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Chemical Kinetics: Chemical Reactions, Reaction Rate
Chemical Kinetics: Chemical Reactions, Reaction Rate
v=
1 dc A
1 dcB 1 dcP 1 dcQ
=
=
=
a dt
b dt
p dt
q dt
(1)
where cI, I=A, B, P, or Q is the concentration of substance. The IUPAC recommends that the
unit of time should always be the second. Reaction rate usually has the units of mol dm-3 s-1. It is
important to bear in mind that the previous definition is only valid for a single reaction, in a
closed system of constant volume.
The quantity
& =
d
dt
(2)
& =
1 dnA
1 dnB 1 dnP 1 dnQ
=
=
=
a dt
b dt
p dt
q dt
(3)
the concentration is usually in mol/dm3, and k is known as the reaction rate coefficient or rate
constant, although it is not really a constant, because it includes everything that affects reaction
rate outside concentration: mainly temperature but also ionic strength, surface area of the
adsorbent or light irradiation. The exponents n and m are called reaction orders and depend on
the reaction mechanism. The stoichiometric coefficients and reaction orders are very often equal,
but only in one step reactions, molecularity (number of molecules or atoms actually colliding),
stoichiometry and reaction order must be the same.
Since many complex reactions proceed in stages via intermediates (eg. ions, molecules or free
radicals), and, since the measured rate is always that of the slowest step, a knowledge of the
overall order, or better, the separate orders with respect to the individual reactants, often enables
the steps to be elucidated. In such circumstances, the rate of reaction cannot be expressed as a
simple equation.
The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature
dependence of the rate constant, and therefore rate, of a chemical reaction. Actually, the
Arrhenius equation gives "the dependence of the rate constant k of chemical reactions on the
temperature T (in Kelvin) and activation energy Ea", as shown below:
k = Ae E a / RT
(5)
where A is the pre-exponential factor or simply the prefactor and R is the gas constant. The units
of the pre-exponential factor are identical to those of the rate constant and will vary depending
on the order of the reaction. It can be seen that either increasing the temperature or decreasing
the activation energy (for example through the use of catalysts) will result in an increase in rate
of reaction. The activation energy can be interpreted as the minimal energy of the molecules to
undergo reaction. This energy is needed, either, to rupture a chemical bond, eg. in free radical
gas reactions, or to allow rearrangements when the molecules collide.
Taking the natural logarithm of the Arrhenius equation yields:
ln k =
Ea 1
+ ln A
R T
(6)
So, when a reaction has a rate constant which obeys the Arrhenius equation, a plot of ln k versus
T -1 gives a straight line, whose slope and intercept can be used to determine Ea and A. This
procedure has become common in experimental chemical kinetics. To determine the activation
energy of a reaction, one must know a rate constant of the reaction at least at two different
temperatures. Applying the Eq. 6, one can easy express
ln
k1 Ea 1 1
=
( )
k2
R T2 T1
(7)
Zero-order reactions are often seen for thermal chemical decompositions where the reaction rate
is independent of the concentration of the reactant (changing the concentration has no effect on
the speed of the reaction). The rate law for a zero-order reaction is
v=k
(8)
where v is the reaction rate, and k is the reaction rate coefficient with units of concentration/time.
If, and only if, this zero-order reaction 1) occurs in a closed system, 2) there is no net build-up of
intermediates and 3) there are no other reactions occurring, it can be shown by solving a mass
balance for the system that:
v=
dc A
=k
dt
(9)
If this differential equation is integrated it gives an equation which is often called the integrated
zero-order rate law
c A = kt + c A0
(10)
where cA represents the concentration of the chemical of interest at a particular time, and cA0
represents the initial concentration. A reaction is zero order if concentration data are plotted
versus time and the result is a linear function. The slope is the zero order rate constant k.
The half-life of a reaction describes the time needed for half of the reactant to be depleted. For a
zero-order reaction the half-life is given by
t1 =
2
c A0
2k
(11)
The rate law for an elementary reaction that is first order with respect to a reactant A is
v=
dc A
= k .c A
dt
(12)
k is the first order rate constant, which has units of 1/time. The integrated first-order rate law
is
ln
cA
= k .t
c0 A
(13)
A plot of ln cA vs. time t gives a linear function with a slope of k. One can easy express the
concentration cA of reactant A at any time t
c A = c 0 A .e k .t
(14)
The half life of a first-order reaction ( t1 2 ) is independent of the starting concentration and is
given by
ln 2
(15)
k
Kinetics of a first-order reaction characterizes also a radioactive decay, the Eq. 15 describes the
time taken for half the radionuclide's atoms to decay.
t1
(16)
or
v = kc AcB
(17)
supposing the same initial concentration of A and B reactants, c0A=c0B=c0. The differential rate
law for the second-order reaction is then
dc
= k .c 2
dt
= k .t
c c0
(18)
(19)
where c is the concentration of reactant at time t (cA=cB=c), and k is the second-order constant,
which has dimension of concentration-1 time-1 (eg. dm3 mol-1s-1). In this case, a characteristic plot
which will produce a linear function is 1/c vs. time t, with a slope of k (Fig. 1).
The half-life equation for a second-order reaction dependent on one second-order reactant is
t1 / 2 =
1
k .c 0
(20)
Task:
Determine the rate constants and the activation energy of the alkaline hydrolysis of ethyl acetate
using sodium hydroxide.
This experiment illustrates a bimolecular reaction (reacting species are ethyl acetate and sodium
hydroxide):
CH3 COO CH2 CH3 + NaOH CH3 COONa + CH3 CH2 OH
(21)
The initial concentrations of the reacting species are the same c0 A = c0 B .
t [min]
VNaOH
[ml]
t = 20C
c
[mol dm-3]
1/ c
[dm3 mol-1]
5
10
15
20
25
30
35
VNaOH
[ml]
t = 30C
c
[mol dm-3]
1/ c
[dm3 mol-1]
1
= f (t ) at given temperature. Fit the experimental
c
points with a linear function. The slope represents the value of the rate constant k at given
temperature. If the time is in minutes, the unit of the rate constants is dm3 mol-1 min-1.
4. Calculate the activation energy Ea according to Eq. 7 (R = 8,314 J.K-1.mol-1).
3. Use MS Excell to create the dependence