Chapter 5

Phases and Solutions

Stability of Phases

Example

Phase Transitions
Spontaneous conversion of one phase into another phase.
Melting (or fusion)
solid liquid
Boiling (or vaporization)
liquid gas
Sublimation
solid gas
Condensation
gas
liquid
Condensation (or deposition) gas
solid
Solidification (or freezing)
liquid solid
Polymorphism (allotropes):
different solid forms of a chemical component
graphite/diamond; calcium carbonate argonite/calcite;
structurally different solid water.
4

Heats of vaporization and fusion for several

common substances

Phase changes and their enthalpy changes

A cooling curve for the conversion of gaseous

water to ice

1/c

Quantitative Aspects of Phase Changes

Within a phase, a change in heat is accompanied by a
change in temperature which is associated with a
change in average Ek as the most probable speed of
the molecules changes.
q = (amount)(molar heat capacity)('T)
During a phase change, a change in heat occurs at a
constant temperature, which is associated with a
change in Ep, as the average distance between
molecules changes.
q = (amount)(enthalpy of phase change)
8

Equilibrium Nature of Phase Changes

Vapour pressure = equilibrium vapour

pressure

Transition temperature temperature at which the 2

phases are in equilibrium and the Gibbs energy is
minimized at the prevailing pressure.

Vapour
pressure

Sublimation
vp

10

Vapour Pressure and Boiling Point

In an open container, at some temperature, the average Ek
of the molecules in the liquid is great enough for bubbles of
vapour to form in the interior, and the liquid boils.
At any lower temperature, the bubbles collapse as soon as
they start to form because external pressure is greater than
the vapour pressure inside the bubbles.
Boiling point is the temperature at which the vapour
pressure equals the external pressure (atm pressure).

11

Critical points and boiling points

Boiling temperature at a
specific pressure
temperature at which the
vapour pressure of a liquid is
equal to the external
pressure.
Normal boiling point
external pressure of 1 atm.
Standard boiling point
external pressure of 1 bar (1
bar = 0.987 atm).
Normal bp of water = 100 C
vs 99.6 C for standard bp.
12

Heating a liquid in a rigid, closed vessel

No boiling occurs. Vapour pressure and density of
vapour rise as temperature is raised. Density of liquid
decreases slightly because of expansion.
When density of vapour = density of remaining liquid,
surface between gas/liquid disappears critical
temperature, Tc of the substance.
Vapour pressure at Tc: critical pressure, Pc.
At and above Tc, a single uniform phase
supercritical phase no liquid phase.
13

Heating a liquid in a rigid, closed vessel

Sc H2O : 374 C, Pc 218 atm.

14

Melting points and triple points

Melting point - temperature at which, under a specified
pressure, the liquid and solid phases of a substance coexist
in equilibrium.
Melting point = freezing point.
Normal freezing point freezing temperature when the
pressure is 1 atm = normal melting point.
Standard freezing point freezing temperature when the
pressure is 1 bar.
Triple point point at which the three phase boundaries
meet solid, liquid, vapour coexist simultaneously in
equilibrium.
Triple point of water: 273.16 K, 611 Pa.
15

Above Tc, no pressure

can force the H2O
molecules into a liquid
state.

Triple point lowest temperature at which the liquid can

exist.
Critical point - upper limit beyond this point, liquid and
gas phase become indistinguishable.

16

Supercritical Fluids
A SCF is defined as a substance above its critical
temperature (TC) and critical pressure (PC).
Supercritical carbon dioxide Tc: 304 K or 31 C, Pc = 72.9
atm.
Density at critical point : 0.45 g cm-3. (0.1 1.2 g cm-3)
Advantages of scCO2
Cheap, readily accessible, easily recycled.
Disadvantages
Not a very good solvent, need surfactants to dissolve
solutes.
17

Phase Diagram
Carbon dioxide
Melting point of solid CO2
increases with pressure.
Triple point above 1 atm
no liquid at normal atm pressures
whatever the temperature.
Cylinders of CO2 contains the
liquid or compressed gas.

Supercritical
fluid

18

Supercritical water

Critical temperature : 374 qC

Critical pressure 218 atm
Properties of the fluid are highly sensitive to pressure.
As the density of scH2O decreases, solution change
from aqueous non-aqueous gaseous solutions.
Dissolve non-polar substances.

19

Example 1: A liquid is in equilibrium with its vapour in a

closed vessel at a fixed temperature. The vessel is
connected by a stopcock to an evacuated vessel. When the
stopcock is opened, will the final pressure of the vapour be
different from its initial value if (a) some liquid remains (b)
all the liquid is first removed?
Solution 1
a) The final pressure will be the same, since the vapor
pressure is constant as long as some liquid is present.
b) The final pressure will be lower, according to Boyles
Law.

