07 Petrucci10e CSM
07 Petrucci10e CSM
07 Petrucci10e CSM
THERMOCHEMISTRY
PRACTICE EXAMPLES
1A
(E) The heat absorbed is the product of the mass of water, its specific heat 4.18 J g 1 C 1 ,
4.18 J
1 kJ
37.0 C 4.0 C
= 32.7 kJ of heat energy
gC
1000 J
(E) The heat absorbed is the product of the amount of mercury, its molar heat capacity, and the
temperature change that occurs.
FG
H
IJ
K
1000 g
1 mol Hg
28.0 J
1 kJ
6.0 20.0 C
mol C
1 kg
200.59 g Hg
1000 J
(E) First calculate the quantity of heat lost by the lead. This heat energy must be absorbed by the
surroundings (water). We assume 100% efficiency in the energy transfer.
qlead = 1.00 kg
4.18 J
35.2 C 28.5 C = 28mwater
g C
mwater =
8.4 103 J
= 3.0 102 g
28 J g -1
(M) We use the same equation, equating the heat lost by the copper to the heat absorbed by the
water, except now we solve for final temperature.
qCu = 100.0 g
x=
0.385 J
4.18 J
x C 100.0 C = 50.0 g x C 26.5 C = q water
gC
gC
3A
1000 g 0.13 J
35.2 C 100.0 C = 8.4 103 J = qwater
1 kg
gC
9389 J
= 37.9 C
-1
247.5 J C
(E) The molar mass of C8 H 8O 3 is 152.15 g/mol. The calorimeter has a heat capacity of
4.90 kJ / C .
qcalor =
h 152.15 g = 3.83 10
1 mol
kJ / mol
Chapter 7: Thermochemistry
3B
(E) The heat that is liberated by the benzoic acids combustion serves to raise the
temperature of the assembly. We designate the calorimeters heat capacity by C .
26.42 kJ
qrxn = 1.176 g
= 31.07 kJ = qcalorim
1g
31.07 kJ
qcalorim = Ct = 31.07 kJ = C 4.96 C
C=
= 6.26 kJ / C
4.96 C
4A
(M) The heat that is liberated by the reaction raises the temperature of the reaction mixture.
We assume that this reaction mixture has the same density and specific heat as pure water.
1.00 g 4.18 J
3
qcalorim = 200.0 mL
30.2 22.4 C = 6.5 10 J= qrxn
1
mL
g
C
Owing to the 1:1 stoichiometry of the reaction, the number of moles of AgCl(s) formed is equal
to the number of moles of AgNO3(aq) in the original sample.
1.00 M AgNO3 1 mol AgCl
1L
moles AgCl = 100.0 mL
qrxn
6.5 103 J 1 kJ
=
= 65. kJ/mol
0.100 mol 1000 J
(M) The assumptions include no heat loss to the surroundings or to the calorimeter, a
solution density of 1.00 g/mL, a specific heat of 4.18 J g 1 C 1 , and that the initial and
final solution volumes are the same. The equation for the reaction that occurs is
NaOH aq + HCl aq NaCl aq + H 2 O l . Since the two reactants combine in a one to
one mole ratio, the limiting reactant is the one present in smaller amount (i.e. the one with
a smaller molar quantity).
1.020 mmol HCl
amount HCl = 100.0 mL
= 102.0 mmol HCl
1 mL soln
1.988 mmol NaOH
amount NaOH = 50.0 mL
= 99.4 mmol NaOH
1 mL soln
Thus, NaOH is the limiting reactant.
1 mmol H 2 O
1 mol H 2 O
56 kJ
qneutr = 99.4 mmol NaOH
= 5.57 kJ
1 mmol NaOH 1000 mmol H 2 O 1 mol H 2 O
1.00 g 4.18 J 1 kJ
qcalorim = qneutr = 5.57 kJ = 100.0 + 50.0 mL
t 24.52 C
1 mL
g C 1000 J
5.57 +15.37
= 0.627t 15.37
t=
= 33.4 C
0.627
5A
263
101.33 J
= 114 J
1 L atm
Chapter 7: Thermochemistry
5B
6A
101.33 J
1 kJ
= +14.6 kJ work done on system.
1 L atm 1000 J
(E) The work is w = +355 J. The heat flow is q = 185 J. These two are related to the energy
change of the system by the first law equation: U = q + w, which becomes
(E) The internal energy change is U = 125 J. The heat flow is q = +54 J. These two are
related to the work done on the system by the first law equation: U = q + w , which becomes
125 J = +54 J + w. The solution to this equation is w = 125 J 54 J = 179 J , which means
that 179 J of work is done by the system to the surroundings.
7A
(E) Heat that is given off has a negative sign. In addition, we use the molar mass of sucrose,
342.30 g/mol.
1 mol C12 H 22 O11 342.30 g C12 H 22 O11
sucrose mass = 1.00 103 kJ
7B
(E) Although the equation does not say so explicitly, the reaction of H+(aq) + OH-(aq)
H2O(l) gives off 56 kJ of heat per mole of water formed. The equation then is the source of
a conversion factor.
1L
0.1045 mol HCl 1 mol H 2 O 56 kJ evolved
heat flow = 25.0 mL
1000 mL
1 L soln
1 mol HCl
1 mol H 2 O
heat flow = 0.15 kJ heat evolved
8A
mice = mwater = 8.00 cm3 0.917 g cm-3 = 7.34 g ice = 7.34 g H2O
1 mol H 2 O
= 0.407 moles of ice
18.015 g H 2 O
qoverall = qice(10 to 0 C) + qfus +qwater(0 to 23.2 C)
moles of ice = 7.34 g ice
J
o
g C
264
kJ
mol
J
g oC
Chapter 7: Thermochemistry
8B
5.00 103 kJ = mice(sp. ht.)iceT + niceH fus + mwater(sp. ht.)waterT + nwaterH vap
J
J
m
5.00 106 J = m(15.0 C)(2.01 o )+(
6.01 103 mol )
g C
18.015 g H O/mol H O
2
+ m(25.0 C)(4.184
J
o
g C
m
J
(44.0 103
)
18.015 g H 2 O/mol
mol
)+
5.00 106 J = m(30.15 J/g) + m(333.6 J/g) + m(104.5 J/g) + m(2.44 103 J/g)
5.00 106 J = m(2.91 103 J/g)
9A
m=
5.00 106 J
= 1718 g or 1.72 kg H2O
2.91 103 J/g
(M) We combine the three combustion reactions to produce the hydrogenation reaction.
C3 H 6 g + 92 O 2 g 3CO 2 g + 3H 2 O l
H comb = H1 = 2058 kJ
H 2 g + 12 O 2 g H 2 O l
H comb = H 2 = 285.8 kJ
3CO 2 g + 4H 2 O l C3 H8 g + 5O 2 g
C 3 H 6 g + H 2 g C3 H 8 g
9B
H comb = H 3 = +2219.9 kJ
H rxn = H1 + H 2 + H 3 = 124 kJ
(M) The combustion reaction has propanol and O2(g) as reactants; the products are CO2(g)
and H2O(l). Reverse the reaction given and combine it with the combustion reaction of
C3H 6 g .
bg
bg
b g bg
bg bg
bg
bg
C H OHblg + O bgg 3CO bgg + 4 H Oblg
C 3 H 7 OH l C3 H 6 g + H 2 O l
C 3 H 6 g + 92 O 2 g 3CO 2 g + 3H 2 O l
3
9
2
H1 = +52.3 kJ
H2 = 2058 kJ
H rxn = H1 + H 2 = 2006 kJ
10A (M) The enthalpy of formation is the enthalpy change for the reaction in which one mole of the
product, C 6 H 13O 2 N s , is produced from appropriate amounts of the reference forms of the
elements (in most cases, the most stable form of the elements).
