Lecture 3

30-09-2008

Lecture:
simple mixtures (cont)
colligative properties
membrane potential
Debye-Hckel limiting law
two-component phase diagrams
new problems

Last lecture problems

Chemical potential of liquid

Ideal solutions
Lets consider vapour (treated as perfect gas)
above the solution. At equilibrium the chemical
potential of a substance in vapour phase must be
equal to its potential in the liquid phase
For pure substance:
In solution:

A* A 0 RT ln p A*
A A 0 RT ln p A

A A* RT ln

pA
p

Francouis Raoult experimentally found that:

p A x A p A* Raoults law:

A A* RT ln x A
Mixtures obeying Raoults law called ideal solutions

Chemical potential of liquid

Molecular interpretation of Raoults law
rate of condensation

k ' p A kx A
rate of evaporation

k
xA
k'
and in case of pure liquid (x A 1):

pA

*
A

k'

Chemical potential of liquid

Similar liquid

Dissimilar liquid
often show strong
deviation

Chemical potential of liquid

Ideal-dilute solutions: Henrys law
In a dilute solution the molecule of solvent
are in an environment similar to a pure
liquid while molecules of solute are not!

pA xA K A
empirical constant

Chemical potential of liquid

Using Henrys law
Example: Estimate molar solubility of
oxygen in water at 25 0C at a partial
pressure of 21 kPa.

pA xA K A
xA

pA
21kPa
4
-1

2.9

10
mol
kg
K A 7.9 104 kPa kg mol-1
molality

[O 2 ] x A H2O 0.29mM

Liquid mixtures
Ideal solutions
If Raoults law applied to

mix G nRT ( A ln p A B ln pB )

we have:

mix G nRT ( x A ln x A xB ln xB )
mix S nR( x A ln x A xB ln xB )
mix H mix G T mix S 0
From molecular prospective it means that interactions of A-A, A-B, and B-B
are the same.

Liquid mixtures
In real solutions we can define excess functions, e.g.
excess entropy:

mix S E mix S mix S Ideal

Model: regular solution

SE 0 H E 0

Molecules are randomly distributed but A-B interaction

is different from A-A and B-B

H E n RT A B
Then: mix G nRT ( A ln A B ln B A B )

suppose:

Benzene/Cyclohexane

Colligative properties
Elevation of boiling point
Depression of freezing point
Osmotic pressure phenomenon
All stem from lowering of the chemical potential of the
solvent due to presence of solute (even in ideal
solution!)

Larger

Colligative properties
Elevation of boiling point
*

A ( g ) A* (l ) RT ln A
ln(1 B )

(l ) A ( g ) Gvap

RT
RT
*
A

Gvap H vap T Svap

(Here we neglect temperature dependence)

For pure liquid:

ln1

H vap
RT

Svap
R

H vap 1 1
ln(1 B )
( *)
*
RT T T
H vap 1 1
H vap T
B
( * )
R T T
R T *2

RT *2
T
B
H vap

Colligative properties
Depression of freezing point
*

A ( s ) A* (l ) RT ln A
RT *2
T
B
H vap
T K f B
Cryoscopic constant

Can be used to measure molar mass of a solute

Colligative properties
Solubility
*

B ( s ) B* (l ) RT ln B
ln B

B ( s) B (l ) G fus

RT
RT
*

G fus H fus T S fus

G fus (T * ) H fus T * S fus 0

H fus 1 1
ln B
( *)
R T T

Colligative properties: Osmosis

Osmosis spontaneous passage of pure solvent into solution separated
by semipermeable membrane

Vant Hoff equation:

[ B ]RT ,

[ B ] nB / V

Osmosis
*

A ( p) A* ( p ) RT ln A
dG SdT Vdp
*

A* ( p ) A ( p )

Vm dp

For dilute solution:

RT B Vm
nB / nA

V / nA

Vant Hoff equation:

[ B ]RT ,

[ B ] nB / V

More generally:

[ B]RT (1 b[ B] ...)
Osmotic virial coefficients

Osmosis: Examples
Calculate osmotic pressure
exhibited by 0.1M solutions of
mannitol and NaCl.
[ B ]RT ,

[ B ] nB / V

Mannitol (C6H8(OH)6)

Osmosis: Examples
alt
s
ing ion
s
rea trat
c
De ncen
co

Isotonic conditions

Inc
co reas
nc
en ing s
tra alt
tio
n

Internal osmotic pressure keeps

the cell inflated

Hypotonic conditions:
cells burst and dye
haemolysis (for blood)

Hypertonic conditions:
cells dry and dye

Application of Osmosis

Using osmometry to determine molar mass of a macromolecule

Osmotic pressure is measured at a series of mass concentrations c and a plot of / c
vs. c is used to determine molar mass.

