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Chapter 4

Chemical Equilibrium

Equilibrium applies to the extent of a reaction, the concentration of product that has appeared after an unlimited time, or once no further change occurs.

Guldberg & Waage, 1862
Guldberg
&
Waage,
1862
At equilibrium: rate forward = rate reverse
At equilibrium:
rate forward = rate reverse

A system at equilibrium is dynamic on the molecular level; no further net change is observed because changes in one direction are balanced by changes in the other.

N 2 O 4 2NO 2 colourless brown At equilibrium, the product and reactant concentrations

N 2 O 4 2NO 2

colourless

brown

At equilibrium, the product and reactant concentrations are constant. K =[NO 2 ] eq /[N 2 O 4 ] eq

33

The range of equilibrium constants

small K large K
small K
large K

Magnitude of K is an indication of how far a reaction proceeds toward product at a given temperature.

intermediate

K

44

Chemical Potential

Change in the Gibbs free energy with respect to amount at constant temperature and pressure.

i

G n

i

T ,P,n

j

i

Intensive variable

For systems with > 1 component, chemical potential does not equal the change in free energy of the pure material because each component interacts with the other, which affects the total energy of the system.

Chemical potential for 1 component system

G

For pure substances, chemical potential = change in Gibbs energy as the amount of material changes.

In chemical reactions: species, number of moles, phase change. H 2 (g) + Cl 2 (g) = 2HCl(g)

2H 2 (g) + O 2 (g) = 2H 2 O(l)

In considering equilibrium, need to consider these changes.

Multi-component system

Broader definition for dG

G T

dT G

dP G n

G n

dG

dn

1

P

1

2

P,n ,n

1

S

2

T ,n ,n

1

V

2

T ,P,n

2

T ,P,n

1

1

2

dG G T

P,n

i

dT G P

T ,n

i

dP

G n

i

i

i

T,P,n (j i)

j

dn

dG

-SdT

VdP

i

dn

i

i

dn

2

Fundamental equation of chemical thermodynamics

Fundamental equations for open systems

dG

dH

SdT

VdP

TdS

VdP

dU

TdS

PdV

dA

-SdT

PdV

i

dn

i

i

i

dn

i

i

i

dn

i

i

i

dn

i

i

i = Gibbs free energy per mole of component i or the partial molar Gibbs free energy

n

1

G

i

G n

i

T ,P,n

j

1

n

2

n

1

1

2

n

G

2

2

i

G

i

n

i

i

i

n

i

i

i

G

i

Chemical potential of a substance is the slope of the total Gibbs energy of a
Chemical potential of a substance is the slope of the total Gibbs energy of a
Chemical potential of a
substance is the slope
of the total Gibbs
energy of a mixture wrt
the amount of the
substance

10

1. Liquid water and ice in equilibrium ice (T,P ) water (T,P ) 2. Cell
1. Liquid water and ice in equilibrium ice (T,P ) water (T,P ) 2. Cell

1. Liquid water and ice in equilibrium

ice

(T,P )

water

(T,P )

2. Cell placed in hypotonic solution

water(cell )

(T,P)

water(solu tion)

(T,P)

A (mix, T,P) < A (pure, T,P) ?

Chemical potential of a pure (1-component) ideal gas

G(T ,P )

G

o

(T )

RT ln

P

P

o

o (T )

P

P

(T ,P )

RT ln

o

Chemical potential of a mixture of ideal gases At equilibrium,

mixed A,

pure A

B

P

A

P_ '

P

A

'

P_

P P

A

B

B

tot

 
P A ' P_ P P A B B tot   Membrane permeable only to A

Membrane permeable only to A

'

P ( pure ) P ( mix ) P

A

A

tot

X

A

Dalton_s law

A

( mix,T ,P

tot

)

A

( pure,T ,P )

A

o

A

o

A

A

( pure,T , X P

A

tot

)

(

pure,T )

(

pure,T )

X

A

P

tot

P

o

tot

RT ln

RT ln P

RT ln X

A

A

( pure,T ,P

tot

)

( mix,T ,P

A

tot

) ( pure,T ,P

A

tot

) RT ln X

A

A

( mix,T ,P

tot

)

A

( pure,T ,P

tot

)

X A < 1
X A < 1

The chemical potential of A in the mixture is always less than the chemical potential of A when pure, at the same total pressure.

