Scribd
Upload
299 views13 pages

Solutions

Chemical potential is defined as the partial derivative of Gibbs free energy with respect to the number of moles of component j at constant pressure, temperature and number of moles of other components. Chemical potential can be applied to other variables as well. Partial molar quantities are defined for volume, enthalpy and entropy. For an ideal solution, the chemical potential is equal to the chemical potential of the pure component plus RT times the natural log of the mole fraction.

Uploaded by

bits_who_am_i
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
299 views13 pages

Solutions

Chemical potential is defined as the partial derivative of Gibbs free energy with respect to the number of moles of component j at constant pressure, temperature and number of moles of other components. Chemical potential can be applied to other variables as well. Partial molar quantities are defined for volume, enthalpy and entropy. For an ideal solution, the chemical potential is equal to the chemical potential of the pure component plus RT times the natural log of the mole fraction.

Uploaded by

bits_who_am_i
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 13

Chemical Potential

G
Chemical Potential j =
n j

P ,T ,ni

Diffusion from high to low


potential.

Chemical potential is a Partial Molar Quantity

For multi - components : G = f(P, T, n j )

Sum of moles of components

Chemical Potential of a Binary (A & B) Mixture


G = f(P , T , n A , n B )

G
G
G
G

dG =
dP +
dT +
dn A +

P T , n A ,nB
T P , n A , nB
n A P ,T ,nB
n B

V dP

S dT

n j

dn B
P ,T , n A

dn j

P ,T , ni

Chem. Potential applied to other variables:

G
=
n j

P ,T

,ni

A
=
n j

,V , n i

H
=
n j

n j
P ,S ,ni

,S ,ni

Measures of Composition
s = solute ; A = solvent; V = Tot. Vol. of solution.
Weight %:
ws
ws % =

Mole Fraction:
Molarity:

Molality:

s =

ns
Ms =
V
ns
ms =
kg A

ws + wA

x 100

ns
ns + n A

Different Composition
Equations for different
Laws

Partial molar Quantities


Let us suppose that a solution is formed by
mixing n1,n2, moles of substances 1,2,.. having
molar volumes V*m,1, V*m,2,. at temp T and
pressure P. Let V* be the total volume of the
unmixed (pure) components at T and P.
V* = n1V*m,1 + n2V*m,2+.. nrV*m,r= niV*m,i
After mixing, we find that volume V of solution is
not in general equal to the unmixed volume : V V*.
e.g., 50 cm3 of ethanol added to 50 cm3 of water
gives 96.5 cm3 at 20C and 1 atm

RANJAN DEY

The difference between V of


solution and V* results
from:
(1) Difference between
intermolecular forces in
the solution and those in
the
pure
component
(2) Diff between the packing
of molecules in solution and
packing in pure components
RANJAN DEY

Other Partial Molar Quantities

Partial Molar Volume:

V
V i =
ni P,T ,n j

Partial Molar Enthalpy:

H i =

n
i P,T ,n j

Partial Molar Entropy:

S
S i =
ni P,T,n j

Solution Volume and Partial Molar Volume


V = n f(T,P, x1,x2,) where n = ni and f is some
function of T, P and mole fractions.
Differentiation of above equation gives :
d V = f(T,P, x1,x2,) dn = Vidni
xi = ni/n or ni = xin
dV = xiVidn for constant T, P, xi
Comparison of expressions for dV gives:
V = niVi for one phase system
Where the V on the LHS is sometimes referred
to as the mean molar volume, Vm of the
solution.
Change in volume of mixing, is given by:mixV =V-V*

Calculation for Partial Molar Volumes


VA

=
n A P ,T ,nB

V = f(nA , nB)

VB

V
=
n B

P ,T ,n A

@ constant P & T

V
V

dV =
dn A +
n A P ,T , nB
n B

dn B
P ,T , n A

dV = V A dn A + V B dn B
Integrate @ constant composition

V = n A V A + nB V B

Slope of V vs nB curve at any


composition gives VB for that comp.
mixV = V V* = i ni ( Vi V*m,i )

RANJAN DEY

Ideal Solution
Ideal solution will be one where the molecules of
the various species are so similar that replacing
molecule of one species with another will not
change the spatial structure or intermolecular
interaction energy in the solution.
For this the molecules must be essentially of same
size and shape.
mixG = G G* = nii ni*i
For an ideal solution : mixG = RT ni ln xi
Equating : nii = ni(*i + RT ln xi )
i = *i (T,P) + RT ln xi
(#1)

Last eqn on previous slide is adopted as


definition of an ideal solution

As xi0, i - .
As xi increases, i increases
at fixed T and P, reaching
chemical pot of the pure i,
*i in the limit xi =1
RANJAN DEY

Thermodynamic properties of
Ideal Solutions
Standard state of each component i of the ideal
liquid solution is defined to be pure liquid i at the
temp T and pressure P of the solution.

mixG = RT ni ln xi
mixV = 0
mixS = -R ni ln xi
mixH = 0

mixS

= -( mixG / T)P,ni

RANJAN DEY

You might also like