20

Example 2: The phase diagram for a substance A has a

solid-liquid line with a positive slope, and that for substance
B has a solid-liquid line with a negative slope. What
macroscopic property can distinguish A from B ?
Solution 2
A: the solid is denser than the liquid.
B: the solid is less dense than the liquid.
Example 3: Why does water vapour at 100 qC cause a more
severe burn than liquid water at 100 qC ? Heat capacity of
liquid water 75.4 J/mol.K; 'Hvap = -40.7 kJ/mol
Solution 3
When liquid water at 100C touches skin, the heat released
is from the lowering of the temperature of the water. The
specific heat of water is approximately 75 J/molK. When
steam at 100C touches skin, the heat released is from the
condensation of the gas with a heat of condensation of
approximately 41 kJ/mol.
21

Chemical Potential, P
Measure of the potential that a substance has for
undergoing change in a system.
At equilibrium, the chemical potential of a substance is
the same throughout a sample, regardless of how many
phases are present.
The phase with the lowest chemical potential at a
specified temperature is the most stable phase.
For a one-component system, molar Gibbs energy =
chemical potential. G P

22

Thermodynamic criterion of equilibrium

At equilibrium, the chemical potential of
a substance is the same throughout a
sample, regardless of how many
phases are present.
At low temperatures and if
pressure is not too low, the
solid phase of a substance
has the lowest chemical
potential.
Above a certain temperature,
another phase may be the
lowest spontaneous
transition to the second
phase.

23

Consider liquid and solid phases of water at a fixed T, P

If Ps(T,P) = Pl(T,P), then liquid water and ice coexist.
If Ps(T,P) > Pl(T,P), then water is in the liquid phase.
If Ps(T,P) < Pl(T,P), then water is in the solid phase.
Fundamental equation
dG

SdT  VdP du

wP

wT P

S

3 rd Law: S ! 0

SdT  V dP

wP

wP T

wP

0
wT P

Negative slope

24

Temperature dependence of phase stability

As temperature is raised,
the chemical potential of a
pure substance decreases:
S > 0 so slope of line is
negative.
Slope decreases from
gas > liquid > solid because
S( g ) ! S( l ) ! S ( s )

As temperature is raised,
change in phase.
25

Response of melting to applied pressure

Most substances melt at a
higher temperature when
subjected to pressure
(exception being water).

wP

wP T

Vm

An increase in pressure
raises the chemical potential
of any pure substance
(because Vm >0).
As Vm(l) > Vm(s), this raises
the melting temperature.
26

For water, Vm(l) < Vm(s).

An increase in pressure
increases the chemical
potential of the solid more
than the liquid.
Melting point is slightly
lowered.

27

The location of phase boundaries

When two phases are in
equilibrium, their chemical
potentials must be equal.
PD ( P ,T ) P E ( P ,T )
In single phase regions, one of
the chemical potentials is lower
than the other. T and P can be
changed independently without
changing phases.
Phase rule: F = 3 P
F = number of degrees of freedom, P= number
of phases that coexist.
28

Consider dP/dT. Let P and T be changed infinitesimally so

that D and E are in equilibrium.
PD o PD  dPD
P E o P E  dP E
dPD

dP E

dP

dG

-SdT  V dP

? S D dT  V D dP

VE  VD dP

dP
dT

S E dT  V E dP

On coexistence line

( SE  SD )dT

D oE

Clapeyron equation

Exact expression for the slope of

the phase boundary
29

Another way is to use express in terms of H and V.

H T S

For P A

PB on the coexistence line,

H D - T SD
? 'HD oE

H E - TSE

T'SD oE 'SD oE

'HD oE

Substitute into Clapeyron equation,

dP
dT

dP

V
D oE

H dT
'V T

T'V

D oE

Integratin g , 'P

H Tf
ln
'V Ti
30

The solid-liquid boundary

Melting accompanied by a molar enthalpy change 'fusH
and occurs at temperature T.
' fus H
' fus S
T
+
dP
dT

fus H
TfusV

+ and small
Integrating,

' fus H T
P* 
ln
' fusV T *

T close
to T*

' fus H
P | P* 
(T  T *)
T * ' fusV

ln

T
T*

T T * T T *
ln1 
|
T*
T*

As pressure is raised, melting

31
temperature rises.

The liquid-vapour boundary

Entropy of vaporization at T
'Svap = 'vapH/T
Clapeyron equation for
liquid-vapour boundary
+
dP H
vap

dT

TvapV

+ and
large
Boiling temperature is more responsive to pressure
than freezing point (because dT/dP is large).

