363

CHAPTER 9

ENERGY, ENTHALPY, AND THERMOCHEMI STRY


The Nature of Energy

15. 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
2
s
m 81 . 9
3.00 m = 118 J

KE = E
total
PE = 196 J 118 J = 78 J

16. Plot a represents an exothermic reaction. In an exothermic process, the bonds in the product
molecules are stronger (on average) than those in the reactant molecules. The net result is
that the quantity of energy (PE) is transferred to the surroundings as heat when reactants are
converted to products.

For an endothermic process (plot b), energy flows into the system as heat to increase the
potential energy of the system. In an endothermic process, the products have higher potential
energy (weaker bonds on average) than the reactants.

17. 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.

18. 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
at m L
J 3 . 101
= 1060 J
E = q + w = 350. J + 1060 = 1410 J

364 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

c. w = PV = 1.00 atm(29.1 L 11.2 L) = 17.9 L atm
at m L
J 3 . 101
= 1810 J
E = q + w = 1037 J 1810 J = 770 J
19. 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
at m L
J 3 . 101
= 12,400 J = 12.4 kJ
E = q + w = 30.9 kJ + (12.4 kJ) = 18.5 kJ

20. E = q + w, 102.5 J = 52.5 J + w, w = 155.0 J
J 3 . 101
at m 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

21. 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
at m L
J 3 . 101
= 3.10 10
3
J
= 3.10 kJ
E = q + w = 40.66 kJ + 3.10 kJ = 37.56 kJ

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

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

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

= 2.03 10
3
J

Note: The sign is minus () 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.


CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 365

23. 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

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

950. J
J 3 . 101
at m 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

Properties of Enthalpy

25. One should try to cool the reaction mixture or provide some means of removing heat since
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.

26. 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 00 . 32
O mol 1
= 3320 kJ; 3320 kJ of heat released
d.
2
H
n =
RT
PV
=
K 298
mol K
atm L 08206 . 0
L 10 0 . 2 atm 0 . 1
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

27. 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
Fe mol 4
kJ 1652
= 1650 kJ; 1650 kJ of heat released
b. 1.00 mol Fe
2
O
3

3 2
O Fe mol 2
kJ 1652
= 826 kJ; 826 kJ of heat released
c. 1.00 g Fe
Fe mol 4
kJ 1652
g 85 . 55
Fe mol 1
= 7.39 kJ; 7.39 kJ of heat released
366 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

d. 10.0 g Fe
g 85 . 55
Fe mol 1
= 0.179 mol Fe; 2.00 g O
2

g 00 . 32
O mol 1
2
= 0.0625 mol O
2
0.179 mol Fe/0.0625 mol O
2
= 2.86; the balanced equation requires a 4 mol Fe/3 mol O
2

= 1.33 mole ratio. O
2
is limiting since the actual mole Fe/mole O
2
ratio is greater than the
required mole ratio.

0.0625 mol O
2

2
O mol 3
kJ 1652
= 34.4 kJ; 34.4 kJ of heat released

28. 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 vaper 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.


29. 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.

30. 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.

31. 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.

32. From Example 9.1, 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 (100. J/60. J) = 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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 367

The Thermodynamics of Ideal Gases

33. 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 15.0 L) = 120. L atm

w = 120. L atm H
J 1000
kJ 1
atm L
J 3 . 101
= 12.2 kJ

H = q
p
= nC
p
T = nC
p

R
) PV ( C
nR
) PV (
p
= ; (PV) = (P
2
V
2
P
1
V
1
)
For an ideal monatomic gas: C
p
=
2
5
R; H =
R
) PV (
R
2
5
|
.
|

\
|
= ) PV (
2
5

H = q
p
=
2
5
(PV) =
2
5
(165 45.0) L atm = 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

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

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

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

\
|
|
.
|

\
|

H =
2
5
(45 L atm) = 113 L atm (Carry an extra significant figure.)
H = 113 L atm
J 1000
kJ 1
atm L
J 3 . 101
= 11.4 = 11 kJ

w = P
ext
V = (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
368 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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)

E = q
v
=
2
3
(PV) =
2
5
(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)

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

\
|
|
.
|

\
|


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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 369

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; hence H and E are state functions. The overall
values of q and w for the two pathways are different; hence q and w are path functions.

