CHM 231

CHEMICAL
EQUILIBRIUM
 Chemical Equilibrium

1. Equilibrium State
2. The Equilibrium Condition
3. The Equilibrium Constant
4. Heterogeneous Equilibria
5. Equilibrium Expressions Involving
Pressures
6. Applications of the Equilibrium Constant
7. Solving Equilibrium Problems
8. Le Chatelier’s Principle

2
 Concept of Equilibrium
Consider this direct reaction,
aA + bB → cC + dD

The reaction stops when the reactants are used up.

However, for a reversible reaction like this
aA + bB cC + dD

the equilibrium is attained when the rate of

forward reaction is equal to the rate of
backward reaction.
Chemical Equilibrium
Reversible Reactions:
A chemical reaction in which the products
can react to re-form the reactants
Chemical Equilibrium:
When the rate of the forward reaction equals the rate
of the reverse reaction and the concentration of
products and reactants remains unchanged
OR the state of a reversible reaction when the two opposing
reactions occur simultaneously
2HgO(s)  2Hg(l) + O2(g)
Arrows going both directions (  ) indicates equilibrium in a chemical equation

At equilibrium, the concentrations of reactants and products do not change with time
even though the forward and reverse reactions are still occurring
 Note: Chemical Equilibrium

• When a reaction reaches equilibrium, the amounts of reactants

and products in the system stay constant.
• The forward and reverse reactions still continue.
• Because they go at the same rate, the amounts of materials do
not change.

5
Equilibrium  Equal
• The rates of the forward and reverse
reactions are equal at equilibrium.
• But that does not mean the concentrations
of reactants and products are equal.
• Some reactions reach equilibrium only after
almost all the reactant molecules are
consumed—we say the position of
equilibrium favors the products.
• Other reactions reach equilibrium when only
a small percentage of the reactant
molecules are consumed—we say the position
of equilibrium favors the reactants.
6
 Equilibrium Constant
• Even though the concentrations of reactants and products are
not equal at equilibrium, there is a relationship between them.
• For the reaction H2(g) + I2(g)  2HI(g) at equilibrium, the
ratio of the concentrations raised to the power of their
coefficients is constant.

HI  2
K eq 
H 2   I 2 
7
Law of Mass Action (The Equilibrium Law)
The law states that “at constant temperature, the rate at
which a substance reacts is directly proportional to the
active masses of the reactant”

Active mass is a thermodynamic quantity

a=fc
a -active mass, f- activity co-efficient (fugacity)
c- molar concentration.

For ideal gaseous and solution reaction, f = 1.

There4, the active mass is equal to molar concn
a=c
 Law of Mass Action (The Equilibrium Law)
Equilibrium Constant in terms of concentration (Kc)
According to the law,
Rf  Aa B b  Rf = K f  A B 
a b
reactants

Rb  C c D d  Rb = K C c D db
products

At equilibrium, R f = Rb i.e, K f Aa B b = K b C c D d

Kf

C  D
c d
 Kc
Kb Aa Bb
Kc is the equilibrium constant in terms of concentration and is unitless

Unitless? This is because we aren’t really using the concentrations and

pressures, but are actually using “activities”
We are actually filling in

Where Po is 1atm and co is 1 mol/L leaving the activity unitless.

 Writing Equilibrium Constant Expressions

• For aA + bB  cC + dD, the equilibrium

constant expression is:
K eq 
C  D 
c d

A a  Bb
• So for the reaction
2 N2O5  4 NO2 + O2, the K  NO 2   O 2 
4

N 2O5 2
eq
equilibrium constant
expression is:

10
 Equilibrium Constants for
Heterogeneous Equilibria

• Pure substances in the solid and liquid state have

constant concentrations.
• Adding or removing some does not change the
concentration because they do not expand to fill the
container or spread throughout a solution.
• Therefore, these substances are not included in the
equilibrium constant expression.
For the reaction CaCO3(s) + 2 HCl(aq)  CaCl2(aq) + CO2(g) + H2O(

K eq 
CaCl 2   CO 2 
HCl2
11
Heterogeneous Equilibria

CaCO3(s) CaO(s) + CO2(g)

Limestone Lime

[CaO][CO2] (1)[CO2]
Keq = = = [CO2]
[CaCO3] (1)

Pure solids and pure liquids are not included.

