*

• How rapidly reactants are consumed and products are formed?

• How reaction rates respond to change in conditions or the
presence of a catalyst?
•Identification of steps by which a reaction takes place
Thermodynamics Spontaneity of the reaction

Kinetics Rate of the reaction

 EMPIRICAL CHEMICAL KINETICS

Investigation of rate and reaction mechanism

• determining stoichiometry
• determining how the concentrations of the reactants and products are
changing with time

Experimental methods
to study kinetics

Spectrophotometry
pH measurement
Conductivity measurements
Titration
Gas chromatography
Polarimetry
 REACTION RATES
Rate of a reaction taking place in a container
of fixed volume, Rate = |Δ[J]|/Δt

Δ[J] ----- change in molar concentration of

species J occurs during a time interval of Δt

Δ[J] is negative, if J is reactant

Modulus sign -------- all rates are positive

Rates at which the reactants are consumed and

products are formed change in the course of a
reaction ---- necessary to consider instantaneous rate ------- rate at a specific
instant

Instantaneous rate of consumption of a reactant is the slope of a graph of its

molar concentration plotted against the time

Slope evaluated as the tangent to the graph at the instant of interest (reported
as positive quantity)

Steeper the slope, greater the rate of the reaction

 RATE OF A CHEMICAL REACTION
Various reactants in a given reaction are consumed at different rates
Various products are formed at different rates
Unique rate ()
----- in terms of the stoichiometric numbers (J) appear in the chemical reaction

----- stoichiometric numbers ----- positive for products and negative for reactants
 = (1/ J) (Δ[J]/Δt)
Modulus sign is removed ----- rate is always positive

Time interval, Δt, allowed to become infinitesimal,

 = (1/J) (d[J]/dt)

Formation of NH3(g): N2(g) + 3H2(g)  2NH3(g)

rate of formation of NH3 is 1.2 mmol dm-3 s-1 under a certain set of conditions

Unique rate of the reaction in terms of change in concentration of NH3

 = (1/ NH3) (d[NH3]/dt) = (1/2)(1.2 mmol dm-3 s-1 ) = 0.6 mmol dm-3 s-1
 EXPERIMENTAL TECHNIQUES
I0
Beer - Lambert Law: A   L [ J ]  log   log T
I
(A) Real time analysis
Composition of a system is analysed while the reaction is in
progress by direct spectroscopic observation of the reaction mixture

Flow Method Different points along the tube

correspond to different times after
the start of the reaction

Large volume is required
Spectrophotometric determination
of the composition at different
positions along the tube is
equivalent to the determination of
the composition of the reaction
mixture at different times after the
mixing
Stopped-flow Technique
Two solutions are mixed rapidly (in
less than 1 ms) – flow is turbulent

After mixing, the flow comes to a

stop, because the plunger stops.

filling of the chamber corresponds to the sudden creation of an initial sample of

the reaction mixture

After mixing, the flow comes to a stop. The reaction mixture can be measured
with time using spectrometer

Lower volume is required (economical)

Flash photolysis (for very fast reactions)
---------- Sample is exposed to a brief flash of light (using laser) that initiates the
reaction and then monitored spectrophotometrically

(B) Quenching methods

 RATE LAWS AND RATE CONSTANTS
Rate of reaction is proportional to molar concentrations of the
reactants raised to a simple power

Instantaneous rate, v = kr[A][B]

kr ------ rate constant ----- characteristic of the reaction being studied -----
independent of the concentration of the species taking part in the reaction,
but depends on temperature

[A], [B] ---- molar concentrations (partial pressures in the case of

gaseous reactants) of the reactants

Rate law ------ experimentally determined equation ----- equation that

expresses the rate of the reaction in terms of the molar concentrations (or
partial pressures) of the species in the overall reaction
v = kr[A][B]

v = kr[A]
 REACTION ORDER
classification of a reaction is based on their order, the power to which
concentration of a species is raised in the rate law

Reactions belonging to the same class have similar kinetic behaviour – their rates
and the concentration of the reactants and products vary with composition in a
similar way
v = kr[A][B]
first order with respect to A, first order with respect to B (over all second order)

v = kr[A]2 second order

overall order of a reaction with a rate law of the form

v = kr[A]a[B]b[C]c…. is a + b + c +…
NO2(g) + CO(g)  NO(g) + CO2(g)
Rate law : v = kr[NO2]2
second order in NO2(g) and no other species is involved in the rate law

rate of the reaction is independent of the concentration of CO, provided that

some CO is present --- the reaction is zeroth-order in CO
[CO]0 = 1
 REACTION ORDER
A reaction need not have an integral order ---- many gas phase reaction do not
v = kr[A]1/2[B]

half order in A first order in B 3/2 order overall

If a rate law is not of the form v = kr[A]a[B]b[C]c….. the reaction does not have
an overall order
ka[H2][Br2]1/2
H2(g) + Br2(g)  2HBr(g) v=
[Br2] + kb[HBr]
Although the reaction is first order in H2, it has an indefinite order with respect
to both Br2 and HBr, and an indefinite order overall (Two rate constants are
needed to express its rate)

A rate law is established experimentally and cannot in general be inferred

from the chemical equation for the reaction

H2(g) + I2(g)  2HI(g) v = kr[H2][I2]

Same stoichiometry as the reaction of hydrogen and bromine, but with a much
simpler rate law
 REACTION ORDER

A typical rate law for the action of an enzyme E on a substrate S

kr[E][S]
v= KM = constant (not a rate constant)
[S] + KM
first order in the enzyme
does not have a specific order with respect to the substrate

Under certain circumstances a complicated rate law without an overall order

may simplify into a law with definite order

Eg:
if the substrate concentration in the enzyme catalysed reaction is so low
that [S] << KM , then ignore [S] in the denominator
kr[E][S]
v=
KM
first order in E and first order in S and overall second order
 DETERMINATION OF RATE LAW

