Pak Hanif Reactions Approaching Equilibrium
Pak Hanif Reactions Approaching Equilibrium
Pak Hanif Reactions Approaching Equilibrium
Reactions
Reaction rates depend on the concentration of reactants (and products) in
characteristic ways that can be expressed in terms of differential equations
known as rate laws. The solutions of these equations are used to predict the
concentrations of species at any time after the start of the reaction.
The rate of a chemical reaction might depend on variables under our control,
such as the pressure, the temperature, and the presence of a catalyst, and
we may be able to optimize the rate by the appropriate choice of conditions.
The study of reaction rates also leads to an understanding of the
mechanisms of reactions, their analysis into a sequence of elementary
steps.
Reactions Approaching Equilibrium
Because all the laws considered so far disregard the possibility that the
reverse reaction is important, none of them describes the overall rate when
the reaction is close to equilibrium. At that stage the products may be so
abundant that the reverse reaction must be taken into account.
In practice, however, most kinetic studies are made on reactions that are far
from equilibrium, and the reverse reactions are unimportant.
We can explore the variation of the composition with time close to chemical
equilibrium by considering the reaction in which A forms B and both forward
and reverse reactions are first-order (as in some isomerization). The
scheme we consider is
Reactions Approaching Equilibrium
=
= []
The concentration of A is reduced by the forward reaction (at a rate k[A]) but
it is increased by the reverse reaction (at a rate k[B]). The net rate of
change is therefore
[]
= + []
If the initial concentration of A is [A]0, and no B is present initially, then at all
times [A] + [B] = [A]0. Therefore,
Reactions Approaching Equilibrium
[]
= + 0
[]
= + + 0
The solution of this first-order differential equation is
+
+
= []0
+
Reactions Approaching Equilibrium
=
Reactions Approaching Equilibrium
Relaxation methods
The term relaxation denotes the return of
a system to equilibrium. It is used in
chemical kinetics to indicate that an
externally applied influence has shifted the
equilibrium position of a reaction, normally
suddenly, and that the reaction is adjusting
to the equilibrium composition
characteristic of the new conditions. We
shall consider the response of reaction
rates to a temperature jump, a sudden
change in temperature.
Reactions Approaching Equilibrium
[2 ]
= 1 2 + 2 [ + ][ ]
= 1 2 + + 2 [ + ] [ ]
= 1 + 2 [ + ] + [ ] 1 2 + 2 [ + ] [ ] + 2 2
neglecting x2
+
1
= 1 + 2 [ ] + [ ] =
because +] ]
+
[ [
=
with = 1 mol/dm3 and molar concentration of pure water is 55.6 mol dm3,
so 2 / = 55.6 and we write K = 1.81 x 10-16, we obtain
1
= 2 + 2
hence
1 1
2 = =
+ 2 (3.7 105 )(1)(2.0 107 )
Answer 1
= [] +[] + [] +[]
The Temperature Dependence of Reaction Rates
ln = ln
The parameter A, which corresponds to the intercept of the line at 1/T = 0 (at
infinite temperature), is called the pre-exponential factor or the frequency
factor. The parameter Ea, which is obtained from the slope of the line
(Ea/R), is called the activation energy. Collectively the two quantities are
called the Arrhenius parameters