Chapter 6

Chemical Potential in
Mixtures

Partial molar quantities

Thermodynamics of mixing
The chemical potentials of liquids

Chapter 7 : Slide 1

Duesberg, Chemical Thermodynamics

 Concentration Units
• There are three major concentration units in use in
thermodynamic descriptions of solutions.
• These are
– molarity
– molality
– mole fraction
• Letting J stand for one component in a solution (the
solute), these are represented by
• [J] = nJ/V (V typically in liters)
• bJ = nJ/msolvent (msolvent typically in kg)
• xJ = nJ/n (n = total number of moles of all species
present in sample)
 PARTIAL MOLAR QUANTITIES

Recall our use of partial pressures:

p = xA p + x B p + …

pA = xA p is the partial pressure

For binary mixtures (A+B): xA + xB= 1

We can define other partial quantities…

Chapter 7 : Slide 3

Duesberg, Chemical Thermodynamics

 PARTIAL MOLAR QUANTITIES: Volume

In a system that contains at least two substances, the total value of

any extensive property of the system is the sum of the
contribution of each substance to that property.

The contribution of one mole of a substance to the volume of a

mixture is called the partial molar volume of that component.

V  f  p, T , nA , nB ...
 V 
VA   
At constant T and p  n A  p ,T ,n  A
 V   V 
dV   dn A   dnB  ...
 n A   nB  Chapter 7 : Slide 4

Duesberg, Chemical Thermodynamics

 Partial molar volume
Add nA of A to mixture

Very Large Mixture of A and B

When you add nA of A to a large mixture of A and B, the composition remains

essentially unchanged. In this case: VA can be considered constant and the volume
change of the mixture is nAVA.  
V

VA     const
 n A  p ,T ,n  A
Likewise for addition of B.
The total change in volume is nAVA + nBVB . (Composition is essentially unchanged).
Scoop out of the reservoir a sample containing nA of A and nB of B its volume is
nAVA + nBVB . Because V is a state function:
V  VAnA  VBChapter
nB 7 :...
Slide 5

Duesberg, Chemical Thermodynamics

 Partial molar volume

Example: What is the change in volume of adding 1 mol of water to a

large volume of water?

The change in  V 
VH 2O    18cm3
volume is 18cm3  nH O 
 2  p ,T

A different answer is obtained if we add 1 mol of water to a large volume

of ethanol.

The change in  V 
VH 2O    14cm3
volume is 14cm3  nH O 
 2  p ,T ,n ( CH 3CH 2OH)
Chapter 7 : Slide 6

Duesberg, Chemical Thermodynamics

 Introduction to mixtures
 Homogeneous mixtures of a
solvent (major component) and
solute (minor component).
 Introduce partial molar property:
contribution that a substance makes
to overall property.

V = nAVA + nBVB
VA is not generally a constant: It
is a function of composition,
because the environment and
therefore their interaction of the The partial molar volumes of water
molecules changes with the and ethanol at 25C. Note the different
composition . scales (water on the left, ethanol on
: the right).
 Exercise
Calculate the density of a mixture of 20 g of water and 100g of ethanol.
MM: EtOH: 46.07g/mol d=0.789 g/ml
• First calculate the mole fractions.
– 20 g H2O = 1.11 mol;
– 100 g EtOH = 2.17 mol
– xH2O = 0.34; xEtOH = 0.66
• Then interpolate from the mixing curve
– VH2O = 17.1 cm3 mol-1;
– VEtOH = 57.4 cm3 mol-1
• Then plug the moles and partial molar
volume
– (1.11 mol)(17.1 cm3/mol) + (2.17
mol)(57.4 cm3/mol) =18.1 cm3 +
125 cm3 = 143.1 cm3
• Finally, the total mass is divided by the
total volume: 120 g/143 cm3 = 0.84 g/
cm3
Task:You mix 300 ml alcohol with a bottle of juice (water, 0.7 l) - Will you
really end up with for your x-mas party supply (1l)? -Of course not…
- How much do you have to mix to get 1 l of the same strength?
 PARTIAL MOLAR QUANTITIES
VA is not generally a constant: It is a function of composition, because
the environment and therefore their interaction of the molecules changes with the composition
:

The partial molar volume of a substance is the slope of the variation of the total volume of
the sample plotted against the composition. In general, partial molar quantities vary with
the composition, as shown by the different slopes at the compositions a and b. Note that
the partial molar volume at b is negative: the overall volume of the sample decreases as a is
Chapter 7 : Slide 9
added.
Duesberg, Chemical Thermodynamics
 PARTIAL MOLAR QUANTITIES
• We can extend the concept of partial molar properties to state
functions, such as Gibbs energy, G. Or Chemical Pot m
G = nAGA + nBGB or G = nAmA + nBmB

