4

Physical transformations
of pure substances

Answers to discussion questions

D4.1

Consider two phases of a system, labeled and . The phase with the lower chemical potential under
the given set of conditions is the more stable phase. First consider the variation of with temperature
at a fixed pressure. We have
"
!
"
!

= S and
= S .
T p
T p
Therefore, if S is larger in magnitude than S , the phase will be favored over the phase as temperature
increases because its chemical potential decreases more rapidly with temperature than for the phase.
We also have
"
!
"
!

= Vm, and
= Vm, .
P T
P T
Therefore, if Vm, is larger than Vm, the phase will be favored over the phase as pressure increases
because the chemical potential of the phase will not increase as rapidly with pressure as that of the
phase. See Example 4.1.

D4.3

Refer to Fig. 4.1 above and Fig. 4.5 in the text. Starting at point A and continuing clockwise on path
p(T ) toward point B, we see a gaseous phase only within the container with water at pressures and
temperatures p(T ). Upon reaching point B on the vapor pressure curve, liquid appears on the bottom of
the container and a phase boundary or meniscus is evident between the liquid and less dense gas above
it. The liquid and gaseous phases are at equilibrium at this point. Proceeding clockwise away from the
vapor pressure curve the meniscus disappears and the system becomes wholly liquid. Continuing along
p(T ) to point C at the critical temperature no abrupt changes are observed in the isotropic fluid. Before
point C is reached, it is possible to return to the vapor pressure curve and a liquidgas equilibrium by
reducing the pressure isothermally. Continuing clockwise from point C along path p(T ) back to point A,
no phase boundary is observed even though we now consider the water to have returned to the gaseous
state. Additionally, if the pressure is isothermally reduced at any point after point C, it is impossible to
return to a liquidgas equilibrium.
When the path p(T ) is chosen to be very close to the critical point, the water appears opaque. At near
critical conditions, densities and refractive indices of both the liquid and gas phases are nearly identical.
Furthermore, molecular fluctuations cause spatial variations of densities and refractive indices on a scale
large enough to strongly scatter visible light. This is called critical opalescence.

TRAPP: CHAP04 2006/3/8 17:05 PAGE 81 #1

82

SOLUTIONS MANUAL
Vapor pressure curve of water
Exploration
Path p(T )

C
Critical point

221.2 bar
p

B
A

D4.5

647.4 K

Figure 4.1 Vapor pressure curve of water

The supercritical fluid extractor consists of a pump to pressurize the solvent (e.g. CO2 ), an oven with
extraction vessel, and a trapping vessel. Extractions are performed dynamically or statically. Supercritical
fluid flows continuously through the sample within the extraction vessel when operating in dynamic
mode. Analytes extracted into the fluid are released through a pressure-maintaining restrictor into a
trapping vessel. In static mode the supercritical fluid circulates repetitively through the extraction vessel
until being released into the trapping vessel after a period of time. Supercritical carbon dioxide volatilizes
when decompression occurs upon release into the trapping vessel.

Advantages

Disadvantages

Current uses

Dissolving power of SCF can

be adjusted with selection of T
and p

Elevated pressures are required

and the necessary apparatus
expensive

Extraction of caffeine, fatty

acids, spices, aromas, flavors,
and biological materials from
natural sources

Select SCFs are inexpensive

and non-toxic. They reduce
pollution

Cost may prohibit large scale

applications

Extraction of toxic salts (with

a suitable chelation agent) and
organics from contaminated
water

Thermally unstable analytes

may be extracted at low
temperature
The volatility of scCO2 makes
it easy to isolate analyte

Modifiers like methanol (110%)

may be required to increase
solvent polarity
scCO2 is toxic to whole cells in
biological applications (CO2 is not
toxic to the environment)

