General Chemistry

Chapter 12 The kinetics of the chemical reaction

Chemical kinetics deals with the rate by which (“how fast”) reagents
are being transformed into reaction products and is about the factors
that influence this reaction rate.
The reaction rate
The rate of a reaction (v from velocity) is defined as the increase of
the concentration of one of the reaction products or the decrease of
the concentration of one of the reagents per time unit. The unit for v
is mole L-1time-1.

d(reaction product) d(reagent)

v= = -
dt dt
General Chemistry

2N2O5(g) → 4NO2 (g) + O2 (g)

d[O2] 1 d[NO2] 1 d[N2O5]

v= = = -
dt 4 dt 2 dt

The NO2 is formed four times as fast as the dioxygen.The N2O5

disappears twice as fast as the dioxygen is formed.
reaction rate = slope of the curve describing the change of the
concentration of the reagent/the reaction product.
General Chemistry

Initial rate Vo
is slope for t = 0

The slope (rate)

decreases as time
goes on
 General Chemistry

The rate equation

reaction equation : H2O2 + 3I- + 2H+ → I3- + 2H2O

Initial conc. (M) initial formation rate vo of I3-
(mol L-1s-1)
[H2O2] [I-] [H+ ]
0.010 0.010 0.00050 1.15 x 10-6
0.020 0.010 0.00050 2.30 x 10-6
0.010 0.020 0.00050 2.30 x 10-6
0.010 0.010 0.00100 1.15 x10-6

rate equation : v = k [H2O2]1[I-]1[H+ ]0

 General Chemistry

k = rate constant is independent of the concentrations but depends on the

temperature.

The order of the reaction relative to one of the reagents equals the power
to which the concentration of that reagent should be raised in the rate
equation.

In the previous example the order towards [H2O2] and [I-] is 1, and
towards [H+ ] it is 0.

The global order of the reaction is the sum of the orders in the reaction
equation (in this case 2 - a second order reaction)
 General Chemistry

First order reactions

A first order reaction is a reaction with global order equal to 1.

e.g. 2N2O5(g) → 4NO2 (g) + O2 (g)
v = k[N2O5]

A pseudo-first order reaction is a reaction of higher order that is carried out in

such a way that the reaction behaves like a first order reaction
e.g. H2O2 + 3I- + 2H+ → I3- + 2H2O
large excess [I-] : constant concentration [I-] so
v = k [H2O2][I-] = kpseudo [H2O2]
 General Chemistry

Assume the initial concentration of a reagent that disappears according to a first

order reaction is a. After a certain time a-x will be left of the initial concentration.
The rate at any moment is given by the equation :
v = k(a-x) = -d(a-x)/dt or also d(a-x)/(a-x) = -k dt
Integration of time 0 (x=0) to time t gives :
ln (a-x) = ln a - kt
This equation agrees with a straight line with slope -k (so descending line).
It is possible to demonstrate that a reaction occurs with (pseudo)first order kinetics
by plotting the logarithm of the concentration of the reagent in the reaction
equation in function of time. Only when there is a linear relationship we are dealing
with a first order reaction.
General Chemistry

[A ] = a-x [A]0 = a
 General Chemistry

Second order reactions

A second order reaction is a reaction with global order 2.

example : 2NO2 (g) → 2NO + O2 (g)

v = k[NO2]2 ; similarly can be derived
v = k(a-x)2 = -d(a-x)/dt of d(a-x)/((a-x)2 = -k dt
after integration:
1 1
= + kt
a-x a

so if the plot of 1/a-x in function of time gives a straight line = second order
kinetics. The slope is k (ascending straight line)
General Chemistry

[A ] = a-x [A]0 = a
 General Chemistry
Half life

The half life of a reagent is the time needed to reduce the concentration
of that reagent to half of its initial value.

