184

CHAPTER 6

THERMOCHEMI STRY

Questions

11. Path-dependent functions for a trip from Chicago to Denver are those quantities that depend
on the route taken. One can fly directly from Chicago to Denver, or one could fly from
Chicago to Atlanta to Los Angeles and then to Denver. Some path-dependent quantities are
miles traveled, fuel consumption of the airplane, time traveling, airplane snacks eaten, etc.
State functions are path-independent; they only depend on the initial and final states. Some
state functions for an airplane trip from Chicago to Denver would be longitude change,
latitude change, elevation change, and overall time zone change.

12. Products have a lower potential energy than reactants when the bonds in the products are
stronger (on average) than in the reactants. This occurs generally in exothermic processes.
Products have a higher potential energy than reactants when the reactants have the stronger
bonds (on average). This is typified by endothermic reactions.

13. 2 C
8
H
18
(l) + 25 O
2
(g) 16 CO
2
(g) + 18 H
2
O(g); the combustion of gasoline is exothermic
(as is typical of combustion reactions). For exothermic reactions, heat is released into the
surroundings giving a negative q value. To determine the sign of w, concentrate on the moles
of gaseous reactants versus the moles of gaseous products. In this combustion reaction, we go
from 25 moles of reactant gas molecules to 16 + 18 = 34 moles of product gas molecules. As
reactants are converted to products, an expansion will occur because the moles of gas
increase. When a gas expands, the system does work on the surroundings, and w is a negative
value.

14. AH = AE + PAV at constant P; from the definition of enthalpy, the difference between AH
and AE, at constant P, is the quantity PAV. Thus, when a system at constant P can do
pressure-volume work, then AH AE. When the system cannot do PV work, then AH = AE at
constant pressure. An important way to differentiate AH from AE is to concentrate on q, the
heat flow; the heat flow by a system at constant pressure equals AH, and the heat flow by a
system at constant volume equals AE.

15. a. The AH value for a reaction is specific to the coefficients in the balanced equation. Be-
cause the coefficient in front of H
2
O is a 2, 891 kJ of heat is released when 2 mol of H
2
O
is produced. For 1 mol of H
2
O formed, 891/2 = 446 kJ of heat is released.

b. 891/2 = 446 kJ of heat released for each mol of O
2
reacted.

16. Use the coefficients in the balanced rection to determine the heat required for the various
quantities.
a. 1 mol Hg
Hg mol
kJ 7 . 90
= 90.7 kJ required
CHAPTER 6 THERMOCHEMISTRY 185

b. 1 mol O
2

2
O mol 2 / 1
kJ 7 . 90
= 181.4 kJ required
c. When an equation is reversed, AH
new
= AH
old
. When an equation is multiplied by some
integer n, then AH
new
= n(AH
old
).
Hg(l) + 1/2 O
2
(g) HgO(s) AH = 90.7 kJ
2Hg(l) + O
2
(g) 2HgO(s) AH = 2(90.7 kJ) = 181.4 kJ; 181.4 kJ released

17. Given:
CH
4
(g) + 2 O
2
(g) CO
2
(g) + 2 H
2
O(l) AH = 891 kJ
CH
4
(g) + 2 O
2
(g) CO
2
(g) + 2 H
2
O(g) AH = 803 kJ

Using Hesss law:

H
2
O(l) + 1/2 CO
2
(g) 1/2 CH
4
(g) + O
2
(g) AH
1
= 1/2(891 kJ)
1/2 CH
4
(g) + O
2
(g) 1/2 CO
2
(g) + H
2
O(g) AH
2
= 1/2(803 kJ)
H
2
O(l) H
2
O(g) AH = AH
1
+ AH
2
= 44 kJ

The enthalpy of vaporization of water is 44 kJ/mol.

Note: When an equation is reversed, the sign on H is reversed. When the coefficients in a
balanced equation are multiplied by an integer, then the value of H is multiplied by the
same integer.

18. A state function is a function whose change depends only on the initial and final states and
not on how one got from the initial to the final state. An extensive property depends on the
amount of substance. Enthalpy changes for a reaction are path-independent, but they do
depend on the quantity of reactants consumed in the reaction. Therefore, enthalpy changes
are a state function and an extensive property.

19. The zero point for
o
f
H values are elements in their standard state. All substances are meas-
ured in relationship to this zero point.

20. a. CH
4
(g) + 2 O
2
(g) CO
2
(g) + 2 H
2
O(l) AH = ?

Utilizing Hesss law:

Reactants Standard State Elements AH = AH
a
+ AH
b
= 75 + 0 = 75 kJ
Standard State Elements Products AH = AH
c
+ AH
d
= 394 572 = 966 kJ

Reactants Products AH = 75 966 = 891 kJ

b. The standard enthalpy of formation for an element in its standard state is given a value of
zero. To assign standard enthalpy of formation values for all other substances, there
needs to be a reference point from which all enthalpy changes are determined. This
reference point is the elements in their standard state which is defined as the zero point.
186 CHAPTER 6 THERMOCHEMISTRY

So when using standard enthalpy values, a reaction is broken up into two steps. The first
step is to calculate the enthalpy change necessary to convert the reactants to the elements
in their standard state. The second step is to determine the enthalpy change that occurs
when the elements in their standard state go to form the products. When these two steps
are added together, the reference point (the elements in their standard state) cancels out
and we are left with the enthalpy change for the reaction.
c. This overall reaction is just the reverse of all the steps in the part a answer. So AH =
+966 75 = 891 kJ. Products are first converted to the elements in their standard state
which requires 966 kJ of heat. Next, the elements in the standard states go to form the
original reactants [CH
4
(g) + 2 O
2
(g)] which has an enthalpy change of 75 kJ. All of the
signs are reversed because the entire process is reversed.

21. No matter how insulated your thermos bottle, some heat will always escape into the
surroundings. If the temperature of the thermos bottle (the surroundings) is high, less heat
initially will escape from the coffee (the system); this results in your coffee staying hotter for
a longer period of time.

22. From the photosynthesis reaction, CO
2
(g) is used by plants to convert water into glucose and
oxygen. If the plant population is significantly reduced, not as much CO
2
will be consumed
in the photosynthesis reaction. As the CO
2
levels of the atmosphere increase, the greenhouse
effect due to excess CO
2
in the atmosphere will become worse.

23. Fossil fuels contain carbon; the incomplete combustion of fossil fuels produces CO(g) instead
of CO
2
(g). This occurs when the amount of oxygen reacting is not sufficient to convert all the
carbon to CO
2
. Carbon monoxide is a poisonous gas to humans.

24. Advantages: H
2
burns cleanly (less pollution) and gives a lot of energy per gram of fuel.
Water as a source of hydrogen is abundant and cheap.

Disadvantages: Expensive and gas storage and safety issues


Exercises

Potential and Kinetic Energy

25. KE =
2
1
mv
2
; convert mass and velocity to SI units. 1 J =
2
2
s
m kg 1

Mass = 5.25 oz
lb 205 . 2
kg 1
oz 16
lb 1
= 0.149 kg

Velocity =
s
m 45
yd 094 . 1
m 1
mi
yd 1760
s 60
min 1
min 60
h 1
h
mi 10 0 . 1
2
=

KE =
2
1
mv
2
=
2
1
0.149 kg
2
s
m 45
|
.
|

\
|
= 150 J
CHAPTER 6 THERMOCHEMISTRY 187

26. KE =
2
1
mv
2
=
2
1
2.0 kg
2
s
m 0 . 1
|
.
|

\
|
= 1.0 J; KE =
2
1
mv
2
=
2
1
1.0 kg
2
s
m 0 . 2
|
.
|

\
|

= 2.0 J
The 1.0-kg object with a velocity of 2.0 m/s has the greater kinetic energy.

27. a. Potential energy is energy due to position. Initially, ball A has a higher potential energy
than ball B because the position of ball A is higher than the position of ball B. In the
final position, ball B has the higher position so ball B has the higher potential energy.

b. As ball A rolled down the hill, some of the potential energy lost by A has been converted
to random motion of the components of the hill (frictional heating). The remainder of the
lost potential energy was added to B to initially increase its kinetic energy and then to
increase its potential energy.

28. Ball A: PE = mgz = 2.00 kg
2
s
m 81 . 9
10.0 m =
2
2
s
m kg 196
= 196 J
At point I: All this energy is transferred to ball B. All of B's energy is kinetic energy at this
point. E
total
= KE = 196 J. At point II, the sum of the total energy will equal
196 J.

At point II: PE = mgz = 4.00 kg 3.00 m = 118 J
KE = E
total
PE = 196 J 118 J = 78 J

Heat and Work

29. E = q + w = 45 kJ + (29 kJ) = 16 kJ

30. E = q + w = 125 + 104 = 21 kJ

31. a. E = q + w = 47 kJ + 88 kJ = 41 kJ

b. E = 82 47 = 35 kJ c. E = 47 + 0 = 47 kJ

d. When the surroundings do work on the system, w > 0. This is the case for a.

