Integrated Rate Expression
The concentration dependence of rate is called differential rate
equation. Integrated rate equation gives a relation between directly
measured experimental quantities i.e. concentrations at different times.
The integrated rate equations are different for reactions of different
orders.
The instantaneous rate of a reaction is given by differential rate law
equations.
For example: For a general reaction
aA +bB —–> Products
the differential rate law equation is :
dx/dt = k[A]a [B]b
The differential form of rate law is transformed to integrated form of rate
law by simple mathematics (calculus).
Zero Order Reaction
A reaction is said to be of zero order, if its rate is independent of the
concentration of the reactants. Consider the general zero order reaction:
R ——–>Product
Let [R] be the concentration of the reactant R and k0 is the rate constant
for the zero order reaction. For the zero order reaction, the rate of the
reaction is independent of the concentration of R. Thus
This form of rate law is known as differential rate equation, Rearranging
the above equation,
-d [R] =k0 dt
Integrating the above equation
-∫ d[R] = k0 ∫ dt
-[R]= k0t + I
where I is the constant of integration. The value of I can be calculated
from the initial concentration.
For example: the initial concentration of R be [R]0, at t=0
-[R]0 = k0 × 0 + I
I = – [R]0
– [R] = K0t – [R]0
K0t = [R]0 – [R]
[R] = -K0t + [R]0
If we plot a graph between [R] against t, we get a straight line with slope
as -k0 and intercept equal to [R]0.
Alternatively, rate constant, k0 can be calculated if we know the
concentration of R at any time t and [R]0. Thus,
k0 = { [R]0 – [R] } / t
where [R]0, is the initial concentration of R, [R] is the concentration at
time t.
Alternatively, if the initial concentration of R is ‘a’ moles per litre and let x
moles of reactants get changed to products in time t. Then, concentration
of R left after time t be (a – x)
R ——-> Products
[R]0 =a
[R] = a – x so that
[R]0 -[R] = a- (a-x) = x
k0 = x/t
x=k0 t
The amount of the substance reacted is proportional to the time.
Zero order reactions generally take place in heterogeneous systems. In
such systems the reactant is adsorbed on the surface of a solid catalyst,
where it is converted into product. The fraction of the surface of the
catalyst covered by the reactant is proportional to the concentration of
the reactants at low values.
After certain concentration limit of the reactant, the surface of the
catalyst becomes fully covered. On further increasing the concentration of
the reactant, the reaction rate does not change. The rate becomes
independent of the concentration and, therefore, becomes zero order
reaction.
For example: The decomposition of NH3, on the surface of finely divided
platinum is first order when the pressure (or concentration) of NH3 in the
system is low. However, at higher pressures (or concentrations) when the
surface of the catalyst (finely divided platinum) becomes fully covered
with layer of NH3, molecules, the reaction becomes zero order reaction.
2 NH3 (g) ——–> N2(g) + 3 H2 (g)
where k1 and k2 are constants. When [NH3] is very low, k2[NH3] can be
neglected in comparison to unity so that the above equation becomes
Rate = k1 [NH3]
This reaction is first order in ammonia.
At higher concentration of ammonia (high pressure), we may neglect 1 as
compared to [NH3] so that the equation becomes
Rate = k [NH3]
This means that rate becomes constant and independent of [NH3] and
therefore, becomes zero order reaction.
Some enzyme catalysed reactions are also zero order reactions.