CHEMICAL POTENTIAL
The concept of calculation of the chemical potential in one- and multi-
component systems
I. Chemical potential of an ideal gas
II. Chemical potential of real gases. Fugacity
III. Chemical potential of liquids
IV. Chemical potential in multicomponent systems. The Gibbs–Duhem
equation
V. Ideal mixtures. The Raoult and Henry laws
VI. Real mixtures and solutions. Thermodynamic significance of
activity. Standard state convention
CHEMICAL POTENTIAL
• The chemical potential drives mass (or species) transfer in a manner
similar to the thermal potential that drives heat transfer from higher
to lower temperatures
• G Gibbs free energy has been introduced to characterize the
equilibrium state of spontaneous processes.
• The calculations are more straightforward if the partial derivative of
G with respect to the composition of the system is used: this will be
called chemical potential.
CHEMICAL POTENTIAL
• The chemical potential is [equivalent definitions]:
• partial molar Gibbs free energy (at constant T and p),
• Gibbs free energy change as an effect of adding
exactly 1 mol substance to the system,
• change of G with changing composition.
• The condition of equilibrium in all systems: the
chemical potentials of a component in each phase must be
the same.
Chemical Potential
• The chemical potential of a pure substance is the same as the
molar Gibbs free energy:
• The chemical potential μi of component i in a mixture is the
partial molar Gibbs free energy:
CHEMICAL POTENTIAL
U, H, A and G are not only state functions but also thermodynamic
potential functions.
I. CHEMICAL POTENTIAL OF AN IDEAL GAS
• The simplest system: the ideal gas.
• Its Gibbs free energy at pressure p and temperature T:
G is the standard molar free energy of the gas (at p = 1 bar and given
T).
• The chemical potential at pressure p is obtained by derivation with
respect to n:
μ is the standard chemical potential: the standard molar free energy
of the pure gas (at p = 1 bar and a given T).
I. CHEMICAL POTENTIAL OF AN IDEAL GAS
• The chemical potential of an ideal gas depends linearly on ln(p) and
the proportionality factor is RT.
• The standard state is reached at p
• If p → 0, then μ → -∞.
I. CHEMICAL POTENTIAL OF A REAL GAS
• Ideal thermodynamic relationship are often not useful with the
measured p values.
• E.g. in the A + B C + D gas phase reaction, the equilibrium
constant K = pCpD/(pApB ) is different at different pressures.
• Chemical potential does not have the advantageous properties when
p is used to calculate its value.
• There is a p-like property [its values can be collected in tables or
graphs], which gives constant K values even at high pressures.
• The same is valid for other formulas containing p. This is the reason
why fugacity was introduced.
I. CHEMICAL POTENTIAL OF A REAL GAS
• The definition of fugacity: for real gases, the measured pressure p in
the formula giving the pressure dependence of the chemical potential
is replaced by effective pressure, which is called fugacity (f):
Two issues should be settled.
• The relationship between fugacity and pressure: f = γp where γ is the
dimensionless fugacity coefficient
• the standard state p of a real gas: a hypothetical state in which the
pressure pθ and it behaves like an ideal gas (no interactions).
I. CHEMICAL POTENTIAL OF A REAL
GAS
• RTlnγ is a measure of the intermolecular forces. At
low pressures, this decreases, so γ = 1 when p = 0.
γ can be given using Z compression factor as follows:
I. CHEMICAL POTENTIAL OF A
REAL GAS
• Reminder:
• Z should be measured, but it is measurable quite well.
• Plot Z as a function of pressure: sometimes larger, sometimes
smaller, but if p → 0, then Z → 1. (We just showed the deviation, but
we did not describe or interpret it.)
I. CHEMICAL POTENTIAL OF A REAL
GAS
• The reasons:
• At high pressure, repulsion forces are
dominant, so the chemical potential of real
gases is higher than for an ideal gas.
• At intermediate pressure, attraction is
dominant, so the chemical potential is lower
than for an ideal gas.
• As p → 0, μ will be the same as for an ideal
gas, as no significant intermolecular
interaction is possible.
III. CHEMICAL POTENTIAL OF LIQUIDS
• How does µ depend on the composition?
• Starting point: in equilibrium, µ is equal in the liquid and gas phases
(this is a general criterion for chemical equilibrium):
• The equality of µ values is true both
for the solute (B) and the solvent (A).
IV. MULTICOMPONENT SYSTEMS. THE
GIBBS–DUHEM EQUATION
• In a multicomponent system (e.g. mixture), the Gibbs free energy is
additive, it can be obtained as the sum of the partial molar Gibbs free
energies (chemical potentials) of the individual components:
• If only the compositions changes (constant T and p):
But from the definition:
Combining the two gives:
IV. MULTICOMPONENT SYSTEMS. THE
GIBBS–DUHEM EQUATION
• The general form for a multicomponent system, called the
Gibbs–Duhem equation:
• Implication: a change in the chemical potential of one of the
components is necessarily accompanied by changes in the
chemical potentials of the other components as well.
