Review for Mid-Term 3, 2015

Based on material in lecture notes 6-8 inclusive.

Mid-term exam will be in the recitation period,

November 23rd, 7-8:20 pm.
Split into two rooms as usual:
Engineering 143 (A-M), Frey 119 (N-Z)
Bring ID, calculator, pencil/pen, etc.

Phase Transition
A phase transition is the spontaneous transformation of one
phase into another at a characteristic T & p.
How do we know the phase of a substance at a given p and T?
Using the Gibbs energy: spontaneous processes have negative
changes in Gibbs free energy. For example, if you want to know the
most stable phase of water at a given pressure and temperature, you
can calculate the Gibbs energies for each of the phases, compare
them and pick the lowest one
Chemical potentials are equivalent to molar Gibbs energies for pure
substances, so the phase with the lowest chemical potential will be the
most stable phase

At the transition temperature and pressure the two

phases have the same chemical potential.

Phase Transition, pure substance

Heat exchange without temperature change
Constant pressure cooling curve for
a substance. Calorimetry can spot a
phase change even if there are no
outward visible changes.

A discontinuity indicates a phase

change. Heat is going towards
changing internal structure, entropy.

Temperature Dependence of a Phase

Recall

dG = SdT Vdp
G

= S
T p

d = S m dT V m dp
G m

= Sm
T p

= Sm
T p

S m ( s ) Sm (l ) S m ( g )

Phase Diagram
Phase Diagram: Shows regions of pressure and temperature where
phases are thermodynamically stable
Phase Boundaries: Separate regions and show p and T where two
phases exist in equilibrium
Critical Point (liquid and
vapor have same density)

Sublimation
Fusion
Liquefaction

Triple point,
3 phases in equilibrium
5

How to find a Phase Boundary?

The thermodynamic criterion of equilibrium is:
At equilibrium, the chemical potential of a substance is the same
throughout a sample, regardless of how many phases are present

If amount dn is transferred from 1 to 2, Gibbs

energy changes by 1dn in location 1 and by
+2dn in location 2

dG = 2 1 dn
If 1 > 2, G is negative, process is spontaneous
If 1 = 2, no change in G, system at equilibrium
1 (p,T)= 2(p,T) p = p(trans)

How to find a Phase Boundary?

Since
So

d = S ,m dT V ,m dp
d = S , m dT V , m dp
We have
d d = S , m S ,m dT V ,m V , m dp
= trs S m dT trsV m dp = 0

How to predict the

phase boundary?

d= d
d- d= 0

So

H
dp trs S m
= trs m
=
dT trsV m T trsV m

exact expression for the slope of a phase boundary applies to phase equilibrium of any pure substance
7

Liquid-Vapor Boundary
Clapeyron equation

Large and positive

H
dp
= Vap
dT
T VapV
Dominated by the gas
V=RT/p
Vapor pressure

(since

d ln p Vap H
=
dT
RT 2
ln p f ln p i =

dx
= d ln x)
x

Clausius-Clapeyron Equation.
Integrate:

Vap H 1
1 Approximate, because
weve assumed pV=nRT

R T f Ti

Clapeyron Equation Example

Calculate the slope of the solid-liquid phase boundary curve for
benzene. At the melting point (278.7 K) at one atmosphere pressure:

fus H m (benzene) = 9.95kJ.mol 1

fusVm (benzene) = 10.3cm3 .mol-1
From:

dp trs H m

=
dT T trsVm

0.08206dm 3 .atm.mol-1.K -1
dp
9950J.mol 1

=
3
3
dT 278.7K 10.3 10 dm
8.314J.mol -1.K -1

solid
p

liquid

= 34.2 atm.K -1

very steep!

Vapor Pressure Example

Find the vapor pressure of a liquid at some temperature

At normal boiling point, the vapor pressure is one atmosphere.