For a first order reaction this means :

ln a/2 = ln a - kt1/2 so kt1/2 = ln 2 meaning t1/2 is also constant = (ln2)/k
The half life can be derived from the graph of a-x in function of the time.

The half life of a second order reaction is dependent of the initial

concentration :
kt1/2 = 1/a
General Chemistry

first order reaction with constant half life

 General Chemistry
Influence of temperature

Arrhenius equation: k = A e-Ea/RT

A = Arrhenius constant, Ea = activation energy (kJ mol-1)
R = gas constant (8.31 J K-1mol-1), T = temperature (in K)
logarithmic : ln k = lnA – Ea/RT
so linear relation between lnk and 1/T, slope is –Ea/R
If Ea and k1 are known at a certain temperature, k2 at another
temperature can be simply derived:

Ea 1 1
k -
ln 1 = -
T1 T2
k2 R
General Chemistry
Reaction profile

Theoretical models

The collision theory

A reaction occurs after a collision

between the reagents (X and Y).
Only collisions with sufficient
kinetic energy and the right
orientation are efficient.
 General Chemistry

The reaction rate = R x f x p

R = collision frequency, proportional to [X][Y] ;
f = energetic = e-Ea/RT
0 < f < 1 (fraction of collisions with sufficient kinetic energy)
p = steric factor
0<p<1
(p = fraction
collisions
with the right orientation)
Figure of kinetic energy-(Maxwell)
distribution at different
temperatures

f is proportional to the green cut-

off(s)
 General Chemistry

Theory of the transition state

reagents transition state products

The equilibrium between reagents and transition

state (TS) is characterized by the equilibrium
constant K‡ :
[TS]
K‡
=
[reagentia]
 General Chemistry

v(formation of products) ~ [TS] ~ K‡ [reagents]

v(formation of products) ~ k[reagents]

so k ~ K‡ (a) ; Also K‡ = e-ΔG‡/RT

thus k ~ eΔS‡/R e-ΔH‡/RT = eΔS‡/R e-Ea/RT (ΔH‡ = Ea)

cf Arrhenius k = A e-Ea/RT
General Chemistry

ΔG‡ is always positive

DG = DG - DG°

ΔH‡ is always positive H = H - H°

ΔS‡ can be positive or negative

S = S - S°
 General Chemistry
The reaction mechanism

Elementary reactions
Many reactions occur in a number of steps, called elementary reactions.
In these elementary reactions, 1 or 2 reacting particles take part.
Intermediates : short lived particles that quickly react away in other elementary
reactions. E.g. : reaction of hydrogen peroxide with iodide :

step 1 I- + H2O2 → IO- + H2O

step 2 IO- + H+ → HIO
step 3 HIO + I- → I2 + I-
step 4 OH- + H+ → H2O
step 5 I2 + I- → I3-
 General Chemistry
The step in the reaction mechanism that detemines the rate of the
global reaction is called the rate determining step.
In the reaction of hydrogen peroxide with iodide this is the first step.
The rate of the first step = global rate = kstep 1 [I-][H2O2]

The molecularity of a reaction is the number of reacting particles in

that (elementary) reaction. In a unimolecular reaction only one
reagent occurs : so first order reaction. The Ea is obtained by collisions
of the reagent with the solvent or any other particles in solution.
In a bimolecular reaction, two particles are colliding with each other,
causing exchange of energy and atoms. Elementary bimolecular
reaction : second order reaction.
 General Chemistry
Chain reactions

In a chain reaction, in some elementary steps reactive intermediates

are formed. These can cause a chain process.
Initiation step : elementary step in which these reactive intermediates
are formed.
Propagation step : reaction of intermediates with other substances to
new intermediates
Termination step : intermediates react with each other without the
formation of new intermediates
 General Chemistry

The reaction of dihydrogen with dibromine :

overall :H2(g) + Br2(g) → 2HBr (g)
The reactive intermediates are radicals (atomic H and Br)

