CHAPTER 6 THERMOCHEMISTRY: ENERGY

FLOW AND CHEMICAL CHANGE

CHEMICAL CONNECTIONS BOXED READING PROBLEMS

B6.1 Plan: Convert the given mass in kg to g, divide by the molar mass to obtain moles, and convert moles to kJ of
energy. Sodium sulfate decahydrate will transfer 354 kJ/mol.
Solution:
 103 g   1 mol Na 2SO4 •10H 2O   354 kJ 
Heat (kJ) =  500.0 kg Na 2SO4 •10H 2O  
 1 kg   322.21 g Na SO •10H O   1 mol Na SO •10H O 
  2 4 2  2 4 2 
= –5.4933x105 = – 5.49x105 kJ

B6.2 Plan: Three reactions are given. Equation 1) must be multiplied by 2, and then the reactions

can be added, canceling substances that appear on both sides of the arrow. Add the H rxn

values for the three reactions to get the H rxn for the overall gasification reaction of 2 moles of

coal. Use the relationship H rxn = m H f (products) – n H f (reactants) to find the heat of combustion of 1 mole
 
of methane. Then find the H rxn for the gasification of 1.00 kg of coal and H rxn for the combustion of the
methane produced from 1.00 kg of coal and sum these values.
Solution:

a) 1) 2C(coal) + 2H 2 O(g)  2CO(g) + 2H 2 (g) H rxn = 2(129.7 kJ)

2) CO(g) + H 2 O(g)  CO 2 (g) + H 2 (g) H rxn = – 41 kJ

3) CO(g) + 3H 2 (g)  CH 4 (g) + H 2 O(g) H rxn = –206 kJ
2C(coal) + 2H 2 O(g)  CH 4 (g) + CO 2 (g)
b) The total may be determined by doubling the value for equation 1) and adding to the other two values.

H rxn = 2(129.7 kJ) + (–41 kJ) + (–206 kJ) = 12.4 = 12 kJ
c) Calculating the heat of combustion of CH 4 :
CH 4 (g) + 2O 2 (g) → CO 2 (g) + 2H 2 O(g)

H rxn = m H f (products) – n H f (reactants)

H rxn = [(1 mol CO 2 )( H f of CO 2 ) + (2 mol H 2 O)( H f of H 2 O)]
– [(1 mol CH 4 )( H f of CH 4 ) + (2 mol O 2 )( H f of O 2 )]

H rxn = [(1 mol)(–395.5 kJ/mol) + (2 mol)(–241.826 kJ/mol)]
– [(1 mol)(–74.87kJ/mol) + (2 mol )(0.0 kJ/mol)]

H rxn = –804.282 kJ/mol CH 4
Total heat for gasification of 1.00 kg coal:
 103 g   1 mol coal   12.4 kJ 
H° = 1.00 kg coal  
 1 kg   12.00 g coal   2 mol coal 
= 516.667 kJ
   
Total heat from burning the methane formed from 1.00 kg of coal:
 103 g   1 mol coal   1 mol CH 4   804.282 kJ 
H° = 1.00 kg coal  
 1 kg   12.00 g coal   2 mol coal   1 mol CH 
= –33511.75 kJ
    4 
Total heat = 516.667 kJ + (–33511.75 kJ) = –32995.083 = –3.30x104 kJ

6-1
END–OF–CHAPTER PROBLEMS

6.1 The sign of the energy transfer is defined from the perspective of the system. Entering the system is positive, and
leaving the system is negative.

6.2 No, an increase in temperature means that heat has been transferred to the surroundings, which makes q negative.

6.3 E = q + w = w, since q = 0.
Thus, the change in work equals the change in internal energy.

6.4 Plan: Remember that an increase in internal energy is a result of the system (body) gaining heat or having work
done on it and a decrease in internal energy is a result of the system (body) losing heat or doing work.
Solution:
The internal energy of the body is the sum of the cellular and molecular activities occurring from skin level
inward. The body’s internal energy can be increased by adding food, which adds energy to the body through the
breaking of bonds in the food. The body’s internal energy can also be increased through addition of work and
heat, like the rubbing of another person’s warm hands on the body’s cold hands. The body can lose energy if it
performs work, like pushing a lawnmower, and can lose energy by losing heat to a cold room.

6.5 a) electric heater b) sound amplifier c) light bulb d) automobile alternator

e) battery (voltaic cell)

6.6 Plan: Use the law of conservation of energy.

Solution:
The amount of the change in internal energy in the two cases is the same. By the law of energy conservation, the
change in energy of the universe is zero. This requires that the change in energy of the system (heater or air
conditioner) equals an opposite change in energy of the surroundings (room air). Since both systems consume the
same amount of electrical energy, the change in energy of the heater equals that of the air conditioner.

6.7 Heat energy; sound energy (impact)


Kinetic energy (falling text)

Potential energy (raised text)

Mechanical energy (raising of text)

Chemical energy (biological process to move muscles)

6.8 Plan: The change in a system’s energy is E = q + w. If the system receives heat, then its q final is greater than
q initial so q is positive. Since the system performs work, its w final < w initial so w is negative.
Solution:
E = q + w
E = (+425 J) + (–425 J) = 0 J

6.9 q + w = –255 cal + (–428 cal) = –683 cal

6.10 Plan: The change in a system’s energy is E = q + w. A system that releases thermal energy has a negative
value for q and a system that has work done on it has a positive value for work. Convert work in calories to
work in joules.
Solution:
 4.184 J 
Work (J) =  530 cal    = 2217.52 J
 1 cal 
E = q + w = –675 J + 2217.52 J = 1542.52 = 1.54x103 J

6-2
  103 J    103 cal   4.184 J  
E = q + w =  0.615 kJ     0.247 kcal    = 1648.4 = 1.65x103 J
 1 kJ   1 kcal   1 cal  
6.11 +
  
     

6.12 Plan: Convert 6.6x1010 J to the other units using conversion factors.
Solution:
C(s) + O 2 (g)  CO 2 (g) + 6.6x1010 J
(2.0 tons)
 1 kJ 
a) E (kJ) = (6.6 x 1010 J)  3  = 6.6x107 kJ
 10 J 
 
 1 cal   1 kcal 
b) E (kcal) = (6.6 x 1010 J)    3
7
 = 1.577x10 = 1.6x10 kcal
7

 4.184 J  10 cal 
 1 Btu 
c) E (Btu) = (6.6 x 1010 J)  7
 = 6.256x10 = 6.3x10 Btu
7

 1055 J 

6.13 CaCO 3 (s) + 9.0x106 kJ  CaO(s) + CO 2 (g)

(5.0 tons)
 103 J 
a) E (J) = (9.0x106 kJ) 
 1 kJ 
= 9.0x109 J
 
 103 J   1 cal 
b) E (cal) = (9.0x106 kJ)  = 2.15105x109 = 2.2x109 cal
 1 kJ   4.184 J 
  
 103 J   1 Btu 
c) E (Btu) = (9.0x106 kJ)  = 8.5308x106 = 8.5x106 Btu
 1 kJ   1055 J 
  

 103 cal   4.184 J 

E (J) = (4.1x103 Calorie)  = 1.7154x107 = 1.7x107 J
 1 Calorie   1 cal 
6.14
  
 103 cal   4.184 J   1 kJ 
E (kJ) = (4.1x103 Calorie)  = 1.7154x104 = 1.7x104 kJ
 1 Calorie   1 cal   103 J 
     

6.15 Plan: 1.0 lb of body fat is equivalent to about 4.1x103 Calories. Convert Calories to kJ with the appropriate
conversion factors.
Solution:
 4.1x103 Cal   103 cal   4.184 J   1 kJ   h 
Time = 1.0 lb   = 8.79713 = 8.8 h
 1.0 lb   1 Cal   1 cal   103 J   1950 kJ 
     

6.16 The system does work and thus its internal energy is decreased. This means the sign will be negative.

6.17 Since many reactions are performed in an open flask, the reaction proceeds at constant pressure. The
determination of H (constant pressure conditions) requires a measurement of heat only, whereas E requires
measurement of heat and PV work.

6.18 The hot pack is releasing (producing) heat, thus H is negative, and the process is exothermic.

6-3
6.19 Plan: An exothermic process releases heat and an endothermic process absorbs heat.
Solution:
a) Exothermic, the system (water) is releasing heat in changing from liquid to solid.
b) Endothermic, the system (water) is absorbing heat in changing from liquid to gas.
c) Exothermic, the process of digestion breaks down food and releases energy.
d) Exothermic, heat is released as a person runs and muscles perform work.
e) Endothermic, heat is absorbed as food calories are converted to body tissue.
f) Endothermic, the wood being chopped absorbs heat (and work).
g) Exothermic, the furnace releases heat from fuel combustion. Alternatively, if the system is defined as the air
in the house, the change is endothermic since the air’s temperature is increasing by the input of heat energy from
the furnace.

6.20 The internal energy of a substance is the sum of kinetic (E K ) and potential (E P ) terms.
E K (total) = E K (translational) + E K (rotational) + E K (vibrational)
E P = E P (atom) + E P (bonds)
E P (atom) has nuclear, electronic, positional, magnetic, electrical, etc., components.

6.21 H = E + PV (constant P)

a) H < E, PV is negative.
b) H = E, a fixed volume means PV = 0.
c) H > E, PV is positive for the transformation of solid to gas.

6.22 Plan: An exothermic reaction releases heat, so the reactants have greater H (H initial ) than the products (H final ).
H = H final – H initial < 0.
Solution:
Reactants
Increasing, H

H = (), (exothermic)

Products

6.23

Products
Increasing, H

H = (+), (endothermic)

Reactants

6.24 Plan: Combustion of hydrocarbons and related compounds require oxygen (and a heat catalyst) to yield
carbon dioxide gas, water vapor, and heat. Combustion reactions are exothermic. The freezing of liquid water is
an exothermic process as heat is removed from the water in the conversion from liquid to solid. An exothermic
reaction or process releases heat, so the reactants have greater H (H initial ) than the products (H final ).

