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Chemical

Chemical
Equilibrium
Equilibrium
Part 1 Part 1
Week Topic Topic Outcomes
3-4 Chemical equilibrium
The Gibbs energy & Helmholtz
energy
The Gibbs energy of a gas in a
mixture
The thermodynamic equilibrium
constant, K
p
for a mixture of ideal
gases
The dependence of
eq
on to T &
P
It is expected that students are
able to:
Interpret the spontaneity of a gas
mixture.
Calculate the Gibbs energy and
the equilibrium partial pressure of
mixing for ideal gases.
Topic Outcomes
(3)
How fast we get the product How much we get the product
Introduction
In each phase of the closed
system, the number of moles
of each substance present
remains constant in time.
Reaction equilibrium:
Is equilibrium with respect to
conversion of 1 set of chemical
species to another set.
Phase equilibrium:
Is equilibrium with respect to
transport of matter between
phases of the system without
conversion of 1 species to
another.
Definition
Reaction Equilibrium:
Involves different chemical species, which may or may not be
present in the same phase.
E.g.: CaCO
3
(s) CaO (s) + CO
2
(g)
N
2
(g) + 3H
2
(g) 2NH
3
(g)
Phase equilibrium:
Involves the same chemical species present in different phases
E.g.: C
6
H
12
O
6
(s) C
6
H
12
O
6
(aq)
Example
Entropy & Equilibrium
Consider an isolated system that is not at material
equilibrium;
The spontaneous chemical rxn / transport / matter btw
phases in this system are irreversible processes that
increase the entropy (S).
The processes continue until the S is maximized
once the S is maximized, further processes can only
decrease S, i.e., violating the 2
nd
Law.
Criteria for equilibrium in an isolated system is the maximization of
the systems entropy, S.
Material equilibrium in Closed System
Ordinarily not isolated: can exchange heat and work with its
surroundings.
By considering the system itself plus the surroundings with
which it interacts to constitute an isolated system
Then, the condition for material equilibrium in the system is
maximization of the total entropy of the system plus its
surroundings:
a maximum at equilibrium
g surroundin system
S S +
Reaction Equilibrium
1. Rxn that involve gases
Chemicals put in container of fixed V,
System is allowed to reach equilib. at const. T &
V in a const.-T bath.
2. Rxn in liquid solutions
E.g.: The system is usually held at atm P
Allowed to reach equilib. at constant T & P.
The Gibbs
The Gibbs
Energy and
Energy and
Helmholtz
Helmholtz
Energy
Energy
(10)
New State Functions
Spontaneity is discussed in context of the approach to
equilibrium of a reactive mixture of gas.
2 new state functions are introduced that express
spontaneity in terms of the properties of the system
only.
Previously: the direction for an arbitrary process in
predicted by S
sys
+ S
surr
> 0.
Reactant Product
Systems at const. V & T Systems at const. P & T
Criterion for determining if the reaction mixture will
evolve toward reactants or products:
K
p
derived
Predict equilibrium conc.
The Helmholtz Energy, A
Material equilib. in a system held at const. T &V (dV
= 0, dT= 0)
dU TdS + SdT SdT + dw
dU d(TS) SdT + dw
d(U TS) SdT + dw
at equilibrium dU TdS + dw
Add & subtract SdT:
Since d(TS) = SdT + SdS
d(U TS) SdT PdV
d(U TS) 0
Const. T & V, dT=0, dV=0, closed syst.
In therm. & mech. Equilib.,P-V work only
At const. T & V, dT=0, dV=0
Since dw = P dV
State function
Helmholtz free energy
A U - TS
The Gibbs Energy
Consider for const.T & P, dw = PdV into dU TdS + dw
dU d(TS) SdT d(PV) + VdP
d(H TS) SdT VdP
d(U + PV TS) SdT + VdP
dU TdS + SdT SdT - PdV - VdP + VdP
d(H TS) 0
At const. T and P, dT=0, dP=0
G H TS U + PV TS
Gibbs free energy,
dA
T,V
0 dG
T,P
0
Equilibrium reached
Const. T, P
Time
G
Equilibrium State
G decreases
S
univ
increase
In a closed system capable of doing only P-V work,
Const. T & V material-equilibrium condition is the
minimization of the A,
Const. T & P material-equilibrium condition is the
minimization of the G.
dA = 0
dG = 0
at equilib., const. T, V
at equilib., const. T, P
Relationship G
equilib
& S
univ
Consider a system in mechanical & thermal equilib.
which undergoes an irreversible chemical reaction /
phase change at const. T & P.
/ T G

