2 The First Law

Answers to discussion questions

D2.1 Work is a precisely defined mechanical concept. It is produced from the application of a force through a
distance. The technical definition 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 θ, where θ 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 defined 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) definition of heat and is based on the definition of work. A less precise definition 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 definition 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 simplifies the calculations involved because one can drop the first
term of eqn 2.40 and need work only with dU = CV dT . In a more sensitive apparatus, Joule would
have observed a small temperature change upon expansion of the ‘real’ gas. Joule’s 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 Joule–Thomson coefficient 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
Joule–Thomson effect. See Section 2.12 for a more complete discussion.

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 24 SOLUTIONS MANUAL

D2.7 The vertical axis of a thermogram represents Cp , 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 T1 and T2 , so there is no reason to
expect Cp 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 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 s−2 ) × (4.0 m) = −2.6 × 103 J = 2.6 × 103 J needed .

On the moon: w = −(65 kg) × (1.60 m s−2 ) × (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 = −pex V [2.8].

pex = (1.0 atm) × (1.013 × 105 Pa atm−1 ) = 1.01 × 105 Pa.

The change in volume is the cross-sectional area times the linear displacement:
 3
1m
V = (100 cm2 ) × (10 cm) × = 1.0 × 10−3 m3 ,
100 cm

so w = −(1.01 × 105 Pa) × (1.0 × 10−3 m3 ) = −1.0 × 102 J as 1 Pa m3 = 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 definition
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 .
 
Vf
w = −nRT ln [2.11]
Vi
 
−1 −1 44.8 dm3
= −(1.00 mol) × (8.314 J K mol ) × (273 K) × ln
22.4 dm3

= −1.57 × 103 J = −1.57 kJ .

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

(b) U = H = 0 .

w = −pex V [2.8], V = (44.8 − 22.4) dm3 = 22.4 dm3 .

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 THE FIRST LAW 25

pex can be computed from the perfect gas law,

pV = nRT ,

nRT (1.00 mol) × (0.08206 dm3 atm K −1 mol−1 ) × (273 K)

so pex = pf = = = 0.500 atm
Vf 44.8 dm3
   
1.013 × 105 Pa 1 m3
w = −(0.500 atm) × × (22.4 dm3 ) ×
1 atm 103 dm3

= −1.13 × 103 Pa m3 = −1.13 × 103 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 nR p1 p2
= = constant; hence, = .
T V T1 T2
   
T2 400 K
p2 = × p1 = × (1.00 atm) = 1.33 atm .
T1 300 K
3
U = nCV ,m T [2.16b] = (n) × ( R) × (400 K − 300 K)
2
3
= (1.00 mol) × ( ) × (8.314 J K −1 mol−1 ) × (100 K)
2
= 1.25 × 103 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 = −pex V [2.8].

pex = (200 Torr) × (133.3 Pa Torr−1 ) = 2.666 × 104 Pa.

V = 3.3 dm3 = 3.3 × 10−3 m3 .

Therefore, w = (−2.666 × 104 Pa) × (3.3 × 10−3 m3 ) = −88 J .

 
Vf
(b) w = −nRT ln [2.11].
Vi

4.50 g
n= = 0.2805 mol, RT = 2.577 kJ mol−1 , Vi = 12.7 dm3 , Vf = 16.0 dm3 .
16.04 g mol−1

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

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 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 = qp = H = −40.656 kJ .
w = −pex V [2.8] where V = Vliq − Vvap ≈ −Vvap because Vliq << Vvap .

nRT
On the assumption that H2 O(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 K −1 mol−1 ) × (373 K) = +3.10 × 103 J = +3.10 kJ .

From eqn 2.21, U = H − ng RT , ng = −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) → H2 (g) + MgCl2 (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.

nRT
w = −pex V [2.8] where Vi ≈ 0, Vf = , pf = pex
pf

nRT
so w = −pex (Vf − Vi ) ≈ −pex Vf = −pex × = −nRT ,
pex

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

Tf
H = dH, dH = nCp,m dT .
Ti

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

Tf
473
(H/J) = d(H/J) = {20.17 + 0.3665(T /K)}d(T /K)
Ti 298
   2 473
0.3665 T 
= (20.17) × (473 − 298) + × 
2 K 
298

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

3 4 4

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 THE FIRST LAW 27

q = H = 2.83 × 104 J = +28.3 kJ .

w = −pex V [2.8] where pex = 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 × 103 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 .