For benzene, T* (b.p.) is 80 C, 353 K. vapH = 30.8 kJ mol-1. What is
the vapor pressure at 20 C, 293 K?

ln p f ln p i =

ln p f ln(1.0) =

p f = 0.117 atm

Vap H 1
1

R T f Ti

30800 1
1

8.314 293 353

UNITS!

or, about 90 torr

Clausius-Clapeyron Example
For water vapH = 40.65 kJmol-1 and the normal boiling
point (at one atm) is 373.15 K. At what temperature does
the vapor pressure of liquid water equal 380.0 Torr?

ln p f ln pi =

vap H 1 1

R T f Ti

1atm = 760 Torr, 380 T = 0.5 atm

Find Tf = 354.3 K

Vapor pressure at different T?

Whats the vapor pressure of water at 25 C and 1 atm?
Clausius-Clapeyron Eqn. Lets find

H 1 1
ln( p f / pi ) = vap the vapor pressure at 298.15K. We
R T f Ti have vapH (100 C) = 40.7 kJmol-1 for
H2O(l).

ln( p298 / 1) =

40700 1
1

8.314 298.15 373.15

So p298.15 = 0.03688 atm or 28.03 torr

= 3.3001

How does this change when the pressure changes from 1 to 10 atm?
Need to think about how the chemical potential changes with pressure.
For a gas (ideal):
For a liquid:

d ( g ) =

RTdp
p

d (l ) = Vm dP
Where dP is the applied P

Vapor pressure change with T (contd)

Liquid and vapor in equilibrium, we can equate these

eqns.
d ( g ) =

Integrate:

RTdp
= d (l ) = Vm (l )dP
p

RT ln ppp

f
i

pf

pf

RTdp
p p = p Vm (l )dP
i
i

= Vm (l )P

Here, we have pi = 28.03 torr, Vm= 18.069 cm3 and we increase pressure
from 1 to 10 atm.

p f 18.069 10 6 101.325 103 9

=
ln
= 0.006647
8.314 298.15
28.03
p f = 28.03 1.006669 = 28.22 torr
Quite a small change!
(Increase)

Example

Clapeyron Equation:

dp
H
= sub
dT ( sub ) T subV

etc.

dp trs S
H
=
= trs
dT trsVm
T trsVm

Example, Contd
dp
dT ( sub )
dp
dT ( vap )

dp
dT ( sub )
dp
dT ( vap )

sub H vapV

vap H subV

subV = vapV =
volume of gas

sub H (40.7 6.0) kJ/mol

=
= 7.78
vap H
6.0 kJ/mol

Mixtures
Energy of simple mixture: non-reactive, binary

Change of due to mixing

A = *A ?

Changes in chemical potential in the mixture

drive all processes.
Liquids, solutions, Raoults and Henrys laws.
Component A conventionally the solvent, B the solute. Ideal,
Ideal Dilute solutions.
Approach this material from several angles...
16

Generalized fundamental equation

At constant n

dG = SdT Vdp

At constant p,T

dG = Adn A B dnB ...

Combining the two

dG = SdT Vdp Adn A B dnB ... G

n A T , p , S ,V

= A

However at constant T, p, dG also equal to maximum non-expansion work

dwadd ,max = Adn A B dnB ...

This work can be achieved by chemical rxn, e.g. via a battery.
Electrical work results from changing chemical composition.
Similarly:

dU = TdS pdV Adn A B dnB ...

Then:

= A
n A S ,V , nB ,T ... 17

Gibbs-Duhem Equation
Since G = n A A nB B and the J depend on composition, for a
binary mixture G may change by

dG = d n A A d nB B = A dn A B d n B n A d A n B d B
However, we know that

G
G
dG =
dn A
dnB = Adn A B dnB
n A
n B

So nAd A nBd B = 0
Gibbs-Duhem Equation
(for a binary mixture at constant p, T)