32

Sample: Estimate the typical size of the effect of

increasing pressure on the boiling point of a liquid.
dP
dT

vap H
TvapV

Troutons constant: 85 J K-1 mol-1

vapV

Vm (g)  Vm (l) | Vm (g)

Molar volume of an ideal gas at 1 atm and slightly above

room temperature ~ 25 dm3 mol-1
dP
85 J K -1 mol 1
|
dT 25 x 10 3 m 3 mol 1

dT
dP

3.4 x 10 3 Pa K 1

0.034 atm K 1

29 K atm 1
33

Clausius-Clapeyron equation
Approximations:
1. Molar volume of gas is
>> molar volume of
liquid, therefore neglect
volume of liquid. Vvap
Vm(g).
2. Assume ideal gas
behavior, so that Vm(g)
= RT/P

dP
dT

'Hvap

T ( RT / P )
dP 'Hvap
dT
2
p
RT
'Hvap
d ln P
dT
2
RT

Assume
independent
of
temperature

Integrating,
P
ln f
Pi

'Hvap 1 1


R Tf Ti

Predict how vapour pressure varies with temperature and

how boiling point varies with pressure
34

Effect of Temperature on Vapour Pressure

Raising the
temperature
of a liquid
increases the
fraction of
molecules
moving fast
enough to
escape into
the liquid and
decreases the
fraction
moving slowly
enough to be
The higher the temperature, the higher the
recaptured. 35
vapour pressure.

Effect of Intermolecular Forces on Vapour Pressure

A linear plot of the relationship
between vapor pressure and
temperature .

'Hvap/R
The weaker the intermolecular
forces are, the higher the vapour
pressure.

36

Using the Clausius-Clapeyron

Equation

SAMPLE PROBLEM
PROBLEM:

SOLUTION:

The vapor pressure of ethanol is 115 torr at 34.90C. If 'Hvap of

ethanol is 40.5 kJ/mol, calculate the temperature (in 0C) when
the vapor pressure is 760 torr.

P2
-'Hvap  1
1 
ln
=
  
P1
R T2 T1

760 torr
ln
115 torr

-40.5 x103 J/mol

8.314 J/mol*K

34.90C = 308.0K
1
1
T2
308K

T2 = 350K = 770C

37

Solid-Vapour Boundary
Enthalpy of sublimation >
Enthalpy of vaporization
'subH = 'fusH + 'vapH
dP
dT

sub H
TsubV

Steeper slope for

sublimation curve than for
vaporization curve.

38

Two-component systems
A(g), yA
T, P
B(g), yB = 1 - yA

A(liq), xA
B(liq), xB = 1 - xA

Total number of variables = 4

T, P, xA, yA
Constraints due to coexistence = 2
PA(l) = PA(g)
PB(l) = PB(g)
Total number of independent variables
F = 4 -2 = 2
Know T, P uniquely determines the
compositions in the liquid and gas
phase.
39

Gibbs phase rule: F = C P + 2

F: number of degrees of freedom (independent variables)
C: number of components
P: number of phases
For 1-component system, F = 3 P
P = 1, F = 2 can vary freely in the T, P region.
P = 2, F = 1 can vary along coexistence curveT(P).
P = 3, F = 0 Triple point.

40

Ideal Solutions
A solution is any homogeneous phase that contains more
than one component.
Solvent - larger proportion of the solution.
Solute component lesser proportion.
A solution is considered to be ideal when there is a
complete uniformity of intermolecular forces, arising from
similarity in molecular size and structure.
Partial vapour pressures of the individual components
within the solution are a good measure of the individual
components measures the escaping tendency of a
molecule from solution.
41

Raoults Law
Francois Raoult: The vapour pressure PA of solvent A is
equal to its mole fraction in the solution multiplied by the
vapour pressure PA* of the pure solvent - Raoults Law
PA = xA PA*
Some mixtures obey Raoults law very well structurally
similar components.
Raoults law assumes a linear dependence.

42

A(g), yA

A: volatile solvent, B: involatile solute.

Solvent and solute do not interact, like in
mixture of ideal gases.

T, P

A(liq), xA
B(liq), xB = 1 - xA

PA*  PA

PA*

PA*  x APA*
(1 - x A )PA*

PA

xB PA* ! 0

PA < PA*

xB

Vapor pressure is lowered in

the mixture

PA* = vapor pressure of pure A at temperature T

43

Both A and B volatile

A(g), yA
T, P
B(g), yB = 1 - yA

A(liq), xA
B(liq), xB = 1 - xA

PA

x APA*

PA  PB

and PB

xB PB*

x APA*  xB PB*

Ideal solutions =
Both components obey
Raoults Law.

