2

Solutions to exercises
The First Law

E2.1(a) The physical definition of work is dw = F dz [2.4].

In a gravitational field 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,
zf zf
w = Fdz = mgdz = mg(zf zi) = mgh where h = (zf zi).
zi zi

On earth: w = (65 kg) (9.81 m s2) (4.0 m) = 2.6 103 J = 2.6 103 J needed .

On the moon: w = (65 kg) (1.60 m s2) (4.0 m) = 4.2 102 J = 4.2 102 J needed .

E2.2(a) This is an expansion against a constant external pressure; hence w = pex6V [2.8].

pex = (1.0 atm) (1.013 105 Pa atm1) = 1.01 105 Pa.

The change in volume is the cross-sectional area

3
times the linear displacement:
. 1m .
6V = (100 cm2) (10 cm) = 1.0 103 m3,
100 cm

so w = (1.01 105 Pa) (1.0 103 m 3) = 1.0 102 J as1 Pa m3 =1J.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 24 #2

E2.3(a) For all cases 6U = 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 definition
of enthalpy, H = U + pV , so 6H = 6U + 6(pV) = 6U + 6(nRT) (perfect gas). Hence, 6H = 0 as
well, at constant temperature for all processes in a perfect gas.
(a) .
. .
Vf
w = nRT ln [2.11]
Vi . .
44.8 dm3
= (1.00 mol) (8.314 J K1 mol1) (273 K) ln
22.4 dm3

= 1.57 103 J = 1.57 kJ .

q = 6U w [First Law]= 0 + 1.57 kJ = +1.57 kJ .

(b) .

w = pex6V [2.8], 6V = (44.8 22.4) dm3 = 22.4 dm3.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 25 #2

 THE FIRST LAW 25

pex can be computed from the perfect gas law,

pV = nRT ,

nRT (1.00 mol) (0.08206 dm3 atm K1 mol1) (273 K)

so pex = pf = = = 0.500 atm
Vf 44.8 dm3

. . 3 . .
1.013 105 Pa 1 m3
w = (0.500 atm) (22.4 dm )
1 atm 103 dm3

= 1.13 103 Pa m 3 = 1.13 103 J = 1.13 kJ .

q = 6U w = 0 + 1.13 kJ = +1.13 kJ .

(c)
Free expansion is expansion against no force, so and q = 6U w = 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 nR p1 p2
= .
= = constant; hence, T1 T2
T V
. . 1.33 atm
. . 400 K
p2 = T 2 p1 = (1.00 atm) = .
T1 300 K
3
6U = nCV ,m6T [2.16b]= (n) ( R) (400 K 300 K)
3 2 1 1
) (100 K)
= (1.00 mol) ( ) (8.314 J K mol
2
= 1.25 103 J = +1.25 kJ .

[constant volume] q = 6U w [First Law]= 1.25 kJ 0 = +1.25 kJ .

E2.5(a) (a) w = pex6V [2.8].

TRAPP: CHAP02 2006/3/8 17:05 PAGE 25 #3

 pex = (200 Torr) (133.3 Pa Torr1) = 2.666 104 Pa.
6V = 3.3 dm3 = 3.3 103 m3.

Therefore, w = (2.666 104 Pa) (3.3 103 m 3) = 88 J .

. .
(b) w = nRT ln Vf [2.11].
Vi

4.50 g 1 3 3

, Vi = 12.7 dm , Vf = 16.0 dm .
n= = 0.2805 mol, RT = 2.577 kJ mol
16.04 g mol1

. .
16.0 dm3
1
w = (0.2805 mol) (2.577 kJ mol ) ln = 167 J .
12.7 dm3

TRAPP: CHAP02 2006/3/8 17:05 PAGE 26 #3

 26 SOLUTIONS MANUAL

E2.6(a) 6H = 6condH = 6vapH = (1 mol) (40.656 kJ mol1) = 40.656 kJ .

Since the condensation is done isothermally and reversibly, the external pressure is constant at 1.00 atm.
Hence,

q = qp = 6H = 40.656 kJ .
w = pex6V [2.8] where 6V = Vliq Vvap Vvap because Vliq << Vvap.

nRT
On the assumption that H2O(g) is a perfect gas, Vvap = and p = pex, since the condensation is
p
done reversibly. Hence,

w nRT = (1.00 mol) (8.314 J K1 mol1) (373 K) = +3.10 103 J = +3.10 kJ .

From eqn 2.21, 6U = 6H 6ngRT , 6ng = 1.00 mol.

6U = (40.656 kJ) + (1.00 mol) (8.314 J K1 mol1) (373.15 K) = 37.55 kJ .

E2.7(a) The chemical reaction that occurs is Mg(s) + 2HCl(aq) H2(g) + MgCl2(aq), M(Mg) =
24.31 g mol1
Work is done against the atmosphere by the expansion of the hydrogen gas product in the reaction.

nRT
w = pex6V [2.8] where Vi 0, Vf = , pf = pex
pf

nRT
so w = pex(Vf Vi) pexVf = pex = nRT ,
pex

15g 1
n= = 0.617 mol, RT = 2.479 kJ mol .
24.31 g mol1

Hence w = (0.617 mol) (2.479 kJ mol1) =1.5 kJ

E2.8(a) (a) q = 6H, since pressure is constant.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 26 #4

 Tf
6H = dH, dH = nCp,mdT .
Ti

d(H/J) = {20.17 + 0.3665(T/K)}d(T/K).

Tf 473
6(H/J) = d(H/J) = {20.17 + 0.3665(T/K)}d(T/K)
Ti 298
. .
0.3665 . .2.473
T
.
.
= (20.17) (473 298) + .
2 K . 298

= (3.530 10 ) + (2.4725 10 ) = 2.83 104.

3 4

TRAPP: CHAP02 2006/3/8 17:05 PAGE 26 #4

 THE FIRST LAW 27

q = 6H = 2.83 104 J = +28.3 kJ .

w = pex6V [2.8] where pex = p.

w = p6V = 6(pV)[constant pressure]= 6(nRT) [perfect gas]= nR6T
= (1.00 mol) (8.314 J K1 mol1) (473 K 298 K)

= 1.45 103 J = 1.45 kJ .

6U = 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; 6H and 6U are the same.