6-4
 Solution:
a) Combustion of ethane: 2C 2 H 6 (g) + 7O 2 (g)  4CO 2 (g) + 6H 2 O(g) + heat
2C2H6 + 7O2 (initial)
Increasing, H

H = (), (exothermic)

4CO2 + 6H2O (final)

b) Freezing of water: H 2 O(l)  H 2 O(s) + heat

H2O(l) (initial)
Increasing, H

H = (), (exothermic)

H2O(s) (final)

6.25 a) Na(s) + 1/2Cl 2 (g)  NaCl(s) + heat

Na(s) + 1/2Cl2(g)

exothermic
Increasing, H

NaCl(s)

b) C 6 H 6 (l) + heat  C 6 H 6 (g)

C6H6(g)
Increasing, H

H = (+), (endothermic)

C6H6(l)

6.26 Plan: Combustion of hydrocarbons and related compounds require oxygen (and a heat catalyst) to yield carbon
dioxide gas, water vapor, and heat. Combustion reactions are exothermic. An exothermic reaction releases heat, so
the reactants have greater H (H initial ) than the products (H final ). If heat is absorbed, the reaction is endothermic and
the products have greater H (H final ) than the reactants (H initial ).
Solution:
a) 2CH 3 OH(l) + 3O 2 (g)  2CO 2 (g) + 4H 2 O(g) + heat
2CH3OH + 3O2 (initial)
Increasing, H

H = (), (exothermic)

2CO2 + 4H2O (final)

6-5
 b) Nitrogen dioxide, NO 2 , forms from N 2 and O 2 .
1/2N 2 (g) + O 2 (g) + heat  NO 2 (g)
NO2 (final)
Increasing, H
H = (+), (endothermic)

1/2N2 + O2 (initial)

6.27 a) CO 2 (s) + heat  CO 2 (g)

CO2(g)
Increasing, H

H = (+), (endothermic)

CO2(s)

b) SO 2 (g) + 1/2O 2 (g)  SO 3 (g) + heat

SO2(g) + 1/2O2(g)
Increasing, H

H = (), (exothermic)

SO3(g)

6.28 Plan: Recall that q sys is positive if heat is absorbed by the system (endothermic) and negative if heat is released
by the system (exothermic). Since E = q + w, the work must be considered in addition to q sys to find ΔE sys .
Solution:
a) This is a phase change from the solid phase to the gas phase. Heat is absorbed by the system so q sys is positive
(+).
b) The system is expanding in volume as more moles of gas exist after the phase change than were present before
the phase change. So the system has done work of expansion and w is negative. ΔE sys = q + w. Since q is
positive and w is negative, the sign of ΔE sys cannot be predicted. It will be positive if q > w and negative if
q < w.
c) ΔE univ = 0. If the system loses energy, the surroundings gain an equal amount of energy. The sum of the
energy of the system and the energy of the surroundings remains constant.

6.29 a) There is a volume decrease; V final < V initial so ΔV is negative. Since w sys = –PΔV, w is positive, +.
b) ∆H sys is – as heat has been removed from the system to liquefy the gas.
c) ∆E sys = q + w. Since q is negative and w is positive, the sign of ΔE sys and ΔE surr cannot be predicted. ΔE sys
will be positive and ΔE surr will be negative if w > q and ΔE sys will be negative and ΔE surr will be positive if
w < q.

6.30 The molar heat capacity of a substance is larger than its specific heat capacity. The specific heat capacity of a
substance is the quantity of heat required to change the temperature of 1 g of a substance by 1 K while the molar
heat capacity is the quantity of heat required to change the temperature of 1 mole of a substance by 1 K.
The specific heat capacity of a substance is multiplied by its molar mass to obtain the molar heat capacity.

6.31 To determine the specific heat capacity of a substance, you need its mass, the heat added (or lost), and the change
in temperature.

6-6
6.32 Specific heat capacity is an intensive property; it is defined on a per gram basis. The specific heat capacity of
a particular substance has the same value, regardless of the amount of substance present.

6.33 Specific heat capacity is the quantity of heat required to raise 1g of a substance by 1 K. Molar heat
capacity is the quantity of heat required to raise 1 mole of substance by 1 K. Heat capacity is also the quantity of
heat required for a 1 K temperature change, but it applies to an object instead of a specified amount of a
substance. Thus, specific heat capacity and molar heat capacity are used when talking about an element or
compound while heat capacity is used for a calorimeter or other object.

6.34 In a coffee-cup calorimeter, reactions occur at constant pressure. q p = H.

In a bomb calorimeter, reactions occur at constant volume. q v = E.

6.35 Plan: The heat required to raise the temperature of water is found by using the equation
q = c x mass x T. The specific heat capacity, c water , is found in Table 6.2. Because the Celsius degree is the same
size as the Kelvin degree, T = 100°C – 25°C = 75°C = 75 K.
Solution:
 J 
q (J) = c x mass x T =  4.184   22.0 g  75 K  = 6903.6 = 6.9x10 J
3

 g K 

 J 
6.36 q (J) = c x mass x T =  2.087   0.10 g    75  10. K  = –17.7395 = –18 J
 g K

6.37 Plan: Use the relationship q = c x mass x T. We know the heat (change kJ to J), the specific heat capacity, and
the mass, so T can be calculated. Once T is known, that value is added to the initial temperature to find the
final temperature.
Solution:
q (J) = c x mass x T T initial = 13.00°C T final = ? mass = 295 g c = 0.900 J/g•K
 103 J 
q =  75.0 kJ   = 7.50x104 J
 1 kJ 
 
4
7.50x10 J = (0.900 J/g•K)(295 g)(T)

T =
 7.50x10 J 
4

 0.900 J 
 295 g   
 gK 
T = 282.4859 K = 282.4859°C (Because the Celsius degree is the same size as the Kelvin degree, T is the
same in either temperature unit.)
T = T final – T initial
T final T + T initial
T final = 282.4859°C + 13.00°C = 295.49 = 295°C

6.38 q (J) = c x mass x T

–688 J = (2.42 J/g•K)(27.7 g)(T)
 688 J 
(T) = = –10.26345 K = –10.26345°C
 2.42 J 
 27.7 g   
 gK 
T = T final – T initial
T initial T final – T
T initial = 32.5°C – (–10.26345°C) = 42.76345 = 42.8°C

6-7
6.39 Plan: Since the bolts have the same mass and same specific heat capacity, and one must cool as the other heats
(the heat lost by the “hot” bolt equals the heat gained by the “cold” bolt), the final temperature is an average of the
two initial temperatures.
Solution:
 T1 + T2    100.C + 55C  
  =   = 77.5°C
 2   2 

6.40 –q lost = q gained

– 2(mass)(c Cu )(T final – 105)°C = (mass)(c Cu )(T final – 45)°C
– 2(T final – 105)°C = (T final – 45)°C
2(105°C) – 2T final = T final – 45°C
210°C + 45°C = T final + 2T final = 3T final
(255°C)/3 = T final = 85.0°C

6.41 Plan: The heat lost by the water originally at 85°C is gained by the water that is originally at 26°C. Therefore
–q lost = q gained . Both volumes are converted to mass using the density.
Solution:
 1.00 g   1.00 g 
Mass (g) of 75 mL =  75 mL    = 75 g Mass (g) of 155 mL = 155 mL    = 155 g
 1 mL   1 mL 
–q lost = q gained
c x mass x T (85°C water)= c x mass x T (26°C water)
– (4.184 J/g°C)(75 g)(T final – 85)°C =(4.184 J/g°C)(155 g)(T final – 26)°C
– (75 g)(T final – 85)°C = (155 g) (T final – 26)°C
6375 – 75T final = 155T final – 4030
6375 + 4030 = 155T final + 75T final
10405 = 230.T final
T final = (10405/230.) = 45.24 = 45°C

6.42 –q lost = q gained

– [24.4 mL(1.00 g/mL)](4.184 J/g°C)(23.5 – 35.0)°C = (mass)(4.184 J/g°C)(23.5 – 18.2)°C
– (24.4)(23.5 – 35.0) = (mass)(23.5 – 18.2)
– (24.4)(–11.5) = (mass)(5.3)
280.6 = (mass)(5.3)
52.943 g = mass
 1 mL 
Volume (mL) =  52.943 g    = 52.943 = 53 mL
 1.00 g 

6.43 Plan: Heat gained by water and the container equals the heat lost by the copper tubing so
q water + q calorimeter = –q copper .
Solution:
T = T final – T initial
Specific heat capacity in units of J/g•K has the same value in units of J/g°C since the Celsius and Kelvin unit are
the same size.
–q lost = q gained = q water + q calorimeter
– (455 g Cu)(0.387 J/g°C)(T final – 89.5)°C
= (159 g H 2 O)(4.184 J/g°C)(T final – 22.8)°C + (10.0 J/°C)(T final – 22.8)°C
– (176.085)(T final – 89.5) = (665.256)(T final – 22.8) + (10.0)(T final – 22.8)
15759.6075 – 176.085T final = 665.256T final – 15167.8368 + 10.0T final – 228
15759.6075 + 15167.8368 + 228 = 176.085T final + 665.256T final + 10.0T final
31155.4443 = 851.341T final
T final = 31155.4443/(851.341) = 36.59573 = 36.6°C

6-8
6.44 –q lost = q gained = q water + q calorimeter
– (30.5 g alloy)(c alloy )(31.1 – 93.0)°C = (50.0 g H 2 O)(4.184 J/g°C)(31.1 – 22.0)°C + (9.2 J/°C)(31.1 – 22.0)°C
– (30.5 g)(c alloy )(–61.9°C) = (50.0 g)(4.184 J/g°C)(9.1°C) + (9.2 J/°C)(9.1°C)
1887.95(c alloy ) = 1903.72 + 83.72 = 1987.44
c alloy = 1987.44/1887.95 = 1.052697 = 1.1 J/g°C