6 C graphite + 132 H 2 g + O 2 g + 12 N 2 g C6 H13O 2 N s
bg
10B (M) The enthalpy of formation is the enthalpy change for the reaction in which one mole of
the product, NH 3 g , is produced from appropriate amounts of the reference forms of the
elements, in this case from 0.5 mol N 2 g and 1.5 mol H 2 g , that is, for the reaction:
bg
1
2
bg
bg
N 2 g + 32 H 2 g NH 3 g
The specified reaction is twice the reverse of the formation reaction, and its enthalpy change is
minus two times the enthalpy of formation of NH 3 g :
bg
2 46.11 kJ = +92.22 kJ
265
Chapter 7: Thermochemistry
o
11A (M) H rxn
=2H of CO 2 g +3H of H 2 O l H of CH 3CH 2 OH l 3H of O 2 g
bg
bg
bg
bg
C 3 H 8 g + 5O 2 g 3CO 2 g + 4 H 2 O l
o
H combustion
=3H of CO 2 g +4H of H 2 O l H of C3 H8 g 5H of O 2 g
= 3 393.5 kJ + 4 285.8 kJ 103.8 kJ 50.00 kJ
bg
bg
bg
bg
o
H combustion
= 4 H of CO 2 g + 5 H of H 2 O l H of C4 H10 g 6.5 H of O 2 g
bg
bg
2220. kJ
2877 kJ
heat of combustion = 0.62 mol C3 H8
+ 0.38 mol C4 H10
1 mol C3 H8
1 mol C4 H10
kJ
mol
)] [6 mol(393.5
kJ
mol
) + 6 mol (285.8
kJ
mol
)]
Hcomb[CH3OCH3(g)] = 31.70
kJ
g
kJ
g
kJ
46.069
= 1460
kJ Hrxn
g
mol
mol
kJ
mol
) + 3 mol (285.8
kJ
mol
266
kJ
mol
)]
Chapter 7: Thermochemistry
b g b g
bg
13A (M) The net ionic equation is: Ag + aq + I aq AgI s and we have the following:
= H f AgI s H f Ag + aq H f I aq
H rxn
= 61.84 kJ/mol +105.6 kJ/mol 55.19 kJ/mol = 112.3 kJ/mol AgI(s) formed
kJ
kJ
) + 1 mol(677.1
)]
mol
mol
INTEGRATIVE EXAMPLE
A. (M) The combustion reactions of C16H32 and C16H34 are shown below
Hf = -10539 kJ
Hf = -10699 kJ/mol = -21398 kJ
Since we are studying the hydrogenation of C16H32 to give C16H34, the final equation has to include the
former as the reactant and the latter as the product. This is done by doubling equation 1 and reversing
equation 2:
(3) 2 C16H32 + 48 O2 32 CO2 + 32 H2O
(4) 32 CO2 + 34 H2O 2 C16H34 + 49 O2
Hf = -21078 kJ
Hf = +21398 kJ
Hf = +320 kJ
Since a hydrogenation reaction involves hydrogen as a reactant, and looking at equation (5), we add
the following reaction to (5):
(6) H2 + O2 H2O
Hf = -285.5 kJ/mol
Hf = +320 kJ
Hf = -571 kJ
Hf = -251 kJ
267
Chapter 7: Thermochemistry
B. (D) This is a multi-stage problem. First, you must determine the amount of material reacted, then
you have to determine the amount of heat generated, and then you have to calculate the effect of that
heat on water evaporation:
1 mol Ca(OH)2
74.12 g Ca(OH) 2
1 mol CaO
= 74.1 g Ca(OH) 2
56.0 g CaO
1 mol CaO
1 mol Ca(OH) 2
H orxn 987 kJ/mol 1 mol 635 kJ/mol 1 mol 286 kJ/mol 1 mol 66 kJ
As stated before, we have to determine the effects of the heat on the water in the reaction. The water
first needs to be heated to 100 C, and then evaporated. The energy needed to heat 82.0 g of the water
remaining in the reaction is:
J m c T 82.0 g 4.187J g 1 o C1 100 o C 20 o C 27.47 kJ
Therefore, 27.47 kJ of energy is used up for the water in the reaction to go from 20 to 100 C. The
energy remaining is -66 (-27.47) = 38.53 kJ.
Since Hvap of water is 44.06 kJ/mol, we can calculate the amount of water evaporated:
1 mol H 2 O
18 g H 2 O
38.53 kJ
15.74 g H 2O evaporated
44.06 kJ
1 mol H 2 O
Based on the above, the contents of the vessel after completion of the reaction are 74.1 g of Ca(OH)2
and 66.3 g of H2O.
268
Chapter 7: Thermochemistry
EXERCISES
Heat Capacity (Specific Heat)
1.
(E)
(a)
(b)
2.
1.00 g
3
4.18 J
3.
1 kJ
29.4 C 22.0 C = +2.9 102 kJ
1L
1 cm
1 g C 1000 J
1000 g 0.903 J
1 kJ
q = 5.85 kg
33.5 C
= 177 kJ
1 kg
gC
1000 J
q = 9.25 L
1000 cm 3
T =
+875 J
= +16.6 C
1 1
12.6 g 4.18 J g C
1000 cal
1kcal
T
21C
1000 g
cal
1.59 kg
0.032
1kg
g C
1.05 kcal
(E) heat gained by the water = heat lost by the metal; heat = mass sp.ht. T
J
(a) 50.0 g 4.18 38.9 22.0 C = 3.53 103 J = 150.0g sp. ht. 38.9 100.0 C
gC
(b)
3.53 103 J
sp.ht. =
= 0.385 J g 1 C 1 for Zn
150.0 g 61.1 C
J
50.0 g 4.18 28.8 22.0 C = 1.4 103 J = 150.0 g sp. ht. 28.8 100.0 C
gC
1.4 103 J
= 0.13 J g 1 C 1 for Pt
150.0 g 71.2 C
J
50.0 g 4.18 52.7 22.0 C = 6.42 103 J = 150.0 g sp. ht. 52.7 100.0 C
gC
sp.ht. =
(c)
6.42 103 J
= 0.905 J g 1 C 1 for Al
150.0 g 47.3 C
J
(E) 50.0 g 4.18 27.6 23.2 C = 9.2 102 J = 75.0 g sp.ht. 27.6 80.0 C
gC
sp.ht. =
4.
9.2 102 J
sp.ht. =
= 0.23 J g 1 C 1 for Ag
75.0 g 52.4 C
5.
J
87 26 o C = 9.56 104 J = qiron
o
g C
J
= 9.56 104 J = 465g 0.449 87 Tl = 1.816 104 J 2.088 102 Tl
gC
qiron
269
Chapter 7: Thermochemistry
Tl =
6.
1.48 104
= 2.2 102 g stainless steel.
66
The precision of this method of determining mass is limited by the fact that some heat leaks
out of the system. When we deal with temperatures far above (or far below) room temperature,
this assumption becomes less and less valid. Furthermore, the precision of the method is
limited to two significant figures by the specific heat of the steel. If the two specific heats were
known more precisely, then the temperature difference would determine the final precision of
the method. It is unlikely that we could readily measure temperatures more precisely than
0.01 C , without expensive equipment. The mass of steel in this case would be measurable to
four significant figures, to 0.1 g. This is hardly comparable to modern analytical balances
which typically measure such masses to 0.1 mg.
66 m = 1.48 104 J
7.
m =
1.024
40.0
C
=
1.00
L
4.18 T f 20.0 C
T
3
1 kg
g C
1L
1 cm
g C
3
4
3
4
1.024 10 T f + 4.10 10 = 4.18 10 T f 8.36 10
1.00 kg Mg
4.10 104 + 8.36 104 = 4.18 103 +1.024 103 T f 12.46 104 = 5.20 103 T f
Tf =
8.
12.46 104
= 24.0 C
3
5.20 10
9.
Tf =
0.385 J
gC
1 mL
3.23 103
= 2.5 J g 1 C 1
3
1.3 10
92.1 g
sp.ht. =
1.26 g
270
Chapter 7: Thermochemistry
10.
11.
12.
(M) The additional water simply acts as a heat transfer medium. The essential relationship
is heat lost by iron = heat gained by water (of unknown mass).
1000 g
J
J
1.23 kg
0.449 o 25.6 68.5 o C = x g H 2 O 4.18 o 25.6 18.5 o C
1 kg
g C
g C
4
1 mL H 2 O
2.37 10
2.37 104 J = 29.7 x
= 798 g H 2 O
= 8.0 102 mL H 2 O
x=
29.7
1.00 g H 2 O
energy transferred
6.052 J
= 1.21 J/K
(25.0 20.0 o C)
T
*Note: since 1K = 1C, it is not necessary to convert the temperatures to Kelvin. The change
in temperature in both K and C is the same.