6H = +28.3 kJ , 6U = 26.8 kJ .

Under constant volume, w = .

q = 6U w = +26.8 kJ .

E2.9(a) For reversible adiabatic expansion

. .1/c
Vi
Tf = Ti [2.28a],
Vf

CV ,m Cp,m R (20.786 8.3145) J K1 mol1

where c = = 1.500,
= = 8.3145 J K1 mol1
R R
so the final temperature is

. .1/1.500
1.0 dm3 = 131K
Tf = (273.15 K)
3.0 dm3

E2.10(a) Reversible adiabatic work is

w = CV 6T [2.27]= n(Cp,m R) (Tf Ti)

where the temperatures are related by

. .1/c CV ,m Cp,m R
Vi
Tf = Ti
Vf [2.28a] where c = = = 3.463.
R R

. . 3 0 dm3
500 103 dm3 .
So Tf = [(27.0 + 273.15) K]
0

TRAPP: CHAP02 2006/3/8 17:05 PAGE 27 #5

1/3.463

= 179 K
. .
2.45g
and w = [(37.11 8.3145) J K1 mol1 ] (179 300) K = 194 J .
44.0 g mol1

TRAPP: CHAP02 2006/3/8 17:05 PAGE 28 #5

 28 SOLUTIONS MANUAL

E2.11(a) For reversible adiabatic expansion . .1.4

1.0 dm3
. Vi .
22 kPa
pf V = p i V [2.29]so pf = pi = (57.4 kPa) =
f i Vf 2.0 dm3

qp 229 J 1
E2.12(a) Cp = [2.24] = = 89.8 J K
6T 2.55 K
so Cp,m = (89.8 J K1)/(3.0mol) = 30J K1 mol1 .
For a perfect gas Cp,m CV ,m = R[2.26].

CV ,m = Cp,m R = (30 8.3) J K1 mol1 = 22 J K1mol1 .

E2.13(a) qp = Cp6T [2.24]= nCp,m6T = (3.0 mol) (29.4 J K1 mol1) (25 K) = +2.2 kJ .

6H = qp [2.23b]= +2.2 kJ .
6U = 6H 6(pV) [from H U + pV ] = 6H 6(nRT) [perfect gas]= 6H nR6T

= (2.2 kJ) (3.0 mol) (8.314 J K1 mol1) (25 K) = (2.2 kJ) (0.62 kJ) = +1.6 kJ .

E2.14(a) In an adiabatic process, q = . Work against a constant external pressure is

. .
1.013 105 Pa
w = pex6V = (600 Torr) (40 10 m3) =
760 Torr 3
3.2 kJ

6U = q + w = 3.2 kJ .
TRAPP: CHAP02 2006/3/8 17:05 PAGE 28 #6
 One can also relate adiabatic work to 6T (eqn 2.27):
w
w = CV 6T = n(Cp,m R)6T so 6T = ,
n(C p,m R)
3.2 103 J

6T = = 38 K .
(4.0 mol) (29.355 8.3145) J K1 mol1
6H = 6U + 6(pV) = 6U + nR6T

= (3.2 kJ) + (4.0 mol) (8.3145 J K1 mol1) (38 K) = 4.5 kJ .

Question. Calculate the final pressure of the gas.

E2.15(a) In an adiabatic process, the initial and final pressures are related by (eqn 2.29)

pf V = pi V
f i

Cp CV + nR 20.8 J K1 + (1.0 mol)(8.31 J K1 mol1)

where = = = = 1.40.
CV CV 20.8 J K1

TRAPP: CHAP02 2006/3/8 17:05 PAGE 29 #6

 THE FIRST LAW 29

Find Vi from the perfect gas law:

nRTi (1.0 mol)(8.31 J K1 mol1)(310K) 1 atm

Vi = =
pi 3.25 atm 1.013 105 Pa

Vi = 7.83 103 m3.

. .1/ . .1/1.40
pi 3.25 atm
3 3 0.0113 m3
so Vf = Vi = (7.83 10 m ) = .
pf 2.50 atm

Find the final temperature from the perfect gas law:

pf Vf (2.50 atm) (0.0113 m 3 ) 1.013 105 Pa

Tf = nR =
(1.0 mol)(8.31 J K1 mol1) 1 atm

Tf = 344 K .

Adiabatic work is (eqn 2.27)

w = CV 6T = (20.8 J K1)(344 310) K = 7.1 102 J .

E2.16(a) At constant pressure

q = 6H = n6vapH Tf = (0.50 mol) (26.0 kJ mol1) 13.0

= kJ

and w = p6V pVvap = nRT = (0.50mol) (8.3145 J K 1 mol1) (250 K),

w = 1.0 103 J = 1.0 kJ .

6U = 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

21
C6H5C2H5(l) + 2 O2(g) 8CO2(g) + 5H2O(1)
6cH = 86f H (CO2, g) + 56f H (H2O, l) 6f H (C6H 5C2H5, l)
= [(8) (393.51) + (5) (285.83) (12.5)] kJ mol1

= 4564.7 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 29 #7

E2.18(a) First 6f H[(CH2)3, g] is calculated, and then that result is used to calculate 6rHfor the isomerization
9 1
(CH2)3(g) + O2(g) 3 CO2(g) + 3H2O(l), 6cH = 2091 kJ mol .
2
6f H [(CH 2) 3, g]= 6cH + 36f H (CO2, g) + 36f H (H2O,g)
= [+2091 + (3) (393.51) + (3) (285.83)] kJ mol1

= +53 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 30 #7

 30 SOLUTIONS MANUAL

(CH2)3(g) C3H6(g), 6 r H =?
6 r H = 6f H (C3H6, g) 6f H [(CH 2) 3, g]

= (20.42 53) kJ mol1 = 33 kJ mol1 .

E2.19(a) For naphthalene the reaction is C10H8(s) + 12O2(g) 10CO2(g) + 4H2O(l).

A bomb calorimeter gives qV = n6cU rather than qp = n6 c H ; thus we need

6 cU = 6 c H 6ngRT [2.21], 6ng = 2 mol.