32. Step 1: E
1
= q + w = 72 J + 35 J = 107 J; step 2: E
2
= 35 J 72 J = 37 J

E
overall
= E
1
+ E
2
= 107 J 37 J = 70. J

33. E = q + w; work is done by the system on the surroundings in a gas expansion; w is
negative.

300. J = q 75 J, q = 375 J of heat transferred to the system

2
s
m 81 . 9
188 CHAPTER 6 THERMOCHEMISTRY

34. a. E = q + w = 23 J + 100. J = 77 J
b. w = PV = 1.90 atm(2.80 L 8.30 L) = 10.5 L atm
atm L
J 3 . 101
= 1060 J
E = q + w = 350. J + 1060 = 1410 J
c. w = PV = 1.00 atm(29.1 L11.2 L) = 17.9 L atm
atm L
J 3 . 101
= 1810 J
E = q + w = 1037 J 1810 J = 770 J

35. w = PV; we need the final volume of the gas. Because T and n are constant, P
1
V
1
= P
2
V
2
.


atm 00 . 2
) atm 0 . 15 ( L 0 . 10
P
P V
V
2
1 1
2
= = = 75.0 L
w = PV = 2.00 atm(75.0 L 10.0 L) = 130. L atm
J 1000
kJ 1
atm L
J 3 . 101

= 13.2 kJ = work
36. w = 210. J = PV, 210 J = P(25 L 10. L), P = 14 atm

37. In this problem, q = w = 950. J.

950. J
J 3 . 101
atm L 1
= 9.38 L atm of work done by the gases
w = PV, 9.38 L atm =
760
. 650
atm (V
f
0.040 L), V
f
0.040 = 11.0 L, V
f
= 11.0 L
38. E = q + w, 102.5 J = 52.5 J + w, w = 155.0 J
J 3 . 101
atm L 1
= 1.530 L atm
w = PV, 1.530 L atm = 0.500 atm V, V = 3.06 L

V = V
f
V
i
, 3.06 L = 58.0 L V
i
, V
i
= 54.9 L = initial volume

39. q = molar heat capacity mol T =
mol C
J 8 . 20
o
39.1 mol (38.0 0.0)C = 30,900 J
= 30.9 kJ
w = PV = 1.00 atm (998 L 876 L) = 122 L atm = 12,400 J = 12.4 kJ
E = q + w = 30.9 kJ + (12.4 kJ) = 18.5 kJ




atm L
J 3 . 101
CHAPTER 6 THERMOCHEMISTRY 189

40. H
2
O(g) H
2
O(l); E = q + w; q = 40.66 kJ; w = PV
Volume of 1 mol H
2
O(l) = 1.000 mol H
2
O(l)
g 996 . 0
cm 1
mol
g 02 . 18
3
= 18.1 cm
3
= 18.1 mL
w = PV = 1.00 atm (0.0181 L 30.6 L) = 30.6 L atm = 3.10 10
3
J
= 3.10 kJ
E = q + w = 40.66 kJ + 3.10 kJ = 37.56 kJ

Properties of Enthalpy

41. This is an endothermic reaction, so heat must be absorbed in order to convert reactants into
products. The high-temperature environment of internal combustion engines provides the
heat.

42. One should try to cool the reaction mixture or provide some means of removing heat because
the reaction is very exothermic (heat is released). The H
2
SO
4
(aq) will get very hot and
possibly boil unless cooling is provided.

43. a. Heat is absorbed from the water (it gets colder) as KBr dissolves, so this is an
endothermic process.

b. Heat is released as CH
4
is burned, so this is an exothermic process.

c. Heat is released to the water (it gets hot) as H
2
SO
4
is added, so this is an exothermic
process.

d. Heat must be added (absorbed) to boil water, so this is an endothermic process.

44. a. The combustion of gasoline releases heat, so this is an exothermic process.

b. H
2
O(g) H
2
O(l); heat is released when water vapor condenses, so this is an exothermic
process.

c. To convert a solid to a gas, heat must be absorbed, so this is an endothermic process.

d. Heat must be added (absorbed) in order to break a bond, so this is an endothermic
process.

45. 4 Fe(s) + 3 O
2
(g) 2 Fe
2
O
3
(s) H = 1652 kJ; note that 1652 kJ of heat is released when
4 mol Fe reacts with 3 mol O
2
to produce 2 mol Fe
2
O
3
.

a. 4.00 mol Fe = 1650 kJ; 1650 kJ of heat released
b. 1.00 mol Fe
2
O
3
= 826 kJ; 826 kJ of heat released
atm L
J 3 . 101
Fe mol 4
kJ 1652
3 2
O Fe mol 2
kJ 1652
190 CHAPTER 6 THERMOCHEMISTRY

c. 1.00 g Fe = 7.39 kJ; 7.39 kJ of heat released
d. 10.0 g Fe
Fe mol 4
kJ 652 1
Fe g 85 . 5 5
Fe mol 1
= 73.9 kJ
2.00 g O
2

2 2
2
O mol 3
kJ 652 1
O g 32.00
O mol 1
= 34.4 kJ
Because 2.00 g O
2
releases the smaller quantity of heat, O
2
is the limiting reactant and
34.4 kJ of heat can be released from this mixture.

46. a. 1.00 mol H
2
O
O H mol 2
kJ 572
2

= 286 kJ; 286 kJ of heat released

b. 4.03 g H
2

2 2
2
H mol 2
kJ 572
H g 016 . 2
H mol 1
= 572 kJ; 572 kJ of heat released
c. 186 g O
2

2 2
2
O mol
kJ 572
O g 32.00
O mol 1
= 3320 kJ; 3320 kJ of heat released
d.
2
H
n =
RT
PV
=
K 298
mol K
atm L 0.08206
L 10 2.0 atm 1.0
8

= 8.2 10
6
mol H
2
8.2 10
6
mol H
2

2
H mol 2
kJ 572
= 2.3 10
9
kJ; 2.3 10
9
kJ of heat released

47. From Example 6.3, q = 1.3 10
8
J. Because the heat transfer process is only 60.%
efficient, the total energy required is 1.3 10
8
J
J . 60
J . 100
= 2.2 10
8
J.
Mass C
3
H
8
= 2.2 10
8
J
8 3
8 3
3
8 3
H C mol
H C g 09 . 44
J 10 2221
H C mol 1

= 4.4 10
3
g C
3
H
8
48. a. 1.00 g CH
4

4 4
4
CH mol
kJ 891
CH g 16.04
CH mol 1
= 55.5 kJ
b. n =
RT
PV
=
K 298
mol K
atm L 0.08206
L 10 00 . 1
torr 760
atm 1
torr . 740
3

= 39.8 mol CH
4
39.8 mol CH
4
4
CH mol
kJ 891
= 3.55 10
4
kJ

49. When a liquid is converted into gas, there is an increase in volume. The 2.5 kJ/mol quantity is
the work done by the vaporization process in pushing back the atmosphere.
Fe mol 4
kJ 1652
g 85 . 55
Fe mol 1

CHAPTER 6 THERMOCHEMISTRY 191

50. AH = AE + PAV; from this equation, AH > AE when AV > 0, AH < AE when AV < 0, and AH
= AE when AV = 0. Concentrate on the moles of gaseous products versus the moles of
gaseous reactants to predict AV for a reaction.

a. There are 2 moles of gaseous reactants converting to 2 moles of gaseous products, so
AV = 0. For this reaction, AH = AE.

b. There are 4 moles of gaseous reactants converting to 2 moles of gaseous products, so
AV < 0 and AH < AE.

c. There are 9 moles of gaseous reactants converting to 10 moles of gaseous products, so
AV > 0 and AH > AE.


Calorimetry and Heat Capacity

51. Specific heat capacity is defined as the amount of heat necessary to raise the temperature of
one gram of substance by one degree Celsius. Therefore, H
2
O(l) with the largest heat
capacity value requires the largest amount of heat for this process. The amount of heat for
H
2
O(l) is:
energy = s m T =
g C
J 18 . 4
o
25.0 g (37.0C 15.0C) = 2.30 10
3
J
The largest temperature change when a certain amount of energy is added to a certain mass of
substance will occur for the substance with the smallest specific heat capacity. This is Hg(l),
and the temperature change for this process is:

T =
g . 550
g C
J 14 . 0
kJ
J 1000
kJ 7 . 10
m s
energy
o

= 140C
52. a. s = specific heat capacity =
g K
J 24 . 0
g C
J 24 . 0
o
= since T(K) = T(C)
Energy = s m T =
g C
J 24 . 0
o
150.0 g (298 K 273 K) = 9.0 10
2
J
b. Molar heat capacity =
mol C
J 26
Ag mol
Ag g 9 . 107
g C
J 24 . 0
o o
=
c. 1250 J =
g C
J 24 . 0
o
m (15.2C 12.0C), m =
2 . 3 24 . 0
1250

= 1.6 10
3
g Ag
53. s = specific heat capacity =
C ) 2 . 25 1 . 55 ( g 00 . 5
J 133
T m
q
o

A
= = 0.890 J/Cg
From Table 6.1, the substance is solid aluminum.
192 CHAPTER 6 THERMOCHEMISTRY

54. s =
C ) 0 . 20 5 . 53 ( g 6 . 125
J 585
o

= 0.139 J/Cg
Molar heat capacity =
mol C
J 9 . 27
Hg mol
g 6 . 200
g C
J 139 . 0
o o
=


55. | Heat loss by hot water | = | heat gain by cooler water |

The magnitudes of heat loss and heat gain are equal in calorimetry problems. The only
difference is the sign (positive or negative). To avoid sign errors, keep all quantities positive
and, if necessary, deduce the correct signs at the end of the problem. Water has a specific
heat capacity = s = 4.18 J/Cg = 4.18 J/Kg (T in C = T in K).