Extraction of herbicides from

soil
scH2 O oxidation of toxic,
intractable organic waste
during water treatment

SCFs have high diffusion rates,

low viscosity, and low surface
tension

Synthetic chemistry, polymer

synthesis and crystallization,
textile processing

O2 and H2 are completely

miscible with scCO2 . This
reduces multi-phase reaction
problems

Heterogeneous catalysis for

green chemistry processes

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PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

D4.7

83

First-order phase transitions show discontinuities in the first derivative of the Gibbs energy with respect to
temperature. They are recognized by finite discontinuities in plots of H, U, S, and V against temperature
and by an infinite discontinuity in Cp . Second-order phase transitions show discontinuities in the second
derivatives of the Gibbs energy with respect to temperature, but the first derivatives are continuous. The
second-order transitions are recognized by kinks in plots of H, U, S, and V against temperature, but most
easily by a finite discontinuity in a plot of Cp against temperature. A -transition shows characteristics
of both first- and second-order transitions and, hence, is difficult to classify by the Ehrenfest scheme. It
resembles a first-order transition in a plot of Cp against T , but appears to be a higher-order transition
with respect to other properties.
At the molecular level first-order transitions are associated with discontinuous changes in the interaction
energies between the atoms or molecules constituting the system and in the volume they occupy. One kind
of second-order transition may involve only a continuous change in the arrangement of the atoms from
one crystal structure (symmetry) to another while preserving their orderly arrangement. In one kind of
8-transition, called an orderdisorder transition, randomness is introduced into the atomic arrangement.
See Figs. 4.18 and 4.19 of the text.

Solutions to exercises
E4.1(a)

On the assumption that the vapor is a perfect gas and that %vap H is independent of temperature, we
may write
p = p e ,

%vap H
R

"

1
1

T
T

"

[4.12], ln

p
= .
p

1
1
R
p
= +
ln
T
T
%vap H
p
#
$
8.314 J K1 mol1
53.3 kPa
1
+
ln
=
= 3.285 103 K 1 .
297.25 K
70.0 kPa
28.7 103 J mol1

Hence, T = 304 K = 31 C .
E4.2(a)

dp
%trs S
=
[4.6].
dT
%trs V
! "
dp
%p
%fus V
%fus S = %fus V
dT
%T
[%fus S and %fus V assumed independent of temperature].
%fus S = [(163.3 161.0) 10

m mol

(100 1) (1.013 105 Pa)

(351.26 350.75) K

= +45.23 J K1 mol1 .
%fus H = Tf %S = (350.75 K) (45.23 J K1 mol1 ) = +16 kJ mol1 .

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84
E4.3(a)

SOLUTIONS MANUAL

The expression for ln p is the indefinite integral of eqn 4.11,

%
%
%vap H
%vap H
d ln p =
dT ; ln p = constant
.
2
RT
RT
Therefore, %vap H = (2501.8 K) R = (2501.8 K) (8.314 J K1 mol1 ) = +20.80 kJ mol1 .

E4.4(a)

(a) The indefinitely integrated form of eqn 4.11 is used as in Exercise 4.3(a).
ln p = constant

%vap H
,
RT

or

log p = constant

%vap H
.
2.303RT

Therefore,
%vap H = (2.303) (1780 K) R = (2.303) (1780 K) (8.314 J K 1 mol1 )
= +34.08 kJ mol1 .
(b) The boiling point corresponds to p = 1.000 atm = 760 Torr.
log 760 = 7.960
E4.5(a)

1780 K
,
Tb

Tb = 350.5 K .