6cH = 5157 kJ mol1 [Table 2.6].
6cU = (5157 kJ mol1) (2) (8.3 103 kJ K1 mol1) (298 K)

= 5152 kJ mol1 .
. .
120 103 g
|q|= |qV | = |n6cU | = (5152 kJ mol1 ) = 4.823 kJ
128.18 g mol1

|q| 4.823 kJ
C= = = 1.58 kJ k1
6T 3.05 K

When phenol is used the reaction is

15
C6H5OH(s) + 6CO2(g) + 3H2O(l).
2 O2(g)
1
6cH = 3054 kJ mol [Table2.6].
3

6 cU = 6 c H 6ngRT , 6ng =
2
= (3054 kJ mol1) + 2( 3 ) (8.314 103 kJ K1 mol1) (298 K)
= 3050 kJ mol1.
10 103 g
1 )
= 0.3241 kJ.
|q|= 1
(3050 kJ mol
94.12 g mol

0.3241 kJ
|q|
6T = C = 1.58 kJ K1 = +0.205 K .

COMMENT . In this case 6cU and 6cH differed by about 0.1 per cent. Thus, to within 3 signicant gures,
it would not have mattered if we had used 6cH instead of 6cU , but for very precise work it would.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 30 #8

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

6solH = 6f H (Ag+, aq) + 6f H (Cl, aq) 6f H (AgCl, s)

= [(105.58) + (167.16) (127.07)] kJ mol1 = +65.49 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 31 #8

 THE FIRST LAW 31

6 r H = +40 kJ mol1.
E2.21(a)
NH3SO2(s) NH3(g) + SO2(g),
6 r H = 6f H (NH3, g) + 6f H (SO2, g) 6f H (NH3SO2, s).

Solving for 6f H (NH3SO2, s) yields

6f H (NH3SO2, s) = 6f H (NH3, g) + 6f H (SO2, g) 6 r H

= (46.11 296.83 40) kJ mol1 = 383 kJ mol1 .

E2.22(a) (a) Reaction (3) = (2) reaction (1) + reaction (2) and 6ng = 1.
The enthalpies of reactions are combined in the same manner as the equations (Hesss law).

6 r H (3) = (2) 6 r H (1) + 6 r H (2)

= [(2) (184.62) + (483.64)] kJ mol1

= 114.40 kJ mol1 .

6rU = 6rH 6ngRT [2.21]= (114.40 kJ mol1) (1) (2.48 kJ mol1)

= 111.92 kJ mol1 .

(b) 6f H refers to the formation of one mole of the compound; hence

6rH (J)
6f H (J) = .
J

184.62

6f H (HCl, g) = kJ mol1 = 92.31 kJ mol1 .
2
483.64

6f H (H2O, g) = kJ mol1 = 241.82 kJ mol1 .
2

E2.23(a) 6 r H = 6 r U + 6ngRT [2.21]; 6ng = +2

= (1373 kJ mol1) + 2 (2.48 kJ mol1) = 1368 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 31 #9

 COMMENT . As a number of these exercises have shown, the use of 6rH as an approximation for 6rU
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) 6 r H /(kJ mol1)
K(s) + 12Cl 2(g) KCl(s) 436.75
KCl(s) + 3 O2(g) KClO3(s) 1
(89.4)
2 2
K(s) + 1 Cl2(g) + 3 O2(g) KClO3(s) 392.1
2 2

Hence, 6f H (KClO3, s) = 392.1 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 32 #9

 32 SOLUTIONS MANUAL

(b) 6 r H /(kJ mol1)

Na(s) + 1 O2(g) + 1 H2(g) NaOH(s) 425.61
2 2
NaOH(s) + CO2(g) NaHCO3(s) 127.5
C(s) + O2(g) CO2(g) 393.51

Na(s) + C(s) + 1 H2(g) + 3 O2(g) NaHCO3(s) 946.6

2 2
Hence, 6f H (NaHCO3, s) = 946.6 kJ mol1 .

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

6r H (T2 ) = 6r H (T1 ) + 6r Cp (T2 T1 ) [Example 2.6].

. .
6r Cp = Cp,m Cp,m [2.37],
Products Reactants

6r Cp = Cp (N2 O4 , g) 2 Cp (NO2 , g) = (77.28) (2) (37.20 J K 1 mol1 )

= +2.88 J K1 mol1,
6r H (373 K) = 6r H (298 K) + 6r Cp 6T
= (57.20 kJ mol1) + (2.88 J K1) (75 K)
= [(57.20) + (0.22)] kJ mol1
= 56.98 kJ mol1 .
. .
E2.26(a) (a) 6rH = 6f H
Products Reactants

6f H [2.34].

6 r H (298 K) = [(110.53) (241.82)] kJ mol1 = +131.29 kJ mol1 .

6 r U (298 K) = 6 r H (298 K) 6ngRT [2.21]

= (131.29 kJ mol1) (1) (2.48 kJ mol1) = +128.81 kJ mol1 .

(b) 6r U (378 K) = 6r H (298 K) (T2 T1 )6r Cp [Example 2.6].

6r Cp = Cp,m (CO,g) + Cp,m (H2 ,g) Cp,m (C,gr) Cp,m (H2 O,g)
= (29.14 + 28.82 8.53 33.58) 103 kJ K1 mol1
= 15.85 103 kJ K1 mol1.
6 r H (378 K) = (131.29 kJ mol1) + (15.85 103 kJ K1 mol1) (80 K)

= (131.29 + 1.27) kJ mol1 = +132.56 kJ mol1 .

6 r U (378 K) = 6 r H (378 K) (1) (8.31 103 kJ K1 mol1) (378 K)

= (132.56 3.14) kJ mol1 = +129.42 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 32 #10

COMMENT . The differences in both 6rH and 6r U between the two temperatures are small and justify
the use of the approximation that 6r C
p is a constant.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 32 #10

 THE FIRST LAW 33

E2.27(a) CuSO4 and ZnSO4 are strong electrolytes; therefore the net ionic equation is
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s).
6 r H = 6f H (Zn2+) + 6f H (Cu) 6f H (Zn) 6f H (Cu2+)

= [(153.89) + (0) (0) (64.77)] kJ mol1 = 218.66 kJ mol1 .

COMMENT. SO24 is a spectator ion and was ignored in the determination above.

E2.28(a) Since enthalpy is a state function, 6 r H for the process (see Fig. 2.1)

Mg2+(g) + 2Cl(g) + 2e MgCl2(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 mol1.