Heat loss by hot water = s m T =
g K
J 18 . 4
50.0 g (330. K T
f
)
Heat gain by cooler water =
g K
J 18 . 4
30.0 g (T
f
280. K); heat loss = heat gain, so:

K
J 209
(330. K T
f
) =
K
J 125
(T
f
280. K)

6.90 10
4
209T
f
= 125T
f
3.50 10
4
, 334T
f
= 1.040 10
5
, T
f
= 311 K

Note that the final temperature is closer to the temperature of the more massive hot water,
which is as it should be.

56. Heat loss by hot water = heat gain by cold water; keeping all quantities positive helps to
avoid sign errors:

g C
J 18 . 4
o
m
hot
(55.0C 37.0C) =
g C
J 18 . 4
o
90.0 g (37.0C 22.0C)
m
hot
=
C 18.0
C 15.0 g 90.0
o
o

= 75.0 g hot water needed

57. Heat loss by Al + heat loss by Fe = heat gain by water; keeping all quantities positive to
avoid sign error:

g C
J 89 . 0
o
5.00 g Al (100.0C T
f
) +
g C
J 45 . 0
o
10.00 g Fe (100.0 T
f
)
=
g C
J 18 . 4
o
97.3 g H
2
O (T
f
22.0C)
4.5(100.0 T
f
) + 4.5(100.0 T
f
) = 407(T
f
22.0), 450 (4.5)T
f
+ 450 (4.5)T
f

= 407T
f
8950

416T
f
= 9850, T
f
= 23.7C
CHAPTER 6 THERMOCHEMISTRY 193

58. Heat released to water = 5.0 g H
2

2
H g
J 120.
+ 10. g methane
methane g
J 50.
= 1.10 10
3
J
Heat gain by water = 1.10 10
3
J =
g C
J 18 . 4
o
50.0 g AT
AT = 5.26C, 5.26C = T
f
25.0C, T
f
= 30.3C

59. Heat gain by water = heat loss by metal = s m T, where s = specific heat capacity.
Heat gain =
g C
J 18 . 4
o
150.0 g (18.3C 15.0C) = 2100 J
A common error in calorimetry problems is sign errors. Keeping all quantities positive helps
to eliminate sign errors.

Heat loss = 2100 J = s 150.0 g (75.0C 18.3C), s =
C 7 . 56 g 0 . 150
J 2100
o

= 0.25 J/Cg
60. Heat gain by water = heat loss by Cu; keeping all quantities positive helps to avoid sign
errors:


g C
J 18 . 4
o
mass (24.9C 22.3C) =
g C
J 20 . 0
o
110. g Cu (82.4C 24.9C)
11(mass) = 1300, mass = 120 g H
2
O

61. 50.0 10
3
L 0.100 mol/L = 5.00 10
3
mol of both AgNO
3
and HCl are reacted. Thus
5.00 10
3
mol of AgCl will be produced because there is a 1 : 1 mole ratio between
reactants.

Heat lost by chemicals = heat gained by solution
Heat gain =
g C
J 18 . 4
o
100.0 g (23.40 22.60)C = 330 J
Heat loss = 330 J; this is the heat evolved (exothermic reaction) when 5.00 10
3
mol of
AgCl is produced. So q = 330 J and H (heat per mol AgCl formed) is negative with a
value of:
H = = 66 kJ/mol
Note: Sign errors are common with calorimetry problems. However, the correct sign for H
can be determined easily from the T data; i.e., if T of the solution increases, then the
reaction is exothermic because heat was released, and if T of the solution decreases, then
the reaction is endothermic because the reaction absorbed heat from the water. For
calorimetry problems, keep all quantities positive until the end of the calculation and then
decide the sign for H. This will help eliminate sign errors.

J 1000
kJ 1
mol 10 00 . 5
J 330
3

194 CHAPTER 6 THERMOCHEMISTRY

62. NaOH(aq) + HCl(aq) NaCl(aq) + H
2
O(l)

We have a stoichiometric mixture. All of the NaOH and HCl will react.
0.10 L
L
mol 0 . 1
= 0.10 mol of HCl is neutralized by 0.10 mol NaOH.
Heat lost by chemicals = heat gained by solution

Volume of solution = 100.0 + 100.0 = 200.0 mL

Heat gain = |
.
|

\
|

mL
g 0 . 1
mL 0 . 200
g C
J 18 . 4
o
(31.3 24.6)C = 5.6 10
3
J = 5.6 kJ
Heat loss = 5.6 kJ; this is the heat released by the neutralization of 0.10 mol HCl. Because
the temperature increased, the sign for H must be negative, i.e., the reaction is exothermic.
For calorimetry problems, keep all quantities positive until the end of the calculation and then
decide the sign for H. This will help eliminate sign errors.

H =
mol 10 . 0
kJ 6 . 5
= 56 kJ/mol

63. Heat lost by solution = heat gained by KBr; mass of solution = 125 g + 10.5 g = 136 g

Note: Sign errors are common with calorimetry problems. However, the correct sign for
H can easily be obtained from the T data. When working calorimetry problems, keep all
quantities positive (ignore signs). When finished, deduce the correct sign for H. For this
problem, T decreases as KBr dissolves, so H is positive; the dissolution of KBr is
endothermic (absorbs heat).

Heat lost by solution =
g C
J 18 . 4
o
136 g (24.2C 21.1C) = 1800 J = heat gained by KBr
H in units of J/g =
KBr g 5 . 10
J 1800
= 170 J/g
H in units of kJ/mol =
J 1000
kJ 1
KBr mol
KBr g 0 . 119
KBr g
J 170
= 20. kJ/mol

64. NH
4
NO
3
(s) NH
4
+
(aq) + NO
3

(aq) H = ?; mass of solution = 75.0 g + 1.60 g = 76.6 g

Heat lost by solution = heat gained as NH
4
NO
3
dissolves. To help eliminate sign errors, we
will keep all quantities positive (q and T) and then deduce the correct sign for H at the end
of the problem. Here, because temperature decreases as NH
4
NO
3
dissolves, heat is absorbed
as NH
4
NO
3
dissolves, so this is an endothermic process (H is positive).

Heat lost by solution =
g C
J 18 . 4
o
76.6 g (25.00 23.34)C = 532 J = heat gained as
NH
4
NO
3
dissolves

CHAPTER 6 THERMOCHEMISTRY 195

H =
J 1000
kJ 1
NO NH mol
NO NH g 05 . 80
NO NH g 60 . 1
J 532
3 4
3 4
3 4
= 26.6 kJ/mol NH
4
NO
3
dissolving

65. Because H is exothermic, the temperature of the solution will increase as CaCl
2
(s)
dissolves. Keeping all quantities positive:

heat loss as CaCl
2
dissolves = 11.0 g CaCl
2

2 2
2
CaCl mol
kJ 5 . 81
CaCl g 98 . 110
CaCl mol 1
= 8.08 kJ

heat gained by solution = 8.08 10
3
J =
g C
J 18 . 4
o
(125 + 11.0) g (T
f
25.0C)
T
f
25.0C =
136 18 . 4
10 08 . 8
3

= 14.2C, T
f
= 14.2C + 25.0C = 39.2C

66. 0.1000 L
HCl mol 2
released heat kJ 118
L
HCl mol 500 . 0
= 2.95 kJ of heat released if HCl limiting

0.3000 L
L
) OH ( Ba mol 100 . 0
2

2
) OH ( Ba mol
released heat kJ 118
= 3.54 kJ heat released if
Ba(OH)
2
limiting

Because the HCl reagent produces the smaller amount of heat released, HCl is limiting and
2.95 kJ of heat are released by this reaction.
Heat gained by solution = 2.95 10
3
J =
g C
J 18 . 4
o
400.0 g T
T = 1.76C = T
f
T
i
= T
f
25.0C, T
f
= 26.8C
67. a. Heat gain by calorimeter = heat loss by CH
4
= 6.79 g CH
4
mol
kJ 802
g 04 . 16
CH mol 1
4

= 340. kJ
Heat capacity of calorimeter =
C 8 . 10
kJ . 340
o
= 31.5 kJ/C
b. Heat loss by C
2
H
2
= heat gain by calorimeter = 16.9C
C
kJ 5 . 31
o
= 532 kJ
A bomb calorimeter is at constant volume, so the heat released/gained = q
V
= AE:
E
comb
=
2 2 2 2
H C mol
g 04 . 26
H C g 6 . 12
kJ 532

= 1.10 10
3
kJ/mol
68. First, we need to get the heat capacity of the calorimeter from the combustion of benzoic
acid. Heat lost by combustion = heat gained by calorimeter.