%fus V
%p [4.6, and Exercise 4.2(a)]
%fus S
! "
Tf %pM
1
Tf %fus V
%p =
=%
[Vm = M/]

%fus H
%fus H

$
#
(278.6 K) (999) (1.013 105 Pa) (78.12 103 kg mol1 )

10.59 103 J mol1

"
!
1
1

879 kg m3
891 kg m3

%T

3.18 K.
Therefore, at 1000 atm, Tf (278.6 + 3.18) K = 281.8 K [8.7 C].
E4.6(a)

The rate of loss of mass of water may be expressed as

dm
dn
=
MH2 O ;
dt
dt

n=

q
%vap H

(dq/dt)
(1.2 103 W m2 ) (50 m2 )
dn
= 1.4 mols1 .
=
=
dt
%vap H
44.0 103 J mol1

dm
= (1.4 mols1 ) (18.02 g mol1 ) = 25 g s1 .
dt
E4.7(a)

Assume perfect gas behavior.

pV
m
, n = , V = 75 m3 .
RT
M
pVM
.
m=
RT
n=

TRAPP: CHAP04 2006/3/8 17:05 PAGE 84 #4

PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

(a) m =
(b) m =
(c) m =

(3.2 kPa) (75 m3 ) (18.02 103 kg mol1 )

(8.314 103 kPa K 1 mol1 ) (298.15 K)

(13.1 kPa) (75 m3 ) (78.11 103 kg mol1 )

(8.314 103 kPa K 1 mol1 ) (298.15 K)

(0.23 Pa) (75 m3 ) (200.59 g mol1 )

(8.314 Pa m3 K 1 mol1 ) (298.15 K)

85

= 1.7 kg .
= 31 kg .

= 1.4 g .

Question. Assuming all the mercury vapor breathed remains in the body, how long would it take to
accumulate 1.4 g? Make reasonable assumptions about the volume and frequency of a breath.

E4.8(a)

The ClausiusClapeyron equation [4.11] integrates to the form [4.12] which may be rewritten as
! "
!
"
%vap H
p2
1
1
ln

.
p1
R
T1
T2
(a)

ln

40 kPa
10 kPa

"

%vap H
8.314 J K 1 mol1

"

"
1
1

,
359.0 K
392.5 K

1.405 = %vap H (2.86 105 J1 mol),

%vap H = 49.1 kJ mol1 .

(b) The normal boiling point corresponds to a vapor pressure of 760 Torr. Using the data at 119.3 C
$ !
" #
"
!
49.1 103 J mol1
1
1
101.3 kPa
=

,
ln
5.3 kPa
392.5 K
Tb
8.314 J K1 mol1
2.950 = 15.04

5905 K
;
Tb

Tb = 488 K = 215 C .

[The accepted value is 218 C.]

(c)
E4.9(a)

%vap H(Tb )
49.1 103 J mol1

= 101 J K1 mol1 .
Tb
488 K
! "
Tf %pM
1
%T = Tf (50 bar) Tf (1 bar)
%
[Exercise 4.5(a)],
%fus H

%vap S(Tb ) =

%fus H = 6.01 kJ mol1 [Table 2.3],

#
$
(273.15 K) (49 105 Pa) (18 103 kg mol1 )
%T =
6.01 103 J mol1
"
!
1
1

= 0.35 K.
1.00 103 kg m3
9.2 102 kg m3
Tf (50 bar) = (273.15 K) (0.35 K) = 272.80 K .

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86

SOLUTIONS MANUAL

%vap H = %vap U + %vap (pV ) = 40.656 kJ mol1 [Table 2.3]

E4.10(a)

%vap (pV ) = p%vap V = p(Vgas Vliq ) pVgas

= RT [per mole, perfect gas]

= (8.314 J K 1 mol1 ) (373.2 K) = 3.102 103 kJ mol1

Fraction =

%vap (pV )
3.102 103 kJ mol1
=
= 0.07630 7.6 per cent
%vap H
40.656 kJ mol1

Solutions to problems
Solutions to numerical problems
P4.1

At the triple point, T3 , the vapor pressures of liquid and solid are equal; hence
1871.2 K
1425.7 K
= 8.3186
; T3 = 196.0 K .
T3
T3
1871.2 K
log(p3 /Torr) =
+ 10.5916 = 1.0447; p3 = 11.1 Torr .
196.0 K

10.5916

P4.3

(a)

%vap S
%vap H
dp
=
=
[4.6, Clapeyron equation]
dT
%vap V
Tb %vap V
=

(b)

14.4 103 J mol1

= +5.56 kPa K1 .
'
(180 K) 14.5 103 1.15 104 m3 mol1
&

(
)
%vap H
dp
dp
=
p 4.11, with d ln p =
dT
p
RT 2
&
'
&
'
14.4 103 J mol1 1.013 105 Pa
= +5.42 kPa K 1 .
=
&
'
8.314 J K 1 mol1 (180 K)2

The percentage error is 2.5 per cent .

