CHAPTER 6

THERMOCHEMISTRY

Questions
13. 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.

14. 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.

15. 2 C8H18(l) + 25 O2(g) → 16 CO2(g) + 18 H2O(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 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.

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

17. a. The ∆H value for a reaction is specific to the coefficients in the balanced equation. Be-
cause the coefficient in front of H2O is a two, 891 kJ of heat is released when 2 mol of
H2O are produced. For 1 mol of H2O formed, 891/2 = 446 kJ of heat is released.

b. 891/2 = 446 kJ of heat released for each mol of O2 reacted.

18. Water has a relatively large heat capacity, so it takes a lot of energy to increase the
temperature of a large body of water. Because of this, the temperature fluctuations of a large
body of water (oceans) are small compared to the temperatures fluctuations of air. Hence,
oceans act as a heat reservoir for areas close to them which results in smaller temperature
changes as compared to areas farther away from the oceans.

198
CHAPTER 6 THERMOCHEMISTRY 199

19. When the enthalpy change for a reaction is negative as is the case here, the reaction is
exothermic. This means that heat is produced (evolved) as C6H12O6(aq) is converted into
products.

20. A coffee-cup calorimeter is at constant (atmospheric) pressure. The heat released or gained
for a reaction at constant pressure is equal to the enthalpy change (∆H) for that reaction. A
bomb calorimeter is at constant volume. The heat released or gained for a reaction at constant
volume is equal to the internal energy change (∆E) for that reaction.

21. Given:

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆H = −891 kJ

CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) ∆H = −803 kJ

Using Hess’s law:

H2O(l) + 1/2 CO2(g) → 1/2 CH4(g) + O2(g) ∆H1 = −1/2(−891 kJ)

1/2 CH4(g) + O2(g) → 1/2 CO2(g) + H2O(g) ∆H2 = 1/2(−803 kJ)
H2O(l) → H2O(g) ∆H = ∆H1 + ∆H2 = 44 kJ

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

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

22. 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.

23. The zero point for ΔH of values are elements in their standard state. All substances are meas-
ured in relationship to this zero point.

24. a. CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l) ∆H = ?

Utilizing Hess’s law:

Reactants → Standard State Elements ∆H = ∆Ha + ∆Hb = 75 + 0 = 75 kJ

Standard State Elements → Products ∆H = ∆Hc + ∆Hd = –394 – 572 = –966 kJ
Reactants → Products ∆H = 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
200 CHAPTER 6 THERMOCHEMISTRY

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 ∆H° =
+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 [CH4(g) + 2 O2(g)] which has an enthalpy change of −75 kJ. All of the
signs are reversed because the entire process is reversed.

25. 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.

26. From the photosynthesis reaction, CO2(g) is used by plants to convert water into glucose and
oxygen. If the plant population is significantly reduced, not as much CO2 will be consumed
in the photosynthesis reaction. As the CO2 levels of the atmosphere increase, the greenhouse
effect due to excess CO2 in the atmosphere will become worse.

27. Fossil fuels contain carbon; the incomplete combustion of fossil fuels produces CO(g) instead
of CO2(g). This occurs when the amount of oxygen reacting is not sufficient to convert all the
carbon to CO2. Carbon monoxide is a poisonous gas to humans.

28. Advantages: H2 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

1 1 kg m 2
29. KE = mv2; convert mass and velocity to SI units. 1 J =
2 s2
1 lb 1 kg
Mass = 5.25 oz × × = 0.149 kg
16 oz 2.205 lb

1.0 × 10 2 mi 1h 1 min 1760 yd 1m 45 m

Velocity = × × × × =
h 60 min 60 s mi 1.094 yd s
2
1 1  45 m 
KE = mv2 = × 0.149 kg ×   = 150 J
2 2  s 
CHAPTER 6 THERMOCHEMISTRY 201

2 2
1 1  1.0 m  1 1  2.0 m 
30. KE = mv2 = × 2.0 kg ×   = 1.0 J; KE = mv2 = × 1.0 kg ×  
2 2  s  2 2  s 
= 2.0 J
The 1.0-kg object with a velocity of 2.0 m/s has the greater kinetic energy.

31. 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.

9.81 m 196 kg m 2
32. Ball A: PE = mgz = 2.00 kg × × 10.0 m = = 196 J
s2 s2
At point I: All this energy is transferred to ball B. All of B's energy is kinetic energy at this
point. Etotal = KE = 196 J. At point II, the sum of the total energy will equal
196 J.
9.81 m
At point II: PE = mgz = 4.00 kg × × 3.00 m = 118 J
s2
KE = Etotal − PE = 196 J − 118 J = 78 J

Heat and Work

33. ΔE = q + w = 45 kJ + (−29 kJ) = 16 kJ

34. a. ΔE = q + w = −47 kJ + 88 kJ = 41 kJ

b. ΔE = 82 − 47 = 35 kJ c. ΔE = 47 + 0 = 47 kJ

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

35. Step 1: ΔE1 = q + w = 72 J + 35 J = 107 J; step 2: ΔE2 = 35 J − 72 J = −37 J

ΔEoverall = ΔE1 + ΔE2 = 107 J − 37 J = 70. J

36. This is a cyclic process (has the same initial and final state). For any cyclic process the
change in a state function like ΔE is zero. For the two step process, ΔEoverall = ΔE1 + ΔE2 = 0,
so ΔE2 = −ΔE1.
Step 1: ΔE1 = q + w = 35 J + 25 J = 60. J
Step 2: ΔE2 = −ΔE1 = −60. J = q + w, −60. J = −5 + w, w = −55 J
The system does 55 J of work on the surroundings in step 2.
202 CHAPTER 6 THERMOCHEMISTRY

37. ΔE = 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

38. a. ΔE = q + w = −23 J + 100. J = 77 J

101.3 J
b. w = −PΔV = −1.90 atm(2.80 L − 8.30 L) = 10.5 L atm × = 1060 J
L atm

ΔE = q + w = 350. J + 1060 = 1410 J

101.3 J
c. w = −PΔV = −1.00 atm(29.1 L − 11.2 L) = −17.9 L atm × = −1810 J
L atm

ΔE = q + w = 1037 J − 1810 J = −770 J

39. w = −PΔV; we need the final volume of the gas. Because T and n are constant, P1V1 = P2V2.
V1 P1 10.0 L(15.0 atm)
V2 = = = 75.0 L
P2 2.00 atm

101.3 J 1 kJ
w = −PΔV = −2.00 atm(75.0 L − 10.0 L) = −130. L atm × ×
L atm 1000 J
= −13.2 kJ = work
40. w = −210. J = −PΔV, −210 J = −P(25 L − 10. L), P = 14 atm

41. In this problem, q = w = −950. J.

1 L atm
−950. J × = −9.38 L atm of work done by the gases
101.3 J
− 650.
w = −PΔV, −9.38 L atm = atm × (Vf − 0.040 L), Vf − 0.040 = 11.0 L, Vf = 11.0 L
760

1 L atm
42. ΔE = q + w, −102.5 J = 52.5 J + w, w = −155.0 J × = −1.530 L atm
101.3 J

w = −PΔV, −1.530 L atm = −0.500 atm × ΔV, ΔV = 3.06 L

ΔV = Vf – Vi, 3.06 L = 58.0 L − Vi, Vi = 54.9 L = initial volume

20.8 J
43. q = molar heat capacity × mol × ΔT = o
× 39.1 mol × (38.0 − 0.0)°C = 30,900 J
C mol
= 30.9 kJ
101.3 J
w = −PΔV = −1.00 atm × (998 L − 876 L) = −122 L atm × = −12,400 J = −12.4 kJ
L atm

ΔE = q + w = 30.9 kJ + (−12.4 kJ) = 18.5 kJ

CHAPTER 6 THERMOCHEMISTRY 203

44. H2O(g) → H2O(l); ΔE = q + w; q = −40.66 kJ; w = −PΔV

18.02 g 1 cm 3
Volume of 1 mol H2O(l) = 1.000 mol H2O(l) × × = 18.1 cm3 = 18.1 mL
mol 0.996 g

101.3 J
w = −PΔV = −1.00 atm × (0.0181 L − 30.6 L) = 30.6 L atm × = 3.10 × 103 J
L atm
= 3.10 kJ
ΔE = q + w = −40.66 kJ + 3.10 kJ = −37.56 kJ

Properties of Enthalpy
45. 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.