Consider this single substance system:

m1 m2

dG = -m1 dn dG = +m2 dn

Total dG = 0 only if m1 = m2
10
 The Partial Molar Gibbs Energy
The partial molar Gibbs energy is called the “chemical potential”
G  f  p, T , nA , nB ...
At constant T and p

 G   G   G 
dG   dn A   dnB  ... μ A   
 n A   nB   n A  p,T,n  A
dG  m AdnA  mB dnB  ... G = nAµA + nBµB
(At equilibrium dG = 0)

The implication of G = f ( p,T, ni ) is that we now write:

dG  SdT  Vdp  m AdnA  mB dnB  ...
Fundamental
dG  SdT  Vdp   mi dni Equation of Chemical
Thermodynamics.
Chapter 7 : Slide 11

Duesberg, Chemical Thermodynamics

 Chemical Potential = Partial Molar Gibbs Energy

In case of constant
temperature and pressure

dG  SdT  Vdp   mi dni

reduces to:

dG   mi dni

The chemical potential of a substance is the slope of the total Gibbs energy
of a mixture with respect to the amount of substance of interest. In
general, the chemical potential varies with composition, as shown for the
two values at a and b. In this case, both chemical potentials are positive.
Chapter 7 : Slide 12

Duesberg, Chemical Thermodynamics

 The Wider Significance of the Chemical Potential

 G   G 
dG   SdT  Vdp     dni  
 ni T , p ,n j  ni T , p ,n j

 H 
dH  TdS  Vdp     dni
 ni  S , p ,n j  H   A 
 
 ni  S , p ,n j
mi  
 ni T ,V ,n j
 A 
dA   SdT  pdV     dni
 ni T ,V ,n j
 U 
 
 U   ni  S ,V ,n j
dU  TdS  pdV     dni
 ni  S ,V ,n j
All extensive thermodynamic properties change with composition!
Chapter 7 : Slide 13

Duesberg, Chemical Thermodynamics

 Chemical Potential
In case of constant temperature
dwadd,max  dG   mi dni
and pressure also:


Example: E-chem cell: dwchem   m j dn j "chemical work"
j

dU  TdS  PdV   m j dn j  U   H 
j mi     
 
 i  S ,V ,n j i  i  S , P ,n j i
n n
dH  TdS  VdP   m j dn j
j
 A   G 
dA   SdT  PdV   m j dn j     
j  ni T ,V ,n j i  ni T , P ,n j i
dG   SdT  VdP   m j dn j
j
 The Gibbs-Duhem Equation
dG  m1dn1  m2 dn2  ...

G  m1n1  m2 n2 (For binary systems)

by differentiating:
dG  m1dn1  m2 dn2  n1dm1  n2 dm2
At equilibrium: dG = 0 recall in case of constant temperature
and pressure dG   mi dni => m1dn1 + m2dn2 = 0

 0  n1dm1  n2 dm2 The Gibbs-Duhem Equation. Mixtures

can not be change independentely: If
or 0   ni dmi one is changed the other changes as
n2 well…
or dm1   dm 2 A similar expression may be deduced
n1
Chapter 7 : Slide 15
for all partial molar quantities
Duesberg, Chemical Thermodynamics
 The Gibbs-Duhem Equation

SdT  VdP   n j d m j  0
j

Chapter 7 : Slide 16

Duesberg, Chemical Thermodynamics

 THE THERMODYNAMICS OF MIXING

Imagine a system of two perfect gases in amounts nA and nB at equal T and p

are separated by a barrier.
The initial total Gibbs energy of the system Gi is given by