Keq = [CO2] Kp = P CO2

12
What Does the Value of Keq Imply?

• When the value of Keq > > 1, we know that when the
reaction reaches equilibrium, there will be many more
product molecules present than reactant molecules.
• The position of equilibrium favors products. LARGE
EQUILIBRIUM
• When the value of Keq < < 1, we know that when the
reaction reaches equilibrium, there will be many more
reactant molecules present than product molecules.
• The position of equilibrium favors reactants. SMALL
EQUILIBRIUM

13
Calculating Keq

• The value of the equilibrium constant may be

determined by measuring the concentrations of all
the reactants and products in the mixture after the
reaction reaches equilibrium, then substituting in
the expression for Keq.
• Although you may have different amounts of
reactants and products in the equilibrium mixture,
the value of Keq will always be the same.
• The value of Keq depends only on the temperature.
• The value of Keq does not depend on the amounts of
reactants or products with which you start.

14
Initial and Equilibrium Concentrations for
H2(g) + I2(g)  2HI(g)
Equili Equilibrium
Initial
brium Constant
[HI] 2

[H2] [I2] [HI] [H2] [I2] [HI] K 

eq
[H ][I ]
2 2

[0.78]2
0.50 0.50 0.0 0.11 0.11 0.78  50
[0.11][0.11]
[0.39]2
0.0 0.0 0.50 0.055 0.055 0.39  50
[0.055][0.055]
[1.17]2
0.50 0.50 0.50 0.165 0.165 1.17  50
[0.165][0.165]
[0.934]2
1.0 0.5 0.0 0.53 0.033 0.934  50
[0.53][0.033]
15
Practice—

1. Calculate Keq for the Reaction

2 NO2(g)  N2O4(g)
at 100 C if the Equilibrium Concentrations Are
[NO2] = 0.0172 M and [N2O4] = 0.0014 M.

2. A Sample of PCl5(g) Is Placed in a 0.500 L

Container and Heated to 160 °C. The PCl5 Is
Decomposed into PCl3(g) and Cl2(g). At Equilibrium,
0.203 Moles of PCl3 and Cl2 Are Formed. Determine
the Equilibrium Concentration of PCl5 if Keq = 0.0635.

16
Equilibrium expression in terms of activities
Kc 
C  D
c d

 aC c aD d  Aa Bb

KA   a b 
 a A  aB  

The concept of activity addresses the deviation from ideal behaviour.

Therefore, it can be defined as an idealized concentration.

KA is exact and does not depend on pressure.

Equilibrium Expressions Involving Pressure
Kp Equilibrium Constant in Terms of Pressure
PCc PDd
Kp  a b where PAa , PBb , PCc and PDd
PA PB
are the partial pressure of various gaseous species at equilibrium.

For the gas phase reaction:

3H2(g) + N2(g)  2NH3(g)
2
PNH3
Kp  3
( PN 2 )( PH 2 )

PN H 3 , PN 2 , PH 2 a r e e q u ilib r iu m p a r tia l p r e s s u r e s
NOTE: The partial pressure of one individual gas
within the overall mixtures, pi, can be expressed as
follows: Pi=Ptotalxi
xi=mole fraction
 Relationship between Kp and Kc
• In a gaseous reaction, the concentration of the gases at any given
temperature is expressed in terms of their partial pressures.
PCc PDd
Kp  a b But for an ideal gas
PA PB
n n
PV  nRT ; P RT ; But  C ; so P  CRT
V V
CCc RT  C Dd RT  CCc C Dd RT 
c d (cd )
Kp  a i.e. a b
C A RT  C B RT  C AC B RT 
a b b ( a b )

Recall C c Dd K p  K c RT 
n
Kc  a b so;
A B


n  cd  ab   i.e change in the amount of gaseous reagents

When n is positive, the no. of molecules of prdts are larger than those of the reactants i.e K p  K c

When n is negative, the no. of molecules of prdts are smaller than those of the reactants i.e K p  K c
When n is zero, the number of molecules of products = the number of molecules of the reactants i.e
K p  Kc
Equilibrium constant in terms of mole fractions, X
Recall: No of moles of A
Mole fraction of A 
No of moles of solution(total)
( X C P) c  X C P 
d
nA
Kp  XA 
( X A P) a  X B P  nA  nB  nC  ..nZ
b

nA
XA 
n

 ( X ) X D  
  P c  d a b 
No of moles of solute
K p   C Molarity(M) 
 ( X A ) X B  
Volume of solution(L)