Entropy of A in mixture higher than when A is pure.

Extent of reaction

Dynamic equilibrium in which both reactants and products are present but have no further tendency to undergo net change. Equilibrium composition corresponds to minimum G.

Extent of reaction (moles) :

n

i

n

i , o

i

where n i is the number of moles at t and v i is the stoichiometric coefficient of the i th chemical species in the reaction; +ve for products and eve for reactants. n i = n i,o + v i dn i = v i d

1414

Gibbs Energy Minimum A + B C + D

A + B
A + B
o o G G A B o G rxn C + D
o
o
G
G
A
B
o
G
rxn
C + D

Reactants (and

products) isolated from other.

G

o

C

G

o

D

Mixed reactants ; mixed reactants and products.

1515

If G reaction < 0 forward reaction is spontaneous. If G reaction > 0, reverse reaction is spontaneous. If G reaction = 0, reaction is at equilibrium.

1616

Ideal gas equilibria

Consider a general gas-phase reaction: A (g, T, P) B (g,T, P)

r

G

where

B

A

o

i

i

RT ln

P

i

o

P

Assume perfect gas behavior,

G

r

(

o

B

G

r

o

RT ln

P

B

P

o

)

(

o

A

RT ln

P

P

B

o

P P

A

o

where Q

P

B

P

A

RT ln

G

r

o = standard chemical potential,

of the pure gas at 1 bar.

Partial pressure P i = X i P

P

A

P

o

o

) Reaction quotient
)
Reaction
quotient

RT lnQ

1717

Q: reaction quotient; 0 when P B = 0 to infinity when P A = 0.

r

r

G

G

o

RT lnQ

Standard reaction Gibbs energy, r G o , is the difference in the standard molar Gibbs energies of reactants and products at 1 bar.

o o o o o G G G B A r B A At equilibrium,
o
o
o
o
o
G G G
B
A
r
B
A
At equilibrium, r G = 0
o
0 G
RT lnQ
r
eq
Rename Q eq = K p
K p does not depend on
pressure and is a function of T
only. Dimensionless number.
o
G
RT ln K
r
P
B
K
P
p
o
G
P
A
r
equilibrium
ln K
P
RT

1818

Q - The Reaction Quotient

At any time, t, the system can be sampled to determine the amounts of reactants and products present. A ratio

of products to reactants, calculated in the same manner

as K tells us whether the system has come to equilibrium (Q = K) or whether the reaction has to proceed further from reactants to products (Q < K) or in the reverse direction from products to reactants (Q > K).

Q

More products make Q larger, more reactants makes Q smaller
More products make Q
larger, more reactants
makes Q smaller

= [products]/[reactants]

Reaction direction and the relative sizes of Q and K.

Reaction Progress
Reaction
Progress
and the relative sizes of Q and K. Reaction Progress Reaction Progress reactants products Equilibrium: no
Reaction Progress
Reaction
Progress

reactants

of Q and K. Reaction Progress Reaction Progress reactants products Equilibrium: no net change reactants products

products

Equilibrium:

no net

change

reactants

of Q and K. Reaction Progress Reaction Progress reactants products Equilibrium: no net change reactants products

products

2020

Consider a general gas-phase reaction at T and P:

A + B C + dD

, , , - stoichiometric numbers
, , , -
stoichiometric numbers

G

r

C

D

A

B

G

r

(

o

C

G

r

o

RT ln

P

C

P

o

)

D

(

o

RT ln

P

D

P

o

)

(

o

A

RT ln

P

P

C

o

P

P

D

o

P P

A

o

P

P

B

o

where G

r

o

RT ln

u

o

C

P

A

P

o

)

u

o

D

B

(

o

u

o

A

RT ln

u

o

B

P

B

P

o

)

K

P

P

C

P

D

P

A

P

B

All P i values are divided by 1 bar, so K p

is unitless

2121

K in terms of mole fractions

K

P

where

P

C

P

D

P

o

P

o

P

A

P

B

P

o

P

o

X P

c

P

o

X

P

D

P

o

X

P

A

P

o

X

B

P

P

o

(

)

P P

o

X X

c

D

X

A

X

B

P

K

X

P

K

P

K x depends on the total pressure. Unitless since P divided by 1 bar.

