Chemical Potential

Thermodynamic Definition:
Chemical Potential is the main thermodynamic tool used to treat
chemical equilibrium. It predicts: 1 mole of i
Spontaneity of a reaction? V,S, nj constant
The composition of reactants and product at equilibrium

U Etrans Erot Evib Eel Eint Emass Phase of

species j
Chemical Potential of species i as being U
the increase in internal energy due to i
addition of this species ni V , S ,n ji

In general variation in internal energy: dU pdV TdS i dni

i
Gibbs energy G as a function of the internal energy is given by
G U pV TS OR dG Vdp SdT i dni
i

G
i Gi The Chemical Potential i is the work which must be supplied keeping T & p constant in

ni T , p ,n ji
order to transfer one mole of species i from a vacuum to a phase, EXCEPT for the
volume work. By definition, it represents the partial molar Gibbs energy, Gi
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 Chemical Potential
,ideal
2. Chemical potential in the liquid phase: i (T ) i (T ) RT ln xi
Application of chemical potentials:

Tools for studying the chemical behaviour of chemical reactions.

aA +bB +cC+ xX + yY + zZ

Therefore, Gibbs energy for this reaction? Work to add the products minus the work to add reactants.

So, Gibbs energy of a reaction can be written as a linear combination of the chemical potential:

Greaction v
products
i i v
reac tan ts
i i

where, i = stoichiometric coefficients

Thus at equilibrium, the Gibbs energy of a reaction is zero because the work to add the products cancels out the work to
remove the reactants.
Concerning chemical equilibria, remember thermodynamic reversibility chemical reversibility of a reaction.

The former corresponds to an infinitely slow transformation with a quasi-equilibrium existing at each infinitesimal stage of the
reaction. The latter relates to the feasibility of the reverse reaction. 2
 Other potentials
1. External potential (Electrostatics): Considering two charges in vacuum, the force exerted is given by Coulombs law.
E gradV 1 qi
f q2
q1
4 0 r 2
r q2 E
Discontinuous distribution of charges
Vtotal
4 0 r i ri

Outer Potential and Volta Potential difference: The p.d. between the exterior of the
surface of a charged object is called the outer potential,. It is a measurable quantity.
Electrical potential around a spherical
object of radius R having a charge Q.
The Gauss surface is here defined as the
outer concentric sphere of radius r.

2. Surface Potential: For all condensed matter: Structure of surface different from internal or bulk structure.
Basic understanding of the following required:

Polarisation of matter
Relative Permittivity
Electric Displacement Vector

Polarisation charges inside a flat capacitor Surface of Polar Liquids,

made of two metal plates and filled by a Adsorbed Ionic surfactants Variation of the relative permittivity of water as a 3
dielectric.
Metal Surfaces function of the frequency of the applied electric field.
 Surface potential in detail
Creation of new surface: Molecules inside the solution get transferred
to the interface.

Why? : Because potential energy at the interface is higher.: Less

intermolecular interactions

Dipole molecules (polar solvents) have a tendency to align at the

interface

The difference in potential across this layer of oriented dipoles is

called Surface potential.

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 Other Potentials
Inner Potential or Galvani Potential: Inner potential of a phase is the sum of the surface and outer potentials

Radial distribution of potential for a metal

sphere of radius R carrying a positive
charge Q, illustrating the Contributions of
the outer potential and the surface
potential. The inner potential is constant
inside the sphere.

The Galvani potential difference: If Galvani Potential is constant

inside each phase, this supposes that all the differences in
Galvani potential between two phases in contact happen in
the interfacial region

g (dip) g (charge)

Dipolar Due to
contributions accumulation of Surface potential, the Volta potential and the Galvani
charges potential differences for two phases in contact. 5