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 Eea = 6egH . 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) + 6hydH (Mg2+) = 0

which yields 6hydH (Mg2+) = 1892 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 33 #11

E2.29(a) The JouleThomson coefficient is the ratio of temperature change to pressure change under conditions
of isenthalpic expansion. So
. . . . 6T
= T [2.51]= lim 6T
p H 6p0 6p H
[ constant over temperature range],
22 K 6p

= = 0.71 K atm1 .
31 atm

TRAPP: CHAP02 2006/3/8 17:05 PAGE 33 #11

 34 SOLUTIONS MANUAL

E2.30(a) The internal energy is a function of temperature and volume, Um = Um(T , Vm), so

. . . .
dUm = U m dT + U m dVm [T = (U m /V) T ].
T Vm Vm T

For an isothermal expansion dT = 0; hence

. .
U m a
dUm =
Vm T mdV = T dV m = dV ,
Vm2 m

. 3 1
Vm,2 Vm,1 a 24.8 dm3 mol1 dV a .24.8 dm mol
6Um = dUm = dVm = a m =
Vm .
2
1.00 dm3mol1
2 Vm .
Vm,1 Vm,2 1.00 dm3 mol1
Vm
a a 23.8a
= + = = 0.9597 a mol dm3.
24.8 dm3 mol1 1.00 dm3 mol1 24.8 dm3 mol1

From Table 1.6, a = 1.352 dm6 atm mol1.

. .
6Um = (0.9597 mol dm3) (1.352 dm63atm mol 2
1.013) 105 Pa
. 1m .
3 1
= (1.30 dm atm mol ) = .
10 dm atm +131 J mol1

RT a
w = for a van der Waals gas. Hence,
p dVm where p = V
m b V m2

. .
w = RT a
dVm + dV m = q + 6Um.
Vm b Vm2

Therefore,
24.8 dm3 mol1 . RT
. 3 mol1
q= dVm = RT ln(Vm b)| 24.8 dm 3 1

1.00 dm3 mol1 Vm b 1.00 dm mol

2
. 24.8 3.9 10
= (8.314 J K1 mol1) (298 K) ln .
= +8.05 103 J mol1
1.00 3.9 102 .

and w = q + 6Um = (8.05 103 J mol1) + (131 J mol1) = 7.92 103 J mol1 .

. 1 .. V . 1 V
. .. .
E2.31(a) = 2.43]; 320 = .
[
V T p V320 T p, 320

TRAPP: CHAP02 2006/3/8 17:05 PAGE 34 #12

 . .
V V (3.9 104/K 2.96 106T/K2),
= 300 +
T p
.
V
. V (3.9 104/K 2.96 106 320/K) 1.34 103K1V .
=
300 + = 300
T p, 320

V320 = V300{(0.75) + (3.9 104) (320) + (1.48 106) (320)2}= (V300) (1.026).

TRAPP: CHAP02 2006/3/8 17:05 PAGE 34 #12

 THE FIRST LAW 35

. .
. .. .
so 320 = 1 V = 1 (1.34 103 K1 V300),
V320 T p, 320 1.026V 300

1.34 103 K1
320 = = 1.31 103 K1 .
1.026

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

. .. . . .
1 V V
T =
[2.44] so = TV .
V p T p T

At constant temperature

. . dV
dV = V dp so dV = T V dp or
p T = T dp.
V

m m dV d
Substituting V = and dV = 2 d yields = = T dp.
V
Therefore, p.
T

8 104 8 104
.
For = 0.08 102 = 8 104, p = =
T 7.35 107 atm 1

E2.33(a) The isothermal JouleThomson coefficient is

7.2 J atm1 mol1

. . 1 1 1
H m = Cp,m = (0.25 K atm ) (29 J K mol ) = .
p T

. .
dH = n H m dp = nCp,m dp,
p T

p2
6H = (nCp,m)dp = nCp,m(p2 p1) [andCpare constant],
p1

6H = (15 mol) (+7.2 J atm 1 mol1) (75 atm) = +8.1 kJ

TRAPP: CHAP02 2006/3/8 17:05 PAGE 35 #13

so q(supplied) = +6H = +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 #13

 36 SOLUTIONS MANUAL

Solutions to numerical problems

pV
P2.1 The temperatures are readily obtained from the perfect gas equation, T = ,
nR
(1.00 atm) (22.4 dm3)
T1 = = 273 K = T3[isotherm].
(1.00 mol) (0.0821 dm3 atm mol1 K1)

Similarly, T2 = 546 K .
In the solutions that follow all steps in the cycle are considered to be reversible.
Step 1 2

w = pex6V = p6V = nR6T [6(pV) = 6(nRT)],

w = (1.00 mol) (8.314 J K1 mol1) (546 273) K = 2.27 103 J .

3 1 1 3

6U = nCV ,m6T = (1.00 mol) (8.314 J K mol ) (273 K) = +3.40 10 J.

2
q = 6U w = +3.40 103J (2.27 103 J) = +5.67 103 J .

6H = qp = +5.67 103 J .

If this step is not reversible, then w, q, and 6H would be indeterminate.

Step 2 3
[constant volume].
3 1 1
) (273 K)
qV = 6U = nCV ,m6T = (1.00 mol) ( ) (8.314 J K mol
2

= 3.40 103 J .

From H U + pV

6H = 6U + 6(pV) = 6U + 6(nRT) = 6U + nR6T

= (3.40 103 J) + (1.00 mol) (8.314 J K1 mol1) (273 K) = 5.67 103 J .

Step 3 1
6U and 6H are zero for an isothermal process in a perfect gas; hence for the reversible compression
. .
V1 1 1 22.4 dm3

q = w = nRT ln = (1.00 mol) (8.314 J K mol ) (273 K) ln

V3 44.8 dm3

= +1.57 103 J , q = 1.57 103 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 36 #14

 THE FIRST LAW 37

Total cycle

State p/atm V /dm3 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 6U/kJ 6H/kJ

12 p constant = pex +5.67 2.27 +3.40 +5.67

23 V constant 3.40 0 3.40 5.67
31 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 fixed, .

Since 6U = q at constant volume, 6U = +2.35 kJ .