Benzene-toluene,
Ethylene bromide-ethylene chloride
Carbon tetrachloride trichloroethylene

44

If the vapour phase is treated as an ideal gas, then

according to Daltons law of partial pressures
Ptotal = P1 + P2
From Raoults law, Ptotal = x1P1* + x2P2*
Ptotal = x1P1* + (1 x1)P2*
Ptotal = P2* + (P1* P2*)x1

Straight line with slope

P1* P2*

45

Slope = (P1* P2*)

Intercept = P2*

Liquid solutions will boil at different temperatures depending

on their composition and vapour pressures of the pure
components.
46

Example problem
An ideal solution can be approximated using the liquid
hydrocarbons hexane and heptane. At 25 C, hexane has
an equilibrium vapor pressure of 151.4 Torr and heptane
has an equilibrium vapor pressure of 45.70 Torr. What is
the equilibrium vapor pressure of a 50:50 molar hexane
and heptane solution in a closed system ?
Using Raoults law,
P1 = (0.50)(151.4 Torr) = 75.70 Torr
P2 = (0.50)(45.70 Torr) = 22.85 Torr
By Daltons law, Ptotal = 75.70 + 22.85 = 98.55 Torr
47

Example problem
A hexane/heptane solution is used to establish a constant
65 C temperature in a closed system that has a pressure
of 500 Torr. At 65 C, the vapor pressures of hexane and
heptane are 674.9 and 253.5 Torr. What is the composition
of the solution ?
Ptotal = P2* + (P1* P2*)x1
x1

Ptot  P2*
P1*  P2*
500  253.5
674.9  253.5

246.5
421.4

0.5850

Mole fraction of hexane : heptane = 0.5850 : 0.4150

48

At 25 qC, hexane has an equilibrium vapor pressure of

151.4 Torr and heptane has an equilibrium vapor pressure
of 45.70 Torr.
P1 = (0.50)(151.4 Torr) = 75.70 Torr (hexane)
P2 = (0.50)(45.70 Torr) = 22.85 Torr (heptane)
By Daltons law, Ptotal = 75.70 + 22.85 = 98.55 Torr
In the gas phase,
y1 = 75.70/98.55 = 0.77
y2 = 22.85/98.55 = 0.23
Vapour always contains relatively more of the more volatile
component than does the liquid.
49

Example problem
At temperature T, the vapor pressure of pure benzene,
C6H6, is 0.256 bar and the vapor pressure of pure toluene
is 0.0925 bar. If the mole fraction of toluene in the solution
is 0.600 and there is some empty space in the system,
what is the total vapor pressure in equilibrium with the
liquid, and what is the composition of the vapor in terms of
mole fraction ?
Using Raoults law, pbenzene = (0.4) x (0.256 bar) = 0.102
bar
Ptoluene = (0.6) x (0.0925 bar) = 0.0555 bar
Ptotal = 0.102 + 0.0555 = 0.158 bar
Vapor phase is enriched in
ytoluene = 0.0555/0.158 = 0.351
benzene over original solution
ybenzene = 0.102/0.158 = 0.646

50

Composition of the vapour

What are the mole fractions of the two components in the
vapour phase ?
*
*
*
*
*
P
P

P
x
P

(
1

x
)
P
P

(
P

P
Total pressure total
1
2
1 1
1
2
2
1
2 ) x1
Let y1 and y2 denote the gas-phase mole fractions,
y1

P1
Ptotal

Rearranging,

x1P1*
P2*  ( P1*  P2* )x1
x1

y 1P2*
P1*  ( P2*  P1* )y 1

Substituting into Ptotal:

Ptotal

P1* P2*
P1*  ( P2*  P1* )y 1
51

Total pressure of the vapour phase vs mole fraction of one

component is not a straight line !
, liquid curve

liquid
L+V

Constant temperature

vapour
, vapour curve

52

Coexistence curve or bubble line

Coexistence curve or dew line

Tie-line connect the

liquid-phase composition
with the vapour-phase
composition.

53

P1

P1

yB(2)

xB(1)
yB(2)

xB(1) xB(4)
yB(4)

yB(4) = xB(1)

xB, yB
xB(4)

At B, liquid phase (xB(1)) with a very small amount of

gas phase (yB(2)). On decreasing the pressure,
composition of the liquid and gas phases change along
the coexistence lines until yB(4) = xB(1). Then, there is
no more liquid left.

54

Lever Rule
How much is in each phase ?