6.45 Benzoic acid is C 6 H 5 COOH, and will be symbolized as HBz.

–q reaction = q water + q calorimeter
 1 mol HBz   3227 kJ   103 J 
–q reaction = – 1.221 g HBz   
4
  1 kJ  = 3.226472x10 J
 122.12 g HBz  1 mol HBz  
q water = c x mass x T = 4.184 J/g°C x 1200 g x T
q calorimeter = C x T = 1365 J/°C x T
–q reaction = q water + q calorimeter
3.226472x104 J = 4.184 J/g°C x 1200 g x T + 1365 J/°C x T
3.226472x104 J = 5020.8(T) + 1365(T)
3.226472x104 J = 6385.8(T)
T = 3.226472x104/6385.8 = 5.052573 = 5.053°C

6.46 a) Energy will flow from Cu (at 100.0°C) to Fe (at 0.0°C).

b) To determine the final temperature, the heat capacity of the calorimeter must be known.
c) – q Cu = q Fe + q calorimeter assume q calorimeter = 0.
– q Cu = q Fe + 0
– (20.0 g Cu)(0.387 J/g°C)(T final – 100.0)°C = (30.0 g Fe)(0.450 J/g°C)(T final – 0.0)°C + 0.0 J
– (20.0 g)(0.387 J/g°C)(T final – 100.0°C) = (30.0 g)(0.450 J/g°C)(T final – 0.0°C)
– (7.74)(T final – 100.0) = (13.5)(T final – 0.0)
774 – 7.74 T final = 13.5T final
774 = (13.5 + 7.74) T final = 21.24T final
T final = 774/21.24 = 36.44068 = 36.4°C

6.47 –q hydrocarbon = q water + q calorimeter

–q hydrocarbon = (2.550 L H 2 O)(1mL /10–3L)(1.00g/mL)(4.184 J/g°C)(23.55 – 20.00)°C
+ (403 J/°C)(23.55 – 20.00)°C
–q hydrocarbon = (2550. g)(4.184 J/g°C)(3.55°C) + (403 J/°C)(3.55°C)
–q hydrocarbon = (37875.66 J) + (1430.65 J) = 39306.31 J
q hydrocarbon = –3.930631x104 J
q hydrocarbon /g = (–3.930631x104 J)/1.520 g = –2.5859x104 = –2.59x104 J/g

6.48 The reaction is: 2KOH(aq) + H 2 SO 4 (aq)  K 2 SO 4 (aq) + 2H 2 O(l)

q (kJ) = (25.0 + 25.0) mL(1.00 g/mL)(4.184 J/g°C)(30.17 – 23.50)°C(1 kJ/103 J) = 1.395364 kJ
(The temperature increased so the heat of reaction is exothermic.)
Amount (moles) of H 2 SO 4 = (25.0 mL)(0.500 mol H 2 SO 4 /L)(10–3 L/1 mL) = 0.0125 mol H 2 SO 4
Amount (moles) of KOH = (25.0 mL)(1.00 mol KOH/L)(10–3 L/1 mL) = 0.0250 mol KOH
The moles show that both H 2 SO 4 and KOH are limiting.
The enthalpy change could be calculated in any of the following ways:
H = –1.395364 kJ/0.0125 mol H 2 SO 4 = – 111.62912 = – 112 kJ/mol H 2 SO 4
H = –1.395364 kJ/0.0250 mol KOH = –55.81456 = –55.8 kJ/mol KOH
(Per mole of K 2 SO 4 gives the same value as per mole of H 2 SO 4 , and per mole of H 2 O gives the same
value as per mole of KOH.)

6.49 Reactants  Products + Energy

H rxn = (–)
Thus, energy is a product.

6-9
6.50 Plan: Recall that H is positive for an endothermic reaction in which heat is absorbed, while H is negative for
an
exothermic reaction in which heat is released.
Solution:
The reaction has a positive H rxn , because this reaction requires the input of energy to break the oxygen-oxygen
bond in O 2 :
O 2 (g) + energy  2O(g)

6.51 Plan: Recall that H is positive for an endothermic reaction in which heat is absorbed, while H is negative for
an
exothermic reaction in which heat is released.
Solution:
As a substance changes from the gaseous state to the liquid state, energy is released so H would be negative for
the condensation of 1 mol of water. The value of H for the vaporization of 2 mol of water would be twice the
value of H for the condensation of 1 mol of water vapor but would have an opposite sign (+H).
H 2 O(g)  H 2 O(l) + Energy 2H 2 O(l) + Energy  2H 2 O(g)
H condensation = (–) H vaporization = (+)2[H condensation ]
The enthalpy for 1 mole of water condensing would be opposite in sign to and one-half the value for the
conversion of 2 moles of liquid H 2 O to H 2 O vapor.

6.52 Plan: Recall that H is positive for an endothermic reaction in which heat is absorbed, while H is negative for an
exothermic reaction in which heat is released. The H rxn is specific for the reaction as written, meaning that
20.2 kJ is released when one-eighth of a mole of sulfur reacts. Use the ratio between moles of sulfur and H to
convert between amount of sulfur and heat released.
Solution:
a) This reaction is exothermic because H is negative.
b) Because H is a state function, the total energy required for the reverse reaction, regardless of how the change
occurs, is the same magnitude but different sign of the forward reaction. Therefore, H = +20.2 kJ.
 20.2 kJ 
c) H rxn =  2.6 mol S8  
 1/ 8  mol S 
= –420.16 = –4.2x102 kJ
 8 
d) The mass of S 8 requires conversion to moles and then a calculation identical to part c) can be performed.
 1 mol S8   20.2 kJ 
H rxn =  25.0 g S8     
= –15.7468 = –15.7 kJ
 256.56 g S8   1/ 8  mol S8 

6.53 MgCO 3 (s)  MgO(s) + CO 2 (g) H rxn = 117.3 kJ

a) Absorbed
b) H rxn (reverse) = –117.3 kJ
 117.3 kJ 
c) H rxn =  5.35 mol CO 2    = –627.555 = –628 kJ
 1 mol CO 2 
 1 mol CO 2   117.3 kJ 
d) H rxn =  35.5 g CO 2     = –94.618 = –94.6 kJ
 44.01 g CO 2   1 mol CO 2 

6.54 Plan: A thermochemical equation is a balanced equation that includes the heat of reaction. Since heat is absorbed
in this reaction, H will be positive. Convert the mass of NO to moles and use the ratio between NO and H to
find the heat involved for this amount of NO.
Solution:
a) 1/2N 2 (g) + 1/2O 2 (g)  (g) H = 90.29 kJ
 1 mol NO   90.29 kJ 
b) H rxn =  3.50 g NO     = –10.5303 = –10.5 kJ
 30.01 g NO   1 mol NO 

6-10
6.55 a) KBr(s)  K(s) + 1/2Br 2 (l) H rxn = 394 kJ
 10 g   1 mol KBr   394 kJ 
3
b) H rxn = 10.0 kg KBr   = –3.3109x104 = –3.31x104 kJ
 1 kg   119.00 g KBr   1 mol KBr 
   

6.56 Plan: For the reaction written, 2 moles of H 2 O 2 release 196.1 kJ of energy upon decomposition. Use this
ratio to convert between the given amount of reactant and the amount of heat released. The amount of H 2 O 2 must
be converted from kg to g to moles.
Solution:
2H 2 O 2 (l)  2H 2 O(l) + O 2 (g) H rxn = –196.1 kJ
 10 g   1 mol H 2 O 2   196.1 kJ 
3
Heat (kJ) = q =  652 kg H 2 O 2   = –1.87915x106 = –1.88x106 kJ
 1 kg   34.02 g H O   2 mol H O 
   2 2   2 2 

6.57 For the reaction written, 1 mole of B 2 H 6 releases 755.4 kJ of energy upon reaction.
B 2 H 6 (g) + 6Cl 2 (g)  2BCl 3 (g) + 6HCl(g) H rxn = –755.4 kJ
 103 g   1 mol B2 H 6   755.4 kJ 
Heat (kJ) = q = 1 kg   = –2.73003x104 = –2.730x104 kJ/kg
 1 kg   27.67 g B H   1 mol B H 
  2 6  2 6 

6.58 4Fe(s) + 3O 2 (g)  2Fe 2 O 3 (s) H rxn = –1.65x103 kJ

 103 g   1 mol Fe   1.65x103 kJ 
a) Heat (kJ) = q =  0.250 kg Fe   = –1846.46 = –1850 kJ
 1 kg   55.85 g Fe   4 mol Fe 
   
 2 mol Fe 2 O3   159.70 g Fe 2O3 

b) Mass (g) of Fe 2 O 3 = 4.85x103 kJ  3 
 1.65x10 kJ   1 mol Fe2 O3 
 = 938.84 = 939 g Fe 2 O 3

6.59 2HgO(s)  2Hg(l) + O 2 (g) H rxn = 181.6 kJ

 1 mol HgO  181.6 kJ 
a) Heat (kJ) = q =  555 g HgO     = 232.659 = 233 kJ
 216.6 g HgO  2 mol Hg 
 2 mol Hg   200.6 g Hg 
b) Mass (g) of Hg =  275 kJ     = 607.544 = 608 g Hg
 181.6 kJ   1 mol Hg 

6.60 Plan: A thermochemical equation is a balanced equation that includes the heat of reaction. Heat is released in this
reaction so H is negative. Use the ratio between H and moles of C 2 H 4 to find the amount of C 2 H 4 that must
react to produce the given quantity of heat.
Solution:
a) C 2 H 4 (g) + 3O 2 (g)  2CO 2 (g) + 2H 2 O(l) H rxn = –1411 kJ
 1 mol C2 H 4   28.05 g C 2 H 4 
b) Mass (g) of C 2 H 4 =  70.0 kJ     = 1.39157 = 1.39 g C 2 H 4
 1411 kJ   1 mol C2 H 4 

6.61 a) C 12 H 22 O 11 (s) + 12O 2 (g)  12CO 2 (g) + 11H 2 O(l) H rxn = –5.64x103 kJ
 1 mol C12 H 22O11   5.64x103 kJ 
b) Heat (kJ) = q = 1 g C12 H 22O11      = –16.47677 = –16.5 kJ/g
 342.30 g C12 H 22O11   1 mol C12 H 22O11 

6.62 Hess’s law: H rxn is independent of the number of steps or the path of the reaction.

6.63 Hess’s law provides a useful way of calculating energy changes for reactions which are difficult or impossible to
measure directly.

