Você está na página 1de 30

# TRAPP: CHAP02 2006/3/8 17:05 PAGE 23 #1

2
The First Law
D2.1 Work is a precisely dened mechanical concept. It is produced from the application of a force through a
distance. The technical denition is based on the realization that both force and displacement are vector
quantities and it is the component of the force acting in the direction of the displacement that is used in
the calculation of the amount of work, that is, work is the scalar product of the two vectors. In vector
notation w = f d = fd cos , where is the angle between the force and the displacement. The
negative sign is inserted to conform to the standard thermodynamic convention.
Heat is associated with a non-adiabatic process and is dened as the difference between the adiabatic
work and the non-adiabatic work associated with the same change in state of the system. This is the
formal (and best) denition of heat and is based on the denition of work. A less precise denition of
heat is the statement that heat is the form of energy that is transferred between bodies in thermal contact
with each other by virtue of a difference in temperature.
At the molecular level, work is a transfer of energy that results in orderly motion of the atoms and
molecules in a system; heat is a transfer of energy that results in disorderly motion. See Molecular
interpretation 2.1 for a more detailed discussion.
D2.3 The difference results from the denition H = U + PV; hence H = U + (PV). As (PV) is
not usually zero, except for isothermal processes in a perfect gas, the difference between H and U
is a non-zero quantity. As shown in Sections 2.4 and 2.5 of the text, H can be interpreted as the heat
associated with a process at constant pressure, and U as the heat at constant volume.
D2.5 In the Joule experiment, the change in internal energy of a gas at low pressures (a perfect gas) is zero.
Hence in the calculation of energy changes for processes in a perfect gas one can ignore any effect due
to a change in volume. This greatly simplies the calculations involved because one can drop the rst
term of eqn 2.40 and need work only with dU = C
V
dT. In a more sensitive apparatus, Joule would
have observed a small temperature change upon expansion of the real gas. Joules result holds exactly
only in the limit of zero pressure where all gases can be considered perfect.
The solution to Problem 2.33 shows that the JouleThomson coefcient can be expressed in terms of
the parameters representing the attractive and repulsive interactions in a real gas. If the attractive forces
predominate, then expanding the gas will reduce its energy and hence its temperature. This reduction
in temperature could continue until the temperature of the gas falls below its condensation point. This
is the principle underlying the liquefaction of gases with the Linde refrigerator, which utilizes the
JouleThomson effect. See Section 2.12 for a more complete discussion.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 24 #2
24 SOLUTIONS MANUAL
D2.7 The vertical axis of a thermogramrepresents C
p
, and the baselines represent the heat capacity associated
with simple heating in the absence of structural transformations or similar transitions. In the example
shown in Fig. 2.16, the sample undergoes a structural change between T
1
and T
2
, so there is no reason to
expect C
p
after the transition to return to its value before the transition. Just as diamond and graphite have
different heat capacities because of their different structures, the structural changes that occur during
the measurement of a thermogram can also give rise to a change in heat capacity.
Solutions to exercises
E2.1(a) The physical denition of work is dw = F dz [2.4].
In a gravitational eld the force is the weight of the object, which is F = mg.
If g is constant over the distance the mass moves, dw may be integrated to give the total work,
w =
_
z
f
z
i
Fdz =
_
z
f
z
i
mgdz = mg(z
f
z
i
) = mgh where h = (z
f
z
i
).
On earth: w = (65 kg) (9.81 ms
2
) (4.0 m) = 2.6 10
3
J = 2.6 10
3
J needed .
On the moon: w = (65 kg) (1.60 ms
2
) (4.0 m) = 4.2 10
2
J = 4.2 10
2
J needed .
E2.2(a) This is an expansion against a constant external pressure; hence w = p
ex
V [2.8].
p
ex
= (1.0 atm) (1.013 10
5
Pa atm
1
) = 1.01 10
5
Pa.
The change in volume is the cross-sectional area times the linear displacement:
V = (100 cm
2
) (10 cm)
_
1 m
100 cm
_
3
= 1.0 10
3
m
3
,
so w = (1.01 10
5
Pa) (1.0 10
3
m
3
) = 1.0 10
2
J as 1 Pa m
3
= 1 J .
E2.3(a) For all cases U = 0, since the internal energy of a perfect gas depends only on temperature. (See
Molecular interpretation 2.2 and Section 2.11(b) for a more complete discussion.) From the denition
of enthalpy, H = U +pV, so H = U +(pV) = U +(nRT) (perfect gas). Hence, H = 0 as
well, at constant temperature for all processes in a perfect gas.
(a) U = H = 0 .
w = nRT ln
_
V
f
V
i
_
[2.11]
= (1.00 mol) (8.314 J K
1
mol
1
) (273 K) ln
_
44.8 dm
3
22.4 dm
3
_
= 1.57 10
3
J = 1.57 kJ .
q = U w [First Law] = 0 + 1.57 kJ = +1.57 kJ .
(b) U = H = 0 .
w = p
ex
V[2.8], V = (44.8 22.4) dm
3
= 22.4 dm
3
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 25 #3
THE FIRST LAW 25
p
ex
can be computed from the perfect gas law,
pV = nRT,
so p
ex
= p
f
=
nRT
V
f
=
(1.00 mol) (0.08206 dm
3
atmK
1
mol
1
) (273 K)
44.8 dm
3
= 0.500 atm
w = (0.500 atm)
_
1.013 10
5
Pa
1 atm
_
(22.4 dm
3
)
_
1 m
3
10
3
dm
3
_
= 1.13 10
3
Pa m
3
= 1.13 10
3
J = 1.13 kJ .
q = U w = 0 + 1.13 kJ = +1.13 kJ .
(c) U = H = 0
Free expansion is expansion against no force, so w = 0 and q = U w = 0 0 = 0 .
COMMENT. An isothermal free expansion of a perfect gas is also adiabatic.
E2.4(a) For a perfect gas at constant volume
p
T
=
nR
V
= constant; hence,
p
1
T
1
=
p
2
T
2
.
p
2
=
_
T
2
T
1
_
p
1
=
_
400 K
300 K
_
(1.00 atm) = 1.33 atm .
U = nC
V,m
T[2.16b] = (n) (
3
2
R) (400 K 300 K)
= (1.00 mol) (
3
2
) (8.314 J K
1
mol
1
) (100 K)
= 1.25 10
3
J = +1.25 kJ .
w = 0 [constant volume] q = U w [First Law] = 1.25 kJ 0 = +1.25 kJ .
E2.5(a) (a) w = p
ex
V [2.8].
p
ex
= (200 Torr) (133.3 Pa Torr
1
) = 2.666 10
4
Pa.
V = 3.3 dm
3
= 3.3 10
3
m
3
.
Therefore, w = (2.666 10
4
Pa) (3.3 10
3
m
3
) = 88 J .
(b) w = nRT ln
_
V
f
V
i
_
[2.11].
n =
4.50 g
16.04 g mol
1
= 0.2805 mol, RT = 2.577 kJ mol
1
, V
i
= 12.7 dm
3
, V
f
= 16.0 dm
3
.
w = (0.2805 mol) (2.577 kJ mol
1
) ln
_
16.0 dm
3
12.7 dm
3
_
= 167 J .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 26 #4
26 SOLUTIONS MANUAL
E2.6(a) H =
cond
H =
vap
H = (1 mol) (40.656 kJ mol
1
) = 40.656 kJ .
Since the condensation is done isothermally and reversibly, the external pressure is constant at 1.00 atm.
Hence,
q = q
p
= H = 40.656 kJ .
w = p
ex
V[2.8] where V = V
liq
V
vap
V
vap
because V
liq
<< V
vap
.
On the assumption that H
2
O(g) is a perfect gas, V
vap
=
nRT
p
and p = p
ex
, since the condensation is
done reversibly. Hence,
w nRT = (1.00 mol) (8.314 J K
1
mol
1
) (373 K) = +3.10 10
3
J = +3.10 kJ .
From eqn 2.21, U = H n
g
RT, n
g
= 1.00 mol.
U = (40.656 kJ) + (1.00 mol) (8.314 J K
1
mol
1
) (373.15 K) = 37.55 kJ .
E2.7(a) The chemical reaction that occurs is Mg(s) + 2HCl(aq) H
2
(g) + MgCl
2
(aq), M(Mg) =
24.31 g mol
1
Work is done against the atmosphere by the expansion of the hydrogen gas product in the reaction.
w = p
ex
V[2.8] where V
i
0, V
f
=
nRT
p
f
, p
f
= p
ex
so w = p
ex
(V
f
V
i
) p
ex
V
f
= p
ex