P4.5

(a)

(1)
p

"

(s)
p

"

= Vm (l) Vm (s)[4.13] = M%
+ !
*
= 18.02 g mol1

! "
1

1
1

1.000 g cm3
0.917 g cm3

"

= 1.63 cm3 mol1 .

(b)

(g)
p

"

(l)
p

"

= Vm (g) Vm (l)
+ !
*
1

= 18.02 g mol

1
0.598 g dm3

1
0.958 103 g dm3

= +3.01 dm3 mol1 .

TRAPP: CHAP04 2006/3/8 17:05 PAGE 86 #6

"

PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

87

At 1.0 atm and 100 C, (l) = (g); therefore, at 1.2 atm and 100 C, (g) (1) %Vvap %p =
(as in Problem 4.4)
(30.1 103 m3 mol1 ) (0.2) (1.013 105 Pa) + 0.6 kJ mol1 .
Since (g) > (l), the gas tends to condense into a liquid.
P4.7

The amount (moles) of water evaporated is ng =

The heat leaving the water is q = n%vap H.
The temperature change of the water is %T =
Therefore, %T =

pH2 O V
.
RT

q
, n = amount of liquid water.
nCp,m

pH2o V %vap H
RTnCp,m

&
' &
'
(3.17 kPa) 50.0 dm3 44.0 103 J mol1
= &
'
&
'
8.314 kPa dm3 K 1 mol1 (298.15 K) 75.5 J K 1 mol1
(250 g/18.02 g mol1 )
= 2.7K.
The final temperature will be about 22 C .
P4.9

(a) Follow the procedure in Problem 4.8, but note that Tb = 227.5 C is obvious from the data.
(b) Draw up the following table. The points are plotted in Fig. 4.2. The slope is
/ C
T /K
1000 K/T
ln p/Torr

57.4
330.6
3.02
0.00

6.4 103 K, so

100.4

133.0

373.6
406.2
2.68
2.46
2.30
3.69

157.3

203.5

227.5

430.5
2.32
4.61

476.7
2.10
5.99

500.7
2.00
6.63

%vap H
= 6.4 103 K,
R

implying that %vap H = +53 kJ mol1 .

P4.11

(a) The phase diagram is shown in Fig. 4.3.

(b) The standard melting point is the temperature at which solid and liquid are in equilibrium at 1 bar.
That temperature can be found by solving the equation of the solidliquid coexistence curve for the
temperature
1 = p3 /bar + 1000(5.60 + 11.727x)x.
&
'
So 11727x 2 + 5600x + 4.362 107 1 = 0.

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88

SOLUTIONS MANUAL

Figure 4.2

Figure 4.3

The quadratic formula yields

,
-1/2
,
-1/2
5600 (5600)2 4 (11 727) (1)
1 1 + (4(11 727))/56002
x=
=
.
2 (11 727)
2 ((11 727)/5600)
The square root is rewritten to make it clear that the! square "
root is of the form {1 + a}1/2 , with
1
1
a 1; thus the numerator is approximately 1 + 1 + a = a, and the whole expression
2
2
reduces to
x 1/5600 = 1.79 104 .
Thus, the melting point is
T = (1 + x) T3 = (1.000179) (178.15 K) = 178.18 K .
(c) The standard boiling point is the temperature at which the liquid and vapor are in equilibrium at
1 bar. That temperature can be found by solving the equation of the liquidvapor coexistence curve
for the temperature. This equation is too complicated to solve analytically, but not difficult to solve
numerically with a spreadsheet. The calculated answer is T = 383.6 K .

