CHEM 3411, Fall 2010

Solution Set 4

In this solution set, an underline is used to show the last signicant digit of numbers. For instance in

x = 2.51693

the 2,5,1, and 6 are all signicant. Digits to the right of the underlined digit, the 9 & 3 in the example, are not
signicant and would be rounded o at the end of calculations. Carrying these extra digits for intermediate values in
calculations reduces rounding errors and ensures we get the same answer regardless of the order of arithmetic steps.
Numbers without underlines (including nal answers) are shown with the proper number of sig gs.

1 Exercise 4.1b pg 153

Question
How many phases are present at each of the points marked in Fig. 4.23b?

Solution

a. 1 - point is entirely inside a single phase region (not on any boundaries).

b. 3 - point on a boundary where 3 phases meet.
c. 3 - (same explanation as b)
d. 2 - point occurs on boundary between two phases (on a single line).

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CHEM 3411, Fall 2010
Solution Set 4

2 Exercise 4.5b pg 153

Given
Iron is heated from Ti = 25 C to Tf = 100 C. Over this temperature range Sm

= 53 J K1 mol1.

In terms of given variables, this is written:

Ti = 25 C

Tf = 100 C

Sm = 53 J K1 mol1

Find
By how much does its chemical potential change?

Strategy
First, temperatures are converted to Kelvin.

Ti = 100 + 273 C = 373 K

Tf = 1000 + 273 C = 1273 K

We can use text book Equation 4.2 (pg 143) to relate temperature changes to changes in chemical potential.
( )

= Sm
T p

which gives the dierential

d = Sm dT

Integrating d over the temperature range gives the change in chemical potential.

Tf

= Sm dT
Ti

= Sm (Tf Ti )
J
= 53 (1273 K 373 K)
K mol
J
= 47700
mol
kJ
= 47.7
mol

where the integral has been easily solved, as weve assumed Sm is constant over this temperature range.

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CHEM 3411, Fall 2010
Solution Set 4

Solution

kJ
= 50
mol

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CHEM 3411, Fall 2010
Solution Set 4

3 Exercise 4.11b pg 153

Given
The vapour pressure of a liquid between 15 C and 35 C ts the expression

log(p/ torr) = 8.750 1625/(T / K)

Find
Calculate . . .

(a) the enthalpy of vaporization

(b) the normal boiling point of the liquid

Strategy
Well start with Equation 4.11 (pg 148).

d ln p vap H
=
dT RT 2
Through rearrangement we solve for vap H .

d ln p
vap H = RT 2
dT

To nd ddTln p
, the given expression for log(p/ torr) can be converted to an expression for ln(p/ torr) using the change
of base formula.

logk x
logb x =
logk b

and this gives the equation

ln(p/ torr) = ln(10) (7.960 1625/ (T / K))

Dierentiating this expression by T gives

ln(dp) ln(10) 1625 K

=
dT T2
(The Torr units were discarded as the units of pressure would only lead to constant shift in the expression for ln(p)
and this constant is lost on dierentiation.)
Lastly we can substitute this expression for ln(dp)
dT into our earlier expression for vap H .

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CHEM 3411, Fall 2010
Solution Set 4

ln(10) 1625 K
vap H T
= R2
T
2

= R ln(10) 1625 K
J
= 8.314 
ln(10) 1625
K


K mol
J
= 31108.5
mol
kJ
= 31.1085
mol

The normal boiling point can be found by solving the given expression p(T ) for the temperature at which p(T ) =
patmosphere where the atmospheric pressure patmosphere = 1.00 atm = 760 torr.

log(760 
torr/  = 8.750 1625/(T / K)
torr)

1625 K
T =
8.750 log 760
= 276.9 K

Solution

(a) vap H = 31.11 mol

kJ

(b) T = 280 K

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CHEM 3411, Fall 2010
Solution Set 4

4 Exercise 4.14b pg 153

Given
On a cold, dry morning after a frost, the temperature was T = 5 C and the partial pressure of water in the
atmosphere fell to pH2 O = 0.30 kPa.

