Multicomponent System

A general term
Describes a system composing more
than 2 components (as compared to
a 1 and 2-component system)
In electronics, biology and synthetic
biology, structural fracture
dynamics, chemistry and molecular
dynamics, color image system,
hydrogeology, material science,
etc.etc.
 Recall: Delta G and
G = spontaneous
G = + non spontaneous
G = 0 in equilibrium
= G/n
 Recall: Gibbs Free Energy
Important in everyday
processes where T and P are
intrinsic variables
A must have fundamental
quantity
 Recall: dG = -SdT + VdP
Given an expression G (T,P)

We can calculate S
(G/T)P

And also V
(G/P)T
 Recall: G = H TS
Reverse that:
H = G + TS

We have S, G, and we know that:

U = H PV

So we can calculate all other

quantities if we know the Gibbs
Free Energy
 Recall: Solid-Liquid Equil.
If we take the temperature to be
constant and we want to know
how G is changing with
dG = -SdT + VdP
dG = VdP

Let G (T, P2) or (T, P2)

(T, P2) = (T, P1) + VmdP

P2

P1
 Recall: Solid-Liquid Equil.
(T, P2) = (T, P1) + VmdP
P2

P1

Vm is small by approximation or
we can say that the solid and
liquids are (I)
Meaning as you change the
pressure, the volume does not
change
Vm is constant (good approx.)
 Recall:1-component, 2-phase system
Component: water
System: Ice + liquid water

dG = 0 ; dnice = dnliquid water

(T, P2) = (T, P1) + Vm(P2 P1)
(T, P2) = (T, P1)
(T)
 Summary
(T)
The Gibbs Free Energy most of
the time is just a function of
temperature
This is a close approximation
And we can say that this is a good
approximation
 Recall: Ideal Gas
dG = -SdT + VdP ; Vm = RT/P
dGm = VmdP
(T,P1) = (T,P1) + RT/PdP
P2

P1

= (T,P1) + RT ln P2/P1
We can reference this to the
standard state.
We can take P1 as 1 bar or 1 atm
as our reference point
 cont.
(T,P) = (T) + RT ln P
= (T) + RT ln P/1atm/bar
(T,P) = (T) + RT ln P

Any questions?
Lets continue now with multi-
component systems
 Recall:1-component, 2-phase system
Component: water
System: Ice + liquid water

What we know?
Species change
They get destroyed while others
get created
 Examples
H2(g) + Cl2(g) = 2HCl2(g)
2H2(g) + O2(g) = 2H2O(l)

H2O(l) H2O(s)

or a cell place in a beaker of

distilled water
 G (T,P,n1,n2)
What if I change n1 and/or n2

dG = (G/T)P,n1,n2dT +
(G/P)T,n1,n2dP +
(G/n1)P,T,n2dn1 +
(G/n2)P,T,n1dn2
(G/T)P,n1,n2 = ?
(G/P)T,n1,n2 = ?
 cont.
We will define the other 2 as

(G/n1)P,T,n2 = 1
(G/n2)P,T,n1 = 2

Rewriting: j

SdT + VdP + idni

i=1
 cont.
G is extensive,
scales with size
of the system

= (G/ni)P,T,n i

is intensive, n obviously scales

scales not with with size of the
size of the system system extensive
 Summary
We can now define the other
fundamental equations with
H = G + TS dH = dG + d(TS)
j

idni
dH= TdS + VdP + i=1
dU=TdS PdV
j

dU= TdS PdV + idni

i=1
dA=-SdT - PdV
j

dA= SdT PdV +

i=1
id ni
 Summary
We can also write in several ways:
j

dH= TdS + VdP + idni

i=1

i = (H/ni)S,P,ni
j

dU= TdS PdV +

i=1
id ni

i = (U/n1)S,V,ni
 cont.
What do we want to prove?

ini = G

or simply i = i

This is our goal

Anyone? or QUIZ?
or HomeWork???
 cont.
G (T,P,n1,n2)
G (T,P,n1,n2)
G (T,P, n1,n2)
G(T,P,n1,n2) = G(T,P, n1,n2)
deriving
(G/n1)(n1/) + (G/n2)(n2/)
= G(T,P, n1,n2)
1 n1 + 2 n2 = G
 cont.