34. For a monoatomic gas, C
v
= (3/2)R and C
p
= (5/2)R.

Step 1: (2.00 mol, 10.0 atm, 10.0 L) (2.00 mol, 10.0 atm, 5.0 L)

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

\
|
|
.
|

\
|

H = q
p
=
2
5
(50. 100.) = 125 L atm 101.3 J L
1
atm
1
= 12.7 kJ

(We will carry all calculations to 0.1 kJ.)

w = PV = (10.0 atm)(5.0 10.0) L = 50. L atm = 5.1 kJ

E = q + w = 12.7 + 5.1 = 7.6 kJ

Step 2: (2.00 mol, 10.0 atm, 5.0 L) (2.00 mol, 20.0 atm, 5.0 L)

E = q
v
= nC
v
AT =
2
3
(PV) =
2
3
(100 50.) = 75 L atm = 7.6 kJ; w = 0 since V = 0

H = E + (PV) = 75 L atm + 50. L atm = 125 L atm = 12.7 kJ

Step 3: (2.00 mol, 20.0 atm, 5.0 L) (2.00 mol, 20.0 atm, 25.0 L)

H = q
p
=
2
5
(PV) =
2
5
(500. 100) = 1.0 10
3
L atm = 101.3 kJ

w = PV = (20.0 atm)(25.0 5.0) L = 400. L atm = 40.5 kJ

E = q + w = 101.3 40.5 = 60.8 kJ

Summary: Step 1 Step 2 Step 3 Total

q 12.7 kJ 7.6 kJ 101.3 kJ 96.2 kJ
w 5.1 kJ 0 40.5 kJ 35.4 kJ
E 7.6 kJ 7.6 kJ 60.8 kJ 60.8 kJ
H 12.7 kJ 12.7 kJ 101.3 kJ 101.3 kJ

35. Consider the constant volume process first.
n = 1.00 10
3
g
g 07 . 30
mol 1
= 33.3 mol C
2
H
6
; C
v
=
mol C
J 60 . 44
mol K
J 60 . 44
o
=
370 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

E = nC
v
T = (33.3 mol)(44.60 J C
1
mol
1
)(75.0 25.0C) = 74,300 J = 74.3 kJ

E = q + w; since V = 0, w = 0; E = q
v
= 74.3 kJ

H = E + PV = E + nRT

H = 74.3 kJ + (33.3 mol)(8.3145 J K
1
mol
1
)(50.0 K)(1 kJ/1000 J)

H = 74.3 kJ + 13.8 kJ = 88.1 kJ

Now consider the constant pressure process.

q
p
= H = nC
p
T = (33.3 mol)(52.92 J K
1
mol
1
)(50.0 K)

q
p
= 88,100 J = 88.1 kJ = H

w = PV = nRT = (33.3 mol)(8.3145 J K
1
mol
1
)(50.0 K) = 13,800 J = 13.8 kJ

E = q + w = 88.1 kJ 13.8 kJ = 74.3 kJ

Summary Constant V Constant P
q 74.3 kJ 88.1 kJ
E 74.3 kJ 74.3 kJ
H 88.1 kJ 88.1 kJ
w 0 13.8 kJ

36. 88.0 g N
2
O
O N g 02 . 44
O N mol 1
2
2
= 2.00 mol N
2
O

At constant pressure, q
p
= H.

H = nC
p
T = (2.00 mol)(38.70 J C
1
mol
1
)(55C 165C)

H = 8510 J = 8.51 kJ = q
p


w = PV = nRT = (2.00 mol)(8.3145 J K
1
mol
1
)(110. K) = 1830 J = 1.83 kJ

E = q + w = 8.51 kJ + 1.83 kJ = 6.68 kJ


Calorimetry and Heat Capacity

37. 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:
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 371

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
38. 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 K
J 24 . 0
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
39. In calorimetry, heat flow is determined into or out of the surroundings. Because E
univ
= 0 by
the first law of thermodynamics, E
sys
= E
surr
; what happens to the surroundings is the
exact opposite of what happens to the system. To determine heat flow, we need to know the
heat capacity of the surroundings, the mass of the surroundings that accepts/donates the heat,
and the change in temperature. If we know these quantities, q
surr
can be calculated and then
equated to q
sys
(q
surr
= q
sys
). For an endothermic reaction, the surroundings (the calorimeter
contents) donates heat to the system. This is accompanied by a decrease in temperature of the
surroundings. For an exothermic reaction, the system donates heat to the surroundings (the
calorimeter), so temperature increases.

q
P
= H; q
V
= E; a coffee-cup calorimeter is at constant (atmospheric) pressure. The heat
released or gained at constant pressure is H. A bomb calorimeter is at constant volume. The
heat released or gained at constant volume is E.