(M) heat capacity =
J
T f 20.0 o C
o
g C
T f 21.2 o C
Heats of Reaction
1000 g 1 mol Ca OH 2
65.2 kJ
13.
14.
1 gal
1L
1 mL 114.2 g C8 H18 1 mol C8 H18
(M)
(a)
(b)
(c)
1 mol C 4 H 10
2877 kJ
= 65.59 kJ
58.123 g C 4 H 10 1 mol C 4 H 10
1 mol C 4 H 10
2877 kJ
heat evolved = 28.4 LSTP C 4 H 10
= 3.65 103 kJ
22.414 LSTP C 4 H 10 1 mol C 4 H 10
Use the ideal gas equation to determine the amount of propane in moles and multiply
this amount by 2877 kJ heat produced per mole.
heat evolved = 1.325 g C 4 H 10
0.08206 L atm
(273.2 23.6) K
mol K
16.
(M)
(a)
q=
2877 kJ
145
. 103 kJ
1 mol C 4 H 10
29.4 kJ
44.10 g C 3 H 8
271
Chapter 7: Thermochemistry
17.
(b)
q=
(c)
q=
1 mL 58.08 g CH 3 2 CO
(M)
(a)
(b)
1 mol CH 4 16.04 g CH 4
1 kg
= 504 kg CH 4 .
890.3 kJ
1 mol CH 4 1000 g
First determine the moles of CH 4 present, with the ideal gas law.
1atm
4
768 mmHg
1.65 10 L
760
mmHg
696 mol CH 4
mol CH 4
L atm
(18.6 273.2) K
0.08206
mol K
890.3 kJ
heat energy = 696 mol CH 4
= 6.20 105 kJ of heat energy
1 mol CH 4
mass = 2.80 107 kJ
6.21 105 kJ
(c)
18.
VH 2O =
4.18
1000 J
1kJ
J
(60.0 8.8) C
g C
1mL H 2 O
2.90 106 mL = 2.90 103 L H 2 O
1g
(M) The combustion of 1.00 L (STP) of synthesis gas produces 11.13 kJ of heat. The
volume of synthesis gas needed to heat 40.0 gal of water is found by first determining the
quantity of heat needed to raise the temperature of the water.
J
3.785 L 1000 mL
1.00 g
heat water = 40.0 gal
4.18
65.0 15.2 C
gC
1 gal
1 L
1 mL
1 kJ
= 3.15 107 J
= 3.15 104 kJ
1000 J
1 L STP
gas volume = 3.15 104 kJ
= 2.83 103 L at STP
11.13 kJ of heat
FG
H
19.
IJ
K
(M) Since the molar mass of H 2 (2.0 g/mol) is 161 of the molar mass of O 2 (32.0 g/mol)
and only twice as many moles of H 2 are needed as O 2 , we see that O 2 g is the limiting
reagent in this reaction.
1 mol O 2 241.8 kJ heat
180.
g O2
bg
272
Chapter 7: Thermochemistry
20.
(M) The amounts of the two reactants provided are the same as their stoichiometric
coefficients in the balanced equation. Thus 852 kJ of heat is given off by the reaction. We
can use this quantity of heat, along with the specific heat of the mixture, to determine the
temperature change that will occur if all of the heat is retained in the reaction mixture.
We make use of the fact that mass sp.ht. T .
102 g Al2 O3
55.8 g Fe 0.8 J
heat = 8.52 105 J = 1 mol Al 2 O3
T
+ 2 mol Fe
1 mol Al2 O3
1 mol Fe g C
T =
8.52 105 J
= 5 103 C
214 g 0.8 J g 1 C 1
(M)
(a) We first compute the heat produced by this reaction, then determine the value of H in
kJ/mol KOH.
J
qcalorimeter = 0.205 + 55.9 g 4.18 24.4 C 23.5 C = 2 102 J heat = qrxn
g C
1 kJ
2 102 J
1000J
H
5 101 kJ / mol
1mol KOH
0.205 g
56.1g KOH
(b)
22.
The here is known to just one significant figure (0.9 C). Doubling the amount
of KOH should give a temperature change known to two significant figures (1.6 C)
and using twenty times the mass of KOH should give a temperature change known
to three significant figures (16.0 C). This would require 4.10 g KOH rather than the
0.205 g KOH actually used, and would increase the precision from one part in five
to one part in 500, or 0.2 %. Note that as the mass of KOH is increased and the
mass of H2O stays constant, the assumption of a constant specific heat becomes less
valid.
(M) First we must determine the heat absorbed by the solute during the chemical reaction,
qrxn. This is the negative of the heat lost by the solution, qsoln. Since the solution (water plus
solute) actually gives up heat, the temperature of the solution drops.
1 L
2.50 mol KI
20.3 kJ
heat of reaction = 150.0 mL
= 7.61 kJ = qrxn
1000 mL
1 L soln
1 mol KI
1.30 g 2.7 J
7.61 103 J
14C
qrxn = qsoln = 150.0 mL
T
T
1.30 g 2.7 J
1 mL g C
150.0 mL
1mL
273
g C
Chapter 7: Thermochemistry
23.
1 mol NH 4 Cl
14.7 kJ
53.49 g NH 4 Cl 1 mol NH 4 Cl
1000 J
1 kJ
= 1400 mL
+ x 4.18 10. 25 C
1 mL
gC
1.00 g
8.8 104
x=
275 x = 8.8 10 + 63 x ;
= 4.2 102 g NH 4 Cl
275 63
Our final value is approximate because of the assumed density (1.00 g/mL). The solutions
density probably is a bit larger than 1.00 g/mL. Many aqueous solutions are somewhat more
dense than water.
4
1 L
7.0 mol NaOH
44.5 kJ
= 1.6 102 kJ
1000 mL
1 L soln
1 mol NaOH
= heat of reaction = heat absorbed by solution OR q rxn = qsoln
1.6 105 J
T
74 C
final T 21C +74 C = 95 C
1.08g 4.00 J
500.mL
1mL
g C
24.
25.
(E) We assume that the solution volumes are additive; that is, that 200.0 mL of solution is
formed. Then we compute the heat needed to warm the solution and the cup, and finally
H for the reaction.
1.02 g
J
J
3
heat = 200.0 mL
4.02 27.8 C 21.1 C + 10 27.8 C 21.1 C = 5.6 10 J
1
mL
g C
C
H neutr. =
26.
5.6 103 J 1 kJ
= 56 kJ/mol
0.100 mol 1000 J
55.6
Since NaOH and HCl react in a one-to-one molar ratio, and since there is twice the volume
of NaOH solution as HCl solution, but the [HCl] is not twice the [NaOH], the HCl solution
is the limiting reagent.
1L
1.86 mol HCl 1 mol H 2 O 55.84 kJ
heat released = 25.00 mL
= 2.60 kJ
1000 mL
1L
1 mol HCl 1 mol H 2 O
= heat of reaction = heat absorbed by solution or qrxn = qsoln
2.60 103 J
8.54 C
1.02 g 3.98 J
75.00 mL
1mL g C
8.54 C + 24.72 C = 33.26 C
T = Tfinal Ti
T final
274
Tfinal = T + Ti
Chapter 7: Thermochemistry
27.
(M)
0.2106 mol C2 H 2
1000 L
m3
1 kg
26.04 g
1299.5 kJ heat evolved
0.2106 mol C2 H 2 = 272.9 kJ = 2.7 102 kJ heat evolved
mol C2 H 2
5.0 L C2 H 2
28.
(M)
1 mol propane
0.1233 mol propane
2219.9 kJ
44.09 g 1 kg
1 m3 1000 L
0.1233 mol C3 H8
2.97 L C3 H8
1 mol 1000 g 1.83 kg 1 m3
273.8 kJ
30.
31.
1 mol H 2 O
J
) (40.6 103
)
18.015 g H 2 O
mol
mH2O = 1.83 g H2O 2 g H2O ( 1 sig. fig.)
4125.8 J = (mH2O)(
275
Chapter 7: Thermochemistry
32.
33.
(E)
571 kJ 1000 J
5.71105 J/kg
kg
1 kJ
1 kg
1000 g 1 L
125.0 J
0.111 L
5
5.71 10 J 1 kg 1.98 g
34.
(M) Assume all N2(l) is converted to N2(g) when vaporized. The number of moles of N2(g)
can be found by using the ideal gas equation.
