Chapter 4
Chemical Equilibrium
11
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.
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.
22
N _{2} O _{4} 2NO _{2}
colourless
brown
At equilibrium, the product and reactant concentrations are constant. K =[NO _{2} ] _{e}_{q} /[N _{2} O _{4} ] _{e}_{q}
33
The range of equilibrium constants
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.
55
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.
6
Multicomponent 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
7 7
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
8
_{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
9
10
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)
11
_{A} (mix, T,P) < _{A} (pure, T,P) ?
Chemical potential of a pure (1component) 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 
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
)
12
( mix,T ,P
A
tot
) ( pure,T ,P
A
tot
) RT ln X
A
A
( mix,T ,P
tot
)
A
( pure,T ,P
tot
)
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.
13
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 ^{t}^{h} 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
Reactants (and
products) isolated from other.
G
o
C
G
o
D
Mixed reactants ; mixed reactants and products.
1515
If G _{r}_{e}_{a}_{c}_{t}_{i}_{o}_{n} < 0 forward reaction is spontaneous. If G _{r}_{e}_{a}_{c}_{t}_{i}_{o}_{n} > 0, reverse reaction is spontaneous. If G _{r}_{e}_{a}_{c}_{t}_{i}_{o}_{n} = 0, reaction is at equilibrium.
1616
Ideal gas equilibria
Consider a general gasphase 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
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.
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
= [products]/[reactants]
19
Reaction direction and the relative sizes of Q and K.
reactants
products
Equilibrium:
no net
change
reactants
products
2020
Consider a general gasphase reaction at T and P:
A + B C + dD
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
22
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.
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}
Equilibrium
Ratio(K) [NO _{2} ] _{e}_{q}
2
Experiment [N _{2} O _{4} ] [NO _{2} ] 
[N 
_{2} O _{4} ] 
[N _{2} O _{4} ] _{e}_{q} 
[NO _{2} ] _{e}_{q} 
^{[}^{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
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
28
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)
2NO(g)
2NO(g) + O _{2} (g)
2NO _{2} (g)
K _{c}_{1} = 4.3 x 10 ^{}^{2}^{5}
K _{c}_{2} = 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)
(1) N _{2} (g) + O _{2} (g) (2) 2NO(g) + O _{2} (g)
2NO(g)
2NO _{2} (g)
N _{2} (g) + 2O _{2} (g)
Q _{c} =
[NO _{2} ] ^{2}
[N _{2} ][O _{2} ] ^{2}
2NO _{2} (g)
Q c1 x Q c2 =
[NO _{2} ] ^{2}
[N _{2} ][O _{2} ]
[NO] ^{2} [O _{2} ]
_{=}
_{Q} _{c}_{1} _{=}
[NO] ^{2}
[N _{2} ][O _{2} ]
Q _{c}_{2} = [NO _{2} ] ^{2}
[NO] ^{2} [O _{2} ]
[NO _{2} ] ^{2}
[N _{2} ] [O _{2} ] ^{2}
(b) K _{c} =
K _{c}_{1} x K _{c}_{2} = (4.3 x 10 ^{}^{2}^{5} ) x (6.4 x 10 ^{9} ) = 2.8 x 10 ^{}^{1}^{5}
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}_{(}_{f}_{w}_{d}_{)} = 261, K _{c}_{(}_{r}_{e}_{v}_{)} = 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}_{_}_{(}_{f}_{w}_{d}_{)} = K ^{1}^{/}^{2} _{c}_{(}_{f}_{w}_{d}_{)} = (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)
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)
(b) NH _{3} (g)
1/2N _{2} (g) + 3/2H _{2} (g)
3434
SOLUTION:
(a) The reference equation is multiplied by 1/3, so K _{c}_{(}_{r}_{e}_{f}_{)} will be to the 1/3 power.
K _{c} = [K _{c}_{(}_{r}_{e}_{f}_{)} ] ^{1}^{/}^{3} = (2.4x10 ^{}^{3} ) ^{1}^{/}^{3} = 0.13
(b) The reference equation is reversed and halved, so K _{c}_{(}_{r}_{e}_{f}_{)} is to the 1/2 power.
K _{c} = [K _{c}_{(}_{r}_{e}_{f}_{)} ] ^{}^{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 _{g}_{a}_{s}
3636
Converting Between K _{c} and K _{p}
A chemical engineer injects limestone (CaCO _{3} ) into the hot flue gas of a coalburning 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)
CaO(s) + CO _{2} (g)
K _{p} = 2.1x10 ^{}^{4} atm (at 1000 K)R = 0.0821 L*atm/mol*K.
37
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} )
38
Calculating K _{c} from Concentration Data
PROBLEM:
In order to study hydrogen halide decomposition, a researcher fills an evacuated 2.00L flask with 0.200mol of HI gas and allows the reaction to proceed at 453 ^{0} C.
2HI(g)
H _{2} (g)
+
I _{2} (g)
At equilibrium, [HI] = 0.078M. Calculate K _{c} .
3939
_{[}_{H}_{I}_{]} _{=}
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)
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)
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 10.0L flask.
(a) 5.00 mol COCl _{2}
(b)
0.100 mol COCl _{2}
42
SOLUTION:
(a) 5.00 mol/10.0 L = 0.500M
(b) 0.100 mol/10.0 L = 0.0100M
Let x = [CO] _{e}_{q} = [Cl _{2} ] _{e}_{q} and 0.500x and 0.0100x = [COCl _{2} ] _{e}_{q} , respectively, for (a) and (b).
K _{c} =
[CO][Cl _{2} ]
[COCl _{2} ]
(a) K _{c} = 8.3x10 ^{}^{4} =
(x) (x)
(0.500x)
assume x is << 0.500 so that we can drop x in the denominator
8.3x10 ^{}^{4} =
(x) (x)
_{(}_{0}_{.}_{5}_{0}_{0}_{)}
4.15x10 ^{}^{4} = x ^{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 0.0100x = 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
44
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.
46
46
Real gas:
G
m
o
G
m
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
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,
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)
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
The effect of added Cl _{2} on the PCl _{3} Cl _{2}  PCl _{5} system.
5353
Concentration (M)
PCl _{3} (g)
+
Cl
_{2} (g)
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)*
*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)
^{(}^{b}^{)} ^{[}^{H} 2 ^{S}^{]} ^{i}^{f} ^{O} 2 ^{i}^{s} ^{a}^{d}^{d}^{e}^{d}^{?}
^{(}^{d}^{)} ^{[}^{H} 2 ^{S}^{]} ^{i}^{f} ^{s}^{u}^{l}^{f}^{u}^{r} ^{i}^{s} ^{a}^{d}^{d}^{e}^{d}^{?}
56
Solution
2H _{2} S(g) + O _{2} (g)
Q =
^{[}^{H} 2 ^{O}^{]} ^{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)
57
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
V)
fewer
moles of
gas
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)
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)
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)
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}
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