Initiation : Br2 → 2Br (thermally or

photochemically)
Propagation : Br + H2 → HBr + H
H + Br2 → HBr + Br

Termination : 2Br → Br2

2H → H2
H + Br → HBr
General Chemistry
 General Chemistry
Explosions

An explosion may be the consequence of a fast increase of the

reaction rate (exothermic reaction) by a rise of the temperature.
Also chain reactions may occur explosively if the amount of reactive
intermediates increases strongly in the propagation
Both mechanisms are present in the explosive reaction between
dihydrogen and dioxygen : 2H2 (g) + O2 (g) → 2H2O (g)
(simplified mechanism of chain reaction)
initiation : H2 → 2H
propagation : H + O2 → HO + O
O + H2 → HO + H (increase of number of radicals)
 General Chemistry
Catalysed reactions

Slow reactions may be speeded up by increasing the temperature.

(Arrhenius : k = A e-Ea/RT )
It is not always possible or convenient (energy cost) to obtain a
sufficienty high temperature.
Another possibility is the use of a catalyst = substance that accelerates
the reaction without being used up itself.
The catalyst has an effect on the reaction mechanism : other reaction
pathway with lower activation energy.
At the same temperature in the catalysed process, more collusions will
be effective than in the non-catalysed reaction.
 General Chemistry
Homogeneous catalysis

The catalyst is in the same phase as the reagents. Example : decomposition

of formic acid is very slow at room temperature without catalyst :
HCOOH (l) → CO(g) + H2O(l)
The reaction is catalysed by concentrated H2SO4 (3 steps)
step 1 : HCOOH + H2SO4 → HCOOH2+ + HSO4-
step 2 : HCOOH2+ → HCO+ + H2O
step 3 : HCO+ + HSO4- → CO + H2SO4

In Nature, homogeneous catalysis occurs a lot : enzymatic reactions in

plants and animals. An enzyme is a biological catalyst (mostly peptide-
based).
General Chemistry

zonder katalysator met katalysator

General Chemistry
Heterogeneus catalysis

The catalyst is in another phase as the reagents.

Often in industry gaseous reagents are absorbed at the surface of a
solid catalyst. E.g. Pt catalyzes reaction between dihydrogen and
dioxygen. The catalyst in a car transforms NO, CO and not combusted
hydrocarbons into N2, CO2 and water.
Other example: decomposition of H2O2 with Co(II) hydroxide in basic
medium.
step 1 : HO2- + 2Co(OH)2(s) + H2O → OH- + 2Co(OH)3 (s)
step 2 : 2Co(OH)3 (s) + HO2- → 2Co(OH)2(s) + O2 + OH- + H2O
The global reaction is the same as the non-catalysed reaction :
2HO2- → O2 + 2OH-
General Chemistry
General Chemistry
General Chemistry
Assignments chapter 12

1. Discuss the factors that determine the reaction rate according to the
collision theory.
2. Discuss the following phrases:
a) The Arrhenius constant A agrees with the value that the rate constant
would have if all collusions were sufficiently energetic.
b) There is a relation between the Arrhenius constant and the orientation of
the reagents during a collusion
c) There is a relation between Arrhenius constant and the entropy of
activation
General Chemistry
3. The bromate ion and the bromide ion react in acidic medium to dibromine.
The initial rate of formation of dibromine (v) is determined in function of the
initial concentrations (in mol/L) of the bromate ions, the bromide ions and
the protons :
[BrO3-] [Br-] [H+] v (mol/L.s)
0.10 0.10 0.10 8.0 10-4
0.20 0.10 0.10 1.6 10-3
0.20 0.20 0.10 3.2 10-3
0.10 0.10 0.20 3.2 10-3
Determine the form of the rate equation.
General Chemistry

4. Aspirin is metabolized (broken down) in the body by a first order

reaction. The half life is three hours. Calculate how many mg aspirin
remains five hours after taking a tablet containing 200mg aspirin.