PHYSICAL CHEMISTRY 2

Lecture 2. Ideality and Criterion for Equilibrium

 Fundamental property relation
• Recall,
  for a closed system in material
equilibrium:

• Accounting for the number of moles in the

system:
 Fundamental property relation
•  

• This equation applies for a single-phase fluid

system with no chemical reactions. The
number of moles in the system is held
constant.
 Fundamental property relation
• Consider: Single-phase open system w/
transfer of each species i in the system
The Gibbs free energy becomes a function of the
number of moles of each species
nG = f(P, T, n1, n2,…,ni,…)
 Fundamental property relation
•  For the closed system case

• For the open system case, this transforms to

 Chemical potentital
•  
μi is called the CHEMICAL POTENTIAL of species
i in the system
Thus, for an open system in equilibrium
 Phase equilibrium
• Consider
  2 phase A and B in chemical equilibrium in
a close system. For each phase:

The total Gibbs free energy of the system is given by

+
 Phase equilibrium
• Recall
  for a closed system in equilibrium. By
comparison,

Mass transfer occur between phases A and B:

Thus,

Mass transfer does not stop in equilibrium. Thus, dniA

cannot be zero.
 Phase equilibrium
•  

Therefore,

The chemical potential of species i in phases A

and B are equal. In general, for a multiphase
system in equilibrium:
 Phase equilibrium
•  

• “Multiple phases at the same T and P are in

equilibrium when the chemical potential of
each species is the same in all phases.”
 Phase equilibrium
•  What if the system is not in equilibrium?
Recall where the equality holds when the system is
in equilibrium.
• Considering changes in no. of moles of species i:

When the system is NOT in equilibrium:

<0
 Phase equilibrium
•  Considering two phases A and B, dniA =-dniB :

This considers mass transfer from B to A; dniA

should be positive. Therefore, should be
negative.
Spontaneous transfer of species i is then from B
to A.
 Phase equilibrium
•  
“Species i flows spontaneously from a phase
with a higher chemical potential to a phase of
lower chemical potential.”
 Partial properties
•  
• The chemical potential is the mole derivative of nG.
• Similarly, we can define the mole derivative of other
molar properties (molar volume, molar enthalpy,
etc.)

is called the partial molar property of species i in a

mixture.
 Partial properties
•  
Partial properties provide a measure of the response
of the total property nM of a mixture at const. T and P
to the addition of a differential amount of species i to
a finite amount of mixture.

The chemical potential is the partial molar Gibbs

energy.
 Partial properties
•  Notations:
Solution properties, M: V, U, S, H, A, G
Partial properties, :
Pure species properties, Mi: Vi, Ui, Si, Hi, Ai, Gi
 Partial properties
• Total
  thermodynamic properties of a homogenous
phase are function of T, P and ni.

The total differential of nM is

At constant n

Note: x denotes differentiation at constant composition

 Partial properties
•Expanding
  dni and d(nM)

Substituting this to the previous expression and

simplifying, we get two equations

and
 Summability relations
•  

This allows for calculation of mixture properties

from partial properties.
 Gibbs/Duhem theorem
•  

Compare with
 Gibbs/Duhem Theorem
•  
At const. T an
 Gibbs/Duhem Theorem
•  

The Gibbs-Duhem theorem shows that the

intensive properties of a system are not
independent but related.
 Gibbs/Duhem Theorem
•  
 Gibbs/Duhem Theorem
•  
• As a consequence of the Gibbs theorem, the
chemical potential of one component of a
mixture cannot change independently of the
chemical potentials of other components.
• In a binary mixture, if one partial molar
quantity increases then the other must
decrease.
 On chemical potential
• The chemical potential μi gives insight to the
fundamental criterion for systems in material
equilibrium.
• G and μi are defined in relation to U and S. The
absolute values of U are unknown. It follows that
the values of μi are also unknown.
 Fugacity
• Recall:
  We derived an equation for the Gibbs
free energy change of an ideal gas

Let the initial condition be at standard pressure

P0:
 Fugacity
•  
For a real gas, we replace the true pressure P by
an effective pressure called the fugacity f.