/ T S T H


S / T H S S S
syst syst syst
syst syst syst surr uni v
= =
+ = + =
/ T G S
syst uni v
=
Closed syst., const. T, V, P-V
work only
G
syst
as the system proceeds to equilib. at const. T
&P corresponds to a proportional S
univ
.
The occurrence of rxn is favored by +ve S
syst
and +ve
S
surr
Work Function: A
at const. T ( ) dw SdT TS U d +
dw dA
w A
dw SdT dA +
w w
by
=
A w
by

Const. T, closed syst.
Closed system in thermal & mechanical equilibrium
Finite isothermal process
Work done by the system
on its surroundings
A carries a greater significance than being simply a
signpost of spontaneous change:
A w
max
=
Change in the Helmholtz energy is equal to the max. work the system can do:
Equality sign reversible proc.
w
by
can be greater or less than
U (int. energy of syst.)
w
by
= U + q (E.g. Carnot
cycle, U = 0 & w
by
>0)
Work Function: G
TS PV U TS H G +
PV A PV TS U G + + VdP PdV dA dG + + =
VdP PdV dw SdT dG + + +
( ) dw SdT TS U d +
dw SdT dA +
PdV dw dG +
const. T & P, closed syst.
From
and H=U+PV
d(PV)=PdV+VdP
V P non
dw PdV dw

+ =
V P non
dw dG

V P non by, V P non


w w G

=
V P non
dw dG

G w
V P non by,

const. T & P, closed syst.
If the P-V work is done in a mechanically reversible
PdV dw dG + Note:
A w
by

Earlier for A;
From dw
w A
Compare A
Compare A
G w
max
V, P non
=

( ) PV d dw dq dH + + =
( ) ( ) PV d dw TdS PV d dw TdS dG
r ev
+ = + + =
dw dq dU + =
( ) VdP dw VdP PdV dw PdV dG
V P non V P non
+ = + + + =

r ev
dw dw =
TdS dq dq
r ev
= =
The max. non-expansion work from a process at cont. P & T is given by the
value of G
(const. T, P)
Reversible change, equality
sign holds & w
by,non-P-V
=
G
From dU
dH=dU+d(PV)
dS=dQ/T
dG=dH-TdS
dH
What G means:
+G : not spontaneous
Zero G : at equilibrium
G : spontaneous
What A means:
+A : not spontaneous
Zero A : at equilibrium
A : spontaneous
Second law of thermodynamics:
Entropy must always increase!
Summary
Gibbs Free Energy Helmholtz Free Energy
S T H G =
S T U A =
Initial & final states of system
at the same values of
P & T
Initial & final states of system
at the same values of
V & T
Working Session
For a phase change on vaporization of 1.0 mol water at 1 atm and 100C,
calculate G and A.
Given: molar volume of H
2
O (l) at 100C is 18.8 cm
3
/mol, R=8.314
J/mol.K=82.06 cm
3
.atm/mol.K
Example 1
You wish to construct a fuel cell based on the oxidation of
hydrocarbon fuel. The 2 choices for a fuel are methane & octane.
The reactions are,
Methane: CH
4
(g) + 2O
2
(g) CO
2
(g) + 2H
2
O (l)
Octane: C
8
H
18
(l) + 25/2 O
2
(g) 8CO
2
(g) + 9H
2
O (l)
Calculate the maximum work and non-expansion work available
through the combustion of these 2 hydrocarbons, on a per mole and
a per gram basis at 298.15 K and 1 bar pressure.
Given at 298.15K: H
combustions
(CH
4,
g)=891kJ/mol;
H
combustions
(C
8
H
8,
l)=5471 kJ/mol; S
m
(CH
4
,g)=186.3 J/mol.K;
S
m
(C
8
H
8
,l)=361.1 J/mol.K; S
m
(O
2
,g)=205.2 J/mol.K;
S
m
(CO
2
,g)=213.1 J/mol.K; S
m
(H
2
O,l)=70 J/mol.K
Differential
Differential
Forms of
Forms of
U
U
,
,
H
H
,
,
A
A
and
and
G
G
All thermodynamic state-function relations can be
derived from six basic equations,
1
st
basic equation it
combines the 1
st
& 2
nd
Laws
Next 3 basic equations are
the definitions of H, A, and G
Finally, the 2 equations are
for the CP and CV equations
PdV TdS dU =
Closed syst., P-V work
only
PV U H + =
TS U A =
TS H G =
Closed syst., in
equilib., P-V work only
V
V
T
U
C