PV nRT
(1.0 atm)(1.0 L) = n(0.08206 L atm/K mol)(77.36 K)
Calorimetry
heat absorbed 5228 cal 4.184 J 1 kJ
=
= 4.98 kJ / o C
o
T
4.39 C
1 cal 1000 J
35.
36.
(a)
1mol C8 H10 O 2 N 4
kcal
kJ
4.184
1014.2
0.3268g
mol
kcal
194.19 g C8 H10 O 2 N 4
T
1.390 C
5.136 kJ/ C
T f = Ti + T = 22.43 C +1.390 C = 23.82 C
2444
(b)
qcomb moles
heat capacity
0.805g 1 mol C4 H8 O
kJ
1.35 mL
mol
1mL
72.11g C4 H8 O
5.136 kJ/ C
276
7.17 C
Chapter 7: Thermochemistry
37.
(M)
(a)
1 g C5 H 10O5
1 mol
C5 H10 O5 g + 5O 2 g 5CO 2 g + 5H 2 O l
H = - 2.34 103 kJ
38.
(M) This is first a limiting reactant problem. There is 0.1000 L 0.300 M = 0.0300 mol
HCl and 1.82 / 65.39 = 0.0278 mol Zn. Stoichiometry demands 2 mol HCl for every 1 mol
Zn. Thus HCl is the limiting reactant. The reaction is exothermic. We neglect the slight
excess of Zn(s), and assume that the volume of solution remains 100.0 mL and its specific
heat, 4.18 J g 1 C 1 . The enthalpy change, in kJ/mol Zn, is
1.00 g 4.18 J
100.0 mL
(30.5 20.3) C
1mL
1kJ
gC
H
39.
(M)
(a) Because the temperature of the mixture decreases, the reaction molecules (the
system) must have absorbed heat from the reaction mixture (the surroundings).
Consequently, the reaction must be endothermic.
(b) We assume that the specific heat of the solution is 4.18 J g 1 C 1 . The enthalpy
change in kJ/mol KCl is obtained by the heat absorbed per gram KCl.
4.18J
0.75 35.0 g
23.6 24.8 C
1 kJ
74.55 g KCl
gC
H =
= +18 kJ / mol
0.75 g KCl
1000 J 1 mol KCl
40.
(M) As indicated by the negative sign for the enthalpy change, this is an exothermic
reaction. Thus the energy of the system should increase.
15.3 kJ
1000 J
T =
98.14 g
1 mol KC 2 H 3O 2
IJ I
K JK
4.18 J
T = 2.25 103 T
g C
2.08 103
= +0.924 C
2.25 103
277
Chapter 7: Thermochemistry
41.
(M) To determine the heat capacity of the calorimeter, recognize that the heat evolved by
the reaction is the negative of the heat of combustion.
1mol C10 H8
5156.1kJ
1.620 g C10 H8
128.2 g C10 H8 1mol C10 H8
heat evolved
7.72 kJ/ C
heat capacity =
=
T
8.44 C
42.
(M) Note that the heat evolved is the negative of the heat absorbed.
1mol C7 H 6 O3
3023kJ
1.201g
138.12 g C7 H 6 O3 1mol C7 H 6 O3
heat evolved
4.28 kJ/C
heat capacity =
=
T
(29.82 23.68) C
(M) The temperature should increase as the result of an exothermic combustion reaction.
1 mol C12 H 22 O11
1 C
5.65 103 kJ
T = 1.227 g C12 H 22 O11
= 5.23 C
342.3 g C12 H 22 O11 1 mol C12 H 22 O11 3.87 kJ
43.
44.
45.
(M) qcomb
. C 4.68 kJ/ C
1123
5.65 103 kJ / mol C10 H 14 O
1mol C10 H 14 O
1.397 g C10 H 14 O
150.2 g C10 H 14 O
(M)
1 mol
0.08556 mol NaCl
58.44 g
3.76 kJ
0.08556 mol NaCl
0.322 kJ = 322 J
1 mol
q mass H2O specific heat T
5.0 g NaCl
4.18 J
(31.0 23.7 C)
gC
278
Chapter 7: Thermochemistry
Pressure-Volume Work
47.
(M)
(a)
(b)
1atm
-PV = 3.5 L (748 mmHg)
= -3.44 L atm or -3.4 L atm
760 mmHg
1 L kPa = 1 J, hence,
101.325 kPa 1J
2
2
-3.44 L atm
= -3.49 10 J or -3.5 10 J
1 atm
1L kPa
1 cal
-3.49 102 J
= -83.4 cal or -83 cal
4.184 J
101.325 kPa 1J
(E) w = PV = 1.23 atm (3.37 L 5.62 L)
= 280. J
1 atm
1L kPa
That is, 280. J of work is done on the gas by the surroundings.
(c)
48.
49.
(E) When the Ne(g) sample expands into an evacuated vessel it does not push aside any matter,
hence no work is done.
50.
(E) Yes, the gas from the aerosol does work. The gas pushes aside the atmosphere.
51.
(M)
(a) No pressure-volume work is done (no gases are formed or consumed).
(b) 2 NO2(g) N2O4(g) ngas = 1 mole. Work is done on the system by the surroundings
(compression).
(c) CaCO3(s) CaO(s) + CO2(g). Formation of a gas, ngas = +1 mole, results in an
expansion. The system does work on the surroundings.
52.
(M)
(a) 2 NO(g) + O2(g) 2 NO2(g) ngas = 1 mole. Work is done on the system by the
surroundings (compression).
(b) MgCl2(aq) + 2 NaOH(aq) Mg(OH)2(s) + 2 NaCl(aq) ngas = 0, no pressure-volume
work is done.
(c) CuSO4(s) + 5 H2O(g) CuSO4 5 H2O(s) ngas = 5 moles. Work is done on the system
by the surroundings (compression).
53.
(E) We can either convert pressure from atm to Pascals, or convert work from Joules to
Latm.We opt for the latter. Since the conversion between J and Latm is 101.33 J/(Latm), the
amount of work is 325 J (1 Latm/101.33 J) = 3.207 Latm. Therefore,
W = -PV
3.207 Latm = (1.0 atm) V. Solving for V, we get a volume of 3.21 L.
279
Chapter 7: Thermochemistry
54.
(E) We note that the work done on the object imparts a potential energy in that object after the
work is done. Therefore,
work = -e p
(E)
(a)
(b)
U = q + w = +58 J + (58 J) = 0
U = q + w = +125 J + (687 J) = 562 J
c)
56.
(E)
(a)
(b)
c)
(E)
(a)
(b)
(c)
(d)
57.
58.
(E)
(a)
(b)
(c)
J
) = 1171.52 J = 1.17 kJ
cal
59.
(E) This situation is impossible. An ideal gas expanding isothermally means that
U = 0 = q + w, or w = q, not w = 2q.
60.
(E) If a gas is compressed adiabatically, the gas will get hotter. Raise the temperature of the
surroundings to an even higher temperature and heat will be transferred to the gas.
61.
(E) We note that since the charge of the system is going from 10 to 5, the net flow of the charge
is negative. Therefore, w = (5 C 10 C) = -5 C. Voltage (V) is J/C. The internal energy of the
system is:
U = q + w = -45 J + (100 J/C)(-5 C) = -45 J + (-500 J) = -545 J
62.
280
Chapter 7: Thermochemistry
Relating H and U
63 (E) According to the First Law of Thermodynamics, the answer is (c). Both (a) qv and (b)
qp are heats of chemical reaction carried out under conditions of constant volume and
constant pressure, respectively. Both U and H incorporate terms related to work as well
as heat.
64.
(E)
(a)
(b)
(c)
66.
Hesss Law
67.
68.
bg
bg
bg
(M)
1
bg
+b2g
bg
b
g bg
Cbgraphiteg + O bgg CO bgg
CObgg + O bgg CO bgg
CO g C graphite + 21 O 2 g
2
1
2
69.
bg
(M)
3
bg
+b2g
2(1)
H = +110.54 kJ
H = 393.51 kJ
H = 282.97 kJ
3 CO 2 g + 4 H 2 O l C3 H 8 g + 5 O 2 g H = +2219.1 kJ
C3 H 4 g + 4 O 2 g 3 CO 2 g + 2 H 2O l H = 1937 kJ
2 H 2 g + O 2 g 2 H 2O l
H = 571.6 kJ
C3H 4 g + 2 H 2 g C3H 8 g
H = 290. kJ
bg
bg
bg
281
Chapter 7: Thermochemistry
70.