It is true for any molar quantities, for binary mixture, we have

n
n
d A = B d B
dVA = B dVB .....etc
nA
nA
More general form of G-D Eq. is

SdT Vdp n j d j = 0
j

http://en.wikipedia.org/wiki/Gibbs-Duhem_relation

18

Gibbs-Duhem Equation

nAd A nBd B = 0
Gibbs-Duhem Equation
(for binary mixture at constant p, T)

Significance is that the chemical potential of one component of

a mixture cannot change without affecting the chemical
potentials of the other components.

http://en.wikipedia.org/wiki/Gibbs-Duhem_relation

19

Review: Partial Molar Quantities

Concept of partial molar quantity and the relation can be applied to
any extensive state function: G, A, H, U, V, S, Cp etc at constant T,p
Integral

V=nAVA+nBVB+..
G=nAA+nBB+..
S=nASA+nBSB+..
Mass

M=nAMA+nBMB+..

http://www.chem.neu.edu/Courses/1382Budil/PartialMolarQuantities.htm

10

Chemical Potential and Mixing

Change of due to mixing
General expression of Gibbs energy for mixture

Gi = n A A* nB B* G f = n A A nB B nAd A nBd B = 0

What is the difference between in its pure state (J* )and in

mix (J) ?
*

p
J = RT ln J*
pJ
*
J

Ideal solution, J = J RT ln xJ

*
o
Real solution A = A RT ln a A = A RT ln a A

Chemical potential drops for mixture

Gibbs-Duhem
At const T, p

B = B* RT ln

KB
a B = Bo RT ln a B
p B*

What is the standard Gibbs energy change for mixing?

mixG ideal = nRT x A ln x A xB ln xB

Use excess function G E = mixG mixG ideal

21

Real solutions
Summary, more details later

(chi) is the mole fraction here.

22

11

G-D equation, Rauolt, Henrys Law

p = p x
p
= a =x
p*
p
=a = x
K

Treat as solvent
Treat as solute

How to find?

A = *A RT ln

pA
p*A

B = B* RT ln

pB
pB*

n Ad A n B d B = 0
x Ad A x B d B = 0

Using GibbsDuhem relation

xA

d B
d B
= xB
dx B
dx B

Goal-I
Change of due to mixing
General expression of Gibbs energy for mixture

Gi = n A A* nB B* G f = n A A nB B nAd A nBd B = 0

Gibbs-Duhem
At const T, p

What is the difference between in pure state ( )and in mixture () ?

A = A* ?
component
A in solution

pA
*
pA

A = A* RT ln
component
A pure liq.

At equilibrium, the chemical potential of each

component has the same value in each phase
where it is present

component A above
soln. and above
pure liq. (ideal gas
assumed)

How to express this in terms of mole fractions: xA, xB,

as we did for ideal gas mixtures?

24

12

Ideal solution: Raoults Law

Ideal solutions obey Raoults Law:

p A = x A p*A or

pA
= xA
p *A

pA*

i.e. the partial vapor pressure relative to

p* equals the molar fraction in the liquid.

pA
*
pA

A = *A RT ln

= *A RT ln x A
mole fraction in liq.

Ideal solutions: both solute and

solvent obey Raoults Law

Mixture of benzene and toluene

25

Raoults Law Example

The vapor pressure of benzene is 53.3 kPa at 60.6 C but it fell
to 49.2 kPa when 51.2 g of an involatile organic compound was
dissolved in 500 g benzene. Calculate the molar mass of the
compound, assume the solution is ideal.

pB = xB pB* and xB =

nB
nB n A

where B = benzene and A

= solute

Hence:
n p*
n ( p* pB )
pB = B B or nA = B B
nA nB
pB

MA =

m A pB
M B mA pB
=
*
nB ( pB pB ) mB ( pB* pB )

nA =

mA
MA

Subs. In:
MA=96.0 g mol-1

13

Vapor Pressure Example

Consider a mixed solution of 1-propanol (1) and 2-propanol (2). Its
ideal at all concentrations. Given p1*=20.9 torr, p2*=45.2 torr at 25 C,
calculate the total vapor pressure and composition of the vapor for
x2=0.75 at this temperature.
Ideal, so p(total) = p1 + p2 = x1p1* + x2p2*
= (0.25)(20.9) + (0.75)(45.2) = 39.1 torr
Daltons law of partial pressures:
y1(mole fraction of 1 in vapor) = p1/p(total) = x1p1*/p(total)
= (0.25)(20.9)/(39.1) = 0.13
Similarly y2 = (0.75)(45.2)/(39.1) = 0.87
Note: y1+y2=1 and the vapor has more of the more volatile component