6H = 6U + 6(pV) = 6U + V 6p [6V = 0].

From the van der Waals equation [Table 1.6]

RT a R6T
p= so 6p = [6Vm = 0 at constant volume].
Vm b V m2 Vm b

RV 6T
Therefore, 6H = 6U + .
Vm b
From the data,

15.0 dm3 3
Vm = mol1, 6T = (341 300) K = 41 K.
= 7.5 dm
2.0 mol

Vm b = (7.5 4.3 102 ) dm3 mol1 = 7.46 dm3 mol1 .

RV 6T (8.314 J K1 mol1) (15.0 dm3) (41 K)

= = 0.68 kJ.
Vm b 7.46 dm3 mol1

Therefore,6H = (2.35 kJ) + (0.68 kJ) = +3.03 kJ .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 37 #15

 38 SOLUTIONS MANUAL

P2.5 This cycle is represented in Figure 2.2. Assume that the initial temperature is 298 K .

2
2.0
p/atm

(a)

(b)
1.0
1

(c)

50 100 150
V/dm3 Figure 2.2

(a) First, note that (constant volume). Then calculate 6U since 6T is known (6T = 298 K)

and then calculate q from the First Law.

7 5
6U = nCV ,m6T [2.16b]; CV ,m = Cp,m R = R R = R,
2 2
. . 1 1
6U = (1.00 mol) 5 (8.314 J K mol ) (298 K) = 6.19 103 J = +6.19 kJ .
2

q = qV = 6U w = 6.19 kJ 0 = +6.19 kJ .

6H = 6U + 6(pV) = 6U + 6(nRT) = 6U + nR6T

= (6.19 kJ) + (1.00 mol) (8.31 103 kJ mol1) (298 K) = +8.67 kJ .

(b) q = 0 (adiabatic).
Because the energy and enthalpy of a perfect gas depend on temperature alone,

6U(b) = 6U(a) = 6.19 kJ , since 6T(b) = 6T(a).

Likewise 6H(b) = 6H (a) = 8.67 kJ .

w = 6U = 6.19 kJ [First Law with q = 0].
(c) 6U = 6H = 0 [isothermal process in perfect gas].
V1
q = w [First Law with 6U = 0]; w = nRT1 ln [2.11].
V3

nRT1 (1.00 mol) (0.08206 dm3 atm K1 mol1) (298 K) 3

V2 = V 1 = =
p1 = 24.45 dm .
1.00 atm

TRAPP: CHAP02 2006/3/8 17:05 PAGE 38 #16

 THE FIRST LAW 39
. .
T2 c
V Tc
=
V T c [2.28b]; hence V V where c = CV ,m = 5
2 3 3= 2
2 3
T3 R 2
(2) (298 K) 5/2
. .
so V3 = (24.45 dm3 ) = 138.3 dm3 .
298 K
. .
22.45 dm3
w = (1.00 mol) (8.314 J K1 mol1) (298 K) ln
138.3 dm3

= 4.29 103 J = +4.29 kJ .

q = 4.29 kJ .

P2.7 The formation reaction is

2C(s) + 3H2(g) 2C6H6(g), 6f H (298 K) = 84.68 kJ mol1.

In order to determine 6f H (350 K) we employ Kirchhoffs law [2.36] with T2 = 350 K, T1 = 298 K,
T2
6f H (T2) = 6f H (T1) + 6rCp dT
T1

.
where 6rC p = JC p,m(J) = C p,m(C 6H 6) 2Cp,m(C) 3Cp,m(H2).
J

From Table 2.2

0.1272 .
.
1 1
Cp,m(C6H6)/(J K mol ) = 14.73 + T,
K
. .
4.77 103 8.54 105 K2
. .
Cp,m(C, s)/(J K1 mol1) = 16.86 + T ,
K T2

. . . .
5 2
1 1 3.26 103 T 0.50 10 K
C p,m(H 2, g)/(J K mol ) = 27.28 +
K ,
T2

. .
. . 1.56 106 K2
1 0.1079T
6 rC p/(J K mol )1 = 100.83 +
K .
T2

. .. .
1
T2
6rCp dT = 100.83 (T2 T1) + 0.1079 K1 (T 2 T 2)

T1 J K1 mol1 2 2 1
. .
1 1
(1.56 106 K 2)
T2 T1
2

TRAPP: CHAP02 2006/3/8 17:05 PAGE 39 #17

 . . (0.1079)(350 298 ) K
2
= 100.83 (52 K) + 1
2

.
1
(1.56 106 ) 1 .
350 298 K

= 2.65 103 K.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 40 #17

 40 SOLUTIONS MANUAL

Multiplying by the units J K1mol1, we obtain

T2
6rCpdT = (2.65 103 K) (J K1mol1) = 2.65 103 J mol1
T1

= 2.65 kJ mol1.
Hence 6f H (350 K) = 6f H (298 K) 2.65 kJ mol1

= 84.68 kJ mol1 2.65 kJ mol1 = 87.33 kJ mol1 .

P2.9 Cr(C6H6)2(s) Cr(s) + 2C6H6(g), 6ng = +2 mol.

6rH = 6rU + 2RT , from [2.21]

= (8.0 kJ mol1) + (2) (8.314 J K1 mol1) (583 K) = +17.7 kJ mol1 .

In terms of enthalpies of formation

6 r H = (2) 6f H (benzene, 583 K) 6f H (metallocene, 583 K)

or 6 r H (metallocene, 583 K) = 26f H (benzene, 583 K) 17.7 kJ mol1.

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

6f H (benzene, 583 K) = 6f H (benzene, 298 K)

+ (Tb 298 K)Cp,m(l) + 6vapH + (583 K Tb)Cp,m(g)
6 (583 K 298 K)Cp,m(gr) 3 (583 K 298 K)Cp,m(H2, g)

where Tb 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 from Table 2.15.

6f H (benzene, 583 K) = (49.0 kJ mol1) + (353 298) K (136.1 J K1 mol1)

+ (30.8 kJ mol1) + (583 353) K (81.67 J K1 mol1)
(6) (583 298) K (8.53 J K1 mol1)
(3) (583 298) K (28.82 J K1 mol1)
= {(49.0) + (7.49) + (18.78) + (30.8) (14.59) (24.64)} kJ mol1
= +66.8 kJ mol1.

