Chemical Equilibrium: General

Concepts

Equilibrium - What Does it Mean?

As quickly as product is being made, some is also
consumed to form reactants
The process is continually occurring, but the
amounts present stop changing
For the reaction N2O4 2NO2

Dynamic Equilibrium
Many reactions are reversible: this is to say that when
the reaction appears to be complete, amounts of both
reactant and product exist.
We show reversible reactions using a double arrow
or
The forward reaction is read left to right, while the
reverse reaction is read right to left.
aA + bB
cC + dD

Dynamic equilibrium is achieved when the rates of

forward and reverse processes become equal
3

In a Closed System
The overall quantities are fixed
Whether we started with all reactant or all product,
we will always have the same composition at
equilibrium under the same conditions

aA + bB
cC + dD
Stoichiometric coefficients (a,b,c,d) are the exponent for
each substance
Called the reaction quotient (Q) at any time,
Q

[C]c [D]d
[A]a [B]b

and the equilibrium law K only when the reaction is known

to be at equilibrium
If Q = K, system is at equilibrium
If Q K, system is not at equilibrium

[Q
]Q
N
O
2
4

2
[[C
]N
O
2
H
3
2]

Write the mass action expressions for the following:

2NO2(g) N2O4(g)

2CO(g) + O2(g) 2 CO2(g)

N2 + 3H2(g) 2NH3(g)

The Equilibrium Constant, K

For a chemical equilibrium to exist in a reaction
mixture, the reaction quotient, Q, must be equal to
the equilibrium constant, K
Symbolized Kc for concentration equilibrium
constant
Changes with temperature
Is a numeric value, specific to the reaction and the
specified states

Equilibrium Constants and Their Reactions

When we multiply an equation by a constant, the
value of the equilibrium constant for the new
equation is raised to the exponent of the multiplier
n* Rxn Kn
When we reverse an equation, the value of K for
the new equation is its inverse (1/K)
When we add reactions, we multiply their K
values for the net reaction.

For the reaction N2(g) + 3H2(g) 2NH3(g), Kc = 500

for a particular temperature. What would be Kc for
the following:
0.002
2NH3(g) N2(g) + 3H2(g)
N2(g) + 3/2H2(g) NH3(g)

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The Equilibrium Constant, Kp

Based on reactions in which the substances are
gaseous
Assumes gas quantities are expressed in
atmospheres in the mass action expression
Compare Kc to KP
Kc

NH3

N2 H2

KP

2
PNH
3

PN 2 PH22

Equilibrium laws for gaseous reactions can be

written in terms of either concentrations or
pressures
10

Kp vs Kc
If PV = nRT, then P/RT = n/V
Substituting P/RT for molar concentration into the mass
action expression, Kc, results in a pressure-based formula
ng = [moles of gas in product] [moles of gas in the reactant]
R = 0.0821 L atm mol-1 K-1

KP = Kc(RT)n

11

cn
K
pcn(RT)K

Consider the reaction of 2NO2(g) N2O4(g)

If the Kp for the reaction is known to be 0.480 at 25 C,

what is the value of Kc at the same temperature?

11.7 = Kc

12

Consider the reaction A(g) + 2B(g) 4C(g) If the Kc

for the reaction is 0.99 at 25 C, what would be the Kp?
A.
B.
C.
D.
E.

0.99
2.0
24
2400
None of these

13

Kp vs Kx (mole fraction)
aA + bB

cC + dD

Jika n=0, maka KP=K

14

Heterogeneous Equilibria

Involve more than one state of matter

Solutions are expressed in M
Gases are expressed in M
Governed by Kc
Solids and liquids are replaced with 1 (constant) in the mass action
expression

15

Write the mass action expression for the following:

Ag+(aq) + Cl-(aq) AgCl(s)
1
KQc
[Ag + ][Cl ]
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4-(aq)

Kc

16

Given the reaction:

3Ca2+(aq) + 2PO43-(aq) Ca3(PO4)2(s)
what is the mass action expression?
[Ca 2+ ]3 [PO43 ]2
A.
Q
[Ca 3 (PO 4 ) 2 ]
[Ca 2+ ]3 [PO 43 ]2
B.
Q
1
[Ca 3 (PO 4 ) 2 ]
C.
Q
2+ 3
3 2
[Ca ] [PO4 ]
1
D.
Q
2+ 3
3 2
[Ca ] [PO 4 ]
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Given the reaction:

3Ca2+(aq) + 2PO43-(aq) Ca3(PO4)2(s)
what is mass action expression for the reverse
reaction?
[Ca 2+ ]3 [PO43 ]2
A.