Gi = nAµA + nBµB

  p 
Gi  nA  m A  RT ln 
 p 
  p 
 nB  m B  RT ln 
 
 p 
The initial and final states considered in the
calculation of the Gibbs energy of mixing of
Chapter 7 : Slide 17
gases at different initial pressures.
Duesberg, Chemical Thermodynamics
 The Thermodynamics of mixing
After mixing each gas exerts a partial pressure pJ, where pA + pB = p. The
final G is given by
  pA 
Gf  nA  m A  RT ln 
 
 p  NA, p, T NB, p, T
  pB 
 nB  m B  RT ln 
 
 p 
pA+ pB = p,T
 mix G  Gf  Gi

Duesberg, Chemical Thermodynamics

 The Thermodynamics of mixing

  pA    pB 
 mix G  Gf  Gi  nA  m A  RT ln    nB  m B  RT ln  
 p   p 
  p    p 
 nA  m A  RT ln    nB  m B  RT ln  
 p   p 

pA pB
 nA RT ln  nB RT ln
p p
NA, p, T NB, p, T

Chapter 7 : Slide 19
pA+ pB = p,T

Duesberg, Chemical Thermodynamics

 The Thermodynamics of Mixing

pA pB
Gmix  nA RT ln  nB RT ln
p p

Writing xA for the mole fraction of

nA n
component A   A
 nx n
nA = xA n therefore pA /p = xA,
(same for any component), so The Gibbs energy of mixing of two
perfect gases and (or of two liquids
that form an ideal solution). The
mixG = nRT (xA ln xA + xB ln xB) Gibbs energy of mixing is negative
for all compositions and
mixG is always negative, since x<1 temperatures, so perfect gases mix
spontaneously in all proportions.
Chapter 7 : Slide 20

Duesberg, Chemical Thermodynamics

 Gas mixtures What About the Enthalpy of
Mixing?
G = H – TS
Compare
Gmix = nRT {xAln xA+ xB ln xB}
Smix = − nR {xAln xA+ xB ln xB}
Therefore
H mix= 0

All due to the effect of entropy

21
 The Entropy of Mixing

 Δ mix G 
Δ mix S   
 T  p ,nA ,nB
 nR( xA ln xA  xBln xB )
which is positive as xA and xB are <1.

Perfect gases mix spontaneously in all proportions

Chapter 7 : Slide 22

Duesberg, Chemical Thermodynamics

 Exercise: at 25C, calculate the Gibbs energy change when the
partition is removed
(cannot used the previous one as different starting pressures)
n A  3 mol,nB  1 mol   
Gi  nA m A  RT ln p A  nB m B  RT ln pB
0 0

 3  m 0 H 2 RT ln(3 p)  1 m 0 N 2  RT ln p
p A  3 p, pB  1 p pf  2 p p f ,A  3
2 p, p f , B  12 p

  
G f  nA m A  RT ln p f , A  nB m B  RT ln p f , B
0 0

 3  m 0 H 2 RT ln( 3 2 p)  1 m 0 N2  RT ln 1 2 p

Gmix  G f  Gi  n A RT ln  p f ,A
3p
 n RT ln 
B
p f ,B
p

 3  RT ln  1 RT ln 12  4 ln 12
3
2
3

ln 1 2  0.69
Gmix  8.314 J / K  298K  4  (0,69)  6.8kJ R  8.314 J / K
T  298K
Duesberg, Chemical Thermodynamics
 Chemical Potential of Liquids
We need to know how the Gibbs energy of a liquid varies
with composition in order to discuss properties of liquid
mixtures (like solutions).

Vapor Pressure = PA* Pure Liquid Mixture Partial Pressure = PA

 
For vapor phase: For vapor phase:
m  m  RT ln
*
A

A
PA*

m A  m A  RT ln PA
P
P

At equilibrium… At equilibrium…
m *A ( g )  m *A (l ) m A ( g )  m A (l )
=A =A =B

 
For liquid phase: For solution:
m  m  RT ln
*
A

A
PA*
P 
m A  m  RT ln

A
PA
P
Combine these expressions…

24
 Total Vapour Pressure of an ideal solution

PA
m A  m  RT ln *
*
A
PA mA  mA
*
 RT ln x A
PA  x A PA
*

This serves to define an ideal solution if true for all values of xA

25
 RAOULT'S LAW
For SOME pairs of liquids, RAOULT'S LAW that
pA = xA pA* is obeyed, so (xi= moluar fraction, * for pure substance)

µA(l) = µA*(l) +RT ln pA/pA*

pA = xA pA*

µA(l) = µA*(l) + RT ln xA .
This defines an IDEAL SOLUTION)

Ptotal  PA  PB
Ptotal  x A PA*  xB PB*
Duesberg, Chemical Thermodynamics
Ptotal  PA*  xB ( PB*  PA* )
 Ideal Mixtures

• Two types of molecules are randomly distributed

• Typically, molecules are similar in size and shape
• Intermolecular forces in pure liquids & mixture are similar
• Examples: benzene & toluene, hexane & heptane

