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Pseudo First Order Reactions

# Pseudo First Order Reactions

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Published by: giridharraju on Dec 07, 2008

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04/13/2011

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Pseudo First Order Reactions
There are circumstances where a second order reaction might appear, in an experiment, to be firstorder. That is when one of the reactants in the rate equation is present in great excess over theother in the reaction mixture.As an example, let's look again at the mixed second order rate law that we treated in the lastsection.In the last section we had the rate law, , with a reaction whose stoichiometryis,2A + B → P + etc (P = product).Sometimes [A]
o
> > [B]
o
.For example, say we prepare the system such that,[A]
o
= 2.0 M, and[B]
o
= 0.001 M.Then, when the reaction has run to completion, (at time = infinity),[A]
inf
= [A]
o
− 2 [B]
o
= 2.0 − 0.001 = 1.998 ≈ 2.0.So [A] is approximately constant throughout the entire reaction.Then the rate law becomes,, (1)which is effectively a first order rate equation. This rate equation has the solution,, (2)where the "effective" first order rate constant is
[A]
o
.You can actually solve this problem as a mixed second order rate problem, as we did in the lastsection, but it is a lot more work.Pseudo first order reactions are sometimes used to find the rate constant of a second order reaction when one of your two components is very expensive and the other one is relativelycheap. You can use an excess of the inexpensive reagent and use a small amount of the expensiveone. Notice that you can still obtain the second order rate constant by dividing the effective firstorder rate constant by the concentration of the excess component.
(3) Simple Third Order Reaction
A simple third order rate law, where component B is a reactant, has the form,, (3)

which can be rearranged for integration as,, (4)and integrated to give,, (5)or, in simplified form,(6) . (6)As usual we define half-life as the time when [B] = ½ [B]
o
, which gives,, (7), (8). (9) Note that in this case the half-life depends on [B]
o2
as opposed to depending on [B]
o
for a simplesecond order reaction, and being independent of [B]
o
for a first order reaction.
Techniques for finding rate laws (NOT from the balanced equation.)
We emphasize that the form of the rate law for a chemical reaction
cannot
be deduced from the balanced reaction equation. It takes new experimental data (or new theories) to get the rate lawfor a reaction. We will mention three methods for determining the rate law for a reaction fromexperimental data.
1. Half-lives
Run several experiments at different initial concentrations to see how the half-life depends on[B]
o
If the half-life does not depend on the initial concentration then the reaction is first order.If the half-life of the reaction is proportional to 1/[B]
o
then the reaction is simple second order. If the half-life is proportinal to 1/[B]
o2
then the reaction is simple third order, and so on. Mixedsecond and third order reactions are more complicated, but half-lives can be defined for thesecases and the dependence of the half-life on [A]
o
and [B]
o
can be used to determine the rate law.

2. Initial Rate Method
The initial rate of a reaction is the reaction rate at
= 0. We will designate the initial rate by
R
o
.One can run several experiments and measure the rate as soon as possible after the reagents have been mixed to determine the initial rates.For example, assume that
R
o
= k[A]
x
[B]
y
[C]
z
.Run several experiments at different starting concentrations and measure
R
o
in each case. We can place the data in a table as follows:[A]
o
[B]
o
[C]
o

R
o
0.010 0.10 0.20 0.04 for experiment number 1,0.020 0.10 0.20 0.08 for experiment number 2,0.010 0.20 0.20 0.16 for experiment number 3, and0.010 0.10 0.10 0.04 for experiment number 4.Compare the first and second experiments. We double [A]
o
and the rate doubles. It looks like
x
=1. Compare the first and third experiments. We double [B]
o
and the rate increases by a factor of 4. It looks like
y
= 2. Notice that there is no change in the rate when we cut [C]
o
in half so therate must not depend on C. This says that
z
= 0.Thus we determine that the rate = k[A]
1
[B]
2
[C]
0
.We don't have to use simple whole number ratios for the concentrations, we can do italgebraically. Take the ratio of the rates from two successive experiments,. (10)To find the exponent of [A] make all the concentrations in the second experiment the same as inthe first experiment except [A]. This gives,. (11)Take the logarithm of both sides to get,, (12)and solve for
x
to get,. (13)This process can be repeated for each of the components in turn.

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