Equilibrium

The Extent of Chemical Reactions

The Dynamic Nature of the Equilibrium State

The Reaction Quotient and the Equilibrium Constant

Expressing Equilibria with Pressure Units: Relation

Between Kc and Kp

Reaction Direction: Comparing Q and K

How to Solve Equilibrium Problems

Reaction Conditions and the Equilibrium State:

Le Chteliers Principle
 Use of the double arrow!
For reactions that do not go to completion

+
H2O (l ) H ( aq ) + OH ( aq )

Size of arrow can represent extent of reaction

+
H2O (l ) H ( aq ) + OH ( aq )
 Implication of the double arrow

Two reactions are occurring One forward and one reverse

The two reactions establish a dynamic equilibrium
rate of forward rxn. is equal to reverse rxn.
concentration of reactants and products is constant
Not equal consider shopping mall
Reaction is considered to be reversible
Are all reactions reversible?

AB2 ( s ) A ( aq ) + 2 B ( aq )
Decomposition
C
The Range of Equilibrium Constants

A) Small K N2 (g) + O2 (g) 2 NO(g) K = 1 x 10 -30

B) Large K 2 CO(g) + O2 (g) 2 CO2 (g) K = 2.2 x 1022

C) Intermediate K 2 BrCl(g) Br2 (g) + Cl2 (g) K=5

 Basic Concepts
Graphical representation of the rates for the forward
and reverse reactions for this general reaction
aA + bB ' cC + dD
 Reaction Quotient

aA + bB rR + dD
CR CD
r d
Q= a b
CA CB
Products over reactants
Exponent is same as coefficient
Omit pure liquids and solids
Omit the solvent in dilute soln.s
 Equilibrium

aA + bB rR + dD
CR rCD d [ R ]r [ D ]d
Q = a b = CONSTANT = K eq
C A CB [ A] [ B ]
a b

WHEN FORWARD AND REVERSE RATE ARE EQUAL!

 Example 16 - 2
What is the equilibrium expression for the
Haber synthesis of ammonia?

N2 + 3 H2 2 NH3
 The State of Equilibrium
For the Nitrogen dioxide - dinitrogen tetroxide equilibrium:
2 NO2 (g, brown) N2O4 (g, colorless)
At equilibrium: ratefwd = raterev
ratefwd = kfwd[NO2]2 raterev = krev [N2O4]

= [N2O4]2 = K
kfwd
kfwd[NO2 = krev [N2O4]
]2
krev [NO2]

See pg 677 for a 2-step mechanism

Initial and Equilibrium Concentrations at 100C
2 NO2 (g, brown) N2O4 (g, colorless)

Initial Equilibrium Ratio

[N2O4] [NO2] [N2O4] [NO2] [NO2]2 [N2O4]

0.1000 0.0000 0.0491 0.1018 0.211

0.0000 0.1000 0.0185 0.0627 0.212

0.0500 0.0500 0.0332 0.0837 0.211

0.0750 0.0250 0.0411 0.0930 0.210

2 NO2 (g, brown) N2O4 (g, colorless)

N2 O4

NO2
 Pure Solids and Liquids
+
H2O (l ) H ( aq ) + OH ( aq )
56M vs 1x10-7

2+
PbCl2 s Pb + 2Cl
 Removal of CO2

CaCO3(s) CaO (s)+CO2 (g) K = ( pCO2 ) eq

 Example 16 - 4
Write the equilibrium constant expression for
the reaction of iron metal with strong
aqueous acid, and indicate the concentration
units for each reagent.

2 Fe (s) + 6 H3O+ (aq) 2 Fe3+ (aq) + 6 H2O (l) + 3 H2 (g)

Writing the Reaction Quotient from the Balanced Equation

Problem: Write the reaction quotient for each of the following reactions:
(a) Write the reaction quotient for decomposition of potassium chlorate:
KClO3 (s) = KCl(s) + O2 (g)
(b) The equilibrium constant for the combustion of butane in oxygen:
C4H10 (g) + O2 (g) = CO2 (g) + H2O(g)
Plan: We first balance the equations, then construct the reaction quotient
Or equilibrium constant as described by equation.
Solution:

(a) 2 KClO3 (s) 2 KCl(s) + 3 O2 (g) Qc =

CKCl2 CO23
CKClO32
(b) 2 C4H10 (g) + 13 O2 (g) 8 CO2 (g) + 10 H2O(g)

[CO2]8 [H2O]10
Kc =
[C4H10]2 [O2]13
 Writing the Equilibrium Constant for
an Overall ReactionI
Problem: Oxygen gas combines with nitrogen gas in the internal
combustion engine to produce nitric oxide, which when out in the
atmosphere combines with additional oxygen to form nitrogen dioxide.
(1) N2 (g) + O2 (g) 2 NO(g) Kc1 = 4.3 x 10-25
(2) 2 NO(g) + O2 (g) 2 NO2 (g) Kc2 = 6.4 x 109
(a) Show that the overall Kc for this reaction sequence is the same as the product of the
Kcs for the individual reactions.
(b) Calculate Kc for the overall reaction.
Plan: We first write the overall reaction by adding the two reactions together and
write the Kc. We then multiply the individual Kcs for the total K.