Therefore 6f H (metallocene, 583 K) = (2 66.8 17.7) kJ mol1 = + 116.0 kJ mol1 .

P2.11 (a) and (b). The table displays computed enthalpies of formation (semi-empirical, PM3 level, PC Spartan
ProTM), enthalpies of combustion based on them (and on experimental enthalpies of formation of H2O(l)
and CO2(g), 285.83 and 393.51 kJ mol1 respectively), experimental enthalpies of combustion (Table
2.5), and the relative error in enthalpy of combustion.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 40 #18

 THE FIRST LAW 41

Compound 6f H /kJ mol1 6cH /kJ mol1(calc.) 6cH /kJ mol1(expt.) %error

CH4(g) 54.45 910.72 890 2.33

C2H6(g) 75.88 1568.63 1560 0.55
C3H8(g) 98.84 2225.01 2220 0.23
C4H10(g) 121.60 2881.59 2878 0.12
C5H12(g) 142.11 3540.42 3537 0.10

The combustion reactions can be expressed as:

. .
3n + 1
CnH2n+2(g) + O2(g) n CO2(g) + (n + 1) H2O(1).
2
The enthalpy of combustion, in terms of enthalpies of reaction, is

6cH = n6f H (CO 2) + (n + 1)6f H (H 2O) 6f H (CnH2n+2),

where we have left out 6f H (O2) = 0. The % error is defined as:

6cH(calc.) 6cH(expt.)
%error = 100%.
6 cH(expt.)

The agreement is quite good.

(c) If the enthalpy of combustion is related to the molar mass by

6cH = k[M/(g mol1)]n

then one can take the natural log of both sides to obtain:
. .
ln . 6cH. = ln |k| + n ln M/(g mol1).
. .
Thus, if one plots ln .6cH .vs. ln [M/(g mol1)], one ought to obtain a straight line with slope n and
y-intercept ln |k|. Draw up the following table.
. .
Compound M/(g mol1) 6cH/kJ mol1 ln M/(g mol1) ln .6c H / kJ mol1 .

CH4(g) 16.04 910.72 2.775 6.814

C2H6(g) 30.07 1568.63 3.404 7.358
C3H8(g) 44.10 2225.01 3.786 7.708
C4H10(g) 58.12 2881.59 4.063 7.966
C5H12(g) 72.15 3540.42 4.279 8.172

The plot is shown in Fig 2.3.

The linear least-squares fit equation is:

ln |6 cH /kJ mol 1 |= 4.30 + 0.903 ln M/(g mol1) R2 = 1.00

These compounds support the proposed relationships, with

n = 0.903 and k = e4.30 kJ mol1 = 73.7 kJ mol1 .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 41 #19

 42 SOLUTIONS MANUAL

9
ln | cH / kJ mol1|

6
2 3 4 5
ln M/(g mol1) 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

C60(s) + 60O2(g) 60CO2(g).

Because the reaction does not change the number of moles of gas, 6cH = 6cU [2.21]. Therefore

6cH = (36.0334 kJ g1) (60 12.011 g mol1) = 25968 kJ mol1 .

Now relate the enthalpy of combustion to enthalpies of formation and solve for that of C 60.

6cH = 606f H (CO2) 606f H (O2) 6f H (C60),

6f H (C60) = 606f H (CO2) 606f H (O2) 6cH

= [60(393.51) 60(0) (25968)] kJ mol1 = 2357 kJ mol1 .

P2.15 (a) 6 r H = 6f H (SiH2) + 6f H (H2) 6f H (SiH4)

= (274 + 0 34.3) kJ mol1 = 240 kJ mol1 .

(b) 6 r H = 6f H (SiH2) + 6f H (SiH4) 6f H (Si2H6)

= (274 + 34.3 80.3) kJ mol1 = 228 kJ mol1 .

P2.17 The temperatures and volumes in reversible adiabatic expansion are related by eqn 2.28a:

. .1/c
Tf = Ti V f where c = CV ,m .
Vi R

From eqn 2.29, we can relate the pressures and volumes:

Cp,m
. . where .
pf = pi V f =
Vi CV ,m

TRAPP: CHAP02 2006/3/8 17:05 PAGE 42 #20

 THE FIRST LAW 43

We are looking for Cp,m, which can be related to c and .

. . . .
CV ,m Cp,m
c = = Cp,m .
CV ,m R
R

Solving both relationships for the ratio of volumes, we have

. .1/ Vf pf . .c
pf . .c so Tf
Tf .
pi = = Ti = Ti
Vi pi

Therefore
. .
. . 202.94 kPa
p
pif 1 1 ln
ln 81.840 kPa
Cp,m = R
. f . = (8.314 J K mol ) . 298.15 K . = 41.40 J K1 mol1 .
ln T
Ti 248.44 K
ln

P2.19 Hm = Hm(T , p).

. . . .
H m H m
dHm = dT + dp.
T p p T

Since dT = 0,
. . . . . .
H m H m 2a
dHm = dp where
p T p T
= Cp,m[2.53]= b .
RT

pf . .
pf 2a b. .
6Hm = dHm = dp = 2a b (pf pi)

pi pi RT RT
(2) (1.352 dm6 atm mol2)
= (0.0387 dm3 mol1)

(0.08206 dm3 atm K1 mol1) (300 K)

(1.00 atm 500 atm)
. .
. . 1.013 105 Pa
1m 3
= (35.5 atm) = 3.60 103 J = +3.60 kJ .
10 dm 1 atm

COMMENT . Note that it is not necessary to know the value of Cp,m.

Solutions to theoretical problems

2 2 (a) dz =
P . 1

TRAPP: CHAP02 2006/3/8 17:05 PAGE 43 #21

. . dx + .
z z dy
x y . [definit
y ion of
x total
differe
ntial].
. . . .
z = (2x 2y + 2), z = (4y 2x 4),
x y y x

dz = (2x 2y + 2) dx+(4y2x4)dy .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 44 #21

 44 SOLUTIONS MANUAL
. .
(b) . . z
z
y x = (2x 2y + 2) = 2, x y = (4y 2x 4) = 2.
y x

. . . . . .
z = y+ 1 z = (x 1),
(c) x x , y x
y

dz = .