K

X

Comparing Q and K to Determine Reaction Direction

PROBLEM:

For the reaction

N 2 O 4 (g)

2NO 2 (g), K c = 0.21 at 100 0 C. 2 (g), K c = 0.21 at 100 0 C. 2 (g), K c = 0.21 at 100 0 C.

At a point during the reaction, [N 2 O 4 ] = 0.12M and [NO 2 ] = 0.55M. Is the reaction at equilibrium? If not, in which direction is it progressing?

2323

Q c =

Solution

[NO 2 ] 2

=

[N 2 O 4 ]

(0.55) 2

(0.12)

=

2.5

Q c is > K c , therefore the reaction is not at equilibrium and will proceed from right to left, from products to reactants, until Q c = K c .

2424

Example problem

6H

18.0mol

If all P reacts to form products,

P

4

4PH

3

1.0 mol

2

2.0 mol

4

(12.0 mol

For H ,

2

For P ,

4

For PH ,

3

0.0 mol

8.0 mol )

Reacted: H 2 12 moles P 4 2 moles Formed: PH 3 8 moles

No matter which species is used, same extent of reaction.

2525

Initial and Equilibrium Concentration Ratios for the

N 2 O 4 -NO 2 System at 200 o C (473 K)

Initial

Ratio(Q) [NO 2 ] 2

at 200 o C (473 K) Initial Ratio( Q ) [NO 2 ] 2 Equilibrium Ratio(

Equilibrium

Ratio(K) [NO 2 ] eq

2

) [NO 2 ] 2 Equilibrium Ratio( K ) [NO 2 ] e q 2 Experiment

Experiment

[N 2 O 4 ] [NO 2 ]

[N

2 O 4 ]

[N 2 O 4 ] eq

[NO 2 ] eq

[N

2 O 4 ] eq

1 0.1000

0.0000

0.0000

3.57x10 -3

0.193

10.4

2 0.0000

0.1000

9.24x10

-4

9.83x10 -3

10.4

3 0.0500

0.0500

0.0500

2.04x10

-3

0.146

10.4

4 0.0750

0.0250

0.00833

2.75x10

-3

0.170

10.5

The individual equilibrium concentrations are different in each case but the ratio of the equilibrium concentrations is constant.

26

The change in Q during the N 2 O 4 -NO 2 reaction

change in Q during the N 2 O 4 -NO 2 reaction K is a special
K is a special value of Q that occurs when the reactant and product terms
K is a special value
of Q that occurs
when the reactant
and product terms
have their
equilibrium values.

27

Example H 2 (g) + CO 2 (g) = H 2 O(g) + CO (g)

T = 298 K, P = 1 bar

Initial no.

H 2 (g)

CO 2 (g)

H 2 O(g)

CO(g)

of moles

ab

00

No.of moles at equil.

a - x

b e x

x

x

Total number of moles at equilibrium = (a e x) + (b e x) + 2x = a + b

Mole

fraction

a

x

b

x

x

x

a

b

a

b

a

b

a

b

f G o (kJ/mol) 0

-394.36

-228.57

-137.17

Q for an overall reaction

If an overall reaction is the sum of two or more

reactions, the overall reaction quotient (or equilibrium constant) is the product of the reaction quotients (or

equilibrium constants) for the steps:

Q overall = Q 1 x Q 2 x Q 3 x n

K overall = K 1 x K 2 x K 3 x n

2929

Writing the Reaction Quotient for an Overall Reaction

Understanding reactions involving N 2 and O 2 , the most abundant gases in air, is essential for solving problems dealing with atmospheric pollution. Here is a reaction sequence between N 2 and O 2 to form nitrogen dioxide, a toxic pollutant that contributes to photochemical smog.

(1)

(2)

N 2 (g) + O 2 (g)

to photochemical smog. (1) (2) N 2 ( g ) + O 2 ( g )
to photochemical smog. (1) (2) N 2 ( g ) + O 2 ( g )

2NO(g)

2NO(g) + O 2 (g)

2NO 2 ( g ) 2 ( g ) 2 (g)

K c1 = 4.3 x 10 -25

K c2 = 6.4 x 10 9

(a) Show that the Q c for the overall reaction sequence is the same as the product of the Q c s of the individual reactions.

