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Physical Chemistry

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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

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

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

= =

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

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