Heat loss = 0.1584 g
g
kJ 42 . 26
= 4.185 kJ
196 CHAPTER 6 THERMOCHEMISTRY

Heat gain = 4.185 kJ = C
cal
T, C
cal
=
C 54 . 2
kJ 185 . 4
o
= 1.65 kJ/C
Now we can calculate the heat of combustion of vanillin. Heat loss = heat gain.
Heat gain by calorimeter =
C
kJ 65 . 1
o
3.25C = 5.36 kJ
Heat loss = 5.36 kJ, which is the heat evolved by combustion of the vanillin.
AE
comb
=
g 2130 . 0
kJ 36 . 5
= 25.2 kJ/g; AE
comb
=
mol
g 14 . 152
g
kJ 2 . 25

= 3830 kJ/mol

Hess's Law

69. Information given:
C(s) + O
2
(g) CO
2
(g) H = 393.7 kJ
CO(g) + 1/2 O
2
(g) CO
2
(g) H = 283.3 kJ
Using Hesss law:
2 C(s) + 2 O
2
(g) 2 CO
2
(g) H
1
= 2(393.7 kJ)
2 CO
2
(g) 2 CO(g) + O
2
(g) H
2
= 2(283.3 kJ)
2 C(s) + O
2
(g) 2 CO(g) H = H
1
+ H
2
= 220.8 kJ

Note: When an equation is reversed, the sign on H is reversed. When the coefficients in a
balanced equation are multiplied by an integer, then the value of H is multiplied by the
same integer.

70. Given:

C
4
H
4
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l) H
comb
= 2341 kJ
C
4
H
8
(g) + 6 O
2
(g) 4 CO
2
(g) + 4 H
2
O(l) H
comb
= 2755 kJ
H
2
(g) + 1/2 O
2
(g) H
2
O(l) H
comb
= 286 kJ

By convention, H
2
O(l) is produced when enthalpies of combustion are given, and because
per-mole quantities are given, the combustion reaction refers to 1 mole of that quantity
reacting with O
2
(g).

Using Hesss law to solve:
C
4
H
4
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l) H
1
= 2341 kJ
4 CO
2
(g) + 4 H
2
O(l) C
4
H
8
(g) + 6 O
2
(g) H
2
= (2755 kJ)
2 H
2
(g) + O
2
(g) 2 H
2
O(l) H
3
= 2(286 kJ)
C
4
H
4
(g) + 2 H
2
(g) C
4
H
8
(g) H = H
1
+ H
2
+ H
3
= 158 kJ




CHAPTER 6 THERMOCHEMISTRY 197

71. 2 N
2
(g) + 6 H
2
(g) 4 NH
3
(g) H = 2(92 kJ)
6 H
2
O(g) 6 H
2
(g) + 3 O
2
(g) H = 3(484 kJ)

2 N
2
(g) + 6 H
2
O(g) 3 O
2
(g) + 4 NH
3
(g) H = 1268 kJ
No, because the reaction is very endothermic (requires a lot of heat to react), it would not be a
practical way of making ammonia because of the high energy costs required.

72. ClF + 1/2 O
2
1/2 Cl
2
O + 1/2 F
2
O H = 1/2(167.4 kJ)
1/2 Cl
2
O + 3/2 F
2
O ClF
3
+ O
2
H

= 1/2(341.4 kJ)
F
2
+ 1/2 O
2
F
2
O H

= 1/2(43.4 kJ)

ClF(g) + F
2
(g) ClF
3
H = 108.7 kJ

73. NO + O
3
NO
2
+ O
2
H = 199 kJ
3/2 O
2
O
3
H = 1/2(427 kJ)
O 1/2 O
2
H = 1/2(495 kJ)
NO(g) + O(g) NO
2
(g) H = 233 kJ

74. We want H for N
2
H
4
(l) + O
2
(g) N
2
(g) + 2 H
2
O(l). It will be easier to calculate H for
the combustion of four moles of N
2
H
4
because we will avoid fractions.

9 H
2
+ 9/2 O
2
9 H
2
O H = 9(286 kJ)
3 N
2
H
4
+ 3 H
2
O 3 N
2
O + 9 H
2
H = 3(317 kJ)
2 NH
3
+ 3 N
2
O 4 N
2
+ 3 H
2
O H = 1010. kJ
N
2
H
4
+ H
2
O 2 NH
3
+ 1/2 O
2
H = (143 kJ)

4 N
2
H
4
(l) + 4 O
2
(g) 4 N
2
(g) + 8 H
2
O(l) H = 2490. kJ

For N
2
H
4
(l) + O
2
(g) N
2
(g) + 2 H
2
O(l) H =
4
kJ . 2490
= 623 kJ
Note: By the significant figure rules, we could report this answer to four significant figures.
However, because the H values given in the problem are only known to 1 kJ, our final
answer will at best be 1 kJ.

75. CaC
2
Ca + 2 C H = (62.8 kJ)
CaO + H
2
O Ca(OH)
2
H = 653.1 kJ
2 CO
2
+ H
2
O C
2
H
2
+ 5/2 O
2
H = (1300. kJ)
Ca + 1/2 O
2
CaO H = 635.5 kJ
2 C + 2 O
2
2 CO
2
H = 2(393.5 kJ)

CaC
2
(s) + 2 H
2
O(l) Ca(OH)
2
(aq) + C
2
H
2
(g) H = 713 kJ





198 CHAPTER 6 THERMOCHEMISTRY

76. P
4
O
10
P
4
+ 5 O
2
H = (2967.3 kJ)
10 PCl
3
+ 5 O
2
10 Cl
3
PO H = 10(285.7 kJ)
6 PCl
5
6 PCl
3
+ 6 Cl
2
H = 6(84.2 kJ)
P
4
+ 6 Cl
2
4 PCl
3
H = 1225.6

P
4
O
10
(s) + 6 PCl
5
(g) 10 Cl
3
PO(g) H = 610.1 kJ

Standard Enthalpies of Formation

77. The change in enthalpy that accompanies the formation of 1 mole of a compound from its
elements, with all substances in their standard states, is the standard enthalpy of formation for
a compound. The reactions that refer to AH
o
f
are:

Na(s) + 1/2 Cl
2
(g) NaCl(s); H
2
(g) + 1/2 O
2
(g) H
2
O(l)

6 C(graphite, s) + 6 H
2
(g) + 3 O
2
(g) C
6
H
12
O
6
(s)
Pb(s) + S(rhombic, s) + 2 O
2
(g) PbSO
4
(s)

78. a. Aluminum oxide = Al
2
O
3
; 2 Al(s) + 3/2 O
2
(g) Al
2
O
3
(s)

b. C
2
H
5
OH(l) + 3 O
2
(g) 2 CO
2
(g) + 3 H
2
O(l)

c. NaOH(aq) + HCl(aq) H
2
O(l) + NaCl(aq)

d. 2 C(graphite, s) + 3/2 H
2
(g) + 1/2 Cl
2
(g) C
2
H
3
Cl(g)

e. C
6
H
6
(l) + 15/2 O
2
(g) 6 CO
2
(g) + 3 H
2
O(l)
Note: H
comb
values assume 1 mole of compound combusted.

f. NH
4
Br(s) NH
4
+
(aq) + Br

(aq)

79. In general, H = n
p
products , f
H

n
r
reactants , f
H

, and all elements in their standard

state have

f
H = 0 by definition.
a. The balanced equation is 2 NH
3
(g) + 3 O
2
(g) + 2 CH
4
(g) 2 HCN(g) + 6 H
2
O(g).

H = (2 mol HCN
HCN , f
H

+ 6 mol H
2
O(g)
O H , f
2
H

)
(2 mol NH
3

3
NH , f
H

+ 2 mol CH
4
) H
4
CH , f

A
H = [2(135.1) + 6(242)] [2(46) + 2(75)] = 940. kJ






CHAPTER 6 THERMOCHEMISTRY 199

b. Ca
3
(PO
4
)
2
(s) + 3 H
2
SO
4
(l) 3 CaSO
4
(s) + 2 H
3
PO
4
(l)
H =
(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 1267
) l ( PO H mol 2
mol
kJ 1433
) s ( CaSO mol 3
4 3 4


(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 814
) l ( SO H mol 3
mol
kJ 4126
) s ( ) PO ( Ca mol 1
4 2 2 4 3

H = 6833 kJ (6568 kJ) = 265 kJ

c. NH
3
(g) + HCl(g) NH
4
Cl(s)

H = (1 mol NH
4
Cl
Cl NH , f
4
H

) (1 mol NH
3

3
NH , f
H

+ 1 mol HCl
HCl , f
H

)
H =
(

|
.
|

\
|
+ |
.
|

\
|

|
.
|

\
|
mol
kJ 92
mol 1
mol
kJ 46
mol 1
mol
kJ 314
mol 1


H = 314 kJ + 138 kJ = 176 kJ

80. a. The balanced equation is C
2
H
5
OH(l) + 3 O
2
(g) 2 CO
2
(g) + 3 H
2
O(g).
H =
(

|
.
|

\
|

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 278
mol 1
mol
kJ 242
mol 3
mol
kJ 5 . 393
mol 2


H = 1513 kJ (278 kJ) = 1235 kJ

b. SiCl
4
(l) + 2 H
2
O(l) SiO
2
(s) + 4 HCl(aq)

Because HCl(aq) is H
+
(aq) + Cl

(aq),

f
H = 0 167 = 167 kJ/mol.
H =
(

|
.
|

\
|
+ |
.
|

\
|

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 286
mol 2
mol
kJ 687
mol 1
mol
kJ 911
mol 1
mol
kJ 167
mol 4