46. 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 H2SO4(aq) will get very hot and
possibly boil unless cooling is provided.

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

b. Heat is released as CH4 is burned, so this is an exothermic process.

c. Heat is released to the water (it gets hot) as H2SO4 is added, so this is an exothermic
process.

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

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

b. H2O(g) → H2O(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.

49. 4 Fe(s) + 3 O2(g) → 2 Fe2O3(s) ΔH = −1652 kJ; note that 1652 kJ of heat is released when
4 mol Fe reacts with 3 mol O2 to produce 2 mol Fe2O3.
− 1652 kJ
a. 4.00 mol Fe × = −1650 kJ; 1650 kJ of heat released
4 mol Fe
− 1652 kJ
b. 1.00 mol Fe2O3 × = −826 kJ; 826 kJ of heat released
2 mol Fe 2 O 3
204 CHAPTER 6 THERMOCHEMISTRY

1 mol Fe − 1652 kJ
c. 1.00 g Fe × × = −7.39 kJ; 7.39 kJ of heat released
55.85 g 4 mol Fe
1 mol Fe − 1652 kJ
d. 10.0 g Fe × × = −73.9 kJ
55.85 g Fe 4 mol Fe
1 mol O 2 − 1652 kJ
2.00 g O2 × × = −34.4 kJ
32.00 g O 2 3 mol O 2

Because 2.00 g O2 releases the smaller quantity of heat, O2 is the limiting reactant and
34.4 kJ of heat can be released from this mixture.

− 572 kJ
50. a. 1.00 mol H2O × = −286 kJ; 286 kJ of heat released
2 mol H 2 O
1 mol H 2 − 572 kJ
b. 4.03 g H2 × × = −572 kJ; 572 kJ of heat released
2.016 g H 2 2 mol H 2
1 mol O 2 − 572 kJ
c. 186 g O2 × × = −3320 kJ; 3320 kJ of heat released
32.00 g O 2 mol O 2
PV 1.0 atm × 2.0 × 10 8 L
d. n H2 = = = 8.2 × 106 mol H2
RT 0.08206 L atm
× 298 K
K mol
− 572 kJ
8.2 × 106 mol H2 × = −2.3 × 109 kJ; 2.3 × 109 kJ of heat released
2 mol H 2

51. From Example 6.3, q = 1.3 × 108 J. Because the heat transfer process is only 60.%
100. J
efficient, the total energy required is 1.3 × 108 J × = 2.2 × 108 J.
60. J

1 mol C3H 8 44.09 g C3H 8

Mass C3H8 = 2.2 × 108 J × × = 4.4 × 103 g C3H8
2221 × 10 J
3
mol C3H 8

1 mol CH 4 − 891 kJ
52. a. 1.00 g CH4 × × = −55.5 kJ
16.04 g CH 4 mol CH 4
1 atm
740. torr × × 1.00 × 10 3 L
PV 760 torr
b. n = = = 39.8 mol CH4
RT 0.08206 L atm
× 298 K
K mol
− 891 kJ
39.8 mol CH4 × = −3.55 × 104 kJ
mol CH 4

53. 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.
CHAPTER 6 THERMOCHEMISTRY 205

54. ∆H = ∆E + P∆V; from this equation, ∆H > ∆E when ∆V > 0, ∆H < ∆E when ∆V < 0, and ∆H
= ∆E when ∆V = 0. Concentrate on the moles of gaseous products versus the moles of
gaseous reactants to predict ∆V for a reaction.

a. There are 2 moles of gaseous reactants converting to 2 moles of gaseous products, so

∆V = 0. For this reaction, ∆H = ∆E.

b. There are 4 moles of gaseous reactants converting to 2 moles of gaseous products, so

∆V < 0 and ∆H < ∆E.

c. There are 9 moles of gaseous reactants converting to 10 moles of gaseous products, so

∆V > 0 and ∆H > ∆E.

Calorimetry and Heat Capacity

55. 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, H2O(l) with the largest heat
capacity value requires the largest amount of heat for this process. The amount of heat for
H2O(l) is:
4.18 J
energy = s × m × ΔT = o × 25.0 g × (37.0°C − 15.0°C) = 2.30 × 103 J
Cg
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:
1000 J
10.7 kJ ×
energy kJ = 140°C
ΔT = =
s×m 0.14 J
× 550. g
o
Cg

0.24 J 0.24 J
56. a. s = specific heat capacity = o
= since ΔT(K) = ΔT(°C)
Cg Kg
0.24 J
Energy = s × m × ΔT = o
× 150.0 g × (298 K − 273 K) = 9.0 × 102 J
Cg
0.24 J 107.9 g Ag 26 J
b. Molar heat capacity = o
× = o
Cg mol Ag C mol
0.24 J 1250
c. 1250 J = × m × (15.2°C − 12.0°C), m = = 1.6 × 103 g Ag
o
Cg 0.24 × 3.2

q 133 J
57. s = specific heat capacity = = = 0.890 J/°C•g
m × ∆T 5.00 g × (55.1 − 25.2) o C
From Table 6.1, the substance is solid aluminum.
206 CHAPTER 6 THERMOCHEMISTRY

585 J
58. s= = 0.139 J/°C•g
125.6 g × (53.5 − 20.0) o C
0.139 J 200.6 g 27.9 J
Molar heat capacity = o
× = o
Cg mol Hg C mol

59. | 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/°C•g = 4.18 J/K•g (ΔT in °C = ΔT in K).
4.18 J
Heat loss by hot water = s × m × ΔT = × 50.0 g × (330. K − Tf)
Kg
4.18 J
Heat gain by cooler water = × 30.0 g × (Tf − 280. K); heat loss = heat gain, so:
Kg
209 J 125 J
× (330. K − Tf) = × (Tf − 280. K)
K K
6.90 × 104 − 209Tf = 125Tf − 3.50 × 104, 334Tf = 1.040 × 105, Tf = 311 K

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

60. Heat loss by hot water = heat gain by cold water; keeping all quantities positive helps to
avoid sign errors:
4.18 J 4.18 J
o
× mhot × (55.0°C − 37.0°C) = o
× 90.0 g × (37.0°C − 22.0°C)
Cg Cg
90.0 g × 15.0o C
mhot = = 75.0 g hot water needed
18.0o C

61. Heat loss by Al + heat loss by Fe = heat gain by water; keeping all quantities positive to
avoid sign error:
0.89 J 0.45 J
o
× 5.00 g Al × (100.0°C − Tf) + o × 10.00 g Fe × (100.0 − Tf)
Cg Cg
4.18 J
= o × 97.3 g H2O × (Tf − 22.0°C)
Cg

4.5(100.0 − Tf) + 4.5(100.0 − Tf) = 407(Tf − 22.0), 450 − (4.5)Tf + 450 − (4.5)Tf
= 407Tf − 8950
416Tf = 9850, Tf = 23.7°C

120. J 50. J
62. Heat released to water = 5.0 g H2 × + 10. g methane × = 1.10 × 103 J
g H2 g methane
CHAPTER 6 THERMOCHEMISTRY 207

4.18 J
Heat gain by water = 1.10 × 103 J = o
× 50.0 g × ∆T
Cg
∆T = 5.26°C, 5.26°C = Tf − 25.0°C, Tf = 30.3°C

63. Heat gain by water = heat loss by metal = s × m × ΔT, where s = specific heat capacity.
4.18 J
Heat gain = o
× 150.0 g × (18.3°C − 15.0°C) = 2100 J
Cg
A common error in calorimetry problems is sign errors. Keeping all quantities positive helps
to eliminate sign errors.
2100 J
Heat loss = 2100 J = s × 150.0 g × (75.0°C − 18.3°C), s = = 0.25 J/°C•g
150.0 g × 56.7 o C

64. Heat gain by water = heat loss by Cu; keeping all quantities positive helps to avoid sign
errors:
4.18 J 0.20 J
o
× mass × (24.9°C − 22.3°C) = o
× 110. g Cu × (82.4°C − 24.9°C)
Cg Cg
11(mass) = 1300, mass = 120 g H2O

65. 50.0 × 10−3 L × 0.100 mol/L = 5.00 × 10−3 mol of both AgNO3 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

4.18 J
Heat gain = o
× 100.0 g × (23.40 − 22.60)°C = 330 J
Cg
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 ΔH (heat per mol AgCl formed) is negative with a
value of:
− 330 J 1 kJ
ΔH = −3
× = −66 kJ/mol
5.00 × 10 mol 1000 J
Note: Sign errors are common with calorimetry problems. However, the correct sign for ΔH
can be determined easily from the ΔT data; i.e., if ΔT of the solution increases, then the
reaction is exothermic because heat was released, and if ΔT 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 ΔH. This will help eliminate sign errors.