40. 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


372 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

41. 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

42. 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 =
g 0 . 150 C 7 . 56
J 2100
o

= 0.25 J C
1
g
1

43. Heat loss by hot water = heat gain by cold water; keeping all quantities positive 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 (37.0 C 22.0C)
m
hot
=
C 0 . 18
C 0 . 15 g 0 . 90
o
o

= 75.0 g hot water needed

44. 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

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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 373

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

46. 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

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

47. 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

48. 0.100 L
L
HCl mol 500 . 0
= 5.00 10
2
mol HCl

0.300 L
L
) OH ( Ba mol 100 . 0
2
= 3.00 10
2
mol Ba(OH)
2


374 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

To react with all the HCl present, 5.00 10
2
/2 = 2.50 10
2
mol Ba(OH)
2
is required.
Because 0.0300 mol Ba(OH)
2
is present, HCl is the limiting reactant.

5.00 10
2
mol HCl
HCl mol 2
kJ 118
= 2.95 kJ of heat is evolved by 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

49. 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 =
J 1000
kJ 1
mol 10 00 . 5
J 330
3

= 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.

50. 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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 375

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

51. 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. H = E + (PV) = E + (nRT) = E + nRT, where n = moles of gaseous products
moles of gaseous reactants.

For this reaction, n = 12 12 = 0, so H = E = 5630 kJ/mol.

52. 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
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

53. 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 heat released = q
v
= E:
376 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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

54. A(l) A(g) H
vap
= 30.7 kJ

w = PV = nRT, where n = n
products
n
reactants
= 1 0 = 1

w = (1 mol)(8.3145 J K
1
mol
1
)(80. + 273 K) = 2940 J; because pressure is constant:

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


Hesss Law

55. 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

56. 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
(g) H = 108.7 kJ

57. C
6
H
4
(OH)
2
C
6
H
4
O
2
+ H
2
H = 177.4 kJ
H
2
O
2
H
2
+ O
2
H = (191.2 kJ)
2 H
2
+ O
2
2 H
2
O(g) H = 2(241.8 kJ)
2 H
2
O(g) 2 H
2
O(l) H = 2(43.8 kJ)
________________________________________________________________
C
6
H
4
(OH)
2
(aq) + H
2
O
2
(aq) C
6
H
4
O
2
(aq) + 2 H
2
O(l) H = 202.6 kJ

58. 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.

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 377

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.

59. 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.

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

61. 2 C + 2 O
2
2 CO
2
H = 2(394 kJ)
H
2
+ 1/2 O
2
H
2
O H = 286 kJ
2 CO
2
+ H
2
O C
2
H
2
+ 5/2 O
2
H = (1300.kJ)
________________________________________________
2 C(s) + H
2
(g) C
2
H
2
(g) H = 226 kJ

Note: The enthalpy change for a reaction that is reversed is the negative quantity of the
enthalpy change for the original reaction. If the coefficients in a balanced reaction are
multiplied by an integer, then the value of H is multiplied by the same integer.

62. 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
378 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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

63. 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

64. 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


Standard Enthalpies of Formation

65. The change in enthalpy that accompanies the formation of one 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(s) + 2 O
2
(g) PbSO
4
(s)

66. 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.
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
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 379

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.

67. 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.

68. a. 4 NH
3
(g) + 5 O
2
(g) 4 NO(g) + 6 H
2
O(g); H =

o
products , f p
H n

o
reactants f, r
H n

H =
(

|
.
|

\
|

|
.
|

\
|
+ |
.
|

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

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 . 90
mol 1
mol
kJ 207
mol 2

(

|
.
|

\
|
+ |
.
|

\
|

mol
kJ 286
mol 1
mol
kJ 34
mol 3 = 140. kJ



380 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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 must be exothermic because each step is exothermic.

