 1 mol C8H18 8 mol CO2 44 .01 g CO2

3 .51777 x 106 J generated x x x x = 2.4 x 102 g CO
2
1000 J 5074.1 kJ 1 mol C8H18 1 mol CO2
Check: The units (g) are correct. The magnitude (240) is reasonable, considering the vehicle is so heavy and
we generate 8 moles of CO2 for each mole of octane.
6.124 Given: methane combustion, 100% efficiency, ¢T = 10.0 °C, house = 30.0 m x 30.0 m x 3.0 m, Cs (air) =
30 J K - 1 mol - 1, 1.00 mol air = 22.4 L Find: m (CH4)
Conceptual Plan: l, w, h : V(m3) : V(cm3) : V(L) : mol (air) then m, Cs, ¢T : qair (J)
(100 cm)3 1L 1 mol air

V = lwh q = mCs ¢T
(1 m)3 1000 cm3 22 .7 L
then qair (J) : qr (J) : q(kJ), then write balanced reaction for methane combustion,
1 kJ
qr = -qair
1000 J
then ¢ rH° = a np ¢ fH° - a n ¢ H° , and then q(kJ) : mol (CH4) : g (CH4)

16 .04g
°
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¢ rH 1 mol
Solution: V = l w h = 30 .0 m x 30 .0 m x 3 .0 m = 2700 m3, then
(100 cm)3
1L 1 mol air Chapter 6 Thermochemistry 233
2700 m3 x x x = 1.18943 x 105 mol air, and then
(1 m)3 1000 cm3 22 .7 L
J 1 kJ
q = mCs ¢T = 1.18943 x 105 mol x 30 7
x 10.0 °C = 3.5683 x 10 J x = 3.5683 x 104 J needed
mol # °C 1000 J
CH4 (g) + 2 O2 (g) : CO2 (g) + 2 H2O (g)

CH4 (g) - 74.6
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
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=[1(¢ fH°(CO2 (g))) + 2(¢ fH°(H2O (g)))] - [1(¢ fH°(CH4 (g))) + 2(¢ fH°(O2 (g)))]
=[( - 393.5 kJ mol - 1) + 2(- 241.8 kJ mol - 1)] - [1( - 74.6 kJ mol - 1) + 2(0.0 kJ mol - 1)]
=[- 877.1 kJ mol - 1] - [ - 74.6 kJ mol - 1]
=- 802.5 kJ mol - 1
1 mol CH4 16 .04 g CH4
qr = - qair = - 3.5683 x 104 kJ x x = 713.7 g CH4 = 700 g CH4
- 802 .5 kJ 1 mol CH4
Check: The units (g) are correct. The magnitude (700) is not surprising since the volume of a house is large.
6.125 Given: water: V = 35 L, Ti = 25.0 °C, Tf = 100.0 °C; fuel = C7H16 , 15% efficiency, d = 0.78 g mL–1
Find: V (fuel)
Conceptual Plan: write balanced reaction then ¢ rH° = a np ¢ fH°(products) - a nr ¢ fH°(reactants) then
L : mL : g then Ti, Tf : ¢T then m, Cs, ¢T : qH2O (J) : qH2O (kJ) : qr (kJ)
1000 mL 1 .0 g 1 kJ
¢T = Tf - qH2O = mH2OCH2O ¢TH2O qr = -qH2O
1L 1 .0 mL 1000
Ti
J
then qr generated (J) : qr used (kJ) : mol C7H16 : g C7H16 : mL C7H16
100 J generated 1 mol C7H16 100.21 g 1 .0 mL