In terms of given variables, this is written:

T = 5 C

p = 0.30 kPa

Find
(a) Will the frost sublime?
(b) What partial pressure of water pH2 O would ensure that the frost remained?

Strategy
In this exercise, the second question answers the rst question, in that once we know the partial pressure of water
pH2 O needed to ensure the frost remains, we know any pH2 O below this will lead to frost sublimation.
The partial pressure needed to prevent sublimation is found by determing the solid-vapor pressure for water at this
temperature; this is the pressure at this temperature on the coexistance curve for ice and water vapor. We know
that if the atmosphere has a lower partial pressure of water than the solid-vapor pressure, then the water vapour
will be favored over the solid and the ice will sublime. At higher partial pressures the solid phase is favored.
We can nd the solid-vapor pressure using Equation 4.12 (pg 149) from our text book
( )
sub H 1 1
p=p e =
R T T

where weve replaced vap H in the original expression with sub H as were concerned with the sublimation
coexistence point instead of the vaporization point.
The sublimation enthalpy vap H is found from the vaporization enthalpy and the fusion enthalpy, vap H and
fus H respectively.

sub H = fus H + vap H

= 6.008 kJ mol1 + 44.016 kJ mol1
= 50.024 kJ mol1
= 5.0024 104 J mol1

Using Equation 4.12 we can calculate the pressure p at temperature T when we know the reference pressure p at the
reference temperature T . As were solving for a p(T ) on the solid/gas coexistence curve, well need the reference to
also fall on this curve. Therefore well use the the triple point of water as our reference giving the following values:

T = 273.16 K

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CHEM 3411, Fall 2010
Solution Set 4

p = 0.61173 kPa

This allows us to nd the solid-vapor pressure p on the solid/gas coexistence curve for the temperature T = 5 C =
268 K.

( )
sub H 1 1
=
R T T
1( )
5.0024 104Jmol 1 1
=  
J
8.314 K
1 1
mol 268 
K 273.16
K
= 0.42409

p = p e
= 0.61173 kPa e0.42409
= 0.40029 kPa

Now that we know the solid-vapor pressure p = 0.40029 kPa at the given temperature, we know the ice will sublime
into any gas system with a partial pressure of water pH2 O < 0.40029 kPa. This gives us the answer to part b as
pH2 O = 0.40029 kPa.
Additionally, can determine that the ice will sublime into the atmosphere as the partial pressure of water is pH2 O =
0.30 kPa.

Solution

(a) Yes.
(b) pH2 O = 0.40029 kPa

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CHEM 3411, Fall 2010
Solution Set 4

5 Exercise 4.17b pg 154

Question
What fraction of the enthalpy of vaporization vap H of ethanol is spent on expanding its vapour?

Strategy
We can use the denition of enthalpy, H = U + pV (Equation 2.18 pg 56) to decompose the enthalpy of vaporization
vap H into an internal energy component vap U and an expansion work component vap (pV ).

vap H = vap U + vap (pV )

Additionally, we can assume the pressure is constant and the liquid volume Vliq is negligible relative to the gas volume
such that

vap (pV ) = p(Vgas Vliq ) pVgas

Next, we can use the ideal gas law pV = nRT to relate pVgas to RT for a molar quantity of gas by assuming the
ethanol vapor is ideal. This gives

vap (pV ) = RT

And thereby the ratio of expansion work vap (pV ) to expansion enthalpy vap H is

vap (pV ) RT
=
vap H vap H

Using text book table 2.3 we nd that ethanol vaporizes at T = 352 K and its expansion enthalpy is 43.5 kJ mol1 .
Substituting these values gives the ratio value

vap (pV ) RT
=
vap H vap H
 
8.3145JK1 1
mol 352 
K
= 
43.5
kJ  1
mol 1 kJ

1000 J


= 0.0673
= 6.73%

Solution

vap (pV )
= 6.73%
vap H

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CHEM 3411, Fall 2010
Solution Set 4

6 Problem 4.4 pg 154

Question
Calculate the dierence in slope of the chemical potential against temperature on either side of (a) the normal freezing
point of water and and (b) the normal boiling point of water. (c) By how much does the chemical potential of water
super cooled to 5.0 C exceed that of ice at that temperature.

