Chemical Equilibrium

Ways of expressing concentration of a solution:

Molarity: It is defined as the number of moles of the solute present in one litre or dm-3 of
solution. It is expressed as M or mol dm-3
Molarity = Number of mole of solute/Volume of solution in litre = n/V = (w/M)/V
where, w is the mass of solute of molar mass ,M, dissolved in V litre of solution.
Molality: It is defined as the number of moles of the solute present in one kg of solvent. It is
expressed as m or mol kg-1of solvent.
Molality = Number of mole of solute/Mass of solvent in kg = n/msolvent = (w/M)/msolvent
where, w is the mass of solute of molar mass ,M, dissolved in m kg of solvent.
Mass percentages: It is defined as the percentage by mass of solute contained in a solution.
Mass percentage of solute = (mass of solute/mass of solution)x100 %
Mole fraction: The mole fraction of component A (XA) in a solution is defined as ratio of
moles of the component to the total number of moles in solution.
Mole fraction of A, XA = moles of substance A/total moles of in solution = nA/(nA+nB+nC+..)
Partial Pressure: The partial pressure of a gas in a mixture is defined as the pressure that it
would exert if it were present alone in container at same temperature. In short, it is the
pressure exerted by a particular gas in a mixture. The partial pressure of a component in a
mixture is calculated as the product of mole fraction of that component and the total pressure.
Pi = Xi x Ptotal.
Dalton's law of partial pressure: It states the total pressure exerted by a mixture of gases is
the sum of the partial pressures of the individual gases. Ptotal.= p1+p2+p3+p4+.....
Reversible reactions: Chemical reactions which take place in both directions are called
reversible reactions. An example of a reversible between gases is the reaction between
hydrogen and iodine to form hydrogen iodide;
2HI(g) H2(g) + I2(g)
Amount
of HI

H2(g)+ I2(g) 2HI(g)

H2(g) + I2(g) 2HI(g)

Time

Chemical Equilibrium: When the rates of forward and backward reactions are equal and the
concentrations of the reactants and products no longer change with time, then the reaction is
said to attain chemical equilibrium. It is dynamic in nature, because at this stage reaction is
not stopped but proceeding from both sides at same speed.
The Equilibrium Law: It states that if a reversible reaction is allowed to reach equilibrium,
then the ratio of the product of the concentrations of the products (raised to appropriate
powers) to the product of the concentrations of the reactants (raised to appropriate powers) is
a constant at a particular temperature. The appropriate power is the coefficient of that
substance in the stoichiometric equation for the reaction. For a reaction of
aA(g) + bB(g) cC(g) + dD(g)
by the equilibrium law,

Kc = [C]c[D]d/[A]a[B]b
a

or, Kp = P Cc P dD /P A P bB
Kc (or Kp) is known as equilibrium constant. The dimensions of Kc are concentration(c+d-a-b)
and the units vary from one equilibrium to another. Similarly, the dimensions of Kp are
pressure(c+d-a-b).
When the equation for a reversible reaction is written in opposite direction, the equilibrium
constant becomes the reciprocal of the original equilibrium constant.
Keq.(reverse reaction) = 1/Keq.(forward reaction)
The value of Keq. is depends on how the equilibrium equation is balanced. e.g.
N2O4(g) NO2(g)

Kc = [NO2]/[N2O4]1/2

N2O4(g) 2NO2(g)

Kc = [NO2]2/[N2O4]

Therefore,
Kc = Kc
Position of equilibrium: The proportion of products to reactants in equilibrium mixture is
described as the position of equilibrium.
aA(g) + bB(g) cC(g) + dD(g)
If the conversion of A and B into C and D is small, the position of equilibrium lies to the left
and the value of Kc is small. But if the equilibrium mixture is largely composed of C and D,
the position of equilibrium lies to the right and Kc value is large. The equilibrium constant,
Kc, (or, Kp) is not the same as the position of equilibrium. Kc of a reaction is constant at a
particular temperature, but a change in external conditions can alter the position of
equilibrium.
Le Chateliers Principle: It states that when a system in chemical equilibrium is disturbed
by change of temperature, pressure or a concentration, the system shifts in equilibrium
composition in a way that tends to encounter this change of variable.

Or, It states that if an external stress is applied to a system in equilibrium, the system adjusts
itself in such a way that the stress is partially offset. The word stress here means a change in
concentration, pressure, volume or temperature that removes the system from the equilibrium.
Factors that effect the position of equilibrium and Kc (or, Kp) of the following reaction:
H = - 92 kJ mol-1