1 n1 + 2 n2 = G

1 + 2 = G

i ni = GT
 Partial Molar Quantity
a thermodynamic quantity
indicates how an extensive property
of a solution/mixture varies with
changes in the molar composition of
the mixture at constant temperature
and pressure
a partial derivative with respect to
the quantity (number of moles) of
the component of interest
 Ex. Partial Molar Volume
the partial molar volume of a
substance X in a mixture is the
change in volume per mole of X
added to the mixture
Ex. 1 mole of water added to a
volume of water will increase the
volume by 18 cm3
Ex. 1 mole of water added to a
volume of ethanol will increase the
volume by 14 cm3
 Mole Fraction
a way of expressing composition of a
mixture
The mole fraction of each component i
is defined as the amount of substance ni
divided by the total amount of
substance in the system n :
n = ni
i
The sum of all the mole fraction is equal
to 1:
Xi = 1
i
 Consider a mixture of A and B
The mole fraction of A would be
moles of A divided by the moles of
A and moles of B:

mole fraction of A = moles of A

moles of A + moles of B
or simply:

mole fraction of A = nA
nA + nB
 A mixture of A and B

A(g) YA P, T
Gas
B(g) YB = 1 - YA

A(l) XA
Liquid
B(l) XB = 1 - XA
 Review

Considering the solution of A

and B to be ideal
Will it obey Raoults Law?
What is the value of G of
mixing A and B?
 Recall: Raoults Law

PT = total pressure PBA = partial

PA* = PA + PB pressure of B A
PT
PA* = pressure
of pure A
PB PB* = pressure
PA of pure B

So what is PA = ?
0 1 what is PB = ?
XB
 cont. Raoults Law
the vapor pressure of an ideal
solution is dependent on the
vapor pressure of each
chemical component and the
mole fraction of the
component present in the
solution
PA = XAPA*
 cont. Raoults Law
At equilibrium, the total vapor
pressure of an ideal solution is

P = XAPA* + XBPB* +

P = XiPi*
i
What is the relation between P and YA
(PA*)(PB*)
P=
(PA*) + (PB* PA*)(YA)

PA*
P

PB PB*
PA

0 1
XB
Recall: 2-component system diagram

p=1
v=3
Vapor
p=2
v=2
T Liq.+Vap. P
p=1
v=3
Liquid

0 1
X
 If we know the total P and T, can we
plot it considering both mole fractions?
(PA*)(PB*)
P=
Phases?
(PA*) + (PB* PA*)(YA)
PA* Liquid

Liq.+Gas

PB*

Gas

0 1
XB , YB
Starting at P1 and lowering it to a point, P2 ,
what will be the relationship of XB and YB?

Liquid
PA* P1
Liq.+Gas

P2
P2
PB*
YB < XB
Gas

0 YB(2) XB(2)
(1) 1
XB , YB
 lowering the pressure further

Liquid
PA*
Liq.+Gas
P2
P3
P3
PB*
YB < XB
Gas

0 YB(3) 1
XB , YB XB(3)
 lowering the pressure further

Liquid
PA*
Liq.+Gas

P3
PB*
YB = XB
Gas

0 1
XB , YB
 lowering the pressure further

Liquid
PA*
Liq.+Gas

PB*

Gas

0
YB 1
XB , YB
Can you think of an application for this?

PA* Liquid

Liq.+Gas

PB*

Gas

0 1
XB , YB
 How much of each component
are there in each phase?

PA* Liquid

Liq.+Gas

PB*

Gas

0 1
XB , YB
 cont.
nA = total number of moles of A
nB = total number of moles of B
ng = total number of moles of gas
nl = total number of moles of liquid

nA = (YA)1(ng)1 = (YA)1(nTotal)
 How much of each component
are there in each phase?

nA = (YA)2(ng)2 + (XA)2(nl)2
= (YA)1 [(ng)2 + (nl)2 ]
PA* Liquid

Liq.+Gas
PB*
Gas

0 1
XB , YB
 cont.

nA = (YA)1(ng)1 = (YA)1(nTotal)

nA = (YA)2(ng)2 + (XA)2(nl)2
= (YA)1 [(ng)2 + (nl)2 ]
 How much of each component
are there in each phase?

PA* Liquid

2
Liq.+Gas

PB*
1
Gas

0 1
XB , YB
 cont.

