Name: Onkar Pardeshi

Roll.no: 12
P.R.N: 12011027
Batch-B1

KINETICS OF THE HYDROLYSIS OF ETHYL ACETATE

Theory
CHEMICAL KINETICS
Chemical reactions, reaction rate
Chemical kinetics is the part of physical chemistry that studies reaction rates. The reaction
rate or rate of reaction for a reactant or product in a particular reaction is intuitively
defined as how fast a reaction takes place. For example, the oxidation of iron under the
atmosphere is a slow reaction which can take many years, but the combustion of butane in a
fire is a reaction that takes place in fractions of a second.
Consider a typical chemical reaction:
aA + bB → pP + qQ A
The lowercase letters (a, b, p and q) represent stoichiometric coefficients, while the
capital letters represent the reactants (A and B) and the products (P and Q).
According to IUPAC's Gold Book definition the reaction rate (v) for a chemical reaction
occurring in a closed system under constant-volume conditions, without a build-up of
reaction intermediates, is defined as:
1 dc
v 1 1 dcP 1 dcQ (1)
A  B
dc  
a dt b p d q dt
dt t
where: cI (I= A, B, P. or Q) – is concentration of substance
The IUPAC recommends that the unit of time should be the second always. Reaction rate
usually has the units of mol dm-3s-1. It is important to on mind that the previous definition is
only valid for a single reaction, in a closed system of constant volume.
The quantity:

1
 (2)

d


Dt

defined by the equation:

1
 
dnA 1 1 dnP 1 dnQ (3)
 B
dn  
a dt b p d q dt
dt t
where: nI - designates the amount of substance I (I=A, B, P, or Q) conventionally expressed
in units of mole
ξ is called the 'rate of conversion' (extent of reaction) and is appropriate when the use of
concentrations is inconvenient, e.g. under conditions of varying volume. In a system of
constant volume, the rate of reaction is equal to the rate of conversion per unit volume
throughout the reaction.
The rate law or rate equation for a chemical reaction is an equation which links the reaction
rate with concentrations or pressures of reactants and constant parameters (normally rate
coefficients and partial reaction orders). To determine the rate equation for a particular
system

2
one combines the reaction rate with a mass balance for the
system. For a generic reaction:
A+B→C B
the simple rate equation is of the form:
v  kcacb (4)
A B
the concentration is usually in mol dm-3 and k is 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, ionic strength, surface area of the
adsorbent or light irradiation.
The exponents a and b 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.
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:
 Ea
k  Ae RT
(5)
where: A – is the pre-exponential factor or simply the
prefactor R – is the molar 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   1
Ea  ln A (6)
T
R
So, when a reaction has a rate constant which obeys the Arrhenius equation, a plot of
1
ln k = f  T 
 
gives a straight line, which slope and intercept can be used to determine thr 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 Equation 6, one can easy express:

ln Ea  1  (7)
k2  
1
k  
1
R  T1 T2 
where: k1 – is rate constant correspond to temperature
T1 k2 – is rate constant correspond to
temperature T2
Since the rate of a given reaction depends on the concentration of the reactants, the speed
of the process falls off as the reaction proceeds, for the reactants being continuously
consumed. The reaction is becoming slower and slower but theoretically never ceases. It is,
therefore, not possible to define the general rate of a reaction, and so in practice the rate is
considered at a particular instant. The rate may be defined in any convenient way, usually,
the rate of change of concentration (c) of one of the reactants or products is chosen. The
experimental data then follow a change of concentration with time (t), and the rate at any
instant is given by the tangent to a curve of the plot:
c = f(t)

THE SECOND-ORDER REACTION

depends on the concentrations of one second-order reactant (scheme C and Equqtion 8), or
two first-order reactants (scheme D and Equation 9):
2A → Products C
A + B → Products D
For a second order reaction, its reaction rate is given by:

v  kc2
A (8)
v  kc A c B
(9)

We will deal with the bimolecular reaction – D, supposing the same initial concentration of
A and B reactants:
c0   c0
A c0B
The differential rate law for the second-order reaction is then:
dc
  kc2
dt (10)
Solving the differential equation, one can obtain:
1
 1
  kt (11)
c c0
where: c – is the concentration of reactant at time t → (
 c)
cA
cB
k – is the second-order constant, which has dimension concentration-1time-1 (eg.
dm3 mol-1s-1

In this case, a characteristic plot which will produce a linear function 1

 f (t) with the
is
c
slope = k (Figure 1).
The half-life of reaction describes the time needed for half of the reactant to be depleted. The
half-life of a second-order reaction, which depends on one second-order reactant, is:
1
t 
1 2 [time] (12)
kc0
Figure 1 Plots c = f(t) and 1/c = f(t) for a second-order reaction