K p  K x P n


n  cd  ab   
Recall: Partial pressure of one
individual gas within the overall
mixtures, pi: Pi=Ptotalxi
 Review
• Kc is equal to the products over the reactants raised to the
power of the coefficient
• Kc is used because:
• Concentrations at equilibrium vary depending on initial conditions
so;
• final ratios of products to reactants change based on initial
concentrations and stoichiometric coefficients
• This is why we use Kc rather than ratios.
• Kc does not change given a constant temperature
• If Kc is much greater than one, K>>1, then products are favored
• If Kc is much less than one, K<< 1, then reactants are favored.
• The last two will be true of all the equilibrium and means that
The magnitude of K tells us whether reactants or products are
favored
• Only gas and aqueous species are included in the equilibrium
constant expressions
 ??? Examples
• Given each of the following equilibrium constants, find
the unknown equilibrium constant.
• Example 1

Given each of the following equilibrium constants, find

the unknown equilibrium constant.
Example 2
 Reaction Quotient (Q)
• Defined the same as K, (products  reactants, raised to
stoichiometric coefficients)
• K is at equlibrium
• Q can be determined at any point in the reaction. i.e.
• At some time, t, when the system is not at equilibrium,
the reaction quotient, Q takes the place of K, the
equilibrium constant, in the law of mass action.

jA + kB  lC + mD
l m
[C ] [ D]
Q j k
[ A] [ B]
Significance of the Reaction Quotient
 If Q = K, the system is at equilibrium
No net reaction
 If Q > K, (Reactants are smaller/Products are bigger than K,
the system shifts to the left
so must shift to adjust)
from the right, consuming products and forming
reactants until equilibrium is achieved
 If Q < K, (Products are smaller/reactants are bigger
the system shifts to
than K, so must shift to adjust)
the right, consuming reactants and forming
products until equilibrium is achieved
Solving for Equilibrium Concentration
Consider this reaction at some temperature:
H2O(g) + CO(g)  H2(g) + CO2(g) K = 2.0

Assume you start with 8 molecules of H2O

and 6 molecules of CO. How many molecules
of H2O, CO, H2, and CO2 are present at
equilibrium?
Here, we learn about “ICE” – An
important problem solving technique. You
will use it for several next aspects in
chemistry!
Solving for Equilibrium Concentration
H2O(g) + CO(g)  H2(g) + CO2(g) K = 2.0

Step #1: We write the law of mass action

for the reaction:

[ H 2][CO 2]
2.0 
[ H 2O][CO ]
Solving for Equilibrium Concentration
Step #2: We “ICE” the problem, beginning
with the Initial concentrations

H2O(g) + CO(g)  H2(g) + CO2(g)

Initial: 8 6 0 0
Change: -x -x +x +x
Equilibrium: 8-x 6-x x x
Solving for Equilibrium Concentration
Step #3: We plug equilibrium concentrations
into our equilibrium expression, and solve for x

H2O(g) + CO(g)  H2(g) + CO2(g)

Equilibrium: 8-x 6-x x x
[ H 2][CO 2]
2.0 
( x)( x)
2.0 
[ H 2O][CO ]

(8  x)(6  x)
x4
Solving for Equilibrium Concentration
Step #4: Substitute x into our equilibrium
concentrations to find the actual concentrations

H2O(g) + CO(g)  H2(g) + CO2(g)

Equilibrium: 8-x 6-x x x

x4
Equilibrium: 8-4=4 6-4=2 4 4
 ????Examples
Calculate the number of moles of H2 that are present at equilibrium if a mixture
of 0.300 mol of CO and 0.300 mol of H2O is heated to 700oC (kc=0.534) in a
10.0 L container.

At a certain temperature, the equilibrium constant, Kc, for this reaction is

53.3. At this temperature, 0.300 mol of H2 and 0.300 mol of I2 were placed in
a 1.00L container to react. What concentration of HI is present at equilibrium?