H = 1579 kJ (1259 kJ) = 320. kJ

c. MgO(s) + H
2
O(l) Mg(OH)
2
(s)
H =
(

|
.
|

\
|
+ |
.
|

\
|

|
.
|

\
|
mol
kJ 286
mol 1
mol
kJ 602
mol 1
mol
kJ 925
mol 1
H = 925 kJ (888 kJ) = 37 kJ

81. a. 4 NH
3
(g) + 5 O
2
(g) 4 NO(g) + 6 H
2
O(g); H = n
p
products , f
H

n
r
reactants , f
H

H =
(

|
.
|

\
|

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 46
mol 4
mol
kJ 242
mol 6
mol
kJ . 90
mol 4 = 908 kJ
200 CHAPTER 6 THERMOCHEMISTRY

2 NO(g) + O
2
(g) 2 NO
2
(g)

H =
(

|
.
|

\
|

|
.
|

\
|
mol
kJ . 90
mol 2
mol
kJ 34
mol 2 = 112 kJ

3 NO
2
(g) + H
2
O(l) 2 HNO
3
(aq) + NO(g)

H =
(

|
.
|

\
|
+ |
.
|

\
|

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 286
mol 1
mol
kJ 34
mol 3
mol
kJ . 90
mol 1
mol
kJ 207
mol 2
140. kJ
Note: All

f
H values are assumed 1 kJ.
b. 12 NH
3
(g) + 15 O
2
(g) 12 NO(g) + 18 H
2
O(g)
12 NO(g) + 6 O
2
(g) 12 NO
2
(g)
12 NO
2
(g) + 4 H
2
O(l) 8 HNO
3
(aq) + 4 NO(g)
4 H
2
O(g) 4 H
2
O(l)



12 NH
3
(g) + 21 O
2
(g) 8 HNO
3
(aq) + 4 NO(g) + 14 H
2
O(g)

The overall reaction is exothermic because each step is exothermic.

82. 4 Na(s) + O
2
(g) 2 Na
2
O(s) H = 2 mol |
.
|

\
|
mol
kJ 416
= 832 kJ

2 Na(s) + 2 H
2
O(l) 2 NaOH(aq) + H
2
(g)

H =
(

|
.
|

\
|

|
.
|

\
|
mol
kJ 286
mol 2
mol
kJ . 470
mol 2 = 368 kJ

2Na(s) + CO
2
(g) Na
2
O(s) + CO(g)

H =
(

|
.
|

\
|

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 5 . 393
mol 1
mol
kJ 5 . 110
mol 1
mol
kJ 416
mol 1 = 133 kJ
In Reactions 2 and 3, sodium metal reacts with the "extinguishing agent." Both reactions are
exothermic, and each reaction produces a flammable gas, H
2
and CO, respectively.

83. 3 Al(s) + 3 NH
4
ClO
4
(s) Al
2
O
3
(s) + AlCl
3
(s) + 3 NO(g) + 6 H
2
O(g)

H =
(

|
.
|

\
|
+ |
.
|

\
|
+ |
.
|

\
|
+ |
.
|

\
|
mol
kJ 1676
mol 1
mol
kJ 704
mol 1
mol
kJ . 90
mol 3
mol
kJ 242
mol 6


(

|
.
|

\
|

mol
kJ 295
mol 3 = 2677 kJ

CHAPTER 6 THERMOCHEMISTRY 201

84. 5 N
2
O
4
(l) + 4 N
2
H
3
CH
3
(l) 12 H
2
O(g) + 9 N
2
(g) + 4 CO
2
(g)

H =
(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 5 . 393
mol 4
mol
kJ 242
mol 12


(

|
.
|

\
|
+ |
.
|

\
|

mol
kJ 54
mol 4
mol
kJ . 20
mol 5 = 4594 kJ

85. 2 ClF
3
(g) + 2 NH
3
(g) N
2
(g) + 6 HF(g) + Cl
2
(g) H = 1196 kJ

H = (6
o
HF , f
H ) (2 ) H 2 H
o
NH , f
o
ClF , f
3 3
A + A
1196 kJ = 6 mol |
.
|

\
|
mol
kJ 271
2
o
ClF , f
3
H 2 mol |
.
|

\
|
mol
kJ 46

1196 kJ = 1626 kJ 2
o
ClF , f
3
H + 92 kJ,
o
ClF , f
3
H =
mol 2
kJ ) 1196 92 1626 ( + +
=
mol
kJ 169

86. C
2
H
4
(g) + 3 O
2
(g) 2 CO
2
(g) + 2 H
2
O(l) H = 1411.1 kJ
H = 1411.1 kJ = 2(393.5) kJ + 2(285.8) kJ
4 2
H C , f
H


1411.1 kJ = 1358.6 kJ , H
4 2
H C , f

4 2
H C , f
H

= 52.5 kJ/mol

Energy Consumption and Sources

87. C(s) + H
2
O(g) H
2
(g) + CO(g) H = 110.5 kJ (242 kJ) = 132 kJ

88. CO(g) + 2 H
2
(g) CH
3
OH(l) H = 239 kJ (110.5 kJ) = 129 kJ

89. C
2
H
5
OH(l) + 3 O
2
(g) 2 CO
2
(g) + 3 H
2
O(l)

H = [2(393.5 kJ) + 3(286 kJ)] (278 kJ) = 1367 kJ/mol ethanol

g 07 . 46
mol 1
mol
kJ 1367

= 29.67 kJ/g

90. CH
3
OH(l) + 3/2 O
2
(g) CO
2
(g) + 2 H
2
O(l)

H = [393.5 kJ + 2(286 kJ)] (239 kJ) = 727 kJ/mol CH
3
OH

g 04 . 32
mol 1
mol
kJ 727

= 22.7 kJ/g versus 29.67 kJ/g for ethanol (from Exercise 89)
Ethanol has a slightly higher fuel value per gram than methanol.


202 CHAPTER 6 THERMOCHEMISTRY

91. C
3
H
8
(g) + 5 O
2
(g) 3 CO
2
(g) + 4 H
2
O(l)

H = [3(393.5 kJ) + 4(286 kJ)] (104 kJ) = 2221 kJ/mol C
3
H
8


g 09 . 44
mol 1
mol
kJ 2221

=
g
kJ 50.37
versus 47.7 kJ/g for octane (Example 6.11)
The fuel values are very close. An advantage of propane is that it burns more cleanly. The
boiling point of propane is 42C. Thus it is more difficult to store propane, and there are
extra safety hazards associated with using high-pressure compressed-gas tanks.

92. 1 mole of C
2
H
2
(g) and 1 mole of C
4
H
10
(g) have equivalent volumes at the same T and P.


10 4
2 2
H C of volume per combustion of Enthalpy
H C of volume per combustion of Enthalpy
=
10 4
2 2
H C of mol per combustion of enthalpy
H C of mol per combustion of enthalpy



10 4
2 2
H C of volume per combustion of Enthalpy
H C of volume per combustion of Enthalpy
=
10 4
10 4
10 4
2 2
2 2
2 2
H C mol
H C g 12 . 58
H C g
kJ 5 . 49
H C mol
H C g 04 . 26
H C g
kJ 9 . 49

= 0.452
More than twice the volume of acetylene is needed to furnish the same energy as a given
volume of butane.

93. The molar volume of a gas at STP is 22.42 L (from Chapter 5).
4.19 10
6
kJ
4
4 4
CH mol
CH L 42 . 22
kJ 891
CH mol 1
= 1.05 10
5
L CH
4

94. Mass of H
2
O = 1.00 gal
mL
g 00 . 1
L
mL 1000
gal
L 785 . 3
= 3790 g H
2
O
Energy required (theoretical) = s m T =
g C
J 18 . 4
o
3790 g 10.0 C = 1.58 10
5
J

For an actual (80.0% efficient) process, more than this quantity of energy is needed since heat
is always lost in any transfer of energy. The energy required is:

1.58 10
5
J
J 0 . 80
J . 100
= 1.98 10
5
J
Mass of C
2
H
2
= 1.98 10
5
J
2 2
2 2
3
2 2
H C mol
H C g 04 . 26
J 10 . 1300
H C mol 1

= 3.97 g C
2
H
2

Additional Exercises
95. 2.0 h
mol
O H g 02 . 18
kJ 6 . 40
O H mol 1
h
kJ 5500
2 2
= 4900 g = 4.9 kg H
2
O
CHAPTER 6 THERMOCHEMISTRY 203

96. From the problem, walking 4.0 miles consumes 400 kcal of energy.
1 lb fat
mi 4
h 1
kcal 400
mi 4
g
kcal 7 . 7
lb
g 454
= 8.7 h = 9 h
97. a. 2 SO
2
(g) + O
2
(g) 2 SO
3
(g); w = PV; because the volume of the piston apparatus
decreased as reactants were converted to products (AV < 0), w is positive (w > 0).

b. COCl
2
(g) CO(g) + Cl
2
(g); because the volume increased (AV > 0), w is negative
(w < 0).

c. N
2
(g) + O
2
(g) 2 NO(g); because the volume did not change (AV = 0), no PV work is
done (w = 0).

