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Unit 2: Chemical Equilibrium and Ionic Equilibrium

Reversible Reactions
There exist a group of reactions in which the direction of chemical change can be easily

reversed by changing the conditions under which the reaction is taking place
E.g. When hydrated copper(II)sulphate is heated the blue colour of the crystals change to

the white appearance of the anhydrous salt CuSO4.5H2O (s) hydrated salt (blue) by adding water CuSO4(s) + 5H2O(g) CuSO4.5H2O (s) CuSO4(s) + 5H2O(g) anhydrous salt (white)

However anhydrous copper(II)sulphate may be changed to the blue hydrated form simply

Reversible Reactions
Because the reaction can easily be reversed it is known as a reversible reaction. The

equation for the reversible reaction is: CuSO4.5H2O (s)


The

CuSO4(s) + 5H2O(g)

indicating that the reaction may proceed in one direction or the other

according to the conditions under which it is carried out


Reversible reactions attain equilibrium during the course of the reaction

Equilibrium
What is equilibrium?

For equilibrium to exist there needs to be sameness and changelessness, e.g. if a cup of hot water is placed on a table then the temperature of the hot water will be different from the surroundings (disequilibrium). However if the cup of hot water is left for awhile then the temperature of the water will eventually be the same as the surroundings (sameness) and it no longer changes (changelessness)
There exists different types of equilibrium, i.e. static and dynamic Static equilibrium occurs when a object is at rest and is in a state of equilibrium, for e.g. two persons

of the same weight on a see-saw


Dynamic equilibrium involves two opposing processes occurring at the same rate, for e.g. walking on a

treadmill
Chemical equilibrium is a kind of dynamic equilibrium

Dynamic Equilibrium
When a chemical reaction takes place in a container which prevents the entry or escape

of any of the substances involved in the reaction, the quantities of these components change as some are consumed and others are formed
Eventually this change will come to an end, after which the composition will remain

unchanged as long as the system remains undisturbed


The system is then said to be in its equilibrium state or at equilibrium A chemical reaction is in equilibrium when there is no tendency for the quantities of

reactants and products to change

The direction in which we write a chemical reaction (and thus which components are

considered reactants and products) is subjective


E.g.

H2 + I2 2 HI (synthesis of hydrogen iodide) and 2 HI H2 + I2 (dissociation of hydrogen iodide)

The equations represent the same chemical reaction system in which the roles of the components are reversed, and both yield the same mixture of components when the change is completed
It makes no difference whether we start with two moles of HI or one mole each of H2 and

I2; once the reaction has run to completion, the quantities of these two components will be the same
Once this equilibrium composition has been attained, no further change in the quantities

of the components will occur as long as the system remains undisturbed

Dynamic Equilibrium
Chemical equilibrium can be represented graphically

A substance having zero initial concentration is the product of the reaction

Dynamic Equilibrium
Whether we start with an equi-molar mixture of H2 and I2 or a pure sample of hydrogen

iodide, the composition after equilibrium is attained will be the same


The equilibrium composition is independent of the direction of the reaction

Dynamic Equilibrium
Consider the equation:

aA + bB

cC + dD

If we combine the two reactants A and B, the forward reaction starts immediately as a

result the forward reaction is favoured or by convention the equilibrium shifts to the right
As the products C and D begin to build up, then the reverse process gets underway i.e.

the reversed reaction is favoured or the equilibrium shifts to the left

Dynamic Equilibrium
The rate at which the equation proceed can be written as

rate of forward reaction = kf[A]a[B]b rate of reverse reaction = kr[C]c[D]d


The proportionality constants kf
and kr

are called rate constants and the quantities in

square brackets represent concentrations


As the reaction proceeds, the rate of the forward reaction diminishes while that of the

reverse reaction increases


Eventually the two processes are proceeding at the same rate, and the reaction is at

equilibrium, i.e. the rate of forward reaction = rate of reverse reaction kf[A]a[B]b = kr[C]c[D]d

Equilibrium Constants
The rate of the reversible reaction is affected by the concentration, temperature and

pressure (gaseous systems)


