Chapter 3 Problems

Problem
At 1 atmosphere pure Ge melts at 1232 K and boils at 2980 K. The triple point occurs at
P=8.4x10-8 atm. Estimate the heat of vaporization of Ge.

Answer
The heat of vaporization is estimated from the Clausius Clapeyron equation on the
" ln P $H vap ln( P0 ) # ln( PTP )
vapor/liquid boundary: =# % $H vap = #R & where P0 is
1 R 1 1
" #
T T0 TTP
atmospheric pressure, PTP is the triple point pressure, T0 is the vaporization temperature
at 1 atm. and TTP is the temperature at the triple point, which we don’t know. We also
assume that ΔHvap is independent of temperature.
! dP "H m
On the S/L line however, = where "Vl #s is the volume difference between
dT T"Vl #s
the solid and liquid phase. This volume difference is much smaller than the volume
difference between the liquid and the vapor. Therefore, the S/L line is nearly vertical and
as a consequence, TTP~Tm. !
!
ln(101325) # ln(101325 $ 8.4 %10#8 )
As a result "H vap = #R $ & 285kJ /mol
1 1
#
2980 1232

1
 Problem
Phase α of species A transforms into phase β at 55 K and 1 atm. The heat capacities of A
in the structures α and β are, respectively, C P0,# = 8.8 " 10 !5 T 3 and C P0,# = 2.38 " 10 !4 T 3 .
Using the Third Law and assuming that a and b are pure crystalline elements, calculate
the entropy and enthalpy of transformation at 55 K and 0 K at 1 atm pressure.

Answer
From the third law, we know that S"o = S !o = 0 @ T = 0 K; ( if they are pure crystalline
elements).

o
T
C Po ,$ T
"S = #
$ dT = 2.93 * 10 !5 T 3
0
T 0

T
C Po ,# T
S$o = " dT = 7.95 * 10 !5 T 3
0
T 0

@ T = 55K, "S$0#% = S %0 ! S$0 = 8.37 J / mol * K

$G"0#! (55 K ) = 0 = $H "0#! % T$S"0#!

" !H %0#$ (55 K ) = +460.2 J / mol

!S$0"# (0 K ) = 0

0
0 0
"H # $% (0K) = "H # $% (55K) + & (C o
P ,% ' CP,0 # )dT = 117.2J /mol
55

2
 Problem
Tin can exist in either the metallic β-Sn phase or in the semiconducting α-Sn phase.
Consider the phase transition from Sn in the β-phase to the α-phase. The enthalpy change
"H # $% associated with the transition at 1 atm. is -2.1 kJ/mol. β-Sn is in equilibrium with
α-Sn at one atm. pressure and T=238.8 K. At 100 atm. the equilibrium temperature is
T=233.8 K.
Estimate the volume difference between the two phases. Which one has the higher
! density? Explain your assumptions.

Answer
Apply the Clausius equation:
dP "S# $%
=
dT "V# $%
We will assume that ΔS and ΔV are independent of temperature and pressure.
"H # $%
"S# $% = = &8.8 J.K &1 .mol&1 .
! T
From the data points, we have dP/dT=-2x106 Pa/K.
"S# $%
Thus "V# $% = = 4.4 cm 3 /mol . The β-phase is denser than the α-phase.
dP /dT
!

3
 Problem
You wish to evaporate Au contacts onto a simple integrated circuit in an evacuated
thermal evaporation system. Au has a boiling point of 3130K and an entropy of
vaporization at 1 atm. of 106.8 J.mol-1.K-1. If the desired vapor pressure of Au in the
vacuum chamber for the deposition process is 10-7 atm, estimate the temperature to which
the Au source must be heated in the thermal evaporator. State your assumptions.

Answer
dP "H vap T "S
Using the Clausius Clapeyron equation, = 2
dT = vap 2vap dT where we assume
P RT RT
that the vaporization enthalpy (=TvapΔSvap) does not depend strongly on temperature and
pressure (Tvap=3130K).
Integrating the Clausium Clapeyron equation, we have:
!
Tvap #Svap $ 1 1 ' -7
ln( P2 ) " ln( P1 ) = & " ) . By plugging in this equation P2=10 atm, P1=1 atm,
R % T1 T2 (
T1=3130K, we obtain T2=1389K

4
 Problem
1-Show that at the triple point the sublimation enthalpy of a material is equal to the sum
of its melting enthalpy and its vaporization enthalpy.
2-Below the triple point (-56°C) the vapor pressure of solid CO2 is given as:
3116
ln( P(atm)) = " + 16.01 with T in K.
T
The molar heat of melting of CO2 is 8.33 kJ. Making some simple assumptions, calculate
the vapor pressure exerted by liquid CO2 at 25°C and explain why solid CO2 is referred
to as “dry ice”. Sketch the phase diagram of CO2 and place the P=1 atm line and the
! T=25°C line with respect to the triple point.