15 J needed ¢ rH° 1 mol 0 .78 g
C7H16 (l) + 11 O2 (g) : 7 CO2 (g) + 8 H2O (g)

C7H16 (l) - 224.4
O2 (g) 0.0
CO2 (g) - 393.5
H2O (g) - 241.8
¢ rH° = a np ¢ fH° - a n ¢ H°
= [7(¢ fH°(CO2 (g))) + 8(¢ fH°(H2O (g)))] - [1(¢ fH°(C7H16 (l))) + 11(¢ fH°(O2 (g)))]
= [- 4688.9 kJ mol - 1] - [ - 224.4 kJ mol - 1]
= - 4464.5 kJ mol - 1
1000 mL 1 .00 g
35 L x x = 35000 g then ¢T = Tf - Ti = 100.0 °C - 25 .0 °C = 75 .0 °C then
1L 1 .00 mL
J 7
1 kJ 4
qH2O = mH2OCH2O ¢TH2O = 35000 g x 4.184 x 75.0 °C = 1.09725 x 10 J x = 1.09725 x 10 kJ
g # °C 1000 J
100 kJ generated 1 mol C7H16 100 .21 g C7H16 1 .0 mL C7H16

qr = - qH2O = - 1.09725 x 104 kJ x x x x =
15 kJ used - 4467.3 kJ 1 mol C H 0 .78 g C H
7 16 7 16
= 2100 mL C7H16 = 2.1 L C7H16

Check: The units (mL) are correct. The magnitude (2 L) is a reasonable volume to have to take on a back-
packing trip.
6.126 Given: m (ice) = 9.0 g; coffee: T1 = 90.0 °C, m = 120.0 g, Cs = CH2O, ¢H°fus = 6.0 kJ mol–1 Find: Tf of coffee
Conceptual Plan: qice = –qcoffee so g (ice) : mol (ice) : qfus(kJ) : qfus (J) : qcoffee (J) then
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1 mol 6 .0 kJ 1000 J
qcoffee = -qice
18.01 g 1 mol 1 kJ
q, m, Cs : ¢T then Ti , ¢T : T2 now we have slightly cooled coffee in contact with 0.0 °C water
q = mCS ¢T ¢T = T2 - Ti
so qice = –qcoffee with m, Cs, Ti : Tf

q = mCs(Tf - Ti) then set qice = –qcoffee
1 mol 6 .0 kJ 1000 J
Solution: 9 .0 g x x x = 2 .9983 x 103 J, qcoffee = - qice = - 2 .9983 x 103 J
18.01 g 1 mol 1 kJ
q - 2 .9983 x 103 J
q = mCS ¢T Rearrange to solve for ¢T. ¢T = = = - 5 .9775 °C then
mCS J
120.0 g x 4 .184 #
g °C
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¢T = T2 - Ti. Rearrange to solve for T2. T2 = ¢T + Ti = - 5 .9775 °C + 90 .0 °C = 84.0225 °C

q = mCs(Tf - Ti) substitute in values and set qH2O = –qcoffee.
J
qH2O = mH2OCH2O(Tf - TH2Oi) = 9.0 g x 4.184 # x (Tf - 0 .0 °C) =
g °C
J
- qcoffee = - mcoffeeCcoffee(Tf - Tcoffee2) = - 120 .0 g x 4 .184 # x (Tf - 84 .0225 °C)
g °C
9 .0 g Tf = - 120 .0 g (Tf - 84.0225 °C) : 9 .0 g Tf = - 120 .0 g Tf + 10082 .7 g :
g - 10082 .7 g
- 10082 .7 g = - 129 .0 Tf : Tf =
°C g = 78.2 °C
- 129 .0
°C
Check: The units (°C) are correct. The temperature is closer to the original coffee temperature since the mass
of coffee is so much larger than the ice mass.
6.127 Given: Cshiraz = 3.40 kJ °C–1, for shiraz: Ti = 23.1 °C, Tf = 15.0 °C, for ice: Cice = 2.108 J g–1 °C–1, ¢Hfus =
6.02 kJ mol–1, for ice/water: Ti = –5.0 °C, Tf = 15.0 °C Find: mass of ice required to cool shiraz.
Conceptual Plan: determine the required heat loss for the shiraz to cool down and equate that to the total
heat required to warm the ice, melt the ice, and warm the water to the final temperature.
3.40 kJ 2.108 J 1 mol 4.184 J
qshiraz = Cshiraz ¢T qice = mCice ¢T qmelt = n¢Hfus qwater = mCwater ¢T
1 °C 1 g °C 18.02 g 1 g °C
Substitute into the equation and solve for mass.