(YA)1(ng)2 + (YA)1(nl)2 = (YA)2(ng)2 + (XA)2(nl)2

[ (YA)1 (YA)2 ](ng)2 = [ (XA)2 (YA)1 ](nl)2

(ng)2 [ (XA)2 (YA)1 ]

=
(nl)2 [ (YA)1 (YA)2 ]
Lever Rule - How much of each
component is there in each phase?
Consider a mixture of A and B
A = gas phase
YA YB T B = liquid phase
T = fixed
2 degrees of freedom
P (T,
T, XB )

XA XB

0 1
XB
 Recall: Phase diagram for the mixture
Bubble Line

PA* Liquid

Liq.+Gas

PB*
Dew Line
Gas

0 1
XB , YB
 Recall: Daltons & Raoults

So from And from Also from Raoults

Daltons Law: Raoults Law: Law:
PA = ? PA = ? PB = XBPB*
= Y AP = XAPA* = (1 XA)PB*
Rearranging:
YA = PA /P
= PA /(PA + PB)
XAPA*
=
XAPA* + XBPB*
 Recall: Daltons & Raoults
XAPA*
=
XAPA* + (1 XA)PB*
XAPA*
=
XAPA* + PB* XAPB*

XAPA*
=
PB* + XA(PA* PB*)
 Recall: Daltons & Raoults
XAPA*
YA =
PB* XA(PB* + PA*)

YAPB*
XA =
PA* + YA(PB* PA*)

PA XAPA*
P = P =
YA YA
 Summary

PA*PB*
P =
PA* + YA(PB* PA*)
Consider a mixture of A and B
A = gas phase
YA YB P B = liquid phase
P = fixed
2 degrees of freedom
T (P,
P, XB)

XA XB

0 1
XB
 Recall: T vs X phase diagram

Dew TB*
Line Vapor

Liq.+Vap.

T
TA* Bubble
Liquid
Line

0 1
XB
Recall: T vs X phase diagram

TB*
Vapor

T
TA* Liquid

0 1
YB XB
XB
Consider a mixture of A and B
A = volatile solvent
B = solute
 Recall: P vs X plot
T = fixed What to
PA* PA*==Xpressure
APA* remember?
= (1ofAXB) PA*
If the solution
behave as
plotted, then
it is an _?_
solution.
0 1
XB
1
XA 0
Consider a sugar solution

PA PA* PA = PA* XAPA*

= PA*(1 XA)
= PAXB
 Recall: H2O phase diagram

1 atm
P

273 T 373
 Problem 2.1
Ten grams of pure sodium
chloride is dissolved in 1000 g of
water. By how much is the
freezing temperature depressed
from its normal melting
temperature of T = 273.15 K?
(Kf = 1.86 K kg mol1).
 Problem 2.1
Ten grams of pure sodium chloride is dissolved in 1000 g
of water. By how much is the freezing temperature
depressed from its normal melting temperature of T =
273.15 K? (Kf = 1.86 K kg mol1).

T = 1.86 x 1000 x 0.01/58.5

T = 0.32 K
Adding salt to water
 Adding salt to water
Adding salt to the water has caused
both the lines to drop down the page,
thus causing the intersection
temperature to change.
Adding salt to water, in addition to
changing its chemical potential,
changes the temperature at which
boiling occurs boiling temperature is
raised, relative to that of pure water.
 Recall: Freezing Point Depression

FPpure solvent > FPsolution

conc. of nonvolatile solute, change in FP

TFP = Kfm
where T = FPsolvent FPsoln
Kf = molal FP depression
constant
m = molal concentration
of solute
 Recall: Boiling Point Elevation

BPpure solvent < BPsolution

conc. of nonvolatile solute, change in BP

TBP = Kbm
where T = BPsoln BPsolvent
Kb = molal BP elevation
constant
m = molal concentration
of solute
 Problem 2.2
Predict the BP of 1.25 m sucrose
solution. (Kb of H2O = 0.512 oC/m)

BPsoln = (0.512 x 1.25) + 100 C

T = 100.64 C
 ?Question? / Point to ponder
Why do we prefer molaLity
m to molaRity M in solving
boiling point elevation and
freezing point depression?
We prefer m because the volume of
the liquid or solution changes with
temperature, whereas that of a mass
does not
Molality is temperature independent
whereas concentration is not
Recall: Vapor Pressure Lowering

