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Chemical Equilibrium
Introduction

1.) Equilibria govern diverse phenomena

 Protein folding, acid rain action on minerals to aqueous reactions
2.) Chemical equilibrium applies to reactions that can occur in both directions:

 reactants are constantly forming products and vice-versa

 At the beginning of the reaction, the rate that the reactants are changing into the
products is higher than the rate that the products are changing into the reactants.
 When the net change of the products and reactants is zero the reaction has
reached equilibrium.

First, system reaches equilibrium

Then, system continually exchanges prod
ucts and reactants, while maintaining
equilibrium distribution.
Reactants Product

At equilibrium the amount of reactants and products are constant, 2

but not necessarily equal
 Chemical Equilibrium
Equilibrium Constant

1.) The relative concentration of products and reactants at equilibrium is a

constant.

2.) Equilibrium constant (K):

 For a general chemical reaction

c d
[C ] [ D]
Equilibrium constant: K
[ A]a [ B]b
Where:
- small superscript letters are the stoichiometry coefficients
- [A] concentration chemical species A relative to standard state

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 Chemical Equilibrium
Equilibrium Constant

2.) Equilibrium constant (K):

 A reaction is favored when K > 1
 K has no units, dimensionless
- Concentration of solutes should be expressed as moles per liter (M).
- Concentrations of gases should be expressed in bars.
► express gas as Pgas, emphasize pressure instead of concentration
► 1 bar = 105 Pa; 1 atm = 1.01325 bar
- Concentrations of pure solids, pure liquids and solvents are omitted
► are unity
► standard state is the pure liquid or solid

3.) Manipulating Equilibrium Constants

Consider the following reaction:
[ H  ][ A ]
K1 
[ HA]
Reversing the reaction results in a reciprocal equilibrium reaction:

[ HA]
K '1   1 / K1
  4
[ H ][ A ]
 Chemical Equilibrium
Equilibrium Constant

3.) Manipulating Equilibrium Constants

If two reactions are added, the new K is the product of the two individual K values:

K1

K2

K3

[ H  ][ A ] [CH  ] [ A ][CH  ]
K1  K2  K3 
[ HA] [ H  ][C ] [ HA][C ]

[ H  ][ A ] [CH  ] [ A ][CH  ]
K 3  K1K 2    5
[ HA]  [ HA][C ]
[ H ][C ]
 Chemical Equilibrium
Equilibrium Constant

3.) Manipulating Equilibrium Constants

 Example:
Given the reactions and equilibrium constants:
Kw= 1.0 x 10-14

KNH3= 1.8 x 10-5

Find the equilibrium constant for the reaction:

Solution:
K1= Kw

K2=1/KNH3
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K3=Kw*1/KNH3=5.6x10-10
 Chemical Equilibrium
Equilibrium and Thermodynamics

1.) Equilibrium constant derived from the thermodynamics of a chemical

reaction.
 deals with the relationships and conversions between heat and other forms of
energy

2.) Enthalpy
 DH – is the heat absorbed or released when the reaction takes place under
constant applied pressure

DH = Hproducts – Hreactants
 Standard enthalpy change (DHo) –
all reactants and products are
in their standard state.
 DHo – negative  heat released
- Exothermic
- Solution gets hot
 DHo – positive  heat absorbed
- Endothermic
- Solution gets cold 7
 Chemical Equilibrium
Equilibrium and Thermodynamics

3.) Entropy
 Measure of a substances “disorder”
 Greater disorder  Greater Entropy
- Relative disorder: Gas > Liquid > solid

DS = Sproducts – Sreactants
 DSo – change in entropy when all species are in standard state.
- positive
product more disorder
- negative 
product less disorder

DSo = +76.4 J/(K.mol) at 25oC

More disorder for aqueous ions than solid

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 Chemical Equilibrium
Equilibrium and Thermodynamics

3.) Entropy
 Increase in temperature results in an increase in Entropy (S)

 Increase occurs for all products and reactants

 Primarily concerned with DS, which is only weakly temperature dependent

- generally treat DS and DH as temperature independent
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 Chemical Equilibrium
Equilibrium and Thermodynamics

4.) Free Energy

 Systems at constant temperature and pressure have a tendency toward
lower enthalpy and higher entropy

 Chemical reaction is favored if:

- DH is negative  heat given off
and
- DS is positive  more disorder

 Chemical reaction is not favored if:

- DH is positive and DS is negative

 Gibbs Free Energy (DG): determines if a reaction is favored or not when both
DH and DS are positive or negative
- A reaction is favored if DG is negative

Free energy: DG = DH -TDS

where T is temperature (Kelvin)
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 Chemical Equilibrium
Equilibrium and Thermodynamics

4.) Free Energy

 Example:

Is the following reaction favored at 25oC?

DHo = -74.85 x 103 J/mol
DSo = -130.4 J/K.mol

Free energy: DG = DH –TDS = (-74.85x103 J/mol) – (298.15K)(-130.4 J/K.mol)

DG = -35.97 kJ/mol  DG negative  reaction favored

Favorable influence of enthalpy is greater than unfavorable influence of entropy

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 Chemical Equilibrium
Equilibrium and Thermodynamics

5.) Free Energy and Equilibrium

 Relate Equilibrium constant to the energetics (DH & DS) of a reaction
 Equilibrium constant depends on DG:

 D G o

K e RT
where
R (gas constant) = 8.314472 J/(K.mol)
T = temperature in kelvins

 The more negative DG  larger equilibrium constant

 Example:

DG = -35.97

 DG
o

 ( 35.97 x 10 3 J / mol )( 8.314472J /( K . mol )( 298.15 K )

K e RT e  2.00 x 10 6
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Because K is very large, HCl is very soluble in water and nearly completely ionized
 Chemical Equilibrium
Equilibrium and Thermodynamics

5.) Free Energy and Equilibrium

 If DGo is negative or K >1 the reaction is spontaneous
- Reaction occurs by just combining the reactants

 If DGo is positive or K < 1, the reaction is not spontaneous

- Reaction requires external energy or process to proceed

Gas flows towards a vacuum. A vacuum does not naturally form.

spontaneous nonspontaneous
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 Chemical Equilibrium
Le Châtelier’s Principal

1.) What Happens When a System at Equilibrium is Perturbed?