Liquid

gas
liquid

x A ( 3 )  y A (1 )
y A (1 )  y A ( 2 )

gas
yA(2)

yA(1) xA(3)
55

Fractional distillation

Liquid phase

Gas phase

56

Temperature-Composition Diagrams
Bubble line
Dew line

Constant pressure
Liquid

Both bubble point and dew point lines are curved !

57

Theoretical plates number of

effective vaporization and
condensation steps that are
required to achieve a condensate
of a given composition from a
given distillate.

58

Gasoline vapors
Condenser
Gas

The process of
fractional distillation.

Gasoline 380C
Kerosene 1500C
Heating oil 2600C
Lubricating oil 3150C-3700C

Crude oil vapors

from heater
Steam
Residue (asphalt, tar)

59

Bubble caps

A bubble cap forces the

vapours and liquid to mix.

Bubble trays hold the bubble

caps. Overflow weir to allow
some liquid to fall back down to
be evaporated again

Fractionating column provides the contacting surface for

mass transfer between the liquid and vapour at a desired
rate.
At each level in the column, vapour from the level or plate
below bubbles through a thin film of liquid C, at a
temperature slightly lower than that of the vapour coming
through the bubble cap. Partial condensation of the vapor
occurs. The lower boiling mixture remains as vapour and
move to the next plate. The vapour leaving each plate is
enriched in the more volatile component compared to the
entering vapour from the plate below. Excess liquid at each
plate is returned to the plates below via overflow tubes, E.
http://www.youtube.com/watch?v=26AN1LfbUPc
61

http://www.metacafe.com/watch/yt-0x28dedmE4/fractional_distillation/

62

Chemical potentials of ideal solutions

At coexistence,

P A ( l ,T , P )

P A ( g ,T , PA )

Assuming ideal gas,

P A ( g ,T , PA ) P A ( g ,T ,1bar )  RT ln

PA
Po

P Ao ( g ,T )  RT ln PA

Substituting into 1st equation,

P A ( l ,T , P )
For pure A,

P Ao ( g ,T )  RT ln PA

P *A ( l ,T , P )

P Ao ( g ,T )  RT ln PA*

For mixture, P A ( l ,T , P ) P *A ( l ,T , P )  RT ln PA*  RT ln PA

P *A ( l ,T , P )  RT

PA
ln *
PA
63

Using Raoults Law: PA = xAPA*

P A ( l ,T , P )
Chemical
potential of
A in mixture

P *A ( l ,T , P )  RT ln x A
Chemical
potential of A
in pure liquid

for an ideal solution

Mole
fraction of A
in mixture

P A ( l ,T , P )( mixture ) d P *A ( l ,T , P )( pure )
Chemical potential for a mixture is always lower than pure
liquid at same T,P.
64

Free energy change in ideal solutions

Before mixing, Gi

n A P A  nB PB

After mixing,

n A P A  RT ln x A  nB PB  RT ln xB

Gf

Gibbs energy of mixing

' mixG

n A P A  RT ln x A  nB PB  RT ln xB  n A P A  nB PB
n ART ln x A  nB RT ln xB

nRT x A ln x A  xB ln xB

nx A RTlnx A  nx B RTlnx B
where n

n A  nB

G VdP  SdT
' mix S
' mix S
' mix H

w' mixG


wT P
nR x A ln x A  xB ln xB 
' mixG  T' mix S

No enthalpy change on mixing for ideal solutions.

' mixV

w' mixG

wP T

No volume change on mixing.

Non-ideal solutions
In ideal solutions, non-interacting molecules. 'Gmix comes
all from entropy of mixing. No change in volume upon
mixing, just like ideal gas.
Non-ideal solutions molecules interact differently with
liquid molecules of another species giving rise to positive or
negative deviation from Raoults Law
A

uAA < 0

uBB < 0

uAB

uAB
Interaction energy 'u = 2uAB (uAA uBB)
Departure from ideality

65

Positive Deviation 'u > 0

Positive deviation:
If strength of interaction
between like molecules A-A
or B-B > A-B, the tendency
will be to force both
components into the vapour
phase. Observed for
dissimilar liquids.
Ethanol/benzene, ethanol/chloroform,
ethanol/water
66

67

Negative deviation 'u < 0

Occurs when the attractions
between components A and B
are strong. Mixing is
energetically favorable in
liquid phase.
Holding back of molecules that
would otherwise go into the
vapour state.
Acetone/chloroform
Cl

3HC

H C Cl

C O
H3C

H-bonding

Cl
68

Minimum boiling azeotrope

At this point,
x1 = y1

Azeotropic composition composition of the liquid and

vapour in equilibrium have the same mole fraction. E.g.
water and ethanol have a minimum boiling point at 78.2 C
and is 96 % ethanol and 4 % water.