nRT
p
ex
= nRT,
n =
15g
24.31 g mol
1
= 0.617 mol, RT = 2.479 kJ mol
1
.
Hence w = (0.617 mol) (2.479 kJ mol
1
) = 1.5 kJ
E2.8(a) (a) q = H, since pressure is constant.
H =
_
T
f
T
i
dH, dH = nC
p,m
dT.
d(H/J) = {20.17 + 0.3665(T/K)}d(T/K).
(H/J) =
_
T
f
T
i
d(H/J) =
_
473
298
{20.17 + 0.3665(T/K)}d(T/K)
= (20.17) (473 298) +
_
0.3665
2
_

_
T
K
_
2

473
298
= (3.530 10
3
) + (2.4725 10
4
) = 2.83 10
4
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 27 #5
THE FIRST LAW 27
q = H = 2.83 10
4
J = +28.3 kJ .
w = p
ex
V[2.8] where p
ex
= p.
w = pV = (pV)[constant pressure] = (nRT) [perfect gas] = nRT
= (1.00 mol) (8.314 J K
1
mol
1
) (473 K 298 K)
= 1.45 10
3
J = 1.45 kJ .
U = q + w = (28.3 kJ) (1.45 kJ) = +26.8 kJ .
(b) The energy and enthalpy of a perfect gas depend on temperature alone (Molecular interpretation
2.2 and Exercise 2.3); hence it does not matter whether the temperature change is brought about at
constant volume or constant pressure; H and U are the same.
H = +28.3 kJ , U = 26.8 kJ .
Under constant volume, w = 0 .
q = U w = +26.8 kJ .
T
f
= T
i
_
V
i
V
f
_
1/c
[2.28a],
where c =
C
V,m
R
=
C
p,m
R
R
=
(20.786 8.3145) J K
1
mol
1
8.3145 J K
1
mol
1
= 1.500,
so the nal temperature is
T
f
= (273.15 K)
_
1.0 dm
3
3.0 dm
3
_
1/1.500
= 131K .
w = C
V
T[2.27] = n(C
p,m
R) (T
f
T
i
)
where the temperatures are related by
T
f
= T
i
_
V
i
V
f
_
1/c
[2.28a] where c =
C
V,m
R
=
C
p,m
R
R
= 3.463.
So T
f
= [(27.0 + 273.15) K]
_
500 10
3
dm
3
3.00 dm
3
_
1/3.463
= 179 K
and w =
_
2.45g
44.0 g mol
1
_
[(37.11 8.3145) J K
1
mol
1
] (179 300) K = 194 J .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 28 #6
28 SOLUTIONS MANUAL
p
f
V

f
= p
i
V

i
[2.29]so p
f
= p
i
_
V
i
V
f
_

= (57.4 kPa)
_
1.0 dm
3
2.0 dm
3
_
1.4
= 22 kPa
E2.12(a) C
p
=
q
p
T
[2.24] =
229 J
2.55 K
= 89.8 J K
1
so C
p,m
= (89.8 J K
1
)/(3.0mol) = 30 J K
1
mol
1
.
For a perfect gas C
p,m
C
V,m
= R[2.26].
C
V,m
= C
p,m
R = (30 8.3) J K
1
mol
1
= 22 J K
1
mol
1
.
E2.13(a)
q
p
= C
p
T [2.24] = nC
p,m
T = (3.0 mol) (29.4 J K
1
mol
1
) (25 K) = +2.2 kJ .
H = q
p
[2.23b] = +2.2 kJ .
U = H (pV) [from H U + pV] = H (nRT) [perfect gas] = H nRT
= (2.2 kJ) (3.0 mol) (8.314 J K
1
mol
1
) (25 K) = (2.2 kJ) (0.62 kJ) = +1.6 kJ .
E2.14(a) In an adiabatic process, q = 0 . Work against a constant external pressure is
w = p
ex
V = (600 Torr)
_
1.013 10
5
Pa
760 Torr
_
(40 10
3
m
3
) = 3.2 kJ
U = q + w = 3.2 kJ .
One can also relate adiabatic work to T (eqn 2.27):
w = C
V
T = n(C
p,m
R)T so T =
w
n(C
p,m
R)
,
T =
3.2 10
3
J
(4.0 mol) (29.355 8.3145) J K
1
mol
1
= 38 K .
H = U + (pV) = U + nRT
= (3.2 kJ) + (4.0 mol) (8.3145 J K
1
mol
1
) (38 K) = 4.5 kJ .
Question. Calculate the nal pressure of the gas.
E2.15(a) In an adiabatic process, the initial and nal pressures are related by (eqn 2.29)
p
f
V

f
= p
i
V

i
where =
C
p
C
V
=
C
V
+ nR
C
V
=
20.8 J K
1
+ (1.0 mol)(8.31 J K
1
mol
1
)
20.8 J K
1
= 1.40.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 29 #7
THE FIRST LAW 29
Find V
i
from the perfect gas law:
V
i
=
nRT
i
p
i
=
(1.0 mol)(8.31 J K
1
mol
1
)(310K)
3.25 atm

1 atm
1.013 10
5
Pa
V
i
= 7.83 10
3
m
3
.
so V
f
= V
i
_
p
i
p
f
_
1/
= (7.83 10
3
m
3
)
_
3.25 atm
2.50 atm
_
1/1.40
= 0.0113 m
3
.
Find the nal temperature from the perfect gas law:
T
f
=
p
f
V
f
nR
=
(2.50 atm) (0.0113 m
3
)
(1.0 mol)(8.31 J K
1
mol
1
)

1.013 10
5
Pa
1 atm
T
f
= 344 K .
w = C
V
T = (20.8 J K
1
)(344 310) K = 7.1 10
2
J .
E2.16(a) At constant pressure
q = H = n
vap
H

T
f
= (0.50 mol) (26.0 kJ mol
1
) = 13.0 kJ
and w = pV pV
vap
= nRT = (0.50mol) (8.3145 J K
1
mol
1
) (250 K),
w = 1.0 10
3
J = 1.0 kJ .
U = w + q = 13.0 1.0 kJ = 12.0 kJ .
COMMENT. Because the vapor is here treated as a perfect gas, the specic value of the external pressure
provided in the statement of the exercise does not affect the numerical value of the answer.
E2.17(a) The reaction is
C
6
H
5
C
2
H
5
(l) +
21
2
O
2
(g) 8CO
2
(g) + 5H
2
O(1)

c
H

= 8
f
H

(CO
2
, g) + 5
f
H

(H
2
O, l)
f
H

(C
6
H
5
C
2
H
5
, l)
= [(8) (393.51) + (5) (285.83) (12.5)] kJ mol
1
= 4564.7 kJ mol
1
.
E2.18(a) First
f
H