(M) The second reaction is the only one in which NO(g) appears; it must be run twice to produce
2NO(g).
2 NH 3 g + 52 O 2 g 2 NO g + 3 H 2 O l
2 H 2
The first reaction is the only one that eliminates NH3(g); it must be run twice to eliminate 2NH3.
N 2 g + 3 H 2 g 2 NH 3 g
2 H1
bg
3 H 3
3
2
Re sult : N 2 g + O 2 g 2 NO g
71.
(M)
2 HCl g + C2 H 4 g + 21 O 2 g C 2 H 4 Cl 2 l + H 2 O l H = 318.7 kJ
Cl 2 g + H 2 O l 2 HCl g + 21 O 2 g
H = 0.5 +202.4 = +101.2 kJ
bg
bg bg
bg
b g bg
bg bg
C H bgg + Cl bgg C H Cl blg
2
72.
73.
H rxn = 2 H1 + 2 H 2 3 H 3
bg
H = 217.5 kJ
(M)
N 2 H 4 l + O2 g N 2 g + 2H 2O l
2 H 2O 2 l 2 H 2 g + 2 O2 g
H = 622.2 kJ
H = 2 187.8 kJ = +375.6 kJ
2H 2 g + O2 g 2H 2O l
H = 2 285.8 kJ = 571.6 kJ
N 2 H 4 l + 2 H 2O 2 l N 2 g + 4 H 2O l
H = 818.2 kJ
(M)
CO g + 21 O 2 g CO 2 g
3C graphite + 6 H 2 g 3CH 4 g
H = 283.0 kJ
H = 3 74.81 = 224.43 kJ
2 H 2 g + O2 g 2 H 2O l
H = 2 285.8 = 571.6 kJ
3CO g 32 O 2 g + 3C graphite
H = 3 +110.5 = +331.5 kJ
bg
bg
bg
bg
bg
bg
bg
bg
bg
bg
4 CO g + 8 H 2 g CO 2 g + 3CH 4 g + 2 H 2 O l H = 747.5 kJ
74.
(M)
CS2 l + 3O 2 g CO 2 g + 2SO 2 g
H = 1077 kJ
2S s + Cl2 g S2 Cl2 l
H = 58.2 kJ
C s + 2 Cl2 g CCl4 l
H = 135.4 kJ
2SO 2 g 2S s + 2 O 2 g
H = 2 296.8 kJ = +593.6 kJ
CO 2 g C s + O 2 g
H = 393.5 kJ = +393.5 kJ
H = 284 kJ
bg
bg
bg
282
Chapter 7: Thermochemistry
75.
(M)
CH 4 g + CO 2 g 2 CO g + 2 H 2 g
H = +247 kJ
2 CH 4 g + 2 H 2 O g 2 CO g + 6 H 2 g
H = 2 +206 kJ = +412 kJ
CH 4 g + 2 O 2 g CO 2 g + 2 H 2 O g
H = 802 kJ
4 CH 4 g + 2 O 2 g 4 CO g + 8 H 2 g
H = 143 kJ
4 produces CH 4 g + 12 O2 g CO g + 2 H 2 g H = 35.8 kJ
76.
(M)
The thermochemical combustion reactions follow.
C 4 H 6 g + 112 O 2 g 4 CO 2 g + 3 H 2 O l
C 4 H 10 g + 132 O 2 g 4 CO 2 g + 5 H 2 O l
H 2 g + 21 O 2 g H 2 O l
bg
bg
bg
bg
bg
bg
bg
bg
bg
bg
bg
H = 2540.2 kJ
H = 2877.6 kJ
H = 285.85 kJ
H = 2540.2 kJ
4 CO 2 g + 5 H 2 O l C4 H10 g + 132 O 2 g
H = 2877.6 kJ = +2877.6 kJ
2 H 2 g + O2 g 2 H 2O l
H = 2 285.8 kJ = 571.6 kJ
C4 H 6 g + 2 H 2 g C4 H10 g
H = 234.2 kJ
77.
(M)
C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l)
H = -2808 kJ
H = 2(1344) kJ
6 CO2(g) + 6 H2O(l) 2 CH3CH(OH)COOH(s) + 6 O2(g)
__________________________________________________________________________
H = -120. kJ
C6H12O6(s) 2 CH3CH(OH)COOH(s)
78.
(M)
[C6H12O6(s) + 6 O2(g) 6 CO2(g) + 6 H2O(l)]
H = (-2808) kJ
H = (72) kJ
[2 CH3CH2OH(l) + 2 CO2(g) C6H12O6(s) ]
__________________________________________________________________________
H = -1368 kJ
CH3CH2OH(l) + 3 O2(g) 2 CO2(g) + 3 H2O(l)
(M)
(a)
bg
bg
bg
bg
H = Hf C 2 H 6 g + Hf CH 4 g Hf C 3 H 8 g Hf H 2 g
283
Chapter 7: Thermochemistry
bg
bg
bg
bg
H = 2 Hf SO 2 g + 2 Hf H 2 O l 2 Hf H 2S g 3Hf O 2 g
(b)
80.
bg
bg
b g
b g
(E) H = Hf H 2 O l + Hf NH 3 g Hf NH 4 + aq Hf OH aq
H = 285.8 + 46.11 132.5 230.0 kJ = +30.6 kJ
81.
(M)
ZnO s + SO 2 g ZnS s + 32 O 2 g ;
bg
H = 878.2 kJ /2 = +439.1 kJ
bg
bg
bg
(M) Most clearly established in Figure 7-18 is the point that the enthalpies of formation
for alkane hydrocarbons are negative and that they become more negative as the length
of the hydrocarbon chain increases (~20 kJ per added CH2 unit). For three hydrocarbons
of comparable chain length, C2H6, C2H4, and C2H6, we can also infer that the one having
only single bonds (C2H6) has the most negative enthalpy of formation. The presence of
a carbon-to-carbon double bond (C2H4) makes the enthalpy of formation more positive,
while the presence of a triple bond (C2H2), makes it more positive still.
83.
84.
85.
g b g b g b g
(E) H = 2 H Febsg + 3 H CO bgg H Fe O bsg 3 H
= 2 b0.00g + 3 b 393.5g b 824.2g 3 b 110.5g = 24.8 kJ
(E) Balanced equation: C H OHblg + 3O bgg 2CO bgg + 3H Oblg
H 2 H [CO (g)] + 3H [ H O(l)] H [ C H OH(l)] 3H [ O (g)]
= 2 b 393.5g + 3 b 285.8g b 277.7g 3 b0.00g = 1366.7 kJ
(M) First we must determine the value of H for C H blg .
86.
bg
CO g
12
bg
bg
bg
173 + 5 b 285.8g 5 b 110.5g 11 b0.00g = 1050 kJ
284
bg
Chapter 7: Thermochemistry
87.
bg
bg
bg
bg
+8326 8723
= 199 kJ / mol
2
(E) H = Hf Al OH 3 s Hf Al 3+ aq 3 Hf OH aq
bg
Hf C 6 H 14 l
89.
b gbg
b g
b g
90.
(M) H = H f Mg 2+ aq + 2 H f NH 3 g + 2 H f H 2 O l H f Mg OH 2 s 2 H f NH 4 + aq
91.
bg
bg
bg
H = H f CaO s + H f CO 2 g H f CaCO3 s
= 635.1 393.5 1207 kJ = +178 kJ
= 2.40106 kJ
1 kg 100.09 g CaCO3 1 mol CaCO3
H = 4 H f CO 2 g + 5 H f H 2 O l H f C4 H10 g 132 H f O 2 g
= 4 393.5 + 5 285.8 125.6 6.5 0.00 kJ = 2877.4 kJ/mol
Now compute the volume of gas needed, with the ideal gas equation, rearranged to: V =
10
756 mmHg
285
1atm
760 mmHg
nRT
.
P
Chapter 7: Thermochemistry
93.