A differential is exact if it satisfies the condition

. .
z . .
=
x y y z x ,

. . . .
z . . z
= 1 = 1,
y x y y + x y = (x 1) = 1.
x x

COMMENT. The total differential of a function is necessarily exact.

. . . . . .
P2.23 U = U(T , V) so dU = U dT + U dV = CV dT + U dV .
T V V T V T

For U = constant, dU = 0, and

. . . . . . . . . .
U U dV U V
dV or CV = = .
CV dT = V dT V T
V T T U T U

This relationship is essentially Eulers chain relation [Further information 2.2].

. . . . . .
H = H(T , p) so dH = H dT + H dp = C pdT + H dp.
T p p T p T

According to Eulers chain relation

. . . . . .
H p dT = 1
p T T H dH p

so, using the reciprocal identity [Further information 2.2],

. . . . . .
H T dH
.
= = - Cp
p T p H dT p

TRAPP: CHAP02 2006/3/8 17:05 PAGE 44 #22

 . . . . p
P2.25 (a) H = U + pV so H V 1+
U = 1 +p = (U/V) .
p U p p

. .
((U + pV)
. .
(b) H (H/V)p V (U/V)p + p
p
= =
=
U p (U/V) p (U/V) p (U/V)p

. .
H p V
so 1 .
= + = 1+ p
U p (U/V) p U p

TRAPP: CHAP02 2006/3/8 17:05 PAGE 45 #22

 THE FIRST LAW 45

V2
P2.27 w = p dV .
V1

V
Inserting = Vm into the virial equation for p we obtain
n
. .
1 nB n2C

p = nRT
+ 2+
+ ... .
V V V3

.
V2 . 1 nB n 2C

Therefore, w = nRT + + + ... dV ,

V1 V V2 V3

. . . .
V2 2 1 1 1 3 1 1

w = nRT ln + n RTB 2
2 + ....
V1 V2 V1 + n RTC V2 V2
2

For n = 1 mol: nRT = (1.0 mol) (8.314 J K1 mol1) (273 K) = 2.27 kJ.
From Table 1.4, B = 21.7 cm3 mol1 and C = 1200 cm6 mol2, so

n2BRT = (1.0 mol) (21.7 cm3 mol1) (2.27 kJ) = 49.3 kJ cm3,
1 n3CRT 1 2 6 2 6
= (1.0 mol) (1200cm mol ) (2.27 kJ) = +1362 kJ cm .
2
2
Therefore,
. . . .
1 1 + (1362 kJ) 1 1
w = 2.27 kJ ln 2 (49.3 kJ) 1000 500 10002 5002
(a)

= (1.57) + (0.049) (4.1 103) kJ = 1.52 kJ = 1.5 kJ .

(b) A perfect gas corresponds to the first term of the expansion of p, so

w = 1.57 kJ = 1.6 kJ .

. .
. . 1 H
T
P2.29 = [2.51 and 2.53],
p H = p T
Cp

.
. . .
= 1 T V V [See problem 2.34 for this result].
Cp T p

TRAPP: CHAP02 2006/3/8 17:05 PAGE 45 #23

 . .
nRT V nR
But V = = .
+ nb or T p
p p

Therefore,
. . . .
1 nRT 1 nRT nRT nb
= =
= p p
Cp V nb .
p C p p C
T
. .
Since b > 0 and Cp > 0, we conclude that for this gas < 0 or < 0. This says that when the

p H
pressure drops during a JouleThomson expansion the temperature must increase .

TRAPP: CHAP02 2006/3/8 17:05 PAGE 46 #23

 46 SOLUTIONS MANUAL

P2.31 nRT n 2a

[Table 1.7].
p= nb V 2
V

na
Hence ,
RV 2

Vm b 1
.
p nR = =.
p
.
R
T V
. . . .
T . . V
For Eulers chain relation, we need to show that p = 1.
p V
V T T p

. . . . . .
T p V 1
Hence, in addition to we need and
p V T p = . . .
V T T
V p

. . nRT 2n2a
p
= +
V T (V nb)2 V3

which can be found from

. . . .
T . p. . na . 2na (V nb),

= +
V p nR RV 2
RV 3
. .
. . . . 2na (V nb).
T = T

V p V nb
RV 3

Therefore,

. . . .
T p
. . . . . . p V T
T p V =
V

p V V T T p .
T
.
V p
. . . .
V nb nRT 2n2a
+
nR (V nb) 2
V3

TRAPP: CHAP02 2006/3/8 17:05 PAGE 46 #24

 . .
= . . 2na (V nb)
T
V nb RV 3

. . . .
T 2na
+ (V nb)
V nb RV 3
. .
=. . 2na
T (V nb)
V nb RV 3
= 1.

TRAPP: CHAP02 2006/3/8 17:05 PAGE 47 #24

 THE FIRST LAW 47

. . T
P2.33 Cp = T V
T V = . . V [reciprocal identity, Further information 2.2]
T
p
V p

. . T 2na (V nb) [Problem 2.31]

T
=
V p V nb RV 3

Introduction of this expression followed by rearrangement leads to

(2na) (V nb)2 nbRTV 2

Cp =
RTV 3 2na(V V.
nb)2

RTV 3
Then, introducing =
2na(V nb)2
to simplify the appearance of the expression

nb 1 b

Vm
= V.
1

For xenon, Vm = 24.6 dm3 mol1, T = 298 K, a = 4.137 dm6 atm mol2, b = 5.16 102 dm3 mol1,

nb b 5.16 101 dm3 mol1 2.09 103,

=
= = 24.6 dm3 mol1
V Vm

(8.206 102 dm3 atm K1 mol1) (298 K) (24.6 dm3 mol1)3

= = 73.0.
(2) (4.137 dm6 atm mol2) (24.6 dm3 mol1 5.16 102 dm3 mol1)2

1 (73.0) (2.09 103) 3 1 3 1

Therefore, Cp = (24.6 dm mol ) = 0.290 dm mol .
72.0

Cp = 20.79 J K1 mol1[Table 2.6], so

0.290 dm3 mol1 0.290 103 m3 mol1
= =
20.79 J K1 mol1 20.79 J K1 mol1

= 1.393 105 K m3 J1 = 1.393 105 K Pa1

= (1.393 105) (1.013 105 K atm1) = 1.41 K atm1 .