The gas equilibrium constant (K) can be expressed using the molar concentration of the

components present in the reaction (Kc) or from the partial pressure of the components present in the system (Kp)

In equilibrium equations, even though the arrows point both ways (

) we usually

associate the left as reactants and the right as products


The products are written at the TOP of the fraction (the numerator) The reactants are written at the BOTTOM of the fraction (the denominator) The concentrations of the products and reactants are always raised to the power of

their coefficient in the balanced chemical equation


If any of the reactants or products are solids or liquids, their concentrations are equal to

one because they are pure substances

Calculations

The following concentrations were measured for an equilibrium mixture at 500 K: [N2] = 3.0 x 10-2 M; [H2] = 3.7 x 10-2 M; [NH3] = 1.6 x 10-2 M. Calculate the equilibrium constant at 500 K for the reaction N2(g) + 3H2(g) 2NH3(g)

Kc = [NH3]2 [N2][H2]3 (1.62 x 10-2)2 (3.0 x 10-2)(3.7 x 10-2)3 Kc = 1.7 x 10-2 Kc = [N2][H2]3 [NH3]2 (3.0 X 10-2)(3.7 X 10-2)3 = 5.9 X 10-3 (1.62 X 10-2)2 OR Kc = 1/ 1.7 X 10-2 = 5.9 X 10-3

The oxidation of sulphur dioxide to give sulphur trioxide is a important step in the

industrial process for the synthesis of sulphuric acid 2SO2(g) + O2(g) 2 SO3(g) The following equilibrium concentrations were measured at 800 K: [SO2] = 3.0 x 10-3 M; [O2] = 3.5 x 10-3 M; [SO3] = 5.0 x 10-2 M. Calculate the equilibrium constant at 800 K for the reaction.

Kc = [SO3]2 [SO2]2[O2] Kc = (5.0 x 10-2)2 (3.0 x 10-3)2 (3.5 x 10-3) Kc = 7.936 x 104

Kc = [SO2]2[O2] = (3.0 x 10-3)2 (3.5 x 10-3) [SO3]2 (5.0 x 10-2)2

= 1.26 x 10-5

1.

An equilibrium mixture of gaseous O2 , NO, and NO2 at 500K contains 1.0 x 10-3 M O2 and 5.0 x 10-2 M NO2. At this temperature, the equilibrium constant Kc for the reaction 2 NO (g) + O2(g) 2NO2(g) is 6.9 x 105 . What is the concentration of NO?

Kc =

[NO2]2 [NO]2[O2]

[NO] =

[NO]2 [O2]Kc

[NO] = (5.0 x 10-2)2 / (1.0 x 10-3) (6.9 x 105) [NO] = 3.6 x 10-6 [NO] = 1.9 x 10-3 M

2.

N2O4 (l) is an important component of rocket fuel. At 25 C N2O4 is a colorless gas that partially dissociates into NO2. Equilibrium is established in the reaction N2O4 (g) 2NO2 (g) at 25 C

Given: 3.00 L container, 7.64 g N2O4 and 1.56 g NO2 What is the Kc for this reaction?

HINT Step 1: Convert grams to moles Step 2: Convert moles to Molarity (moles/L) Step 3: Write the Equilibrium constant for Kc Kc = 4.61 x 10-3

3. The H2/CO ratio in mixtures of carbon monoxide and hydrogen (called synthesis gas) is increased by the water gas shift reaction CO(g) + H2O(g) CO2(g) + H2 (g), which has an equilibrium constant Kc = 4.24 at 800K. Calculate the equilibrium concentrations of CO2, H2, CO and H2O at 800K if only CO and H2O are present initially at concentrations of 0.150M. 4. Calculate the equilibrium concentrations of N2O4 and NO2 at 25C in a vessel that contains an initial N2O4 concentration of 0.0500M. The equilibrium constant for the reaction N2O4(g) 2NO2(g) is 4.64 x 10-3 at 25C

Source: McMurray & J., Fay, R. (1998). Chemistry 2nd Edition, New Jersey- Prentice-hall Inc. p.520