In order to predict the sign of w for a reaction, compare the coefficients of all the product
gases in the balanced equation to the coefficients of all the reactant gases. When a balanced
reaction has more moles of product gases than moles of reactant gases (as in b), the reaction
will expand in volume (V positive), and the system does work on the surroundings. When
a balanced reaction has a decrease in the moles of gas from reactants to products (as in a), the
reaction will contract in volume (V negative), and the surroundings will do compression
work on the system. When there is no change in the moles of gas from reactants to products
(as in c), V = 0 and w = 0.

98. a. N
2
(g) + 3 H
2
(g) 2 NH
3
(g); from the balanced equation, 1 molecule of N
2
will react
with 3 molecules of H
2
to produce 2 molecules of NH
3
. So the picture after the reaction
should only have 2 molecules of NH
3
present. Another important part of your drawing
will be the relative volume of the product container. The volume of a gas is directly
proportional to the number of gas molecules present (at constant T and P). In this
problem, 4 total molecules of gas were present initially (1 N
2
+ 3 H
2
). After reaction,
only 2 molecules are present (2 NH
3
). Because the number of gas molecules decreases
by a factor of 2 (from 4 total to 2 total), the volume of the product gas must decrease by a
factor of 2 as compared to the initial volume of the reactant gases. Summarizing, the
picture of the product container should have 2 molecules of NH
3
and should be at a
volume which is one-half the original reactant container volume.

b. w = PAV; here the volume decreased, so AV is negative. When AV is negative, w is
positive. As the reactants were converted to products, a compression occurred which is
associated with work flowing into the system (w is positive).

99. a. C
12
H
22
O
11
(s) + 12 O
2
(g) 12 CO
2
(g) + 11 H
2
O(l)
b. A bomb calorimeter is at constant volume, so heat released = q
V
= E:
E =
mol
g 30 . 342
g 46 . 1
kJ 00 . 24

= 5630 kJ/mol C
12
H
22
O
11

c. PV = nRT; at constant P and T, PV = RTn, where n = moles of gaseous products
moles of gaseous reactants.
At constant P and T: H = E + PV = E + RTn
For this reaction, n = 12 12 = 0, so H = E = 5630 kJ/mol.
204 CHAPTER 6 THERMOCHEMISTRY

100. w = PV; n = moles of gaseous products moles of gaseous reactants. Only gases can do
PV work (we ignore solids and liquids). When a balanced reaction has more moles of
product gases than moles of reactant gases (n positive), the reaction will expand in volume
(V positive), and the system will do work on the surroundings. For example, in reaction c,
n = 2 0 = 2 moles, and this reaction would do expansion work against the surroundings.
When a balanced reaction has a decrease in the moles of gas from reactants to products (n
negative), the reaction will contract in volume (V negative), and the surroundings will do
compression work on the system, e.g., reaction a, where n = 0 1 = 1. When there is no
change in the moles of gas from reactants to products, V = 0 and w = 0, e.g., reaction b,
where n = 2 2 = 0.

When V > 0 (n > 0), then w < 0, and the system does work on the surroundings (c and e).

When V < 0 (n < 0), then w > 0, and the surroundings do work on the system (a and d).

When V = 0 (n = 0), then w = 0 (b).

101. E
overall
= E
step 1
+ E
step 2
; this is a cyclic process, which means that the overall initial state
and final state are the same. Because E is a state function, E
overall
= 0 and E
step 1
=
E
step 2
.

E
step 1
= q + w = 45 J + (10. J) = 35 J

E
step 2
= E
step 1
= 35 J = q + w, 35 J = 60 J + w, w = 25 J

102. 2 K(s) + 2 H
2
O(l) 2 KOH(aq) + H
2
(g) H = 2(481 kJ) 2(286 kJ) = 390. kJ
5.00 g K
K mol 2
kJ . 390
K g 10 . 39
K mol 1
= 24.9 kJ
24.9 kJ of heat is released on reaction of 5.00 g K.
24,900 J =
C g
J 18 . 4
o
(1.00 10
3
g) T, T =
3
10 00 . 1 18 . 4
900 , 24

= 5.96C
Final temperature = 24.0 + 5.96 = 30.0C

103. HNO
3
(aq) + KOH(aq) H
2
O(l) + KNO
3
(aq) H = 56 kJ

0.2000 L
L
HNO mol 0.400
3

3
HNO mol
released heat kJ 56
= 4.5 kJ heat released if HNO
3
limiting
0.1500 L
L
KOH mol 0.500

KOH mol
released heat kJ 56
= 4.2 kJ heat released if KOH limiting

Because the KOH reagent produces the smaller quantity of heat released, KOH is limiting
and 4.2 kJ of heat released.



CHAPTER 6 THERMOCHEMISTRY 205

104. Na
2
SO
4
(aq) + Ba(NO
3
)
2
(aq) BaSO
4
(s) + 2 NaNO
3
(aq) H = ?


1.00 L
4 2
4 4 2
SO Na mol
BaSO mol 1
L
SO Na mol 2.00
= 2.00 mol BaSO
4
if Na
2
SO
4
limiting
2.00 L
2 3
4 2 3
) NO ( Ba mol
BaSO mol 1
L
) NO ( Ba mol 750 . 0
= 1.50 mol BaSO
4
if Ba(NO
3
)
2
limiting

The Ba(NO
3
)
2
reagent produces the smaller quantity of product, so Ba(NO
3
)
2
is limiting and
1.50 mol BaSO
4
can form.

Heat gain by solution = heat loss by reaction
Mass of solution = 3.00 L
mL
g 2.00
L
mL 1000
= 6.00 10
3
g
Heat gain by solution =
g C
J 37 . 6
o
6.00 10
3
g (42.0 30.0)C = 4.59 10
5
J
Because the solution gained heat, the reaction is exothermic; q = 4.59 10
5
J for the
reaction.
AH =
4
5
BaSO mol 50 . 1
J 10 59 . 4
= 3.06 10
5
J/mol = 306 kJ/mol

105. |q
surr
| = |q
solution
+ q
cal
|; we normally assume that q
cal
is zero (no heat gain/loss by the calori-
meter). However, if the calorimeter has a nonzero heat capacity, then some of the heat
absorbed by the endothermic reaction came from the calorimeter. If we ignore q
cal
, then q
surr
is
too small, giving a calculated AH value that is less positive (smaller) than it should be.

106. The specific heat of water is 4.18 J/Cg, which is equal to 4.18 kJ/Ckg.
We have 1.00 kg of H
2
O, so: 1.00 kg
kg C
kJ 4.18
o
= 4.18 kJ/C
This is the portion of the heat capacity that can be attributed to H
2
O.

Total heat capacity = C
cal
+
O H
2
C , C
cal
= 10.84 4.18 = 6.66 kJ/C

107. Heat released = 1.056 g 26.42 kJ/g = 27.90 kJ = heat gain by water and calorimeter
Heat gain = 27.90 kJ = |
.
|

\
|
+
|
|
.
|

\
|
T
C
kJ 6.66
T kg 0.987
kg C
kJ 4.18
o o

27.90 = (4.13 + 6.66)T = (10.79)T, T = 2.586C

2.586C = T
f
23.32C, T
f
= 25.91C


206 CHAPTER 6 THERMOCHEMISTRY

108. For Exercise 83, a mixture of 3 mol Al and 3 mol NH
4
ClO
4
yields 2677 kJ of energy. The
mass of the stoichiometric reactant mixture is:

|
.
|

\
|
+ |
.
|

\
|

mol
g 49 . 117
mol 3
mol
g 98 . 26
mol 3 = 433.41 g
For 1.000 kg of fuel: 1.000 10
3
g
g 41 . 433
kJ 2677
= 6177 kJ

In Exercise 84, we get 4594 kJ of energy from 5 mol of N
2
O
4
and 4 mol of N
2
H
3
CH
3
. The
mass is |
.
|

\
|
+ |
.
|

\
|

mol
g 08 . 46
mol 4
mol
g 02 . 92
mol 5 = 644.42 kJ.

For 1.000 kg of fuel: 1.000 10
3
g
g 42 . 644
kJ 4594
= 7129 kJ
Thus we get more energy per kilogram from the N
2
O
4
/N
2
H
3
CH
3
mixture.

109. 1/2 D 1/2 A + B AH = 1/6(403 kJ)
1/2 E + F 1/2 A AH = 1/2(105.2 kJ)
1/2 C 1/2 E + 3/2 D AH = 1/2(64.8 kJ)


F + 1/2 C A + B + D AH = 47.0 kJ

110. To avoid fractions, let's first calculate H for the reaction:

6 FeO(s) + 6 CO(g) 6 Fe(s) + 6 CO
2
(g)

6 FeO + 2 CO
2
2 Fe
3
O
4
+ 2 CO H = 2(18 kJ)
2 Fe
3
O
4
+ CO
2
3 Fe
2
O
3
+ CO H = (39 kJ)
3 Fe
2
O
3
+ 9 CO 6 Fe + 9 CO
2
H = 3(23 kJ)

6 FeO(s) + 6 CO(g) 6 Fe(s) + 6 CO
2
(g) H = 66 kJ
So for FeO(s) + CO(g) Fe(s) + CO
2
(g), H =
6
kJ 66
= 11 kJ.

111. a. H = 3 mol(227 kJ/mol) 1 mol(49 kJ/mol) = 632 kJ

b. Because 3 C
2
H
2
(g) is higher in energy than C
6
H
6
(l), acetylene will release more energy
per gram when burned in air. Note that 3 moles of C
2
H
2
has the same mass as 1 mole of
C
6
H
6
.