qshiraz = –(qice + qmelt + qwater)
Solution: qshiraz = Cshiraz ¢T = (3.40 kJ °C–1)(15.0 °C – 23.1 °C) = – 27.54 kJ = – 2.754 x 104 J
qshiraz = –(qice + qmelt + qwater)
2.108 J 6.02 x 103J 1 mol 4.184 J
–2.754 x 104 = – ( m a b )(0.0 °C – (–5.0 °C)) + m +ma b )(15.0 °C – 0.0 °C))
1 g °C 1 mol 18.02 g 1 g °C
2.754 x 104 = 10.54m + 334.073m + 62.76m 2.754 x 104 = 407.373m m = 67.604 g = 67.6 g
Check: Because water has a higher heat capacity than the wine it should take a mass of ice less than a typ-
ical bottle of wine to cool the wine to the desired temperature. Taking other factors into consideration (heat
required to warm the ice and heat required to melt the ice), a mass of 67.6 g is reasonable.
6.128 Given: liquid water at –10.0 °C, Cs (ice) = 2.11 J g–1 °C–1; ¢H°fus = – 332 J g–1 (@ 0.0 °C)
Find: ¢H, ¢U, q, and w for freezing at –10.0 °C
Conceptual Plan: assume exactly 1 g H2 O for all calculations (report answers as J g –1 ) and constant
P = 1 bar. Construct the following path: According to Hess’s Law ¢ H1 + ¢ H2 + ¢ H3 = ¢H 4
= ¢H°fus @ –10.0 °C
step 2
Liquid @ 0.0 °C : solid @ 0.0 °C
c step 1 T step 3 at constant P, ¢H = q
Liquid @ –10.0 °C : solid @ –10.0 °C For steps 1 and 3 q = mCs ¢T
step 4
Look up the density of liquid and solid water at 0.0 °C. (Assume the density of each phase does not
change significantly at –10.0 °C.)
dL = 0.9998 g mL–1 and dS = 0.917 g mL–1
g : mL : L then VL, VS : ¢V then P, ¢V : w (L bar) : w (J) then q, w : ¢U
1 mL 1 mL 1L 100 .0 J
L: S: 0 .9998 g 0.917 g
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¢V = w = -P¢V ¢U = q
1000 mL
VS - VL 1 L # bar + w
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J
Solution: ¢H1 = q1 = mCS ¢T = 1 g x 4 .184 x (0 .00 °C - ( - 10 .0 °C)) = +41 .84 J,
g # °C
J
¢H2 = q2 = m¢H = 1 g x - 332 = - 332 J,
g
J
¢H3 = q3 = mCS ¢T = 1 g x 2.11 # x (- 10 .00 °C - 0 .0 °C) = - 21.1 J
g °C
so ¢H4 = q4 = ¢H1 + ¢H2 + ¢H3 = + 41 .84 J - 332 J - 21 .1 J = - 311.3 J = - 311 J/g.
1 mL 1L 1 mL 1L
VL = 1 g x x = 0 .00100020004 L and VS = 1 g x x = 0 .0010905 L
0 .9998 g 1000 mL 0.917 g 1000 mL
then ¢V = VS - VL = 0 .0010905 L - 0 .00100020004 L = 9 .02999 x 10 - 5 L

