Chemical Potential

•  Combining the First and Second Laws for a closed system, dU = TdS − pdV
•  Considering
(extensive properties)
€

•  Hence

•  For an open system, that is, one that can gain or lose mass, U will also
change from mass transfer. (Why?)
•  Therefore U becomes a function of “n”, # of moles.
•  Hence
(more complete definition)

•  The chemical potential is defined as

For an open system.

•  The chemical potential is the change in internal energy (at constant S,V),
when one mole of the substance is added/removed

•  For Gibbs Free Energy,

•  Substituting

•  And we have CHEMICAL POTENTIAL, or

partial molar Gibbs free energy

•  For multiple constituents (at same p,T)

 Equilibria for Complex Systems
•  We need to extend our discussions of equilibrium to include systems which have:
–  Multiple phases e.g. liquid/vapor
–  Multiple constituents e.g., water and salt
•  For an isolated system not in equilibrium, irreversible processes will occur spontaneously
and entropy will increase until eventually it reaches a state where entropy is a maximum.
In this state, all irreversible processes will have ceased and any remaining processes
must be reversible. The system is then in equilibrium.

•  For an open system at constant

(c= # of constituents) the equilibrium condition is that where
ENTROPY IS A MAXIMUM

•  These constraints represent ‘macroscale’ variations: they apply to bulk system

e.g.
•  For an open system that undergoes small transitions at constant

Internal Energy is a minimum!

U

•  Need to generalize the condition of equilibrium for system with phases

and c chemical constituents.

Where we are heading:

We would like to get the criteria for equilibrium between phases, and
make it general enough to cover more than one chemical component
•  Let each chemical constituent have its chemical potential represented by
•  Let the number of moles of each species be

•  Heterogeneous System: a system consisting of 2 or more phases which are

separated from each other by a surface of discontinuity in one or more of
the intensive variables.

•  Question: what condition on the intensive variables are necessary and

sufficient to ensure equilibrium after the constraint that the phases are
isolated is relaxed?

•  Assumption: no chemical reactions occur and the bulk system remains

isolated (from surroundings)

•  After the constraint (phase partition) is relaxed (removed), each phase

behaves as an independent, open system (one that is free to exchange
mass with another phase). Assuming no chemical reactions occur, (so mass
transfer can’t take place by chemical reaction), the condition for equilibrium
in each phase is
Internal Energy is a minimum!
•  An important property of extensive variables, such as U, is that the total U
is of course additive
Summation is over all phases

i.e.

•  Additivity property applies to other variables as well:

For each constituent

•  Now write the condition for equilibrium as,

•  Expression for dU for one phase is,

(1)

Chemical potential of
each constituent
•  Each chemical constituent is free to exist in any phase.
•  Generalizing to the present system (sum over phases)

(2)
α=1

•  Now from the statement of equilibrium, are subject to constraints

according to,

(3)

•  The total variation (change) of must be identically zero (for

system as a whole.)
•  Consider a two phase system denoting the two
phases. For this system (1) becomes,

(4)

•  Invoking the constraints in (3) above,

For each of the constituents

•  Therefore (4) becomes,

(5)

•  Since are independent, arbitrary variations, (5) can only

be satisfied when the coefficients are identically zero.

•  i.e.
Internal Energy is a minimum

•  Implies that the criteria for equilibria (extend to > 2 phases) are:
 Gibbs Phase Rule
•  Consider a multi-phase, multi-constituent system that is in equilibrium,
characterized by a common T and p between phases and by the mole fractions
of each component in various phases.
•  Gibbs phase rule allows for the determination of the VARIANCE of a system,
that is, the number of intensive variables that can be freely specified without
causing the system to depart from its equilibrium point.
•  Denote the mole fractions of the kth component in the jth phase as

Total # of moles in jth phase

•  For a system of φ phases and c components, there are φ × c mole fractions.

(Each constituent exists in each phase.)
•  Hence the total number of intensive variables at equilibrium is,

•  Not all intensive variables are independent. To find the number of truly
independent intensive variables, we must examine their DEPENDENCY, or
constraints that the intensive variables must satisfy to still maintain equilibrium.
Constraints to be applied to the multiphase system:

1.  Mass Conservation: the sum of the mole fractions must sum to unity

•  This equation holds for each phase, thus in general there are constraints
arising from this condition

2.  Constraint on chemical potentials:

At equilibrium, for each component,

•  This condition gives constraints for each constituent. Applying this

condition to each of the c constituents gives c × constraints

•  So, the total variance is w = 2 + ϕ ⋅ c − ϕ − c ⋅ (ϕ −1)

= 2 −ϕ +c
 w = 2+c −ϕ Gibbs Phase Rule

c is the number of components

φ is the number of phases
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w is the number of independent intensive variables (“degrees of freedom”)

APPLICATIONS

1.  Homogenous fluid (or gas)

Homogenous;
one phase only

Two intensive variables may be freely specifiable.