[(CH
2
)
3
, g] is calculated, and then that result is used to calculate
r
H

## for the isomerization

(CH
2
)
3
(g) +
9
2
O
2
(g) 3 CO
2
(g) + 3H
2
O(l),
c
H

= 2091 kJ mol
1
.

f
H

[(CH
2
)
3
, g] =
c
H

+ 3
f
H

(CO
2
, g) + 3
f
H

(H
2
O,g)
= [+2091 + (3) (393.51) + (3) (285.83)] kJ mol
1
= +53 kJ mol
1
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 30 #8
30 SOLUTIONS MANUAL
(CH
2
)
3
(g) C
3
H
6
(g),
r
H

=?

r
H

=
f
H

(C
3
H
6
, g)
f
H

[(CH
2
)
3
, g]
= (20.42 53) kJ mol
1
= 33 kJ mol
1
.
E2.19(a) For naphthalene the reaction is C
10
H
8
(s) + 12O
2
(g) 10CO
2
(g) + 4H
2
O(l).
A bomb calorimeter gives q
V
= n
c
U

rather than q
p
= n
c
H

; thus we need

c
U

=
c
H

n
g
RT [2.21], n
g
= 2 mol.

c
H

= 5157 kJ mol
1
[Table 2.6].

c
U

= (5157 kJ mol
1
) (2) (8.3 10
3
kJ K
1
mol
1
) (298 K)
= 5152 kJ mol
1
.
|q| = |q
V
| = |n
c
U

| =
_
120 10
3
g
128.18 g mol
1
_
(5152 kJ mol
1
) = 4.823 kJ
C =
|q|
T
=
4.823 kJ
3.05 K
= 1.58 kJ k
1
When phenol is used the reaction is
C
6
H
5
OH(s) +
15
2
O
2
(g) 6CO
2
(g) + 3H
2
O(l).

c
H

= 3054 kJ mol
1
[Table2.6].

c
U

=
c
H

n
g
RT, n
g
=
3
2
= (3054 kJ mol
1
) + (
3
2
) (8.314 10
3
kJ K
1
mol
1
) (298 K)
= 3050 kJ mol
1
.
|q| =
10 10
3
g
94.12 g mol
1
(3050 kJ mol
1
) = 0.3241 kJ.
T =
|q|
C
=
0.3241 kJ
1.58 kJ K
1
= +0.205 K .
COMMENT. In this case
c
U

and
c
H

## differed by about 0.1 per cent. Thus, to within 3 signicant gures,

it would not have mattered if we had used
c
H

c
U

## , but for very precise work it would.

E2.20(a) The reaction is AgCl(s) Ag
+
(aq) + Cl

(aq).

sol
H

=
f
H

(Ag
+
, aq) +
f
H

(Cl

, aq)
f
H

(AgCl, s)
= [(105.58) + (167.16) (127.07)] kJ mol
1
= +65.49 kJ mol
1
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 31 #9
THE FIRST LAW 31
E2.21(a)
NH
3
SO
2
(s) NH
3
(g) + SO
2
(g),
r
H

= +40 kJ mol
1
.

r
H

=
f
H

(NH
3
, g) +
f
H

(SO
2
, g)
f
H

(NH
3
SO
2
, s).
Solving for
f
H

(NH
3
SO
2
, s) yields

f
H

(NH
3
SO
2
, s) =
f
H

(NH
3
, g) +
f
H

(SO
2
, g)
r
H

## = (46.11 296.83 40) kJ mol

1
= 383 kJ mol
1
.
E2.22(a) (a) Reaction (3) = (2) reaction (1) + reaction (2) and n
g
= 1.
The enthalpies of reactions are combined in the same manner as the equations (Hesss law).

r
H

(3) = (2)
r
H

(1) +
r
H

(2)
= [(2) (184.62) + (483.64)] kJ mol
1
= 114.40 kJ mol
1
.

r
U

=
r
H

n
g
RT [2.21] = (114.40 kJ mol
1
) (1) (2.48 kJ mol
1
)
= 111.92 kJ mol
1
.
(b)
f
H

## refers to the formation of one mole of the compound; hence

f
H

(J) =

r
H

(J)

J
.

f
H

(HCl, g) =
184.62
2
kJ mol
1
= 92.31 kJ mol
1
.

f
H

(H
2
O, g) =
483.64
2
kJ mol
1
= 241.82 kJ mol
1
.
E2.23(a)
r
H

=
r
U

+ n
g
RT [2.21]; n
g
= +2
= (1373 kJ mol
1
) + 2 (2.48 kJ mol
1
) = 1368 kJ mol
1
.
COMMENT. As a number of these exercises have shown, the use of
r
H

as an approximation for
r
U

is often valid.
E2.24(a) In each case, the strategy is to combine reactions in such a way that the combination corresponds to the
formation reaction desired. The enthalpies of the reactions are then combined in the same manner as the
equations to yield the enthalpies of formation.
(a)

r
H

/(kJ mol
1
)
K(s) +
1
2
Cl
2
(g) KCl(s) 436.75
KCl(s) +
3
2
O
2
(g) KClO
3
(s)
1
2
(89.4)
K(s) +
1
2
Cl
2
(g) +
3
2
O
2
(g) KClO
3
(s) 392.1
Hence,
f
H

(KClO
3
, s) = 392.1 kJ mol
1
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 32 #10
32 SOLUTIONS MANUAL
(b)
r
H

/(kJ mol
1
)
Na(s) +
1
2
O
2
(g) +
1
2
H
2
(g) NaOH(s) 425.61
NaOH(s) + CO
2
(g) NaHCO
3
(s) 127.5
C(s) + O
2
(g) CO
2
(g) 393.51
Na(s) + C(s) +
1
2
H
2
(g) +
3
2
O
2
(g) NaHCO
3
(s) 946.6
Hence,
f
H

(NaHCO
3
, s) = 946.6 kJ mol
1
.
E2.25(a) When the heat capacities of all substances participating in a chemical reaction are assumed to be constant
over the range of temperatures involved Kirchoffs law [2.36] integrates to

r
H

(T
2
) =
r
H

(T
1
) +
r
C

p
(T
2
T
1
) [Example 2.6].

r
C

p
=

Products
C

p,m

Reactants
C

p,m
[2.37],

r
C

p
= C

p
(N
2
O
4
, g) 2 C

p
(NO
2
, g) = (77.28) (2) (37.20 J K
1
mol
1
)
= +2.88 J K
1
mol
1
,

r
H

(373 K) =
r
H

(298 K) +
r
C

p
T
= (57.20 kJ mol
1
) + (2.88 J K
1
) (75 K)
= [(57.20) + (0.22)] kJ mol
1
= 56.98 kJ mol
1
.
E2.26(a) (a)
r
H

Products

f
H

Reactants

f
H

[2.34].

r
H

## (298 K) = [(110.53) (241.82)] kJ mol

1
= +131.29 kJ mol
1
.

r
U

(298 K) =
r
H

(298 K) n
g
RT [2.21]
= (131.29 kJ mol
1
) (1) (2.48 kJ mol
1
) = +128.81 kJ mol
1
.
(b)
r
U

(378 K) =
r
H

(298 K) (T
2
T
1
)
r
C

p
[Example 2.6].

r
C

p
= C

p,m
(CO,g) + C

p,m
(H
2
,g) C

p,m
(C,gr) C

p,m
(H
2
O,g)
= (29.14 + 28.82 8.53 33.58) 10
3
kJ K
1
mol
1
= 15.85 10
3
kJ K
1
mol
1
.