66. NaOH(aq) + HCl(aq) → NaCl(aq) + H2O(l)

We have a stoichiometric mixture. All of the NaOH and HCl will react.
1.0 mol
0.10 L × = 0.10 mol of HCl is neutralized by 0.10 mol NaOH.
L
208 CHAPTER 6 THERMOCHEMISTRY

Heat lost by chemicals = heat gained by solution

Volume of solution = 100.0 + 100.0 = 200.0 mL
4.18 J  1.0 g 
Heat gain = ×  200.0 mL ×  × (31.3 – 24.6)°C = 5.6 × 103 J = 5.6 kJ
 mL 
o
Cg

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 ΔH 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 ΔH. This will help eliminate sign errors.
− 5.6 kJ
ΔH = = −56 kJ/mol
0.10 mol

67. 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
ΔH can easily be obtained from the ΔT data. When working calorimetry problems, keep all
quantities positive (ignore signs). When finished, deduce the correct sign for ΔH. For this
problem, T decreases as KBr dissolves, so ΔH is positive; the dissolution of KBr is
endothermic (absorbs heat).
4.18 J
Heat lost by solution = o
× 136 g × (24.2°C − 21.1°C) = 1800 J = heat gained by KBr
Cg
1800 J
ΔH in units of J/g = = 170 J/g
10.5 g KBr
170 J 119.0 g KBr 1 kJ
ΔH in units of kJ/mol = × × = 20. kJ/mol
g KBr mol KBr 1000 J

68. NH4NO3(s) → NH4+(aq) + NO3−(aq) ΔH = ?; mass of solution = 75.0 g + 1.60 g = 76.6 g

Heat lost by solution = heat gained as NH4NO3 dissolves. To help eliminate sign errors, we
will keep all quantities positive (q and ΔT) and then deduce the correct sign for ΔH at the end
of the problem. Here, because temperature decreases as NH4NO3 dissolves, heat is absorbed
as NH4NO3 dissolves, so this is an endothermic process (ΔH is positive).
4.18 J
Heat lost by solution = o
× 76.6 g × (25.00 − 23.34)°C = 532 J
Cg
Heat gained as NH4NO3 dissolves = 532 J
532 J 80.05 g NH 4 NO 3 1 kJ
ΔH = × × = 26.6 kJ/mol NH4NO3 dissolving
1.60 g NH 4 NO 3 mol NH 4 NO 3 1000 J

69. Because ΔH is exothermic, the temperature of the solution will increase as CaCl2(s)
dissolves. Keeping all quantities positive:
1 mol CaCl 2 81.5 kJ
heat loss as CaCl2 dissolves = 11.0 g CaCl2 × × = 8.08 kJ
110.98 g CaCl 2 mol CaCl 2
CHAPTER 6 THERMOCHEMISTRY 209

4.18 J
heat gained by solution = 8.08 × 103 J = o
× (125 + 11.0) g × (Tf − 25.0°C)
Cg
8.08 × 103
Tf − 25.0°C = = 14.2°C, Tf = 14.2°C + 25.0°C = 39.2°C
4.18 × 136

0.500 mol HCl 118 kJ heat released

70. 0.1000 L × × = 2.95 kJ of heat released if HCl limiting
L 2 mol HCl

0.100 mol Ba(OH) 2 118 kJ heat

0.3000 L × × = 3.54 kJ heat released if Ba(OH)2 limiting
L mol Ba(OH) 2
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.
4.18 J
Heat gained by solution = 2.95 × 103 J = o
× 400.0 g × ΔT
Cg

ΔT = 1.76°C = Tf − Ti = Tf − 25.0°C, Tf = 26.8°C

1.56 kJ
71. Heat gain by calorimeter = o
× 3.2°C = 5.0 kJ = heat loss by quinine
C
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, qV = ∆E.
− 5.0 kJ − 25 kJ 108.09 g
ΔEcomb = = −25 kJ/g; ΔEcomb = × = −2700 kJ/mol
0.1964 g g mol

2.67 kJ
72. Heat loss by butter = heat gain by calorimeter = (27.3°C − 23.5°C) × o
= 10. kJ
C
Heat loss = 10. kJ, which is the heat evolved (exothermic reaction) by the combustion of
0.30 g butter. Because we are at constant volume, qV = ∆E.
− 10. kJ
ΔEcomb = = −33 kJ/g
0.30 g

1 mol CH 4 802 kJ
73. a. Heat gain by calorimeter = heat loss by CH4 = 6.79 g CH4 × ×
16.04 g mol
= 340. kJ
340. kJ
Heat capacity of calorimeter = = 31.5 kJ/°C
10.8 o C
31. 5 kJ
b. Heat loss by C2H2 = heat gain by calorimeter = 16.9°C × o
= 532 kJ
C
A bomb calorimeter is at constant volume, so the heat released/gained = qV = ∆E:
− 532 kJ 26.04 g
ΔEcomb = × = −1.10 × 103 kJ/mol
12.6 g C 2 H 2 mol C 2 H 2
210 CHAPTER 6 THERMOCHEMISTRY

74. 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.
26.42 kJ
Heat loss = 0.1584 g × = 4.185 kJ
g
4.185 kJ
Heat gain = 4.185 kJ = Ccal × ΔT, Ccal = = 1.65 kJ/°C
2.54 o C
Now we can calculate the heat of combustion of vanillin. Heat loss = heat gain.
1.65 kJ
Heat gain by calorimeter = o
× 3.25°C = 5.36 kJ
C
Heat loss = 5.36 kJ, which is the heat evolved by combustion of the vanillin.
− 5.36 kJ − 25.2 kJ 152.14 g
∆Ecomb = = −25.2 kJ/g; ∆Ecomb = × = −3830 kJ/mol
0.2130 g g mol

Hess's Law
75. Information given:
C(s) + O2(g) → CO2(g) ΔH = −393.7 kJ
CO(g) + 1/2 O2(g) → CO2(g) ΔH = −283.3 kJ

Using Hess’s law:

2 C(s) + 2 O2(g) → 2 CO2(g) ΔH1 = 2(−393.7 kJ)
2 CO2(g) → 2 CO(g) + O2(g) ΔH2 = −2(−283.3 kJ)
2 C(s) + O2(g) → 2 CO(g) ΔH = ΔH1 + ΔH2 = −220.8 kJ

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

76. Given:
C4H4(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l) ΔHcomb = −2341 kJ
C4H8(g) + 6 O2(g) → 4 CO2(g) + 4 H2O(l) ΔHcomb = −2755 kJ
H2(g) + 1/2 O2(g) → H2O(l) ΔHcomb = −286 kJ

By convention, H2O(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 O2(g).

Using Hess’s law to solve:

C4H4(g) + 5 O2(g) → 4 CO2(g) + 2 H2O(l) ΔH1 = −2341 kJ
4 CO2(g) + 4 H2O(l) → C4H8(g) + 6 O2(g) ΔH2 = −(−2755 kJ)
2 H2(g) + O2(g) → 2 H2O(l) ΔH3 = 2(−286 kJ)
C4H4(g) + 2 H2(g) → C4H8(g) ΔH = ΔH1 + ΔH2 + ΔH3 = −158 kJ
CHAPTER 6 THERMOCHEMISTRY 211

77. 2 N2(g) + 6 H2(g) → 4 NH3(g) ΔH = −2(92 kJ)

6 H2O(g) → 6 H2(g) + 3 O2(g) ΔH = −3(−484 kJ)
2 N2(g) + 6 H2O(g) → 3 O2(g) + 4 NH3(g) ΔH = 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.