CHAPTER 6 THERMOCHEMISTRY 207

112. I(g) + Cl(g) ICl(g) H = (211.3 kJ)
1/2 Cl
2
(g) Cl(g) H = 1/2(242.3 kJ)
1/2 I
2
(g) I(g) H = 1/2(151.0 kJ)
1/2 I
2
(s) 1/2 I
2
(g) H = 1/2(62.8 kJ)

1/2 I
2
(s) + 1/2 Cl
2
(g) ICl(g) H = 16.8 kJ/mol =
ICl ,
o
f
H

113. Heat gained by water = heat lost by nickel = s m T, where s = specific heat capacity.
Heat gain =
g C
J 18 . 4
o
150.0 g (25.0C 23.5C) = 940 J
A common error in calorimetry problems is sign errors. Keeping all quantities positive helps
to eliminate sign errors.

Heat loss = 940 J =
g C
J 444 . 0
o
mass (99.8 25.0) C, mass =
8 . 74 444 . 0
940

= 28 g

114. Heat gain by calorimeter =
C
kJ 56 . 1
o
3.2C = 5.0 kJ = heat loss by quinine
Heat loss = 5.0 kJ, which is the heat evolved (exothermic reaction) by the combustion of
0.1964 g of quinone. Because we are at constant volume, q
V
= AE.
E
comb
=
g 1964 . 0
kJ 0 . 5
= 25 kJ/g; E
comb
=
mol
g 09 . 108
g
kJ 25

= 2700 kJ/mol
115. a. C
2
H
4
(g) + O
3
(g) CH
3
CHO(g) + O
2
(g) H = 166 kJ [143 kJ + 52 kJ] = 361 kJ

b. O
3
(g) + NO(g) NO
2
(g) + O
2
(g) H = 34 kJ [90. kJ + 143 kJ] = 199 kJ

c. SO
3
(g) + H
2
O(l) H
2
SO
4
(aq) H = 909 kJ [396 kJ + (286 kJ)] = 227 kJ

d. 2 NO(g) + O
2
(g) 2 NO
2
(g) H = 2(34) kJ 2(90.) kJ = 112 kJ

ChemWork Problems
The answers to the problems 116-123 (or a variation to these problems) are found in OWL. These
problems are also assignable in OWL.

Challenge Problems

124. Only when there is a volume change can PV work be done. In pathway 1 (steps 1 + 2), only
the first step does PV work (step 2 has a constant volume of 30.0 L). In pathway 2 (steps 3 +
4), only step 4 does PV work (step 3 has a constant volume of 10.0 L).
208 CHAPTER 6 THERMOCHEMISTRY

Pathway 1: w = PV = 2.00 atm(30.0 L 10.0 L) = 40.0 L atm
atm L
J 3 . 101

= 4.05 10
3
J
Pathway 2: w = PV = 1.00 atm(30.0 L 10.0 L) = 20.0 L atm
atm L
J 3 . 101

= 2.03 10
3
J
Note: The sign is negative because the system is doing work on the surroundings (an
expansion). We get different values of work for the two pathways; both pathways have the
same initial and final states. Because w depends on the pathway, work cannot be a state
function.

125. A(l) A(g) H
vap
= 30.7 kJ; at constant pressure, H = q
p
= 30.7 kJ

Because PV = nRT, at constant pressure and temperature: w = PV = RTn, where:

n = moles of gaseous products moles of gaseous reactants = 1 0 = 1

w = RTn = 8.3145 J/Kmol(80. + 273 K)(1 mol) = 2940 J = 2.94 kJ

E = q + w = 30.7 kJ + (2.94 kJ) = 27.8 kJ

126. Energy needed =
mol
kJ 5640
O H C g 3 . 342
O H C mol 1
h
O H C g 10 . 20
11 22 12
11 22 12 11 22 12
3

= 3.3 10
5
kJ/h
Energy from sun = 1.0 kW/m
2
= 1000 W/m
2
=
2 2
m s
kJ 0 . 1
m s
J 1000
=
10,000 m
2

h
min 60
min
s 60
m s
kJ 0 . 1
2
= 3.6 10
7
kJ/h
Percent efficiency =
hour per energy total
hour per used energy
100 =
kJ 10 6 . 3
kJ 10 3 . 3
7
5

100 = 0.92%

127. Energy used in 8.0 hours = 40. kWh =
h
s 3600
s
h kJ . 40
= 1.4 10
5
kJ
Energy from the sun in 8.0 hours =
h
min 60
min
s 60
m s
kJ . 10
2
8.0 h = 2.9 10
4
kJ/m
2
Only 19% of the sunlight is converted into electricity:

0.19 (2.9 10
4
kJ/m
2
) area = 1.4 10
5
kJ, area = 25 m
2


128. a. 2 HNO
3
(aq) + Na
2
CO
3
(s) 2 NaNO
3
(aq) + H
2
O(l) + CO
2
(g)

H = [2(467 kJ) + (286 kJ) + (393.5 kJ)] [2(207 kJ) + (1131 kJ)] = 69 kJ
CHAPTER 6 THERMOCHEMISTRY 209

2.0 10
4
gallons
mL
g 42 . 1
qt
mL 946
gal
qt 4
= 1.1 10
8
g of concentrated nitric
acid solution
1.1 10
8
g solution
solution g 0 . 100
HNO g 0 . 70
3
= 7.7 10
7
g HNO
3

7.7 10
7
g HNO
3

3 2
3 2
3
3 2
3
3
CO Na mol
CO Na g 105.99
HNO mol 2
CO Na mol 1
HNO g 63.02
HNO mol 1

= 6.5 10
7
g Na
2
CO
3

7.7 10
7
g HNO
3

3 3
3
HNO mol 2
kJ 69
HNO g 02 . 63
HNO mol 1
= 4.2 10
7
kJ
4.2 10
7
kJ of heat was released.

b. They feared the heat generated by the neutralization reaction would vaporize the
unreacted nitric acid, causing widespread airborne contamination.

129. 400 kcal
kcal
kJ 18 . 4
= 1.7 10
3
kJ ~ 2 10
3
kJ
PE = mgz =
|
|
.
|

\
|

|
|
.
|

\
|

cm 100
m 1
in
cm 54 . 2
in 8
s
m 81 . 9
lb 205 . 2
kg 1
lb 180
2
= 160 J ~ 200 J
200 J of energy is needed to climb one step. The total number of steps to climb are:
2 10
6
J
J 200
step 1
= 1 10
4
steps

130. H
2
(g) + 1/2 O
2
(g) H
2
O(l) H =
) l ( O H ,
o
f
2
H = 285.8 kJ; we want the reverse reaction:
H
2
O(l) H
2
(g) + 1/2 O
2
(g) H = 285.8 kJ

w = PAV; because PV = nRT, at constant T and P, PAV = RTAn, where An = moles of
gaseous products moles of gaseous reactants. Here, n = (1 mol H
2
+ 0.5 mol O
2
) (0) =
1.50 mol.

E = H PV = H RTn
E = 285.8 kJ
|
|
.
|

\
|
- mol 1.50
J 1000
kJ 1
K 298 mol J/K 8.3145
E = 285.8 kJ 3.72 kJ = 282.1 kJ

131. There are five parts to this problem. We need to calculate:

(1) q required to heat H
2
O(s) from 30. C to 0C; use the specific heat capacity of H
2
O(s)

(2) q required to convert 1 mol H
2
O(s) at 0C into 1 mol H
2
O(l) at 0C; use AH
fusion

210 CHAPTER 6 THERMOCHEMISTRY

(3) q required to heat H
2
O(l) from 0C to 100.C; use the specific heat capacity of H
2
O(l)

(4) q required to convert 1 mol H
2
O(l) at 100.C into 1 mol H
2
O(g) at 100.C;
use AH
vaporization

(5) q required to heat H
2
O(g) from 100.C to 140.C; use the specific heat capacity of
H
2
O(g)

We will sum up the heat required for all five parts, and this will be the total amount of heat
required to convert 1.00 mol of H
2
O(s) at 30.C to H
2
O(g) at 140.C.

q
1
= 2.03 J/Cg 18.02 g [0 (30.)]C = 1.1 10
3
J

q
2
= 1.00 mol 6.02 10
3
J/mol = 6.02 10
3
J

q
3
= 4.18 J/Cg 18.02 g (100. 0)C = 7.53 10
3
J

q
4
= 1.00 mol 40.7 10
3
J/mol = 4.07 10
4
J

q
5
= 2.02 J/Cg 18.02 g (140. 100.)C = 1.5 10
3
J

q
total
= q
1
+ q
2
+ q
3
+ q
4
+ q
5
= 5.69 10
4
J = 56.9 kJ

132. When a mixture of ice and water exists, the temperature of the mixture remains at 0C until
all of the ice has melted. Because an ice-water mixture exists at the end of the process, the
temperature remains at 0C. All of the energy released by the element goes to convert ice into
water. The energy required to do this is related to AH
fusion
= 6.02 kJ/mol (from Exercise 131).