Maximum-boiling azeotrope

Henrys Law
In ideal solutions, the solute and the solvent obey Raoults
law.
For real solutions at low concentrations, although the
vapour pressure of the solute is proportional to its mole
fraction, the constant of proportionality is not the vapour
pressure of the pure substance.
PB = xBKB
xB: mole fraction of the solute; KB: empirical constant (with
dimensions of pressure) chosen so that the plot of the
vapour pressure of B against its mole fraction is tangent to
the experimental curve at xB = 0.
71

Mixtures for which the solute obeys Henrys law and the
solvent obeys Raoults law ideal-dilute solutions.
1. xB 1
B is the solvent.
Raoults law applies
PB = xBPB*
B molecules sees mostly
other B molecules.
2. xB 0
B is the solute.
Henrys law applies
PB = xBKB
KB depends on A.
Positive deviation: KB > PB*
Negative deviation: KB < PB*
72

In dilute solution, the solvent

molecules are in an
environment that differs only
slightly from that of the pure
solvent. Solute particles are
in an environment totally
unlike that of the pure solute.

73

74

Liquid-Gas System
Liquid/gas solutions are not ideal, therefore Raoults law
does not apply. Examples of liquid/gas solutions, fizzy
drinks, oxygen in water, carbon dioxide in water.
HCl high solubility in water.
Oxygen low solubility, 0.0013 M.
William Henry (1774 1836) found that the mass of gas
mB dissolved by a given volume of solvent at constant
temperature is proportional to the pressure of the gas in
equilibrium with the solution.
mB = kBPB
B: solute, kB is the Henrys law
constant.
75

Gas solubility in water decreases with rising temperature.

Gases have weak intermolecular forces and as
temperature rises, more gas particles re-enters the gas
phase.
Thermal pollution
Water taken from lakes,
rivers for cooling of
liquids, gases,
equipment. This water
has to be cooled before
it exits the plant.

K = P/b

For practical reason, Henrys law is expressed in terms

of the molality, b, of the solute: PB = bBKB

77

Hyperbaric oxygen chamber treatment of certain

diseases CO poisoning, diseases caused by anaerobic
bacteria gas gangrene and tetanus.
Scuba diving air is supplied at a higher pressure so that
pressure within divers chest matches pressure exerted by
the surrounding water (1 atm for every 10 m descent).
Nitrogen is much more soluble in fatty tissues than in
water, so it tends to dissolve in the central nervous system,
bone marrow, fat reserves nitrogen narcosis, bends,
arterial embolisms.

78

Example: Estimate the molar solubility of oxygen in

water at 25 qC and a partial pressure of 21 kPa,
PB = bBKB where KB = 7.9 x 104 kPa kg mol-1
bO2

PO2
KO2

21 kPa
7.9 x 10 4 kPa kg mol 1

Taking density of water

[O2 ]

bN2
bN2

bO x UH O
2

PN2
K N2
PN2
K N2

2.9 x 10 4 mol kg 1

0.99709 kg dm -3

0.29 mmol kg -1 x 0.99709 kg dm - 3

79 kPa
1.56 x 10 5 kPa kg mol 1
21 kPa
1.56 x 10 5 kPa kg mol 1

0.29 mmol dm - 3

5.1 x 10 4 mol kg 1
1.3 x 10 4 mol kg 1
79

Example problem
The Henrys law constant Ki for CO2 in water is 1.67 x 108
Pa at some temperature T. If the pressure of CO2 in
equilibrium with water were 1.00 x 106 Pa, what is the mole
fraction of CO2 in the solution ? Can you estimate the
molarity of the CO2 solution ?
Solution:
PCO2 = KCO2xCO2

Mole
fraction

where KCO2 = 1.67 x 108 Pa

1.00 x 106 Pa = 1.67 x 108 Pa xCO2

xCO2 = 0.00599
xCO2 = nCO2/(nCO2 + nH2O) nCO2/nH2O = 0.00599
1 mole water = 18 g = 18 cm3 = 0.018 L
Molarity of CO2 solution = 0.00599/0.018 L = 0.333 M

80

Example problem
The partial pressure of carbon dioxide gas into a bottle of
coca cola is 4 atm at 25 qC. What is the solubility of CO2 ?
The Henrys law constant for CO2 dissolved in water is 1.67
x 108 Pa.
PCO2 = KCO2xCO2

where KCO2 = 1.67 x 108 Pa

4.00 x 105 Pa = 1.67 x 108 Pa xCO2

xCO2 = 0.0024
xCO2 = nCO2/(nCO2 + nH2O) nCO2/nH2O = 0.0024
1 mole water = 18 g = 18 cm3 = 0.018 L
Molarity of CO2 solution = 0.0024/0.018 L = 0.13 M

Colligative Properties of Solutions

Properties of solutions in the dilute limit.
Property of a solution with a non-volatile solute may be
different from that of the pure solvent. Properties are
independent of the identity of the solute molecules but
related only to the number of solute molecules colligative
properties.
Concentrations in
(a)Mole fraction xB = nB/(nA + nB) | nB/nA
(b)Molality: mB = moles solute/kg solvent = nB/(nAMA) where
MA is the mass in kg of 1 mole of solvent.