E2.9(a) For reversible adiabatic expansion

 1/c
Vi
T f = Ti [2.28a],
Vf

CV ,m Cp,m − R (20.786 − 8.3145) J K −1 mol−1

where c = = = = 1.500,
R R 8.3145 J K −1 mol−1
so the final temperature is
 1/1.500
1.0 dm3
Tf = (273.15 K) × = 131K .
3.0 dm3

E2.10(a) Reversible adiabatic work is

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

where the temperatures are related by

 1/c
Vi CV ,m Cp,m − R
T f = Ti [2.28a] where c = = = 3.463.
Vf R R
 1/3.463
500 × 10−3 dm3
So Tf = [(27.0 + 273.15) K] × = 179 K
3.00 dm3
 
2.45g
and w = × [(37.11 − 8.3145) J K −1 mol−1 ] × (179 − 300) K = −194 J .
44.0 g mol−1

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 28 SOLUTIONS MANUAL

E2.11(a) For reversible adiabatic expansion

 γ  1.4
γ γ Vi 1.0 dm3
p f Vf = pi Vi [2.29]so pf = pi = (57.4 kPa) × = 22 kPa
Vf 2.0 dm3

qp 229 J
E2.12(a) Cp = [2.24] = = 89.8 J K−1
T 2.55 K

so Cp,m = (89.8 J K−1 )/(3.0mol) = 30 J K−1 mol−1 .

For a perfect gas Cp,m − CV ,m = R[2.26].

CV ,m = Cp,m − R = (30 − 8.3) J K −1 mol−1 = 22 J K−1 mol−1 .

E2.13(a) qp = Cp T [2.24] = nCp,m T = (3.0 mol) × (29.4 J K −1 mol−1 ) × (25 K) = +2.2 kJ .

H = qp [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

 
1.013 × 105 Pa
w = −pex V = (−600 Torr) × × (40 × 10−3 m3 ) = −3.2 kJ
760 Torr

U = q + w = −3.2 kJ .

One can also relate adiabatic work to T (eqn 2.27):

w
w = CV T = n(Cp,m − R)T so T = ,
n(Cp,m − R)
−3.2 × 103 J
T = = −38 K .
(4.0 mol) × (29.355 − 8.3145) J K −1 mol−1
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 final pressure of the gas.

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

γ γ
p f Vf = p i V i

Cp CV + nR 20.8 J K−1 + (1.0 mol)(8.31 J K−1 mol−1 )

where γ = = = = 1.40.
CV CV 20.8 J K−1

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 THE FIRST LAW 29

Find Vi from the perfect gas law:

nRTi (1.0 mol)(8.31 J K−1 mol−1 )(310K) 1 atm

Vi = = ×
pi 3.25 atm 1.013 × 105 Pa
Vi = 7.83 × 10−3 m3 .
 1/γ  1/1.40
pi 3.25 atm
so V f = Vi = (7.83 × 10−3 m3 ) = 0.0113 m3 .
pf 2.50 atm
Find the final temperature from the perfect gas law:

p f Vf (2.50 atm) × (0.0113 m3 ) 1.013 × 105 Pa

Tf = = ×
nR (1.0 mol)(8.31 J K−1 mol−1 ) 1 atm

Tf = 344 K .

Adiabatic work is (eqn 2.27)

w = CV T = (20.8 J K−1 )(344 − 310) K = 7.1 × 102 J .

E2.16(a) At constant pressure

q = H = nvap H Tf = (0.50 mol) × (26.0 kJ mol−1 ) = 13.0 kJ

and w = −pV ≈ −pVvap = −nRT = −(0.50mol) × (8.3145 J K−1 mol−1 ) × (250 K),

w = −1.0 × 103 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 specific 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

C6 H5 C2 H5 (l) + 21
2 O2 (g) → 8CO2 (g) + 5H2 O(1)
c H = 8f H (CO2 , g) + 5f H (H2 O, l) − f H (C6 H5 C2 H5 , l)
= [(8) × (−393.51) + (5) × (−285.83) − (−12.5)] kJ mol−1

= −4564.7 kJ mol−1 .

E2.18(a) First f H [(CH2 )3 , g] is calculated, and then that result is used to calculate r H for the isomerization

c H = −2091 kJ mol−1 .
9
(CH2 )3 (g) + O2 (g) → 3 CO2 (g) + 3H2 O(l),
2
f H [(CH2 )3 , g] = −c H + 3f H (CO2 , g) + 3f H (H2 O,g)
= [+2091 + (3) × (−393.51) + (3) × (−285.83)] kJ mol−1

= +53 kJ mol−1 .

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 30 SOLUTIONS MANUAL

(CH2 )3 (g) → C3 H6 (g), r H =?

r H = f H (C3 H6 , g) − f H [(CH2 )3 , g]

= (20.42 − 53) kJ mol−1 = −33 kJ mol−1 .