(b) Calculate the K c for the overall reaction.

3030

SOLUTION:

(a)

SOLUTION : (a) (1) N 2 ( g ) + O 2 ( g ) (2)

(1) N 2 (g) + O 2 (g) (2) 2NO(g) + O 2 (g)

N 2 ( g ) + O 2 ( g ) (2) 2NO( g ) +
N 2 ( g ) + O 2 ( g ) (2) 2NO( g ) +
N 2 ( g ) + O 2 ( g ) (2) 2NO( g ) +

2NO(g)

( g ) + O 2 ( g ) (2) 2NO( g ) + O 2
( g ) + O 2 ( g ) (2) 2NO( g ) + O 2

2NO 2 (g)

N 2 (g) + 2O 2 (g)

Q c =

[NO 2 ] 2

[N 2 ][O 2 ] 2

2 ( g ) Q c = [NO 2 ] 2 [N 2 ][O 2 ]
2 ( g ) Q c = [NO 2 ] 2 [N 2 ][O 2 ]

2NO 2 (g)

Q c1 x Q c2 =

[NO] 2
[NO] 2

[NO 2 ] 2

[N 2 ][O 2 ]

Q c1 x Q c2 = [NO] 2 [NO 2 ] 2 [N 2 ][O 2

[NO] 2 [O 2 ]

=

Q c1 =

[NO] 2

][O 2 ] [NO] 2 [O 2 ] = Q c 1 = [NO] 2 [N

[N 2 ][O 2 ]

Q c2 = [NO 2 ] 2

[NO] 2 [O 2 ]

[NO 2 ] 2

[N 2 ] [O 2 ] 2

(b) K c =

K c1 x K c2 = (4.3 x 10 -25 ) x (6.4 x 10 9 ) = 2.8 x 10 -15

3131

Q for a forward and reverse reaction

2SO

2(g)

Q c(fwd)

O

2(g)

[SO ]

3

2

[SO

2

2

] [O

2

]

2SO

Reverse reaction

2SO

Q c(r)

3(g)

2SO

[SO

2

2

] [O

2

]

[SO ]

3

2

2(g)

1

Q

c(fwd)

3(g)

O

2(g)

A reaction quotient

(or equilibrium constant) for a

forward reaction

is the reciprocal of

the reaction quotient

(or equilibrium constant) for the reverse reaction.

K c(fwd) = 261, K c(rev) = 1/261 = 3.83 x 10 -3

3232

Q for a reaction with coefficients multiplied by a common factor

SO

2(g)

 

'

Q

c

(fwd)

'

Q

c

(fwd)

n(aA

Q'

Q

n

1

2

O

2(g)

SO

3(g)

[SO ]

3

[SO

2

][O

2

]

1/2

K c_(fwd) = K 1/2 c(fwd) = (261) 1/2 = 16.2

Q

1/2

c(fwd)

[SO ]

3

2

[SO

2

2

] [O

2

]

bB

cC

dD)

[C] [A]

c

[D]

d

a [B]

b

n

and

1/2

A particular K has meaning only in relation to a particular balanced

equation.

K'

K

n

3333

Determining the Equilibrium Constant for an Equation Multiplied by a Common Factor

PROBLEM: For the ammonia formation reaction

N 2 (g) + 3H 2 (g)

2NH 3 ( g ) 3 ( g ) 3 (g)

the equilibrium constant, K c , is 2.4x10 -3 at 1000 K. If we change the coefficients of the equation, which we_ll call the reference (ref) equation, what are the values of K c for the following balanced equations?

(a) 1/3N 2 (g) + H 2 (g)

2/3NH 3 ( g ) 3 ( g ) 3 (g)

(b) NH 3 (g)

(a) 1/3N 2 ( g ) + H 2 ( g ) 2/3NH 3 ( g
(a) 1/3N 2 ( g ) + H 2 ( g ) 2/3NH 3 ( g

1/2N 2 (g) + 3/2H 2 (g)

3434

SOLUTION:

(a) The reference equation is multiplied by 1/3, so K c(ref) will be to the 1/3 power.