TRAPP: CHAP04 2006/3/8 17:05 PAGE 88 #8

PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

89

(d) The slope of the liquidvapor coexistence curve is given by

%vap H '
dp
=
dT
T %vap V '
so %vap H ' = T %vap V '

dp
.
dT

The slope can be obtained by differentiating the equation for the coexistence curve.
dp
dlnp
dlnp dy
=p
=p
,
dT
dT
dy dT
!
"
10.413
dp
2
0.70
15.996 + 2(14.015)y 3(5.0120)y (1.70) (4.7224) (1 y)
=
dT
y2
! "
p
.

Tc
At the boiling point, y = 0.6458, so
dp
= 2.851 102 bar K 1 = 2.851 kPa K 1
dT
#
$
*
+
(30.3 0.12) dm3 mol1
'
and %vap H = (383.6 K)
2.851 kPa K 1
3 3
1000 dm m
= 33.0 kJ mol1 .

Solutions to theoretical problems

P4.13

%G
p

"

G
p

"

G
p

"

= V V .

Therefore, if V = V , %G is independent of pressure. In general, V = V , so that %G is nonzero,

though small, since V V is small.
P4.15

pV
RT
(p = initial pressure of gas and emerging gaseous mixture).
m
Amount of vapor carried away = .
M
m/M
.
Mole fraction of vapor in gaseous mixture =
(m/M) + (pV /RT )
Amount of gas bubbled through liquid =

Partial pressure of vapor = p =

p (mRT /PVM)
mPA
m/M
p =
=
,
(m/M) + (pV /RT )
mA + 1
(mRT /PVM) + 1

A=

RT
.
PVM

For geraniol, M = 154.2 g mol1 , T = 383 K, V = 5.00 dm3 , p = 1.00 atm, and m = 0.32 g, so
'
&
8.206 102 dm3 atm K 1 mol1 (383 K)
A=
&
' &
' = 40.76 kg1 .
(1.00 atm) 5.00 dm3 154.2 103 kg mol1

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90

SOLUTIONS MANUAL

Therefore
'
&
'
0.32 103 kg (760 Torr) 40.76 kg1
= 9.8 Torr .
p=
&
' &
'
0.32 103 kg 40.76 kg1 + 1
&

P4.17

In each phase the slopes are given by

!

"

= Sm [4.1].

The curvatures of the graphs of . against T are given by

!

2
T 2

"

Sm
T

"

1
Cp,m [Problem 3.26].
T

Since Cp,m is necessarily positive, the curvatures in all states of matter are necessarily negative. Cp,m
is often largest for the liquid state, though not always, but it is the ratio Cp,m /T that determines the
magnitude of the curvature, so no precise answer can be given for the state with the greatest curvature.
It depends upon the substance.
P4.19

Sm = Sm (T , p).
"
"
"
!
!
!
Cp,m
Sm
Sm
Sm
dSm =
dT +
dp.
=
[Problem 3.26] ,
T p
p T
T p
T
!
"
!
"
Sm
Vm
=
[Maxwell relation] .
p T
T p
!
"
Vm
dqrev = T dSm = Cp,m dT T
dp.
T p
! "
! "
q
p
%Hm
CS =
= Cp,m TVm
= Cp,m Vm
[4.7] .
T s
T s
%Vm

Solutions to applications
P4.21

(a) The Dieterici equation of state is purported to have good accuracy near the critical point. It does fail
badly at high densities where Vm begins to approach the value of the Dieterici coefficient b. We will
use it to derive a practical equation for the computations.
pr =

e2 Tr e2/Tr Vr
[Table 1.7].
2Vr 1

Substitution of the Dieterici equation of state derivative (pr /Tr )Vr = (2 + Tr Vr )pr /Tr2 Vr into the
reduced form of eqn 3.48 gives
!