In ideal solutions, the partial vapor pressure of component

A is simply given by Raoult’s Law:
PA  x P *
A A

vapor pressure of pure A

mole fraction of A in solution

27
 The Measurement of Vapor Pressure of Solutions

Chapter 7 : Slide 28

Duesberg, Chemical Thermodynamics

 Raoult's law
Similar liquids can form an
Large spheres = solvent molecules
ideal solution obeying small spheres = solute molecules.
Raoult’s Law

A pictorial representation of the molecular

basis of Raoult's law. The solute hinder the
escape of solvent moleculesChapter
into 7the vapour,
: Slide 29 but
Duesberg, Chemical Thermodynamics
do not hinder their return
 Example

• A solution is prepared by dissolving 1.5 mol C10H8 in 1.00 kg

benzene. The v.p. of pure benzene is 94.6 torr at this
temperature (25oC). What is the partial v.p. of benzene in the
solution?
• Solution: We can use Raoult’s law, but first we need to know
the mole fraction of benzene.
• MM benzene = 78.1 g/mol, so 1.00 kg = 12.8 mol.
• xbenz = 12.8 mol / (12.8 mol + 1.5 mol) = 0.895
• pbenz = xbenz p*benz = (0.895)(94.6 torr) = 84.7 torr

Chapter 7 : Slide 30
 Deviations from Raoult’s Law
CS2 and dimethoxymethane: Positive trichloromethane/acetone: Negative
deviation from ideal (Raoult’s Law) behavior. deviation from ideal (Raoult’s Law) behavior.

Methanol, ethanol, propanol

mixed with water. Which one
is which? (All show positive
deviations from ideal behavior)

31
 Raoult and Henry
PA  x A PA* as x A  1
Raoult’s law

(Raoult’s Law)
Henry’s law

PA  x Ak H , A as x A  0
Henry’s behavior: Henry’s law constant: k H , A  PA*
 The Henry’s law constant reflects the intermolecular interactions between
the two components.
 Solutions following both Raoult’s and Henry’s Laws are called ideal-dilute
solutions.
32
 Ideal-dilute solutions
 Raoult’s law generally describes well solvent vapour pressure when
solution is dilute, but not the solute vapour pressure
 Experimentally found (by Henry) that vp of solute is proportional to its
mole fraction, but proportionality constant is not the vp of pure solute.

Henry’s Law
pB = xBKB

33
 Ideal-Dilute Solutions (Henry’s Law)
For real solutions at low concentrations i.e. xB << xA the vapor pressure of
a the solute is proportional to its mole fraction but the proportionality
constant is not pA* but some empirical constant KB

pB = xBKB Henry’s Law

In a dilute solution, the solvent molecules are in an

environment that differs only slightly from that of the
pure solvent. The solute particles, however, are in an
Chapter
environment totally unlike that of the pure7 : Slide 34
solute.
Duesberg, Chemical Thermodynamics
 Gas solubility
Henry’s law constants for gases dissolved in water at 25°C
KH/(kPa m mol )
3 1

Ammonia, NH3 5.69

Carbon dioxide, CO2 2.937
Helium, He 282.7
Hydrogen, H2 121.2
Methane, CH4 67.4
Nitrogen, N2 155
Oxygen, O2 74.68

Concentration of 4 mg/L of oxygen is required to support aquatic life,

what partial pressure of oxygen is required for this?
35
 Application-diving
Gas narcosis caused by nitrogen in normal air dissolving into nervous
tissue during dives of more than 120 feet [35 m]
Pain due to expanding or contracting trapped gases, potentially leading to
Barotrauma. Can occur either during ascent or descent, but are potentially
most severe when gases are expanding.
Decompression sickness due to evolution of inert gas bubbles.
Table 1
Increasing severity of nitrogen narcosis symptoms with depth in feet and
pressures in atmospheres.
Depth P Total P N2 Symptoms

100 4.0 3.0 Reasoning measurably slowed.

Joviality; reflexes slowed; idea

150 5.5 4.3
fixation.

Euphoria; impaired concentration;

200 7.1 5.5
drowsiness.

Mental confusion; inaccurate

250 8.3 6.4
observations.
Stupefaction; loss of perceptual
300 10. 7.9
faculties.
 The experimental partial vapour
pressures of a mixture of
chloroform (trichloromethane) and
acetone (propanone) based on the
data in Example 7.3. The values of
K are obtained by extrapolating the
dilute solution vapour pressures as
explained in the Example.