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

Fe, Al2O3

Pressure: In the above reaction, 4 moles of reactants react to form 2 moles of product. So, if
the pressure of the above system at equilibrium is increased at constant temperature, the
position of equilibrium will shift towards the less number of mole side (as less volume is
available to occupy at higher pressure), i.e. to the right side. But the concentration of
reactants and product will be adjusted in the new equilibrium such a way that the value of Kc
(or, Kp) remains the same. Similarly, the decrease of pressure will shift the position of
equilibrium to the left side and value of Kc (or, Kp) remains the same.
Volume: In the above reaction, the higher number of moles of reactants (4) react to form
lower number of product (2). If the volume of the above system at equilibrium is increased at
constant temperature and pressure, the position of equilibrium will shift towards higher
number of mole side (to occupy the higher available volume), i.e. to the left. The reverse will
occur if the volume is decreased. But in both cases the value of Kc (or, Kp) remains the same.
Temperature: The above reaction is exothermic (H = -ve) in the forward direction, so the
reverse reaction will be endothermic. If the temperature of the above system at equilibrium is
increased at constant volume, the position of equilibrium will shift to the direction in which
the added energy will be consumed. So, NH3 will decompose to H2 and N2 by absorbing the
added energy, i.e. the position of equilibrium will shift to the left. In this process, the
concentration of product (NH3) will decrease and that of reactants (H2 and N2) will increase.
So, the value of Kc (or, Kp) will decrease. Reverse effect will be observed if the temperature
of the above system is decreased. Exactly reverse effect will be observed with endothermic
reversible reaction. So, a temperature increase favours an endothermic reaction and a
temperature decrease fovours an exothermic reaction.
Addition of reactants or product: If a reactant is added to the above system at equilibrium
at constant pressure or constant volume, the position of equilibrium will shift to the right side
to keep the value of Kc (or, Kp) constant. The reverse effect will be observed if certain amount
of product is added to the above system at equilibrium.
Catalyst: Catalyst enhances the rate of reaction by lowering the reaction activation energy. It
lowers the activation energy of the forward reaction to the same extent as it lowers the
reverse reaction. This means that both the forward and reverse rates are affected to exactly
the same degree. But, the initial states of the reactants and the final states of the products
remain the same. So, the presence of a catalyst does not alter the equilibrium constant, Kc (or,
Kp), nor does it shift the position of an equilibrium system and will speed up both the forward
and reverse rates to achieve the equilibrium much faster.
.
Heterogenious Equilibrium: A reversible reaction involving reactants and products that are
in different phases leads to heterogenious equilibrium. For example, when CaCO3 heated in a
closed vessel, following equilibrium is established:
3

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

At equilibrium, we expected the equilibrium constant
Kc = [CaO][CO2]/[CaCO3]
Both CaCO3 and CaO are pure solid, their concentrations do not change as the reaction
proceed. Because the concentration of a pure solid at a particular temperature is constant and
does not depend on the quantity of solid. Above equation can be rearranged as:
Kc[CaCO3]/[CaO] = [CO2]
At equilibrium at a particular temperature all the terms of the left hand side of the above
equation are constant and will be equal to a new equilibrium constant, Kc, given by
Kc[CaCO3]/[CaO] = Kc = [CO2] mol dm-3
Similarly, the partial pressures of CaCO3 and CaO at a particular temperature are constant, so
Kp is given by
Kp = KpPCaCO3/PCaO = PCO2
i.e. Kp = PCO2 atm.
Calculation of equilibrium Canstant:
Degree of dissociation: The fraction of molecules that dissociate is called degree of
dissociation. It is represented by . The amount of substances in equilibrium mixture formed
from one mole of PCl5 are as follows:
PCl5(g)

PCl3(g) + Cl2(g)

No. of mole before dissociation

1
No. of mole after dissociation
1-
(at equilibrium)
Let the volume of the vessel be V litre,
therefore,

[PCl5] = (1- /V ,

[PCl3] = /V,

Total no. of mole

0
1
1+

[Cl2] = /V

or, Kc = 2/V(1-)

Kc = [PCl3][Cl2]/ [PCl5]

If C in the initial concentration of PCl5, the C is related with V by, C = 1/V, now putting it in
the above equation,
Kc = 2C/(1-
If is very small in comparison with 1, then , Kc = 2C

or, ( Kc /C)

So, the degree of dissociation, increases with the decrease of concentration of the
substance to be decomposed and vice versa.
Similarly, Kp = PPCl3.PCl2/PPCl5

if P is the total pressure, then

PPCl3 = PCl2 = P/(1+,

and

PPCl5 = P(1-/(1+ )

Now putting these values in above equilibrium expression

Kp = 2P/(1If is very small, 1-

1, then , Kp = 2P

or, p/P)

So, the degree of dissociation, increases with the decrease of total pressure and vice versa.
Calculation of from some physical parameters: If one molecule of a substance
dissociates into n number of molecules, then one mole of a substance will give n moles of
dissociated products. So, the total amount of undissociated (1-) and dissociated (n)
substance will be equal to (1-
+ n) moles, or, {1+(n-1)molesThis is given by
(Actual number of molecules)/(Expected number of molecules) = 1+(n-1)
(Actual number of moles)/(Expected number of moles) = 1+(n-1)
(Actual pressure)/(Expected pressure) = 1+(n-1)
(Actual volume)/(Expected volume) = 1+(n-1)
(Expected molecular mass)/ (Measured molecular mass) = 1+(n-1)

Problem: A molar mass determination gave a value of 82.5 g mol-1 for dinitrogen tetraoxide,
N2O4, at 250 C, calculate the degree of dissociation at this temperature.
The dissociation that occurs is
Here, n = 2,

N2O4(g) 2NO2(g)
therefore, Calculated molar mass/ Measured molar mass = 1+

92.0/82.5 = 1+,

Degree of dissociation, = 0.115, i.e. 11.5%