 Change concentration, temperature, pressure or add other chemicals

 Equilibrium is re-established
- Reaction accommodates the change in products, reactants, temperature,
pressure, etc.
- Rates of forward and reverse reactions re-equilibrate

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 Chemical Equilibrium
Le Châtelier’s Principal

1.) What Happens When a System at Equilibrium is Perturbed?

 Le Châtelier’s Principal:
- the direction in which the system proceeds back to equilibrium is such that
the change is partially offset.

Consider this reaction:

At equilibrium:
To return to equilibrium
(balance), some (not all)
CO and H2 are converted
to CH3OH
Add excess CO(g):

If all added CO was converted to CH3OH, then reaction

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would be unbalanced by the amount of product
 Chemical Equilibrium
Le Châtelier’s Principal

2.) Example:

Consider this reaction:

[ Br - ][Cr2O72- ][ H  ]8
K  1  10 11 at 25 o C
[ BrO 3- ][Cr 3 ]2

At one equilibrium state:

[H  ]  5.0 M [Cr2O72- ]  0.10 M [Cr 3 ]  0.0030 M

[Br  ]  1.0 M [BrO 3- ]  0.043 M
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 Chemical Equilibrium
Le Châtelier’s Principal

2.) Example:

What happens when:

[Cr2O 72- ] increased from 0.10 M to 0.20 M

According to Le Châtelier’s Principal, reaction should go back to left to
off-set dichormate on right:

Use reaction quotient (Q), Same form of equilibrium equation, but not at
equilibrium:

Q
[ Br - ][Cr2O72- ][ H  ]8

1.0 0.20 5.0 8
 2  10 11  K
[ BrO3- ][Cr 3 ]2 0.043 0.0030 2 17
 Chemical Equilibrium
Le Châtelier’s Principal

2.) Example:

Because Q > K, the reaction must go to the left to decrease numerator and
increase denominator.

Continues until Q = K:

1. If the reaction is at equilibrium and products are added (or reactants

removed), the reaction goes to the left

2. If the reaction is at equilibrium and reactants are added ( or products

removed), the reaction goes to the right

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 Chemical Equilibrium
Le Châtelier’s Principal

3.) Affect of Temperature on Equilibrium

Combine Gibbs free energy and Equilibrium Equations:

D  DH o  TDS 
o
 G
K e RT e RT

e
 DH o

RT
 DS
R

 DH o DS o
e RT e R

Only Enthalpy term is temperature dependent:

 DH o
K(T )  e RT
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 Chemical Equilibrium
Le Châtelier’s Principal

3.) Affect of Temperature on Equilibrium

1. Equilibrium constant of an endothermic reaction (DHo = +) increases if

the temperature is raised.
D
DH = +

2. Equilibrium constant of an exothermic reaction (DHo = -)decreases if the

temperature is raised.

D
DH = -

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 Chemical Equilibrium
Le Châtelier’s Principal

4.) Thermodynamics vs. Kinetics

 Thermodynamics predicts if a reaction will occur
- determines the state at equilibrium

 Thermodynamics does not determine the rate of a reaction

- Will the reaction occur instantly, in minutes, hours, days or years?

DG = -

spontaneous

Diamonds Graphite
- While reaction is spontaneous, takes millions of years to occur

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 Chemical Equilibrium
Solubility Product

1.) Equilibrium constant for the reaction which a solid salt dissolves to give
its constituent ions in solution
 Solid omitted from equilibrium constant because it is in a standard state

 Example:

K sp  [ Hg 22  ][Cl- ]2  1.2  10 18

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 Chemical Equilibrium
Solubility Product

1.) Saturated Solution – contains excess, undissolved solid

 Solution contains all the solid capable of dissolving under
the current conditions
 Example:

Find [Cu2+] in a solution saturated with Cu4(OH)6(SO4) if [OH-] is

fixed at 1.0x10-6M. Note that Cu4(OH)6(SO4) gives 1 mol of SO42- for
4 mol of Cu2+?
K sp  2.3  10 69

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 Chemical Equilibrium
Solubility Product

2.) If an aqueous solution is left in contact with excess solid, the solid will
dissolve until the condition of Ksp is satisfied
 Amount of undissolved solid remains constant
 Excess solid is required to guarantee ion concentration is consistent with Ksp

3.) If ions are mixed together such that the concentrations exceed Ksp, the
solid will precipitate.

4.) Solubility product only describes part of the solubility of a salt

 Only includes dissociated ions
 Ignores solubility of solid salt

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 Chemical Equilibrium

Common ion effect – a salt will be less soluble if one of

its constituent ions is already present in the solution.

Decrease in the solubility of MgF2 by

PbCl2 precipitate because the
the addition of NaF
ion product is greater than Ksp.
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 Chemical Equilibrium

Common Ion Effect

1.) Affect of Adding a Second Source of an Ion on Salt Solubility

 Equilibrium re-obtained following Le Châtelier’s Principal
 Reaction moves away from the added ion

Find [Cu2+] in a solution saturated with Cu4(OH)6(SO4) if [OH-] is

fixed at 1.0x10-6M and 0.10M Na2SO4 is added to the solution.

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