To calculate Kp using KC, the following equation is used

Kp = Kc (RT)n n = (Total moles of gas on the products side) (Total moles of gas on the reactants side) Therefore for the equation: aA + bB cC + dD n = (d + c) - (a + b) [The coefficients] R = 0.0821 L.atm mol-1K-1 from the ideal gas law constant (PV = nRT) T = temperature in Kelvin

Factors that Alter the Composition of an Equilibrium Mixture


The principal goal of a chemical reaction is to effect the maximum conversion of reactants to

products
For reversible reactions this may prove difficult as the reaction can take place in two

directions
However in utilizing Le Chateliers principle one is able to alter conditions in order to get the

maximum concentration of a desired substance


Several factors that can be exploited to alter the composition of an equilibrium mixture are

(a) temperature (b) pressure and volume (c) concentration (d) catalyst

Le Chateliers Principle
Le Chateliers 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 tend to annul the effect of the change

Effect of Temperature Change


If the temperature is increased, then according to Le Chateliers principle, the reaction

that is favoured is the reaction that lowers the temperature i.e. endothermic reaction
If the temperature is decreased, the according to Le Chateliers principle the reaction that

increases the temperature is favoured i.e. exothermic reaction

Effect of Pressure
The effect of pressure is much more noticeable in reactions occuring in the gaseous state If the pressure is increased then the reaction that is favoured is the one that lowers the

pressure, that is the reaction that has fewer number of molecules present in the reaction mixture
Types of reaction Increase the number of molecules left to right 2O3(g) 3O2(g) Decrease in the number of molecules from left o right N2(g) + 3H2(g) 2NH3(g) No change in the number of molecules left to right H2(g) + I2(g) 2 HI Effect of increase in total Effect of decrease in pressure total pressure Equilibrium shifts to the left producing more O3 Equilibrium shifts to the right producing more NH3 No effect equilibrium maintained Equilibrium shifts to the right producing more O2 Equilibrium shifts to the left producing more N2 and H2 No effect equilibrium maintained

Effect of Concentration
If the concentration of the reactant or product decreases then the reaction that is

favoured is the one that replenishes the decreased concentration.


In addition if the concentration of the reactant or product increases then the reaction that

is favoured is the one that uses up the reactant or product

Effect of Catalyst
A catalyst does not affect the equilibrium position, it only enables you get to the point of

equilibrium faster
If a reaction mixture is not at equilibrium, at catalyst accelerates the rate at which the

equilibrium is reached, but it does not affect the composition of the equilibrium mixture
A catalyst speeds up both the forward and reverse reactions by lowering the activation

energy

Industrial Application of Chemical Equilibrium


Industrial preparation of ammonia (Haber Process) Industrial preparation of hydrogen iodide

Haber Process

N2(g) + 3H2(g)

2NH3(g)

Source: http://www.chemguide.co.uk/physical/equilibria/haberflow.gif

N2(g) + 3H2(g)
(a)

2NH3(g)

exothermic

Pressure Ammonia is produced from its element with a reduction of volume If the pressure of the system is increased (keeping the temp. and conc. constant), then Le Chateliers principle dictates that the system will oppose that change, i.e. reduce the pressure To achieve this the reaction proceeds in the direction the produces the lesser volume An increase in pressure favours the production of ammonia

N2(g) + 3H2(g)
(b) Temperature

2NH3(g) exothermic

The production of ammonia is exothermic, therefore according to Le Chateliers

principle a decrease in temperature favours the production of ammonia


As a result a catalyst of finely divided reduced iron is introduced to speed up the reaction

rate inspite the low temperature

N2(g) + 3H2(g) (c) Concentration

2NH3(g) exothermic

An increase in the concentration of either N2 or H2 would result in the increase

production of ammonia
However in practice there is no advantage of increasing either reactants. This is because

the gases are mixed in the theoretical proportion of N2: H2, 1:3 by volume

H2(g) + I2(g)

2HI(g) exothermic

(a) Decrease in Temperature (b) Increase in concentration of reactants (c) Change in pressure does not affect the equilibriumWhy?