2.  Mixture of two gases

Free variables are any two among . The third freely specified variable is the
relative concentration of the gases

3.  Liquid water is equilibrium with water vapor

MONOVARIANT!

Since vapor pressure (saturation vapor pressure in this case) is function of T only, free
variable is just T (or if T is specified), which is the Clausius Clapeyron Equation
4.  For liquid water in equilibrium with vapor and ice,

“No Freedom”

This is the triple point. Single choice of

 Surface Tension
•  Concept of surface tension has particular relevance to cloud physics.
Phases in contact are separated by a thin transitional film—a few molecules
thick.
transition layer
gas
drop
interior
(Not to scale here of course)

•  Molecules in transition layer are subject to a net inward force due to

molecules in the droplet interior.
Atkins, Physical Chemistry: “a molecule in the
Center of
bulk has a lower potential energy than one
mass
F outward free in the gas, and it takes energy to dig out
“deep” a molecule from the bulk and deposit it in the
interior gas. … so the molecules are under the
F inward influence of a force which tends to draw them
into the bulk.”
 Transition layer
Molecules in drop interior
experience a symmetrical
Liquid attractive force—these forces
are the Van der Waal forces that
keep liquid intact—at ‘normal’
molecular separation distances
these forces are attractive.

Molecules in surface layer experience an

inward directed attractive force.

•  This net inward force gives rise to a tension on the surface of the droplet,
which has units of force per unit length, or energy per unit area.

•  The force F, when multiplied by the distance , is the amount of work that
must be done to move a molecule from the drop’s interior to the surface
layer. F is the attractive force in the liquid.
{Inward pull exerted on the surface layer molecules results in a surface tension}

Energy / unit area or force / unit length

•  Surface tension represents energy stored in the surface of a drop since work
must be expended to change the shape of a liquid volume.

“Work” is essentially the work that

must be done to overcome
intermolecular force when moving a
molecule from interior to surface.

{Surface tension is the work required to change the area of a surface by one unit}

•  Surface tension allows a liquid volume to achieve a minimum surface to volume

ratio (a sphere!) - more molecules can be “bulk” rather than “surface” molecules
 Contribution of Surface Tension to U
•  We have seen that dU for a reversible process is,

•  Properties of surface phase allow it to be regarded as an independent

phase, so then

•  Where is the contribution from surface tension

Increase in surface area

Work done in system
 Equilibrium Conditions for Two Phases Considering the
Surface Phase Separating Them
•  Consider 2 bulk phases and a surface phase separating them,

′ ″

•  Consider each phase to be ‘isolated’ from one another initially, and then
“remove” the partitions separating the phases. Seek conditions for
equilibrium. Assume bulk system remains isolated from environment.
•  The extensive variables for this system are,
Surface area of interface
(with negligible volume)

•  Condition for equilibrium is

included here if there are

more than one curved interface.
•  If only one curved interface, this is really not a constraint.
•  For a 2 phase system we can expand the equilibrium condition as before,
now including the phase

′, ″ phase
phase

Additivity
(1)

•  Now the constraints that must be satisfied for the equation to satisfy
equilibrium conditions are,
Make the following assumptions:
1.  Assume the system undergoes a small variation in which

2.  The ″ phase is a sphere of radius

•  Therefore can be written in terms of and is,

Use in expression

•  With these assumptions, the constraints are,

 (2)
Internal Energy is a minimum!
•  As before, represent arbitrary, independent variations.
Hence (2) will be satisfied only when the coefficients vanish.
•  The conditions for equilibrium are then, generalizing the assumptions above
to any set of variations,

•  The mechanical equilibrium condition is the so called Laplace formula,

Surface tension
a
Curvature term

•  , pressure in drop interior is greater than pressure adjacent to drop by the

term. Pressure in interior must be greater to prevent drop collapse due to
inward directed tension force.
 Calculations: Water-Vapor Interface
vapor
a
droplet

•  What is pressure difference between the drop interior and that in the
surrounding vapor?
•  Assume vapor is saturated, and

•  So pressure difference is about 1.5 atm. 

 •  Another look at the Laplace relationship

provides the difference in outside and inside pressures of a spherical drop

in equilibrium with its vapor.
•  The Laplace formula can also be derived from the definition of surface
tension, using only the concept of work.

•  Reversible work that must be done on a “system” in order to increase its

surface area A by an amount dA is

Consider this system

to be in equilibrium
a

vapor
pressure for
drop of
radius ‘a’ Frictionless piston

Piston supplies a pressure P2 to the liquid– liquid is

extruded through an infinitely fine syringe to form the drop.
•  The applied pressure P2 is just enough to cause the drop to grow.
(equilibrium is maintained though…)
•  Differential work done by piston on bulk liquid

•  Differential work done by drop on surrounding vapor,

•  The work required to increase the surface area must balance these:

•  For spherical drop

•  Substituting

Laplace Formula
 Phase Rule for Systems with Curved Interfaces
•  For systems with phases and c constituents with non-curved interfaces,

•  Now need to generalize this result to include curved interfaces. Now we

have

•  What is variance of this system, w?

w=intensive variables - constraints
•  Constraints are dependencies among the intensive variables.
•  Another intensive variable considered in this case is the “surface excess”,
which arises due to “adsorption” of any constituent into the curved
interfaces.