K c = [K c(ref) ] 1/3 = (2.4x10 -3 ) 1/3 = 0.13

(b) The reference equation is reversed and halved, so K c(ref) is to the -1/2 power.

K c = [K c(ref) ] -1/2 = (2.4x10 -3 ) -1/2 = 20.

3535

Equilibrium Constant in Concentration Units

Relation between K c and K p

PV

nRT

so

K

P

n

V

P

RT

cRT

P P

C

D

P P

A

B

[C] [D]

[A] [B]

RT

[C] [D]

[A] [B]

RT

K p = K c (RT)

Note: only for gas = n gas

3636

Converting Between K c and K p

A chemical engineer injects limestone (CaCO 3 ) into the hot flue gas of a coal-burning power plant to form lime (CaO), which scrubs SO 2 from the gas and forms gypsum. Find K c for the following reaction, if CO 2 pressure is in atmospheres.

CaCO 3 (s)

if CO 2 pressure is in atmospheres. CaCO 3 (s) CaO(s) + CO 2 (g) K
if CO 2 pressure is in atmospheres. CaCO 3 (s) CaO(s) + CO 2 (g) K

CaO(s) + CO 2 (g)

K p = 2.1x10 -4 atm (at 1000 K)R = 0.0821 L*atm/mol*K.

Example problem: the Gibbs energies of formation of NO 2 (g) and N 2 O 4 (g) are 51.30 and 102 kJ/mol, respectively (standard state: 1 bar and 25 C). Assume ideal behavior and calculate for the reaction N 2 O 4 2NO 2 , K p (standard state: 1 bar) and K c (standard state: 1 mol/dm 3 )

Calculating K c from Concentration Data

PROBLEM:

In order to study hydrogen halide decomposition, a researcher fills an evacuated 2.00-L flask with 0.200mol of HI gas and allows the reaction to proceed at 453 0 C.

2HI(g)

and allows the reaction to proceed at 453 0 C. 2HI( g ) H 2 (

and allows the reaction to proceed at 453 0 C. 2HI( g ) H 2 (

H 2 (g)

+

I 2 (g)

At equilibrium, [HI] = 0.078M. Calculate K c .

3939

[HI] =

Solution

0.200 mol

2.00 L

= 0.100 M

Let x be the amount of [H 2 ] at equilibrium. Then x will also be the concentration of [I 2 ] and the change in of [HI] will be the original concentration minus the stoichiometric amount that reacted, 2x, or 0.078M.

4040

concentration (M)

2HI(g)

concentration (M) 2HI( g ) H 2 ( g ) + I 2 ( g )
concentration (M) 2HI( g ) H 2 ( g ) + I 2 ( g )

H 2 (g)

+

I 2 (g)

initial

change

equilibrium

0.100

0

-2x

+

x

0.100 - 2x

x

[HI] = 0.078 = 0.100 - 2x

;

x = 0.011M

0

+

x

x

Q c =

[H 2 ] [I 2 ]

=

[HI] 2

[0.011][0.011]

(0.078) 2

= 0.020 = K c

4141

Calculating Equilibrium Concentration with Simplifying Assumptions

PROBLEM: Phosgene is a potent chemical warfare agent that is now outlawed by international agreement. It decomposes by the reaction

COCl 2 (g) CO(g) + Cl 2 (g)

by the reaction COCl 2 ( g ) CO( g ) + Cl 2 ( g
by the reaction COCl 2 ( g ) CO( g ) + Cl 2 ( g

K c = 8.3x10 -4 (at 360 0 C)

Calculate [CO], [Cl 2 ], and [COCl 2 ] when the following amounts of phosgene decompose and reach equilibrium in a 10.0-L flask.

(a) 5.00 mol COCl 2

(b)

0.100 mol COCl 2

SOLUTION:

(a) 5.00 mol/10.0 L = 0.500M

(b) 0.100 mol/10.0 L = 0.0100M

Let x = [CO] eq = [Cl 2 ] eq and 0.500-x and 0.0100-x = [COCl 2 ] eq , respectively, for (a) and (b).