94. (M) The reaction for the combustion of lactic acid is:
C3H6O3(s) + 3 O2(g) 3 CO2(g) + 3 H2O(l)
H = 3 H f CO 2 g + 3 H f H 2 O l H f C3 H 6 O3 s 3 H f O 2 g
= 3 393.5 + 3 285.8 (694) 3 0.00 kJ
-1344 kJ per mole of lactic acid
4 qt
1L
1000 mL 1.00 g 1 kg
2.205 lb
3.3 102 lb
1 gal 1.06 qt
1L
1 mL 1000 g
1 kg
1 Btu
heat (Btu) 3.3 102 lb
(145F 48F) 3.2 104 Btu
lb F
1 cal
5 C 1 kcal
(145F 48F)
8.1 10 3 kcal
g C
9 F 1000 cal
4.184 kJ
3.4 10 4 kJ
1 kcal
96. (M) Potential energy = mgh = 7.26 kg 9.81 ms-2 168 m = 1.20 104 J. This potential energy is
converted entirely into kinetic energy just before the object hits, and this kinetic energy is
converted entirely into heat when the object strikes.
heat
1.20 10 4 J
t
3.5 C
1000 g 0.47 J
mass sp. ht.
7.26 kg
1 kg
g C
This large a temperature rise is unlikely, as some of the kinetic energy will be converted into
forms other than heat, such as sound and the fracturing of the object along with the surface it
strikes. In addition, some heat energy would be transferred to the surface.
286
Chapter 7: Thermochemistry
g C
)]
heat
J
(mass H 2 O 4.184
)
t
g C
The heat of combustion of anthracene is 7067 kJ/mol, meaning that burning one mole of
anthracene releases 7067 kJ of heat to the calorimeter.
1.354 g C14 H10
heat cap.
7067 kJ
1 mol C14 H10
(35.63 - 24.87) C
kJ
g C
983.5 g 4.184 10 3
3.033 104 J
1 g C7 H 6 O 2
1kJ
4.184 J
(30.25 C 24.96 C) 2.61 104 J
heat absorbed by water 1181 g H 2 O
g C
4.2 103 J
7.9 102 J/ C
30.25 C 24.96 C
4.184 J
(29.81C 24.98 C) 2.35 104 J
g C
2.35 10 4 J 3.8 10 3 J 1 kJ
30.5 kJ/g
0.895 g
1000 J
1 g coal 1 kg
1 metric ton
43.9 kJ/mol H 2 O
g H2
1 mol H 2
2 mol H 2 O 1 kcal
287
Chapter 7: Thermochemistry
This difference should equal the heat of vaporization, that is, the enthalpy change for the following
reaction.
H 2 O(l)
H 2 O(g)
2 NO 2
(2) N 2 (g) 2 O 2 (g)
H 66.36 kJ
2 NO 2(g)
N 2O 3(g)
H 16.02 kJ
O 2(g)
N 2 (g) 2 O 2 (g)
N 2 O3 (g) 1 2 O 2 (g) H 82.38 kJ
101. (M) First we determine the moles of gas, then the heat produced by burning each of the components.
1atm
385 L
760 mmHg
PV
n
15.4 mol
RT (22.6 273.2) K 0.08206 L atm mol1 K 1
739 mm Hg
1.14 104 kJ
100.0 mol gas 1mol CH 4
2.69 103 kJ
100.0 mol gas 1mol C 2 H 6
total heat 1.14 104 kJ 2.69 103 kJ 2.0 103 kJ 1.61 104 kJ or 1.61 104 kJ heat evolved
102. (M)
CO(g) 3H 2 (g)
CH 4 (g) H 2 O(g)
(methanation)
2 C(s) 2 H 2 O(g)
2 CO(g) 2 H 2 (g)
2 (7.24)
CO(g) H 2 O(g)
CO 2 (g) + H 2 (g)
(7.25)
2 C(s) 2 H 2 O(g)
CH 4 (g) CO 2 (g)
103. (D)
CH 4 (g) 2 O 2 (g)
CO 2 (g) 2 H 2 O(l)
288
Chapter 7: Thermochemistry
C3 H8 (g) 5O 2 (g)
3CO 2 (g) 4 H 2 O(l)
H 2 (g) 1 2 O 2 (g)
H 2 O(l)
CO(g) 1 2 O 2 (g)
CO 2 (g)
283.0 kJ
20 kJ
1mol CO
C3 H8 combustion 0.031mol C3 H8
total enthalpy of combustion
2220.kJ
69 kJ
1mol C3 H8
1mol gas
22.414 LSTP
26.2 kJ/L
1mol CH 4 22.414 LSTP
Thus, sewage gas produces more heat per liter at STP than does coal gas.
104. (M)
(a) CH 4 (g) 2 O 2 (g)
CO 2 (g) 2 H 2 O(l) is the combustion reaction
H rxn H f [CO 2 (g)] 2H f [H 2 O(l)] H f [CH 4 (g)] 2 H [O 2 (g)]
f
(393.5 kJ) 2 (285.8 kJ) (74.81kJ) 2 0.00 kJ 890.3kJ
1atm
744 mm Hg
0.100 L
760 mmHg
PV
n
0.00400 mol CH 4
3.18 kJ
heat used to melt ice 9.53 g ice
18.02 g ice
1 mol H 2 O(s)
289
Chapter 7: Thermochemistry
Since 3.56 kJ of heat was available, and only 3.18 kJ went into melting the ice, the
combustion
must be incomplete.
(b) One possible reaction is: 4 CH 4 (g) 7 O 2 (g)
2 CO 2 (g) 2CO(g) 8 H 2 O(l) , but
this would generate but 3.00 kJ of energy under the stated conditions. The molar
production of CO2 (g) must be somewhat greater than that of CO(g).
105. (E)
(a) The heat of reaction would be smaller (less negative) if the H 2 O were obtained as a
gas rather than as a liquid.
(b) The reason why the heat of reaction would be less negative is that some of the 1410.9
kJ of heat produced by the reaction will be needed to convert the H 2 O from liquid to
gas.
(c)
106. (D) First we compute the amount of butane in the cylinder before and after some is
withdrawn; the difference is the amount of butane withdrawn.
T = (26.0 + 273.2)K = 299.2 K
2.35atm 200.0 L
PV
19.1mol butane
RT 0.08206 L atm mol1 K 1 299.2 K
1.10 atm 200.0 L
PV
n2
2877 kJ
2.91 104 kJ
1mol C4 H10
290
Chapter 7: Thermochemistry
To begin the calculation of the heat absorbed by the water, we compute the mass of the
water.
1000 cm3 1.00 g
1.33 105 g H 2 O
mass H 2 O 132.5 L
1L
1cm3
heat absorbed 1.33 105 g
4.184 J
1kJ
(62.2 C 26.0 C)
2.01 104 kJ
g C
1000 J
0.70 kJ work
2802.5 kJ
1mol C6 H12 O6
303g C6 H12 O6
108. (M) H f [C 4 H 10 (g)] 125.6 kJ/mol from Table 7-2.
The difference between C 4 H 10 and C 7 H 16 amounts to three CH 2 groups. The difference in
their standard enthalpies of formation is determined as follows.
21kJ
63kJ/mol
difference 3mol CH 2 groups
mol CH 2 groups
Thus
H f [C7 H16 (l)] 125.6 kJ/mol 63kJ/mol 189 kJ/mol
Now we compute the enthalpy change for the combustion of heptane.
C7 H16 (l) 11 O 2 (g)
7 CO 2 (g) 8 H 2 O(l)
C 2 H 6 (g) 7 2 O 2 (g)
2 CO 2 (g) 3H 2 O(l)
291
Chapter 7: Thermochemistry
heat
43.6 kJ 22.4 L
977 kJ/mol
1.00 L 1 mol
Reaction H2SO4(l)
H2SO4(aq) ~ 1.00M
o
H f
-814.0 kJ/mol
-909.3 kJ/mol
q = mol(-909.3 kJ/mol) mol(-814.0 kJ/mol) = -47.65 kJ
47650 J released by dilution and absorbed by the water.
47650 J
Use q = mct
t =
23C
500 g(4.2 J g -1 C-1 )
111. (M)
CO(g) + 3 H2(g)
2 C(s) + 2 H2O(g)
CO(g) + H2O(g)
2 C(s) + 2 H2O(g)
CH4(g) + H2O(g)
2 CO(g) + 2 H2(g)
CO2(g) + H2(g)
CH4(g) + CO2(g)
(methanation)
(2 7.24)
(7.25)
292
-206.1 kJ
+262.6 kJ
-41.2 kJ
15.3 kJ
Chapter 7: Thermochemistry
112. (M)
(765.5/760)atm
0.582L
2.40 102 mol
-1
-1
(0.08206 L atm K mol ) 298.15K
1.103g
molar mass
46.0 g/mol
2.40 102 mol
moles of CO 2 2.108/44.01 0.04790 (0.0479 mol C in unknown)
n
area
(3.1416)(6.00 cm)2 (1m/100cm) 2
1.320 104 Pa
0.130 atm difference
Use: P1 V1 P2 V2
101325 Pa atm -1
((745/760) 0.130atm) (0.9161L)
V2
1.04 L
(745/760)atm
745
101 J
-PV
(1.04 0.916) 0.121 L atm = w ( 0.121 L atm)
12 J
760
L atm
1.320 104 Pa
115. (M)
+ 155.3 kJ
+ 320.1 kJ
+ 57.3 kJ
+532.7 kJ
Thus, using Hess's Law, H = +532.7 kJ. For U we must assume a temperature, say, 373 K.
