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EQUILIBRIUM
Q; Explain General Expression?
Reactions don't stop when they come to equilibrium. But the forward and reverse
reactions are in balance at equilibrium, so there is no net change in the concentrations
of the reactants or products, and the reaction appears to stop on the macroscopic scale.
Chemical equilibrium is an example of a dynamic balance between opposing forces
the forward and reverse reactions not a static balance.

Let's look at the logical consequences of the assumption that the reaction between
ClNO2 and NO eventually reaches equilibrium.

ClNO2(g) + NO(g) NO2(g) + ClNO(g)

The rates of the forward and reverse reactions are the same when this system is at
equilibrium.

At equilibrium: rateforward = ratereverse

Substituting the rate laws for the forward and reverse reactions into this equality gives
the following result.

At equilibrium: kf(ClNO2)(NO) = kr(NO2)(ClNO)

But this equation is only valid when the system is at equilibrium, so we should replace
the (ClNO2), (NO), (NO2), and (ClNO) terms with symbols that indicate that the
reaction is at equilibrium. By convention, we use square brackets for this purpose. The
equation describing the balance between the forward and reverse reactions when the
system is at equilibrium should therefore be written as follows.

At equilibrium: kf[ClNO2][NO] = kr[NO2][ClNO]

Rearranging this equation gives the following result.

Since kf and kr are constants, the ratio of kf divided by kr must also be a constant. This
ratio is the equilibrium constant for the reaction, Kc. The ratio of the concentrations
of the reactants and products is known as the equilibrium constant expression.

No matter what combination of concentrations of reactants and products we start with,


the reaction will reach equilibrium when the ratio of the concentrations defined by the
equilibrium constant expression is equal to the equilibrium constant for the reaction.
We can start with a lot of ClNO2 and very little NO, or a lot of NO and very little
ClNO2. It doesn't matter. When the reaction reaches equilibrium, the relationship
between the concentrations of the reactants and products described by the equilibrium
constant expression will always be the same. At 25oC, this reaction always reaches
equilibrium when the ratio of these concentrations is 1.3 x 104.

The procedure used in this section to derive the equilibrium constant expression only
works with reactions that occur in a single step, such as the transfer of a chlorine atom
from ClNO2 to NO. Many reactions take a number of steps to convert reactants into
products. But any reaction that reaches equilibrium, no matter how simple or complex,
has an equilibrium constant expression that satisfies the rules in the following:

Rules for Writing Equilibrium Constant Expressions

 Even though chemical reactions that reach equilibrium occur in both directions,
the reagents on the right side of the equation are assumed to be the "products"
of the reaction and the reagents on the left side of the equation are assumed to
be the "reactants."
 The products of the reaction are always written above the line in the
numerator.
 The reactants are always written below the line in the denominator.
 For homogeneous systems, the equilibrium constant expression contains a term
for every reactant and every product of the reaction.
 The numerator of the equilibrium constant expression is the product of the
concentrations of the "products" of the reaction raised to a power equal to the
coefficient for this component in the balanced equation for the reaction.
 The denominator of the equilibrium constant expression is the product of the
concentrations of the "reactants" raised to a power equal to the coefficient for
this component in the balanced equation for the reaction.

Equilibria Expressed in Partial Pressures

Chemists usually study gas-phase equilibria by following the partial pressures of the
gases in the reaction. We can understand why this is possible by rearranging the ideal
gas equation to give the following relationship between the pressure of a gas and its
concentration in moles per liter.

We can therefore characterize the following reaction

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

with an equilibrium constant defined in terms of units of concentration

or an equilibrium constant defined in terms of partial pressures.

What is the relationship between Kp and Kc for a gas-phase reaction? According to the
rearranged version of the ideal gas equation, the pressure of a gas is equal to the
concentration of the gas times the product of the ideal gas constant and the
temperature in units of kelvin.

We can therefore calculate the value of Kp for a reaction by multiplying each of the
terms in the Kc expression by RT.

Collecting terms in this example gives the following result.

Kp = Kc x (RT)-2

In general, the value of Kp for a reaction can be calculated from Kc with the following
equation.

In this equation, n is the difference between the number of moles of products and the
number of moles of reactants in the balanced equation.

Q; Explain Reaction Quotient?


Reaction quotient is the ratio of the concentrations of the products of
a reaction to the concentrations of the reactants.

Each concentration is raised to the power of the stoichiometric coefficient in


the chemical formula.

Finding the Reaction Quotient

In general, for the reaction:

aA + bB → cC + dD

The reaction quotient, Q is


Q = [C]c[D]d/[A]a[B]b
To illustrate how the reaction quotient is used, let's consider the following gas-phase
reaction.

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

The equilibrium constant expression for this reaction is written as follows.

By analogy, we can write the expression for the reaction quotient as follows.

Qc can take on any value between zero and infinity. If the system contains a great deal
of HI and very little H2 and I2, the reaction quotient is very large. If the system
contains relatively little HI and a great deal of H2 and I2, the reaction quotient is very
small.

At any moment in time, there are three possibilities.

1. Qc is smaller than Kc. The system contains too much reactant and not enough
product to be at equilibrium. The value of Qc must increase in order for the reaction to
reach equilibrium. Thus, the reaction has to convert some of the reactants into products
to come to equilibrium.

2. Qc is equal to Kc. If this is true, then the reaction is at equilibrium.

3. Qc is larger than Kc. The system contains too much product and not enough reactant
to be at equilibrium. The value of Qc must become smaller before the reaction can come
to equilibrium. Thus, the reaction must convert some of the products into reactants to
reach equilibrium.

Q; Write the Example of Equilibrium Reaction in


Solid, Liquid and Gases Phases?
Heterogeneous reaction.
For solid:
H o +c =H +CO
2 (g) (s) (g) (g)

For liquid:
Q; Explain extent of Reaction and Equilibrium
Constant?
To predict the extent of a reaction :
From the magnitude of equilibrium constant, we can predict not only the direction of a
reaction but also the extent to which a reaction proceeds.
There may be three values of equilibrium constant:
A very high value of equilibrium constant
A very small value of equilibrium constant
A moderate value of equilibrium constant
When the value of equilibrium constant is very high:
A very high value of equilibrium
constant indicates that the forward is almost complete and in other words we can say that
the reactants are very unstable and they react spontaneously.
For example:
the equilibrium constant for the reaction 2O3 3O2 is very large i.e. 1 x 1055.
This indicates that the forward is almost complete and ozone (O3) is very unstable.
When the value of equilibrium constant is very small:
A very small value of equilibrium
constant indicates that there is very little tendency for the reaction to occur in the forward
direction and in other words we can say that the reactants are very stable.
For example:
the equilibrium constant for the reaction 2HF H2 + F2 is very small i.e.
1 x 10-13.
This indicates that the forward occurs with negligible speed and hydrogen fluoride (HF) is
very stable.
When the value of equilibrium constant moderate:
When the value of equilibrium
constant is neither very high nor very small, we conclude that the reaction occurs both in
forward and backward direction and equilibrium will be attained after certain period of time.
For example:
the equilibrium constant for the reaction N2 +3H2 NH3 is 10, which is a
moderate value.