Strategy
To solve parts (a) and (b) well use Equation 4.13 (part 2 pg 150) that relates how the temperature derivative (slope)

of chemical potential, T , changes across a coexistence curve.
( ) ( )
() () trs H
= Sm () + Sm () = trs S =
T p T p Ttrs

where and denote the two phases.

For part (a) were interested in the dierence between the liquid l and solid s phases, the fusion transition fus H ,
which gives the following expression.
( ) ( )
(l) (s) fus H
= Sm (l) + Sm (s) = fus S =
T p T p Tf

Substituting in the enthalpy and temperature of waters fusion transition, fus H = 6.008 kJ mol1 and Tf = 273.15 K
respectively as found in Table 2.3 of our text book, gives

( ) ( )
(l) (s) fus H
=
T p T p Tf
6.008 kJ mol1
=
273.15 K
= 0.021995 kJ mol1 K1
= 21.995 J mol1 K1

Likewise for part (b) were interested in the dierence between the gas g and the liquid l phases which is the
vaporization transition vap H.
( ) ( )
(g) (l) vap H
= Sm (g) + Sm (l) = vap S =
T p T p Tv

Substituting in vap H = 40.656 kJ mol1 and Tv = 373.15 K from Table 2.3 gives

( ) ( )
(g) (l) vap H
=
T p T p Tv
40.656 kJ mol1
=
373.15 K
= 0.108953 kJ mol1 K1
= 108.953 J mol1 K1

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CHEM 3411, Fall 2010
Solution Set 4

For part (c) were interested in calculating the dierence in chemical potential of liquid water at 5 C, (l, 5 C)
and the chemical potential of solid water at the same temperature (s, 5 C) and well call this quantity x.

x = (l, 5 C) (s, 5 C)

To calculate x well take advantage of the normal freezing point of water, which implies that at T = 0 C solid water
and liquid water have the same chemical potential: (l, 0 C) = (s, 0 C)
Therefore we can subtract (l, 0 C) (s, 0 C) (as this quantity is 0) from the expression were working to solve.

x = (l, 5 C) (s, 5 C)
= (l, 5 C) (s, 5 C) [ (l, 0 C) (s, 0 C)]
= [ (l, 5 C) (l, 0 C)] [ (s, 5 C) (s, 0 C)]
= (l) (s)

In the third equation above weve rearranged the righthand side so as to place the dierence in chemical potentials at
the two temperatures in brackets for each phase. We call this quantity () where () = (, 5 C) (, 0 C)
and species either the liquid (l) or solid (s) phase.
We can calculate (l) and (s) using Equation 4.2 (pg 143) which gives the change in chemical potential with
temperature.
( )

= Sm
T p

Hence the change in chemical potential for the phase can be calculated as

Tf ( )

() = dT
Ti T p
Tf
= Sm dT
Ti
= Sm (Tf Ti )

where Sm is assumed temperature independent.

Using Tf Ti = T = 5 K and the standard entropies of liquid water Sm (l) and solid water Sm (s) we get the
following expressions for chemical potential changes

(l) = Sm (l)T

(s) = Sm (s)T

Substituting these expression into our equation for x gives

x = (l) (s)
= [Sm (l) Sm (s)] T

The above term in brackets, the dierence in entropy of liquid and solid water, is just the opposite of the entropy of
fusion fus S which we know from part (a).

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CHEM 3411, Fall 2010
Solution Set 4

x = [Sm (l) Sm (s)] T

= fus ST
( )
= +21.995 J mol1  5 
K
1
K
= 109 J mol1

We are reminded that x is just the dierence in chemical potentials that we were solving.

(l, 5 C) (s, 5 C) = x = 109 J mol1

This positive dierence in chemical potential between liquid and solid phases implies higher free energy for the liquid
phase relative to the solid phase (ice) and explains why ice is favorable at this temperature.

Solution

(a) ( ) ( )
(l) (s)
= 22.00 J mol1 K1
T p T p

(b) ( ) ( )
(g) (l)
= 108.95 J mol1 K1
T p T p

(c)
(l, 5 C) (s, 5 C) = x = 100 J mol1

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