positive)
The value of changes at T = TI and when the sign of the numerator 1

TRAPP: CHAP02 2006/3/8 17:05 PAGE 47 #25

m
. Hence nb
changes sign ( 1 is
V

b RTbV 3 2a(Vm b)2

= 1 at T = TI or = 1 implying that TI = ,
Vm 2na(V nb) Vm
2 RbV 2

TRAPP: CHAP02 2006/3/8 17:05 PAGE 48 #25

 48 SOLUTIONS MANUAL

. . . .2
2a b
that is, TI = 1 Vm = .
Rb Vm

2a (2) (4.137 dm6 atm mol2)

For xenon, = = 1954 K
Rb (8.206 102 dm3 atm K1 mol1) (5.16 102 dm3 mol1)
2

. 2 .
5.16 10
and so TI = (1954 K) 1 = 1946 K .
24.6

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.

. .
2TV TV p

P2.35 Cp,m CV ,m = [2.57].

nT [2.49]= n T V

. .
p nR
= [Problem 2.31].
T V
V nb

. . 1
V = V
T = . T . .

p
V p

Substituting,

. .
p
T T V .
Cp,m CV ,m =
. .
T
. . n V p
T
Also T 2na (V nb) [Problem 2.31].
=
V p V nb RV 3
Substituting,
RT
Cp,m CV ,m = (V nb) = R
T 2na V nb)
(
(V nb) RV 3

1 1 2a(Vm b)3
with = 2na or = 1 .
2 RTV 3
m
1 3) (V nb)
(RTV
8a
Now introduce the reduced variables and use Tc = , Vc = 3b.
27Rb

TRAPP: CHAP02 2006/3/8 17:05 PAGE 48 #26

After rearrangement,

.
4T V 3

TRAPP: CHAP02 2006/3/8 17:05 PAGE 49 #26

 THE FIRST LAW 49

For xenon, Vc = 118.1 cm3 mol1, Tc = 289.8 K. The perfect gas value for Vm may be used as any error
1
introduced by this approximation occurs only in the correction term for .

Hence, Vm 2.45 dm3, Vc =118.8 cm3 mol1, Tc = 289.8 K, and Vr = 20.6 and Tr =1.03; therefore

1 (61.8 1)2
=1
(4) (1.03) = 0.90, giving 1.1
(20.6)3

and

Cp,m CV ,m 1.1 R = 9.2 J K1 mol1 .

.
P2.37 (a) 1 . . 1 . . .
= H T V m Vm [2.53 and Problem 2.34].
Cp p T = T p
Cp

RT 2 . . R
Vm = V m
+ aT so T p = + 2aT .
p p

. .
1 RT RT 2 aT 2
2
= + 2aT
Cp p aT = .
p

. . . .
(b) p V m . .
CV = Cp TV m = Cp T p
T V T p T V .

RT .
But, p = aT 2
V
m
. .
p R RT(2aT)
=
T V Vm aT 2 (Vm aT 2) 2
R 2aRT 2 p 2ap2
= + = + .
(RT/p) (RT/p)2 T R

Therefore
.
. . . 2ap2
CV = Cp T R p
+ 2aT + R
p T

= Cp
TRAPP: CHAP02 2006/3/8 17:05 PAGE 49 #27
 . .
RT 2apT 2apT
1 . .
+
p R
p
.
.
R
,T
1
+

TRAPP: CHAP02 2006/3/8 17:05 PAGE 50 #27

 50 SOLUTIONS MANUAL

Solutions to applications

P2.39 Taking the specific enthalpy of digestible carbohydrates to be 17 kJ g1 (Impact I.2.2), the serving of
pasta yields

q = (40 g) (17 kJ g1) = 680 kJ.

Converting to Calories (kcal) gives:

1 Cal
q = (680 kJ) = 162 Cal.
4.184 kJ
As a percentage of a 2200-Calorie diet, this serving is
162 Cal
7.4%
100% = .
2200 Cal
1.5 g 1
25 kJ
P2.41 (a) q = n6cH = 1 (5645 kJ mol ) =
.
342.3 g mol
(b) Effective work available is 25 kJ 0.25 = 6.2 kJ.
Because w = mgh, and m 65 kg
6.2 103 J
h = 9.7 m .
65 kg 9.81 m s2

(c) The energy released as heat is

. .
2.5 g 1

q = 6rH = n6cH = (2808 kJ mol ) = 39 kJ .

180 g mol1

(d) If one-quarter of this energy were available as work a 65 kg person could climb to a height h
given by
1 q 39 103 J
= = 15 m .
q = w = mgh so h = 4mg 4(65 kJ) (9.8 m s2)
4

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 from a peak in the thermogram. The area under the thermogram is 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 sufficiently 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 coefficient of thermal expansion is

. .
1 V 6V
= T p
so 6V V 6T .
V V 6T

TRAPP: CHAP02 2006/3/8 17:05 PAGE 50 #28

 THE FIRST LAW 51

This change in volume is equal to the change in height (sea level rise, 6h) 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 2C rise in temperature

6V = (2.1 104 K1) (1.37 109 km3) (2.0 K) = 5.8 105 km3
6V 3
so 6h = km = 1.6m .
= 1.6 10
A
Since the rise in sea level is directly proportional to the rise in temperature, 6T = 1C would lead to
6h = 0.80 m and 6T = 3.5C would lead to 6h = 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 H
=
Cp p T
. .
H
and we estimate from the enthalpy and pressure data. We are given both enthalpy and heat
p T

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 51 #29

52 SOLUTIONS MANUAL

(a) At 300 K. . .
1 1H
The regression analysis gives the slope as 18.0 J g MPa ,
p T
18.0 kJ kg1 MPa1
so = = 23.5 K MPa1 .

0.7649 kJ kg1 K1 = 23.5 K MPa1

(b) At 350 K. H
. .

The regression analysis gives the slopeas 14.5 J g 1 MPa

1
,
p T
14.5 kJ kg1 MPa1
so = = 14.0 K MPa1 .
1.0392 kJ kg1 K1

TRAPP: CHAP02 2006/3/8 17:05 PAGE 52 #30