=
P
P
T
H
C

=
Closed syst., in
equilib., P-V work only
The Gibbs Equations
Closed syst., rev.
proc., P-V work only
VdP TdS dH + =
PdV TdS dU =
SdT PdV dA =
SdT VdP dG =
Equivalent Expressions
V
P
H
and T
S
H
S P
=

P
V
U
and T
S
U
S V
=

V
P
G
and S
T
G
S P
=

P
V
A
and S
S
A
T V
=

V T
T
P
V
S

P T
T
V
P
S

P S
S
V
P
T

S V
V
T
S
P

The last two are extremely


valuable.
Maxwell Relations
The first two are little
used.
The equations relate the isothermal P & V variations of
entropy to measurable properties.
Dependence of G & A on P, V, T
Most reactions of interest to chemist are carried out
under const. P rather than const. V conditions.
V
P
G
and S
T
G
S P
=

G, T
G ,P
Macroscopic change in P & T, 2
nd
expression
integrate
( ) ( )

= =
P
P
P
P
VdP' P T, G P T, G dG
o o
o o
Initial P, P =
1 bar
This equation takes on different form for liq. & solids &
for gaseous.
Liquids & Solids
Independent of P over a limited range in P,
( ) ( ) ( ) ( )
o o o o o
o
P P V P T, G VdP' P T, G P T, G
P
P
+ + =

Systems changes appreciably with P
( ) ( ) ( ) ( )
o
o o o
o o
P
P
l n T G dP'
P'
nRT
T G VdP' T G P T, G
P
P
P
P
nRT + = + = + =

Gaseous
Gibbs-Helmholtz Equation
More useful to obtain an expression for T dependence
of G/T than for T dependence of G,
[ ] [ ]
2 T
H
T
TS G
T
G
T
S
T
G
T
G
T
1

dT
1/ T d
G
T
G
T
1
T
G/ T
2 2 2
P
P P
=
+
= =

=
+

[ ]
[ ]
[ ]
[ ]
( ) H T
T
H
1/ T d
dT
T
G/ T
1/ T
G/ T
2
2
P P
= =

Can also be written [ ]


2
T
1
dT
1/ T d
=
Preceding equation also applies to the change in G &
H associated with a process

2
1
2
1
T
T
T
T
T
Hd
T
G
d
1
( ) ( )
( )