[Ca 3 (PO 4 ) 2 ]

[Ca 2+ ]3 [PO 43 ]2
B.
Q
1
[Ca 3 (PO 4 ) 2 ]
C.
Q
2+ 3
3 2
[Ca ] [PO4 ]
1
D.
Q
2+ 3
3 2
[Ca ] [PO 4 ]
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The Significance of K Values

If K is large, the reaction is efficient (makes
product effectively)
If K is small, the reaction is inefficient (makes
little product)
If 10-3 < K < 103, the reaction has much of both
product and reactant present
At equilibrium, the Q = K

19

Equilibrium Positions
Equilibrium positions are a combination of
concentrations that allow Q = K
There are an infinite number of possible
equilibrium positions

20

Equilibrium Shifts
Le Chteliers principle - a system at equilibrium
(Q = K) when upset by a disturbance that causes
(Q K) will shift to offset the stress
A shift to the right is when the forward reaction is
dominant (Q < K)
A shift to the left is when the reverse direction is
dominant (Q > K)

21

Factors Affecting Quantities Present at

Equilibrium
Concentration affects the value of Q, and helps
predict the reaction progress
Pressure and volume of gases both affect the value
of Q and predict the reaction progress
P n/V, hence increasing gas pressure increases
molarity
M = n/V, hence increasing volume decreases the
molarity of a gas

22

Temperature Affects the Value of K

Endothermic reactions increase K with increasing
temperature
Exothermic reactions decrease K with increasing
temperature
Shift effects may be predicted using heat as a
variable in the mass action expression

23

An Approach to Using Le Chteliers Principle

Write the mass action expression for the reaction
Examine the relationship between the affected
concentration and Q (direct or indirect)
Compare Q to K
If the change causes Q > K, reaction shifts left
If the change causes Q < K, reaction shifts right
If the change has no effect on Q - no shift expected

24

Cu(H2O)62+(aq) + 4NH3(aq) [Cu(NH3)42+](aq) + 6H2O(l)

What is expected if:

Initially, Q = K
[NH3] is inverse to Q

NH3(aq) is added

increasing [NH3] decreases Q

Q < K shifts right
Cu2+ is added which forms
Cu(H2O)62+
Cu NH 2+
3 4

Q
Cu(H 2 O)6 2+ NH 3

Initially, Q = K
[Cu2+] is inverse to Q
increasing [Cu2+] decreases Q
Q < K shifts right
25

In the reaction: N2(g) + 3H2(g) 2NH3(g) What will

happen if pressure is increased?
2

NH3
Q
3
N2 H2

Increasing pressure affects all gases

There are more moles of gas on reactant side, hence

effect is larger

Increasing pressure of product decreases Q

Q < K shifts right

26

In the reaction:
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq)
What will happen if PO43- is removed?
Q is proportional to the [PO43-]
Decreasing [PO43-] decreases Q
Q < K shifts right
Q

PO4

OH

H3 PO 4
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Temperature Effects
The product efficiency of the reaction depends on
the temperature, and whether the reaction is
endothermic or exothermic
Write mass action expression with heat term as if
it were a concentration and predict shifts as before
Figure 14.6 The effect of temperature on the
equilibrium Cu(H2O)42++ 4Cl
CuCl42 + 4H2O.
In the center, an equilibrium mixture of the two
complexes. When the solution is cooled in ice (left),
the equilibrium shifts toward the blue Cu(H2O)42+.
When heated in boiling water (right), the equilibrium
shifts toward CuCl42-. This behavior indicates that the
reaction is endothermic in the forward direction.
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Learning Check

3
[Q
P
O
]
4
H
-4
heat

The reaction
H3PO4(aq) + 3OH-(aq) 3H2O(l) + PO43-(aq) is
exothermic. What will happen if the system is cooled?

Since the reaction is exothermic, heat is a product

Heat is directly proportional to Q

Decreasing the temperature appears to decrease Q

Q < K (actually because K increased) shifts to the right

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Catalysts and Equilibrium

The catalyst lowers
the Ea for both the
forward and reverse
reaction.
The change in Ea
affects the kr and kf
equally
Catalysts have no
effect on equilibrium

30

Q
H
C
c0.2719
3O
2O
4K
2H

Determining Kc From Equilibrium

Concentrations

When all concentrations at equilibrium are known, use

the mass action expression to find Kc

Learning Check:

In the reaction
H2C2O4(g) + H2O(l) H3O+(aq) + HC2O4-(aq),

1 mol H2C2O4 is placed into a liter of water. If the

equilibrium concentrations of H3O+(aq) and HC2O4-(aq)
are both 0.21 M, what is value of Kc?
Kc = 5.58 10-2

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2
2
N
O
2

3
1
K

4
.
8

1
0
c
O

Determining Equilibrium Concentrations from Kc

When all concentrations but one are known, use the

mass action expression to relate the concentrations to
Kc
Learning Check

In the reaction N2(g) + O2(g) 2NO(g), Kc = 4.8 10-31 If

the concentrations of N2 and NO are both 2 M, what is the
concentration of O2 at equilibrium?