The fugacity is a function of temperature and

pressure.
 Fugacity
•  We define φ  fugacity coefficient

The fugacity coefficient is dependent on the

temperature, pressure, and identity of the gas.
 Fugacity
•For  a real gas
 Fugacity
•  For an ideal gas
 Fugacity
•  Subtracting the two previous expressions
 Fugacity
•  

As P’  0, gas behaves ideally and f’ becomes

equal to the pressure; f’/P’  1. Taking this limit
 Fugacity
•  
 Fugacity
•  
Recall Z (compressibility factor) = PV/RT
For ideal gas, Videal = RT/P
For real gas, V = ZRT/P
 Fugacity
• Recall
Z = 1  ideal gas
Z < 1  real gas at low to moderate pressures –
attractive forces stronger than repulsive forces –
Φ < 1 and f < P; G less than that of an ideal gas
Z > 1  real gas at high pressures – repulsive
forces stronger than attractive forces – Φ > 1
and f > P; G greater than that of an ideal gas
Fugacity
 Activity
• The
  chemical potential of an ideal solution is given
by

For a real mixtures, this becomes

Where a  activity of species i in the solution

 activity coefficient – degree of departure of

species i from ideal solution behavior
 Activity
• Ideal solution model
- Approximated when the chemical species in a
solution are chemically similar
 Chemical Equilibrium
•Consider
  general reaction
aA1 + bA2 + … eAm + fAm+1 + …
Transpose reactants to the RHS
0  -aA1 – bA2 - … + eAm + fAm+1 +…
Let v1 = -a, v2 = -b,…, vm = e, vm+1 = f,…
0  v1A1 + v2A2 + … + vmAm + vm+1Am+1 + …

Where vi is the stoichiometric number of species I

(-)  reactants (+)  products
 Chemical equilibrium
• Extent of reaction ξ
During a reaction, the number of moles of each
substance is proportional to its stoichiometric
coefficient where the proportionality constant is
the same for all species i
Δn = ni – ni,0 = viξ
Ex. N2 + 3H2  NH3
 Chemical equilibrium
•  As derived from phase equilibrium:

For a single phase

dni  change in total no. of moles of i in a

closed system
 Chemical equilibrium
•  For a finite extent of reaction

For infinitesimal extent of reaction

Thus becomes
(
cannot be zero.
 Chemical equilibrium
• Thus,
  the general criterion for chemical
equilibrium is

“The chemical potential of the reactants balance

the chemical potential of the products.”
This holds true for any system in chemical
equilibrium regardless of how it is achieved.
 Chemical equilibrium
•  At constant T,P

Thus,
 Chemical equilibrium
•  At equilibrium, G is minimized.

• In a chemical reaction, the chemical potential

of each species vary until G is minimized.
•  change in Gibb’s free energy of a reaction
 Chemical equilibrium
•  Example: For A ⇌ B

• When at equilibrium, .
Since G is being minimized
• When , forward reaction is spontaneous.
• When reverse reaction is spontaneous.
Chemical equilibrium
• At equilibrium:
ΔrG = 0
• If ΔrG <0, forward
reaction is spontaneous:
exergonic reaction
• If ΔrG > 0, reverse
reaction is spontaneous,
endergonic reaction
 Chemical equilibrium
• The
  Gibbs free energy of an ideal gas can be
written as

• Like the Gibbs energy, the chemical potential

of a species can be written as:
 Chemical equilibrium
•  For A ⇌ B
 Chemical equilibrium
•   standard Gibbs free energy of the reaction

• Q  reaction quotient
 Chemical equilibrium
•  At equilibrium Therefore,

K  equilibrium constant
 Chemical equilibrium
•  For A ⇌ B

Cases:
a) When > 0, the equilibrium constant K<1 and
PA > PB; reactant A is favoured.
b) When < 0, the equilibrium constant K>1 and
PB > PA; product B is favoured.
 Chemical equilibrium
•  For a general reaction,

• The standard Gibbs free energy is calculated

from

 standard Gibbs energy of formation

 Chemical equilibrium
•  For a general reaction:

ai  activity of each species i in the reaction

 Chemical equilibrium
• In
  equilibrium, K is given by

K  thermodynamic equilibrium constant –

expressed in terms of activities or fugacities
For elementary applications, a is replaced by molar
concentrations or partial pressures (P/Po where Po is
1 bar). These are only approximations which
deviate severely for electrolyte solutions or for
gaseous systems at high pressures.
 Chemical equilibrium
• Write K in terms of equilibrium activities and
for elementary applications for the following
reactions
a) N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
b) H2 (g) + ½ O2 (g) ⇌ H2O (l)
c) 6 CO2 (g) + 6 H2O (g) ⇌ C6H12O6 (s) + 6 O2 (g)
d) CaCO3(s) ⇌ CaO (s) + CO2 (g)
 Chemical equilibrium
• Calculate the equilibrium constant for the
ammonia synthesis reaction at 298 K and
show how K is related to the partial pressures
of the species at equilibrium when the overall
pressure is low enough for gases to be treated
as perfect.
Use: ΔfGo(NH3,g) = -16.5 kJ mol-1
 Degree of dissociation, α
• fraction
  of reactant that has decomposed at
equilibrium
 Degree of dissociation
• The standard Gibbs energy of the reaction:
H2O (g)  H2 (g) + ½ O2 (g)
is 118.08 kJ mol-1 at 2300 K. What is the degree
of dissociation of H2O at 2300 K and 1.00 bar?