78. ClF + 1/2 O2 → 1/2 Cl2O + 1/2 F2O ΔH = 1/2(167.4 kJ)

1/2 Cl2O + 3/2 F2O → ClF3 + O2 ΔH = −1/2(341.4 kJ)
F2 + 1/2 O2 → F2O ΔH = 1/2(−43.4 kJ)
ClF(g) + F2(g) → ClF3 ΔH = −108.7 kJ

79. C6H4(OH)2 → C6H4O2 + H2 ΔH = 177.4 kJ

H2O2 → H2 + O2 ΔH = −(−191.2 kJ)
2 H2 + O2 → 2 H2O(g) ΔH = 2(−241.8 kJ)
2 H2O(g) → 2 H2O(l) ΔH = 2(−43.8 kJ)
C6H4(OH)2(aq) + H2O2(aq) → C6H4O2(aq) + 2 H2O(l) ΔH = −202.6 kJ

80. 2 NH3 + 3 N2O → 4 N2 + 3 H2O ΔH = −1010. kJ

3 N2H4 + 3 H2O → 3 N2O + 9 H2 ΔH = −3(−317 kJ)
9 H2 + 9/2 O2 → 9 H2O ΔH = 9(−286 kJ)
4 N2 + 8 H2O → 4 N2H4 + 4 O2 ΔH = −4(−623 kJ)
2 NH3(g) + 1/2 O2(g) → N2H4(l) + H2O(g) ΔH = −141 kJ

81. CaC2 → Ca + 2 C ΔH = −(−62.8 kJ)

CaO + H2O → Ca(OH)2 ΔH = −653.1 kJ
2 CO2 + H2O → C2H2 + 5/2 O2 ΔH = −(−1300. kJ)
Ca + 1/2 O2 → CaO ΔH = −635.5 kJ
2 C + 2 O2 → 2 CO2 ΔH = 2(−393.5 kJ)
CaC2(s) + 2 H2O(l) → Ca(OH)2(aq) + C2H2(g) ΔH = −713 kJ

82. P4O10 → P4 + 5 O2 ΔH = −(−2967.3 kJ)

10 PCl3 + 5 O2 → 10 Cl3PO ΔH = 10(−285.7 kJ)
6 PCl5 → 6 PCl3 + 6 Cl2 ΔH = −6(−84.2 kJ)
P4 + 6 Cl2 → 4 PCl3 ΔH = −1225.6
P4O10(s) + 6 PCl5(g) → 10 Cl3PO(g) ΔH = −610.1 kJ

Standard Enthalpies of Formation

83. 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 ∆H of are:

Na(s) + 1/2 Cl2(g) → NaCl(s); H2(g) + 1/2 O2(g) → H2O(l)

212 CHAPTER 6 THERMOCHEMISTRY

6 C(graphite, s) + 6 H2(g) + 3 O2(g) → C6H12O6(s)

Pb(s) + S(rhombic, s) + 2 O2(g) → PbSO4(s)

84. a. Aluminum oxide = Al2O3; 2 Al(s) + 3/2 O2(g) → Al2O3(s)

b. C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(l)

c. NaOH(aq) + HCl(aq) → H2O(l) + NaCl(aq)

d. 2 C(graphite, s) + 3/2 H2(g) + 1/2 Cl2(g) → C2H3Cl(g)

e. C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l)

Note: ΔHcomb values assume 1 mole of compound combusted.

f. NH4Br(s) → NH4+(aq) + Br−(aq)

85. In general, ΔH° = ∑ np ΔH f , products − ∑ nr ΔH f , reactants , and all elements in their standard
state have ΔH f = 0 by definition.

a. The balanced equation is 2 NH3(g) + 3 O2(g) + 2 CH4(g) → 2 HCN(g) + 6 H2O(g).

ΔH° = (2 mol HCN × ΔH f , HCN + 6 mol H2O(g) × ΔH f , H 2O )

− (2 mol NH3 × ΔH f , NH 3 + 2 mol CH4 × ∆H f , CH )
4

ΔH° = [2(135.1) + 6(−242)] − [2(−46) + 2(−75)] = −940. kJ

b. Ca3(PO4)2(s) + 3 H2SO4(l) → 3 CaSO4(s) + 2 H3PO4(l)

  − 1433 kJ   − 1267 kJ  
ΔH° = 3 mol CaSO 4 (s)  + 2 mol H 3 PO 4 (l) 
  mol   mol  

  − 4126 kJ   − 814 kJ  
− 1 mol Ca 3 (PO 4 ) 2 (s)  + 3 mol H 2SO 4 (l) 
  mol   mol  
ΔH° = −6833 kJ − (−6568 kJ) = −265 kJ

c. NH3(g) + HCl(g) → NH4Cl(s)

ΔH° = (1 mol NH4Cl × ΔH f , NH 4Cl ) − (1 mol NH3 × ΔH f , NH 3 + 1 mol HCl × ΔH f , HCl )

  − 314 kJ    − 46 kJ   − 92 kJ 
ΔH° = 1 mol   − 1 mol   + 1 mol  
  mol    mol   mol 

ΔH° = −314 kJ + 138 kJ = −176 kJ

CHAPTER 6 THERMOCHEMISTRY 213

86. a. The balanced equation is C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(g).

  − 393.5 kJ   − 242 kJ    − 278 kJ 
ΔH° = 2 mol   + 3 mol   − 1 mol  
  mol   mol    mol 
ΔH° = −1513 kJ − (−278 kJ) = −1235 kJ

b. SiCl4(l) + 2 H2O(l) → SiO2(s) + 4 HCl(aq)

Because HCl(aq) is H+(aq) + Cl−(aq), ΔH f = 0 − 167 = −167 kJ/mol.

  − 167 kJ   − 911 kJ    − 687 kJ   − 286 kJ 

ΔH° = 4 mol   + 1 mol   − 1 mol   + 2 mol  
  mol   mol    mol   mol 
ΔH° = −1579 kJ − (−1259 kJ) = −320. kJ

c. MgO(s) + H2O(l) → Mg(OH)2(s)

  − 925 kJ    − 602 kJ   − 286 kJ 
ΔH° = 1 mol   − 1 mol   + 1 mol 
  mol    mol   mol 
ΔH° = −925 kJ − (−888 kJ) = −37 kJ

87. a. 4 NH3(g) + 5 O2(g) → 4 NO(g) + 6 H2O(g); ΔH° = ∑ np ΔH f , products − ∑ nr ΔH f , reactants

  90. kJ   − 242 kJ    − 46 kJ 
ΔH° = 4 mol   + 6 mol   − 4 mol   = −908 kJ
  mol   mol    mol 
2 NO(g) + O2(g) → 2 NO2(g)

  34 kJ    90. kJ  
ΔH° = 2 mol   − 2 mol    = −112 kJ
  mol    mol  

3 NO2(g) + H2O(l) → 2 HNO3(aq) + NO(g)

  − 207 kJ   90. kJ     34 kJ   − 286 kJ 
ΔH° = 2 mol   + 1 mol    − 3 mol   + 1 mol  
  mol   mol     mol   mol 
−140. kJ
Note: All ΔH f values are assumed ±1 kJ.

b. 12 NH3(g) + 15 O2(g) → 12 NO(g) + 18 H2O(g)

12 NO(g) + 6 O2(g) → 12 NO2(g)
12 NO2(g) + 4 H2O(l) → 8 HNO3(aq) + 4 NO(g)
4 H2O(g) → 4 H2O(l)
12 NH3(g) + 21 O2(g) → 8 HNO3(aq) + 4 NO(g) + 14 H2O(g)

The overall reaction is exothermic because each step is exothermic.

214 CHAPTER 6 THERMOCHEMISTRY

 − 416 kJ 
88. 4 Na(s) + O2(g) → 2 Na2O(s) ΔH° = 2 mol   = −832 kJ
 mol 
2 Na(s) + 2 H2O(l) → 2 NaOH(aq) + H2(g)

  − 470. kJ     − 286 kJ 
ΔH° = 2 mol    − 2 mol   = −368 kJ
  mol     mol 
2Na(s) + CO2(g) → Na2O(s) + CO(g)

  − 416 kJ   − 110.5 kJ    − 393.5 kJ 

ΔH° = 1 mol   + 1 mol   − 1 mol   = −133 kJ
  mol   mol    mol 

In Reactions 2 and 3, sodium metal reacts with the "extinguishing agent." Both reactions are
exothermic, and each reaction produces a flammable gas, H2 and CO, respectively.