Another example
The Henrys law constant for a solute B in a solvent A is

8.21x103 kPa. What is the vapor pressure of B in a

solution of molality = 0.25 mol/kg? The molar mass of
the solvent A is 74.1 g/mol.

pB = xB K B
pB = bB K B

Weve been given K in mole fraction (pressure)

units and we need to convert it to solve the
problem.

0.25 mol/kg is 0.25 moles of B in 1000g of A. 1000g of A

contains 1000/74.1 or 13.5 moles. Mole fraction of B is hence

xB = 0.25

(0.25 13.5)

Therefore

= 0.0182.

p B = xB K B

pB = 0.0182 8.21103 = 149 kPa

14

Departure from Raoults Law & Ideal Dilute Solutions

When mixture components are structurally different, see strong
deviation from Raoults law. But when
1) The major component is nearly pure (its x1), it still obeys Raoults law
2) The minor component is nearly absent (its x0), its pressure obeys Henrys law
then this solution is called an ideal dilute solution.
Note: even when solute x 0, some solutions do not follow Henrys law

KB is some empirical
constant
29

Henrys Law
For real solutions at low concentrations,
although the vapor pressure of the solute is
proportional to the mole fraction, the
constant of proportionality is not the vapor
pressure of the pure substance

pB = x B K B

when xB 0, K B pB*

KB is a measured slope as xB0 with

dimensions of pressure.
The solute behaves entirely differently from when its pure state,
since its molecules are surrounded by solvent molecules.
For an ideal-dilute solution: the solvent obeys
Raoults law and the solute obeys Henrys law
30

15

Units
Henrys law constants are often expressed in terms of

molality:

Molality is the molar concentration per mass of

solvent, has units of moles/kg.

Compare Molarity, the molar concentration per

volume and has units of moles/dm3, for example.
B (solute) pB = xB K B

B (solute)

pB = bB K B

Mole fraction is dimensionless, KB has

units of pressure.
Molality bB has dimensions of mol kg-1,
KB has units of Pa.kg.mol-1

Henrys Law Example

The mole fraction of CO2 in the atmosphere has risen from
0.000314 in 1960 to 0.000397 in 2013. Use Henrys law to
calculate the change in concentration in the oceans (in molality)
at 25 C, assuming K(CO2) = 3.01x103 kPa.kg.mol-1 in water at
25 C.
Henrys Law: pB = bBKB (concentration in molality)
The partial pressure of solute in vapor is its concentration in solution times
its Henrys law constant. So:
p(CO2)= 0.000314 x 101.3 kPa = 0.0318 kPa.
b(CO2) = 0.0318 kPa/ (3.01x103 kPa.kg.mol-1) = 0.01057x10-3 mol.kg-1
For the higher concentration:
p(CO2)= 0.000397 x 101.3 kPa = 0.0402 kPa.
b(CO2) = 0.0402 kPa/ (3.01x103 kPa.kg.mol-1) = 0.01336x10-3 mol.kg-1
Increase of about 26%.