K c =

[CO][Cl 2 ]

[COCl 2 ]

(a) K c = 8.3x10 -4 =

(x) (x)

(0.500-x)

assume x is << 0.500 so that we can drop x in the denominator

8.3x10 -4 =

(x) (x)

(0.500)

4.15x10 -4 = x 2

x 2.0 x 10 -2
x 2.0 x 10 -2
(0.500 - x) = 4.8x10 -2
(0.500 - x) = 4.8x10 -2

CHECK: 0.020/0.500 = 0.04 or 4% percent error

[CO] = [Cl 2 ] = x = 2 x 10 -2 M

[COCl 2 ] = 0.500 M e x = 0.480 M

43

(b) K c = 8.3x10 -4 =

(x) (x)

(0.010 - x)

Dropping the -x will give a value for x = 2.9x10 -3 M.

(0.010 - x) 0.0071M

CHECK: 0.0029/0.010 = 0.29 or 29% percent error

Using the quadratic formula produces x = 2.5x10 -3 and 0.0100-x = 7.5x10 -3 M

[CO] = [Cl 2 ] = x = 2.5 x 10 -3 M

[CoCl 2 ] = 1.00 x 10 -2 M e x = 7.5 x 10 -3 M

Units of the Equilibrium Constant

s

An equilibrium constant expressed in terms of activities or fugacities is called a thermodynamic equilibrium constant. Dimensionless (divided by unit quantity: 1 bar, 1 M, 1 mol kg -1 ). Denoted by superscript zero.

s

Practical equilibrium constant has units which depend on the reaction.

A

B

Z

K

[Z]

c [A][B]

3

dm mol

1

4545

Deviations from Ideal Behavior

Ideal behavior

G

m

G

o

m

G

r

r

G

o

G

r

r

G

o

RT ln P P

o

RT ln

RT ln

P

B

P

A

C

B

C

A

Real gases: attract each other weakly at large distances (corresponding to low pressures) and repel strongly when closer (at high pressures).

Gilbert Newton Lewis (1875 e 1946): fugacity (f) Fugacity is the pressure adjusted for lack of ideality.

Real gas:

G

m

o

G

m

a
a

RT ln f f

o

The ratio of the fugacity of a substance in any state to the fugacity in the standard state is known as the activity, a.

Since the fugacity in the standard state = 1 bar, the fugacity of a gas is numerically equal to its activity. Therefore,

G

m

G

o

m

RT ln(a)

4747

Molar Gibbs energy of a real gas. 48

Molar Gibbs energy of a real gas.

48

Fugacities of N 2 gas at 0º C

P (atm)

Fugacity

(atm)

1

0.99955

10

9.956

50

49.06

100

97.03

150

145.1

200

194.4

300

301.7

400

424.8

600

743.4

800

1196

1000

1839

4949

Equilibrium in Nonideal Systems

For gases, use fugacity or activity of the species instead. If the pressures are low enough then use pressures instead.

a

gas

f

gas

P

o

G

r

o

RT lnK o

a

where K o a is the dimensionless equilibrium constant in terms of activities.

K

o

a

a

C

a

D

a

A

a

B

eq

5050

Chemical Equilibrium in Solution

Define chemical potential for molecules in solutions as i = o i + RT ln a i

activity a i = i .x i the mole fraction.

where i is the activity coefficient, x i is

aA +

bB cC

+

dD

Expressing the equilibrium constant in terms of activities,

K

a

a

c

C

a

d

D

a

a

A

a

b

B

c

d

D

C

a

b

B

A

x x

c

C

d

D

x

a

A

x

b

B

For uncharged species in solution, behaviour close to ideal, so K can be expressed in concentrations, mole fractions,

Number of moles of solute in 1 kg of solvent 5151
Number of moles
of solute in 1 kg of
solvent
5151

molalities. For ions, activities must be used.

LeLe ChatelierChatelier\\ss PrinciplePrinciple

When a chemical system at equilibrium is subjected to a stress, the system will return to equilibrium by shifting to reduce the stress.

If the concentration increases, the system reacts to consume some of it.

If the concentration decreases, the system reacts to produce some of it.