For the decomposition of phosphorous pentachloride to phosphorous trichloride

and chlorine at 400.K the Kc is 1.1x10-2. Given that 1.0g of phosphorous
pentachloride is added to a 250mL reaction flask, find the final concentrations
of each species and the percent decomposition

Consider the reaction below. A reaction mixture at 780 oC initially contains [CO]=0.500
M and [H2]= 1.00M. At equilibrium, the CO concentration is 0.15 M. What is the value
of the equilibrium constant?
 Homogeneous Equilibria
• An equilibrium in which the reactants and the products are in the
same phase
• Homogeneous gaseous equilibria CASE 1
A + B 2C e.g

H 2( g )  I 2( g ) 2 HI ( g )

t=0; a b
t=t; a-x b-x 2x
• If V (in dm3) is the total volume of the reaction mixture; then;
ax bx 2x
V V V

Kc 
2
[ HI ]

 
2x
V
2


4x2
[ H 2][ I 2]  a  x  b  x  a  x b  x 
  
 V  V 
• Kc is independent of the volume
• In terms of partial pressure

PC2
Kp 
PA  PB
nA n n
But, PA   P, PB  B  P, PC  C  P
N N N

where, N  n A  nB  nC  Total number of moles

P  Total external pressure

PA , PB & PC are the partial pressures of A, B and C respectively

2
 nC 
  P
 N  nC2
Therefore, K p  
 nA   nB  n A  nB
  P 
   P 
N  N 
 Homogeneous Liquid Equilibria
• CASE A(l) + B(l) C(l) + D(l)
e.g. CH3COOH (l) +C2H5OH (l) CH3COOC2H5 (l) +H2O (l)
t=0; a b 0 0
t=t; a-x b-x x x
x x
  
 V  V  x2
Kc  
 a  x   b  x  a  x b  x 
  
 V   V 
• This equation is the general expression for liquid equilibria. However, in
the example above where water molecule is involved, the expression
can be written as
CH 3COOC 2 H 5 H 2O  Kc
 Kc 
' CH 3COOC 2 H 5 
Kc 
CH 3COOH C2 H 5OH  H 2O CH 3COOH C2 H 5OH 
• The above expression is written in terms of K c' because the concn. of
water is taken to be constant. K c' has the unit of [Concn]-1 but Kc has no
unit
 Heterogeneous Equilibria
 An equilibrium in which the reactants and the products
are NOT in the same phase
The position of a heterogeneous equilibrium does not
depend on the amounts of pure solids or liquids present
e.g. 3Fe(s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)

Kc 
Fe3O 4 H 2 
4

1  H 2 
4

H2 
4

Fe3 H 2O4 1  H 2O H 2O

4 4

Note: Concentration of substances in solid phase/pure liquid phase is

taken to be unity.

In terms of pressure; PH42

Kp 
PH42O
FACTORS AFFECTING EQUILIBRIUM
• Temperature,
• Concentration of the reactants and products
• Volume and pressure of the reactants and products,
• catalyst.
Note: catalyst does not change the position of equilibrium,
but affects the reaction equally in both directions.
It however speeds up the rate at which equilibrium is reached
 LeChatelier’s Principle
States that “if a chemical system is in equilibrium and
one of the factors involved in the equilibrium is
altered, the equilibrium will shift, so as to neutralize
the effect of the change”

When a system at equilibrium is placed under

stress, the system will undergo a change in
such a way as to relieve that stress.

Translated: The system undergoes a

temporary shift in order to restore
equilibrium.
 Effect of change in Concentration on
equilibrium
• Change in Concentration
• Reaction shifts away from added species
• Reaction shifts toward subtracted species
• Adding a reactant will decrease the
amount of the other reactants and
increase the amount of the
• For the generic reaction above: products until a new position of
• Adding A shifts the reaction right. equilibrium is found.
• Subtracting A shifts the reaction left.
• Adding B shifts the reaction right. • Removing a product will increase
the amounts of the other products
• Subtracting B shifts the reaction left.
and decrease the amounts of the
• Adding C shifts the reaction left. reactants.
• Subtracting C shifts the reaction right • You can use to this to drive a
• Adding D shifts the reaction left. reaction to completion!
• Subtracting D shifts the reaction right • Remember: Adding more of a solid
or liquid does not change its
concentration and, therefore, has
no effect on the equilibrium.
 Volume and Pressure (in gases)
• Increase volume, and therefore decrease in pressure:
shifts toward the side with more moles of gas
• Decrease volume, and therefore increase in pressure it
shifts toward the side with less moles of gas
4 mols 2mol
reactant product

Low pressure High pressure

Shifted further to the left Shifted further to the right
 Temperature Change
• NB: Alters the value of Kc/Kp (unlike all other changes)