VPpure solvent > VPsolution

conc. of solute, change in VP

P = XsoluteVPsolvent
where P = VPpure solvent VPsolution
Xsolute = mole fraction
of solute
VPsolvent = VP of pure solvent
 Problem 2.3

Calculate the vapor pressure of a

2.0 M aqueous solution of sucrose
(342.3 g/mol) at 30 oC. Vapor
pressure of pure water at 30 C is
31.82 mm Hg.
(water = 0.99565 g/mL)
 Problem 2.3
Calculate the vapor pressure of a 2.0 M aqueous
solution of sucrose (342.3 g/mol) at 30 oC. Vapor
pressure of pure water at 30 C is 31.82 mm Hg.
(water = 0.99565 g/mL)

P = 0.9651 x 31.82

P = 30.72 mm Hg
 Recall: Osmotic Pressure
= nRT/V
= MRT

where = osmotic pressure

n = moles of solute
M = molarity of solution
R = gas law constant
T = absolute temperature
 Problem 2.4
The average osmotic pressure of
seawater is about 30.0 atm at 25 oC.
Calculate the molar concentration of
an aqueous solution of sucrose
(C12H22O11) that has the same osmotic
pressure with seawater.
 Problem 2.4
The average osmotic pressure of seawater is about 30.0
atm at 25 oC. Calculate the molar concentration of an
aqueous solution of sucrose (C12H22O11) that has the
same osmotic pressure with seawater.

M = 30 / (0.0821 x 298.15)

M = 1.23 M
 Definition of Terms
Cryoscopy
measurement of the degree of
dissociation or molar mass of solute using
freezing point depression data
comes from Greek kryos meaning frost

Ebullioscopy
measurement of molar mass of solute
using boiling point elevation data
from the Latin (e)bullire meaning
bubbly
 Recall: T plot
also recall:
cont.
 cont.

and at constant T and P, assuming an

ideal mixture, we can relate this to the
mole fraction of the component/solute:
 ?Question?

Who said that the amount of

gas dissolved in a liquid or
solid is in direct proportion to
the partial pressure of the gas?

William Henry
 Henrys Law

At a constant temperature, the

amount of a given gas dissolved
in a given type and volume of
liquid is directly proportional to
the partial pressure of that gas
in equilibrium with that liquid.
 Ideal Dilute Solutions

In an ideal dilute solution, the

solvent obeys Raoults law but
the solute obeys Henrys law.
 Henrys Law

P = KHc
where P = partial pressure of the
solute above the solution
KH = Henrys law constant
(L-atm/mol)
c = molar concentration
of solute
 Henrys Law

P = KHX
where P = partial pressure of the
solute above the solution
KH = Henrys law constant (atm)
X = mole fraction of the solute
 Henrys Law

c = K HP
where P = partial pressure of the
solute above the solution
KH = Henrys law constant
(mol/L-atm)
c = molar concentration
of solute
 cont.
again recall the chemical potential,
assuming an ideal dilute mixture at
constant T and P, we can replace the
mole fraction:
KH m
c
P* m
c
 Problem 2.5
What is the concentration of
molecular oxygen in water at
25 C? The atmosphere above
the water has a pressure of
105 Pa and contains 21% of
oxygen.
KH O2 = 1.28 103 mol/L-atm
 Problem 2.5
What is the concentration of molecular oxygen in water at
25 C? The atmosphere above the water has a pressure of
105 Pa and contains 21% of oxygen. KH O2 = 1.28 103

PO2 = 0.21 x 105 = 2.1 x 104

= 0.21 atm
[O2] = 0.21 x (1.28 x 103)
= 2.69 x 104 M
Consider a liquid A and liquid B
Recall if we have pure A:
A
A*(l,T,P) = A(g,T) +
RT ln PA/P
At coexistence, we have:
A(l,T,P) = A(g,T,PA)

B Considering them ideal:

A(g,T,PA) = A(g,T) +
RT ln PA/P
:
A(l,T,PA) = A(g,T) +
RT ln PA/P
 Summary
We will have a convenient form of
A in an ideal liquid mixture:
A(l,T,P) = A*(l,T,P) + RT ln PA/P*