E2.19(a) For naphthalene the reaction is C10 H8 (s) + 12O2 (g) → 10CO2 (g) + 4H2 O(l).
A bomb calorimeter gives qV = nc U rather than qp = nc H ; thus we need

c U = c H − ng RT [2.21], ng = −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 .
 
120 × 10−3 g
|q| = |qV | = |nc U | = × (5152 kJ mol−1 ) = 4.823 kJ
128.18 g mol−1
|q| 4.823 kJ
C= = = 1.58 kJ k−1
T 3.05 K

When phenol is used the reaction is

C6 H5 OH(s) + 2 O2 (g)
15
→ 6CO2 (g) + 3H2 O(l).
c H = −3054 kJ mol−1 [Table2.6].

c U = c H − ng RT ,
3
ng = −
2
= (−3054 kJ mol−1 ) + ( 23 ) × (8.314 × 10−3 kJ K −1 mol−1 ) × (298 K)
= −3050 kJ mol−1 .
10 × 10−3 g
|q| = × (3050 kJ mol−1 ) = 0.3241 kJ.
94.12 g mol−1
|q| 0.3241 kJ
T = = = +0.205 K .
C 1.58 kJ K−1

COMMENT. In this case c U and c H differed by about 0.1 per cent. Thus, to within 3 significant figures,
it would not have mattered if we had used c H instead of 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 .

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 THE FIRST LAW 31

r H = +40 kJ mol−1 .
E2.21(a)
NH3 SO2 (s) → NH3 (g) + SO2 (g),
r H = f H (NH3 , g) + f H (SO2 , g) − f H (NH3 SO2 , s).

Solving for f H (NH3 SO2 , s) yields

f H (NH3 SO2 , s) = f H (NH3 , g) + f H (SO2 , 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 ng = −1.
The enthalpies of reactions are combined in the same manner as the equations (Hess’s 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 − ng 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

r H (J)
f H (J) = .
νJ
−184.62
f H (HCl, g) = kJ mol−1 = −92.31 kJ mol−1 .
2
−483.64
f H (H2 O, g) = kJ mol−1 = −241.82 kJ mol−1 .
2

E2.23(a) r H = r U + ng RT [2.21]; ng = +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) + 21 Cl2 (g) → KCl(s) −436.75
KCl(s) + 23 O2 (g) → KClO3 (s) 2 × (89.4)
1

K(s) + 21 Cl2 (g) + 23 O2 (g) → KClO3 (s) −392.1

Hence, f H (KClO3 , s) = −392.1 kJ mol−1 .

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 32 SOLUTIONS MANUAL

(b) r H /(kJ mol−1 )

Na(s) + 21 O2 (g) + 21 H2 (g) → NaOH(s) −425.61
NaOH(s) + CO2 (g) → NaHCO3 (s) −127.5
C(s) + O2 (g) → CO2 (g) −393.51

Na(s) + C(s) + 21 H2 (g) + 23 O2 (g) → NaHCO3 (s) −946.6

Hence, f H (NaHCO3 , 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 Kirchoff’s law [2.36] integrates to

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

r Cp = −
νCp,m
νCp,m [2.37],
Products Reactants

r Cp = Cp (N2 O4 , g) − 2 Cp (NO2 , 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 Cp 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 = νf H − νf H [2.34].
Products Reactants

r H (298 K) = [(−110.53) − (−241.82)] kJ mol−1 = +131.29 kJ mol−1 .

r U (298 K) = r H (298 K) − ng 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) − (T2 − T1 )r Cp [Example 2.6].

r Cp = Cp,m
(CO,g) + C (H ,g) − C (C,gr) − C (H O,g)
p,m 2 p,m p,m 2

= (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 Cp is a constant.

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 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).

r H = f H (Zn2+ ) + f H (Cu) − f H (Zn) − f H (Cu2+ )

= [(−153.89) + (0) − (0) − (64.77)] kJ mol−1 = −218.66 kJ mol−1 .

COMMENT. SO2−
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)

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 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 Eea = −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 (Mg2+ ) = 0

which yields hyd H (Mg2+ ) = −1892 kJ mol−1 .