89. 3 Al(s) + 3 NH4ClO4(s) → Al2O3(s) + AlCl3(s) + 3 NO(g) + 6 H2O(g)

  − 242 kJ   90. kJ   − 704 kJ   − 1676 kJ 

ΔH° = 6 mol   + 3 mol   + 1 mol   + 1 mol  
  mol   mol   mol   mol 

  − 295 kJ 
− 3 mol   = −2677 kJ
  mol 

90. 5 N2O4(l) + 4 N2H3CH3(l) → 12 H2O(g) + 9 N2(g) + 4 CO2(g)

  − 242 kJ   − 393.5 kJ  
ΔH° = 12 mol   + 4 mol  
  mol   mol  

  − 20. kJ   54 kJ 
− 5 mol   + 4 mol   = −4594 kJ
  mol   mol 

91. 2 ClF3(g) + 2 NH3(g) → N2(g) + 6 HF(g) + Cl2(g) ΔH° = −1196 kJ

ΔH° = (6 ΔH of , HF ) − (2 ΔH of, ClF3 + 3 ΔH of, NH 3 )

 − 271 kJ   − 46 kJ 
−1196 kJ = 6 mol   − 2 ΔH f , ClF3 − 2 mol  
o

 mol   mol 
(−1626 + 92 + 1196) kJ − 169 kJ
−1196 kJ = −1626 kJ − 2 ΔH of , ClF3 + 92 kJ, ΔH of , ClF3 = =
2 mol mol

92. C2H4(g) + 3 O2(g) → 2 CO2(g) + 2 H2O(l) ΔH° = −1411.1 kJ

ΔH° = −1411.1 kJ = 2(−393.5) kJ + 2(−285.8) kJ − ΔH f , C 2 H 4

−1411.1 kJ = −1358.6 kJ − ΔH f , C 2 H 4 , ΔH f , C 2 H 4 = 52.5 kJ/mol

CHAPTER 6 THERMOCHEMISTRY 215

Energy Consumption and Sources

93. C(s) + H2O(g) → H2(g) + CO(g) ΔH° = −110.5 kJ − (−242 kJ) = 132 kJ

94. CO(g) + 2 H2(g) → CH3OH(l) ΔH° = −239 kJ − (−110.5 kJ) = −129 kJ

95. C2H5OH(l) + 3 O2(g) → 2 CO2(g) + 3 H2O(l)

ΔH° = [2(−393.5 kJ) + 3(−286 kJ)] − (−278 kJ) = −1367 kJ/mol ethanol
− 1367 kJ 1 mol
× = −29.67 kJ/g
mol 46.07 g

96. CH3OH(l) + 3/2 O2(g) → CO2(g) + 2 H2O(l)

ΔH° = [−393.5 kJ + 2(−286 kJ)] − (−239 kJ) = −727 kJ/mol CH3OH

− 727 kJ 1 mol
× = −22.7 kJ/g versus −29.67 kJ/g for ethanol (from Exercise 95)
mol 32.04 g

Ethanol has a slightly higher fuel value per gram than methanol.

97. C3H8(g) + 5 O2(g) → 3 CO2(g) + 4 H2O(l)

ΔH° = [3(−393.5 kJ) + 4(−286 kJ)] − (−104 kJ) = −2221 kJ/mol C3H8
− 2221 kJ 1 mol − 50.37 kJ
× = versus −47.7 kJ/g for octane (Example 6.11)
mol 44.09 g g
The fuel values are very close. An advantage of propane is that it burns more cleanly. The
boiling point of propane is −42°C. Thus it is more difficult to store propane, and there are
extra safety hazards associated with using high-pressure compressed-gas tanks.

98. 1 mole of C2H2(g) and 1 mole of C4H10(g) have equivalent volumes at the same T and P.
Enthalpy of combustion per volume of C 2 H 2 enthalpy of combustion per mol of C 2 H 2
=
Enthalpy of combustion per volume of C 4 H10 enthalpy of combustion per mol of C 4 H10

− 49.9 kJ 26.04 g C 2 H 2
×
Enthalpy of combustion per volume of C 2 H 2 g C2H 2 mol C 2 H 2
= = 0.452
Enthalpy of combustion per volume of C 4 H10 − 49.5 kJ 58.12 g C 4 H10
×
g C 4 H10 mol C 4 H10
More than twice the volume of acetylene is needed to furnish the same energy as a given
volume of butane.

99. The molar volume of a gas at STP is 22.42 L (from Chapter 5).
1 mol CH 4 22.42 L CH 4
4.19 × 106 kJ × × = 1.05 × 105 L CH4
891 kJ mol CH 4
216 CHAPTER 6 THERMOCHEMISTRY

3.785 L 1000 mL 1.00 g

100. Mass of H2O = 1.00 gal × × × = 3790 g H2O
gal L mL
4.18 J
Energy required (theoretical) = s × m × ΔT = o
× 3790 g × 10.0 °C = 1.58 × 105 J
Cg

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:
100. J
1.58 × 105 J × = 1.98 × 105 J
80.0 J
1 mol C 2 H 2 26.04 g C 2 H 2
Mass of C2H2 = 1.98 × 105 J × × = 3.97 g C2H2
1300. × 10 J3
mol C 2 H 2

Additional Exercises
5500 kJ 1 mol H 2 O 18.02 g H 2 O
101. 2.0 h × × × = 4900 g = 4.9 kg H2O
h 40.6 kJ mol

102. From the problem, walking 4.0 miles consumes 400 kcal of energy.
454 g 7.7 kcal 4 mi 1h
1 lb fat × × × × = 8.7 h = 9 h
lb g 400 kcal 4 mi

103. a. 2 SO2(g) + O2(g) → 2 SO3(g); w = −PΔV; because the volume of the piston apparatus
decreased as reactants were converted to products (∆V < 0), w is positive (w > 0).

b. COCl2(g) → CO(g) + Cl2(g); because the volume increased (∆V > 0), w is negative
(w < 0).

c. N2(g) + O2(g) → 2 NO(g); because the volume did not change (∆V = 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 (ΔV 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 (ΔV 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), ΔV = 0 and w = 0.

104. a. N2(g) + 3 H2(g) → 2 NH3(g); from the balanced equation, 1 molecule of N2 will react
with 3 molecules of H2 to produce 2 molecules of NH3. So the picture after the reaction
should only have 2 molecules of NH3 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 N2 + 3 H2). After reaction,
only 2 molecules are present (2 NH3). Because the number of gas molecules decreases
CHAPTER 6 THERMOCHEMISTRY 217

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 NH3 and should be at a
volume which is one-half the original reactant container volume.

b. w = −P∆V; here the volume decreased, so ∆V is negative. When ∆V 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).

105. a. C12H22O11(s) + 12 O2(g) → 12 CO2(g) + 11 H2O(l)

b. A bomb calorimeter is at constant volume, so heat released = qV = ΔE:

− 24.00 kJ 342.30 g
ΔE = × = −5630 kJ/mol C12H22O11
1.46 g mol

106. w = −PΔV; Δn = 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 (Δn positive), the reaction will expand in volume
(ΔV positive), and the system will do work on the surroundings. For example, in reaction c,
Δn = 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 (Δn
negative), the reaction will contract in volume (ΔV negative), and the surroundings will do
compression work on the system, e.g., reaction a, where Δn = 0 − 1 = −1. When there is no
change in the moles of gas from reactants to products, ΔV = 0 and w = 0, e.g., reaction b,
where Δn = 2 − 2 = 0.

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

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

When ΔV = 0 (Δn = 0), then w = 0 (b).

107. The kcals in one serving size of cookies is:

8 kcal 4 kcal 4 kcal
4 g fat × + 20 g carbs × + 2 g protein × = 120 kcal
g fat g carb g protein
4.184 kJ 1 mile
120 kcal × × = 3.0 miles
kcal 170 kJ

108. 2 K(s) + 2 H2O(l) → 2 KOH(aq) + H2(g) ΔH° = 2(−481 kJ) − 2(−286 kJ) = −390. kJ
1 mol K − 390. kJ
5.00 g K × × = −24.9 kJ
39.10 g K 2 mol K
24.9 kJ of heat is released on reaction of 5.00 g K.
4.18 J 24,900
24,900 J = × (1.00 × 103 g) × ΔT, ΔT = = 5.96°C
g Co
4.18 × 1.00 × 103
Final temperature = 24.0 + 5.96 = 30.0°C
218 CHAPTER 6 THERMOCHEMISTRY

109. HNO3(aq) + KOH(aq) → H2O(l) + KNO3(aq) ΔH = −56 kJ

0.400 mol HNO 3 56 kJ heat released

0.2000 L × × = 4.5 kJ heat released if HNO3 limiting
L mol HNO3

0.500 mol KOH 56 kJ heat released

0.1500 L × × = 4.2 kJ heat released if KOH limiting
L mol KOH

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

110. 2 NO2 → 2 NO + 2 O ΔH = 2(233 kJ)

2 NO + 2 O3 → 2 NO2 + 2 O2 ΔH = 2(−199 kJ)
3 O2 → 2 O3 ΔH = −(−427 kJ)
O2(g) → 2 O(g) ΔH = 495 kJ

111. |qsurr| = |qsolution + qcal|; we normally assume that qcal 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 qcal, then qsurr is
too small, giving a calculated ∆H value that is less positive (smaller) than it should be.