(1) N2 (g) + O2 (g) 2 NO(g)

(2) 2 NO(g) + O2 (g) 2 NO2 (g)

overall: N2 (g) + 2 O2 (g) 2 NO2 (g)

 Writing the Reaction Quotient for an Overall
ReactionII
(a) cont. [NO] 2
Kc (overall) =
[N2][O2]2

For the individual steps:

[NO]2
(1) N2 (g) + O2 (g) 2 NO(g) Kc1 =
[N2] [O2]
[NO ]2
(2) 2 NO(g) + O2 (g) 2 NO2 (g) Kc2 = 2
[NO]2 [O2]
[NO] 2 [NO ]2 [NO ]2
Kc1 x Kc2 = x 2 = 2 The same!
[N2] [O2] [NO] [O2]
2 [N2][O2] 2

(b) K = Kc1 x Kc2 = (4.3 x 10-25)(6.4 x 109) = 2.8 x 10-15

 Ways of Expressing the K (and Q)

Form of Chemical Equation Form of Q

Reference reaction: A B K(ref) = [B]

[A]
Reverse reaction: B A K= 1 = [A]
K(ref) [B]
Reaction as sum of two steps:
K1 = [C] ; K2 = [B]
(1) A C [A] [C]

(2) C B Koverall = K1 x K2 = K(ref) Koverall = K1 x K2

A B
[C] [B] [B]
= x = = K(ref)
[A] [C] [A]
 Lab Examples
2+ +
KSCN + Fe( NO3 ) 3 FeSCN + K + 3 NO 3

3+ 2+
SCN + Fe FeSCN
3+ 2+
+ Fe FeSCN
2+
+ SCN FeSCN

3+ 2+
SCN + Fe FeSCN
 3+ 2+
SCN + Fe FeSCN
Solution with Fe3+, SCN-, and FeSCN
Add NaF turned Clear
Removal of FeSCN
How? What did we observe?
Add Fe3+ - turned red
So SCN Still around!
Add SCN - no change
So no Fe3+ around to react
3+ 3
Fe + 6 F FeF 6
 Equilibrium - Le Chateliers
+
+ [ A ][ B ]
AB A +B K=
[ AB]

How will the equilibrium shift?

Look at the Reaction Quotient

[ A ][ B ]+If Q < K the rxn shifts right
Q= If Q = K the rxn is at equil.
[ AB ]
If Q > K the rxn shifts left
 Reaction Direction and the
Relative Sizes of Q and K

Fig. 17.5
 Equilibrium - Le Chateliers

When a system that is at equilibrium is

subject to a stress that disturbs the
system, the system will proceed in a
direction that will bring the system back to
equilibrium by relieving that stress.
 Equilibrium - Le Chateliers
+
+ [ A ][ B ]
AB A +B K=
[ AB]
If we add product? Shifts left!
If we add reactant? Shifts right!
If we add reagent that reacts with B+? Shifts right!
If we increase the temperature?
If exothermic HEAT is a product Shifts left!
If endothermic HEAT is a reactant Shifts right!
 From Lab: Cu2+ + NH3
2+
Cu + 2OH Cu (OH ) 2 ( s )
+
NH 3 + H 2O NH 4 + OH
2+
Cu (OH ) 2 ( s ) + 4 NH 3 Cu ( NH ) + 2OH
3 4

Add HCl -
Dark Blue turned Cloudy then Clear Light Blue
+
H + OH H 2O
 The Effect of a Change in ConcentrationI
Given an equilibrium equation such as :
CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)
If one adds ammonia to the reaction mixture at equilibrium, it will force
the reaction to go to the right producing more product. Likewise, if one
takes ammonia from the equilibrium mixture, it will force the reaction
back to produce more reactants by recombining H2 and HCN to give
more of the initial reactants, CH4 and NH3.
CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)
Forces equilibrium to
Add NH3 produce more product.

CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)

Remove NH3
Forces the reaction equilibrium to go back
to the left and produce more of the reactants.
 The Effect of a Change in ConcentrationII
CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)
If to this same equilibrium mixture one decides to add one of the
products to the equilibrium mixture, it will force the equilibrium back
toward the reactant side and increase the concentrations of reactants.
Likewise, if one takes away some of the hydrogen or hydrogen cyanide
from the product side, it will force the equilibrium to replace it.
CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)
Forces equilibrium to go Add H2
toward the reactant direction.

CH4 (g) + NH3 (g) HCN(g) + 3 H2 (g)

Remove HCN
Forces equilibrium to make more
produce and replace the lost HCN.
 Temperature
3+ 2+
SCN + Fe FeSCN
Cold water
got darker
Hot water
got lighter

3+ 2+
SCN + Fe FeSCN + Heat
 The Effect of a Change in Temperature
Only temperature changes will alter the equilibrium constant, and that is
why we always specify the temperature when giving the value of Kc.

The best way to look at temperature effects is to realize that temperature

is a component of the equation, the same as a reactant, or product. For
example, if you have an exothermic reaction, heat (energy) is on the
product side of the equation, but if it is an endothermic reaction, it will
be on the reactant side of the equation.
O2 (g) + 2 H2 (g) 2 H2O(g) + Energy = Exothermic
Electrical energy + 2 H2O(g) 2 H2 (g) + O2 (g) = Endothermic
A temperature increase favors the endothermic direction and a
temperature decrease favors the exothermic direction.
A temperature rise will increase Kc for a system with a positive H0rxn
A temperature rise will decrease Kc for a system with a negative H0rxn
 Effect of Various Disturbances
on an Equilibrium System
Disturbance Net Direction of Reaction Effect on Value of K
Concentration
Increase [reactant] Toward formation of product None
Decrease [reactant] Toward formation of reactant None
Pressure (volume)
Increase P Toward formation of lower
amount (mol) of gas None
Decrease P Toward formation of higher
amount (mol) of gas None
Temperature
Increase T Toward absorption of heat Increases if H0rxn> 0
Decreases if H0rxn< 0
Decrease T Toward release of heat Increases if H0rxn< 0
Decreases if H0rxn> 0
Catalyst added None; rates of forward and reverse
reactions increase equally None
 The Effect of a Change in Pressure (Volume)
Pressure changes are mainly involving gases as liquids and solids
are nearly incompressible. For gases, pressure changes can occur in
three ways:
Changing the concentration of a gaseous component

Adding an inert gas (one that does not take part in the reaction)

Changing the volume of the reaction vessel

When a system at equilibrium that contains a gas undergoes a change

in pressure as a result of a change in volume, the equilibrium position
shifts to reduce the effect of the change.
If the volume is lower (pressure is higher), the total number of gas
molecules decrease.
If the volume is higher (pressure is lower), the total number of gas
molecules increases.
Predicting the Effect of Temperature and Pressure
Problem: How would you change the volume (pressure) or temperature
in the following reactions to increase the chemical yield of the products?
(a) 2 SO2 (g) + O2 (g) 2 SO3 (g); H0 = 197 kJ
(b) CO(g) + 2 H2 (g) CH3OH(g); H0 = -90.7 kJ
(c) C(s) + CO2 (g) 2 CO(g); H0 = 172.5 kJ

Plan: For the impact of volume (pressure), we examine the reaction for
the side with the most gaseous molecules formed. For temperature, we
see if the reaction is exothermic, or endothermic. An increase in pressure
will force a reaction toward fewer gas molecules.
Solution: To get a higher yield of the products you should:
(a) Increase the pressure, and increase the temperature.
(b) Increase the pressure, and decrease the temperature.
(c) Decrease the pressure, an increase in the
temperature will increase the product yield.
 Thermodynamics and Keq
Keq is related to reaction favorability.
If Gorxn < 0, reaction is product-favored.
Gorxn is the change in free energy as
reactants convert completely to products.
But systems often reach a state of
equilibrium in which reactants have not
converted completely to products.
How to describe thermodynamically ?
Grxn versus Gorxn
Under any condition of a reacting system, we can
define Grxn in terms of the reaction quotient, Q

Grxn = Gorxn + RT ln Q

If Grxn < 0 then reaction proceeds to right

If Grxn > 0 then reaction proceeds to left

 G and the Equilibrium Constant

At equilibrium, G=0 and Q=K. Then

G = G + RT lnQ o

0 = G + RT ln K
o

which rearranges to :
G = - RT ln K
o
Thermodynamics and Keq

Keq is related to reaction favorability and

so to Gorxn.
The larger the negative value of Gorxn
the larger the value of K.