69. In general: H =

o
products , f p
H n

, H n
o
reactants f, r
and all elements in their standard
state have
o
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
o
HCN , f
H + 6 mol H
2
O(g) H
o
O H , f
2
H )
(2 mol NH
3

o
NH , f
3
H + 2 mol CH
4

o
CH , f
4
H )

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

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
o
Cl NH , f
4
H ) (1 mol NH
3

o
NH , f
3
H + 1 mol HCl
o
HCl , f
H )
H =
(

|
.
|

\
|
mol
kJ 314
mol 1
(

|
.
|

\
|
+ |
.
|

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

H = 314 kJ + 138 kJ = 176 kJ

d. 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 242
mol 3
mol
kJ 5 . 393
mol 2
(

|
.
|

\
|
mol
kJ 278
mol 1

H = 1513 kJ (278 kJ) = 1235 kJ
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 381

e. SiCl
4
(l) + 2 H
2
O(l) SiO
2
(s) + 4 HCl(aq)
Because HCl(aq) is H
+
(aq) + Cl

(aq),
o
f
H = 0 - 167 = -167 kJ/mol.
H =
(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 911
mol 1
mol
kJ 167
mol 4

(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 286
mol 2
mol
kJ 687
mol 1
H = 1579 kJ (1259 kJ) = 320. kJ

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

H =
(

|
.
|

\
|
mol
kJ 925
mol 1
(

|
.
|

\
|
+ |
.
|

\
|
mol
kJ 286
mol 1
mol
kJ 602
mol 1

H = 925 kJ (888 kJ) = 37 kJ

70. 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

71. 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

72. For Exercise 70, 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

382 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

In Exercise 71, 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.

73. 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
o
NH , f
o
ClF , f
3 3
H 2 H + )

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


74. C
2
H
4
(g) + 3 O
2
(g) 2 CO
2
(g) + 2 H
2
O(l) H = 1411 kJ

H = 1411.1 kJ = 2(393.5) kJ + 2(285.8) kJ
o
H C , f
4 2
H

1411.1 kJ = 1358.6 kJ
o
H C , f
4 2
H ,
o
H C , f
4 2
H = 52.5 kJ/mol

75. 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.

76. 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


Energy Consumption and Sources

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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 383

78. 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
kJ 37 . 50
g 096 . 44
mol 1
mol
kJ 2221

= versus 47.7 kJ/g for octane (Example 9.8)

The two 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.

79. 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

80. 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 068 . 46
mol 1
mol
kJ 1367

= 29.67 kJ/g

81. 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

Ethanol has a higher fuel value than methanol.

82. 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

384 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

Additional Exercises

83. 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. Ba(OH)
2
(aq) + 2 HCl(aq) 2 H
2
O(l) + BaCl
2
(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)

84. The specific heat capacities are: 0.89 J C
1
g
1
(Al) and 0.45 J C
1
g
1
(Fe). Al would be
the better choice. It has a higher heat capacity and a lower density than Fe. Using Al, the
same amount of heat could be dissipated by a smaller mass, keeping the mass of the amplifier
down.

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

0.2000 L
L
HNO mol 0.400
3
= 8.00
2
10

mol HNO
3

0.1500 L
L
KOH mol 0.500
= 7.50
2
10

mol KOH
Because the balanced reaction requires a 1 : 1 mole ratio between HNO
3
and KOH, and
because fewer moles of KOH are actually present as compared with HNO
3
, KOH is the
limiting reagent.

7.50
2
10

mol KOH
KOH mol
kJ 56
= 4.2 kJ; 4.2 kJ of heat is released.
86. |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.

87. The specific heat of water is 4.18 J C
1
g
1
, which is equal to 4.18 kJ C
1
kg
1


We have 1.00 kg of H
2
O, so: 1.00 kg
kg C
kJ 18 . 4
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

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

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 385

Heat gain = 27.90 kJ = |
.
|

\
|
+
|
|
.
|

\
|
T
C
kJ 66 . 6
T kg 987 . 0
kg C
kJ 18 . 4
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
89. H
2
(g) + 1/2 O
2
(g) H
2
O(l) H =
o
) l ( O H , f
2
H = 285.8 kJ

H
2
O(l) H
2
(g) + 1/2 O
2
(g) H = 285.8 kJ

E = H PV = H nRT
E = 285.8 kJ (1.50 0 mol)(8.3145 J K
1
mol
1
)(298 K)
|
|
.
|

\
|
J 1000
kJ 1

E = 285.8 kJ 3.72 kJ = 282.1 kJ
90. 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.

91. 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).

386 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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).

92. H = E + PV, H = E + (PV), E = H (PV)

Assume that H
2
O(g) is ideal. (PV) = (nRT) = RTn at constant T

We go from n = 0 to n = 1, thus n = 1. [H
2
O(l) is a liquid.]