U = H -ngasRT = +532.7 kJ 10 mol(8.314472 J K-1 mol-1)(373 L)(1 kJ/1000 J) = +501.7 kJ
The value for U is only an estimate because it is based on a H value that has been obtained
using Hesss law. Hesss law provides only an approximate value for the enthalpy change. To
293
Chapter 7: Thermochemistry
obtain a more precise value for the U, one would use bomb calorimetry. As well, the water
formed is assumed to be a vapor (gas). In reality, a portion of that water will exist as a liquid.
116. (M) First, list all of the pertinent reactions, normalizing them so that each uses the same amount of NH3:
Hrxn-1 = 2(0 kJ/mol) + 6(-241.8 kJ/mol) [4(-46.11 kJ) + 3(0 kJ/mol)] = -1266.4 kJ
Clearly, rxn-1, the oxidation of NH3(g) to N2(g) is the most exothermic reaction.
117. (D)
H =
373 K
298 K
Cpdt =
373 K
298 K
373 K
373 K
J
J
dt + 0.00377 2
Tdt + 0.5 105
298K
298K
K mol
K mol
T 2 373 K
J
J
373 K
0.5 105
H = 28.58
T 298 K + 0.00377 2
K mol
K mol 2 298 K
H = 28.58
J K 373 K -2
T dt
mol 298K
373 K
JK 1
mol T 298 K
2
373 K 2
298 K
J
J
H = 28.58
(373 K 298 K) + 0.00377 2
K mol
2
2
K mol
JK 1
1
+ 0.5 105
118. (D) In this problem, there are four distinct heating regimes: (1) heating the ice from -5 C to
the melting point at 0 C, (2) heat required to melt the ice, Hfus, (3) heating the water from 0 C to the
boiling point at 100 C, and (4) heat required to vaporize the water, Hvap. Each part is solved
separately below. However, we must first calculate the temperature dependent heat capacity of ice
and water in their given temperature ranges. We also note that melting ice to water at 273 K requires
an enthalpy (Hfus) of 6.01 kJ/mol, and boiling water requires an enthalpy (Hvap) of 44.0 kJ/mol.
294
Chapter 7: Thermochemistry
273
T2
Cp (ice) 1.0187 T 1.49 10 1.0187
1.49 102 T 1337.71 kJ kg 1 K 1
268K
2
268
273K
Cp (water)
373K
273K
T4
T3
T2
1.0 107
1.0 104 3.92 102
8.7854 T 318.95 kJ kg 1 K 1
4
3
2
273
Now we use the above data to determine the q values:
1 mol H 2 O 6.01 kJ
3.34 kJ
0.01801 kg
mol
1 mol H 2 O 44.0 kJ
24.41 kJ
0.01801 kg
mol
q TOT 415.59 kJ
O2(g)
29.37 J K-1mol-1
H2O(g)
33.58 J K-1mol-1
q = nCp
H2(g)
75.0 K
75.0 K
(1)(28.84)(75.0) J
= 2163 J
75.0 K
()(29.37)(75.0) J
= 1101.4 J
(1)(33.58)(75.0) J
= 2518.5 J
H2(g) + 1/2O2(g)
1
H2(g) + /2O2(g)
3.26 kJ
-242.56 kJ
-241.82 kJ
H2O(g)
2.52 kJ
H2O(g)
o
25 C
100 C
Chapter 7: Thermochemistry
FEATURE PROBLEMS
120. (M) 1 F = 5/9 C = 0.555 C 1 lb = 453.6 g
Ep = mgh
q = m (sp. ht.)T
lb m ft
s2
lb m ft 0.3048 m 0.4536 kg
Ep = 7.57 103
s2
ft
lb
2
kg m
Ep = 1047
= 1047 J = 1.05 kJ
s2
The statement is validated.
121. (D)
(a)
C)
-1 o
J
g oC
)(0.556 C)
q = 1054 J
q = 1.05 kJ
Specific Heat (J g
q = 453.6 g(4.184
-1
1
0.8
0.6
0.4
Equation of Line
y = 23.9x + 0.0113
0.2
0
0
(b)
(c)
0.01
0.02
0.03
-1
(Atomic Mass)
0.04
0.05
The equation of the line is: specific heat = 23.9 (atomic mass) + 0.0113
0.23 J g-1 C = 23.9 (atomic mass) + 0.0113
23.9
atomic mass =
= 109 u or 110 u (2 sig fig);
0.23 0.0113
Cadmiums tabulated atomic mass is 112.4 u.
450 J
sp.ht. =
= 0.40 J g 1 o C1 = 0.0113 + 23.9/atomic mass
o
75.0 g 15. C
23.9
atomic mass =
= 61.5 u or 62 u The metal is most likely Cu (63.5 u) .
0.40 0.0113
296
Chapter 7: Thermochemistry
T ( C)
122. (D) The plots maximum is the equivalence point. (Assume T = 0 at 0 mL of added NaOH,
(i.e., only 60 mL of citric acid are present), and that T = 0 at 60 mL of NaOH (i.e. no citric acid
added).
9
Plot of T versus Volume of NaOH
8
7
6
5
4
3
2
1
0
0
10
15
20
25
30
35
40
45
50
55
60
(a)
The equivalence point occurs with 45.0 mL of 1.00 M NaOH(aq) [45.0 mmol NaOH]
added and 15.0 mL of 1.00 M citric acid [15.0 mmol citric acid]. Again, we assume
that T = zero if no NaOH added (VNaOH = 0 mL) and T = 0 if no citric acid is added
(VNaOH = 60).
(b)
Heat is a product of the reaction, as are chemical species (products). Products are
maximized at the exact stoichiometric proportions. Since each reaction mixture has the
same volume, and thus about the same mass to heat, the temperature also is a
maximum at this point.
(c)
aq
123. (M)
(a) The reactions, and their temperature changes, are as follows.
(1st)
NH 3 conc. aq + HCl aq NH 4 Cl aq
T = 35.8 23.8 C = 12.0 C
b
g b g
b g
T = 13.2 19.3 C = 6.1 C
(2nd,a) NH bconc. aq g NH bgg
(2nd,b) NH bgg + HClbaq g NH Clbaq g
T = 42.9 23.8 C = 19.1 C
The sum of reactions b2nd,a g + b2nd, bg produces the same change as the 1 reaction.
st
(b)
We now compute the heat absorbed by the surroundings for each. Hesss law is
demonstrated if H1 = H2a + H2b , where in each case H = q .
297
Chapter 7: Thermochemistry
124. (D) According to the kinetic-molecular theory of gases, the internal energy of an ideal gas,
U, is proportional to the average translational kinetic energy for the gas particles, ek,
which in turn is proportional to 3/2 RT. Thus the internal energy for a fixed amount of an
ideal gas depends only on its temperature, i.e., U = 3/2 nRT, where U is the internal energy
(J), n is the number of moles of gas particles, R is the gas constant (J K-1 mol-1), and T is
the temperature (K). If the temperature of the gas sample is changed, the resulting change
in internal energy is given by U = 3/2 nRT.
(a)
(b)
The heat flow at constant pressure qp is the H for the process (i.e., qp = H) and
we know that H = U w and w = PV = nRT.
Hence, qp = U w = U (nRT) = U + nRT and qp = nCpT and
U = 3/2 nRT Consequently qp = nCpT = nRT + 3/2 nRT (divide both sides
by nT) Now, Cp = R + 3/2 R = 5/2 R = 20.8 J/K.mol.