1 2
1
1
1
2
2
T T
T H
T
T G
T
T G 1 1 Assumption: H is
independent of T
over the T interval of
interest
Integral must be evaluated
numerically using tabulated H
f
&
T-dependent expressions of C
p,m
for reactants & products
Example 2
The value of G
f
for Fe(g) is 370.7 kJ mol
1
at 298.15 K,
and H
f
for Fe(g) is 416. 3 kJ mol
1
at the same
temperature. Assuming that H
f
is constant in the
interval 250 400 K. Calculate G
f
for Fe(g) at 400 K.
Gibbs Energy of
Gibbs Energy of
Gas Mixture
Gas Mixture
G of a Gas in a Mixture
Conditions for equilibrium in a reactive mixture of ideal
gases,
Derived in terms of the
i
of the chemical
constituents.
Chemical potential of a reactant/product species
changes as its conc. in the reaction mixture changes.
2 important processes occur
The mixing of reactants
The conversion of
reactants to products
Barrier removed
R
1
R
2
R
1
R
2
R
1
R
2
R
1 R
2
R
2
R
2
R
1
R
1
Barrier
Equilibrium Condition
Pd membrane
Permeable to
H
2
, not to Ar
H
2
pressure (not total P) is same on both sides of the membrane,
Equilib. reached with respect to the conc. of H
2
mi xt ur e
H
pur e
H
2 2
=
at equilibrium
of a Gas in Mixture
( ) ( ) ( )
o o
P P l n nRT T G P T, G + =
( ) ( ) ( )

+ = =
o
o
P
P
l n RT T P T, P T,
2
2 2 2 2 2
H
H H
mi xt ur e
H H
pur e
H
of a gas in a mix. depends
logarithmically on its partial P,
P
A
= x
A
P
( ) ( ) ( )
A A A A
mi xt ur e
A
x RTl n
P
P
l n RT T x l n RT
P
P
l n RT T P T, +

+ = +

+ =
o
o
o
o
( ) ( )
A
pur e
A
mi xt ur e
A
x l n RT P T, P T, + =

A
mixture
<
A
pure
Substance flows from to
Diffusion continue until partial P both
sides of the barrier are equal
Mixing are spontaneous if no barrier.
Conclusion
x
A
< 0
( ) ( )
A
pur e
A
mi xt ur e
A
x l n RT P T, P T, + =
G of a Gas of Mixing for Ideal Gas
Chemical potential of a
reactant/product species changes
through mixing with other species.
Quantitative relationship between
G
mixing
& the mole fractions of
individual constituents of the mixture.
Consider Xe, Ar, Ne, He
Compare G initial state & final state
(uniformly distributed)
Calculation the G
Initial state Final state
Xe m, Xe m, Ar Ar Ne m, Ne He m, He
Xe Ar Ne He i
G n G n G n G n
G G G G G
+ + + =
+ + + =

( ) ( )
( )
( )
Xe Xe m, Xe
Ar m, Ar Ar
Ne Ne m, Ne He He m, He f
RTl nx G n
RTl nx G n
RTl nx G n RTl nx G n G
+ +
+ +
+ + + =
Gibbs energy of mixing
(G
f
-G
i
)
x
i
< 1, each term in the last expression is ve
G
mixing
< 0 mixing is spontaneous process
Gibbs Energy of Binary Mixture
Consider mixture of A (x
A
= x) & B
(x
B
= 1 x),
T = 298.15 K
G
mixing
= 0 (x
A
=0 & x
A
=1)
Pure substance
G
mixing
= min (x
A
=0.5)
Largest decrease in G arises
from mixing (A & B equal
amount)
( ) ( ) [ ] x 1 l n x 1 xl nx nRT G
mi xi ng
+ =
Entropy of Binary Mixture
Entropy of mixing,


=
i
i i
P
mi xi ng
mi xi ng
l nx x nR
T
G
S
T = 298.15 K
x
A
=0 x
A
=0.5, increase
Each components of mixture
expands to larger final volume
S
mixing
arises from the
dependence of S on V at const.
T
Each component contributes
equally to S
Example 3
Consider the system consists of 4 separate
subsystems containing He, Ne, Ar & Xe.
Assume that the separate compartments
contain 1.0 mol of He, 3.0 mol of Ne, 2.0 mol of
Ar & 2.5 mol of Xe at 298.15 K. The pressure in
each compartment is 1 bar.
a. Calculate G
mixing
b. Calculate S
mixing