16

More detailed summary for real solution

Ideal dilute solution: xA1 and xB0
pB = xB K B
p
K x
B = B* RT ln B* = B* RT ln B * B
pB
pB

p A = x A p *A
p
A = *A RT ln *A = *A RT ln x A
pA
o
= A RT ln x A where Ao = *A

= Bo RT ln xB

Solvent

o
*
where B = B RT ln

pA
= aA = A xA
p*A

KB
p*B

Activity: a A
Activity coefficient: A

A = *A RT ln a A = *A RT ln A x A
Standard state

Limiting behavor

Ao = *A
Solute

As x A 1, a A x A , A 1

pB
a
= aB = B xB Activity: B
Activity coefficient: B
KB

B = Bo RT ln aB = Bo RT ln B xB
Standard state

The activity is an effective mole fraction

Bo = B* RT ln

KB
pB*

Limiting behavor

As xB 0, aB xB , B 33
1

The Validity of Raoults & Henrys Laws

Can you read the figure?

34

17

Colligative Properties

Increase of boiling point

Eq. of solvent: in pure g & mix l

Solubility
(dissolve salt in water)

A, g (T ) = A, l (T ) RT ln x A

Eq. of solute in: pure s & mix l

B , s ( T ) = B , l (T ) RT ln x B

A, s (T ) = A,l (T ) RT ln x A

Osmosis

Decrease of freezing point

Eq. of solvent in: pure s & mix l

(water purification)
Eq. of solvent in: pure l & mix l

*A , ( p ) = *A , ( p ) RT ln x A

The simplest example is 1+2 system:

(1) a pure solvent phase, which may be vapor, liquid, or solid
(2) a solution phase.
(3) an interface between the two phases that is not crossed by the solute

There is no reference in these properties to the identities of the

solutes and/or solvents - strictly dependent upon composition
35

Chemical Potential of Solvent

Presence of solute decreases
(solvent), resulting in reduced
freezing point and increased boiling
point.
It is an entropy effect, because it
occurs even for ideal solutions. When
solute is present, there is an
additional contribution to the entropy
of the liquid. Hence a smaller change
in entropy on vaporization.

For b.p. change, look for the temperature at which chemical potentials
of vapor and solvent molecules are the same at 1 atm pressure. Same
for melting

18

Elevation of Boiling point

Pure liquid:
In solution:

*A, g (T * ) = A,l (T * )

vap (T * ) = 0

Al (T ) = A*l (T ) RT ln xA = *A g (T )

ln xA =

vap (T )
RT

Gibbs-Helmholtz equation:

H

T T = T 2
p
Integral:

H

vap = vap 2 m
T
T T p

H
d ln x A
= vap 2
dT
RT

vap (T ) vap (T * )
1 1
H

= vap Hm * ln xA = vap m 1 1
T
T*
T
T

R T T*

Boiling at T*

Further simplification gives:

xB

vap H m T
RT *2

T = Kx B ; K =

constant, K

T = KxB ; K =

RT *2
vap H m

See
justification
5.1
37

Depression of freezing point

RT *2
fus H m

Boiling at T

T = K b b ; K b =

RT *2
fus H m A

(same ideas)

A =mol/kg for
solvent

T depends on the solvent, change is biggest for solvents with high boiling
points. For practical applications, mole fraction of B is proportional to molality, b
(mol kg-1), in dilute solutions, and Kb is the empirical boiling-point constant

*
A, g

boiling
(T ) = A,l (T ) RT ln x A

Same argument applies also for freezing

*A, s (T ) = A,l (T ) RT ln x A

T = K f b; K f =

RT *2
fus H m A
39

19

Osmosis

solvent
particle

= gh

*A,( l ) ( p ) = A,( l ) ( p )
=

*
A,( l )

What is in balance?

( p ) RT ln x A

p+

A+B

*A,( l ) ( p ) *A,( l ) ( p) =

V dp V
m

Vant Hoff Eq.

= B RT

Vm = RT ln xA RTxB

xB=nB/nA, approx.