125. (D)
(a)
Here we must determine the volume between 2.40 atm and 1.30 atm using PV = nRT
L atm
0.100 mol 0.08206
298 K
2.445 L atm
K
mol
V=
=
P
P
For P = 2.40 atm: V = 1.02 L
For P = 2.30 atm: V = 1.06 L PV = 2.30 atm 0.04 L = 0.092 L atm
For P = 2.20 atm: V = 1.11 L PV = 2.20 atm 0.05 L = 0.11 L atm
For P = 2.10 atm: V = 1.16 L PV = 2.10 atm 0.05 L = 0.11 L atm
For P = 2.00 atm: V = 1.22 L PV = 2.00 atm 0.06 L = 0.12 L atm
For P = 1.90 atm: V = 1.29 L PV = 1.90 atm 0.06 L = 0.12 L atm
For P = 1.80 atm: V = 1.36 L PV = 1.80 atm 0.07 L = 0.13 L atm
For P = 1.70 atm: V = 1.44 L PV = 1.70 atm 0.08 L = 0.14 L atm
For P = 1.60 atm: V = 1.53 L PV = 1.60 atm 0.09 L = 0.14 L atm
For P = 1.50 atm: V = 1.63 L PV = 1.50 atm 0.10 L = 0.15 L atm
For P = 1.40 atm: V = 1.75 L PV = 1.40 atm 0.12 L = 0.17 L atm
For P = 1.30 atm: V = 1.88 L PV = 1.30 atm 0.13 L = 0.17 L atm
total work = PV = 1.45 L atm
Expressed in joules, the work is 1.45 L atm 101.325 J/L atm = 147 J.
298
Chapter 7: Thermochemistry
2.50
(b)
Pressure (atm)
2.00
1.50
1.00
0.50
0.00
1.00
(c)
1.10
1.20
1.30
1.40
1.50
1.60
Volume (L)
1.70
1.80
1.90
2.00
The total work done in the two-step expansion is minus one times the total of the
area of the two rectangles under the graph, which turns out to be 1.29 Latm or
-131 J. In the 11-step expansion in (b), the total area of the rectangles is 1.45 L atm
or -147 J. If the expansion were divided into a larger number of stages, the total area
of the rectangles would be even greater. The maximum amount of work is for an
expansion with an infinite number of stages and is equal to the area under the
pressure-volume curve between V = 1.02 L and 1.88 L. This area is also obtained as
the integral of the expression:
(e)
Because the internal energy of an ideal gas is a function only of temperature, and the
temperature remains constant, U = 0. Because U = q + w = 0, q = w. This
means that 209 J corresponds to the maximum work of compression, and 152 J
corresponds to the minimum work of compression.
(f)
299
Chapter 7: Thermochemistry
126. (D) We use the data in Table 7.1 to generate the plot, with the Cp of Ti added in to
demonstrate how it fits in with the data. Below are the data table and the plot
Element
Mg
Al
P
S
Fe
Cu
As
Se
Te
Pb
AW
1/Aw
Cp
24.3 0.041152
26.98 0.037064
30.97 0.032289
32.06 0.031192
55.85 0.017905
63.55 0.015736
74.92 0.013348
78.96 0.012665
127.6 0.007837
207.19 0.004826
Ti
47.88 0.020886
AW*Cp
1.024 24.8832
0.903 24.36294
0.777 24.06369
0.706 22.63436
0.449 25.07665
0.385 24.46675
0.329 24.64868
0.321 25.34616
0.202 25.7752
0.128 26.52032
0.523 25.04124
30
Ti
25
Atomic Weight Cp
20
15
10
0
0
50
100
150
200
250
Atomic Weight
We can see that all the values in general center around 24 J/(molK) for all elements. This is
known as the rule of Dulong-Petit. It is illustrated below in another way by plotting Cp versus
the inverse of the atomic number. The slope of this line is ~24 J/(molK):
300
Chapter 7: Thermochemistry
1.2
Cp
0.8
0.6
Ti
0.4
0.2
0
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
0.04
0.045
1/(Atomic Weight)
SELF-ASSESSMENT EXERCISES
127. (E)
(a) H: Enthalpy of the system, or the heat of the system at constant pressure
(b) PV: Work done by the system (or on the system) through volume change at constant
pressure
(c) H 0f : Enthalpy of formation of a compound at standard conditions
(d) Standard State: The pure element or compound under a pressure of 1 bar at a specified
temperature
(e) Fossil fuel: A fuel source generated by the decomposition of plant and animal matter in the
crust of the earth
128. (E)
(a) Law of conservation of energy: Energy is neither created nor destroyed (or stated differently,
in the interaction between the system and the surroundings, the total energy of the system
remains constant).
(b) Bomb calorimetry: A method of determining heats of reaction (mainly combustion).
(c) Function of state: A function that only depends on the state of the system, such as initial and
final conditions, and is insensitive to how the state was established
(d) Enthalpy diagram: A diagram that represents the enthalpy change in a system
(e) Hesss Law: The enthalpy change of a process can be determined by summation of
enthalpies of individual and elementary steps
129. (E)
(a) System vs. surroundings: System is what we are studying. Surroundings is everything else.
301
Chapter 7: Thermochemistry
(b) Heat vs. work: Heat is the flow of thermal energy. Work involves physical movement of an
entity (whether microscopic or macroscopic)
(c) Specific heat vs. heat capacity: Heat capacity is the quantity of energy required to change
the temperature of a substance by 1 degree. Specific heat is the heat capacity of 1 g of a
substance.
(d) Constant volume vs. constant pressure process: A system where the reaction is done at a
constant volume to eliminate work done by the system is a constant volume system. In a
constant pressure system, there can be expansion and contraction and therefore work can be
done.
130. (E) The answer is (b), Al, because it has the highest heat capacity.
131. (E) The answer is (c). We know that m1cT1=- m2cT2, where m1 and m2 are the masses of
each quantity of water. Therefore, the equation above can be expanded and simplified as
follows:
75 (Tf-80) = -100 (Tf-20)
Solving for Tf gives a value of 45.7 C.
132. (E) The answer is (d). U = q + w. Since q = -100 J, w = +200 J, or the system has 200 J of work
done on it.
133. (E) The answer is (a). The heat generated by NaOH is absorbed by the system.
134. (E) The answer is (b). As graphite is burned in O2, it generates CO2. Enthalpy of formation of
CO2 is therefore the same as enthalpy of combustion of C.
135. (E) The answer is (a), because qV and qP are not the same.
136. (E)
(a) We have to solve for the heat capacity (Cp) of Fe:
mCpT (H2O) = - mCpT (Fe)
(981g)(4.189)(12.3 C) = (1220)(CP(Fe) )(92.1 C)
(1) CO + O2 CO2
(2) C + O2 CO2
-283.0 kJ/mol
-393.5 kJ/mol
302
Chapter 7: Thermochemistry
To determine the H of of CO, reverse and double equation (1) and double equation (2):
(1) 2 CO2 2 CO + O2
(2) 2C + 2 O2 2 CO2
(3) 2 C + O2 2 CO
566.0 kJ
-787.0 kJ
-221.0 kJ
or -110.5 kJ/mol of CO
Now, we use the equation for the formation of COCl2 with equation (3) times .
(4) CO + Cl2 COCl2
(3) C + O2 CO
(3) C + O2 + Cl2 COCl2
-108.0 kJ
-110.5 kJ
-218.5 kJ
Chapter 7: Thermochemistry
Then, there should be a subheading for work, discussing the various forms of work (such as P-V
work, for instance). A discussion of heat should contain subheadings for enthalpy at constant
volume and pressure.
145. (M) The concept map of the use of enthalpy in chemical reactions has several major
subheadings. After the definition of enthalpy, there should be three major subheadings:
(1) expressing enthalpy graphically using enthalpy diagrams, (2) enthalpy of change for phase
transformation, and (3) standard states and standard transformations. Then, under standard
states and transformations, there would be further subheadings discussing (1) enthalpy of
reaction, and (2) enthalpy of formation. Hesss law would be a subtopic for #1.
146. (M) This concept map starts with the root term, terms in thermodynamics. It is then split into
the major subheadings, (1) path-dependent and (2) path-independent quantities. The remainder
is very similar to question 144.
304