100 .0 J
then, w = - P¢V = - 1 bar x 9 .02999 x 10 - 5 L x = - 0 .009030 J = - 0 .009 J g - 1
1 L # bar
and ¢U = q + w = - 311 .3 J - 0 .009030 J = - 311 J g - 1
Check: The units (J g–1) are correct. We expect freezing to release less energy at –10 °C because we are below
the normal freezing point. The work is negligible since the volume change is so small.
6.129 Given: the relationship between temperature and kinetic energy for an ideal gas Find: molar heat capacity
at constant volume (Cv) and molar heat capacity and constant pressure (Cp)
Conceptual Plan: use the kinetic energy formula and substitute the velocity with the root mean square
velocity of a gas, then find ¢U under the different conditions of constant volume and pressure.
1 2 3RT
KE = mv mrms = ¢U = q + w
2 A M
Solution:
1 2 3RT 1 2 3
KE = mv , for an ideal gas v = urms = and so KEavg = NAmurms = RT then
2 A M 2 2
3 3 3 3
¢Usys = KE2 - KE1 = RT2 - RT1 = R¢T. At constant V ¢Usys = CV ¢T so CV = R.
2 2 2 2
At constant P, ¢Usys = q + w = qP - P¢V = ¢H - P¢V, but since PV = nRT, for one mole of an
ideal gas at constant P P¢V = R¢T, so ¢Usys = q + w = qP - P¢V = ¢H - P¢V = ¢H - R¢T then
3 5 5
R¢T = ¢H - R¢T or ¢H = R¢T = CP ¢T so CP = R.
2 2 2
6.130 Given: fixed amount of an ideal gas; step 1: V1 = 12.0 L to V2 = 24.0 L at constant P = 1.0 bar; step 2: gas
cooled at constant V = 24.0 L to original T; step 3: V1 = 24.0 L to V2 = 12.0 L Find: q for entire process
Solution: For the expansion: w1 = –(24.0 L – 12.0 L)(1.0 bar) = –12.0 L bar; for the constant V step: w2 = 0
since there is no PV work at constant volume; for the contraction: w3 = –nRT ln (V2/V1) = –PV ln (V2/V1)
= –(1.0 bar)(12.0 L) ln (12.0 L/24.0 L) = 8.3 L · bar, then wtotal = w1 + w2 + w3 = –12.0 L bar + 0 + 8.3 L bar
101 J
wtotal = - 3 .7 L # bar x # = –3.7 x 102 J. Since the system ends where it started ¢U = 0 and, therefore,
L bar
q = –w = 3.7 x 102 J.
Check: The units (J) are correct. The total energy change over the entire cycle is 0 since we end where we
started, but this does not mean that q has to be 0.
6.131 Given: ¢Hvap = 40.7 kJ mol–1 at T = 373 K, 454 g H2O Find: q, w, ¢U, ¢H for evaporation of water
Conceptual Plan: convert mass of water to moles and use the enthalpy of vaporization to find q,
g 1 mol
mol = -1 q = n¢Hvap
g mol 18.02 g
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Then find the difference in volume between the liquid and gaseous water using density and the ideal
gas law (assume P = 1 bar), then
238 Chapter 6mThermochemistry
0.9998 g bar L Chapter 6 Thermochemistry 237
d = dH2O = PV = nRT 0.08314 ¢V = VG - VL
V mL mol K
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determine the work and ¢U
100 J
w = - P¢V ¢U = q + w
1L bar
Solution:
1 mol 40 .7 kJ
q = ¢H = 454 g x x = 1025.405 kJ = 1030 kJ and w = - P¢V. Assume that P = 1 bar
18.02 g 1 mol
1 mL 1L
(exactly) and ¢V = VG - VL, where VL = 454 g x x = 0 .4540908 L and PV = nRT.
0.9998 g 1000 mL
1 mol L #bar
454 g x x 0 .08314 x 373 K
nRT 18 .02 g mol #K

Rearrange to solve for VG. VG = = = 781.3038 L
P 1 bar
¢V = VG - VL = 781.3038 L - 0 .4540908 L = 780 .8497 L and so

100 .0 J
w = - P¢V = - 1.0 bar x 780 .8497 L x = - 78084.97 J = - 7.81 x 104 J = - 78.1 kJ.
1 L # bar
Finally ¢U = q + w = 1025.405 kJ - 78.08497 kJ = 947.320 kJ = 9.5 x 102 kJ.
6.132 Given: Ti = 80 °C, Tf = 110 °C, H2O (l) Cm = 75.3 kJ mol–1 K–1, H2O (g) Cm = 25.0 kJ mol–1 K–1,
¢Hvap = 40.7 x 103 J mol–1 at 100 °C Find: q, w, ¢U, ¢H for change of state of 1.0 mol H2O
Conceptual Plan: determine total q by adding up heat required to raise the temperature of water from
80 °C to 100 °C, convert H2O (l) to H2O (g), and raising temperature of gaseous water from 100 °C to 110 °C
q = nCm ¢T q = n¢Hvap qtotal = q1 + q2 + q3 ...
then find the difference in volume between the liquid and gaseous water using density and the ideal gas
law (assume P = 1 bar), then
m 0.9998 g bar L
d = dH2O = PV = nRT 0.08314 ¢V = VG - VL
V mL mol K
determine the work and ¢U

