PARTIAL MOLAR QUANTITIEs

O PARTIAL MOLARPROPERTIES
Consider a thermodynamic extensive property such as volume, free energy, heat content,heat
capacity, the value of which, for a homogeneoussystem, is completelydetermined by the stateof
the system, e.g., temperature, pressure and the amount ofvarious constituents present and maybe
denoted by the general symbolX. Thus,
T, m, 712,713,..., ni )
where, P = pressure, T = temperature and 711,112,713,... are the number of moles of the consituents
respectively, and X is a thermodynamicproperty.
If there is a small change in the pressure, temperature of the system, as well as in the amount
of its constituents, then the change in the property X is given by
dnl +
DPT n n n Pn n n Dni P,Tn n
dn2 + + dni +
Dni Tn n n
mie derivative ani is called the partial molar property for the constituent1,
P,Tn n
and is represented by writing a bar over the symbolfor the particular property, i.e., Xl. So, partial
molar quantity for a given system means the increase in an extensive property on account
of addition of one mole of its respectiveconstituent,at constant temperatureand
pre88ure, to such a large amount of the systemthat there is no perceptible change inits
concentration. Therefore,
ax
1' and
anl ... On2 P, T, nl, n3, ... Onl P, T, n,2,n3, ...
Making the above changes, equation (1) can be written as,

DT P,nl, nt2,n3,... dT+i1 dnl, +X2 dn2 + ... +Xi + ...

At constant pressure (dP = 0) and constant temperature (dT = 0), we have from equation
T dnl +X2 + + dni +

(222)
 Integrating equation (3) for a system of definite composition
represented by 211,712,na, ... n
we have,

i
Differentiating equation (4) at constant pressure and-emperature, but varying
composition,
we have
T= dX1 + XI + + dX3 + X3 + , (n, + dni) + ,

+ (Xl dnl + X3 + + Xi + (5)

Comparing equations (3) and (5), we have
nidX1+n2dX2+n3dX3+ + nidXt+
Equation (6) applies to a system of definite compositionand is the basis of the Gibbs-Duhem
equation, first derived by Gibbs (1875) and Duhem (1886).
[Il Physical Significance of Partial MolarQuantities
The corresponding equations for some extensive thermodynamic properties are
, E=EniÉi,
EniÄi, S=EniSi
G = EniGi =
A = Enr4i

where
ant T, 711,...

Dni

Dni

ani

ant
The term Pi is equal to partial molar Gibbsenergy Gi, but is not equal to partial molar
Helmholtz energy Ai.
In a single componentsystem, the partial molar quantities are identicalwith the molar
quantities, i.e.,
E H , and so on.
i
The partial molar quantities are intensive properties and do not depend on the size of the
system also. For example, if all the n's in, sayHL•= get increased at a constant temperature and
En
pressure, the partial molar quantity Hi will not increase, but will remain constant as the total
quantity (H, increases in the same proportion.
 01) Relations Between Partial Molar Quantities obtained by differentiatingthe
nie relation between partial molar quantities canofbe
a homogoneous system. Suppose
thermodynamic relations between the extensive properties pressure and the amountswe
differentiate G = H —TS with respect to ni at constant temperature, of
all other species, i.e.,
as
ani , p, ani , P,
or
same form as for the extensive
So, the relation betweenpartial molar quantitiesis of the
properties for the entire system.
can also be obtainedby
qhe equations for derivatives of partial molar quantitiesof a homogeneous system.On
relations for extensive properties
differentiating the thermodynamic
differentiating.

we get
with respect to ni at constant temperature, pressure and amounts of all other species,

öni ...

ööi
or
This relation shows that when the temperature is changed at constant pressure and
composition,the differential change in Pi is proportionalto the negative of the partial molar
entropy of component i. Similarly, we can show

This equation shows that when the pressure is changed at constant temperatureand
composition,the differential change in Pi is proportionalto the partial molar volumeof the
component i. Although the molar volume and entropy of a substance are positive, the partial molar
volume and partial molar entropy may be negative.

Problem1. The partial molar volumesfor a carbon tetrachloride (l)—benzene (2) solution at 250C
found as follows:
0.0 0.3 0.5 0.7 1.0

0.1793 o. 1122 0.1001 0.0983 0.09719

71/Lmor1
VI/Lmor1 0.08927 0.09844 0.1064 0.1092 0.1123

(a) Calculate the molar volumeof an equimolar

(b) What is the volume change on mixing 1 and 2 to form one mole of an equimolar solution?
Solution. (a) V = 0.5 (0.1001) +0.5(0.1064) = 0.1033 L mole-I
 0.01007 Lmor l
the volume of a mole of solution is 0.01007 L greater than that of the two components.

C] PARTIAL MOLAR FREE ENERGY, CONCEPT OF CHEMICAL POTENTIAL

When the partial molar quantity (X)is the free energy (G), then equation (2) can be written as,
dnl
OPT n n P, T, n2, 713,...

dn,2 + + dnt +
anl P, T,nl, n.J,

or dG= dT + Gl dnl + dn2 + ... + ... G, dnt + .

or dG =

where, PI = Gl, = G2, ... and so on.