E = H (8.3145 J K
1
mol
1
)(298 K)(1 mol) = H 2480 J

H = 242 kJ/mol (286 kJ/mol) = 44 kJ/mol

E = 44 kJ 2.48 kJ, E = 41.52 kJ = 42 kJ

93. 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

94. 400 kcal
kcal
kJ 18 . 4
= 1.67 10
3
kJ 2 10
3
kJ

PE = mgz =
|
|
.
|

\
|

|
|
.
|

\
|

cm 100
m 1
m
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
st ep 1
= 1 10
4
steps

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

1.00 L
L
mol 00 . 2
= 2.00 mol Na
2
SO
4
; 2.00 L
L
mol 750 . 0
= 1.50 mol Ba(NO
3
)
2

The balanced equation requires a 1 : 1 mole ratio between Na
2
SO
4
and Ba(NO
3
)
2
. Because we
have fewer moles of Ba(NO
3
)
2
present, it is limiting and 1.50 mol BaSO
4
will be produced
[there is a 1 : 1 mole ratio between Ba(NO
3
)
2
and BaSO
4
].

Heat gain by solution = heat loss by reaction

Mass of solution = 3.00 L
mL
g 00 . 2
L 1
mL 1000
= 6.00 10
3
g
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 387

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

96. 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).

97. 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

Challenge Problems

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

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

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


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

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

5. q required to heat H
2
O(g) from 100.
o
C to 140.
o
C; use the specific heat capacity of
H
2
O(g)
388 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

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.
o
C to H
2
O(g) at 140.
o
C.

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

q
2
= 1.00 mol 6.01 10
3
J/mol = 6.01 10
3
J

q
3
= 4.18 J C
1
g
1
18.02 g (100. 0)
o
C = 7.53 10
3
J

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

q
5
= 2.02 J C
1
g
1
18.02 g (140. 100.)
o
C = 1.5 10
3
J

q
total
= q
1
+ q
2
+ q
3
+ q
4
+ q
5
= 5.68 10
4
J = 56.8 kJ

99. Molar heat capacity of H
2
O(l) = 4.184 J K
1
g
1
(18.015 g/mol) = 75.37 J K
1
mol
1

Molar heat capacity of H
2
O(g) = 2.02 J K
1
g
1
(18.015 g/mol) = 36.4 J K
1
mol
1

Using Hesss law and the equation H = nC
p
T:
H
2
O(l, 298.2 K) H
2
O(l, 373.2 K) H
1
= 1 mol(75.37 J K
1
mol
1
)(75.0 K)(1 kJ/1000 J)
= 5.65 kJ
H
2
O(l, 373.2 K) H
2
O(g, 373.2 K) H
2
= 1 mol(40.66 kJ/mol) = 40.66 kJ
H
2
O(g, 373.2 K) H
2
O(g, 298.2 K) H
3
= 1 mol(36.4 J K
1
mol
1
)(75.0 K)(1 kJ/1000 J)
= 2.73 kJ

H
2
O(l, 298.2 K) H
2
O(g, 298.2 K)
K 2 . 298 , vap
H = H
1
+ H
2
+ H
3
= 43.58 kJ/mol

Using
o
f
H values in Appendix 4 (which are determined at 25 C):

AH
vap
= 242 kJ (286 kJ) = 44 kJ

To two significant figures, the two calculated AH
vap
values agree (as they should).

100. 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%

CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 389

101. 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 15% of the sunlight is converted into electricity:

0.15 (2.9 10
4
kJ/m
2
) area = 1.4 10
5
kJ, area = 32 m
2

102. If the gas is monoatomic:
C
v
=
2
3
R = 12.47 J K
1
mol
1
and C
p
=
2
5
R = 20.79 J K
1
mol
1

If the gas is behaving ideally, then C
p
C
v
= R = 8.3145 J K
1
mol
1
.
At constant volume: q
v
= 2079 J = nC
v
T

C
v
=
) K 0 . 300 0 . 400 )( mol 1 (
J 2079
T n
J 2079

= = 20.79 J K
1
mol
1


Because C
v
3/2 R = 12.47 J, the gas is not a monoatomic gas.