Similarities
Liquid(solid)/vapor
Clausius-Clapeyron equation for
sublimation or vaporization

Solution/vapor:boiling point
Applicability: dilute solution

Solution/solid:freezing point
Applicability: dilute solution

Solution/solid: solubility
Applicability: dilute solution

Solution/solvent: osmosis
Vant Hoff equation
Applicability: dilute solution

vap
T

= R ln

p
po

p
po

d ln p vap H
=
dT
RT 2

= R ln x A

H
d ln x A
= vap 2
dT
RT

*A , (T , p ) = A , (T , p ) RT ln x A
d ln x A fus H
=
dT
RT 2

(T )
con (T )
= fus
= R ln x A
T
T

B* , ( T , p ) = B , ( T , p ) RT ln x B

40

*A , (T , p ) = A , (T , p ) RT ln x A
vap (T )

= molar concn.

A, (T , p) = Ao, (T , po ) RT ln

B = nB / V

(T )
con (T )
= fus
= R ln x B
T
T

d ln x B fus H
=
dT
RT 2

*A , ( p ) = *A , ( p ) RT ln x A
= *A , ( p ) V m RT ln x A
V m = RT ln x A RTx B

20

Quiz (9th November, 2012)

What is the freezing point of a 0.2 molal solution of
sucrose in water? [fusH (H2O)=6.02 kJmol-1,
Tfus(H2O)=273.15K]
What is the value of Kf for an organic solvent, molar mass
= 84g, whose Tfus= 279.6 K and fusH = 2.68 kJ mol-1? If a
0.2 molal solution of hexane in this solvent was prepared,
calculate the freezing point depression.

Solutions
Approximate for small T-T* and small xB, then:

RT *2
T =
x B = K f xB
fus H m
This is our working equation. But we see the amount of solute is given in
mole fraction here, and we need to convert to molal concentration, i.e. mB
moles/kg of solvent. Remember:

xB =

mB
1000

MA

T = K f

mB

mB M A
For dilute solutions, where MA is the molar
1000 g kg -1
mass of the solvent in g and mB << 1000/MA.

MA
mB
1000

21

Solutions, Contd
Now we can just substitute in the information we have:.
We find the freezing point depression in a 0.2 molal solution of sucrose is -0.37 K,
so the freezing point is 273.15 - 0.37 = 272.78 K.

For the organic solvent, we find

Kf = 8.314 x 279.62/2680 = 242.5 K
For 0.2 molal solution, T = 0.2x242.5x84/1000 = 0.2x20.3 K = 4.1 K, so
Tfus = 275.5K

Example
The addition of 100g of a compound (A) to 750g of CCl4 (B)
lowered the freezing point of the solvent by 10.5K.
Calculate the molar mass of the compound.
Note: Kf (CCl4) = 30 K kg mol-1

m
MB = B
nB

Depression of freezing point :

T = K f b
Kf =

nB = m AbB

RT *2
fus H m A

b is molality (mol/kg) of solute,

A=mol/kg of solvent

Hence:

MB =

mB K f
m A T

and M B =

100g (30K kg mol 1 )

= 3.8 102 g/mol
0.75kg 10.5K

22

Solubility example
The enthalpy of fusion of napthalene is 18.80 kJ mol1 and its melting
point is 81C. Calculate its ideal solubility in benzene at 25C.
Naphthalene dissolves until its chemical potential equalizes in the solution
and the vapor. Hence we can use the Gibbs-Helmholtz/modified ClausiusClapeyron equation:
fus H 1 1 18.8 103 1
1

* =

= 1.20
R T T
8.314 354.15 298.15
B here is the solute,
xB = e 1.20 = 0.301
naphthalene

ln xB =

Assume x(Nap) n(Nap)/n(Bz), so in 1000 g of solvent:

n(Nap) (0.301)(1000/78) = 3.85 mol. Hence molality is 3.85.
M(Nap) = 128 g, so 3.85 mol = 493 g in 1000g benzene.
Actually, xB=0.3 corresponds to closer to 5.5 mol/1000g

Constituents and Components

Constituent: A chemical species that is present in a system. For example,
a mixture of water and ethanol has 2 constituents
Component: A chemically independent component of the system. The
number of components in a system, C, is the minimum
number of independent species needed to define the
composition of all of the phases present in the system
Number of Phases, P = 2
Number of Constituents = 3
Number of Components, C = 2*
*CaCO3 can be expressed in terms of 2 components in two different
phases from the stoichiometry of the reaction