82

All colligative properties

stem from reduction of the
chemical potential of the
liquid solvent as a result of
the presence of the solute.
P Amix ( l ,T , P )  P Apure ( l ,T , P )

Lowering of the liquids

chemical potential has a
greater effect on the
freezing point than on the
boiling point.

83

Four Colligative Properties

Vapour pressure depression: 'PA
Boiling point elevation:

'Tb

Tb  Tb*

Kb

R(Tb* )2
'vap H

Freezing point depression

'Tf
Kf

Osmotic pressure:

PA  PA*

Tf  Tf*

 xB PA*
K b xB

K f xB

*
R(Tfus
)2
'fus H

nB
RT
V
84

Vapour pressure of pure liquid reflects the tendency of the

solution towards greater entropy. When a solute is present,
the disorder of the condensed phase is higher than that of the
pure liquid, and there is a decreased tendency to form the
vapour lower vapour pressure higher boiling point.
85

The effect of a solute on the vapor

pressure of a solution.

86

How does the amount of solute affect the

magnitude of the vapour pressure ?
1. Vapour pressure lowering just Raoults law.

PA

'PA

x APA*

(1  xB )PA*

PA  PA*

 xB PA*  0

87

Using Raoults Law to Find the Vapor

Pressure Lowering
PROBLEM: Calculate the vapor pressure lowering, 'P, when 10.0 mL of
glycerol (C3H8O3) is added to 500. mL of water at 50.0C. At this
temperature, the vapor pressure of pure water is 92.5 torr and
its density is 0.988 g/mL. The density of glycerol is 1.26 g/mL.

SOLUTION:
10.0 mL C3H8O3 x
500.0 mL H2O

'P =

1.26 g C3H8O3

mL C3H8O3
0.988 g H2O
mL H2O

mol C3H8O3
92.09 g C3H8O3
mol H2O
18.02 g H2O

0.137 mol C3H8O3

0.137 mol C3H8O3 + 27.4 mol H2O

92.5 torr

= 0.137 mol C3H8O3

= 27.4 mol H2O

= 0.461 torr
88

Heterogeneous equilibrium for boiling

point elevation

P*A ( g )

P*A ( l )  RT ln x A

89

Elevation of boiling point

In the presence of a solute at a mole fraction, xB, the boiling
point increases from T* to T*+'T where

Kb

'T = KbxB

*2
b

RT
' vap H

For practical applications, express mole fraction of B in its

molality, mb, in the solution

'T = Kbmb

K b'

M AR(Tb* )2
'vap H

where Kb is the empirical boiling-point constant of the

solvent.
90

Derivation
Assuming 'vap H constant,

P * ( g ) P *A ( l )  RT ln x A
A

Rearranging,
lnx A

lnx A

P * ( g )  P *A ( l )

'vapG

RT

RT

ln (1 - xB )

'vap H 1
R

1


T T *

If xB  1, then ln(1 - xB ) |  xB
1 2 1 3
x  x ...)
3
2
' vap H 1 1


R T* T

(from ln(1 - x) - x d ln x A
dT

1 d ( 'vapG / T )
R
dT

d ln xA

'vapH
RT 2

dT

'vap H
RT 2

xB

Also T | T*,
'T
1
1 T T *

|
T* T
TT *
T *2

Integratin g ,
ln x A

d ln x A

T
1 ' vap H
dT

2
R T* T

? xB

'T

'vapH'T
RT * 2
RT * 2
xB
'vap H

KxB
91

Heterogeneous equilibrium for lowering of

freezing point
Nonvolatile solutes will make it harder for
solvent molecules to crystallize at their
normal melting point.
At the freezing point, the
chemical potentials of A in
the 2 phases are equal:
P*A ( s )

P*A ( l )  RT ln x A

92

Depression of freezing point

'T = -KfxB

Kf

RTf

*2

' fus H

where 'T is the freezing point depression and 'fusH is the

enthalpy of fusion of the solvent.
Larger depressions are observed in solvents with low
enthalpies of fusion and high melting points.

