Chap. 6: Reaction Equilibrium in Ideal Gas Mixtures 6.1: Chemical Potentials in an ideal Gas Mixture 6.

2: Ideal-Gas Reaction Equilibrium 6.3: Temperature Dependence of the Equilibrium Constant 6.4: Ideal-Gas Equilibrium Calculations 6.6: Shifts in Ideal-Gas Reaction Equilibria

6.1: Chemical Potentials in an Ideal Gas Mixture

i(T, P) Intensive property d = dGm = -SmdT + VmdP At constant T (dT = 0): d = VmdP For an ideal gas, Vm = (RT/P) d = (RT/P)dP If the gas undergoes an isothermal change of 2 P dP P states from P1 to P2: 1 d RT P RT d ln P P
2 2 1

T , P2

T, P 1

P2 RT ln P 1

Generally, we have (T, P ) values in the table, P T RT ln , where P 1 bar thus P See Fig-6.1 on p. 175.
2. Chemical potentials in an ideal gas mixtures

For an ideal gas mixture: (1) PV = ntotRT (2) Pi = iP The standard state of component i of an ideal gas at temperature T is defined to be pure ideal gas i at T and pressure P = 1 bar.

The condition for phase equilibrium between the mixture and pure i is: i =i*, where i : The chemical potential of the ith component in the gas mixture at T. i *: The chemical potential of pure i at (T, Pi*). For an ideal gas mixture: i(T, P, 1, 2, ) =i*(T, iP) = i*(T, Pi) The chemical potential of pure gas i at T, Pi:
* i i

RT ln

Pi P

Equ - 6.4 *

Equ-6.4 is a way to use the chemical potential to of pure gas i to calculate the mixture one.

6.2: Ideal Gas Reaction Equilibrium

Example: for the ideal gas reaction aA + bB cC + dD In equilibrium: aA + bB = cC + dD

Pi RT ln , where i P PA P b d
B

A, B, C, D PB P 0 PB b ln P PC c ln P PD d ln P

aRT ln

bRT ln

PC cRT ln P c
C

PD dRT ln P PA a ln P

RT

Because
GT i

Gm for a pure substance

Therefore, the equilibriu m condition Equ - 6.5 * becomes : G G

RT

PA ln P
PC c P a P

PB ln P
PD PB d P b P

PC ln P

PD ln P

RT ln

PA

, Note : Pi is at equilibriu m

Define the equilibriu m constant K P for gas phase reactions :

PC ,eq PA,eq

c a

PD ,eq PB ,eq

d b

a b c d

, then, G

RT ln K P

If we still remember the " stoichiome tric number" :

RT
i

ln

Pi ,eq P

RT
i

ln

Pi ,eq P Pi ,eq
i

GT

RT ln
i

Pi ,eq P

Define : K P i
GT RT

GT

RT ln K P and K P

( K P is dimensionl ess) N2

Example :

N 2 ( g ) 3H 2 ( g ) PNH 3 ,eq Pi ,eq

2 NH 3 ( g )
2

1,

H2

3,

NH 3

KP i

P PN 2 ,eq P PH 2 ,eq P
3

 Example 6.1: see p. 179

Equilibrium Constant Define the molar concentration, Ci, of species i in the mixture as Ci = ni /V . Note: for an ideal gas, Ci = Pi /RT
If aA bB P C A,eq RT P
a

fF dD , then
f

C F ,eq RT
KP

C D ,eq RT P C B ,eq RT P

C F ,eq
b

C
a

C D ,eq C B ,eq

C
b

C A,eq

C RT P

a b f d

C F ,eq K
P

C C A,eq

C D ,eq C C B ,eq

d b

C RT P

a b f d

1 mol Where C 1 mol L 1L Define the " Standard Concentrat ion Equilibriu m Constant K C . K
C i

Ci ,eq C

, if we let n
i

, K

RTC P

Similarly, define " Mole - Fraction Equilibriu m Constant K . K

, where K

P P

3. Qualitative discussion of chemical

equilibrium 0 < KP < 1) KP >> 1: Reactant Product

Reactant Product

3) Moderate KP: incomplete reactions, for

example,

N2 + 3H2 2NH3

6.3: Temperature dependence of the equilibrium constant

G RT
Gm ,i i i

G RT 2 d dT

1 d G , because G RT dT
Gm ,i i i i dGm ,i

d dt

dT
dGm S m dT

Gibbs Equation : dGm

S m dT Vm dP
S m ,i i i

dT
d ln K P dT

S m ,i

d G dT S RT

S H RT 2

G RT 2

G T S RT 2

Equ - 6.36* :
d ln K P

d ln K P dT

H RT 2
2 1 T2 d ln K P

Van' t Hoff Equation

H dT 2 RT
ln K P T1 T2 T1 T1

H dT 2 RT

ln K P T2 K P T2 ln K P T1

H T dT 2 RT

H T dT (Need H T to evaluate this) RT 2

If T
P P

T2 T1 is small, H T is usually a constant, then : H R 1 T1 1 T2

K T2 ln K T1

 Example 6.2: Change of KP with T, p. 183.

Find KP at 600 K for N2O4(g) 2NO2(g) (a) Using the approximation that H is independent of T. (b) Using the approximation that CP is independent of T. (c) Using the NIST-JANAF tables (see 5.9) Solution: Read p. 183 184.