r
H

## (378 K) = (131.29 kJ mol

1
) + (15.85 10
3
kJ K
1
mol
1
) (80 K)
= (131.29 + 1.27) kJ mol
1
= +132.56 kJ mol
1
.

r
U

(378 K) =
r
H

## (378 K) (1) (8.31 10

3
kJ K
1
mol
1
) (378 K)
= (132.56 3.14) kJ mol
1
= +129.42 kJ mol
1
.
COMMENT. The differences in both
r
H

and
r
U

## between the two temperatures are small and justify

the use of the approximation that
r
C

p
is a constant.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 33 #11
THE FIRST LAW 33
E2.27(a) CuSO
4
and ZnSO
4
are strong electrolytes; therefore the net ionic equation is
Zn(s) + Cu
2+
(aq) Zn
2+
(aq) + Cu(s).

r
H

=
f
H

(Zn
2+
) +
f
H

(Cu)
f
H

(Zn)
f
H

(Cu
2+
)
= [(153.89) + (0) (0) (64.77)] kJ mol
1
= 218.66 kJ mol
1
.
COMMENT. SO
2
4
is a spectator ion and was ignored in the determination above.
E2.28(a) Since enthalpy is a state function,
r
H

## for the process (see Fig. 2.1)

Mg
2+
(g) + 2Cl(g) + 2e

MgCl
2
(aq)
is independent of path; therefore the change in enthalpy for the path on the left is equal to the change in
enthalpy for the path on the right. All numerical values are in kJ mol
1
.
Figure 2.1
The cycle is the distance traversed upward along the left plus the distance traversed downward on the
right. The sum of these distances is zero. Note that E
ea
=
eg
H

## . Therefore, following the cycle up

the left and down the right and using kJ units,
(150.5) (641.32) + (167.2) + (241.6) + (737.7 + 1450.7)
+ 2 (364.7) + 2 (383.7) +
hyd
H

(Mg
2+
) = 0
which yields
hyd
H

(Mg
2+
) = 1892 kJ mol
1
.
E2.29(a) The JouleThomson coefcient is the ratio of temperature change to pressure change under conditions
of isenthalpic expansion. So
=
_
T
p
_
H
[2.51] = lim
p0
_
T
p
_
H

T
p
[ constant over temperature range],
=
22 K
31 atm
= 0.71 K atm
1
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 34 #12
34 SOLUTIONS MANUAL
E2.30(a) The internal energy is a function of temperature and volume, U
m
= U
m
(T, V
m
), so
dU
m
=
_
U
m
T
_
V
m
dT +
_
U
m
V
m
_
T
dV
m
[
T
= (U
m
/V)
T
].
For an isothermal expansion dT = 0; hence
dU
m
=
_
U
m
V
m
_
T
dV
m
=
T
dV
m
=
a
V
2
m
dV
m
,
U
m
=
_
V
m,2
V
m,1
dU
m
=
_
V
m,1
V
m,2
a
V
2
m
dV
m
= a
_
24.8 dm
3
mol
1
1.00 dm
3
mol
1
dV
m
V
2
m
=
a
V
m

24.8 dm
3
mol
1
1.00 dm
3
mol
1
=
a
24.8 dm
3
mol
1
+
a
1.00 dm
3
mol
1
=
23.8a
24.8 dm
3
mol
1
= 0.9597 a mol dm
3
.
From Table 1.6, a = 1.352 dm
6
atm mol
1
.
U
m
= (0.9597 mol dm
3
) (1.352 dm
6
atmmol
2
)
= (1.30 dm
3
atm mol
1
)
_
1m
10 dm
_
3

_
1.013 10
5
Pa
atm
_
= +131 J mol
1
.
w =
_
p dV
m
where p =
RT
V
m
b

a
V
2
m
for a van der Waals gas. Hence,
w =
_ _
RT
V
m
b
_
dV
m
+
_
a
V
2
m
dV
m
= q + U
m
.
Therefore,
q =
_
24.8 dm
3
mol
1
1.00 dm
3
mol
1
_
RT
V
m
b
_
dV
m
= RT ln(V
m
b)|
24.8 dm
3
mol
1
1.00 dm
3
mol
1
= (8.314 J K
1
mol
1
) (298 K) ln
_
24.8 3.9 10
2
1.00 3.9 10
2
_
= +8.05 10
3
J mol
1
.
and w = q + U
m
= (8.05 10
3
J mol
1
) + (131 J mol
1
) = 7.92 10
3
J mol
1
.
E2.31(a)
=
_
1
V
__
V
T
_
p
[2.43];
320
=
_
1
V
320
__
V
T
_
p, 320
.
_
V
T
_
p
= V
300
(3.9 10
4
/K + 2.96 10
6
T/K
2
),
_
V
T
_
p, 320
= V
300
(3.9 10
4
/K + 2.96 10
6
320/K) = 1.34 10
3
K
1
V
300
.
V
320
= V
300
{(0.75) + (3.9 10
4
) (320) + (1.48 10
6
) (320)
2
} = (V
300
) (1.026).
TRAPP: CHAP02 2006/3/8 17:05 PAGE 35 #13
THE FIRST LAW 35
so
320
=
_
1
V
320
__
V
T
_
p, 320
=
_
1
1.026V
300
_
(1.34 10
3
K
1
V
300
),

320
=
1.34 10
3
K
1
1.026
= 1.31 10
3
K
1
.
COMMENT. Knowledge of the density at 300 K is not required to solve this exercise, but it would be required
to obtain numerical values of the volumes at the two temperatures.
E2.32(a) The isothermal compressibility is

T
=
_
1
V
__
V
p
_
T
[2.44] so
_
V
p
_
T
=
T
V.
At constant temperature
dV =
_
V
p
_
T
dp so dV =
T
V dp or
dV
V
=
T
dp.
Substituting V =
m