[ B ]RT (1 b[ B ] ...)
gh

c/M
h
RT
bRT

c ...
2
c gM gM

Membrane potential

Electrochemical potential
j j z j N Ae j 0 RT ln[ j ] z j F

Fext
Fcyt

Example: membrane potential

Na 0 RT ln[ Na in ] z Na F in Na 0 RT ln[ Na out ] z Na F out

RT [ Na out ]
ln

F [ Na in ]

Na+
Na+

P-

PNa+

Na salt of a protein

Na+

P-

PNa+

Na+

Activities

the aim: to modify the equations to make them applicable to real solutions

Generally:

pA
*
A RT ln *
pA

vapour pressure of A above solution

vapour pressure of A above pure A

For ideal solution

*

A A* RT ln A

(Raoults law)

For real solution

*

A A* RT ln a A

activity of A

a A A as A 1

A A* RT ln A RT ln A
activity coefficient of A

Activities
Ideal-dilute solution: Henrys law
*

B B* RT ln

pB
KB
*

RT
ln
RT ln B
B
*
*
pB
pB

B 0

B B 0 RT ln B

Real solutes
*

B B RT ln aB
0

p B K B B

pB
aB
KB

Example: Biological standard state

Biological standard state: lets define chemical potential of hydrogen at pH=7

H H 0 RT ln aH
H H 0 7 RT ln(10) H 0 40kJ / mol

Activities
Margules equation

ln A B 2

ln B A 2

Gmix nRT ( A ln a A B ln aB )
Gmix nRT ( A ln A B ln B A ln A B ln B )
Gmix nRT ( A ln A B ln B A B )

H E n RT A B

Raoults law
Henrys law
p A Ae p A*

Ion Activities
a

0 RT ln a

b
b0

standard state: ideal solution at molality b0=1mol/kg

Alternatively:

0 RT ln b RT ln ideal RT ln
ideal solution of the same molality b

In ionic solution there is no experimental way to separate contribution of cations

and anions

Gm ideal ideal RT ln

ideal RT ln ; ideal RT ln
In case of compound MpXq:

Gm p q Gm ideal RT ln p q

Debye-Hckel limiting law

Coulomb interaction is the main reason for
departing from ideality
Oppositely charged ions attract each other
and will form shells (ionic atmosphere)
screening each other charge
The energy of the screened ion is lowered
as a result of interaction with its
atmosphere

Debye-Hckel limiting law

In a limit of low concentration the activity coefficient can be calculated as:
1

log z z AI 2 , A 0.509 for water

where: I

1
zi 2 (bi / b 0 )

2 i

Ionic strength of the solution

Example: calculate mean activity coefficient of 5 mM solution of KCL at 25C.

1
I (b b ) / b 0 b / b 0 5g103
2
log z z AI

0.92

0.509*(5g103 )1/ 2 0.036

Debye-Hckel limiting law

Extended D-H law:

log z z AI

log

z z AI
1 BI

Phase Diagrams

Phase diagrams
- what is the composition (number
of phases and their amount and
composition) at equilibrium at a
given temperature;
- what happens to the system
when is cools down/heats up
- we can predict the structure and
the properties of the system at
low temperature.

iron-carbon diagram

Phase diagrams

water-surfactant-oil

Thats the base of all modern

engineering from swiss knife
to food and cosmetics!

iron-carbon diagram

Phase diagrams
Constituent a chemical species that is present
Component a chemically independent constituent of the system (i.e.
not connected by a chemical reaction)