[O2] = 4.2 1030 M

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For the reaction : 2A(aq) + B(aq) 3C(aq), the

equilibrium concentrations are: A = 2.0 M, B = 1.0
M and C = 3.0 M. What is the expected value of Kc
at this temperature?
A. 14
B. 0.15
C. 1.5
D. 6.75

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Determining Equilibrium Concentrations from

Kc When Initial Concentrations are Given
Write the mass action expression
Using concentrations present, compare Q vs K to
predict shift direction
Set up ICE (Initial, Change, Equilibrium) table
Allow reaction to proceed as expected, using x to
represent the quantity
Substitute equilibrium terms from table into mass action
expression and solve

34

QKshiftrgh2.0-x

2
D
Q

B
A
2
2
.Q
5
0
5
.
0

2
x
2
6.251
0,
For the reaction A + B 2D, K = 10,000, what are the
equilibrium concentrations if we start with 2.0 M A, 2.0 M B,
and 5.0 M D?

I (M) 2.0
C (M) -x
E (M) 2.0 - x

2 .0
-x
2.0 - x

2D

5.0
+ 2x
5.0 + 2x

x = 1.91

[A] = [B] = 0.09 M

[D] = 8.82 M

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How Does This Relate to Equilibrium?

G = -RT ln K

Thus, if you can find G, you can find K

Dont forget that the G that you use must be
for the temperature that you are using.
H - TS = -RT ln K
Thus,

ln K

RT

18.9 Equilibrium constants can be estimated from standard free energy changes

36

Learning Check
Determine the value of K at 298 K and 500 K
CaCO3(s) CO2(g) + CaO(s)
Hrxn = 178 kJ

Srxn = 160.7 J/K

G0298,rxn = [-394.4 + (-604.2)] - [-1128.8] = 130.2 kJ

G298,rxn = 130.2 kJ
G0500,rxn= 178 (500 K 0.1607 kJ mol-1 K-1) = 97.8 kJ
G500,rxn = 97.8 kJ
G = -RT ln K

CaCO3

CO2

CaO

K = e(-G/RT)
K298 = e(-130.2/(0.008314 298))

Hf

1207

393.5 635.5

Sf

92.9

213.6

= 1.5 10-23
K500 = 6.06 10-11

Gf,298 1128.8

40

394.4 604.2

18.9 Equilibrium constants can be estimated from standard free energy changes

37

Learning Check
Determine the Value of K at 298 K and 500 K
2C6H6(l) + 15O2(g) 12CO2(g) + 6H2O(g)

G = H- TS = -RT ln K; K = e(G/RT)
K298 = e(+7146.6/(0.008314 298))
= e2884 huge!
K500 = e1862
Hrxn = -6285.8 kJ
Srxn = 3128.8 J/K
G298 = -6368 kJ
G500 = -7850.2 kJ

C6H6

O2

CO2

H2O

Hf

+49.0

393.5

241.8

Sf

173.3

205.0

213.6

188.7

Gf298

+124.3

394.4

228.6

18.9 Equilibrium constants can be estimated from standard free energy changes

38

Your Turn!
Given that H = -97.3 kJ , S = -122.1 J mol-1 K-1, the
pressure of HCl is 2 atm, and that of H2O is 1.0 atm, What is
the value of K at 500. K?
MgO(s) + 2HCl(g) H2O(g) + MgCl2(s)
A. 0.99
G = -97.3 - (500 -0.1221)
B. 1.01
C. 8.20
-36.25 kJ
D. 0.27
E. None of these -(-36.54/(0.008314 500))

6.11 103
18.9 Equilibrium constants can be estimated from standard free energy changes

39

Simplifications: Dropping the x Term in

Binomials
In a mass action expression we sometimes get very
complicated mathematical problems
If the equilibrium constant is small, the change to
reach equilibrium (x term) is also small
In binomial terms, compare the constant to the value
of K: if the constant is > 400K, then the x term may
be dropped
Use a proof to show that the dropped x term was
sufficiently small
dropped x term ?
0.05
(2-x) x = K
constant of binomial
40

N
O

p
2
4
K

p
x

1
6
3
.
5

1
0
2
0
.
2
0
Q

0
2
K.s2hiftrgh

For the reaction 2A(g) B(g) given that the Kp = 3.5 10-16
at 25 C, and we place 0.2 atm A into the container, what will
be the pressure of B at equilibrium?
2A

B
I
C
E

0.2
-2x
0.2 - 2x
0.2

0 atm
+x
x

x = 1.4 10-17

[B] = 1.4 10-17 M

proof: is 1.4 10-17/0.2 < 0.05?

41

In the reaction shown, K = 1.8 10-5

HC2H3O2(aq) + H2O(l) H3O+(aq) + C2H3O2-(aq)
If we start with 0.3 M HC2H3O2, what will be the
equilibrium concentration of C2H3O2-?
A.
B.
C.
D.

0.3 M
0.002 M
0.04 M
0.5 M

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