E2.29(a) The Joule–Thomson coefficient µ is the ratio of temperature change to pressure change under conditions
of isenthalpic expansion. So
   
∂T T T
µ= [2.51] = lim ≈ [µ constant over temperature range],
∂p H p→0 p H p
−22 K
µ= = 0.71 K atm−1 .
−31 atm

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 34 SOLUTIONS MANUAL

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

   
∂Um ∂Um
dUm = dT + dVm [πT = (∂Um /∂V )T ].
∂T Vm ∂Vm T

For an isothermal expansion dT = 0; hence

 
∂Um a
dUm = dVm = πT dVm = dVm ,
∂Vm T Vm2



24.8 dm3 mol−1  3 −1
Vm,2 Vm,1 a dVm a 24.8 dm mol
Um = dUm = dVm = a =−
Vm,1 Vm,2 Vm2 1.00 dm3 mol−1 Vm2 Vm 1.00 dm3 mol−1
a a 23.8a
=− −1
+ −1
= = 0.9597 a mol dm−3 .
24.8 dm mol 3
1.00 dm mol 3
24.8 dm3 mol−1

From Table 1.6, a = 1.352 dm6 atm mol−1 .

Um = (0.9597 mol dm−3 ) × (1.352 dm6 atm mol−2 )

   
−1 1m 3 1.013 × 105 Pa
= (1.30 dm atm mol ) ×
3
× = +131 J mol−1 .
10 dm atm


RT a
w = − p dVm where p = − for a van der Waals gas. Hence,
Vm − b Vm2

 

RT a
w=− dVm + dVm = −q + Um .
Vm − b Vm2

Therefore,

24.8 dm3 mol−1  
RT 24.8 dm3 mol−1
q= dVm = RT ln(Vm − b)|1.00 dm3 mol−1
1.00 dm3 mol−1 Vm − b
 
24.8 − 3.9 × 10−2
= (8.314 J K −1 mol−1 ) × (298 K) × ln = +8.05 × 103 J mol−1 .
1.00 − 3.9 × 10−2

and w = −q + Um = −(8.05 × 103 J mol−1 ) + (131 J mol−1 ) = −7.92 × 103 J mol−1 .

     
1 ∂V 1 ∂V
E2.31(a) α= [2.43]; α320 = .
V ∂T p V320 ∂T p, 320

 
∂V
= V300 (3.9 × 10−4 /K + 2.96 × 10−6 T /K 2 ),
∂T p
 
∂V
= V300 (3.9 × 10−4 /K + 2.96 × 10−6 × 320/K) = 1.34 × 10−3 K −1 V300 .
∂T p, 320

V320 = V300 {(0.75) + (3.9 × 10−4 ) × (320) + (1.48 × 10−6 ) × (320)2 } = (V300 ) × (1.026).

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 THE FIRST LAW 35

    
1 ∂V 1
so α320 = = × (1.34 × 10−3 K −1 V300 ),
V320 ∂T p, 320 1.026V300

1.34 × 10−3 K −1
α320 = = 1.31 ×10−3 K−1 .
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
κT = − [2.44] so = −κT V .
V ∂p T ∂p T

At constant temperature
 
∂V dV
dV = dp so dV = κT V dp or = −κT dp.
∂p T V

m m dV dρ
Substituting V = and dV = − 2 dρ yields =− = −κT dp.
ρ ρ V ρ
δρ
Therefore, ≈ κT δp.
ρ
δρ 8 × 10−4 8 × 10−4
For = 0.08 × 10−2 = 8 × 10−4 , δp ≈ = = 1.1 × 103 atm .
ρ κT 7.35 × 10−7 atm−1

E2.33(a) The isothermal Joule–Thomson coefficient is

 
∂Hm
= −µCp,m = (−0.25 K atm−1 ) × (29 J K −1 mol−1 ) = −7.2 J atm−1 mol−1 .
∂p T

 
∂Hm
dH = n dp = −nµCp,m dp,
∂p T

p2
H = (−nµCp,m )dp = −nµCp,m (p2 − p1 ) [µandCp are constant],
p1

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.

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 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 mol−1 K −1 )

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

w = −pex V = −pV = −nRT [(pV ) = (nRT )],

w = −(1.00 mol) × (8.314 J K −1 mol−1 ) × (546 − 273) K = −2.27 × 103 J .

3
U = nCV ,m T = (1.00 mol) × × (8.314 J K −1 mol−1 ) × (273 K) = +3.40 × 103 J.
2
q = U − w = +3.40 × 103 J − (−2.27 × 103 J) = +5.67 × 103 J .

H = qp = +5.67 × 103 J .

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

Step 2 → 3
w = 0 [constant volume].

3
qV = U = nCV ,m T = (1.00 mol) × ( ) × (8.314 J K −1 mol−1 ) × (−273 K)
2
= −3.40 × 103 J .

From H ≡ U + pV

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

= (−3.40 × 103 J) + (1.00 mol) × (8.314 J K −1 mol−1 ) × (−273 K) = −5.67 × 103 J .

Step 3 → 1
U and H are zero for an isothermal process in a perfect gas; hence for the reversible compression
 
V1 22.4 dm3
−q = w = −nRT ln = (−1.00 mol) × (8.314 J K −1 mol−1 ) × (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 U/kJ H/kJ

1→2 p constant = pex +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 fixed, w = 0 .