THERMODINAMICS OF ONE-COMPONENT
SYSTEMS I.
Definition of phase and component
II. Phase diagrams. Phase diagram of CO2 , water and He.
III. Phase stability and phase transitions
IV. The use of chemical potential to describe the equilibria in one-
component multiphase systems
V. The effect of pressure on phase equilibria
VI. The effect of temperature on phase equilibria. The Clapeyron
equation.
VII. Liquid-vapor systems: Clausius–Clapeyron equation. Entropy of
evaporation: Trouton’s rule.
VIII. Ehrenfest classification of phase transitions
THERMODINAMICS OF ONE-COMPONENT
SYSTEMS
• Principles of discussion:
• Equilibrium systems (states) are described and studied. (Phases are
stable or phase transitions happen depending on T, p, V and xi .)
• In equilibrium, chemical potentials (μ) for all components in all
phases are the same.
• Equilibrium exists only in a closed system.
• The changes (phase transitions) are reversible. (Phase transitions
between solid phases are often irreversible.)
• The time needed for a phase transition is not discussed.
I. DEFINITION OF PHASE AND
COMPONENT
• Definition of phase: a phase of a substance is a form of matter that is
uniform throughout in chemical composition and physical state.
• In a given phase, one or more components may be present (e.g. NH3,
air).
• Definition of component: a chemically independent constituent (e.g.
element, compound, ion) of a system.
• A given component may be present in one or more phases of a
system (e.g. H2O may be present in ice, water and water vapor if
they are in equilibrium).
I. DEFINITION OF PHASE AND
COMPONENT
Phases:
• Gaseous (vapor) state (g) (gaseous phase)
• pure gases (1 component) or mixtures of gases (multicomponent
systems) – these can be described precisely.
• Liquid state (l) (liquid phase)
• pure liquid (1 component) or mixture of liquids or solution
(2 or more components).
• Solid state (s) (solid phase)
• 1 component – in more than 1 structural forms: allotropes,
e.g. for C (carbon, C60, C70) , P (Phosphorus, α -P4, β -P4), S (Sulfur, S2,
α -S 8 ) ice.
• multicomponent systems: alloys, solid solutions, etc.
• [Plasma state: it is not common but important.]
II. PHASE DIAGRAMS
• Experimentally defined diagrams.
They reflect equilibrium states.
II. PHASE DIAGRAMS
▪ Areas: only one phase is stable
(gas laws apply within such an area).
―Lines (phase boundaries): two
phases are stable, they are in
equilibrium.
• Triple point (T3): three phases are
stable in equilibrium.
• Critical point (Tc): at temperatures higher than Tc, there is
the gas phase, at lower temperatures, the vapor phase.
▪ Supercritical state
II. PHASE DIAGRAMS
• Phase diagram of CO2:
• Since the triple point is
above 1 atm, the fluid
does not exist at
atmospheric pressure.
• In a CO2 gas cylinder,
there is liquid or high pressure gas.
• Solid CO2 sublimates so
it is called "dry ice".
II. PHASE DIAGRAMS
• Phase diagram of H2O:
• The melting point of
ice decreases with
increasing pressure!
(The density of H2O(l)
is higher and molar
volume is lower than
for ice.)
• At high pressures,
there are different
crystalline forms of
ice (II, III, V, VI, VII).
II. PHASE DIAGRAMS
• • Phase diagram of He:
• on the one hand, it reflects
special behavior (liquid-liquid transition,
superfluidity),
• on the other hand, it is
indispensable in the physics
of low temperatures
III. PHASE STABILITY AND PHASE
TRANSITIONS
III. PHASE STABILITY AND PHASE
TRANSITIONS
• Phase transitions:
• In equilibrium, the chemical potential of a
component is the same in the entire system (in all
phases):
• there is equilibrium inside a phase and
• there is equilibrium between the phases.
• If that is not true, spontaneous processes will start in the system
that will result in the equalization of chemical potentials.
• One of these processes is the phase transition (i.e.
one phase transforms into another), which is a
physical change.
IV. THE USE OF CHEMICAL POTENTIAL
TO DESCRIBE PHASE TRANSITIONS
• Look at a system with constant p and T, where μ is not the same
in all phases, i.e. there is equilibrium in the system.
• If μ1 > μ2, than dn amount of substance is transferred from state
1 to state 2 (this can be either physical or chemical
transformation).
IV. THE USE OF CHEMICAL POTENTIAL
TO DESCRIBE PHASE TRANSITIONS
• It is well-known how the chemical potential changes with changing
the conditions (T, p):
• Gibbs phase rule for calculating the number of
degrees of freedom of an equilibrium mixture of n
components coexisting as p phases:
Degrees of freedom = n + 2 - p
• Summarizing the T-dependence of the different states:
• the μ chemical potential
decreases with increasing T. The
slope increases in the solid → liquid
→ gas direction (since the entropy
of the system increases in this
order).
• When changing T and p, phase
transitions occur (forth and back).
• Phase transitions occur at well defined
temperatures and depend on the pressure p