6-11
6.64 Plan: Two chemical equations can be written based on the description given:
C(s) + O 2 (g)  CO 2 (g) H 1 (1)
CO(g) + 1/2O 2 (g)  CO 2 (g) H 2 (2)
The second reaction can be reversed and its H sign changed. In this case, no change in the coefficients is
necessary since the CO 2 cancels. Add the two H values together to obtain the H of the desired reaction.
Solution:
C(s) + O 2 (g)  CO 2 (g) H 1
CO 2 (g)  CO(g) + 1/2O 2 (g) –H 2 (reaction is reversed)

Total C(s) + 1/2O 2 (g)  CO(g) H rxn = H 1 + – (H 2 )

How are the H values for each reaction determined? The H 1 can be found by using the heats of formation in
Appendix B:
H 1 = [H f (CO 2 )] – [H f (C) + H f (O 2 )] = [–393.5 kJ/mol] – [0 + 0] = –393.5 kJ/mol.
The H 2 can be found by using the heats of formation in Appendix B:
H 2 = [H f (CO 2 )] – [H f (CO) + 1/2H f (O 2 )] = [–393.5] – [–110.5 kJ/mol + 0)] = –283 kJ/mol.
H rxn = H 1 + – (H 2 ) = –393.5 kJ + – (–283.0 kJ) = –110.5 kJ

6.65 Plan: To obtain the overall reaction, add the first reaction to the reverse of the second. When the second reaction
is reversed, the sign of its enthalpy change is reversed from positive to negative.
Solution:
Ca(s) + 1/2O 2 (g)  CaO(s) H = –635.1 kJ
CaO(s) + CO 2 (g)  CaCO 3 (s) H = –178.3 kJ (reaction is reversed)
Ca(s) + 1/2O 2 (g) + CO 2 (g) CaCO 3 (s) H = –813.4 kJ

6.66 2NOCl(g)  2NO(g) + Cl 2 (g) H = –2(–38.6 kJ)

2NO(g)  N 2 (g) + O 2 (g) H = –2(90.3 kJ)
2NOCl(g)  N 2 (g) + O 2 (g) + Cl 2 (g) H = 77.2 kJ + (– 180.6 kJ) = –103.4 kJ

6.67 Plan: Add the two equations, canceling substances that appear on both sides of the arrow. When matching the
equations with the arrows in the Figure, remember that a positive H corresponds to an arrow pointing up while a
negative H corresponds to an arrow pointing down.
Solution:
1) N 2 (g) + O 2 (g)  2NO(g) H = 180.6 kJ
2) 2NO(g) + O 2 (g)  2NO 2 (g) H = –114.2 kJ

3) N 2 (g) + 2O 2 (g)  2NO 2 (g) H rxn = +66.4 kJ

In Figure P6.67, A represents reaction 1 with a larger amount of energy absorbed, B represents reaction 2 with
a smaller amount of energy released, and C represents reaction 3 as the sum of A and B.

6.68 1) P 4 (s) + 6Cl 2 (g)  4PCl 3 (g) H 1 = –1148 kJ

2) 4PCl 3 (g) + 4Cl 2 (g)  4PCl 5 (g) H 2 = – 460 kJ

3) P 4 (s) + 10Cl 2 (g)  4PCl 5 (g) H overall = –1608 kJ

Equation 1) = B, equation 2) = C, equation 3) = A

6.69 Plan: Vaporization is the change in state from a liquid to a gas: H 2 O(l)  H 2 O(g) . The two equations
describing the chemical reactions for the formation of gaseous and liquid water can be combined to yield the
equation for vaporization.
Solution:
1) Formation of H 2 O(g): H 2 (g) + 1/2O 2 (g)  H 2 O(g) H = –241.8 kJ
2) Formation of H 2 O(l): H 2 (g) + 1/2O 2 (g)  H 2 O(l) H = –285.8 kJ

6-12
 Reverse reaction 2 (change the sign of H) and add the two reactions:
H 2 (g) + 1/2O 2 (g)  H 2 O(g) H = –241.8 kJ
H 2 O(l)  H 2 (g) + 1/2O 2 (g) H = +285.8 kJ

H 2 O(l)  H 2 O(g) H vap = 44.0 kJ

6.70 C(s) + 1/4S 8 (s)  CS 2 (l) H = +89.7 kJ

CS 2 (l)  CS 2 (g) H = +27.7 kJ

C(s) + 1/4S 8 (s)  CS 2 (g) H = +117.4 kJ

6.71 C (diamond) + O 2 (g)  CO 2 (g) H = –395.4 kJ

CO 2 (g)  C(graphite) + O 2 (g) H = –(–393.5 kJ)
C(diamond)  C(graphite) H = – 1.9 kJ


6.72 The standard heat of reaction, H rxn , is the enthalpy change for any reaction where all substances are in their
standard states. The standard heat of formation, H f , is the enthalpy change that accompanies the formation of
one mole of a compound in its standard state from elements in their standard states. Standard state is 1 atm for
gases, 1 M for solutes, and the most stable form for liquids and solids. Standard state does not include a specific
temperature, but a temperature must be specified in a table of standard values.

6.73 The standard heat of reaction is the sum of the standard heats of formation of the products minus the sum of the
standard heats of formation of the reactants multiplied by their respective stoichiometric coefficients.

H rxn = m H f (products) – n H f (reactants)

6.74 Plan: H f is for the reaction that shows the formation of one mole of compound from its elements in their
standard states.
Solution:
a) 1/2Cl 2 (g) + Na(s)  NaCl(s) The element chlorine occurs as Cl 2 , not Cl.
b) H 2 (g) + 1/2O 2 (g)  H 2 O(g) The element hydrogen exists as H 2 , not H, and the formation of water is written
with water as the product.
c) No changes

6.75 Plan: Formation equations show the formation of one mole of compound from its elements. The elements must be
in their most stable states ( H f = 0).
Solution:
a) Ca(s) + Cl 2 (g)  CaCl 2 (s)
b) Na(s) + 1/2H 2 (g) + C(graphite) + 3/2O 2 (g)  NaHCO 3 (s)
c) C(graphite) + 2Cl 2 (g)  CCl 4 (l)
d) 1/2H 2 (g) + 1/2N 2 (g) + 3/2O 2 (g)  HNO 3 (l)

6.76 a) 1/2H 2 (g) + 1/2I 2 (s)  HI(g)

b) Si(s) + 2F 2 (g)  SiF 4 (g)
c) 3/2O 2 (g)  O 3 (g)
d) 3Ca(s) + 1/2P 4 (s) + 4O 2 (g)  Ca 3 (PO 4 ) 2 (s)

6.77 Plan: The enthalpy change of a reaction is the sum of the heats of formation of the products minus the sum of the
heats of formation of the reactants. Since the H f values (Appendix B) are reported as energy per one mole, use
the appropriate stoichiometric coefficient to reflect the higher number of moles.

6-13
 Solution:

H rxn = m H f (products) – n H f (reactants)

a) H rxn = {2 H f [SO 2 (g)] + 2 H f [H 2 O(g)]} – {2 H f [H 2 S(g)] + 3 H f [O 2 (g)]}
= [(2 mol)(–296.8 kJ/mol) + (2 mol)(–241.826 kJ/mol)] – [(2 mol)(–20.2 kJ/mol) + (3 mol)(0.0 kJ/mol)]
= –1036.9 kJ
b) The balanced equation is CH 4 (g) + 4Cl 2 (g)  CCl 4 (l) + 4HCl(g)

H rxn = {1 H f [CCl 4 (l)] + 4 H f [HCl(g)]} – {1 H f [CH 4 (g)] + 4 H f [Cl 2 (g)]}

H rxn = [(1 mol)(–139 kJ/mol) + (4 mol)(–92.31 kJ/mol)] – [(1 mol)(–74.87 kJ/mol) + (4 mol)(0 kJ/mol)]
= –433 kJ


6.78 H rxn = m H f (products) – n H f (reactants)

a) H rxn = {1 H f [SiF 4 (g)] + 2 H f [H 2 O(l)]} – {1 H f [SiO 2 (s)] + 4 H f [HF(g)]}
= [(1 mol)(–1614.9 kJ/mol) + (2 mol)(–285.840 kJ/mol)]
– [(1 mol)(–910.9 kJ/mol) + (4 mol)(–273 kJ/mol)]
= –184 kJ
b) 2C 2 H 6 (g) + 7O 2 (g)  4CO 2 (g) + 6H 2 O(g)

H rxn = {4 H f [CO 2 (g)] + 6 H f [H 2 O(g)]} – {2 H f [C 2 H 6 (g)] + 7 H f [ O 2 (g)]}
= [(4 mol)(–393.5 kJ/mol) + (6 mol)(–241.826 kJ/mol)] – [(2 mol)(–84.667 kJ/mol) + (7 mol)(0 kJ/mol)]
= –2855.6 kJ (or –1427.8 kJ for reaction of 1 mol of C 2 H 6 )

