The Chemical Potential

For processes involving diffusion mass transport we can, however, define a
thermodynamic intensive driving force responsible specifically for the total energy change
accompanying the diffusion mass transfer of molecules from one region to another. This
driving force can be defined simply as a partial derivative representing the variation of the
total internal energy of a region with respect to an increment in the number of moles of one
particular species in the region when no other extensive properties are altered. This partial
derivative is an important intensive property called the chemical potential. By reason of its
definition the chemical potential is an intensive property because whenever it is multiplied
by the extensive property change in moles of a particular molecular species within a system
the result is identically the internal energy change of the system resulting only from this
change in moles, and not from the change in any other extensive property.
In elementary physics the energy per unit mass, per mole, or per particle involved in
moving the mass, mole, or particle from one region to another is generally defined as a
potential. Table I lists several types of potentials (driving forces) which are important in
thermodynamic applications. A potential therefore can always be regarded as a driving
force for a mass change. The chemical potential is a driving force of this type. Physically the
driving force represented by the chemical potential results from the same molecular actions
which give rise to a partial vapor pressure in a liquid or a partial pressure in a gas. Each of
these has the ability to expel molecules of a given type out of a multi-component phase.
The energy change within a system accompanying a change in the number of moles
of a given component of the system by molecular processes can now be defined as a type of
work which results from a difference in a chemical potential driving force between the
system and its surroundings. As is the case of other types of work, in order to evaluate
quantitatively the work of a chemical potential driving force it is first necessary to define a
system. In accordance with the principles discussed in section 14,this work is then defined
as the product of a chemical potential of a component outside the system on its external
boundary and a change in the number of moles of this component inside the system. When
the number of moles of a molecular species increases in a system, work must be done on the
system to overcome the molecular forces tending to expel molecules of this species.
Consequently, in accordance with the sign convention, the work relative to the system
receiving this increase in moles within it must be a negative number.
Although we have discussed the chemical potential as a thermodynamic driving force
for the diffusion mass transport, its utility is not confined to this particular process alone.
Because of its definition the chemical potential is a driving force for changes in moles of a
molecular species in a system not only by means of diffusion mass transfer but by any other
molecular process as well. The most important example is the role of the chemical potential
within a system as the driving force for changes in moles brought about in the system by
chemical reactions.