6.4: Ideal gas equilibrium calculations

GT = -RTlnKP to determine KP GT KP by thermodynamic calculations The equilibrium composition of an ideal gas reaction is a function of T and P (or T and V) and the initial composition (mole numbers) n1,0 , n2,0 , , of the mixture. The equilibrium extent of reaction eq ni ni,eq - ni,0 = ieq ni = ni,0 + ieq

 The specific steps to find the equilibrium composition of an ideal gas reaction mixture:
1) Calculate GT of the reaction: GT f GT ,i i i Using a table of GT or HT and ST values.

2) Calculate KP using G = -RTlnKP

4) (b) If the reaction is running at fixed T and V, use Pi = niRT/V and ni = ni,0 + ieq to express Pi in terms of eq . 5) Substitute the Pis (expressed as a function of eq) into the equilibrium constant expression and solve for eq : P
i

KP

6) Calculate the equilibrium mole numbers from eq and the expressions for ni in step 3).

Example: see p. 187 about the ICE table.

N2 (g) Initial (mol) : 1.0 Change (mol) : -z Equilibriu m (mol) : 1.0 - z In equilibriu m, ntot 1.0 z nN 2
N2

3H 2 ( g ) 2.0 - 3z 2.0 - 3z 2.0 3z nH 2 ntot

2 NH 3 ( g ) 0.50 2z 0.50 2 z 0.50 2 z

3.5 2 z mol nNH 3 ntot 0.50 2 z 3.5 2 z

ntot

1.0 z , 3.5 2 z

H2

2.0 3z , 3.5 2 z

Thus, if P is fixed, PN 2 or, if V is fixed, PN 2 V

N2 P

nN 2 RT
2 PNH 3

1.0 z P, 3.5 2 z 1.0 z RT 3.5 2 z V

Reaction Quotient : QP If QP
K P , " "; if QP

3 PN 2 PH 2 K P , " Equilibriu m"; if QP K P , " ".

 Example 6.4: see p. 187.

Suppose that a system initially contains 0.300 mol of N2O4(g) and 0.500 mol of NO2(g) and the equilibrium is attained at 25 C and 2.00 atm. Find the equilibrium composition.

 (1) G 298 i (2) G 298

f G298 ,i i

1 97.89
KP

2 51.31 e

4.73 kJ/mol 0.148

RT ln K P

G298 RT

4730 J/mol 8.31447 J/mol K 298.15K

(3) " ICE" table :

N 2O 4 ( g )

2NO 2 ( g )

Initial (mol) 0.300 0.500 Change (mol) -x 2x Equilibriu m (mol) 0.300 - x 0.500 2 x Thus, ntot 0.300 x 2 0.500 2 x 0.800 x mol nN 2 O 4 0.300 x mol, nNO 2 0.500 2 x mol 0.500 2 x 0.800 x
NO 2

(4) Mole fractions and partial pressures : nN 2 O 4 nNO 2 0.300 - x , NO 2 N 2O 4 ntot 0.800 x ntot PN 2O 4
N 2O 4

0.300 - x P, PNO 2 0.800 x

0.500 2 x P 0.800 x

(5) K

PNO 2 / P

PN 2O 4 / P 0.500 2 x 2 0.800 x
2

0.148 0.148

P P

0.300 x 0.800 x

P P 1520 torr 750 torr

0.250 2 x 4 x 2 P P , where 2 0.240 0.500 x x P P

4.0730 x 2 2.0365 x 0.2325 0 x1 0.324 mol, x2 0.176 mol, we need x2 , not x1! (6) nN 2O 4 nNO 2 0.300 x 0.500 2 x 0.300 0.500 2 0.176 0.176 0.476 mol 0.148 mol

 Example 6.5: Self-reading, see p. 189.

KP = 6.51 at 800 K for the ideal gas reaction: 2A + B C + D. If 3.000 mol of A, 1.000 mol of B, and 4.000 mol of C are placed in an 8000-cm3 vessel at 800 K, find the equilibrium amounts of all species.

6.6: Shifts in ideal gas reaction equilibrium

Pi

1) QP < KP : reaction shifts to right

3) QP = KP : reaction in equilibrium
2. Isobaric temperature change
d ln K P dT

H RT 2

1 dK P K P dT

H RT 2

dK P dT

KP

H RT 2

dK P Because K P and RT 2 is always positive. The sign of is dT determined by H .

 If H > 0 (endothermic reaction), dT > 0

will lead to dKP > 0. The reaction will because KP(current) > KP(original) = QP If H < 0 (exothermic reaction), dT > 0 will lead to dKP < 0. The reaction will because KP(current) < KP(original) = QP 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.

3. Isothermal pressure change: An increase in P at constant T in a closed

4.

5.

1)
2)

system shifts the equilibrium in the direction in which the system volume decreases. Isochoric addition of inert gas: Reaction not shifts because QP = KP due to the no change of partial pressures of reactants and products. Addition of a reactant gas: See p. 196 197. At const-T, const-V: reaction shift to right. At const-T, const-P: Tricky!!

 Le Chteliers Principle:

In a system at equilibrium, a change in one of the variables that determines the equilibrium will shift the equilibrium in the direction counteracting the change in that variable.
6. Shifts in system with more than one reaction

Determined by experiments!