When no reaction takes place, Constituents = Components

When a reaction can occur, the number of components is the
minimum number of species which specifies the composition
of all of the phases (or: smallest number of independently variable
chemical species to describe the composition of each phase)

47

23

Examples
Consider the thermal decomposition of ammonium chloride:
Number of Phases, P = 2
Number of Constituents = 3
Number of Components, C = 1*
*NH3 and HCl are fixed in stoichoimetric proportions by the reaction, and
compositions of both phases can be specified by NH4Cl
N.B., if additional HCl or NH3 were added to the system, decomposition
of the NH4Cl would not give the correct gas phase compositions, and
either HCl or NH3 would be invoked as a 2nd component

Number of Phases, P = 2
Number of Constituents = 3
Number of Components, C = 3*
*At room temperature, O2 (g) and H2 (g) do not react to form water, so
they are not in equilibrium: regarded as independent constituents

48

Variance and Degrees of Freedom

The variance, F, is the number of intensive variables in a system that
can be changed independently without disturbing the number of phases
in equilibrium.
In a single-component, single-phase system (C=1, P=1) the pressure
and temperature may be changed independently without disturbing the
number of phases in equilibrium:
F = 2, system is bivariant, or has two degrees of freedom
If two phases are in equilibrium in a single-component system (C=1,
P=2) (e.g., a liquid and its vapor), the temperature (or pressure) can be
changed, but there must be an accompanying dependent change in
pressure (or temperature) to preserve the phases in equilibrium
F = 1, system has one degree of freedom
If three phases are in equilibrium (C=1, P=3) (e.g.: s, l and g), neither the
T nor p can be changed, otherwise the equilibrium is not preserved.
F = 0, system has no degrees of freedom

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24

Phase Rule

By J. W. Gibbs

Degrees of freedom for several phases in equilibrium

F =CP2
1. Count the number of intensive variables (p and T count as 2)
2. Specify composition of the phase by mole fractions of C-1 components
x1, + x2, ++ xC,=
Since there are P phases, total number of composition variables is P(C - 1),
and total number of intensive variables is P(C - 1) + 2
3. At equilibrium, chemical potential of J must be same in every phase
J, = J, = .... for P phases
There are P - 1 equations of this kind for each component J. If there are C
components, total number of equations is C(P - 1)
4. Each equation reduces our freedom to vary any of the P(C - 1) + 2 intensive
variables, so the number of degree of freedom is
F = P(C - 1) + 2 - C(P - 1) = C - P + 2
50

Understand the changes given phase diagram

Consider pure water

What happens going from a to e?

a In gas phase, cooled at constant p, F = 2
(for fixed p, F=1,T can be varied at will)
b Liquid appears at the phase transition
(at Tb), and F = 1. (for fixed p, F=0, T = Tb)
c Lowering T takes liquid to single phase
liquid region, F = 2, (for fixed p, F=1,T
can be varied at will)
d Liquid-solid phase transition at Tf, with
F =1, and at constant p, T is not under our
control
e Lowering T further results in single solid
phase with F = 2, (for fixed p, F=1,
T can be varied at will)
51

25

Two Component System

Liquid B

Liquid/Vapor pressure diagrams (at fixed T):

p&x are free variable for single phase
Only one variable along phase boundary, x or p

Liquid

Liquid A

For two component system, C = 2, and F = 4 P.

3 free variables for single phase, use T, P, x (mole fraction).
If either T or p is held constant, remaining variance is F = 3 P, 2 variables
Phase diagrams of P & x for stable phases at constant T
Phase diagrams of T & x for stable phases at constant p

As xA goes from 0 to 1
p<pB*

What is p= p(x)?

p>pA*
Vapor B

A(g)+B(g)
A(g)+B(g)
A(l)+B(l)

Vapor

Vapor A

pB*<p<pA*

A(l)+B(l)

52

Liquid/vapor boundary of 2 Component System

What is p= p(x)?