• For an endothermic reaction (DH= positive)

• Think of heat as a reactant
• raising the temperature shifts the reaction to the
products
• Lowering the temperature shifts the reaction to the
reactants

• For an exothermic reaction (DH= negative)

• Think of heat as a product
• raising the temperature shifts the reaction to the
reactants
• Lowering the temperature shifts the reaction to the
products
 ???? Review:
• Change in Concentration
• Reaction shifts away from added species
• Reaction shifts toward subtracted species
• Change in Volume
• Increase volume it shifts toward the side with more moles of gas
• Decrease volume it shifts toward the side with less moles of gas
• Change in Pressure
• Increase in pressure shifts toward the side with less moles of gas
• Decrease in pressure shifts toward the side with more moles of gas
• Change in Temperature
• Only way to alter the equilibrium constant
• For an endothermic reaction
• raising the temperature shifts the reaction to the products
• Lowering the temperature shifts the reaction to the reactants
• For an exothermic reaction
• raising the temperature shifts the reaction to the reactants
• Lowering the temperature shifts the reaction to the products
 Relationship between ∆G,T, ∆H, ∆E and
the equilibrium constant
• The change in free energy, ∆G, of a reaction and the equilibrium
constant, K, are related to each other by the expression
G   RT ln K
• The value of equilibrium constant varies with temperature change.
• The relationship between the equilibrium constants at two different
temperatures and the enthalpy change is given by
K p2 H o  T2  T1 
log   
K p1 2.303R  T 1 T2 

K p and K p are the equilibrium constants at temperature T2 and T1 respectively

2 1

• In terms of change in internal energy (E o ), the equation becomes

K p2 E o  T2  T1 
log   
K p1 2.303R  T 1 T2 
 Free Energy and Equilibrium

Equation to relate K or Q with G.

• G: Gibbs free energy

• R: related to energy, so use 8.314 J/mol*K
• T: Kelvin
Example
• Find Kc at 273K, using the values below.

Species Gfo
Kc 
NH 3 
2

N2* 0 kJ/mol N 2 H 2 3

H2* 0 kJ/mol
Go of the species = G Prdt – G React
NH3 -16.4 kJ/mol
Go =2(-16.4kJ/mol) –(0 + 3(0)) = 32.4 kJ/mol

OR

Note: remember anything in its standard state is zero, I wouldn’t HAVE to give you this on an exam.
 Relating temperature, H and K
Deriving the Van’t hoff equation.
ΔGo   RT ln K ΔGo  H  T S
No T here so
 R Tln K  H o  TS o differentiatn
tends to 0

ln K   Ho
RT  TS o
RT ln K   Ho
RT  S o
R

Differentiate wrt T

1/T =T-1= -1T-2
dln K H o =-1/T2 Integratn
dT RT 2 is opposite of
differrn..
Integrate under two Ks K2
H o T2
dT
 d ln K 
K1
R T1 dT 2
T
ΔHo  1  2
ln K 
K2
K1     ln K 2  ln K 1 
ΔHo  1 1 
   
R  T  T1 R  T2 T1 

K 2 ΔH  1 1  K 2 ΔH  T2 - T1 
o o
   K2 ΔHo  T2 - T1 
ln  ln    log   
K1 R  T1 T2  K1 R  T2T1  K 1 2.303R  T2T1 
If equilibrium constant K1 at a certain temperature T1 is known
K2 at a different temperature T2, can be found
Note: Vant Hoff equation is related to what we know of Le
Chatelier's principle;

if the reaction is exothermic, ΔH∘<0, and

if you increase the temperature from T1 to T2>T1 then
(1/T1−1/T2)>0. The RHS of the equation is therefore negative
meaning that lnK2<lnK1⇒K2<K1 which implies that the equilibrium
position has shifted to the left.

Note that the last step (the integration) makes the assumption that
ΔH∘ is a constant over the temperature range T1 to T2.
Note that this is, in general, not true but if the temperature range
isn't too huge you will get pretty accurate results from the use of
this equation.
Van’t Hoff Equation: Graphs

Experimentally you can use this to determine the H of reaction.

 Example
Use the graph to answer the
following:
• Is the reaction endothermic or
exothermic?
Endothermic: 1/T decrease
y= -2.144x105x+2559
as ln K Decreases
So K decreases as T increases=endothermic

• What is H