Recall Raoults Law

A(l,T,P) = A*(l,T,P) + RT ln XA
 Summary
A(l,T,P) = A*(l,T,P) + RT ln XA

XA = 0 1

of pure liquid
 Summary
The chemical potential of the
liquid in the solution, A is
always less than that of the
pure liquid A* at the same
temperature, T and pressure, P.
Implications of this is clearly
demonstrated in osmotic
pressure
Consider a liquid A and liquid B

B
 Liquid mixture of A and B
Recall G:
A + B G = nXAA + nXBB
Recall A:
G = nXA(A* + RT ln XA)
+ nXB(B* + RT ln XB)

Rearranging:
Gmix= nRT (XAlnXA +
XBlnXB)
 Summary
Gmix= nRT (XAlnXA + XBlnXB)
The G of mixing of the liquid is
similar to that of a gas
There is no interaction between
the particles of the mixture
Therefore we can say that
entropy contributes to the
mixing
 Recall: G = VdP + SdT
Smix = -[(Gmix)/T]P
= - nR(XAlnXA + XBlnXB)
Hmix = Gmix + TSmix
=0
Vmix = -[(Gmix)/P]T
=0
 Summary
The H of mixing of the
liquid is negligible since
there is no interaction
between the particles
Similarly Vmixing is also
zero due to the fact that in
an ideal solution there will
be no interaction between
the components particles.
Consider a liquid A and liquid B
For a non ideal liquid A:
A
A*(l,T,P) < 0

We have an interaction
between particles of A
A- - -A
AA < 0
B
Similarly we have an
interaction between B
B---B
BB < 0
 Liquid mixture of A and B
Mixing:
A + B A --- B A --- B
AB AB

Now we have 2 :
AB + AB

If we take also the first

interactions:
mix= 2AB (AA +BB)
 = 2AB (AA +BB)
The possible values of is
either negative or positive
We can say now that there is
an energy of mixing unlike in
the ideal mixture.
If its positive, then the
interaction between like
particles are favorable
 Positive deviation: > 0
Hmix Vmix
Gmix = n/4 () +
nRT (XAlnXA + XBlnXB)
Gmix(non-ideal) > Gmix(ideal)
ex. acetone and carbon
disulfide
 Problem 2.6
Given two liquids, A and B. A
being carbon disulfide and B
acetone. If the liquids are mix
together and the mixture is not
ideal, draw a phase diagram
showing the relationship
between P and composition of
the mixture. (Note: use dotted line
for non-ideal, straight line for ideal)
 CS2 : b.p. = 319 K
C3H6O : b.p. = 330 K

PA*
P

PB PAcetone*
PA

0 1
XB
 CS2:C3H6O mixture
PC3H6O> XC3H6OP*C3H6O
P*CS
2 PCS2 > XCS2P*CS2

PT(n.i.) > PT(ideal)

P*C H O
3 6

0 1
XC H O
3 6
 Negative deviation: < 0
Gmix(non-ideal) < Gmix(ideal)

Unlike in the positive deviation,

the interaction between
dissimilar species is favorable.

ex. acetone and chloroform

 Negative deviation: < 0
For a non ideal liquid
mixture like acetone and
H 3C
chloroform, H-bonding
O
C=O exist.
H 3C Theres an interaction
The species
H between different
species.
will prefer
to be in the CCl
liquid phase Cl
rather than Cl Simply, mixing is
in the gas. favorable.
 CHCl3 : b.p. = 335 K
C3H6O : b.p. = 330 K

P*C3H6O

P*CHCl3

0 1
XCHCl3
 CHCl3:C3H6O mixture
PC3H6O< XC3H6OP*C3H6O

PCHCl3< XCHCl3P*CHCl3
P*C3H6O
PT(n.i.) < PT(ideal)

P*CHCl3

0 1
XB
 Recall: Ideal Dilute Solutions

XCS2 = XB 1
P*CS = P*B
2

P*C H O
3 6

0 1
XCS = XB
XCS2 = XB 0 2
 Recall: Ideal Dilute Solutions
Case 2: XB 0 Case 1: XB 1
PB = XBKB PB = XBP*B
obeys Henrys obeys Raoults
P* B