93

For dilute solutions, mole fraction is proportional to the

molality of the solute, mb,

'T = -Kf mb

K f'

*
M AR(Tfus
)2
'Hfus

where Kf is the empirical freezing-point constant for the

solvent. Also called the cryoscopic constant.
Once the freezing-point constant of a solvent is known, the
depression of freezing point may be used to measure the
molar mass of a solute.

94

Example: A solution contains 1.50 g of solute in 30.0 g of

benzene and its freezing point is 3.74 C. The freezing point
of pure benzene is 5.48 C. Calculate the molar mass of the
solute.
Kf = 4.90 K kg mol-1
Solution: 'T 3.74  5.48 1.74 K
'T

mb

K f mb ? mb

T
Kf

Wsolute / Msolute
? Msolute
Wsolvent

1.74 K
4.90 K kg mol 1

0.355 mol kg-1

1.50 g
0.355 molkg 1 x 30.0 g

0.141 kg mol -1

141 g mol -1

95

Osmotic Pressure
Assume a system consisting of two compartments which
are separated by a semi-permeable membrane. Solvent
molecules A can pass freely through this membrane, but
solute molecules B cannot pass the membrane.
Osmosis is the spontaneous passage of solvent molecules
from the pure solvent (higher A concentration) into the
solution (lower concentration of A).

96

osmotic pressure

pure
solvent
semipermeable
membrane

Applied pressure
needed to prevent
volume increase

solution

net
movement
of solvent
solute
molecules

solvent
molecules

97

At equilibrium:

P A ( l , P  S ,T )

P *A ( l , P ,T )

P *A ( l , P  S ,T )  RT ln x A

P *A ( l , P ,T )

P *A ( l , P  S ,T )  P *A ( l , P ,T )  RT ln x A




?

0,

dG = -SdT + VdP
At constant T,
dG

d P *A

*
A dP

The osmotic pressure, , is the pressure that must be

applied to the solution to stop the influx of solvent. At
equilibrium, the chemical potential of the solvent must be
the same on each side of the membrane.
98

Integrating from P o P + S,
P *A (,P

 S ,T ) 

P *A ( l , P ,T

P S

*
V AdP

*
V AS

Assuming volume
constant of P

So

RT

*
ln x A  V AS

But ln x A

ln(1  x B ) |  xB

RT ( n B / n A )  (VA / n A )S

nB / n A
0

But VA | VA + VB = V as VB << VA
RT ( nB )  SV

SV

RTnB

Vant Hoff equation

99

Vant Hoff equation

For dilute solutions, the osmotic pressure is given by vant
Hoff equation:
Vsoln = nsoluteRT
Used for determination of molar masses of macromolecules
such as proteins and synthetic polymers.
Important for life cell wall membranes isotonic solution is
8.9 g/l of NaCl.

100

Example problem
What is the osmotic pressure of a 0.01 m solution of sucrose in
water? How high would a column of diluted sucrose be at
equilibrium? Assume 25 C and the density of the solution is
1.01 g/ml.
Solution
0.01 m solution contains 0.01 mole of sucrose in 1000 g of
water.
Volume of solution = 1000 g /1.01 g/ml = 990.1 ml = 0.9901 L
(0.9901 L) = (0.01 mol) x (0.08314 L.bar mol-1 K-1) x 298 K
= 0.250 bar
Substantial osmotic pressure
for such a dilute solution
101

0.250 bar = 0.250 x 105 Pa = 0.250 x 105 Nm-2

P = hg
0.250 x 105 Nm-2 = h x 1010 kg m-3 x 9.81 m.s-2
h = 2.52 m

102

Determining Molar Mass from Osmotic Pressure

PROBLEM: Biochemists have discovered more than 400 mutant varieties of
hemoglobin, the blood protein that carries oxygen throughout
the body. A physician studying a variety associated with a fatal
disease first finds its molar mass (M). She dissolves 21.5 mg
of the protein in water at 5.00C to make 1.50 mL of solution and
measures an osmotic pressure of 3.61 torr. What is the molar
mass of this variety of hemoglobin?
SOLUTION:

n
V

RT

3.61 Torr/760 Torr.atm 1

(0.0821 L.atm.mol 1K 1 )(278.1 K)

Number of moles in 1.50 ml

2.08 x 10 - 4 mol/L

2.08 x 10 -4 mol/L x 1.50 x 10 -3 L

3.12 x 10 -7 mol

Molecular weight

21.5 x 10 -3 g
3.12 x 10 -7 mol

6.89 x 10 4 g.mol 1
103