and dV =
m

2
d yields
dV
V
=
d

=
T
dp.
Therefore,

T
p.
For

= 0.08 10
2
= 8 10
4
, p
8 10
4

T
=
8 10
4
7.35 10
7
atm
1
= 1.1 10
3
atm .
E2.33(a) The isothermal JouleThomson coefcient is
_
H
m
p
_
T
= C
p,m
= (0.25 Katm
1
) (29 J K
1
mol
1
) = 7.2 J atm
1
mol
1
.
dH = n
_
H
m
p
_
T
dp = nC
p,m
dp,
H =
_
p
2
p
1
(nC
p,m
)dp = nC
p,m
(p
2
p
1
) [andC
p
are constant],
H = (15 mol) (+7.2 J atm
1
mol
1
) (75 atm) = +8.1 kJ
so q(supplied) = +H = +8.1 kJ .
Solutions to problems
Assume all gases are perfect unless stated otherwise. Unless otherwise stated, thermochemical data are
for 298 K.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 36 #14
36 SOLUTIONS MANUAL
Solutions to numerical problems
P2.1 The temperatures are readily obtained from the perfect gas equation, T =
pV
nR
,
T
1
=
(1.00 atm) (22.4 dm
3
)
(1.00 mol) (0.0821 dm
3
atmmol
1
K
1
)
= 273 K = T
3
[isotherm].
Similarly, T
2
= 546 K .
In the solutions that follow all steps in the cycle are considered to be reversible.
Step 1 2
w = p
ex
V = pV = nRT [(pV) = (nRT)],
w = (1.00 mol) (8.314 J K
1
mol
1
) (546 273) K = 2.27 10
3
J .
U = nC
V,m
T = (1.00 mol)
3
2
(8.314 J K
1
mol
1
) (273 K) = +3.40 10
3
J.
q = U w = +3.40 10
3
J (2.27 10
3
J) = +5.67 10
3
J .
H = q
p
= +5.67 10
3
J .
If this step is not reversible, then w, q, and H would be indeterminate.
Step 2 3
w = 0 [constant volume].
q
V
= U = nC
V,m
T = (1.00 mol) (
3
2
) (8.314 J K
1
mol
1
) (273 K)
= 3.40 10
3
J .
From H U + pV
H = U + (pV) = U + (nRT) = U + nRT
= (3.40 10
3
J) + (1.00 mol) (8.314 J K
1
mol
1
) (273 K) = 5.67 10
3
J .
Step 3 1
U and H are zero for an isothermal process in a perfect gas; hence for the reversible compression
q = w = nRT ln
V
1
V
3
= (1.00 mol) (8.314 J K
1
mol
1
) (273 K) ln
_
22.4 dm
3
44.8 dm
3
_
= +1.57 10
3
J , q = 1.57 10
3
J .
If this step is not reversible, then q and w would have different values which would be determined by
the details of theprocess.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 37 #15
THE FIRST LAW 37
Total cycle
State p/atm V/dm
3
T/K
1 1.00 22.44 273
2 1.00 44.8 546
3 0.50 44.8 273
Thermodynamic quantities calculated for reversible steps
Step Process q/kJ w/kJ U/kJ H/kJ
1 2 p constant = p
ex
+5.67 2.27 +3.40 +5.67
2 3 V constant 3.40 0 3.40 5.67
3 1 Isothermal, reversible 1.57 +1.57 0 0
Cycle +0.70 0.70 0 0
COMMENT. All values can be determined unambiguously for the reversible cycle. The net result of the overall
process is that 700 J of heat has been converted to work.
P2.3 Since the volume is xed, w = 0 .
Since U = q at constant volume, U = +2.35 kJ .
H = U + (pV) = U + Vp [V = 0].
From the van der Waals equation [Table 1.6]
p =
RT
V
m
b

a
V
2
m
so p =
RT
V
m
b
[V
m
= 0 at constant volume].
Therefore, H = U +
RVT
V
m
b
.
From the data,
V
m
=
15.0 dm
3
2.0 mol
= 7.5 dm
3
mol
1
, T = (341 300) K = 41 K.
V
m
b = (7.5 4.3 10
2
) dm
3
mol
1
= 7.4

6 dm
3
mol
1
.
RVT
V
m
b
=
(8.314 J K
1
mol
1
) (15.0 dm
3
) (41 K)
7.4

6 dm
3
mol
1
= 0.68 kJ.
Therefore,H = (2.35 kJ) + (0.68 kJ) = +3.03 kJ .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 38 #16
38 SOLUTIONS MANUAL
P2.5 This cycle is represented in Figure 2.2. Assume that the initial temperature is 298 K .
2
(b)
V/dm
3
(c)
3
(a)
100 50 150
2.0
1.0
p
/
a
t
m
1
Figure 2.2
(a) First, note that w = 0 (constant volume). Then calculate U since T is known (T = 298 K)
and then calculate q from the First Law.
U = nC
V,m
T [2.16b]; C
V,m
= C
p,m
R =
7
2
R R =
5
2
R,
U = (1.00 mol)
_
5
2
_
(8.314 J K
1
mol
1
) (298 K) = 6.19 10
3
J = +6.19 kJ .
q = q
V
= U w = 6.19 kJ 0 = +6.19 kJ .
H = U + (pV) = U + (nRT) = U + nRT
= (6.19 kJ) + (1.00 mol) (8.31 10
3
kJ mol
1
) (298 K) = +8.67 kJ .
Because the energy and enthalpy of a perfect gas depend on temperature alone,
U(b) = U(a) = 6.19 kJ , since T(b) = T(a).
Likewise H(b) = H (a) = 8.67 kJ .
w = U = 6.19 kJ [First Law with q = 0].
(c) U = H = 0 [isothermal process in perfect gas].
q = w [First Law with U = 0]; w = nRT
1
ln
V
1
V
3
[2.11].
V
2
= V
1
=
nRT
1
p
1
=
(1.00 mol) (0.08206 dm
3
atm K
1
mol
1
) (298 K)
1.00 atm
= 24.4

5 dm
3
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 39 #17
THE FIRST LAW 39
V
2
T
c
2
= V
3
T
c
3
[2.28b]; hence V
3
= V
2
_
T
2
T
3
_
c
where c =
C
V,m
R
=
5
2
so V
3
= (24.4

5 dm
3
)
_
(2) (298 K)
298 K
_
5/2
= 138.

3 dm
3
.
w = (1.00 mol) (8.314 J K
1
mol
1
) (298 K) ln
_
22.4

5 dm
3
138.3 dm
3
_
= 4.29 10
3
J = +4.29 kJ .
q = 4.29 kJ .
P2.7 The formation reaction is
2C(s) + 3H
2
(g) 2C
6
H
6
(g),
f
H

## (298 K) = 84.68 kJ mol

1
.
In order to determine
f
H

## (350 K) we employ Kirchhoffs law [2.36] with T

2
= 350 K, T
1
= 298 K,

f
H

(T
2
) =
f
H

(T
1
) +
_
T
2
T
1

r
C
p
dT
where
r
C
p
=

J

J
C
p,m
(J) = C
p,m
(C
6
H
6
) 2C
p,m
(C) 3C
p,m
(H
2
).
From Table 2.2
C
p,m
(C
6
H
6
)/(J K
1
mol
1
) = 14.73 +
_
0.1272
K
_
T,
C
p,m
(C, s)/(J K
1
mol
1
) = 16.86 +
_
4.77 10
3
K
_
T
_
8.54 10
5
K
2
T
2
_
,
C
p,m
(H
2
, g)/(J K
1
mol
1
) = 27.28 +
_
3.26 10
3
K
_
T
_
0.50 10
5
K
2
T
2
_
,

r
C
p
/(J K
1
mol
1
) = 100.83 +
_
0.1079T
K
_

_
1.56 10
6
K
2
T
2
_
.
_
T
2
T
1

r
C
p
dT
J K
1
mol
1
= 100.83 (T
2
T
1
) +
_
1
2
_
_
0.1079 K
1
_
(T
2
2
T
2
1
)
(1.56 10
6
K
2
)
_
1
T
2

1
T
1
_
= 100.83 (52 K) +
_
1
2
_
(0.1079)(350
2
298
2
) K
(1.56 10
6
)
_
1
350

1
298
_
K
= 2.65 10
3
K.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 40 #18
40 SOLUTIONS MANUAL
Multiplying by the units J K
1
mol
1
, we obtain
_
T
2
T
1

r
C
p
dT = (2.65 10
3
K) (J K
1
mol
1
) = 2.65 10
3
J mol
1
= 2.65 kJ mol
1
.
Hence
f
H

(350 K) =
f
H

1
= 84.68 kJ mol
1
2.65 kJ mol
1
= 87.33 kJ mol
1
.
P2.9 Cr(C
6
H
6
)
2
(s) Cr(s) + 2C
6
H
6
(g), n
g
= +2 mol.

r
H

=
r
U

## + 2RT, from [2.21]

= (8.0 kJ mol
1
) + (2) (8.314 J K
1
mol
1
) (583 K) = +17.7 kJ mol
1
.
In terms of enthalpies of formation

r
H

= (2)
f
H

(benzene, 583 K)
f
H

(metallocene, 583 K)
or
r
H

(metallocene, 583 K) = 2
f
H

## (benzene, 583 K) 17.7 kJ mol

1
.
The enthalpy of formation of benzene gas at 583 K is related to its value at 298 K by

f
H

(benzene, 583 K) =
f
H

(benzene, 298 K)
+ (T
b
298 K)C
p,m
(l) +
vap
H

+ (583 K T
b
)C
p,m
(g)
6 (583 K 298 K)C
p,m
(gr) 3 (583 K 298 K)C
p,m
(H
2
, g)
where T
b
is the boiling temperature of benzene (353 K). We shall assume that the heat capacities of graph-
ite and hydrogen are approximately constant in the range of interest and use their values fromTable 2.15.