P*A

0 1
XB
 Problem 2.7
Benzene and toluene form an
ideal mixture, i.e. they obey
Raoults law. At 20 C, the
pressure of benzene and toluene
are 0.747 and 0.223 of their
partial pressure respectively.
What is the pressure above a
mixture of these two liquids
that contains 12 mol% of
benzene?
 Problem 2.8
Given a liquid mixture of A and
B at 50 C. What is the
composition of B in the gas
phase if the molar fraction of A
in the liquid phase is 0.9 and the
vapor pressures of pure A and
pure B are 0.67 bar and 1.2 bar
respectively.
+ deviation, azeotrope

0 1
 deviation, azeotrope

0 1
 Summary
Recall the 4 colligative properties
nsolvent >>> nsolute
A(l,T,P) < A*(l,T,P)
A(l,T,P) = A(g,T,P)
You can derive the equation of the
4 properties from the chemical
potential
 Summary
Lets consider vapor pressure
lowering
P = PA PA*
= XAPA* PA*
= PA*(XA 1)
= (1 XA)PA*
= (XBPA*)
<0
 Summary
How about boiling point elevation?
A(l,T,P) = A(g,T,P)

obeys Raoults law

A*(l,T,P) + RT ln XA
solute is nonvolatile

= A*(g,T,P)
A*(l,T,P) + RT ln XA = A*(g,T,P)
 Summary
Rearranging:
ln XA = 1/RT [ A*(g) A*(l) ]
vaporization

ln XA = Gvap / RT

we do not want the log/ln

we do want a T not just the T
 Summary
Simplify ln XA in terms of solute:
ln XA = ln (1 XB)
solute, small amt.

= XB
= nB / nA + nB
= nB / nA
we also need m (molality) so
 Summary
We multiply the n with M (mass):
(nB / nA) (MA/MA)
nB/MA = molality
MA/nA = molar mass

= (mB)(MMA)
going back to our previous eq.
(mB)(MMA) = Gvap / RT
mB = Gvap / RT(MMA)
 Summary
we eliminated the log, but still no
delta T
how do we get that?
remember, everything is very small
so one thing to get a very small
change in T is to get the derivative
with respect to T
so take the derivative of both side
with respect to T
 Summary
/T [ mB = Gvap / RT(MMA) ]
(mB/T)P = [1/R(MMA)]
[(Gvap/T) /T]P
Recall the Gibbs-Helmholtz eq.

incorporating that to the previous eq.

 Summary
(G/T)/T = H/T
(mB/T)P = Hvap/T2R(MMA)
rewriting
dT = (T2R(MMA)/Hvap) dmB
since we are putting small
amounts of solute B, dmB = mB + 0
rewriting
dT = (T2R(MMA)/Hvap) mB
 Summary
dT = (T2R(MMA)/Hvap) mB
rewriting

Tb2R(MMA)
T = mB
Hvap

T = KB mB
 Historical background
Fragrant eau de Cologne is a dilute
perfume introduced in Cologne (Germany)
in 1709 by Jean Marie Farina.
The word perfume comes from the Latin
per fumem, meaning through smoke.
It was probably a modification of a popular
formula made before 1700 by Paul
Feminis, an Italian in Cologne, and was
based on bergamot and other citrus oils.
The water of Cologne was believed to
have the power to ward off bubonic
plague.
 cont.
Eau de Cologne perfume is made
from about 8085 per cent water and
1215 per cent ethanol. Volatile
esters make up the remainder, and
provide both the smell and colour.
These esters are stable in the dark,
butdegrade in strong sunlight, which
explains why so many perfumes are
sold in bottles of darkened or frosted
glass.
 Changing the perceived concentration
Adding alcohol to an aqueous
perfume increases the pressure
of the gases above the liquid.
WHY?
The vapor pressure of alcohol
is higher than that of water.
What can we say in terms of
the activities of the
components?
 Changing the perceived concentration
We can say that the activity,
a, of the organic components
imparting the smell will
increase.
This increases the perceived
concentration of the esters.
And increasing a(ester) has the
effect of making the cologne
more pungent.
 Changing the perceived concentration
So what?
The product requires less ester
because the alcohol increases
its perceived concentration.
Incidentally, the manufacturer
will save money this way.
NOTE: Essential oils are very
expensive.
 Thermodynamic activity, a
The concept of activity was
introduced in the early 20th
century by G. N. Lewis.
The values of activity, a, and
concentration [c ] are the same
for very dilute solutions, so the
ratio of a and c is one because
the real and perceived
concentrations are the same.
 Thermodynamic activity, a
As a working definition, the
activity may be said to be the
perceived concentration and is
therefore somewhat of a fudge
factor.
But more formally, the activity
a is defined by:
 Thermodynamic activity, a