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

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

From the van der Waals equation [Table 1.6]

RT a RT
p= − so p = [Vm = 0 at constant volume].
Vm − b Vm2 Vm − b

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

15.0 dm3
Vm = = 7.5 dm3 mol−1 , T = (341 − 300) K = 41 K.
2.0 mol

Vm − b = (7.5 − 4.3 × 10−2 ) dm3 mol−1 = 7.46̄ dm3 mol−1 .

RV T (8.314 J K −1 mol−1 ) × (15.0 dm3 ) × (41 K)

= = 0.68 kJ.
Vm − b 7.46̄ dm3 mol−1

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

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 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
3
V/dm 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.

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

q = qV = 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 .

(b) q = 0 (adiabatic).
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].

V1
q = −w [First Law with U = 0]; w = −nRT1 ln [2.11].
V3

nRT1 (1.00 mol) × (0.08206 dm3 atm K−1 mol−1 ) × (298 K)

V 2 = V1 = = = 24.45̄ dm3 .
p1 1.00 atm

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

 THE FIRST LAW 39

 c
T2 CV ,m 5
V2 T2c = V3 T3c [2.28b]; hence V3 = V2 where c = =
T3 R 2
 5/2
(2) × (298 K)
so V3 = (24.45̄ dm ) × 3
= 138.3̄ dm3 .
298 K
 
−1 −1 22.45̄ dm3
w = (−1.00 mol) × (8.314 J K mol ) × (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) → 2C6 H6 (g), f H (298 K) = −84.68 kJ mol−1 .

In order to determine f H (350 K) we employ Kirchhoff’s law [2.36] with T2 = 350 K, T1 = 298 K,

T2
f H (T2 ) = f H (T1 ) + r Cp dT
T1

where r Cp = νJ Cp,m (J) = Cp,m (C6 H6 ) − 2Cp,m (C) − 3Cp,m (H2 ).

J

From Table 2.2

 
0.1272
Cp,m (C6 H6 )/(J K−1 mol−1 ) = 14.73 + T,
K

   
−1 −1 4.77 × 10−3 8.54 × 105 K 2
Cp,m (C, s)/(J K mol ) = 16.86 + T− ,
K T2

   
−1 −1 3.26 × 10−3 0.50 × 105 K 2
Cp,m (H2 , g)/(J K mol ) = 27.28 + T− ,
K T2

   
−1 −1 0.1079T 1.56 × 106 K 2
r Cp /(J K mol ) = −100.83 + − .
K T2

  
T2 r Cp dT 1
= −100.83 × (T2 − T1 ) + 0.1079 K −1 (T22 − T12 )
T1 J K−1 mol−1 2
 
1 1
− (1.56 × 106 K 2 ) −
T2 T1
 
1
= −100.83 × (52 K) + (0.1079)(3502 − 2982 ) K
2
 
1 1
− (1.56 × 10 )
6
− K
350 298
= −2.65 × 103 K.

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 40 SOLUTIONS MANUAL

Multiplying by the units J K −1 mol−1 , we obtain

T2
r Cp dT = −(2.65 × 103 K) × (J K−1 mol−1 ) = −2.65 × 103 J mol−1
T1

= −2.65 kJ mol−1 .
Hence f H (350 K) = f H (298 K) − 2.65 kJ mol−1

= −84.68 kJ mol−1 − 2.65 kJ mol−1 = −87.33 kJ mol−1 .

P2.9 Cr(C6 H6 )2 (s) → Cr(s) + 2C6 H6 (g), ng = +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) = 2f 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)

+ (Tb − 298 K)Cp,m (l) + vap H + (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.

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, PC Spartan
ProTM ), enthalpies of combustion based on them (and on experimental enthalpies of formation of H2 O(l)
and CO2 (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 40 — #18

 THE FIRST LAW 41

Compound f H /kJ mol−1 c H /kJ mol−1 (calc.) c H /kJ mol−1 (expt.) %error

CH4 (g) −54.45 −910.72 −890 2.33

C2 H6 (g) −75.88 −1568.63 −1560 0.55
C3 H8 (g) −98.84 −2225.01 −2220 0.23
C4 H10 (g) −121.60 −2881.59 −2878 0.12
C5 H12 (g) −142.11 −3540.42 −3537 0.10

The combustion reactions can be expressed as:

 
3n + 1
Cn H2n+2 (g) + O2 (g) → n CO2 (g) + (n + 1) H2 O(1).
2
The enthalpy of combustion, in terms of enthalpies of reaction, is

c H = nf H (CO2 ) + (n + 1)f H (H2 O) − f H (Cn H2n+2 ),

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

c H (calc.) − c H (expt.)
%error = × 100%.
c H (expt.)