100 J
w = - P¢V ¢U = q + w
1 L bar
Solution:
q = q1 + q2 + q3 = ¢H, where
J
q1 = nC¢T = 1 .0 mol x 75.3 x (100 °C - 80 °C)) = + 1506 J,
mol # °C
J
q2 = n¢H = 1 .0 mol x 40.7 x 103 = 4.07 x 104 J and
mol
J
q3 = nC¢T = 1 .0 mol x 25.0 x (110 °C - 100 °C)) = +250 J, so
mol # °C
q = q1 + q2 + q3 = ¢H = +1506 J + 4.07 x 104 J + 250 J = 42456 J = 42500 J = 42 .5 kJ
and w = - P¢V. Assume that P = 1 bar (exactly) and ¢V = VG - VL where
18 .02 g 1 mL 1L
VL = 1.0 mol x x x = 0.01802 L and PV = nRT. Rearrange to solve for VG.
1 mol 0.9998 g 1000 mL
L # bar
1.0 mol x 0 .08314 x (110 + 273) K
nRT mol # K
VG = = = 31.84262 L and so
P 1 bar
¢V = VG - VL = 31.84262 L - 0 .01802 L = 31 .82818 L and

100.0 J
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w = - P¢V = - 1 .0 bar x 31 .82818 L x = - 3182 .818 J = - 3200 J = - 3 .2 kJ.

1 L # bar
Finally ¢U = q + w = 5826 J - 3182 .818 J = 2643.182 J = 2600 J = 2.6 kJ.
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239
6.133 Given: equation for combustion of octane (see problem 93.c), ¢ rH = –1303 kJ mol–1 at 298 K Find: ¢ rU
Conceptual Plan: assume the volume of the liquid is negligible compared to the volume of the gases and
determine the volume change for the reaction
bar L
¢V = VG - VL = ¢VG PV = nRT 0.08314
mol K
then (assuming P = 1 bar) find work and use the work and the given heat for 1 mole of octane to determine
¢U
100 J
¢w = - P¢V ¢U = q + w
1 L bar
Solution:
C8H18 (l) + 25/2 O2 (g) : 8 CO2 (g) + 9 H2O (l); q = ¢H = - 1303 kJ mol - 1, and w = - P¢V. Assume that
P = 1 bar (exactly) and ¢V = ¢VG since the gas volumes are so much larger than the liquid volumes. The
25
change in the number of moles of gas ¢nG = 8 mol - mol = - 4.5 mol and P¢V = ¢nRT. Rearrange to
2
L #bar
-4.5 mol x 0 .08314 x 298 K
¢nRT mol #K
solve for ¢VG. ¢VG = = = - 111.4907 L and so
P 1 bar
100.0 J
w = - P¢V = - 1.0 bar x (- 111.4907 L) x = + 11149.07 J = + 11000 J = + 11 kJ.
1 L # bar
Finally ¢U = q + w = - 1303 kJ + 11 .14907 kJ = - 1291.8509 kJ = - 1292 kJ.
6.134 Given: CCal = 34.65 kJ K–1, methanol = 1.765 g, Ti = 294.33 K, Tf = 295.84 K Find: ¢ rH for combustion of
ethanol
Conceptual Plan: write the balanced equation for the combustion of ethanol and then determine the heat
from the calorimeter and relate it to the heat of reaction.
C2H6O (l) + 3 O2 (g) : 2 CO2 (g) + 3 H2O (l) qCal = C¢T qCal = - qr
Relate the heat of reaction to the change in internal energy and then calculate the number of moles of
ethanol to find the change in internal energy on a per mole basis.
1 mol g
¢U = q + w mol =
46.07 g g mol-1
Determine ¢H by relating it to ¢U and the change in the number of moles of gas.