6.79 Plan: The enthalpy change of a reaction is the sum of the heats of formation of the products minus the sum of the
heats of formation of the reactants. Since the H f values (Appendix B) are reported as energy per one mole, use

the appropriate stoichiometric coefficient to reflect the higher number of moles. In this case, H rxn is known and
H f of CuO must be calculated.
Solution:

H rxn = m H f (products) – n H f (reactants)

Cu 2 O(s) + 1/2O 2 (g)  2CuO(s) H rxn = –146.0 kJ

H rxn = {2 H f [CuO(s)]} – {1 H f [Cu 2 O(s)] + 1/2 H f [O 2 (g)]}
–146.0 kJ = {(2 mol) H f [CuO(s)]} – {(1 mol)(–168.6 kJ/mol) + (1/2 mol)(0 kJ/mol)}
–146.0 kJ = 2 mol H f [CuO(s)] + 168.6 kJ
314.6 kJ
H f [CuO(s)] =  = –157.3 kJ/mol
2 mol

6.80 H rxn = m H f (products) – n H f (reactants)

C 2 H 2 (g) + 5/2O 2 (g)  2CO 2 (g) + H 2 O(g) H rxn = –1255.8 kJ

H rxn = {2 H f [CO 2 (g)] + 1 H f [H 2 O(g)]} – {1 H f [C 2 H 2 (g)] + 5/2 H f [O 2 (g)]}
–1255.8 kJ = {(2 mol)(–393.5 kJ/mol) + (1 mol)(–241.826 kJ/mol)}
– {(1 mol) H f [C 2 H 2 (g)] + (5/2 mol)(0.0 kJ/mol)}
–1255.8 kJ = –787.0 kJ – 241.8 kJ – (1 mol) H f [C 2 H 2 (g)]
227.0 kJ
H f [C 2 H 2 (g)] = = 227.0 kJ/mol
 1 mol

6-14
6.81 Plan: The enthalpy change of a reaction is the sum of the heats of formation of the products minus the sum of
the heats of formation of the reactants. Since the H f values (Appendix B) are reported as energy per one mole,
use the appropriate stoichiometric coefficient to reflect the higher number of moles. Hess’s law can also be used
to calculate the enthalpy of reaction. In part b), rearrange equations 1) and 2) to give the equation wanted.
 
Reverse the first equation (changing the sign of H rxn ) and multiply the coefficients (and H rxn ) of the second
reaction by 2.
Solution:
2PbSO 4 (s) + 2H 2 O(l)  Pb(s) + PbO 2 (s) + 2H 2 SO 4 (l)

H rxn = m H f (products) – n H f (reactants)

a) H rxn = {1 H f [Pb(s)] + 1 H f [PbO 2 (s)] + 2 H f [H 2 SO 4 (l)]}
– {2 H f [PbSO 4 (s)] + 2 H f [H 2 O(l)]}
= [(1 mol)(0 kJ/mol) + (1 mol)(–276.6 kJmol) + (2 mol)(–813.989 kJ/mol)]
– [(2 mol)(–918.39 kJ/mol) + (2 mol)(–285.840 kJ/mol)]
= 503.9 kJ
b) Use Hess’s law:

PbSO 4 (s)  Pb(s) + PbO 2 (s) + 2SO 3 (g) H rxn = –(–768 kJ) Equation has been reversed.

2SO 3 (g) + 2H 2 O (l)  2H 2 SO 4 (l) H rxn = 2(–132 kJ)

2PbSO 4 (s) + 2H 2 O(l)  Pb(s) + PbO 2 (s) + 2H 2 SO 4 (l) H rxn = 504 kJ

6.82 Plan: The enthalpy change of a reaction is the sum of the heats of formation of the products minus the sum of the
heats of formation of the reactants. Since the H f values (Appendix B) are reported as energy per one mole, use
the appropriate stoichiometric coefficient to reflect the higher number of moles. Convert the mass of stearic acid

to moles and use the ratio between stearic acid and H rxn to find the heat involved for this amount of acid. For
part d), use the kcal/g of fat relationship calculated in part c) to convert 11.0 g of fat to total kcal and compare to
the 100. Cal amount.
Solution:
a) C 18 H 36 O 2 (s) + 26O 2 (g)  18CO 2 (g) + 18H 2 O(g)

b) H rxn = m H f (products) – n H f (reactants)

H rxn = {18 H f [CO 2 (g)] + 18 H f [H 2 O(g)]} – {1 H f [C 18 H 36 O 2 (s)] + 26 H f [O 2 (g)]}
= [(18 mol)(–393.5 kJ/mol) + (18 mol)(–241.826 kJ/mol)] – [(1 mol)(–948 kJ/mol) + (26 mol)(0 kJ/mol)]
= –10,487.868 = –10,488 kJ
 1 mol C18 H36 O 2  10, 487.868 kJ 
c) q (kJ) = 1.00 g C18 H36 O2     = –36.8681 = –36.9 kJ
 284.47 C18 H36 O2  1 mol C18 H36 O2 
 1 kcal 
q (kcal) =  36.8681 kJ    = –8.811688 = –8.81 kcal
 4.184 kJ 
 8.811688 kcal 
d) q (kcal) = 11.0 g fat    = 96.9286 = 96.9 kcal
 1.0 g fat 
Since 1 kcal = 1 Cal, 96.9 kcal = 96.9 Cal. The calculated calorie content is consistent with the package
information.

6.83 a) H 2 SO 4 (l)  H 2 SO 4 (aq)


H rxn = {1 H f [H 2 SO 4 (aq)]} – {1 H f [H 2 SO 4 (l)]}
= [(1 mol)(–907.51 kJ/mol)] – [(1 mol)(–813.989 kJ/mol)]
= –93.52 kJ

6-15
 b) q (J) = c x mass x T
 3.50 J   1.060 g 
93.52 kJ x 103 J/kJ =   x 1000. mL    x Tfinal  25.0C 
 g•C   1 mL 
 3.50 J 
9.352x104 J =   x 1060. g  x Tfinal  25.0C 
 g•C 
9.352 x 104 J = (T final )3710 J/ºC – 9.2750x104 J
T final = 50.1995 = 50.2°C
c) Adding the acid to a large amount of water releases the heat to a large mass of solution and thus, the potential
temperature rise is minimized due to the large heat capacity of the larger volume.

6.84 Plan: Use the ideal gas law, PV = nRT, to calculate the volume of one mole of helium at each temperature.
Then use the given equation for ΔE to find the change in internal energy. The equation for work, w = –PΔV, is
needed for part c), and q P = ΔE + PΔV is used for part d). For part e), recall that ΔH = q P .
Solution:
nRT
a) PV = nRT or V =
P
T = 273 + 15 = 288 K and T = 273 + 30 = 303 K
 L•atm 
 0.0821  288 K 
mol•K 
= 
nRT
Initial volume (L) = V = = 23.6448 = 23.6 L/mol
P 1.00 atm 
 L•atm 
 0.0821 mol • K   303 K 
Final volume (L) = V =
nRT
=   = 24.8763 = 24.9 L/mol
P 1.00 atm 
b) Internal energy is the sum of the potential and kinetic energies of each He atom in the system (the balloon). The
energy of one mole of helium atoms can be described as a function of temperature, E = 3/2nRT, where n = 1 mole.
Therefore, the internal energy at 15°C and 30°C can be calculated. The inside back cover lists values of R with
different units.
E = 3/2nRT = (3/2)(1.00 mol) (8.314 J/mol•K)(303 – 288)K = 187.065 = 187 J
c) When the balloon expands as temperature rises, the balloon performs PV work. However, the problem specifies
that pressure remains constant, so work done on the surroundings by the balloon is defined by the equation:
w = –PV. When pressure and volume are multiplied together, the unit is L•atm, so a conversion factor is needed
to convert work in units of L•atm to joules.
 101.3 J 
w = –PV =  1.00 atm  (24.8763  23.6448) L    = –124.75 = –1.2x10 J
2

 1 L•atm 
d) q P = E + PV = (187.065 J) + (124.75 J) = 311.815 = 3.1x102 J
e) H = q P = 310 J.
f) When a process occurs at constant pressure, the change in heat energy of the system can be described by a state
function called enthalpy. The change in enthalpy equals the heat (q) lost at constant pressure: H = E + PV =
E – w = (q + w) – w = q P

6.85 a) Respiration:
C 6 H 12 O 6 (s) + 6O 2 (g)  6CO 2 (g) + 6H 2 O(g)

H rxn = m H f (products) – n H f (reactants)
= {6 H f [CO 2 (g)] + 6 H f [H 2 O(g)]} – {1 H f [C 6 H 12 O 6 (s)] + 6 H f [O 2 (g)]}
= [(6 mol)(–393.5 kJ/mol) + (6 mol)(–241.826 kJ/mol)] – [(1 mol)(–1273.3 kJ/mol) + (6 mol)(0.0 kJ/mol)]
= –2538.656 = – 2538.7 kJ

6-16
 Fermentation:
C 6 H 12 O 6 (s)  2CO 2 (g) + 2CH 3 CH 2 OH(l)

H rxn = {2 H f [CO 2 (g)] + 2 H f [CH 3 CH 2 OH(l)]} – [1 H f [C 6 H 12 O 6 (s)]}
= [(2 mol)(–393.5 kJ/mol) + (2 mol)(–277.63 kJ/mol)] – [(1 mol)(–1273.3 kJ/mol)] = –68.96 = – 69.0 kJ
b) Combustion of ethanol:
CH 3 CH 2 OH(l) + 3O 2 (g)  2CO 2 (g) + 3H 2 O(g)

H rxn = {2 H f [CO 2 (g)] + 3 H f [H 2 O(g)]} – {1 H f [CH 3 CH 2 OH(l)] + 3 H f [O 2 (g)]}

H rxn = [(2 mol)(–393.5 kJ/mol) + (3 mol)(–241.826 kJ/mol)] – [(1 mol)(–277.63 kJ/mol) + (3 mol)(0.0 kJ/mol)]
= –1234.848 = – 1234.8 kJ
Heats of combustion/mol C:
 2538.656 kJ   1 mol C6 H12 O6 
Sugar:    = –423.1093 = –423.11 kJ/mol C
 1 mol C6 H12 O6   6 mol C 
 1234.848 kJ   1 mol CH3CH 2 OH 
Ethanol:    = –617.424 = –617.42 kJ/mol C
 1 mol CH3CH 2 OH   2 mol C 
Ethanol has a higher value.