5252

Effect of a change in concentration

PCl 3 (g)

+

Cl 2 (g)

PCl 5 ( g ) 5 ( g ) 5 (g)

The equilibrium shifts to the right if a reactant is added or a product is removed. The equilibrium shifts to the left if a reactant is removed or a product is added. At 523 K,

Q

c

[PCl ]

5

[PCl

3

][Cl

2

]

24.0

K

c

is added. At 523 K, Q c [PCl ] 5 [PCl 3 ][Cl 2 ] 24.0

The effect of added Cl 2 on the PCl 3 -Cl 2 - PCl 5 system.

5353

The Effect of Added Cl 2 on the PCl 3 -Cl 2 -PCl 5 System
The Effect of Added Cl 2 on the PCl 3 -Cl 2 -PCl 5 System

Concentration (M)

PCl 3 (g)

+

Cl

2 (g)

5 System Concentration (M) PCl 3 ( g ) + Cl 2 ( g ) PCl
5 System Concentration (M) PCl 3 ( g ) + Cl 2 ( g ) PCl

PCl 5 (g)

Original equilibrium

Disturbance

New initial

Change

0.200

0.125

 

+0.075

0.200

0.200

-x

-x

0.600

0.600

+x

New equilibrium

0.200 - x

0.200 - x

0.600 + x

(0.637)*

0.037
0.037

*Experimentally determined value.

5454

At equilibrium,

K

K

c(original)

c(new )

0.600

24.0

(0.200)(0.125)

0.637

24.0

(0.163)(0.163)

At a given temperature, K c does not change with a change in concentration.

5555

Predicting the Effect of a Change in Concentration on the Equilibrium Position

PROBLEM:

To improve air quality and obtain a useful product, chemists often remove sulfur from coal and natural gas by treating the fuel contaminant hydrogen sulfide with O 2 ;

2H 2 S(g) + O 2 (g)

What happens to

(a)

[H 2 O] if O 2 is added?

(c)

[O 2 ] if H 2 S is removed?

2S(s ) + 2H 2 O( g ) s ) + 2H 2 O( g ) s) + 2H 2 O(g)

(b) [H 2 S] if O 2 is added?

(d) [H 2 S] if sulfur is added?

Solution

2H 2 S(g) + O 2 (g)

Q =

[H 2 O] 2

2H 2 S( g ) + O 2 ( g ) Q = [ H 2

[H 2 S] 2 [O 2 ]

(a)

When O 2 is added,

(b)

When O 2 is added,

(c)

When H 2 S is removed,

(d)

2S(s) + 2H 2 O(g)

Effect of a change in pressure

s

Changing the concentration of a gaseous component.

s

Adding an inert gas e no effect on the equilibrium

position because the volume and moles of the reactant

and product gases do not change.

s Changing the volume of the reaction vessel large shift in the equilibrium.

sHalve the volume, pressure doubles.

sPCl 3 (g) + Cl 2 (g) PCl 5 (g)

sIf pressure doubles, Q c < K

Q c

[PCl ]

5

[PCl

3

][Cl

2

]

5858

The effect of pressure (volume) on an equilibrium system.

lower P (higher V) more moles of gas
lower P
(higher
V)
more
moles of
gas

+

+
+
+
on an equilibrium system. lower P (higher V) more moles of gas + higher P (lower
on an equilibrium system. lower P (higher V) more moles of gas + higher P (lower
higher P
higher
P

(lower

V)

fewer

moles of

gas

on an equilibrium system. lower P (higher V) more moles of gas + higher P (lower

5959

Predicting the Effect of a Change in Volume (Pressure) on the Equilibrium Position

PROBLEM:

How would you change the volume of each of the following reactions to increase the yield of the products ?

(a) CaCO 3 (s)

increase the yield of the products ? (a) CaCO 3 ( s ) CaO( s )
increase the yield of the products ? (a) CaCO 3 ( s ) CaO( s )

CaO(s) + CO 2 (g)

CO 2 is the only gas present. To increase its yield, we should increase the volume (decrease the pressure).

(b) S(s) + 3F 2 (g)

SF 6 ( g ) 6 ( g ) 6 (g)

There are more moles of gaseous reactants than products, so we should decrease the volume (increase the pressure) to shift the reaction to the right.

6060

(c)

Solution

Cl 2 (g) + I 2 (g)

2ICl(g ) g ) g)

There are an equal number of moles of gases on both sides of the reaction, therefore a change in volume will have no effect.

6161

Example: effect of total pressure

N 2