Gorxn = - RT lnK
where R = 8.31 J/Kmol
 Thermodynamics and Keq
Gorxn = - RT lnK
Calculate K for the reaction
N2O4 2 NO2 Gorxn = +4.8 kJ
Gorxn = +4800 J = - (8.31 J/K)(298 K) ln K

4800 J
lnK = - = - 1.94
(8.31 J/K)(298K)
K = 0.14
When Gorxn > 0, then K < 1 - reactant favored
When Gorxn < 0, then K >1 - product favored
 The Equilibrium Constant
At a given temperature 0.80 mole of N2 and
0.90 mole of H2 were placed in an
evacuated 1.00-liter container. At
equilibrium 0.20 mole of NH3 was present.
Calculate Kc for the reaction.
 The Equilibrium Constant
N 2(g) + 3 H 2(g) 2 NH 3(g)
Initial 0.80 M 0.90 M 0
 The Equilibrium Constant
N 2(g) + 3 H 2(g) 2 NH 3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
 The Equilibrium Constant
N 2(g) + 3 H 2(g) 2 NH 3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Equilibrium 0.70 M 0.60 M 0.20 M
 The Equilibrium Constant
N 2(g) + 3 H 2(g) 2 NH 3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Equilibrium 0.70 M 0.60 M 0.20 M

Kc =
[ NH 3 ]
2
( 0.20)
2

3 = 3 = 0.26
[ N 2 ][ H 2 ] (0.70)(0.60)
 Predicting Reaction Direction and Calculating
Equilibrium Concentrations I
Problem: Two components of natural gas can react according to the
following chemical equation:
CH4(g) + 2 H2S(g) CS2(g) + 4H2(g)
In an experiment, 1.00 mol CH4, 1.00 mol CS2, 2.00 mol H2S, and
2.00 mol H2 are mixed in a 250 mL vessel at 960C. At this temperature,
Kc = 0.036. (a) In which direction will the reaction go?
(b) If [CH4] = 5.56 M at equilibrium, what are the concentrations of the
other substances?
Plan: To find the direction, we calculate Qc using the calculated
concentrations from the data given, and compare it with Kc. (b) Based
upon (a), we determine the sign of each component for the reaction table
and then use the given [CH4] at equilibrium to determine the others.
Solution:
[H2S] = 8.00 M, [CS2] = 4.00 M
1.00 mol = 4.00 M and [H2 ] = 8.00 M
[CH4] =
0.250 L
 Predicting Reaction Direction and Calculating
Equilibrium Concentrations II
[CS2] [H2]4 4.00 x (8.00)4 = 64.0
Qc = =
[CH4] [H2S] 2 4.00 x (8.00)2

Comparing Qc and Kc: Qc > Kc (64.0 > 0.036, so the reaction goes to
the left. Therefore, reactants increase and products decrease their
concentrations.
(b) Setting up the reaction table, with x = [CS2] that reacts,
which equals the [CH4] that forms.
Concentration (M) CH4 (g) + 2 H2S(g) CS2(g) + 4 H2(g)

Initial 4.00 8.00 4.00 8.00

Change +x +2x -x -4x
Equilibrium 4.00 + x 8.00 + 2x 4.00 - x 8.00 - 4x
Solving for x at equilibrium: [CH4] = 5.56 M = 4.00 M + x
x = 1.56 M
Predicting Reaction Direction and Calculating
Equilibrium Concentrations (p. 735)III

x = 1.56 M = [CH4]

Therefore:

[H2S] = 8.00 M + 2x = 8.00 M + 2(1.56 M) = 11.12 M

[CS2] = 4.00 M - x = 4.00 M - 1.56 M = 2.44 M

[H2] = 8.00 M - 4x = 8.00 M - 4(1.56 M) = 1.76 M

[CH4] = 1.56 M
 Using the Quadratic Formula to Solve for the Unknown
Given the Reaction between CO and H2O:
Concentration (M) CO(g) + H2O(g) CO2(g) + H2(g)
Initial 2.00 1.00 0 0
Change -x -x +x +x
Equilibrium 2.00-x 1.00-x x x

[CO2][H2] (x) (x) x 2

Qc = = = = 1.56
[CO][H2O] (2.00-x)(1.00-x) x - 3.00x + 2.00
2

We rearrange the equation: 0.56x2 - 4.68x + 3.12 = 0

ax2 + bx + c = 0
quadratic equation: - b + b 2 - 4ac
x=
2a [CO] = 1.27 M
[H2O] = 0.27 M
x = 4.68 (-4.68) - 4(0.56)(3.12) = 7.6 M
2
[CO2] = 0.73 M
2(0.56) and 0.73 M [H2] = 0.73 M