f
H

## (benzene, 583 K) = (49.0 kJ mol

1
) + (353 298) K (136.1 J K
1
mol
1
)
+ (30.8 kJ mol
1
) + (583 353) K (81.67 J K
1
mol
1
)
(6) (583 298) K (8.53 J K
1
mol
1
)
(3) (583 298) K (28.82 J K
1
mol
1
)
= {(49.0) + (7.49) + (18.78) + (30.8) (14.59) (24.64)} kJ mol
1
= +66.8 kJ mol
1
.
Therefore
f
H

## (metallocene, 583 K) = (2 66.8 17.7) kJ mol

1
= + 116.0 kJ mol
1
.
P2.11 (a) and (b). The table displays computed enthalpies of formation (semi-empirical, PM3 level, PCSpartan
Pro
TM
), enthalpies of combustion based on them(and on experimental enthalpies of formation of H
2
O(l)
and CO
2
(g), 285.83 and 393.51 kJ mol
1
respectively), experimental enthalpies of combustion
(Table 2.5), and the relative error in enthalpy of combustion.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 41 #19
THE FIRST LAW 41
Compound
f
H

/kJ mol
1

c
H

/kJ mol
1
(calc.)
c
H

/kJ mol
1
(expt.) %error
CH
4
(g) 54.45 910.72 890 2.33
C
2
H
6
(g) 75.88 1568.63 1560 0.55
C
3
H
8
(g) 98.84 2225.01 2220 0.23
C
4
H
10
(g) 121.60 2881.59 2878 0.12
C
5
H
12
(g) 142.11 3540.42 3537 0.10
The combustion reactions can be expressed as:
C
n
H
2n+2
(g) +
_
3n + 1
2
_
O
2
(g) n CO
2
(g) + (n + 1) H
2
O(1).
The enthalpy of combustion, in terms of enthalpies of reaction, is

c
H

= n
f
H

(CO
2
) + (n + 1)
f
H

(H
2
O)
f
H

(C
n
H
2n+2
),
where we have left out
f
H

(O
2
) = 0. The % error is dened as:
%error =

c
H

(calc.)
c
H

(expt.)

c
H

(expt.)
100%.
The agreement is quite good.
(c) If the enthalpy of combustion is related to the molar mass by

c
H

= k[M/(g mol
1
)]
n
then one can take the natural log of both sides to obtain:
ln

c
H

## = ln |k| + n ln M/(g mol

1
).
Thus, if one plots ln

c
H

## vs. ln [M/(g mol

1
)], one ought to obtain a straight line with slope n and
y-intercept ln |k|. Draw up the following table.
Compound M/(g mol
1
)
c
H/kJ mol
1
ln M/(g mol
1
) ln

c
H

/ kJ mol
1

CH
4
(g) 16.04 910.72 2.775 6.814
C
2
H
6
(g) 30.07 1568.63 3.404 7.358
C
3
H
8
(g) 44.10 2225.01 3.786 7.708
C
4
H
10
(g) 58.12 2881.59 4.063 7.966
C
5
H
12
(g) 72.15 3540.42 4.279 8.172
The plot is shown in Fig 2.3.
The linear least-squares t equation is:
ln |
c
H

/kJ mol
1
| = 4.30 + 0.903 ln M/(g mol
1
) R
2
= 1.00
These compounds support the proposed relationships, with
n = 0.903 and k = e
4.30
kJ mol
1
= 73.7 kJ mol
1
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 42 #20
42 SOLUTIONS MANUAL
ln M/(g mol
1
)
l
n
|

c
H

/

k
J

m
o
l

1
|
2
6
7
8
9
3 4 5
Figure 2.3
The agreement of these theoretical values of k and n with the experimental values obtained in P2.10 is
rather good.
P2.13 The reaction is
C
60
(s) + 60O
2
(g) 60CO
2
(g).
Because the reaction does not change the number of moles of gas,
c
H =
c
U [2.21]. Therefore

c
H

= (36.0334 kJ g
1
) (60 12.011 g mol
1
) = 25968 kJ mol
1
.
Now relate the enthalpy of combustion to enthalpies of formation and solve for that of C
60.

c
H

= 60
f
H

(CO
2
) 60
f
H

(O
2
)
f
H

(C
60
),

f
H

(C
60
) = 60
f
H

(CO
2
) 60
f
H

(O
2
)
c
H

## = [60(393.51) 60(0) (25968)] kJ mol

1
= 2357 kJ mol
1
.
P2.15 (a)
r
H

=
f
H

(SiH
2
) +
f
H

(H
2
)
f
H

(SiH
4
)
= (274 + 0 34.3) kJ mol
1
= 240 kJ mol
1
.
(b)
r
H

=
f
H

(SiH
2
) +
f
H

(SiH
4
)
f
H

(Si
2
H
6
)
= (274 + 34.3 80.3) kJ mol
1
= 228 kJ mol
1
.
P2.17 The temperatures and volumes in reversible adiabatic expansion are related by eqn 2.28a:
T
f
= T
i
_
V
f
V
i
_
1/c
where c =
C
V,m
R
.
From eqn 2.29, we can relate the pressures and volumes:
p
f
= p
i
_
V
f
V
i
_

where =
C
p,m
C
V,m
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 43 #21
THE FIRST LAW 43
We are looking for C
p,m
, which can be related to c and .
c =
_
C
V,m
R
_

_
C
p,m
C
V,m
_
=
C
p,m
R
.
Solving both relationships for the ratio of volumes, we have
_
p
f
p
i
_
1/
=
V
f
V
i
=
_
T
f
T
i
_
c
so
p
f
p
i
=
_
T
f
T
i
_
c
.
Therefore
C
p,m
= R
ln
_
p
f
p
i
_
ln
_
T
f
T
i
_ = (8.314 J K
1
mol
1
)
_
_
_
_
ln
_
202.94 kPa
81.840 kPa
_
ln
_
298.15 K
248.44 K
_
_
_
_
_
= 41.40 J K
1
mol
1
.
P2.19
H
m
= H
m
(T, p).
dH
m
=
_
H
m
T
_
p
dT +
_
H
m
p
_
T
dp.
Since dT = 0,
dH
m
=
_
H
m
p
_
T
dp where
_
H
m
p
_
T
= C
p,m
[2.53] =
_
2a
RT
b
_
.
H
m
=
_
p
f
p
i
dH
m
=
_
p
f
p
i
_
2a
RT
b
_
dp =
_
2a
RT
b
_
(p
f
p
i
)
=
(2) (1.352 dm
6
atm mol
2
)
(0.08206 dm
3
atm K
1
mol
1
) (300 K)
(0.0387 dm
3
mol
1
)
(1.00 atm 500 atm)
= (35.5 atm)
_
1 m
10 dm
_
3