bar L
¢H = ¢U + P¢V = ¢U + ¢nRT 0.08314
mol K
Solution: C2H6O (l) + 3 O2 (g) : 2 CO2 (g) + 3 H2O (l);
kJ
qCal = C¢T = 34.65 x (295 .84 K - 294.33 K) = 52.3215 kJ = - qr = - ¢ rU and
K
1 mol
n = 1.765 g x = 0 .038312929 mol.
46 .07 g
There is no work, since w = - P¢V and there is no volume change in a bomb calorimeter. On a per mole
-52.3215 kJ
basis, qr = ¢ rU = = - 1365 .6356 kJ mol- 1 = - 1370 kJ mol - 1 . Since this is not a
0 .038312929 mol
constant pressure problem, ¢ rU Z ¢ rH . In fact, ¢ rH = ¢ rU + ¢nRT . In this case the change in the
number of moles of gas ¢nG = 2 mol - 3 mol = - 1 mol and so

L # bar 100 .0 J 1 kJ
¢ rH = ¢ rU + ¢nRT = - 1365 .6356 kJ mol - 1 + a - 1 mol x 0 .08314 # x 295 K x # x b
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mol K 1 L bar 1000 J

= - 1363.1830 kJ mol - 1 = - 1360 kJ mol - 1
Check: This answer is in the same ballpark as the answer in Problem 90, which had gaseous water239
as a
product.
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241
Conceptual Problems
6.135 (d) Only one answer is possible. ¢Usys = – ¢Usurr.
6.136 (a) False. An isothermal process has ¢Usys = 0.
(b) False. w 0 for expansions.
(c) True. If ¢Usys = 0 and ¢Usys = q + w and w < 0, then q > 0.
(d) False. An isothermal process has ¢Usys = 0.

6.137 (a) At constant P, ¢Usys = q + w = qP + w = ¢H + w so ¢Usys - w = ¢H = q.
6.138 Refrigerator A contains only air, which will cool quickly, but will not stabilize the temperature. Refrigerator
B contains containers of water, which require a great deal of energy to cool on day 1, but which will remain
stable at a cold temperature on day 2.
6.139 The aluminum cylinder will be cooler after 1 hour because it has a lower heat capacity than water (less heat
needs to be pulled out for every °C temperature change).
6.140 Given: mA = 2mB, CB = 4 CA Find: which substance has larger temperature change?
Conceptual Plan: relate the heat lost by one substance to the heat gained by the other substance and then
substitute and solve to establish the relationship between ¢TA and ¢TB
qA = mACA ¢TA = - qB = mB CB ¢TB
Solution:
Since q = mCS ¢T, mA = 2 mB, CB = 4 CA, qA = - qB we can substitute into the equation to get
qA = mACA ¢TA = - qB = - mBCB ¢TB : (2 mB)CA ¢TA = - mB(4 CA)¢TB
-mB(4 CA) -4
: ¢TA = ¢TB = ¢TB = - 2¢TB or the temperature change for substance A is twice the
(2 m )C 2
B A
magnitude of the temperature change for substance B.
6.141 Given: 2418 J heat produced; 5 J work done on surroundings at constant P Find: ¢U, ¢H, q, and w
¢U = q + w
–1
Solution: Since heat is released from the system to the surroundings, q = – 2418 J mol .
Since the system is doing work on the surroundings, w = –5 J. At constant P, ¢H = q = –2.418 kJ mol–1;
¢U = q + w = - 2418 J mol - 1 - 5 J mol - 1 = - 2423 J mol - 1.
Check: The units (kJ) are correct. The magnitude of the answer makes physical sense because both terms are
negative and the amount of work done is negligibly small.
6.142 The internal energy of a chemical system is the sum of its kinetic energy and its potential energy. It is this
potential energy that is the energy source in an exothermic chemical reaction. Under normal circumstances,
chemical potential energy (or simply chemical energy) arises primarily from the electrostatic forces between
the protons and electrons that compose the atoms and molecules within the system. In an exothermic reac-
tion, some bonds break and new ones form, and the protons and electrons go from an arrangement of higher
potential energy to one of lower potential energy. As they rearrange, their potential energy is converted into
kinetic energy. Heat is emitted in the reaction and so it feels hot to the touch.
6.143 (b) If ¢ V is positive and the reaction is endothermic, then w = - P ¢V 6 0. Since
¢Usys = q + w = qP + w = ¢H + w if w is negative then ¢H 7 ¢Usys. If ¢V is positive and the

reaction is exothermic, then ¢H < ¢U.
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Chemistry A Molecular Approach Canadian 2nd Edition Tro Solutions Manual 1

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qxd 1/30/16 12:01 PM Page 199

1. Solution Manual for Chemistry A Molecular Approach Canadian 2nd

200 Chapter 6 Thermochemistry

202 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 201

(b) If a reaction is reversed, the sign of ¢H is reversed.