The symbolg is known as partial molar free energy,Gibbs potential, molar chemical
potential or briefly chemical potential, a functiondescribedby Gibbs.It may eitherbe
represented by G, following the notation of Lewis and Randall or by after Gibbs. Thus,

ani T,P, ...

in the mixture,the
is called the chemicalpotential of the ith component.For any substance i addition
chemical potential is defined as the increase in free energy which results on the ofone mole
the systemso that
of that substance at constant temperature and pressure, to such a large quantity of
there is no appreciable change in the composition of the system.
Physical Significance of Chemical Potential
(i) When we add a small amount dni moles of a componenti to a system at constant
mole
temperature, pressure and compositionof other components,the increase in free enerBTper
of the componentadded is given by the equation
dG = Pi dni

or Pi = Dni , P, 711,...
mixture,the
So, the significanceof chemical potential is stated as, 'for any componenti in a
infinitesimal
value of Pi gives the increase in free energy which occurs due to the addition of an
number of moles of that component, to the mixture per mole of the component added.'
and,
An infinitesimal quantity of component is added so that the composition of the mixture
therefore, the value of Pi does not change.
same
(ii) The chemical potential Pi is an intensive property of the system, so it must have the
value everywherewithin the system at equilibrium.
to that
(iii) The matter tends to flow spontaneously from a region of high chemicalpotential
of low chemicalpotential.
 tendency of componenti, If
may be termed as escapingcomponent has th
chemical potential a largo
(iv)
in a system is high, this a small escaping
chemicalpotentialof a component is low,the component has tendency ng
if the chemical potential of a system. Let
tendency and regions a, the chemi
Supposea substance is present two in two different and up, respectively Suppose an
regions be
potentials of the substance in these to
to
p. Then according equation, dG = dnt' We
from region a
dn of the substance is transferred
get = (+ dn)
dGa = ga(—dn) and dGß
substance is given by
'Ihe total change in free energy of the
dG + dGB
or
of substance from region a to ß willoccur
If > up, then dG is negative. So, the transfer
from a region of higher chemical potentialto
spontaneously.So, the substance flows spontaneously the substance acquires the same chemiQ
that of lower chemical potential. This flow continues till the system will be in equilibrium
potential in both the regions.At this stage, O and so
in a system is directly
Therefore,we can say that the chemical potential of a component
proportional to its escaping tendency.
GIBBS-DUHEM EQUATION
At constant temperature and constant pressure, equation (7) may be written as,
(dG)T,p + + + +.
If the system has definite compositionhaving 711,712,... ni mole of the constituents 1, 2, i,
respectively, then on integrating equation (8), we get
PI + P12+ + ni
Equation (9) shows that free energy of a system at constant pressure and temperature, canbe
expressed as a sum of ng products for the individual components of the system.
Differentiating equation (9), we get
dG = dnl + dgl + dn2 + du,2+ + Pi dni + ni dui
or dG = (PI dnl + dn2 + ... + Pi dn,•)+ (m dul + d112+ ... ni dpi) ... (10)
Accordingto equation (8), the first term of right hand side of equation (1()) is equal to dG,at
constant temperature and pressure. Thus, at constant temperature and pressure for a systemOf
definite composition, we have
dgl + dP2 + ... + ni dui = 0 ... (11)
... (12)
For a binary system, equation (11) suggests that g cannot
change independently of the Other
constituents since dgl = —n,-zdß2, if increases, must
decrease accordingly.
Dividing equation (11) by n, where n = + + ng
Xl dßl + x2 dut2 +x3 dug
+ .. (13)
where Xl, x3 are the mole fractions of the respective
constituents.
Equations (10), (11) and (13) are different
forms of Gibb8-Duhem equation. Equation (12)
shows that at constant temperature and pressure,
independently with change in compositionbut the chemical potential does not change
system, then accordingto equation (12), we varies in a related way. Consider a two component
have
 dul + nt2dP2 = 0

d\L1 = —E ? . dP2 ••• (14)

or nl
This shows that if on changing the compositionof the system, there is a change in chemical
potentialof the first component equal to dßl, the chemical potential of the secondcomponent
changesby dP2 which means that d!L2is not independent but is related to dill, accordingto
equation (14).
GIBBS DUHEM-MARGULES EQUATION
The equation which provides information concerning the partial vapour pressure and the
compositionof various components in a solution is known as Gibbs Duhem Margules equation.
The equation can be derived starting with Gibbs-Duhemequation which for a binary solution is
written as :
- SdT+VdP+n1 + ...(1)
At constant temperature dT = 0, and at constant pressure dP = 0, hence equation (1) reduces
to
dill + dg,2 = 0
Dividing this equation by the total moles of the solution, i.e., by + 712,we get
nl n2
and $2 = Therefore,
(711 + 712) (711 + 712)

...(2)
Chemical potential of any component (i) is a fnction of temperature, pressure and mole fraction

dPi= dT + dP + dxt

At constant temperature and pressure, dT = 0 and dP = O,hence,

d PI = Oxi dxz

Substituting the value of dul and from equation (3) in equation (2) we get,

dX1 +X2 dX2 = 0

öX2

qhe chemical potential of a component i is expressed in terms of fugacity as

+RT1nfi
Differentiatingwith respect to Xiat constant T and P, we get

On substituting the value of L.H.S. of the last equation in equation (4), we get
ölnfl Inh
d'I + Xl
öX2