The activity a and the activity

coefficient are both dimension-
less quantities, which explains
why we must include the
additional c term, thereby
ensuring that a also has no
units.
 Thermodynamic activity, a

where a = activity
= activity coefficient
c = concentration
c = 1M
 Problem 2.9
A tooth filling is made of a silver
amalgam that comprises 37 mol
% silver. What is the activity of
the mercury, a(Hg)?
Note: The word amalgam comes from
the Greek malagma meaning to make
soft, because a metal becomes pliable
when dissolved in mercury. Another
English word from the same root
ismalleable.
 Problem 2.9
X(Hg) + X(Ag) = 1
X(Hg) = 1 X(Ag) = 0.63

And since, the activity of the

mercury a(Hg) is the same as its
mole fraction, X(Hg),

X(Hg) = a(Hg) = 0.63

 Problem 2.10
Hydrogen gas is mixed with a
nitrogen bath gas. The overall
pressure is P . If the mole
fraction of the hydrogen is
expressed as 10 per cent, what
is its activity?
Note: The activity of a pure gas is its
pressure in multiples of the total
pressure, P.
 Problem 2.10
10% = 0.1 ; P = 1

By definition, X(X) = partial

pressure, P(X), so:

a(H2) = X(H2)
= P(H2) P
= 0.1/1
= 0.1
 Activity of solutions
We can consider several situations:
The activity of a liquid mixture or mixture of
liquids.
The activity of solute in a solvent.
The activity of ions in a solution.

Not a good idea to suggest that the

activity of a liquid in a mixture is
equal to its mole fraction X because
of complications due to
intermolecular interactions
 Activity of solutions
The activity a and concentration
c may be considered to be
wholly identical if the
concentration is tiny.
For all these other situations,
we will employ the Debye
Hckel laws to calculate the
activity coefficient .
 Activity of solutions
Knowing the value of , we
then say that a = (c c )
Remember to remove the
concentration units because a
is dimensionless.
DebyeHckel theory is
derived from the knowledge
of electrostatic considerations
 DebyeHckel

The DebyeHckel theory

suggests that the probability
of finding ions of the opposite
charge within the ionic
atmosphere increases with
increasing attractive force.
 Ionic interactions
We assume the ions have an energy
distribution as defined by the
Boltzmann distribution law.
We can say that electrostatic forces
affect the behavior and the mean
positions of all ions in solution
Larger-charge ions are more likely to
associate strongly than ions having a
smaller charge
 Recall: Maxwell-Boltzmann law
The thermodynamic temperature
is the sole requirement to describe
it.
Molecules do not have the same
energies but a distribution of
energies.
It shows few particles having large
and tiny energies while majority
possesses lesser energies.
Energy distribution of N2
Electrostatic interaction
 Electrostatic interaction

where = electrostatic interaction

z+, z = magnitude ionic charge
r = inter-ionic distance
= relative permittivity
 Ternary system
C = components
=3

F =5P
Gibbs-Roozeboom diagram
A, B & C represents
A pure substances
AB AC
edges represents
binary systems

B C
BC
 Gibbs-Roozeboom diagram
A A point inside the
triangle represents
a ternary systems
XA + X B + X C = 1

B C
 Partially
AB Miscible
& AC : miscible Liquids
; BC : partially miscible
b & c represents B-rich
plait point the point in A and C-rich phases
which compositions of 2 respectively that are at
phases in equilibrium equilibrium
plait point
becomes identical
bc tie line
d1 d2 represents
a composition of B- P=1 d2 d3 represents
rich layer a composition of C-
rich layer
d2 c
b
d1
P=2 d3
B C
Partially Miscible Liquids
b & c represents B-rich
A and C-rich phases
respectively that are at
equilibrium

bc tie line

P=1

c
b
P=2
B C
CH3COOH-CHCl3-H2O
 Further readings

Common Ion Effects

Double Salt Formation
Salting Out