CaCO3 ( s
)
Phase1

CaO( s ) CO2 ( g )
Phase2

C2

Phase3

Variance the number of intensive variables that can be changed

independently without disturbing the number of phases at equilibrium.
Phase rule (J.W. Gibbs):
F=C-P+2
number of phases
variance
number of components
Indeed: number of variables would be:
number of equations:

P*(C-1)+2
C*(P-1)

One component diagrams

C=1 therefore F=C-P+2=3-P

One component diagrams

Detection of phase transitions and building a phase diagram is based on
calorimetry measurements

Two-components diagrams
C=2 therefore F=4-P.
We have to reduce degree of freedom e.g. by fixing T=const

Vapour pressure diagrams

Raoults Law

p A x A p A*

p B xB p B *

p p A pB pB* x A ( p A* pB* )

Two-components diagrams
The composition of vapour
pA
y

;
From Daltons law: A
p
From Raoults law: p A x A p A *;

yA

pA *
;
pB * ( p A * pB *) x A

pB
p
p B xB p B *

yB

yB 1 y A

p*A
pB*

Two components diagrams

Two components diagrams

Two components diagrams

The lever rule

n l n l

Two-components diagrams
Temperature-composition diagrams
Distillation of mixtures

Two-components diagrams
Temperature-composition diagrams
Azeotropes

Azeotrope, evaporation w/o change in composition

n l

A-B interacation stabilize the mixture

A-B interacation destabilize the mixture

Two components diagrams

Immiscible liquids

Will boil at lower temperature!

p p A pB

Two components diagrams

Liquid-liquid phase diagrams

Two components diagrams

mix G nRT ( A ln A B ln B A B )

mix G 0 ln
(1 2 ) 0

Upper critical solution T

Two components diagrams

Lower critical temperature is usually caused by breaking a weak complex

of two components

Two components diagrams

Upper critical temperature is less

than the boiling point

Boiling occur before liquids are fully

miscible

Liquid-solid phase diagrams

Eutectic
composition

Liquid-solid phase diagrams

Eutectic halt

Liquid-solid phase diagrams

Reacting systems

Incongruent melting: compounds melts into

components

Liquid crystals

Mesophase an intermedediate phase between

solid and liquid. Example: liquid crystal
Liquid crystal substance having a liquid-like
imperfect order in at least one direction and longrange positional or orientational order in at least one
another direction
Nematic
Nematic

Smectic
Smectic

Cholesteric
Cholesteric

Nematic crystals in LCD

Problems I
5.6a The addition of 100 g of a compound to 750 g of CCl4
lowered the freezing point of the solvent by 10.5 K. Calculate
the molar mass of the compound.
5.14a The osmotic pressure of solution of polystyrene in
toluene were measured at 25 C and the pressure was
expressed in terms of the height of the solvent of density
1.004g/cm3. Calculate the molar mass of polystyrene:
c [g/dm3] 2.042 6.613 9.521 12.602
h [cm]
0.592 1.910 2.750 3.600
5.20(a) Estimate the mean ionic activity coefficient and activity
of a solution that is 0.010 mol kg1 CaCl2(aq) and 0.030 mol
kg1 NaF(aq).

Problems II
Atkins 6.9b: sketch the phase diagram of
the system NH3/N2H4 given that the two
substances do not form a compound and
NH3 freezes at -78C, N2H4 freezes at
+2C, eutectic formed with mole fraction
of N2H4 0.07 and melts at -80C.
Atkins 6.10b Describe the diagram and
what is observed when a and b are
cooled down

Home problem analysis

4.7a: An open vessel containing (a) water, (b) benzene, (c)
mercury stands in a laboratory measuring 5.0 m 5.0 m 3.0
m at 25C. What mass of each substance will be found in the
air if there is no ventilation? (The vapour pressures are (a) 3.2
kPa, (b) 13.1 kPa, (c) 0.23 Pa.)
4.9a Calculate the melting point of ice under a pressure of 50
bar. Assume that the density of ice under these conditions is
approximately 0.92 g cm3 and that of liquid water is 1.00 g
cm3.
5.2a At 25C, the density of a 50 per cent by mass ethanol
water solution is 0.914 g cm3. Given that the partial molar
volume of water in the solution is 17.4 cm 3 mol1, calculate the
partial molar volume of the ethanol.