6.86 a) Reactions:
1) C 21 H 44 (s) + 32O 2 (g)  21CO 2 (g) + 22H 2 O(g)
2) C 21 H 44 (s) + 43/2O 2 (g)  21CO(g) + 22H 2 O(g)
3) C 21 H 44 (s) + 11O 2 (g)  21C(s) + 22H 2 O(g)
Heats of combustion:

1) H rxn = {21 H f [CO 2 (g)] + 22 H f [H 2 O(g)]} – {[1 H f [C 21 H 44 (s)] + 32 H f [O 2 (g)]}
= [(21 mol)(–393.5 kJ/mol) + (22 mol)(–241.826 kJ/mol)]
– [(1 mol)(–476 kJ/mol) + (32 mol)(0.0 kJ/mol)]
= –13,107.672 = –13,108 kJ

2) H rxn = {21 H f [CO(g)] + 22 H f [H 2 O(g)]} – {1 H f [C 21 H 44 (s)] + 43/2 H f [O 2 (g)]}
= [(21 mol)(–110.5 kJ/mol) + (22 mol)(–241.826 kJ/mol)]
– [(1 mol)(–476 kJ/mol) + (43/2 mol)(0.0 kJ/mol)] = –7164.672 = –7165 kJ

3) H rxn = {21 H f [C(s)] + 22 H f [H 2 O(g)]} – {1 H f [C 21 H 44 (s)] + 11 H f [O 2 (g)]}
= [(21 mol)(0.0 kJ/mol) +(22 mol)(–241.826 kJ/mol)] – [(1 mol)(–476 kJ/mol) + (11 mol)(0.0 kJ/mol)]
= –4844.172 = –4844 kJ
 1 mol C21H 44   13107.672 kJ 
b) q (kJ) =  254 g C21H 44   
4
 = –1.12266x10 = –1.12x10 kJ
4

 296.56 g C H
21 44   1 mol C H
21 44 
c) The moles of C 21 H 44 need to be calculated one time for multiple usage. It must be assumed that the remaining
87.00% of the candle undergoes complete combustion.
Moles C 21 H 44 = (254 g C 21 H 44 )(1 mol C 21 H 44 /296.56 g C 21 H 44 ) = 0.856488 mol
q = (0.87)(0.856488 mol)(–13107.672 kJ/mol) + (0.0800)(0.856488 mol)(–7164.672 kJ/mol)
+ (0.0500)(0.856488 mol)(–4844.172 kJ/mol)] = –1.04655x104 = –1.05x104 kJ


6.87 a) EO(l) → EO(g) H vap = 569.4 J/g(44.05 g/mol)(1 kJ/1000 J) = 25.08 kJ/mol

H vap = {1 H f [EO(g)]} – {1 H f [EO(l)]}

25.08 kJ/mol = { H f [EO(g)]} – [(1 mol)(–77.4 kJ/mol)]

H f [EO(g)] = –52.32 kJ/mol
EO(g) → CH 4 (g) + CO(g)

H rxn = {1 H f [CH 4 (g)] + 1 H f [CO(g)]} – {1 H f [EO(g)]}

H rxn = [(1 mol)(–74.87 kJ/mol) + (1 mol)(–110.5 kJ/mol)] – [(1 mol)(–52.32 kJ/mol)]

6-17
 
H rxn = –133.0 kJ/mol
b) Assume that you have 1.00 mole of EO(g). 1.00 mole of EO(g) produces 1.00 mole or 16.04 g of CH 4 (g) and
1.00 mole or 28.01 g of CO(g). There is a total product mass of 16.04 g + 28.01 g = 44.05 g.
q = c x mass x T

133.0 kJ  
1000 J 
q  1 kJ 
ΔT = =
c x mass  2.5 J/gC  44.05 g 
ΔT = 1207.7ºC
ΔT = T final – T initial
1207.7ºC = T final – 93ºC
T final = 1300.72 = 1301°C

6.88 a) 3N 2 O 5 (g) + 3NO(g) → 9NO 2 (g)


H rxn = {9 H f [NO 2 (g)]} – {3 H f [N 2 O 5 (g)] + 3 H f [NO(g)]}
= [(9 mol)(33.2 kJ/mol)] – [(3 mol)(11 kJ/mol) + (3 mol)(90.29 kJ/mol)]
 = –5.07 = –5 kJ
 1.50x102 mol   5.07 kJ   103 J 
b)  9 molecules product   = –76.05 = –76.0 J
 1 molecule product   9 moles product   1 kJ 

   

 4 qt   1 L   1 mL   0.692 g   1 mol C8 H18   5.44x103 kJ 

6.89 a) Heat (kJ) =  20.4 gal      3      
 1 gal   1.057 qt   10 L   mL   114.22 g   1 mol C8 H18 
= –2.54435678x106 = –2.54x106 kJ


b) Distance (km) = 2.54435678x106 kJ    1h
4
  65 mi   1 km 
 5.5x10 kJ    
3
  1 h   0.62 mi  = 4.84995x10 = 4.8x10 km
3

c) Only a small percentage of the chemical energy in the fuel is converted to work to move the car; most of the
chemical energy is lost as waste heat flowing into the surroundings.

6.90 q = c x mass x T
In this situation, all of the samples have the same mass, 50. g, so mass is not a variable.
All also have the same q value, 450. J. So, 450. J α (c x ΔT). c, specific heat capacity, and ΔT are inversely
proportional. The higher the ΔT, the lower the value of specific heat capacity:
ΔT: B > D > C > A
Specific heat capacity: B < D < C < A


6.91 ClF(g) + 1/2O 2 (g)  1/2Cl 2 O(g) + 1/2OF 2 (g) H rxn = 1/2(167.5 kJ) = 83.75 kJ

F 2 (g) + 1/2O 2 (g)  OF 2 (g) H rxn = 1/2(–43.5 kJ) = –21.75 kJ

1/2Cl 2 O(g) + 3/2OF 2 (g)  ClF 3 (l) + O 2 (g) H rxn = –1/2(394.1 kJ) = –197.05 kJ

ClF(g) + F 2 (g)  ClF 3 (l) H rxn = –135.1 kJ

6.92 a) AgNO 3 (aq) + NaI(aq)  AgI(s) + NaNO 3 (aq)

 103 L   5.0 g AgNO3   1 mol AgNO3 
Moles of AgNO 3 =  50.0 mL  
 1 mL   1L
 
    169.9 g AgNO3 
= 1.47145x10–3 mol AgNO 3
 103 L   5.0 g NaI   1 mol NaI 
Moles of NaI =  50.0 mL  
 1 mL   1 L  
    149.9 g NaI 
= 1.6677785x10–3 mol NaI

6-18
 The AgNO 3 is limiting, and will be used to finish the problem:
 1 mol AgI   234.8 g AgI 

Mass (g) of AgI = 1.47145x103 mol AgNO3    
 1 mol AgNO3   1 mol AgI 
= 0.345496 = 0.35 g AgI
b) Ag+(aq) + I–(aq)  AgI(s)

H rxn = {1 H f [AgI(s)]} – {1 H f [Ag+(aq)] + 1 H f [I–(aq)]}
= [(1 mol)(–62.38 kJ/mol)] – [(1 mol)(105.9 kJ/mol) + (1 mol)(–55.94 kJ/mol)]
= –112.3 kJ

c) H rxn = q = c x mass x T
 112.3 kJ   1 mol AgI  
 
 mol AgI   1 mol AgNO3 
 3
 1.47145x10 mol AgNO3 
  103 J 


T = H rxn /c x mass =   
 4.184 J    1.00 g    1 kJ 
 g•K    50.0  50.0  mL  mL  
   
= 0.39494 = 0.39 K

6.93 Plan: Use conversion factors to solve parts a) and b). For part c), first find the heat of reaction for the combustion
of methane by using the heats of formation of the reactants and products. The enthalpy change of a reaction is the
sum of the heats of formation of the products minus the sum of the heats of formation of the reactants. Since the
H fo values (Appendix B) are reported as energy per one mole, use the appropriate stoichiometric coefficient to
reflect the higher number of moles. For part e), convert the amount of water in gal to mass in g and use the
relationship q = c x mass x T to find the heat needed; then use the conversion factors between joules and therms
and the cost per therm to determine the total cost of heating the water.
Solution:
 1 cal   4.184 J   453.6 g  1.0 C   1.00 lb F 
a)       = 1054.368 = 1.1x10 J/Btu
3

 g C  1 cal  1 lb  1.8  F  1 Btu 

 100, 000 Btu   1054.368 J 
b) E = 1.00 therm   
8
 = 1.054368x10 = 1.1x10 J
8

 1 therm   Btu 
c) CH 4 (g) + 2O 2 (g) → CO 2 (g) + 2H 2 O(g)