_
1.013 10
5
Pa
1 atm
_
= 3.60 10
3
J = +3.60 kJ .
COMMENT. Note that it is not necessary to know the value of C
p,m
.
Solutions to theoretical problems
P2.21 (a) dz =
_
z
x
_
y
dx +
_
z
y
_
x
dy [denition of total differential].
_
z
x
_
y
= (2x 2y + 2),
_
z
y
_
x
= (4y 2x 4),
dz = (2x 2y + 2) dx+(4y2x4)dy .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 44 #22
44 SOLUTIONS MANUAL
(b)

y
_
z
x
_
=

y
(2x 2y + 2) = 2,

x
_
z
y
_
=

x
(4y 2x 4) = 2.
(c)
_
z
x
_
y
=
_
y +
1
x
_
,
_
z
y
_
x
= (x 1),
dz =
_
y +
1
x
_
dx + (x - 1) dy .
A differential is exact if it satises the condition

x
_
z
y
_
=

y
_
z
x
_
,

y
_
z
x
_
=

y
_
y +
1
x
_
= 1,

x
_
z
y
_
=

x
(x 1) = 1.
COMMENT. The total differential of a function is necessarily exact.
P2.23 U = U(T, V) so dU =
_
U
T
_
V
dT +
_
U
V
_
T
dV = C
V
dT +
_
U
V
_
T
dV.
For U = constant, dU = 0, and
C
V
dT =
_
U
V
_
T
dV or C
V
=
_
U
V
_
T
_
dV
dT
_
U
=
_
U
V
_
T
_
V
T
_
U
.
This relationship is essentially Eulers chain relation [Further information 2.2].
H = H(T, p) so dH =
_
H
T
_
p
dT +
_
H
p
_
T
dp = C
p
dT +
_
H
p
_
T
dp.
According to Eulers chain relation
_
H
p
_
T
_
p
T
_
H
_
dT
dH
_
p
= 1
so, using the reciprocal identity [Further information 2.2],
_
H
p
_
T
=
_
T
p
_
H
_
dH
dT
_
p
= - C
p
.
P2.25 (a) H = U + pV so
_
H
U
_
p
= 1 + p
_
V
U
_
p
= 1 +
p
(U/V)
p
.
(b)
_
H
U
_
p
=
(H/V)
p
(U/V)
p
=
_
((U + pV)
V
_
p
(U/V)
p
=
(U/V)
p
+ p
(U/V)
p
so
_
H
U
_
p
= 1 +
p
(U/V)
p
= 1 + p
V
Up
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 45 #23
THE FIRST LAW 45
P2.27
w =
_
V
2
V
1
p dV.
Inserting
V
n
= V
m
into the virial equation for p we obtain
p = nRT
_
1
V
+
nB
V
2
+
n
2
C
V
3
+ ...
_
.
Therefore, w = nRT
_
V
2
V
1
_
1
V
+
nB
V
2
+
n
2
C
V
3
+ ...
_
dV,
w = nRT ln
V
2
V
1
+ n
2
RTB
_
1
V
2

1
V
1
_
+
1
2
n
3
RTC
_
1
V
2
2

1
V
2
2
_
+ ....
For n = 1 mol: nRT = (1.0 mol) (8.314 J K
1
mol
1
) (273 K) = 2.27 kJ.
From Table 1.4, B = 21.7 cm
3
mol
1
and C = 1200 cm
6
mol
2
, so
n
2
BRT = (1.0 mol) (21.7 cm
3
mol
1
) (2.27 kJ) = 49.3 kJ cm
3
,
1
2
n
3
CRT =
1
2
(1.0 mol)
2
(1200cm
6
mol
2
) (2.27 kJ) = +1362 kJ cm
6
.
Therefore,
(a)
w = 2.27 kJ ln 2 (49.3 kJ)
_
1
1000

1
500
_
+ (1362 kJ)
_
1
1000
2

1
500
2
_
= (1.57) + (0.049) (4.1 10
3
) kJ = 1.52 kJ = 1.5 kJ .
(b) A perfect gas corresponds to the rst term of the expansion of p, so
w = 1.57 kJ = 1.6 kJ .
P2.29 =
_
T
p
_
H
=
1
C
p
_
H
p
_
T
[2.51 and 2.53],
=
1
C
p
_
T
_
V
T
_
p
V
_
[See problem 2.34 for this result].
But V =
nRT
p
+ nb or
_
V
T
_
p
=
nR
p
.
Therefore,
=
1
C
p
_
nRT
p
V
_
=
1
C
p
_
nRT
p

nRT
p
nb
_
=
nb
C
p
.
Since b > 0 and C
p
> 0, we conclude that for this gas < 0 or
_
T
p
_
H
< 0. This says that when the
pressure drops during a JouleThomson expansion the temperature must increase .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 46 #24
46 SOLUTIONS MANUAL
P2.31
p =
nRT
V nb

n
2
a
V
2
[Table 1.7].
Hence T =
_
p
nR
_
(V nb) +
_
na
RV
2
_
(V nb) ,
_
T
p
_
V
=
V nb
nR
=
V
m
b
R
=
1
_
p
T
_
V
.
For Eulers chain relation, we need to show that
_
T
p
_
V
_
p
V
_
T
_
V
T
_
p
= 1.
_
T
p
_
V
we need
_
p
V
_
T
and
_
V
T
_
p
=
1
_
T
V
_
p
.
_
p
V
_
T
=
nRT
(V nb)
2
+
2n
2
a
V
3
which can be found from
_
T
V
_
p
=
_
p
nR
_
+
_
na
RV
2
_

_
2na
RV
3
_
(V nb),
_
T
V
_
p
=
_
T
V nb
_

_
2na
RV
3
_
(V nb).
Therefore,
_
T
p
_
V
_
p
V
_
T
_
V
T
_
p
=
_
T
p
_
V
_
p
V
_
T
_
T
V
_
p
=
_
V nb
nR
_

_
nRT
(V nb)
2
+
2n
2
a
V
3
_
_
T
V nb
_

_
2na
RV
3
_
(V nb)
=
_
T
V nb
_
+
_
2na
RV
3
_
(V nb)
_
T
V nb
_

_
2na
RV
3
_
(V nb)
= 1.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 47 #25
THE FIRST LAW 47
P2.33 C
p
= T
_
V
T
_
p
V =
T
_
T
V
_
p
V [reciprocal identity, Further information 2.2]
_
T
V
_
p
=
T
V nb

2na
RV
3
(V nb) [Problem 2.31]
Introduction of this expression followed by rearrangement leads to
C
p
=
(2na) (V nb)
2
nbRTV
2
RTV
3
2na(V nb)
2
V.
Then, introducing =
RTV
3
2na(V nb)
2
to simplify the appearance of the expression
C
p
=
_
_
_
1
nb
V
1
_
_
_V =
_
_
_
_
1
b
V
m
1
_
_
_
_
V.
For xenon, V
m
= 24.6 dm
3
mol
1
, T = 298 K, a = 4.137 dm
6
atmmol
2
, b = 5.1610
2
dm
3
mol
1
,
nb
V
=
b
V
m
=
5.16 10
1
dm
3
mol
1
24.6 dm
3
mol
1
= 2.09 10
3
,
=
(8.206 10
2
dm
3
atmK
1
mol
1
) (298 K) (24.6 dm
3
mol
1
)
3
(2) (4.137 dm
6
atmmol
2
) (24.6 dm
3
mol
1
5.16 10
2
dm
3
mol
1
)
2
= 73.0.
Therefore, C
p
=
1 (73.0) (2.09 10
3
)
72.0
(24.6 dm
3
mol
1
) = 0.290 dm
3
mol
1
.
C
p
= 20.79 J K
1
mol
1
[Table 2.6], so
=
0.290 dm
3
mol
1
20.79 J K
1
mol
1
=
0.290 10
3
m
3
mol
1
20.79 J K
1
mol
1
= 1.393 10
5
Km
3
J
1
= 1.393 10
5
KPa
1
= (1.393 10
5
) (1.013 10
5
Katm
1
) = 1.41 K atm
1
.
The value of changes at T = T
I
and when the sign of the numerator 1
nb
V
changes sign ( 1 is
positive). Hence
b
V
m
= 1 at T = T
I
or
RTbV
3
2na(V nb)
2
V
m
= 1 implying that T
I
=
2a(V
m
b)
2
RbV
2
m
,
TRAPP: CHAP02 2006/3/8 17:05 PAGE 48 #26
48 SOLUTIONS MANUAL
that is, T
I
=
_
2a
Rb
_