112. The specific heat of water is 4.18 J/°C•g, which is equal to 4.18 kJ/°C•kg.
4.18 kJ
We have 1.00 kg of H2O, so: 1.00 kg × o
= 4.18 kJ/°C
C kg
This is the portion of the heat capacity that can be attributed to H2O.

Total heat capacity = Ccal + C H 2O , Ccal = 10.84 − 4.18 = 6.66 kJ/°C

113. Heat released = 1.056 g × 26.42 kJ/g = 27.90 kJ = heat gain by water and calorimeter
 4.18 kJ   6.66 kJ 
Heat gain = 27.90 kJ =  o × 0.987 kg × ΔT  +  o × ΔT 
 C kg   C 
27.90 = (4.13 + 6.66)ΔT = (10.79)ΔT, ΔT = 2.586°C

2.586°C = Tf − 23.32°C, Tf = 25.91°C

114. For Exercise 89, a mixture of 3 mol Al and 3 mol NH4ClO4 yields 2677 kJ of energy. The
mass of the stoichiometric reactant mixture is:
 26.98 g   117.49 g 
 3 mol ×  +  3 mol ×  = 433.41 g
 mol   mol 
− 2677 kJ
For 1.000 kg of fuel: 1.000 × 103 g × = −6177 kJ
433.41 g
CHAPTER 6 THERMOCHEMISTRY 219

In Exercise 90, we get 4594 kJ of energy from 5 mol of N2O4 and 4 mol of N2H3CH3. The
 92.02 g   46.08 g 
mass is  5 mol ×  +  4 mol ×  = 644.42 kJ.
 mol   mol 
− 4594 kJ
For 1.000 kg of fuel: 1.000 × 103 g × = −7129 kJ
644.42 g

Thus we get more energy per kilogram from the N2O4/N2H3CH3 mixture.

115. 1/2 D → 1/2 A + B ∆H = −1/6(−403 kJ)

1/2 E + F → 1/2 A ∆H = 1/2(−105.2 kJ)
1/2 C → 1/2 E + 3/2 D ∆H = 1/2(64.8 kJ)
F + 1/2 C → A + B + D ∆H = 47.0 kJ

116. To avoid fractions, let's first calculate ΔH for the reaction:

6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g)

6 FeO + 2 CO2 → 2 Fe3O4 + 2 CO ΔH° = −2(18 kJ)

2 Fe3O4 + CO2 → 3 Fe2O3 + CO ΔH° = −(−39 kJ)
3 Fe2O3 + 9 CO → 6 Fe + 9 CO2 ΔH° = 3(−23 kJ)
6 FeO(s) + 6 CO(g) → 6 Fe(s) + 6 CO2(g) ΔH° = −66 kJ
− 66 kJ
So for FeO(s) + CO(g) → Fe(s) + CO2(g), ΔH° = = −11 kJ.
6

117. a. ΔH° = 3 mol(227 kJ/mol) − 1 mol(49 kJ/mol) = 632 kJ

b. Because 3 C2H2(g) is higher in energy than C6H6(l), acetylene will release more energy
per gram when burned in air. Note that 3 moles of C2H2 has the same mass as 1 mole of
C6H6.

118. I(g) + Cl(g) → ICl(g) ΔH = −(211.3 kJ)

1/2 Cl2(g) → Cl(g) ΔH = 1/2(242.3 kJ)
1/2 I2(g) → I(g) ΔH = 1/2(151.0 kJ)
1/2 I2(s) → 1/2 I2(g) ΔH = 1/2(62.8 kJ)

1/2 I2(s) + 1/2 Cl2(g) → ICl(g) ΔH = 16.8 kJ/mol = ΔH of , ICl

119. Heat gained by water = heat lost by nickel = s × m × ΔT, where s = specific heat capacity.
4.18 J
Heat gain = o
× 150.0 g × (25.0°C − 23.5°C) = 940 J
Cg
A common error in calorimetry problems is sign errors. Keeping all quantities positive helps
to eliminate sign errors.
0.444 J 940
Heat loss = 940 J = × mass × (99.8 − 25.0) °C, mass = = 28 g
o
Cg 0.444 × 74.8
220 CHAPTER 6 THERMOCHEMISTRY

120. Cu + CuO → Cu2O ∆H° = −(11 kJ)

Cu2O + 1/2 O2 → 2 CuO ∆H° = 1/2(−288 kJ)

Cu(s) + 1/2 O2(g) → CuO(s) ∆H° = −155 kJ/mol = ∆H of, CuO

121. a. C2H4(g) + O3(g) → CH3CHO(g) + O2(g) ΔH° = −166 kJ − [143 kJ + 52 kJ] = −361 kJ

b. O3(g) + NO(g) → NO2(g) + O2(g) ΔH° = 34 kJ − [90. kJ + 143 kJ] = −199 kJ

c. SO3(g) + H2O(l) → H2SO4(aq) ΔH° = −909 kJ − [−396 kJ + (−286 kJ)] = −227 kJ

d. 2 NO(g) + O2(g) → 2 NO2(g) ΔH° = 2(34) kJ − 2(90.) kJ = −112 kJ

ChemWork Problems
1 mol He
122. 313 g He × = 78.2 mol; q = molar heat capacity × mol × ΔT
4.003 g He
20.8 J
q= o
× 78.2 mol × (−41.6°C) = −67,700 J = −67.7 kJ
C mol
101.3 J
w = −PΔV = −1.00 atm × (1643 L − 1910. L) = 267 L atm × = 2.70 × 104 J = 27.0 kJ
L atm
ΔE = q + w = −67.7 kJ kJ + 27.0 kJ = −40.7 kJ

123. Work is done by the surroundings on the system when there is a compression. This will occur
when the moles of gas decrease when going from reactants to products. This will occur for
reactions a and c. The other reactions have an increase in the moles of gas as reactants are
converted to products. In these reactions, the system does PV work on the surroundings.

124. Heat is released when water freezes and when H2 and O2 react to form water. So reactions b
and d are exothermic. All the other reactions refer to breaking a bond to form the individual
atoms. Energy must be added in order to break a bond so these are endothermic processes.

1 mol B 2 H 6 2035 kJ heat released

125. 54.0 g B2H6 × × = 3.97 × 103 kJ heat released
27.67 g B 2 H 6 mol B 2 H 6

126. V = 10.0 m × 4.0 m × 3.0 m = 1.2 × 102 m3 × (100 cm/m)3 = 1.2 × 108 cm3

Assuming the density of water is 1.0 g/cm3, the mass of water is 1.2 × 108 g.
4.18 J
q = specific heat capacity × mass × ΔT = o
× (1.2 × 108 g) × (24.6oC − 20.2oC)
Cg
q = 2.2 × 109 J = 2.2 × 106 kJ

127. HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq) ΔH = −56 kJ

0.50 mol HCl 56 kJ heat released
0.1500 L × × = 4.2 kJ heat released if HCl limiting
L mol HCl
CHAPTER 6 THERMOCHEMISTRY 221

1.00 mol NaOH 56 kJ heat released

0.0500 L × × = 2.8 kJ heat released if NaOH limiting
L mol NaOH
Because the NaOH reagent produces the smaller quantity of heat released, NaOH is limiting
and 4.2 kJ of heat released.
4.184 J
q = specific heat capacity × mass × ΔT, 2800 J = o
× 200.0 g × ΔT, ΔT = 3.3oC
Cg
This is an exothermic reaction so the temperature will increase by 3.3oC. Tfinal = 48.2oC +
3.3oC = 51.5oC

128. We want ΔH for N2H4(l) + O2(g) → N2(g) + 2 H2O(l). It will be easier to calculate ΔH for
the combustion of four moles of N2H4 because we will avoid fractions.