Heat loss by element = heat gain by ice cubes at 0C

Heat gain = 109.5 g H
2
O
O H mol
kJ 02 . 6
g 02 . 18
O H mol 1
2
2
= 36.6 kJ
Specific heat of element =
C ) 0 195 ( g 0 . 500
J 600 , 36
T mass
q
o

= = 0.375 J/Cg

Integrative Problems

133. N
2
(g) + 2 O
2
(g) 2 NO
2
(g) AH = 67.7 kJ


2
N
n =
K 373
mol K
atm L 08206 . 0
L 250 . 0 atm 50 . 3
RT
PV

= = 2.86
2
10

mol N
2


2
O
n =
K 373
mol K
atm L 08206 . 0
L 450 . 0 atm 50 . 3
RT
PV

= = 5.15
2
10

mol O
2
CHAPTER 6 THERMOCHEMISTRY 211

2.86
2
10

mol N
2

2
2
N mol 1
NO mol 2
= 5.72
2
10

mol NO
2
produced if N
2
is limiting.
5.15
2
10

mol O
2

2
2
O mol 2
NO mol 2
= 5.15
2
10

mol NO
2
produced if O
2
is limiting.
O
2
is limiting because it produces the smaller quantity of product. The heat required is:
5.15
2
10

mol NO
2

2
NO mol 2
kJ 7 . 67
= 1.74 kJ

134. a. 4 CH
3
NO
2
(l) + 3 O
2
(g) 4 CO
2
(g) + 2 N
2
(g) + 6 H
2
O(g)


o
rxn
H = 1288.5 kJ = [4 mol(393.5 kJ/mol) + 6 mol(242 kJ/mol)]
)] H ( mol 4 [
o
NO CH , f
2 3
A
Solving:
o
NO CH , f
2 3
H = 434 kJ/mol

b. P
total
= 950. torr
torr 760
atm 1
= 1.25 atm;
2 2
N total N
P P _ = = 1.25 atm 0.134
= 0.168 atm


K 373
mol K
atm L 08206 . 0
L 0 . 15 atm 168 . 0
n
2
N

= = 0.0823 mol N
2

0.0823 mol N
2



2
2
N mol 1
N g 02 . 28
= 2.31 g N
2

135. Heat loss by U = heat gain by heavy water; volume of cube = (cube edge)
3


Mass of heavy water = 1.00 10
3
mL
mL
g 11 . 1
= 1110 g
Heat gain by heavy water =
g C
J 211 . 4
o
1110 g (28.5 25.5)C = 1.4 10
4
J
Heat loss by U = 1.4 10
4
J =
g C
J 117 . 0
o
mass (200.0 28.5)C, mass = 7.0 10
2
g U
7.0 10
2
g U
g 05 . 19
cm 1
3
= 37 cm
3
; cube edge = (37 cm
3
)
1/3
= 3.3 cm





212 CHAPTER 6 THERMOCHEMISTRY

Marathon Problems

136. Pathway I:

Step 1: (5.00 mol, 3.00 atm, 15.0 L) (5.00 mol, 3.00 atm, 55.0 L)

w = PV = (3.00 atm)(55.0 L 15.0 L) = 120. L atm
w = 120. L atm
J 1000
kJ 1
atm L
J 3 . 101
= 12.2 kJ
Step 1 is at constant pressure. The heat released/gained at constant pressure = q
p
= H.
From the problem, H = nC
p
T for an ideal gas. Using the ideal gas law, lets substitute
for T.

(PV) = (nRT) = nRT for a specific gas sample. So: T =
nR
(PV)

H = q
p
= nC
p
T = nC
p

R
(PV) C
nR
(PV)
p
= ; Note: (PV) = (P
2
V
2
P
1
V
1
)
For an ideal monatomic gas, C
p
=
2
5
R; substituting into the above equation:
H =
R
(PV)
R
2
5
|
.
|

\
|
= ) PV (
2
5

H = q
p
=
2
5
(PV) =
2
5
(3.00 atm 55.0 L 3.00 atm 15.0 L) = 300. L atm
H = q
p
= 300. L atm
J 1000
kJ 1
atm L
J 3 . 101
= 30.4 kJ
E = q + w = 30.4 kJ 12.2 kJ = 18.2 kJ

Note: We could have used E = nC
v
T to calculate the same answer (E = 18.2 kJ).

Step 2: (5.00 mol, 3.00 atm, 55.0 L) (5.00 mol, 6.00 atm, 20.0 L)

In this step, neither pressure nor volume are constant. We will need to determine q in a
different way. However, it will always hold for an ideal gas that E = nC
v
T and H =
nC
p
T.

E = nC
v
T = n PV
2
3
nR
) PV (
R
2
3
= |
.
|

\
|
|
.
|

\
|

E =
2
3
(120. 165) L atm = 67.5 L atm (Carry an extra significant figure.)
E = 67.5 L atm
J 1000
kJ 1
atm L
J 3 . 101
= 6.8 kJ
CHAPTER 6 THERMOCHEMISTRY 213

H = nC
p
T = n PV
2
5
nR
) PV (
R
2
5
= |
.
|

\
|
|
.
|

\
|

H =
2
5
(120. 165) L atm = 113 L atm (Carry an extra significant figure.)
w = PV = (6.00 atm)(20.0 55.0) L = 210. L atm
w = 210. L atm
J 1000
kJ 1
atm L
J 3 . 101
= 21.3 kJ
E = q + w, 6.8 kJ = q + 21.3 kJ, q = 28.1 kJ

Summary: Path I Step 1 Step 2 Total

q 30.4 kJ 28.1 kJ 2.3 kJ
w 12.2 kJ 21.3 kJ 9.1 kJ
E 18.2 kJ 6.8 kJ 11.4 kJ
H 30.4 kJ 11 kJ 19 kJ

Pathway II:

Step 3: (5.00 mol, 3.00 atm, 15.0 L) (5.00 mol, 6.00 atm, 15.0 L)

Step 3 is at constant volume. The heat released/gained at constant volume = q
v
= E.
E = nC
v
T = n PV
2
3
nR
) PV (
R
2
3
= |
.
|

\
|
|
.
|

\
|

E = q
v
=
2
3
(PV) =
2
3
(6.00 atm 15.0 L 3.00 atm 15.0 L)
E = q
v
=
2
3
(90.0 45.0) L atm = 67.5 L atm
E = q
v
= 67.5 L atm
J 1000
kJ 1
atm L
J 3 . 101
= 6.84 kJ
w = PV = 0 because V = 0

H = E + (PV) = 67.5 L atm + 45.0 L atm = 112.5 L atm = 11.40 kJ

Step 4: (5.00 mol, 6.00 atm, 15.0 L) (5.00 mol, 6.00 atm, 20.0 L)

Step 4 is at constant pressure so q
p
= H.
H = q
p
= nC
p
T = PV
2
5
nR
) PV (
R
2
5
= |
.
|

\
|
|
.
|

\
|

214 CHAPTER 6 THERMOCHEMISTRY

H =
2
5
(120. 90.0) L atm = 75 L atm
H = q
p
= 75 L atm
J 1000
kJ 1
atm L
J 3 . 101
= 7.6 kJ
w = PV = (6.00 atm)(20.0 15.0) L = 30. L atm
w = 30. L atm
J 1000
kJ 1
atm L
J 3 . 101
= 3.0 kJ
E = q + w = 7.6 kJ 3.0 kJ = 4.6 kJ

Summary: Path II Step 3 Step 4 Total

q 6.84 kJ 7.6 kJ 14.4 kJ
w 0 3.0 kJ 3.0 kJ
E 6.84 kJ 4.6 kJ 11.4 kJ
H 11.40 kJ 7.6 kJ 19.0 kJ

State functions are independent of the particular pathway taken between two states; path
functions are dependent on the particular pathway. In this problem, the overall values of H
and E for the two pathways are the same (see the two summaries of results); hence H and
E are state functions. However, the overall values of q and w for the two pathways are
different; hence q and w are path functions.

137. C
x
H
y
+ |
.
|

\
| +
2
/2 2 y x
O
2
x CO
2
+ y/2 H
2
O
[x(393.5) + y/2 (242)]
o
H C
H
y x
= 2044.5, (393.5)x 121y
y x
H C
H = 2044.5
d
gas
= ,
RT
MM P -
where MM = average molar mass of CO
2
/H
2
O mixture
0.751 g/L =
K 473
mol K
atm L 08206 . 0
MM atm 00 . 1

, MM of CO
2
/H
2
O mixture = 29.1 g/mol
Let a = mol CO
2
and 1.00 a = mol H
2
O (assuming 1.00 total moles of mixture)

(44.01)a + (1.00 a) 18.02 = 29.1; solving: a = 0.426 mol CO
2
; mol H
2
O = 0.574 mol
Thus:
x
y
x
y
= = 69 . 2 ,
2
426 . 0
574 . 0
, y = (2.69)x
For whole numbers, multiply by three, which gives y = 8, x = 3. Note that y = 16, x = 6 is
possible, along with other combinations. Because the hydrocarbon has a lower density than
Kr, the molar mass of C
x
H
y
must be less than the molar mass of Kr (83.80 g/mol). Only C
3
H
8

works.

CHAPTER 6 THERMOCHEMISTRY 215

2044.5 = 393.5(3) 121(8)
o
H C
o
H C
8 3 8 3
H , H = 104 kJ/mol