_
1
b
V
m
_
2
=
27
4
T
c
_
1
b
V
m
_
2
.
For xenon,
2a
Rb
=
(2) (4.137 dm
6
atmmol
2
)
(8.206 10
2
dm
3
atmK
1
mol
1
) (5.16 10
2
dm
3
mol
1
)
= 1954 K
and so T
I
= (1954 K)
_
1
5.16 10
2
24.6
_
2
= 1946 K .
Question. An approximate relationship for of a van der Waals gas was obtained in Problem 2.30. Use
it to obtain an expression for the inversion temperature, calculate it for xenon, and compare to the result
above.
P2.35
C
p,m
C
V,m
=

2
TV
n
T
[2.49] =
TV
n
_
p
T
_
V
[2.57].
_
p
T
_
V
=
nR
V nb
[Problem 2.31].
V =
_
V
T
_
p
=
1
_
T
V
_
p
.
Substituting,
C
p,m
C
V,m
=
T
_
p
T
_
V
n
_
T
V
_
p
.
Also
_
T
V
_
p
=
T
V nb

2na
RV
3
(V nb) [Problem 2.31].
Substituting,
C
p,m
C
V,m
=
RT
(V nb)
T
(V nb)

2na
RV
3
(V nb)
= R
with =
1
1
2na
(RTV
3
)
(V nb)
2
or
1

= 1
2a(V
m
b)
3
RTV
3
m
.
Now introduce the reduced variables and use T
c
=
8a
27Rb
, V
c
= 3b.
After rearrangement,
1

= 1
(3V
r
1)
2
4T
r
V
3
r
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 49 #27
THE FIRST LAW 49
For xenon, V
c
= 118.1 cm
3
mol
1
, T
c
= 289.8 K. The perfect gas value for V
m
may be used as any error
introduced by this approximation occurs only in the correction term for
1

.
Hence, V
m
2.45 dm
3
, V
c
=118.8 cm
3
mol
1
, T
c
= 289.8 K, and V
r
= 20.6 and T
r
=1.03; therefore
1

= 1
(61.8 1)
2
(4) (1.03) (20.6)
3
= 0.90, giving 1.1
and
C
p,m
C
V,m
1.1 R = 9.2 J K
1
mol
1
.
P2.37 (a)
=
1
C
p
_
H
p
_
T
=
1
C
p
_
T
_
V
m
T
_
p
V
m
_
[2.53 and Problem 2.34].
V
m
=
RT
p
+ aT
2
so
_
V
m
T
_
p
=
R
p
+ 2aT.
=
1
C
p
_
RT
p
+ 2aT
2

RT
p
aT
2
_
= =
aT
2
C
p
.
(b)
C
V
= C
p
TV
m
_
p
T
_
V
= C
p
T
_
V
m
T
_
p
_
p
T
_
V
.
But, p =
RT
V
m
aT
2
.
_
p
T
_
V
=
R
V
m
aT
2

RT(2aT)
(V
m
aT
2
)
2
=
R
(RT/p)
+
2aRT
2
(RT/p)
2
=
p
T
+
2ap
2
R
.
Therefore
C
V
= C
p
T
_
R
p
+ 2aT
_

_
p
T
+
2ap
2
R
_
= C
p

RT
p
_
1 +
2apT
R
_

_
1 +
2apT
R
_

_
p
T
_
,
C
V
= C
p
R
_
1 +
2apT
R
_
2
.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 50 #28
50 SOLUTIONS MANUAL
Solutions to applications
P2.39 Taking the specic enthalpy of digestible carbohydrates to be 17 kJ g
1
(Impact I.2.2), the serving of
pasta yields
q = (40 g) (17 kJ g
1
) = 680 kJ.
Converting to Calories (kcal) gives:
q = (680 kJ)
1 Cal
4.184 kJ
= 162 Cal.
As a percentage of a 2200-Calorie diet, this serving is
162 Cal
2200 Cal
100% = 7.4% .
P2.41 (a) q = n
c
H

=
1.5 g
342.3 g mol
1
(5645 kJ mol
1
) = 25 kJ .
(b) Effective work available is 25 kJ 0.25 = 6.2 kJ.
Because w = mgh, and m 65 kg
h
6.2 10
3
J
65 kg 9.81 m s
2
= 9.7 m .
(c) The energy released as heat is
q =
r
H = n
c
H

=
_
2.5 g
180 g mol
1
_
(2808 kJ mol
1
) = 39 kJ .
(d) If one-quarter of this energy were available as work a 65 kg person could climb to a height h
given by
1
4
q = w = mgh so h =
q
4mg
=
39 10
3
J
4(65 kJ) (9.8 m s
2
)
= 15 m .
P2.43 First, with the pure sample, record a thermogram over a temperature range within which P undergoes a
structural change, as can be inferred froma peak in the thermogram. The area under the thermogramis the
enthalpy change associated with the structural change for the given quantity of P. Then, with an identical
mass of the suspected sample, record a thermogram over the same temperature range. Assuming that
the impurities in P undergo no structural change over the temperature rangea reasonable assumption
if the impurities are monomers or oligomers and if the temperature range is sufciently narrowthen
the peak in the test sample thermogram is attributable only to P. The ratio of areas under the curve in the
test sample to the pure sample is a measure of the purity of the test sample.
P2.45 The coefcient of thermal expansion is
=
1
V
_
V
T
_
p

V
VT
so V VT.
TRAPP: CHAP02 2006/3/8 17:05 PAGE 51 #29
THE FIRST LAW 51
This change in volume is equal to the change in height (sea level rise, h) times the area of the ocean
(assuming that area remains constant). We will use of pure water, although the oceans are complex
solutions. For a 2

C rise in temperature
V = (2.1 10
4
K
1
) (1.37 10
9
km
3
) (2.0 K) = 5.8 10
5
km
3
so h =
V
A
= 1.6 10
3
km = 1.6m .
Since the rise in sea level is directly proportional to the rise in temperature, T = 1

h = 0.80 m and T = 3.5

## C would lead to h = 2.8 m .

COMMENT. More detailed models of climate change predict somewhat smaller rises, but the same order
of magnitude.
P2.47 We compute from
=
1
C
p
_
H
p
_
T
and we estimate
_
H
p
_
T
from the enthalpy and pressure data. We are given both enthalpy and heat
capacity data on a mass basis rather than a molar basis; however, the masses will cancel, so we need not
convert to a molar basis.
(a)
(b)
Figure 2.4
TRAPP: CHAP02 2006/3/8 17:05 PAGE 52 #30
52 SOLUTIONS MANUAL
(a) At 300 K.
The regression analysis gives the slope as 18.0 J g
1
MPa
1

_
H
p
_
T
,
so =
18.0 kJ kg
1
MPa
1
0.7649 kJ kg
1
K
1
= 23.5 KMPa
1
= 23.5 K MPa
1
.
(b) At 350 K.
The regression analysis gives the slope as 14.5 J g
1
MPa
1

_
H
p
_
T
,
so =
14.5 kJ kg
1
MPa
1
1.0392 kJ kg
1
K
1
= 14.0 KMPa
1
.