202 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 201

(b) Given: 215 kJ Find: Cal

(c) Given: 567 Cal Find: J

(d) Given: 2.85 x 103 J Find: cal

6.34 (a) Given: 231 cal Find: kJ

(b) Given: 132 x 104 kJ Find: kcal

1 kJ 4.184 J 1000 cal

1000 J 1 cal 1 kcal

(c) Given: 4.99 x 103 kJ Find: kWh

204 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 203

(d) Given: 2.88 x 104 J Find: Cal

6.35 (a) Given: 2387 Cal Find: J

6.36 (a) Given: 745 kWh Find: J

kWh is much larger than a Joule, so the answer increases.

3.60 x 106 J 1 Cal

204 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 203

Internal Energy, Heat, and Work

204 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 203

206 Chapter 6 Thermochemistry

¢U = q + w = 155 J - 77000 J = - 77000 J = - 77 kJ.

Heat, Heat Capacity, and Work

6.48 Given: 1.50 kg sand, Ti = 25.0 °C, Tf = 100.0 °C Find: q

6.49 (a) Given: 25 g gold, Ti = 27.0 °C, q = 2.35 kJ Find: Tf

¢T = = = 734 .375 °C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

206 Chapter 6 Thermochemistry

(c) Given: 25 g aluminum, Ti = 27.0 °C, q = 2.35 kJ Find: Tf

¢T = = = 104 .10°C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

¢T = = = 22 .488°C finally ¢T = Tf - Ti. Rearrange to solve for Tf.

Solution: ¢T = Tf - Ti = 55.4 °C - 23 .0 °C = 32.4 °C and q = mCs ¢T. Rearrange to solve for m.

(b) Given: sand, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 62.1 °C Find: m

Solution: ¢T = Tf - Ti = 62.1 °C - 23 .0 °C = 39.1 °C then q = mCs ¢T. Rearrange to solve for m.

208 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 207

(c) Given: ethanol, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 44.2 °C Find: m

Solution: ¢T = Tf - Ti = 44.2 °C - 23 .0 °C = 21.2 °C then q = mCs ¢T. Rearrange to solve for m.

(d) Given: water, q = 1.95 x 103 J, Ti = 23.0 °C, Tf = 32.4 °C Find: m

Solution: ¢T = Tf - Ti = 32.4 °C - 23 .0 °C = 9.4 °C then q = mCs ¢T. Rearrange to solve for m.

6.51 Given: Vi = 0.0 L, Vf = 2.5 L, P = 1.1 bar Find: w (J)

6.52 Given: ¢V = 0.50 L, P = 1.0 bar Find: w (J)

then P, ¢V : w (L bar) : w (J) finally q, w : ¢Usys

Solution: ¢V = Vf - Vi = 0.85 L - 0 .10 L = 0.75 L then

208 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 207

then P, ¢V : w (L bar) : w (J) finally q, w : ¢Usys

Solution: ¢V = Vf - Vi = 1.22 L - 5.55 L = - 4.33 L then

w = - ¢nRT = - ( 12 )(8.314 J K - 1 mol - 1)(298.15 K) = - 1239 J mol - 1 = - 1.239 kJ mol - 1

Enthalpy and Thermochemical Stoichiometry

210 Chapter 6 Thermochemistry Chapter 6 Thermochemistry 209

6.59 (a) Combustion is an exothermic process; ¢H is negative.

(b) Evaporation requires an input of energy, so it is endothermic; ¢H is positive.

(c) Condensation is the reverse of evaporation, so it is exothermic; ¢H is negative.

6.60 (a) Sublimation requires an input of energy, so it is endothermic; ¢H is positive.

(b) Combustion is an exothermic process; ¢H is negative.

(c) Since the temperature drops, this is an endothermic process; ¢H is positive.