Vapor pressure diagrams:

Partial pressures of components of an ideal solution of two volatile liquids are related
to the composition of the mixture by Raoults Law

p A = x A p *A

= x

*
B

Total vapor pressure is

p = pA + pB = xApA* + xBpB* = pB*+ (pA*-pB*)xA
i.e., linear variation of vapor pressure at fixed T with changed composition

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26

Composition of the Vapor

Compositions of liquid and vapor in equilibrium are not necessarily the
same, vapor should be richer in the more volatile component

pA = y A p

A(g)+B(g)

pB = y B p
A(l)+B(l)

For an ideal mixture, partial pressures may be expressed in terms of

mole fractions in the liquid (see equations on previous page)

yA =

x A p*A
,
p ( p*A pB* ) x A
*
B

yB = 1 y A

If pA*>pB*, yA>xA (vapor richer in

more volatile component).
The total vapor pressure as
composition of the vapor:

p=

p*A pB*
p*A ( p*B p*A ) y A
54

Combining the Vapor & Liquid diagrams

Better understand the phase transition between vapor and liquid by combining
the two previous diagrams into one. The horizontal axis shows the overall
composition, zA, of the system:
Liquid & vapor
coexist

p=

p = pB* p*A pB* x A

p*A pB*
p*A ( pB* p*A ) y A
p
A(g)+B(g)

A(l)+B(l)

55

27

What happens as p is varied

All points above the solid diagonal correspond to a system under high pressure where
there is only a liquid phase (zA = xA, composition of liquid)
All points on lower curve correspond to a system with low pressure where only the
vapor phase exists (applied pressure less than the vapor pressure, so zA = yA)
Points between lines are systems where two phases exist: 1 liquid & 1 vapor
pA*

Line of constant overall composition: isopleth

pB*
56

Interpretations of the Diagrams

The horizontal axis shows the overall composition, zA, of the system:
p<p3
p3<p<p1
p>p1
A(g)+B(g)
A(g)+B(g)
A(l)+B(l)

aa1

A(l)+B(l)

a 1 a 2 a 3

a 3 a 4

Lowering the pressure on a liquid by drawing out a piston:

start at point a: Here, F = 2 and P = 1; only the liquid phase exists; changes to system
do not affect overall composition, so system moves down vertical line that passes
through a, until point a1 is reached (pressure reduced to p1)
57

28

The Lever Rule

Can get n/n

T-x and p-x diagrams summary

58

p,T diagram

2 component system: F=2+2-Phase

Variables: p, T, x
p,T,x
A(g)+B(g)
A(l)+B(l)

xA,yA,zA
p,x diagram

T,x diagram
TB*

TA*
59

29

Critical Solution Temperatures

Tuc

60

Critical Solution Temperatures, contd

Weak compound

61

30

Phases
a. Ideal solution behavior.
b. A low (T)-boiling azeotrope
c. A eutectic point
d. Congruent melting
e. Incongruent melting
f. Partial miscibility in 1 or more phases
g. Compound formation
h. Complete miscibility in all phases

A+AB

L+AB
L+ B
AB+B

Solid-Liquid Phase Diagrams

Compound
Eutectic Point
formation
for A+A2B
system

peritectic point
L+B
AB2 melts

L+A

L+A2B

AB2+B

AB2

A2B

Peaks represent
compound formation.
Increasing temperature
(up) along dotted line
includes incongruent
melting as it crosses the
horizontal line. Here the
AB2 melts but there is
excess B, so the melt
contains L and B (solid).

A2B+AB2

31

Completely Miscible Solids

Looks like a gas/vapor diagram, but now solid/liquid

T,x diagram
TB*

liquid

Liquid and solid in equilibrium with

Proportions given by lever rule

solid

TA*

32