Core Paper Presentation

Partial molar heat content and Chemical potential,

significance and factors affecting, Gibb’s- duhem
equation
Presented by
Swarnalata Swain
Ph.D. Scholar

Centre for Nano and Material Sciences, JAIN University, Bangalore

Outline…
• Heat content and molar heat content
• Partial molar heat content
• Free energy and Gibbs free energy
• Chemical potential/ Partial molar Gibbs free
energy
• Significance of chemical potential
• Variation of chemical potential with
temperature and pressure
• Gibbs duhem equation
Heat content and molar heat content…
Heat content/enthalpy is the H= enthalpy,
total amount of heat stored in E= energy
a system in form of PE P= pressure
V= volume
H= E+PV

Molar heat content/ molar enthalpy n= number of

is the change in enthalpy for a unit moles of reactant
mass of compound

ΔHm= ΔH/n
 ,

Partial molar heat content…

,

Variation in enthalpy with the amount of one component while the

temperature, pressure and all other compositions are kept constant.
The molar enthalpy   is,
Molar enthalpy kg/ mole

H= xA HA+ xB HB+ a xAxB

H (kJ/mol) is the enthalpy  
xA, xB  are the compositions of A and B
a  is a non-ideal parameter.
The partial molar enthalpy is represented
Mole fraction A by a line tangent to H at composition of
Fig.1 Binary liquid system the mixture xA, m
Where HA is the partial molar enthalpy of
component A and HB is the partial molar
enthalpy of component B
https://demonstrations.wolfram.com/PartialMolarEnthalpy/img/popup_1.png
Free energy/ Gibb’s free energy…
Free energy refers to the
amount of
internal energy of a
thermodynamic system that
is available to perform
work.

Gibbs free energy is
the energy that may be
converted into work in a
system that is at constant
temperature and pressure.
ΔG = ΔH -T ΔS

https://qph.fs.quoracdn.net/main-qimg-545916b5b8b046f37c30d845bb751757.webp
https://www.google.com/url?sa=i&url=https%3A%2F%2Fwww.pinterest.com%2Fpin
%2F579979258233649744%2F&psig=AOvVaw1zqQrCcsC7F7On6V92dqpd&ust=1610210843257000&source=images&cd=vfe&ved=0CAIQjRxqFwoTCMDQ6oPljO4CFQAAAAAdAAAAABAO
Chemical potential/ molar Gibb’s free energy…

Chemical potential of a chemical substance μ, can be simply defined as the chemical

energy(Uc) possessed by 1 mole of the substance.
μ= Uc / N
Derivation…
In terms of free energy,
G = f( T, P, n1, n2, n3…..ni)
For an infinitesimal free energy change,
dG = (ӘG/ ӘT ) P ,N dT + (ӘG/ ӘP)  T, N dP  +(ӘG/ Әni ) T ,P ,n1.....nj dni  

= (ӘG/ ӘT ) P ,N dT + (ӘG/ ӘP)  T, N dP + μ1dn1  + μ2dn2 + .........  μi dni

= -S dT + V dP + μ1dn1  + μ2dn2 + .........  μi dni

Where μ1 , μ2 .... and  μi are chemical potentials of components 1, 2 .... and i , respectively.
If temperature and pressure remain constant, then
(dG) T, P = μ1dn1  + μ2dn2 + .........  μidni           

If a system has definite composition having n1 , n2... ni moles of constituent 1, 2, .... i, 
respectively , Then on integrating above equation,
(G) T, P ,N = μ1n1  + μ2n2 + .........  μini , (G = μ)  
Chemical potential is the change in the total free energy of the system that results on
addition of one mole of substance at a constant temperature and pressure, to such a large
quantity of the system that there is no appreciable change in the overall composition of the
Significance of chemical potential…
 Chemical potential determines the stability of substances such as
chemical species, compounds and solution.

 As the chemical potential is an extensive value of the system, when

the system is at equilibrium it should have same value throughout.

 Chemical potential is useful to prove several rules like henrys law,

Gibbs-Duhem equation and many others law.

 μi is also related to escaping tendency of i. If chemical potential of a

component in a system is high, it posses a large escaping potential
and vice versa.

 Matter tends to flow from high region of chemical potential to low

region of chemical potential.
Effect of temperature and pressure…
At constant temperature
dG = (ӘG/ ӘT ) P ,ni dT

= [Ә/ ӘT((ӘG/ Әni ) T, P ,ni]

dG = V dP-S dT + μidni

(ӘG/ ӘT ) P ,ni = - S

At constant pressure
μi = (ӘG/ Әni ) T, P ,ni

(Ә μi /ӘP)T, ni = [Ә/ ӘP(ӘG/ Әni]T, ni

dG = V dP-S dT + μidni

(ӘG/ ӘP ) T,ni = V
Gibbs duhem equation…
(G) T, P ,N = μ1n1  + μ2 n2 + .........  μini                                         

Free energy of the system at constant pressure and temperature, can be expressed as a sum of
nμ for the individual components of the system. The total differential of G is written as
dG  = μ1dn1  + n1dμ1 + μ2dn2 + n2dμ2   .........  μidni + nidμi                       

= (μ1dn1 + μ2dn2 + .....  μidni) +  (n1dμ + n2dμ2 +..... nidμi)       

(n1dμ + n2dμ2 +..... nidμi = 0)  at constant T, P                 

This simple relationship is known as Gibbs-Duhem equation.

System having two component, gives equation

n1dμ1 + n2dμ2   =  0   or dμ1 = -(n2/n1)dμ2

THANK YOU