At constant pressure: q
p
= nC
p
T

q
p
= E w = 1305 J (150. J) = 1455 J (Gas expansion, so system does work on
surroundings.)
C
p
=
) K 0 . 550 0 . 600 )( mol 1 (
J 1455
T n
q
p

= = 29.1 J K
1
mol
1


C
p
C
v
= 29.1 20.79 = 8.3 J K
1
mol
1
= R

The gas is behaving ideally since C
p
C
v
= R.

103. For an isothermal (constant T) process involving the expansion or compression of a gas, AE =
nC
v
AT = 0 (AH is also zero). Because AE = q + w = 0, q = w = (P
ex
AV). So if the
expansion or compression occurs against some nonzero external pressure, w = 0 and q = 0.
Instead, q = w = P
ex
AV (if the gas expands or contracts against some constant pressure).






390 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

104. a. Using Hess's law and the equation H = nC
p
T:

CH
3
Cl(248C) + H
2
(248C) CH
4
(248C) + HCl(248C) H
1
= -83.3 kJ
CH
3
Cl(25C) CH
3
Cl(248C) H
2
= 1 mol(48.5 J C
1
mol
1
)(223C)
= 10,800 J = 10.8 kJ
H
2
(25C) H
2
(248C) H
3
= 1(28.9)(223)(1 kJ/1000 J) = 6.44 kJ
CH
4
(248C) CH
4
(25C) H
4
= 1(41.3)(223)(1/1000) = 9.21 kJ
HCl(248C) HCl(25C) H
5
= 1(29.1)(223)(1/1000) = 6.49 kJ

CH
3
Cl(25C) + H
2
(25C) CH
4
(25C) + HCl(25C) H = H
1
+ H
2
+ H
3
+ H
4
+ H
5


H = 83.3 kJ + 10.8 kJ + 6.44 kJ 9.21 kJ 6.49 kJ = 81.8 kJ

b. H = ) H H (
o
HCl , f
o
CH , f
4
+ (
o
Cl CH , f
3
H + ) H
o
H , f
2

81.8 kJ = (75 kJ 92 kJ)
o
Cl CH , f
3
H ( + 0),
o
Cl CH , f
3
H = 85 kJ/mol
105. H
2
O(s) H
2
O(l) H = H
fus
; for 1 mol of supercooled water at 15.0C (or 258.2 K),
H
fus, 258.2 K
= 10.9 kJ/2.00 mol = 5.45 kJ/mol. Using Hesss law and the equation H =
nC
p
T:

H
2
O(s, 273.2 K) H
2
O(s, 258.2 K) H
1
= 1 mol(37.5 J K
1
mol
1
)(15.0 K)
= 563 J = 0.563 kJ
H
2
O(s, 258.2 K) H
2
O(l, 258.2 K) H
2
= 1 mol(5.45 kJ/mol) = 5.45 kJ
H
2
O(l, 258.2 K) H
2
O(l, 273.2 K) H
3
= 1 mol(75.3 J K
1
mol
1
)(15.0 K)
= 1130 J = 1.13 kJ

______________________________________________________________________________________________________________

H
2
O(s, 273. 2 K) H
2
O(l, 273.2 K) H
fus, 273.2
= H
1
+ H
2
+ H
3


H
fus, 273.2
= 0.563 kJ + 5.45 kJ + 1.13 kJ, H
fus, 273.2
= 6.02 kJ/mol

106. a. The gas will flow out of the 4.0 L bulb into the 20.0-L bulb. Eventually, the gas will be
evenly dispersed throughout the two bulbs. The pressure will be the same inside both bulbs.

The moles of gas (n) and the temperature (T) are constant. However, as the gas expands from
4.0 L to 24.0 L, the pressure will decrease.

P
initial
= P
i
=
i
V
nRT
=
L 0 . 4
) K 305 )( mol K atm L 08206 . 0 ( mol 4 . 2
1 1
= 15 atm

P
final
= P
f
=
f
i i
V
V P
=
L 0 . 24
) L 0 . 4 ( atm 15
= 2.5 atm

b. Assuming the gas behaves ideally, then AE = nC
v
AT and AH = nC
p
AT. Because AT = 0, AE
= 0 and AH = 0. From AE = q + w = 0, q = w. Here we have an expansion of a gas where w
= P
ex
AV. The gas is expanding against a vacuum (P
ex
= 0), so w = 0. We call this a free
expansion of a gas. Work can only occur in the expansion of a gas when the gas expands
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 391

against a certain nonzero external pressure. Because w = 0, q = w = 0. For a free expansion
of an ideal gas at a constant temperature, AE = 0, AH = 0, q = 0, and w = 0. If the expansion
occurs against some nonzero constant external pressure, then AE = 0, AH = 0, q = w =
P
ex
AV.

c. The driving force is the natural tendency of processes to spontaneously proceed toward states
that have the highest probability of existing. In this problem the gas mixed evenly throughout
both bulbs is the most probable (likely) state to occur. This driving force is related to entropy,
which will be discussed in detail in Chapter 10.


