CHAPTER 6

Reaction Equilibrium in Ideal Gas Mixtures

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

Next few chapters: Reactions and phase equilibria in increasingly complex systems P-V work only & closed systems

1st law of thermodynamics: energy conservation 2nd law of thermodynamics: at equilibrium

dS + dSsurr = 0

Suniv = max

i i i

=0

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

all ideal gases What will be the composition of the mixture at equilibrium? How the equilibrium composition depends on P, V and T?

Important We are not concerned with how the system reaches the equilibrium (eg. how long it takes or whether a catalyst is required, you will deal with this in Chem 132) Knowing what the equilibrium is and characterizing it is important in its own!!!

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB
Ideal gas law:

cC + dD

all ideal gases

P Vm = RT
dG =
dGm =

Independently of the system:

SdT + V dP
Sm dT + Vm dP

dGm = d
Thermal equilibrium with the surroundings constant T (usual condition for gas rxn)

partial pressures change as rxn proceeds

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

all ideal gases Thermal equilibrium with the surroundings constant T (usual condition for gas rxn)

partial pressures change as rxn proceeds

d =

Sm dT + Vm dP

as rxn proceeds, chemical potentials change until the equilibrium condition is reached

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

all ideal gases individual components

d = Vm dP
Ideal gas law:

P Vm = RT
1

d = RT

P2 P1

dP P
P2 P

Choose:

P1 = P

(T, P2 )

(T, P ) = RT ln

(T, P ) = (T ) + RT ln

P P

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

(T, P ) = (T ) + RT ln
An important observation

P P

= Hm

T Sm
constant T

(T, P )

(T ) =

Hm

T Sm

ideal gas

(T, P )

(T ) =

T Sm
R ln P P

Sm = S (T, P )

S (T ) =

dependence on P in an ideal gas at constant T is a purely entropic effect

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

mixtures of ideal gases

P V = ntot RT
For the mixture:

P =

Pi

Pi = xi P

xi =

i Since in a mixture of ideal gases there are no interactions, the partial pressure Pi of each component i is the same as it would be if ni moles of i were in a volume V at T alone

ni ntot

Standard state for each component:

T and P = 1 bar

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

mixtures of ideal gases

P V = ntot RT

T, Pi
pure gas i

T, P n1 , n2 , . . . Pi = P xi
mixture

ntot = n1 + n2 + . . .
Pi =
pressure of pure gas i

mechanical equilibrium semipermeable membrane only i can go through

Pi = Pi
for ideal gases only

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD

mixtures of ideal gases

P V = ntot RT

T, Pi
pure gas i

T, P n1 , n2 , . . . Pi = P xi
mixture

phase equilibrium condition

i (T, P, x1 , x2 , . . . ) = i (T, Pi )
but

i (T, Pi ) = i (T ) + RT ln Pi P

Pi P

i (T, P, x1 , x2 , . . . ) = i (T ) + RT ln

each gas in the mixture behaves just as it would if all by itself only for ideal gases

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

aA + bB cC + dD
=0

ideal gas reaction equilibrium

i i i

equilibrium condition only for ideal gases

GT =

RT ln KP

KP =

PC,eq P PA,eq P

PD,eq P PB,eq P

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

equilibrium condition only for ideal gases

GT =

RT ln KP

KP =
KP =

Pi,eq P

standard equilibrium constant

Dimensionless Derived directly from the laws of thermodynamics for ideal gases Good approximation for real gases at low pressure

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

Equilibrium constant (remove Po):

KP =
i

(Pi,eq )

has dimensions!

Standard concentration equilibrium constant: molar concentration

ci,eq Kc = c i

ni ci = P = ci RT V c = 1 mol/L
Kx =

KP = Kc

RT c P

n/mol

Mole-fraction equilibrium constant:

(xi,eq )
i

K P = Kx

P P

n/mol

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

equilibrium condition only for ideal gases

GT =

RT ln KP

KP =
KP =

Pi,eq P

standard equilibrium constant

For ideal gases, the standard equilibrium constant depends only on T, not P. But the composition of the mixture does depend on both P and T. It is possible to measure the equilibrium constant and get the Gibbs free energy of the reaction but it is more convenient to calculate the latter from the Gibbs free energy of formation and get the equilibrium constant from it.

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

some important observations

GT =
1)

RT ln KP

KP =e

GT RT

0 < KP < KP >> 1, products are favored KP << 1, reactants are favored GT = HT T ST HT < 0 ST > 0
constant T products are favored products are favored

2) if 3) if

1) T 2) High T

GT GT

HT T ST

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

temperature dependence of the equilibrium constant

ln KP =

GT RT

d ln KP GT = dT RT 2

1 d GT RT dT

d ln KP HT = dT RT 2
vant Hoff equation

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

temperature dependence of the equilibrium constant

d ln KP HT = dT RT 2
vant Hoff equation

d ln KP =

HT dT RT 2

K (T2 ) ln P = KP (T1 )

T2 T1

HT dT RT 2

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

How to calculate the equilibrium composition

aA + bB

cC + dD

nA,0 nC,0 nD,0 nB,0

initial composition

nA,eq

nC,eq nD,eq

nB,eq
equilibrium composition

ni,eq

ni,0 =

ni =

i eq

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

How to calculate the equilibrium composition

aA + bB
(1) Calculate

cC + dD

GT =
i

i
GT RT

f GT,i

(2) Calculate

KP =e

(3) Determine the equilibrium composition

Pi,eq = xi,eq P =

KP =

ni,eq ni,0 + i eq P = P ntot ntot i ni,0 + i eq i P ntot P

RXN EQUILIBRIUM IN IDEAL GAS MIXTURES

shifts in ideal-gas reaction equilibria (Le Chateliers principle)

aA + bB
(1) Isobaric temperature change

cC + dD

An increase in T at constant P in a closed system shifts the equilibrium in the direction in which the system absorbs heat from the surroundings (2) Isothermal pressure change An increase in P at constant T in a closed system shifts the equilibrium in the direction in which the systems volume decreases (3) Isochoric addition of inert gas No shift in the equilibrium (4) Addition of a reactant gas It depends...