•  “Surface excess”
 The nature of the interface
(Gibbs adsorption isotherm)

IDEALIZED REAL

There is some nonzero thickness And in a multicomponent system, species

associated with “the interface”… concentrations vary across this distance.

The thin layer near the interface may be rich or

deficient in some of the species (e.g., a detergent
accumulates at an oil-water interface).

Please note notation change in the next slide

(source: Atkins, Physical Chemistry)
 Gibbs adsorption isotherm (continued)

For phases α and β, if the bulk (homogeneous) phases contain amounts of species J
n (Jα ) and n (Jβ )
Then we can deduce how much is in the “interface”:

n (Jσ ) = n J - [ n (Jα ) + n (Jβ ) ]

€
This “excess” amount of material can be expressed as an amount per unit area of the interface
by defining the surface excess:
n (Jσ )
ΓJ =
€ σ
where σ is the area of the interface. Both the number of moles at the interface and the surface
excess property can take on positive or negative values.

€
We can apply criteria of equilibrium to deduce that

σdγ + ∑ n (Jσ )dµJ = 0 (constant T)

J

and to derive the “Gibbs surface tension equation”:

€ dγ = −∑ ΓJ dµJ
J
•  Intensive variables for this system—
VARIABLE NUMBER
1.  Common T
2.  Adsorption of c constituents into curved interfaces
3.  Specification for mole fractions of each bulk phase
4.  Pressure in each bulk phase
(pressure generally not same due to curvature)
5.  Mean radius of curvature for each curved interface
•  Total number of specified variables,

•  Now examine constraints

1.  Mole fractions must sum to 1 in each bulk phase
-This condition does not apply to surface phases
2.  Chemical potential for each constituent must be equal
between all phases
3.  Mechanical equilibrium must hold at all interfaces
•  Total constraints,
•  Hence total variance is
•  EXAMPLE 1: System of uniform T, in which a droplet of radius ‘a’ is
surrounded by pure H2O vapor

•  Hence Because a took the

place of v or ρ

•  These variations that describe system:

•  Specify one variable, say T, and study dependence of

•  EXAMPLE 2: System of uniform T in which a drop of pure H2O of radius ‘a’

is surrounded by humid air of total pressure p.
H 2O

“air”
•  To study the dependence of , must hold T and p fixed.

a
NUCLEATION THERMODYNAMICS
Consider the formation of a pure water droplet by condensation from the vapor
phase. This process will first be considered without any foreign particle or
nucleating surface. This process is known as
-HOMOGENEOUS NUCLEATION-
Process is also referred to as SPONTANEOUS NUCLEATION
- Formation of embryonic droplet by chance collision of several tens to several
hundred H2O molecules
Question: Under what conditions does the embryo remain intact and grow into a
cloud droplet?

-We will examine the relationship between vapor pressure and surface curvature

KELVIN’S EQUATION

We will study this system (droplet and vapor molecules) from the perspective of
Gibbs free energy.
Consider the following system:

vapor molecules
T, ev
R

T,e v temperature and vapor pressure in drop’s environment constants.

chemical potentials of vapor and liquid molecules

number of vapor molecules prior to embryo formation

number of vapor molecules after embryo formation

number of molecules in embryo

Change in Gibbs free energy,

(1)

We are most interested in conditions for which or

Consists of embryo plus remaining free molecules

Hence System Gibbs free energy prior to embryo formation

(2)

This is an equilibrium process with respect to vapor so is the same before and
after nucleation embryo formation.
Unit volume
Number of molecules ‘n’ in the embryo
Change in Gibbs free energy,

(1)

We are most interested in conditions for which or

Consists of embryo plus remaining free molecules

Hence System Gibbs free energy prior to embryo formation

(2)

This is an equilibrium process with respect to vapor so is the same before and
after nucleation embryo formation.
Unit volume
Number of molecules ‘n’ in the embryo

We will use this to substitute,

so that we can make the
equation a function of R
Equation (2) can be written as,
(3)
Bulk Surface
thermodynamic energy Energy required to form
term term or curve surface with
surface tension
Need to derive an expression for , difference in
Gibbs free energy between liquid vapor phases

For constant T, and using

dµ = (v l − v v )dp ≈ −v v dp (4)

µl − µv = − ∫ v v dev (5) For vapor

€
Use the Ideal Gas Equation and integration limits go from
being the saturated liquid (same as saturated vapor) to the actual vapor:
e
€
µl − µv = − ∫ kTd lnev (6)
es
Note the limits of integration

When equilibrium is established and

When non-equilibrium exists,

Integration yields, e
µl − µv = −kT ln S
es

€
Hence (3) becomes,

With

Consider plot of vs