Marathon Problems

107. X CO
2
(g) + H
2
O(l) + O
2
(g) + A(g) H = 1893 kJ/mol (unbalanced)

To determine X, we must determine the moles of X reacted, the identity of A, and the moles of A
produced. For the reaction at constant P (H = q):


rxn O H
q q
2
= = 4.184 J C
-1
g
-1
(1.000 10
4
g)(29.52 - 25.00 C)(1 kJ/1000 J)
q
rxn
= 189.1 kJ (carrying extra significant figures)

Because H = 1893 kJ/mol for the decomposition reaction, and because only -189.1 kJ of heat
was released for this reaction, 189.1 kJ (1 mol X/1893 kJ) = 0.100 mol X were reacted.

Molar mass of X =
X mol 100 . 0
X g 7 . 22
= 227 g/mol

From the problem, 0.100 mol X produced 0.300 mol CO
2
, 0.250 mol H
2
O, and 0.025 mol O
2
.
Therefore, 1.00 mol X contains 3.00 mol CO
2
, 2.50 mol H
2
O, and 0.25 mol O
2
.


1.00 mol X = 227 g = 3.00 mol CO
2 |
.
|

\
|
mol
g 0 . 44
+ 2.50 mol H
2
O |
.
|

\
|
mol
g 0 . 18


+ 0.25 mol O
2 |
.
|

\
|
mol
g 0 . 32
+ (mass of A)

Mass of A in 1.00 mol X = 227 g 132 g 45.0 g 8.0 g = 42 g A

To determine A, we need the moles of A produced. The total moles of gas produced can be
determined from the gas law data provided in the problem. Because H
2
O(l) is a product, we need
to subtract
O H
2
P from the total pressure.

n
total
=
RT
PV
; P
total
= P
gases
+
O H
2
P ; P
gases
= 778 torr 31 torr = 747 torr
392 CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY

1V = height area; area = r
2
; V = (59.8 cm)()(8.00 cm)
2
|
|
.
|

\
|
3
cm 1000
L 1
= 12.0 L

T = 273.15 + 29.52 = 302.67 K

n
total
=
RT
PV
=
) K 67 . 302 (
mol K
atm L 08206 . 0
) L 0 . 12 (
torr 760
atm 1
torr 747
|
|
.
|

\
|
= 0.475 mol = mol CO
2
+ mol O
2
+ mol A
Mol A = 0.475 mol total 0.300 mol CO
2
0.025 mol O
2
= 0.150 mol A

Because 0.100 mol X reacted, 1.00 mol X would contain 1.50 mol A, which from a previous
calculation represents 42 g A.

Molar mass of A =
A mol 50 . 1
A g 42
= 28 g/mol

Because A is a gaseous element, the only element that is a gas and has this molar mass is N
2
(g).
Thus A = N
2
(g).

a. Now we can determine the formula of X.

X 3 CO
2
(g) + 2.5 H
2
O(l) + 0.25 O
2
(g) + 1.5 N
2
(g). For a balanced reaction, X =
C
3
H
5
N
3
O
9
, which, for your information, is nitroglycerine.

b. w = PV = 778 torr
|
|
.
|

\
|
torr 760
atm 1
(12.0 L 0) = 12.3 L atm

12.3 L atm
|
|
.
|

\
|


1 1
1 1
mol K atm L 08206 . 0
mol K J 3145 . 8
= 1250 J = 1.25 kJ, w = 1.25 kJ


c. E = q + w, where q = H since at constant pressure. For 1 mol of X decomposed:

w = 1.25 kJ/0.100 mol = 12.5 kJ/mol

E = H + w = 1893 kJ/mol + (12.5 kJ/mol) = 1906 kJ/mol

108. 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
CHAPTER 9 ENERGY, ENTHALPY, AND THERMOCHEMISTRY 393

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 is less dense 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.

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