9 H2 + 9/2 O2 → 9 H2O ΔH = 9(−286 kJ)

3 N2H4 + 3 H2O → 3 N2O + 9 H2 ΔH = −3(−317 kJ)
2 NH3 + 3 N2O → 4 N2 + 3 H2O ΔH = −1010. kJ
N2H4 + H2O → 2 NH3 + 1/2 O2 ΔH = − (−143 kJ)
4 N2H4(l) + 4 O2(g) → 4 N2(g) + 8 H2O(l) ΔH = −2490. kJ
− 2490. kJ
For N2H4(l) + O2(g) → N2(g) + 2 H2O(l) ΔH = = −623 kJ
4
Note: By the significant figure rules, we could report this answer to four significant figures.
However, because the ΔH values given in the problem are only known to ±1 kJ, our final
answer will at best be ±1 kJ.
129. An element in its standard state has a standard enthalpy of formation equal to zero. At 25oC
and 1 atm, chlorine is found as Cl2(g) and hydrogen is found as H2(g). So these two elements
(a and b) have enthalpies of formation equal to zero. The other two choices (c and d) do not
have the elements in their standard state. The standard state for nitrogen is N2(g) and the
standard state for chlorine is Cl2(g).

Challenge Problems
130. 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).
101.3 J
Pathway 1: w = −PΔV = −2.00 atm(30.0 L − 10.0 L) = −40.0 L atm ×
L atm
= −4.05 × 103 J
101.3 J
Pathway 2: w = −PΔV = −1.00 atm(30.0 L − 10.0 L) = −20.0 L atm ×
L atm
= −2.03 × 103 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.
222 CHAPTER 6 THERMOCHEMISTRY

131. A(l) → A(g) ΔHvap = 30.7 kJ; at constant pressure, ΔH = qp = 30.7 kJ

Because PV = nRT, at constant pressure and temperature: w = −PΔV = −RTΔn, where:

Δn = moles of gaseous products − moles of gaseous reactants = 1 − 0 = 1

w = −RTΔn = −8.3145 J/K•mol(80. + 273 K)(1 mol) = −2940 J = −2.94 kJ

ΔE = q + w = 30.7 kJ + (−2.94 kJ) = 27.8 kJ

20. × 103 g C12 H 22 O11 1 mol C12 H 22 O11 5640 kJ

132. Energy needed = × × = 3.3 × 105 kJ/h
h 342.3 g C12 H 22 O11 mol

1000 J 1.0 kJ
Energy from sun = 1.0 kW/m2 = 1000 W/m2 = 2
=
sm s m2
1.0 kJ 60 s 60 min
10,000 m2 × 2
× × = 3.6 × 107 kJ/h
sm min h
energy used per hour 3.3 × 105 kJ
Percent efficiency = × 100 = × 100 = 0.92%
total energy per hour 3.6 × 10 7 kJ

40. kJ h 3600 s
133. Energy used in 8.0 hours = 40. kWh = × = 1.4 × 105 kJ
s h
10. kJ 60 s 60 min
Energy from the sun in 8.0 hours = 2
× × × 8.0 h = 2.9 × 104 kJ/m2
sm min h
Only 19% of the sunlight is converted into electricity:

0.19 × (2.9 × 104 kJ/m2) × area = 1.4 × 105 kJ, area = 25 m2

134. a. 2 HNO3(aq) + Na2CO3(s) → 2 NaNO3(aq) + H2O(l) + CO2(g)

ΔH° = [2(−467 kJ) + (−286 kJ) + (−393.5 kJ)] − [2(−207 kJ) + (−1131 kJ)] = −69 kJ
4 qt 946 mL 1.42 g
2.0 × 104 gallons × × × = 1.1 × 108 g of concentrated HNO3
gal qt mL
70.0 g HNO 3
1.1 × 108 g solution × = 7.7 × 107 g HNO3
100.0 g solution
1 mol HNO 3 1 mol Na 2 CO 3 105.99 g Na 2 CO 3
7.7 × 107 g HNO3 × × ×
63.02 g HNO 3 2 mol HNO 3 mol Na 2 CO 3
= 6.5 × 107 g Na2CO3
1 mol HNO 3 − 69 kJ
7.7 × 107 g HNO3 × × = −4.2 × 107 kJ
63.02 g HNO 3 2 mol HNO 3

4.2 × 107 kJ of heat was released.

CHAPTER 6 THERMOCHEMISTRY 223

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

4.18 kJ
135. 400 kcal × = 1.7 × 103 kJ ≈ 2 × 103 kJ
kcal

 1 kg  9.81 m  2.54 cm 1m 
PE = mgz = 180 lb ×  × ×  8 in × ×  = 160 J ≈ 200 J
 2.205 lb  s 2
 in 100 cm 

200 J of energy is needed to climb one step. The total number of steps to climb are:
1 step
2 × 106 J × = 1 × 104 steps
200 J

136. H2(g) + 1/2 O2(g) → H2O(l) ΔH° = ΔH of , H 2O ( l ) = −285.8 kJ; we want the reverse reaction:

H2O(l) → H2(g) + 1/2 O2(g) ΔH° = 285.8 kJ

w = −P∆V; because PV = nRT, at constant T and P, P∆V = RT∆n, where ∆n = moles of

gaseous products – moles of gaseous reactants. Here, Δn = (1 mol H2 + 0.5 mol O2) – (0) =
1.50 mol.

ΔE° = ΔH° − PΔV = ΔH° − RTΔn

 1 kJ 
ΔE° = 285.8 kJ −  8.3145 J/K • mol × 298 K × × 1.50 mol 
 1000 J 
ΔE° = 285.8 kJ − 3.72 kJ = 282.1 kJ

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

(1) q required to heat H2O(s) from −30. °C to 0°C; use the specific heat capacity of H2O(s)

(2) q required to convert 1 mol H2O(s) at 0°C into 1 mol H2O(l) at 0°C; use ∆Hfusion

(3) q required to heat H2O(l) from 0°C to 100.°C; use the specific heat capacity of H2O(l)

(4) q required to convert 1 mol H2O(l) at 100.°C into 1 mol H2O(g) at 100.°C;
use ∆Hvaporization

(5) q required to heat H2O(g) from 100.°C to 140.°C; use the specific heat capacity of
H2O(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 H2O(s) at −30.°C to H2O(g) at 140.°C.

q1 = 2.03 J/°C•g × 18.02 g × [0 – (−30.)]°C = 1.1 × 103 J

q2 = 1.00 mol × 6.02 × 103 J/mol = 6.02 × 103 J

224 CHAPTER 6 THERMOCHEMISTRY

q3 = 4.18 J/°C•g × 18.02 g × (100. – 0)°C = 7.53 × 103 J

q4 = 1.00 mol × 40.7 × 103 J/mol = 4.07 × 104 J

q5 = 2.02 J/°C•g × 18.02 g × (140. – 100.)°C = 1.5 × 103 J

qtotal = q1 + q2 + q3 + q4 + q5 = 5.69 × 104 J = 56.9 kJ

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

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

1 mol H 2 O 6.02 kJ
Heat gain = 109.5 g H2O × × = 36.6 kJ
18.02 g mol H 2 O
q 36,600 J
Specific heat of element = = = 0.375 J/°C•g
mass × ΔT 500.0 g × (195 − 0) o C

1 mol N 2 O
139. 88.0 g N2O × = 2.00 mol N2O
44.02 g N 2 O

At constant pressure, qp = ΔH.

ΔH = (2.00 mol)(38.7 J/°C • mol)(55°C − 165°C) = −8510 J = −8.51 kJ = qp

w = −PΔV = −nRΔT = −(2.00 mol)(8.3145 J/K•mol)(−110. K) = 1830 J = 1.83 kJ

ΔE = q + w = −8.51 kJ + 1.83 kJ = −6.68 kJ

Integrative Problems

140. Na2SO4(aq) + Ba(NO3)2(aq) → BaSO4(s) + 2 NaNO3(aq) ΔH = ?

2.00 mol Na 2 SO 4 1 mol BaSO 4
1.00 L × × = 2.00 mol BaSO4 if Na2SO4 limiting
L mol Na 2 SO 4
0.750 mol Ba ( NO 3 ) 2 1 mol BaSO 4
2.00 L × × = 1.50 mol BaSO4 if Ba(NO3)2 limiting
L mol Ba ( NO 3 ) 2

The Ba(NO3)2 reagent produces the smaller quantity of product, so Ba(NO3)2 is limiting and
1.50 mol BaSO4 can form.