Excess Functions:

We discuss properties of real solutions in terms excess functions

XE. The excess entropy for example is defined as:
Chapter 7 : Slide 37

Duesberg, Chemical Thermodynamics

S E = mix S- mix S ideal.
 SUMMARY

• Partial molar quantities and the Gibbs-Duhem equation. Tells us how

chemical potentials vary with composition of a mixture.
• Chemical potentials µ of liquids are accessed via µ for the vapor in
equilibrium.
• Raoult's Law, Henry’s Law

• Real and ideal gases  activity

• In general µ = µs + RT ln a.

Chapter 7 : Slide 38

Duesberg, Chemical Thermodynamics

 Colligative Properties
Colligative properties are the properties of dilute solutions that
depend only on the number of solute particles present.

They include:

1. The elevation of boiling point

2. The depression of boiling point
3. The osmotic pressure

All colligative properties stem from the reduction of the solvents m by

the presence of the solute.

µA(l) = µA*(l) + RT ln xA
Chapter 7 : Slide 39

Duesberg, Chemical Thermodynamics

 Colligative properties
 Chemical potential of a solution (but not
vapour or solid) decreases by a factor
(RTlnxA) in the presence of solute
 Molecular interpretation is based on an
enhanced molecular randomness of the
solution
 Get empirical relationship for FP and BP
(related to enthalpies of transition)

T f  K f m
Tb  K b m
40
Boiling-point elevation Tb = KbbB
Freezing-point depression Tf = KfbB
where bB is the molality of the solute B in the solution
 The Elevation of Boiling Point
Want to know T at which:

µA*(g) = µA*(l) + RT ln xA

Presence of a solute at xB causes an increase in the boiling temp from

T * to T * + T where:
RT *2
T = KxB K
 vap H

b is the molality of the solute (proportional to xB).

T = K bb Kb is the ebullioscopic constant of the solvent.

The Depression of Freezing Point

Identical arguments lead to: T = K f b where Kf is the cryoscopic constant.
Chapter 7 : Slide 42

Duesberg, Chemical Thermodynamics

 Examples:

7.8(b) Calculate the cryoscopic and ebullioscopic constants of

naphthalene.

7.10(b) The addition of 5.0 grams of a compound to 250 grams of

naphthalene lowered the freezing point of the solvent by 0.780 K.
Calculate the molar mass of the compound.

Chapter 7 : Slide 43

Duesberg, Chemical Thermodynamics

 Osmosis – for Greek word “push”
Spontaneous passage of a pure solvent into a solution separated from it
by a semi-permeable membrane (membrane permeable to the solvent,
but not to the solute)
Osmotic pressure – P – the pressure that must be applied to the solution
to stop the influx of the solvent

Van’t Hoff equation:

P = [B] R T
where [B] = nB/V

Osmometry - determination of molar mass by measurement of

osmotic pressure – macromolecules (proteins and polymers)
Chapter 7 : Slide 44

Duesberg, Chemical Thermodynamics

 Osmosis

Height Solution
Proportional
to Osmotic
Pressure P

Solvent A with chemical Semipermeable

potential mA*(p) Membrane
Chapter 7 : Slide 45

Duesberg, Chemical Thermodynamics

 Osmosis

It is assumed that the van’t Hoff equation is only the first term of a virial-
like expression:

P = [B] R T {1 + B[B] + . . . }

EXAMPLE: Using Osmometry to determine the molar mass of a macromolecule.

Osmotic pressures of PVC in cyclohexanone are given below. The pressures are given in
terms of heights of solution (with r = 0.980 g cm-3) in balance with the osmotic pressure.
Determine the molar mass of the polymer.

c / (g L-1) 1.00 2.00 4.00 7.00 9.00

h / cm 0.28 0.71 2.01 5.10 8.00

c is the mass concentration Chapter 7 : Slide 46

Duesberg, Chemical Thermodynamics

 Activities  How can we adjust previous equations to account for deviations
from ideal behavior?
1. solvent
2. solute

Solvent activity:

General form of the chemical potential of a real OR ideal solvent:

mA = mA* + RT ln (pA/pA*)

Ideal solution – Raoult’s law is obeyed:

mA = mA* + RT ln xA i.e xA = pA/pA*

Real solution – we can write:

mA = mA* + RT ln aA Chapter 7 : Slide 47

Duesberg, Chemical Thermodynamics

 Solvent activity
aA is the activity of A – essentially an “effective” mole fraction

aA = pA/pA*

Illustration: The vapor pressure of 0.5 M KNO3 (aq) at 100oC is 749.7 Torr, what is the
activity of water in the solution?