Answer
1-If H is a state function, we can go from s to v by two different routes with the same ΔH.
The two different routes are direct sublimation or melting and then vaporization. At the
triple point all the phases can exist in equilibrium and these three processes can occur.
Therefore "H s#v = "H s#l + "H l #v .
& ln P
2-Using the expression, we can calculate "H s#v = $R % = $R % 3116 . We obtain
&1/T
"H s#v =25.9kJ/mol. Using the information about "H s#l , we obtain
!
"H l #v = "H s#v $ "H s#l =17.6 kJ/mol. We now use the Clausius Clapeyron equation to
estimate the vapor pressure of the liquid at 25°C using the triple point as the starting
!
# P25C & )H l *v # 1 1! &
! point: ln% (=" % " (.
! $ P"56C ' R $ 300K 217K '
The pressure at the triple point is obtained from the expression for ln(P) given in the
question: P-56°C=5.21 atm. We obtain P25C~75 atm>>1 atm.
CO2 is called dry ice because at room temperature it sublimates directly from solid to gas
! without producing a “wet” liquid phase.
The phase diagram is as follows:

5
 Problem
The ice of an outdoor skating rink is at the ambient temperature of -2.5°C. Calculate in
Pa the minimum pressure (applied for example by the blade of a skate) required to melt
the ice.
At 0°C, the specific volume of water is 1 cm3/g and that of ice is 1.090 cm3/g. The heat of
fusion is 333.5 J/g

Answer
Ice is less dense than water therefore increasing pressure lowers the melting temperature.
The problem asks to find the pressure where ice will melt at -2.5°C=270.5 K.
We know that at 1 atm and 273 K water and ice are in equilibrium. We use the Clausius
equation to calculate the pressure variation of the melting point:
dP "H s#l "H s#l 270.5 dT
=
dT T"Vs#l
$ "P = %
"Vs#l 273 T
333.5J /g $ 270.5 ' 7
P1 = P0 + "8 3
ln& ) = 3.42 #10 Pa * 337atm.
"9 #10 m /g % 273 (
!

6
 Problem
Pure ice, initially at -2°C, is compressed adiabatically and reversibly until it melts.
1) Sketch on a P/T phase diagram how you would find the solution (i.e. the path of the
compression and show on the diagram how you would identify the melting pressure and
temperature graphically). (10 points)
2) Calculate the temperature and pressure at which melting starts? (20 points)
To solve this problem you will need a few approximations:
- The temperature ranges are small enough that the molar volume of water is
approximately constant (be careful, this is not the same as stating that α=0~)
- Remember that ln(1-x)~-x if x<<1

CP=2 kJ.kg-1.K-1; ρ =920 kg.m-3; α =150 ppm.K-1, Lm=334 kJ.kg-1,

ιχε ιχε

ρwater=1000 kg.m-3, β~0

# "P &
Hint: to solve question 2, you may find useful to calculate % (
$ "T ' S

Answer
1) The adiabatic and reversible compression heats the solid. In a P-T phase diagram, the
! line.
compression path will intersect the S/L equilibrium

2) The simplest way of thinking about this problem is to think about finding the intercept
between two curves: the S/L equilibrium curve and the P(T) function during
compression.
The S/L equilibrium curve is given by the Clapeyron equation. You already know from
class and problem sets that it’s very steep and close to being a line. You can use the
simplest approximation to derive the P(T) function for the S/L equilibrium:
dP "hS #L
= and assume that you are interested in this function over a small range of
dT T (v L $ v S )
temperatures therefore T on the right side of the equation is approximately constant and
equal to Tm=273 K. You can also integrate this equation rigorously and you can convince
yourselves that if you are integrating over a small T interval, assuming ln(1-x)~-x takes
! you to the same result.
Hence, the equation for the S/L equilibrium line is:

7
 Lm
PS / L (T ) = P 0 + #1 (
T # Tm ) where P0 is the pressure at T=Tm: P0=1 atm. Since
Tm ( " # " S )
#1
L

ρwater>ρice, the slope is negative, as it should be.

Now we need to find PAC(T), which is the trajectory in the P/T plane during the adiabatic
! compression.
# "P &
Since the compression is adiabatic and reversible, we can write: dP = % ( dT .
$ "T ' S
Integrating this equation will give us PAC(T).
# "P & # " S &
Using a Maxwell relation, we have % ( = % (
$ "T ' S $ " V ' P
!
# "S &
We use the “recipe” discussed in class to find % ( :
$ "V ' P
# "S & # "S & # "S & # "S &
dS = % ( dV + % ( dP!= % ( [)VdT * +VdP ] + % ( dP
$ "V ' P $ "P 'V $ "V ' P $ "P 'V
# "S & !
dS = % ( )VdT + ...
$ "V ' P
I am not interested in the term in dP as what I wrote is sufficient for me to identify
! !S $
# & .
! " !V %P
# "S & C # "S & # " P & C
We have % ( )VdT = P hence % ( = % ( = P
$ "V ' P T $ "V ' P $ "T ' S T)V

# "P &
One of you noticed a much easier way to find % ( . We have seen in class that
$ "T ' S
! !
CP
dS = dT " #VdP . Therefore, S=const dS=0, from which we quickly obtain
T
# "P & C
% ( = P !
$ "T ' S T)V
! In any case, integrating this equation using the approximations allowed in the problem
and again assuming that the T interval over which we integrate is small, we get
C
! PAC (T ) = P 0 + P (T # Ti ) where P0 is the pressure when T=Ti= 271 K: P0=1 atm.
"VTi
The problem is now reduced to finding the intersection between two lines:
Lm C
PAC(T)=PS/L(T)  #1 (
T # Tm ) = P (T # Ti ) .
Tm ( " L # " S )
#1
Ti$V
!
Solving for T, I get T=271.5 K and plugging into any of the expressions for P, I get
P~225 atm.
!