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 

CH4 (g) 16.04 –910.72 2.775 6.814

C2 H6 (g) 30.07 –1568.63 3.404 7.358
C3 H8 (g) 44.10 –2225.01 3.786 7.708
C4 H10 (g) 58.12 –2881.59 4.063 7.966
C5 H12 (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 |c H /kJ mol−1 | = 4.30 + 0.903 ln M/(g mol−1 ) R2 = 1.00

These compounds support the proposed relationships, with

n = 0.903 and k = −e4.30 kJ mol−1 = −73.7 kJ mol−1 .

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

 42 SOLUTIONS MANUAL

9
ln | ∆cH / kJ mol–1|

6
2 3 4 5
ln M/(g mol–1) 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, 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 C60.

c H = 60f H (CO2 ) − 60f H (O2 ) − f H (C60 ),

f H (C60 ) = 60f H (CO2 ) − 60f H (O2 ) − c H

= [60(−393.51) − 60(0) − (−25968)] kJ mol−1 = 2357 kJ mol−1 .

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

= (274 + 0 − 34.3) kJ mol−1 = 240 kJ mol−1 .

(b) r H = f H (SiH2 ) + f H (SiH4 ) − f H (Si2 H6 )

= (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:
 1/c
Vf CV ,m
T f = Ti where c = .
Vi R

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

 γ
Vf Cp,m
pf = pi where γ = .
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 γ .

   
CV ,m Cp,m Cp,m
cγ = × = .
R CV ,m R

Solving both relationships for the ratio of volumes, we have

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

Therefore
    
pf 202.94 kPa
ln ln
p  81.840 kPa 
Cp,m = R  i  = (8.314 J K −1 mol−1 ) × 
    = 41.40 J K−1 mol−1 .
Tf 298.15 K 
ln ln
Ti 248.44 K

P2.19 Hm = Hm (T , p).
   
∂Hm ∂Hm
dHm = dT + dp.
∂T p ∂p T

Since dT = 0,
    
∂Hm ∂Hm 2a
dHm = dp where = −µCp,m [2.53] = − −b .
∂p T ∂p T RT

pf
pf    
2a 2a
Hm = dHm = − − b dp = − − b (pf − pi )
pi pi RT RT
(2) × (1.352 dm6 atm mol−2 )
=− − (0.0387 dm3 mol−1 )
(0.08206 dm3 atm K −1 mol−1 ) × (300 K)
× (1.00 atm − 500 atm)
   
1m 3 1.013 × 105 Pa
= (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

   
∂z ∂z
P2.21 (a) dz = dx + dy [definition of total differential].
∂x y ∂y x
   
∂z ∂z
= (2x − 2y + 2), = (4y − 2x − 4),
∂x y ∂y x

dz = (2x − 2y + 2) dx+(4y−2x−4)dy .

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 44 SOLUTIONS MANUAL

   
∂ ∂z ∂ ∂ ∂z ∂
(b) = (2x − 2y + 2) = −2, = (4y − 2x − 4) = −2.
∂y ∂x ∂y ∂x ∂y ∂x
     
∂z 1 ∂z
(c) = y+ , = (x − 1),
∂x y x ∂y x

 
1
dz = y+ dx + (x - 1) dy .
x

A differential is exact if it satisfies the condition

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

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

     
∂U ∂U ∂U
P2.23 U = U(T , V ) so dU = dT + dV = CV dT + dV .
∂T V ∂V T ∂V T
For U = constant, dU = 0, and
         
∂U ∂U dV ∂U ∂V
CV dT = − dV or CV = − =− .
∂V T ∂V T dT U ∂V T ∂T U

This relationship is essentially Euler’s chain relation [Further information 2.2].

     
∂H ∂H ∂H
H = H(T , p) so dH = dT + dp = Cp dT + dp.
∂T p ∂p T ∂p T

According to Euler’s chain relation

     
∂H ∂p dT
= −1
∂p T ∂T H dH p

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

     
∂H ∂T dH
=− = - µCp .
∂p T ∂p H dT p
   
∂H ∂V p
P2.25 (a) H = U + pV so =1+p = 1+ .
∂U p ∂U p (∂U/∂V ) p
 
(∂(U + pV )
 
(b) ∂H (∂H/∂V )p ∂V p (∂U/∂V )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

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 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 n2 C
p = nRT + 2 + 3 + ... .
V V V