Heat gain by solution = heat loss by reaction

1000 mL 2.00 g
Mass of solution = 3.00 L × × = 6.00 × 103 g
L mL
CHAPTER 6 THERMOCHEMISTRY 225

6.37 J
Heat gain by solution = o
× 6.00 × 103 g × (42.0 − 30.0)°C = 4.59 × 105 J
Cg

Because the solution gained heat, the reaction is exothermic; q = −4.59 × 105 J for the
reaction.
− 4.59 × 105 J
∆H = = −3.06 × 105 J/mol = −306 kJ/mol
1.50 mol BaSO 4

141. N2(g) + 2 O2(g) → 2 NO2(g) ∆H = 67.7 kJ

PV 3.50 atm × 0.250 L
n N2 = = = 2.86 × 10 −2 mol N2
RT 0.08206 L atm
× 373 K
K mol
PV 3.50 atm × 0.450 L
n O2 = = = 5.15 × 10 −2 mol O2
RT 0 .08206 L atm
× 373 K
K mol
2 mol NO 2
2.86 × 10 −2 mol N2 × = 5.72 × 10 −2 mol NO2 produced if N2 is limiting.
1 mol N 2
2 mol NO 2
5.15 × 10 −2 mol O2 × = 5.15 × 10 −2 mol NO2 produced if O2 is limiting.
2 mol O 2

O2 is limiting because it produces the smaller quantity of product. The heat required is:
67.7 kJ
5.15 × 10 −2 mol NO2 × = 1.74 kJ
2 mol NO 2

142. a. 4 CH3NO2(l) + 3 O2(g) → 4 CO2(g) + 2 N2(g) + 6 H2O(g)

ΔH orxn = −1288.5 kJ = [4 mol(−393.5 kJ/mol) + 6 mol(−242 kJ/mol)] −

[4 mol (∆H of , CH 3 NO 2 )]

Solving: ΔH of , CH 3 NO 2 = −434 kJ/mol

1 atm
b. Ptotal = 950. torr × = 1.25 atm; PN 2 = Ptotal × χ N 2 = 1.25 atm × 0.134
760 torr
= 0.168 atm
0.168 atm × 15.0 L
n N2 = = 0.0823 mol N2
0.08206 L atm
× 373 K
K mol
28.02 g N 2
0.0823 mol N2 × = 2.31 g N2
1 mol N 2

143. Heat loss by U = heat gain by heavy water; volume of cube = (cube edge)3
1.11 g
Mass of heavy water = 1.00 × 103 mL × = 1110 g
mL
226 CHAPTER 6 THERMOCHEMISTRY

4.211 J
Heat gain by heavy water = o
× 1110 g × (28.5 – 25.5)°C = 1.4 × 104 J
Cg
0.117 J
Heat loss by U = 1.4 × 104 J = o
× mass × (200.0 – 28.5)°C, mass = 7.0 × 102 g U
Cg
1 cm 3
7.0 × 102 g U × = 37 cm3; cube edge = (37 cm3)1/3 = 3.3 cm
19.05 g

Marathon Problems
144. Pathway I:

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

w = −PΔV = −(3.00 atm)(55.0 L − 15.0 L) = −120. L atm

101.3 J 1 kJ
w = −120. L atm × × = −12.2 kJ
L atm 1000 J

Step 1 is at constant pressure. The heat released/gained at constant pressure = qp = ΔH.

From the problem, ΔH = nCpΔT for an ideal gas. Using the ideal gas law, let’s substitute
for ΔT.
Δ(PV)
Δ(PV) = Δ(nRT) = nRΔT for a specific gas sample. So: ΔT =
nR
Δ(PV) C Δ(PV)
ΔH = qp = nCpΔT = nCp × = p ; Note: Δ(PV) = (P2V2 − P1V1)
nR R
5
For an ideal monatomic gas, Cp = R; substituting into the above equation:
2
 5  Δ(PV) 5
ΔH =  R  = Δ(PV )
 2  R 2

5 5
ΔH = qp = Δ(PV) = (3.00 atm × 55.0 L − 3.00 atm × 15.0 L) = 300. L atm
2 2
101.3 J 1 kJ
ΔH = qp = 300. L atm × × = 30.4 kJ
L atm 1000 J

ΔE = q + w = 30.4 kJ − 12.2 kJ = 18.2 kJ

Note: We could have used ΔE = nCvΔT to calculate the same answer (ΔE = 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 ΔE = nCvΔT and ΔH =
nCpΔT.
CHAPTER 6 THERMOCHEMISTRY 227

 3   Δ(PV )  3
ΔE = nCvΔT = n  R    = ΔPV
 2   nR  2
3
ΔE = (120. − 165) L atm = −67.5 L atm (Carry an extra significant figure.)
2
101.3 J 1 kJ
ΔE = −67.5 L atm × × = −6.8 kJ
L atm 1000 J
 5   Δ(PV )  5
ΔH = nCpΔT = n  R    = ΔPV
 2   nR  2
5
ΔH = (120. − 165) L atm = −113 L atm (Carry an extra significant figure.)
2
w = −PΔV = −(6.00 atm)(20.0 − 55.0) L = 210. L atm
101.3 J 1 kJ
w = 210. L atm × × = 21.3 kJ
L atm 1000 J

ΔE = 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
ΔE 18.2 kJ −6.8 kJ 11.4 kJ
ΔH 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 = qv = ΔE.

 3   Δ(PV )  3
ΔE = nCvΔT = n  R    = ΔPV
 2   nR  2
3 3
ΔE = qv = Δ(PV) = (6.00 atm × 15.0 L − 3.00 atm × 15.0 L)
2 2
3
ΔE = qv = (90.0 − 45.0) L atm = 67.5 L atm
2
101.3 J 1 kJ
ΔE = qv = 67.5 L atm × × = 6.84 kJ
L atm 1000 J

w = −PΔV = 0 because ΔV = 0

ΔH = ΔE + Δ(PV) = 67.5 L atm + 45.0 L atm = 112.5 L atm = 11.40 kJ

228 CHAPTER 6 THERMOCHEMISTRY

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 qp = ΔH.

 5   Δ(PV )  5
ΔH = qp = nCpΔT =  R    = ΔPV
 2   nR  2
5
ΔH = (120. − 90.0) L atm = 75 L atm
2
101.3 J 1 kJ
ΔH = qp = 75 L atm × × = 7.6 kJ
L atm 1000 J

w = −PΔV = − (6.00 atm)(20.0 − 15.0) L = −30. L atm

101.3 J 1 kJ
w = −30. L atm × × = −3.0 kJ
L atm 1000 J

ΔE = 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
ΔE 6.84 kJ 4.6 kJ 11.4 kJ
ΔH 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 ΔH
and ΔE for the two pathways are the same (see the two summaries of results); hence ΔH and
ΔE are state functions. However, the overall values of q and w for the two pathways are
different; hence q and w are path functions.

 2 x + y/2 
145. CxHy +   Ο2 → x CO2 + y/2 H2O
 2 

[x(−393.5) + y/2 (−242)] − ΔH Co x H y = −2044.5, − (393.5)x − 121y − ΔH C x H y = −2044.5

P • MM
dgas = , where MM = average molar mass of CO2/H2O mixture
RT
1.00 atm × MM
0.751 g/L = , MM of CO2/H2O mixture = 29.1 g/mol
0.08206 L atm
× 473 K
K mol
Let a = mol CO2 and 1.00 − a = mol H2O (assuming 1.00 total moles of mixture)

(44.01)a + (1.00 − a) × 18.02 = 29.1; solving: a = 0.426 mol CO2 ; mol H2O = 0.574 mol
CHAPTER 6 THERMOCHEMISTRY 229

y
0.574 y
Thus: = , 2.69 = , y = (2.69)x
2
0.426 x 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 CxHy must be less than the molar mass of Kr (83.80 g/mol). Only C3H8
works.

−2044.5 = −393.5(3) − 121(8) − ΔH oC3H8 , ΔH oC3H8 = −104 kJ/mol