H rxn = {1 H f [CO 2 (g)] + 2 H f [H 2 O(g)]} – {1 H f [CH 4 (g)] + 2 H f [O 2 (g)]}
= [(1 mol)(–393.5 kJ/mol) + (2 mol)(–241.826 kJ/mol)] – [(1 mol)(–74.87 kJ/mol) + (2 mol)(0.0 kJ/mol)]
= –802.282 = –802.3 kJ/mol CH 4
 1.054368x108 J   1 kJ   1 mol CH 4 
Moles of CH 4 = 1.00 therm     3   
 1 therm
   10 J   802.282 kJ 
= 131.4211 = 1.3x102 mol CH 4
 $0.66   1 therm 
d) Cost =    = 0.005022 = $0.0050/mol
 therm   131.4211 mol 
 4 qt   1 L   1 mL   1.0 g 
e) Mass (g) of =  318 gal      3  
6
 = 1.203406x10 g
 1 gal   1.057 qt   10 L   mL 
 4.184 J 
q = c x mass x T = 
 g C
 6
 1.203406x10 g

   42.0  15.0 C  = 1.359464x10
8
J

  $0.66 
 
Cost = 1.359494x108 J   1 therm
8   = 0.850999 = $0.85
 1.054368x10 J   1 therm 

6-19
  1018 J   1 kJ   1 mol CH 4   16.04 g CH 4   1 kg 
6.94 a) Mass (kg) of =  5600 EJ   = 1.12x1014 kg CH 4
 1 EJ   103 J   802 kJ   1 mol CH   103 g 
    4  
 1 yr 
b) Years =  5600 EJ   2  = 14 yr
 4.0x10 EJ 
 1 L   1 mL   1.00 g   4.184 J   1 kJ   1 mol CH 4 
c) Moles of CH 4 = 1.00 qt  
1.057 qt
  3  
mL   g C   100.0  25.0  C   3   802 kJ 
   10 L      10 J   
= 0.370172 mol CH 4
 16.04 g CH 4  1L   103 m3   35.3 ft 3 
Volume (ft3) of CH 4 =  0.370172 mol CH 4        3 
 1 mol CH 4  0.72 g CH 4   1 L   1 m 
= 0.291105 = 0.29 ft3
 1 kJ   1 mol CH 4   16.04 g CH 4     103 m3   35.3 ft 3 
 
d) Volume = 2x1013 J  3    
1L
    3  
 10 J   802 kJ   1 mol CH 4   0.72 g CH 4   1 L   1 m 
= 1.9611x107 = 2x107 ft3

6.95 The reaction is exothermic. The argon atoms in the chamber after the reaction are moving with greater kinetic
energy, indicating an increase in temperature.

6.96 H 2 SO 4 (aq) + 2NaOH(aq) → Na 2 SO 4 (aq) + 2H 2 O(l)

2H+(aq) + 2OH–(aq) → 2H 2 O(l)

H rxn = {2 H f [H 2 O(l)]} – {2 H f [H+(aq)] + 2 H f [OH–(aq)]}
= [(2 mol)(–285.84 kJ/mol)] – [(2 mol)(0 kJ/mol) + (2 mol)(–229.94 kJ/mol)]
= –111.8 kJ
1 mole of H 2 SO 4 reacts with 2 moles of NaOH.
 1.00 L   1.00 mL   1.030 g 
Mass (g) of H 2 SO 4 solution = 1 mol H 2SO 4     3  
 0.50 mol H 2 SO 4   10 L   1.00 mL 
= 2060 g H 2 SO 4 solution
 40.00 g NaOH   100 g solution 
Mass (g) of NaOH solution =  2 mol NaOH     = 200. g NaOH solution
 1 mol NaOH   40 g NaOH 
q = c x mass x T
 103 J 
111.8 kJ   
ΔT =
q
=  1 kJ  = 11.82ºC
c x mass 4.184 J/g C   2060 + 200  g 
31ºC + 11.82ºC = 42.82 = 43ºC
This temperature is above the temperature at which a flammable vapor could be formed so the temperature
increase could cause the vapor to explode.

6.97 a) 2C 12 H 26 (l) + 37O 2 (g) → 24CO 2 (g) + 26H 2 O(g)


b) H rxn = {24 H f [CO 2 (g)] + 26 H f [H 2 O(g)]} – {2 H f [C 12 H 26 (g)] + 37 H f [O 2 (g)]}
4
–1.50x10 kJ = [(24 mol)(–393.5 kJ/mol) + (26 mol)(–241.826 kJ/mol)]
– [(2 mol) H f [C 12 H 26 (g)] + (37 mol)(0.0 kJ/mol)]
–1.50x104 kJ = –9444.0 kJ + –6287.476 kJ – [(2 mol) H f [C 12 H 26 (g)] + 0.0 kJ]
–1.50x104 kJ = –15,731.476 kJ – (2 mol) H f [C 12 H 26 (g)]
–1.50x104 kJ + 15,731.476 kJ = –(2 mol) H f [C 12 H 26 (g)]

6-20
 731.476 kJ = –(2 mol) H f [C 12 H 26 (g)]
H f [C 12 H 26 (g)] = –365.738 = – 3.66x102 kJ
 4 qt   1 L   1 mL   0.749 g C12 H 26   1 mol C12 H 26   1.50x104 kJ 
c) Heat (kJ) =  0.50 gal      3     170.33 g C H   2 mol C H 
 1 gal   1.057 qt   10 L   mL  12 26   12 26 
4
= –6.2403x10 = –6.2x10 kJ 4

 1.055 kJ   0.50 gal 

d) Volume (gal) = 1250. Btu    4  = 0.010566 = 1.1x10 gal
–2

 1 Btu   6.2403x10 kJ 


6.98 Plan: Heat of reaction is calculated using the relationship H rxn = m H f (products) – n H f (reactants) .
The heats of formation for all of the species, except SiCl 4 , are found in Appendix B. Use reaction 3, with its

given H rxn , to find the heat of formation of SiCl 4 (g). Once the heat of formation of SiCl 4 is known, the heat of
reaction of the other two reactions can be calculated. When reactions 2 and 3 are added to obtain a fourth
reaction, the heats of reaction of reactions 2 and 3 are also added to obtain the heat of reaction for the fourth
reaction.
Solution:
a) (3) SiCl 4 (g) + 2H 2 O(g)  SiO 2 (s) + 4HCl(g)

H rxn = {1 H f [SiO 2 (s)] + 4 H f [HCl(g)]} – {1 H f [SiCl 4 (g)] + 2 H f [H 2 O(g)]}
–139.5 kJ = [(1 mol)(–910.9 kJ/mol) + (4 mol)(–92.31 kJ/mol)] – [ H f [SiCl 4 (g)] + (2 mol)(–241.826 kJ/mol)]
–139.5 kJ = –1280.14 – [ H f [SiCl 4 (g)] + (–483.652 kJ)]
1140.64 kJ = – H f [SiCl 4 (g)] + 483.652 kJ
H f [SiCl 4 (g)] = –656.988 kJ/mol
The heats of reaction for the first two steps can now be calculated.
1) Si(s) + 2Cl 2 (g)  SiCl 4 (g)

H rxn = {1 H f [SiCl 4 (g)]} – {1 H f [Si(s)] + 2 H f [Cl 2 (g)]}
= [(1 mol)(–656.988 kJ/mol)] – [(1 mol)(0 kJ/mol) + (2 mol)(0 kJ/mol)] = –656.988 = –657.0 kJ
2) SiO 2 (s) + 2C(graphite) + 2Cl 2 (g)  SiCl 4 (g) + 2CO(g)

H rxn = {1 H f [SiCl 4 (g)] + 2 H f [CO(g)]}
– {1 H f [SiO 2 (g)] + 2 H f [C(graphite)] +2 H f [Cl 2 (g)]}
= [(1 mol)(–656.988 kJ/mol) + (2 mol)(–110.5 kJ/mol)]
– [(1 mol)(–910.9 kJ/mol) + (2 mol)(0 kJ/mol) + (2 mol)(0 kJ/mol)]
= 32.912 = 32.9 kJ
b) Adding reactions 2 and 3 yields:

(2) SiO 2 (s) + 2C(graphite) + 2Cl 2 (g)  SiCl 4 (g) + 2CO(g) H rxn = 32.912 kJ

(3) SiCl 4 (g) + 2H 2 O(g)  SiO 2 (s) + 4HCl(g) H rxn = –139.5 kJ

2C(graphite) + 2Cl 2 (g) + 2H 2 O(g) → 2CO(g) + 4HCl(g) H rxn = –106.588 kJ = –106.6 kJ
o
Confirm this result by calculating H rxn
using Appendix B values.
2C(graphite) + 2Cl 2 (g) + 2H 2 O(g) → 2CO(g) + 4HCl(g)

H rxn = {2 H f [CO(g)] + 4 H f [HCl(g)]} – {2 H f [C(graphite)] + 2 H f [Cl 2 (g)] + 2 H f [H 2 O(g)]}
= [(2 mol)(–110.5 kJ/mol) + (4 mol)(–92.31 kJ)
– [(2 mol)(0 kJ/mol) + (2 mol)(0 kJ/mol) + (2 mol)(–241.826 kJ/mol)]
= –106.588 = –106.6 kJ

6-21
6.99 Plan: Use PV = nRT to find the initial volume of nitrogen gas at 0°C and then the final volume at 819°C. Then
the relationship w = –PΔV can be used to calculate the work of expansion.
Solution:
a) PV = nRT

1 mol   0.0821
L•atm 
mol•K   273 K 
Initial volume at 0°C + 273 = 273 K = V =
nRT
=   = 22.4133 L
P 1.00 atm 
1 mol   0.0821
L•atm 
1092 K 
nRT  mol•K 
Final volume at 819°C + 273 = 1092 K = V = = = 89.6532 L
P 1.00 atm 
ΔV = V final – V initial = 89.6532 L – 22.4133 L = 67.2399 L
w = –PV = –(1 atm) x 67.2399 L = –67.2399 atm•L
 1J 
w (J) =  67.2399 atm•L   3  = –6812.553 = –6.81x10 J
3