As xA  1 (solute concentration is nearing zero), aA  xA,

aA = gA xA gA  1 and aA  xA

For a real solution, we can write:

mA = mA* + RT ln xA + RT ln gA

Standard state is the pure liquid solvent at 1 bar Chapter 7 : Slide 48

Duesberg, Chemical Thermodynamics

 Solute activity  approach ideal dilute (Henry’s law) behavior as xB  0

Ideal-dilute: pB = KB xB

mB = mB* + RT ln (pB/pB*)
= mB* + RT ln (KB /pB*) + RT ln xB

The second term on the rhs of the above equation is composition

independent, so we may define a new reference state:

mB+ = mB* + RT ln (KB /pB*)

So that:
mB = mB+ + RT ln xB
Chapter 7 : Slide 49

Duesberg, Chemical Thermodynamics

 Real solutes – permit deviations from ideal-dilute behavior

mB = mB+ + RT ln aB

Where aB = pB/KB and aB = gB xB

Note: As xB  0, aB  xB and gB  1

Chapter 7 : Slide 50

Duesberg, Chemical Thermodynamics

 Measuring Activity
Use the following information to calculate the activity and activity
coefficient of chloroform in acetone at 25oC, treating it first as a
solvent and then as a solute with KB = 165 Torr.

xC 0 0.2 0.4 0.6 0.8 1.0

pC / Torr 0 35 82 142 200 273

Chloroform regarded as solvent
a = p / p* a 0 0.13 0.30 0.53 0.73 1.0

g = a / xC g 0.65 0.75 0.87 0.91 1.0

Chloroform regarded as solute
a = p / KB a 0 0.21 0.50 0.86 1.21 1.65

g = a / xC g 1 1.05 1.25 1.43 1.51 Chapter1.65

7 : Slide 51

Duesberg, Chemical Thermodynamics

 Activities in terms of molalities, bB:
For an ideal-dilute solute we had written in terms of mole fractions:
mB = mB+ + RT ln xB

with
mB+ = mB* + RT ln (KB /pB*)

Molality in terms of mole fraction:

bB = nB / MA MA = nA * Mr(A)

bB = nB / ( nA * Mr(A) )

xB = nB / (nA+nB)  nB / nA

bB = xB / Mr(A)  xB = bB Mr(A)
Chapter 7 : Slide 52

Duesberg, Chemical Thermodynamics

 Activities in terms of molalities, bB:

xB = bB Mr(A)

mB = mB+ + RT ln xB

mB = mB+ + RT ln bB + RT ln Mr(A)

mB = mB + RT ln bB

mB = mB at standard molality b = 1 mol kg-1

Chapter 7 : Slide 53

Duesberg, Chemical Thermodynamics

 Activities in terms of molalities, bB:

As bB  0, mB  -∞

In other words, as a solution becomes increasingly diluted, the

solution becomes more stabilized – It becomes difficult to remove
the last little bit of solute.

To allow for deviations from ideality we introduce (in the normal way)
aB = gB bB (assuming unit-less)

Then:

mB = mB + RT ln aB

Chapter 7 : Slide 54

Duesberg, Chemical Thermodynamics

 Osmotic pressure
Van’t Hoff equation

P  MRT

55
 Phase diagrams of mixtures
We will focus on
two-component
systems
(F = 4 ─ P), at
constant pressure of
1 atm
(F’ = 3 ─ P), depicted
as temperature-
composition
diagrams.
56
 Fractional Distillation-volatile liquids

Important in oil refining

57
 Exceptions-azeotropes
Azeotrope: boiling without changing
High-boiling and Low-boiling

Favourable interactions between components Unfavourable interactions between

reduce vp of mixture components increase vp of mixture
Trichloromethane/propanone Ethanol/water (min at 4% water, 78°C)
HCl/water (max at 80% water, 108.6°C)

58
 Liquid-Liquid (partially miscible)
 Hexane/nitrobenzene as
example
 Relative abundances in 2 phases
given by Lever Rule
n’l’ = n’’l’’
 Upper critical Temperature is
limit at which phase separation
occurs. In thermodynamic terms
the Gibbs energy of mixing
becomes negative above this
temperature

59
 Other examples

Nicotine/water
Water/triethylamine Weak complex at low temperature disrupted
Weak complex at low temperature disrupted at higher T. Thermal motion homogenizes
at higher T. mixture again at higher T.
60
Liquid-solid phase diagrams

61