V2  
1 nB n2 C
Therefore, w = −nRT + 2 + 3 + ... dV ,
V1 V V V
   
V2 1 1 1 3 1 1
w = −nRT ln + n RTB
2
− + n RTC − 2 + ....
V1 V2 V1 2 V22 V2

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 cm3 mol–1 and C = 1200 cm6 mol–2 , so

n2 BRT = (1.0 mol) × (−21.7 cm3 mol−1 ) × (2.27 kJ) = −49.3 kJ cm3 ,
1 3 1
n CRT = (1.0 mol)2 × (1200cm6 mol−2 ) × (2.27 kJ) = +1362 kJ cm6 .
2 2
Therefore,
   
1 1 1 1
w = −2.27 kJ ln 2 − (49.3 kJ) × − + (1362 kJ) × −
(a) 1000 500 10002 5002
= (−1.57) + (0.049) − (4.1 × 10−3 ) 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 .

  
∂T 1 ∂H
P2.29 µ= =− [2.51 and 2.53],
∂p H Cp ∂p T
   
1 ∂V
µ= T − V [See problem 2.34 for this result].
Cp ∂T p
 
nRT ∂V nR
But V = + nb or = .
p ∂T p p
Therefore,
   
1 nRT nRT nRT 1 −nb
µ= −V − = − nb = .
Cp p p p Cp Cp
 
∂T
Since b > 0 and Cp > 0, we conclude that for this gas µ < 0 or < 0. This says that when the
∂p H
pressure drops during a Joule–Thomson expansion the temperature must increase .

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

 46 SOLUTIONS MANUAL

P2.31 nRT n2 a
p= − 2 [Table 1.7].
V − nb V

 p   na 
Hence T = × (V − nb) + × (V − nb) ,
nR RV 2

 
∂T V − nb Vm − b 1
= = =   .
∂p V nR R ∂p
∂T V

    
∂T ∂p ∂V
For Euler’s chain relation, we need to show that = −1.
∂p V ∂V T ∂T p
     
∂T ∂p ∂V 1
Hence, in addition to we need and =   .
∂p V ∂V T ∂T p ∂T
∂V p

 
∂p −nRT 2n2 a
= + 3
∂V T (V − nb) 2 V

which can be found from

   p   na   2na 
∂T
=
+ − × (V − nb),
∂V p nR RV 2 RV 3
     
∂T T 2na
= − × (V − nb).
∂V p V − nb RV 3

Therefore,
   
∂T ∂p
     
∂T ∂p ∂V ∂p V ∂V T
=  
∂p V ∂V T ∂T p ∂T
∂V p
   
V − nb −nRT 2n2 a
× + 3
nR (V − nb)2 V
=    
T 2na
− × (V − nb)
V − nb RV 3
   
−T 2na
+ × (V − nb)
V − nb RV 3
=    
T 2na
− × (V − nb)
V − nb RV 3
= −1.

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

 THE FIRST LAW 47

 
∂V T
P2.33 µCp = T −V =   − V [reciprocal identity, Further information 2.2]
∂T p ∂T
∂V p

 
∂T T 2na
= − (V − nb) [Problem 2.31]
∂V p V − nb RV 3

Introduction of this expression followed by rearrangement leads to

(2na) × (V − nb)2 − nbRTV 2

µCp = × V.
RTV 3 − 2na(V − nb)2

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

  
nbζ  bζ
 1−
1− 
 V V =  V  V.
µCp =    ζ −1
m

ζ −1

For xenon, Vm = 24.6 dm3 mol−1 , T = 298 K, a = 4.137 dm6 atm mol−2 , b = 5.16 × 10−2 dm3 mol−1 ,

nb b 5.16 × 10−1 dm3 mol−1

= = = 2.09 × 10−3 ,
V Vm 24.6 dm3 mol−1
(8.206 × 10−2 dm3 atm K −1 mol−1 ) × (298 K) × (24.6 dm3 mol−1 )3
ζ = = 73.0.
(2) × (4.137 dm6 atm mol−2 ) × (24.6 dm3 mol−1 − 5.16 × 10−2 dm3 mol−1 )2

1 − (73.0) × (2.09 × 10−3 )

Therefore, µCp = × (24.6 dm3 mol−1 ) = 0.290 dm3 mol−1 .
72.0

Cp = 20.79 J K−1 mol−1 [Table 2.6], so

0.290 dm3 mol−1 0.290 × 10−3 m3 mol−1
µ= =
20.79 J K −1 mol−1 20.79 J K −1 mol−1
= 1.393 × 10−5 K m3 J−1 = 1.393 × 10−5 K Pa−1

= (1.393 × 10−5 ) × (1.013 × 105 K atm−1 ) = 1.41 K atm−1 .