 9.87 x 10 atm•L 
b) q = c x mass x T
 28.02 g 
Mass (g) of N 2 = 1 mol N 2    = 28.02 g
 1 mol N 2 
q 6.812553x103 J
T = = = 243.132 = 243 K = 243°C
(c)(mass)  28.02 g  (1.00 J/g•K)
6.100 Plan: Note the numbers of moles of the reactants and products in the target equation and manipulate equations

1-5 and their H rxn values so that these equations sum to give the target equation. Then the manipulated
o 
H rxn values will add to give the H rxn value of the target equation.
Solution:
Only reaction 3 contains N 2 O 4 (g), and only reaction 1 contains N 2 O 3 (g), so we can use those reactions as a
starting point. N 2 O 5 appears in both reactions 2 and 5, but note the physical states present: solid and gas. As
a rough start, adding reactions 1, 3, and 5 yields the desired reactants and products, with some undesired
intermediates:

Reverse (1) N 2 O 3 (g)  NO(g) + NO 2 (g) H rxn = –(–39.8 kJ) = 39.8
kJ

Multiply (3) by 2 4NO 2 (g)  2N 2 O 4 (g) H rxn = 2(–57.2 kJ) = –114.4 kJ

(5) N 2 O 5 (s)  N 2 O 5 (g) H rxn = (54.1 kJ) = 54.1
kJ
N 2 O 3 (g) + 4NO 2 (g) + N 2 O 5 (s)  NO(g) + NO 2 (g) + 2N 2 O 4 (g) + N 2 O 5 (g)
To cancel out the N 2 O 5 (g) intermediate, reverse equation 2. This also cancels out some of the undesired NO 2 (g)
but adds NO(g) and O 2 (g). Finally, add equation 4 to remove those intermediates:

Reverse (1) N 2 O 3 (g)  NO(g) + NO 2 (g) H rxn = –(–39.8 kJ) = 39.8 kJ

Multiply (3) by 2 4NO 2 (g)  2N 2 O 4 (g) H rxn = 2(–57.2 kJ) = –114.4 kJ

(5) N 2 O 5 (s)  N 2 O 5 (g) H rxn = 54.1 kJ

Reverse (2) N 2 O 5 (g)  NO(g) + NO 2 (g) + O 2 (g) H rxn = –(–112.5 kJ) = 112.5

(4) 2NO(g) + O 2 (g)  2NO 2 (g) H rxn = –114.2 kJ

Total: N 2 O 3 (g) + N 2 O 5 (s)  2N 2 O 4 (g) H rxn = –22.2 kJ

6-22
6.101 Plan: The enthalpy change of a reaction is the sum of the heats of formation of the products minus the sum of the
heats of formation of the reactants. Since the H f values (Appendix B) are reported as energy per one mole, use

the appropriate stoichiometric coefficient to reflect the higher number of moles. In this case, H rxn of the second
reaction is known and H f of N 2 H 4 (aq) must be calculated. For part b), calculate H rxn

for the reaction
between N 2 H 4 (aq) and O 2 , using the value of H f for N 2 H 4 (aq) found in part a); then determine the moles of

O 2 present by multiplying volume and molarity and multiply by the H rxn for the reaction.
Solution:
a) 2NH 3 (aq) + NaOCl(aq) → N 2 H 4 (aq) + NaCl(aq) + H 2 O(l)

H rxn = {1 H f [N 2 H 4 (aq)] + 1 H f [NaCl(aq)] + 1 H f [H 2 O(l)]}
– {2 H f [NH 3 (aq)] + 1 H f [NaOCl(aq)]}
Note that the Appendix B value for N 2 H 4 is for N 2 H 4 (l), not for N 2 H 4 (aq), so this term must be calculated. In
addition, Appendix B does not list a value for NaCl(aq), so this term must be broken down into
H f [Na+(aq)] and H f [Cl–(aq)].
–151 kJ = [ H f [N 2 H 4 (aq)] + (1 mol)(–239.66 kJ/mol) + (1 mol)(–167.46 kJ/mol) + (1 mol)(–285.840 kJ/mol)]
– [(2 mol)(–80.83 kJ/mol) + (1 mol)(–346 kJ/mol)]
–151 kJ = [ H f [N 2 H 4 (aq)] + (– 692.96 kJ)] – [–507.66 kJ]
–151 kJ = [ H f [N 2 H 4 (aq)] + (–185.3 kJ)
H f [N 2 H 4 (aq)] = 34.3 = 34 kJ
 2.50x104 mol 

b) Moles of O 2 = 5.00x103 L  
 1L
 = 1.25 mol O 2
 
N 2 H 4 (aq) + O 2 (g) → N 2 (g) + 2H 2 O(l)

H rxn = {1 H f [N 2 (g)] + 2 H f [H 2 O(l)]} – {1 H f [N 2 H 4 (aq)] + 1 H f [O 2 (g)]}
= [(1 mol)(0 kJ/mol) + (2 mol)(–285.840 kJ/mol)] – [(1 mol)(34.3 kJ/mol) + (1 mol)(0 kJ/mol]
= –605.98 kJ
 605.98 kJ 
Heat (kJ) = 1.25 mol O 2    = –757.475 = –757 kJ
 1 mol O 2 

6.102 CO(g) + 2H 2 (g) → CH 3 OH(l)


H rxn = {1 H f [CH 3 OH(l)]} – {1 H f [CO(g)] + 2 H f [H 2 (g)]}
= [(1 mol)(–238.6 kJ/mol)] – [(1 mol)(–110.5 kJ mol) + (2 mol)(0.0 kJ/mol)]
= –128.1 kJ
Find the limiting reactant:

Moles of CO =
PV
=
112 kPa 15.0 L   1 atm 
  = 0.5641135 mol CO
 L•atm  101.325 kPa
 0.0821 mol•K    273  85 K 
RT  
 
 1 mol CH 3 OH 
Moles of CH 3 OH from CO =  0.5641135 mol CO    = 0.5641135 mol CH 3 OH
 1 mol CO 

Moles of H 2 =
PV
=
 744 torr 18.5 L   1 atm 
  = 0.6338824 mol H 2
 L•atm   760 torr 
RT
 0.0821
mol•K 
  273  75  K 

 1 mol CH3OH 
Moles of CH 3 OH from H 2 =  0.6338824 mol H 2    = 0.3169412 mol CH 3 OH
 2 mol H 2 
H 2 is limiting.

6-23
  128.1 kJ 
Heat (kJ) =  0.6338824 mol H 2    = –40.6002 = –40.6 kJ
 2 mol H 2 

6.103 Plan: First find the heat of reaction for the combustion of methane. The enthalpy change of a reaction is the sum
of the heats of formation of the products minus the sum of the heats of formation of the reactants. Since the
H f values (Appendix B) are reported as energy per one mole, use the appropriate stoichiometric coefficient to
reflect the higher number of moles. Convert the mass of methane to moles and multiply that mole number by the
heat of combustion.
Solution:
a) The balanced chemical equation for this reaction is:
CH 4 (g) + 2O 2 (g)  CO 2 (g) + 2H 2 O(g)

H rxn = {1 H f [CO 2 (g)] + 2 H f [H 2 O(g)]} – {1 H f [CH 4 (g)] + 2 H f [O 2 (g)]}
= [(1 mol)(–393.5 kJ/mol) + (2 mol)(–241.826 kJ/mol)] – [(1mol)(–74.87 kJ/mol) + (2 mol)(0.0 kJ/mol)]
= –802.282 kJ
 1 mol 
Moles of CH 4 =  25.0 g CH 4    = 1.5586 mol CH 4
 16.04 g CH 4 

 802.282 kJ 
Heat (kJ) = 1.5586 mol CH 4    = –1250.4 = –1.25x10 kJ
3

 1 mol CH 4 
b) The heat released by the reaction is “stored” in the gaseous molecules by virtue of their specific heat capacities,
c, using the equation q = c x mass x T. The problem specifies heat capacities on a molar basis, so we modify the
equation to use moles, instead of mass. The gases that remain at the end of the reaction are CO 2 and H 2 O. All of
the methane and oxygen molecules were consumed. However, the oxygen was added as a component of air,
which is 78% N 2 and 21% O 2 , and there is leftover N 2 .
 1 mol CO 2 
Moles of CO 2 (g) = 1.5586 mol CH 4    = 1.5586 mol CO 2 (g)
 1 mol CH 4 
 2 mol H 2 O 
Moles of H 2 O(g) = 1.5586 mol CH 4    = 3.1172 mol H 2 O(g)
 1 mol CH 4 
 2 mol O 2 
Moles of O 2 (g) reacted = 1.5586 mol CH 4    = 3.1172 mol O 2 (g)
 1 mol CH 4 
Mole fraction N 2 = (79%/100%) = 0.79
Mole fraction O 2 = (21%/100%) = 0.21
 0.79 mol N 2 
Moles of N 2 (g) =  3.1172 mol O 2 reacted    = 11.72661 mol N 2
 0.21 mol O 2 
q = c x mass x T
 103 J 
q = 1250.4 kJ   = 1.2504x106 J
 1 kJ 
 
6
1.2504x10 J = (1.5586 mol CO 2 )(57.2 J/mol°C)(T final – 0.0)°C
+ (3.1172 mol H 2 O)(36.0 J/mol°C)(T final – 0.0)°C
+ (11.72661 mol N 2 )(30.5 J/mol°C)(T final – 0.0)°C
1.2504x106 J = 89.15192 J/°C(T final ) + 112.2192 J/°C(T final ) + 357.6616 J/°C(T final )
1.2504x106 J = (559.03272 J/°C)T final
T final = (1.2504x106 J)/(559.0324 J/°C) = 2236.72 = 2.24x103°C

6-24