Ur
Vr

"

Tr

= Tr

pr
Tr

"

Vr

pr =

2pr
Tr V r

(Ur = U/pc Vc ).

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PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

91

Integration along the isotherm Tr from an infinite volume to Vr yields the practical computational
equation.

%Ur (Tr , Vr ) =

2pr (Tr , Vr )
dVr .
Tr V r
Tr constant

The integration is performed with mathematical software.

(c) (Tr , Vr ) = pc %Ur /Vr where pc = 72.9 atm.

Carbon dioxide should have solvent properties similar to liquid carbon tetrachloride (8 9)
when the reduced pressure is in the approximate range
0.85 to 0.90 when Tr = 1

(a)

2
3
4

Ur

Tr = 1

Tr = 1.2

7
0.5

(b)

1.5

Tr = 1.5

2.5
pr

3.5

4.5

Solubility parameter of carbon dioxide

20

15
!
atm
Tr= 1.5

10

5
0.75

0.8

T r= 1

0.85

0.9
pr

0.95

Figure 4.4

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92
P4.23

SOLUTIONS MANUAL

C (graphite) ! C (diamond) , %r G' = 2.8678 kJ mol1 at Tc . Tc = 25 C.

We want the pressure at which %r G = 0; above that pressure the reaction will be spontaneous. Equation
3.50 determines the rate of change of %r G with p at constant T .
(1)

%r G
p

"

= %r V = (VD VG )M

where M is the molar mass of carbon; VD and VG are the specific volumes of diamond and graphite,
respectively.
%r G( Tc , p) may be expanded in a Taylor series around the pressure p' = 100 kPa at Tc .
#
&
'$
&
'
&
'
%r G Tc , p'
(2)
'
'
%r G( Tc , p) = %r G Tc , p +
p p'
p
T
! 2
"
&
'
&
'3
1 %r G' (T , p' )
2
p p' + p p' .
+
2
2
p
T

We will neglect the third- and higher-order terms; the derivative of the first-order term can be
calculated with eqn 1. An expression for the derivative of the second-order term can be derived with
eqn 1.

(3)

2 %r G
p2

"

.!

VD
p

"

VG
p

" /
T

M = {VG T (G) VD T (D)} M [2.52 with 2.22].

Calculating the derivatives of eqns 1 and 2 at Tc and p' ,

#
&
'$
! 3" !
"
%r G Tc , p'
cm
12.01 g
(4)
= (0.284 0.444)

= 1.92 cm3 mol1 ,

p
g
mol
T

(5)

&
'$
2 %r G Tc , p'
= {0.444(3.04 108 ) 0.284(0.187 108 )}
p2
T
$ !
#
"
12.01 g
cm3 kPa1

g
mol
= 1.56 107 cm3 (kPa)1 mol1 .

AQ: Kindly
provide closing
bracket

It is convenient to convert the value of %r G' to the units cm3 kPa mol1 ,
#
! 3 3" # 5 $
2 dm3 bar K1 mol1
10 Pa
10 cm
'
1 8.315 10
%r G = 2.8678 kJ mol

.
bar
8.315J K1 mol1
dm3
(6) %r G' = 2.8678 106 cm3 kPa mol1 .

Setting = p p' , eqns 2 and 36 give

2.8678 106 cm3 kPa mol1 (1.92 cm3 mol1 ) + (7.80 108 cm3 kPa1 mol1 ) 2 = 0

TRAPP: CHAP04 2006/3/8 17:05 PAGE 92 #12

PHYSICAL TRANSFORMATIONS OF PURE SUBSTANCES

93

when %r G( Tc , p) = 0. One real root of this equation is

= 1.60 106 kPa = p p' or
p = 1.60 106 kPa 102 kPa

= 1.60 106 kPa = 1.60 104 bar .

Above this pressure the reaction is spontaneous. The other real root is much higher: 2.3 107 kPa.
Question. What interpretation might you give to the other real root?

TRAPP: CHAP04 2006/3/8 17:05 PAGE 93 #13