nbζ
The value of µ changes at T = TI and when the sign of the numerator 1 − changes sign (ζ − 1 is
V
positive). Hence

bζ RTbV 3 2a(Vm − b)2

= 1 at T = TI or =1 implying that TI = ,
Vm 2na(V − nb)2 Vm RbVm2

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 48 SOLUTIONS MANUAL

   2  
2a b 27 b 2
that is, TI = × 1− = Tc 1 − .
Rb Vm 4 Vm

2a (2) × (4.137 dm6 atm mol−2 )

For xenon, = = 1954 K
Rb (8.206 × 10−2 dm3 atm K −1 mol−1 ) × (5.16 × 10−2 dm3 mol−1 )
 2
5.16 × 10−2
and so TI = (1954 K) × 1 − = 1946 K .
24.6
Question. An approximate relationship for µ 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.

 
α 2 TV αTV ∂p
P2.35 Cp,m − CV ,m = [2.49] = [2.57].
nκT n ∂T V
 
∂p nR
=
[Problem 2.31].
∂T
V V − nb
 
∂V 1
αV = =   .
∂T p ∂T
∂V p

Substituting,

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

1 1 2a(Vm − b)3
with λ = or =1− .
2na λ RTVm3
1− × (V − nb)2
(RTV 3 )
8a
Now introduce the reduced variables and use Tc = , Vc = 3b.
27Rb
After rearrangement,

1 (3Vr − 1)2
=1− .
λ 4Tr Vr3

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

 THE FIRST LAW 49

For xenon, Vc = 118.1 cm3 mol−1 , 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 .
λ
Hence, Vm ≈ 2.45 dm3 , Vc =118.8 cm3 mol−1 , Tc = 289.8 K, and Vr = 20.6 and Tr =1.03; therefore

1 (61.8 − 1)2
=1− = 0.90, giving λ ≈ 1.1
λ (4) × (1.03) × (20.6)3

and

Cp,m − CV ,m ≈ 1.1 R = 9.2 J K−1 mol−1 .

     
P2.37 (a) 1 ∂H 1 ∂Vm
µ=− = T − Vm [2.53 and Problem 2.34].
Cp ∂p T Cp ∂T p

 
RT ∂Vm R
Vm = + aT 2 so = + 2aT .
p ∂T p p

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

     
(b) ∂p ∂Vm ∂p
CV = Cp − αTVm = Cp − T .
∂T V ∂T p ∂T V

RT
But, p = .
Vm − aT 2
 
∂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
  
R p 2ap2
C V = Cp − T + 2aT × +
p T R
     
RT 2apT 2apT p
= Cp − 1+ × 1+ × ,
p R R T
 
2apT 2
CV = C p − R 1 + .
R

TRAPP: “CHAP02” — 2006/3/8 — 17:05 — PAGE 49 — #27

 50 SOLUTIONS MANUAL

Solutions to applications

P2.39 Taking the specific 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:

1 Cal
q = (680 kJ) × = 162 Cal.
4.184 kJ

As a percentage of a 2200-Calorie diet, this serving is

162 Cal
× 100% = 7.4% .
2200 Cal

1.5 g
P2.41 (a) q = nc H = × (−5645 kJ mol−1 ) = −25 kJ .
342.3 g mol−1

(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 s−2

(c) The energy released as heat is

 
q = −r H = −nc H = −
2.5 g
× (−2808 kJ mol−1 ) = 39 kJ .
180 g mol−1

(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
q = w = mgh so h= = = 15 m .
4 4mg 4(65 kJ) × (9.8 m s−2 )

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 range—a reasonable assumption
if the impurities are monomers or oligomers and if the temperature range is sufficiently narrow—then
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 V
α= ≈ so V ≈ αV T .
V ∂T p V T

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, h) times the area of the ocean
(assuming that area remains constant). We will use α 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 × 109 km3 ) × (2.0 K) = 5.8 × 105 km3

V
so h = = 1.6 × 10−3 km = 1.6m .
A
Since the rise in sea level is directly proportional to the rise in temperature, T = 1◦ C would lead to
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 µ from

 
1 ∂H
µ=−
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.  
∂H
The regression analysis gives the slope as −18.0 J g−1 MPa−1 ≈ ,
∂p T
−18.0 kJ kg−1 MPa−1
so µ = − = 23.5 K MPa−1 .
0.7649 kJ kg−1 K −1 = 23.5 K MPa−1
(b) At 350 K.  
∂H
The regression analysis gives the slope as −14.5 J g−1 MPa−1 ≈ ,
∂p T
−14.5 kJ kg−1 MPa−1
so µ = − = 14.0 K MPa−1 .
1.0392 kJ kg−1 K −1

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