Isolation method
v = kr[A][B]2
--- all reactants except one are present in large excess
--- if reactant B is in large excess, it is a good approximation to take its
concentration as constant throughout the reaction (does not change)

approximate [B] by its initial value [B]0 (excess)

v = kr,eff [A]
kr,eff = kr[B]02

the true rate law has been forced into first-order ------ the effective rate
law is classified as pseudofirst order
kr,eff = effective rate constant for a given fixed concentration of B

If A is in excess: v = kr,eff[B]2 (pseudosecond order rate law)

kr,eff = kr[A]0
 DETERMINATION OF RATE LAW
Method of initial rates - often used in conjunction with the isolation method

------- the instantaneous rate is measured at the beginning of the reaction for
several different initial concentrations of reactants

If the initial rate is

--------- doubled when the concentration of an isolated reactant A is doubled ---
the reaction is first order in A
---------- quadrupled when the concentration of an isolated reactant A is
doubled ------ the reaction is second order in A

rate law for a reaction with A isolated , v = kr[A]a

initial rate of the reaction, v0 = kr,eff[A]0a

Taking logarithms,
log v0 = log kr,eff + a log [A]0
For a sereis of initial concentrations, a plot of logarithms of initial rates against
logarithms of initial concentrations of A, log v0 vs log [A]0 ---- straight line
with slope a (order of the reaction with respect to A)
 INTEGRATED RATE LAWS
Rate law expresses the rate of the reaction at a given instant (when the reaction
mixture has a particular composition)

Integrated rate law is an expression that gives the concentration of a species

as a function of the time
------- predict the concentration of a species at any time after the
start of the reaction.
------- help to find the rate constant and order of the reaction

ZEROTH ORDER REACTIONS

A  products
Rate of a zeroth order reaction is constant

Rate of consumption of A = kr
Amount of reactant consumed by a time t is the rate of its consumption multiplied
by the time for which the reaction has been in progress

Concentration of A after a time t, [A]t = [A] 0 - krt

------ applies until all the reactants has been used up at t = [A] 0/kr
 INTEGRATED RATE LAWS

FIRST ORDER REACTIONS

For a reaction A  products: first order rate law, v = kr[A]

integrated rate law ln ([A]/[A] 0) = -krt

[A]0 --- initial concentration [A] ---- concentration at time t

ln ([A]t/[A]0) against t is a straight line if the reaction is first order

slope = -kr

[A] = [A] 0e-krt

exponential decay - common feature of all first

order reaction

the concentration of the reactant decays

exponentially with time
 INTEGRATED RATE LAWS
SECOND ORDER REACTIONS OF TYPE A  PRODUCTS
v = kr[A]2
second order rate law
If the concentration of A at t = 0 is [A]0

(1/[A]0 ) - (1 /[A]t) = -krt

Plot of 1 /[A]t against t is a straight line

Slope --- rate constant
[A]0
[A]t =
1 + krt[A]0

Concentration of A at any time after the

start of the reaction
 INTEGRATED RATE LAWS

Although the initial decay of a second order reaction may be rapid, the
concentration approaches zero more slowly than in a first-order reaction
with the same initial rate

Reactants that decay by a second order process die away more slowly at low
concentrations than would be expected if the decay were first order
 HALF-LIVES
Half-life, t1/2, of a reactant is the time it takes for the concentration of the
species to fall to half its initial value
For a reaction A  products: first order rate law , v = kr[A]

integrated rate law ln ([A]/[A] 0) = -krt

Half life of A that decays ------ substitute [A]t = [A]0/2 and t = t1/2

½[A]0
krt1/2 = -ln = ln 2
[A]0

t1/2 = (ln 2)/kr

for a first order reaction, the half-life of

a reactant is independent of its
concentration
If the concentration of A at some arbitrary stage of reaction is [A], then the
concentration will fall to ½[A] after an interval of (ln 2)/kr whatever the actual
value of [A]
 HALF-LIVES

In each successive period of duration t1/2,

the concentration of a reactant in a
first-order reaction decays to half its value
at the start of that period

After n such periods, the concentration

is (1/2)n of its initial concentration

For a second order reaction A  products

1/[A] = 1/[A]0 + krt
Half life of a reactant in a second order
1/([A]0/2) = 1/[A]0 + krt1/2 reaction varies with the initial concentration

Half life increases as the concentration of the

t1/2 = 1/([A]0kr) reactant fall during the reaction
 TEMPERATURE DEPENDENCE OF REACTION RATES

plot of ln kr vs 1/T gives a straight line

kr = rate constant
T = temperature (K) at which kr is measured

ln kr = intercept + slope x (1/T)

Arrhenius equation
ln kr = ln A – (Ea/RT)
kr = Ae–Ea/RT
A (has the same units as kr) ---- pre-exponential factor
Ea(molar energy, kilojoules per mole) ----- activation energy
Both A and Ea are called Arrhenius parameters

High Ea corresponds to a reaction rate that is very sensitive to temperature

(Arrhenius plot has a steep slope)
A reaction with zero Ea has a rate largely independent of temperature
Recombination of radicals in gas phase
 TEMPERATURE DEPENDENCE OF REACTION RATES

Once the activation energy of a reaction is known, the value of a rate

constant kr,2 at a temperature T2 from the value of kr,1 at another
temperature T1 can be found out

ln kr,1 = ln A – Ea/RT1

ln kr,2 = ln A – Ea/RT2

ln kr,2 – ln kr,1 = – Ea/RT2 + Ea/RT1

ln (kr,2 /kr,1) = (Ea/R) (1/T1 – 1/T2)

 Reaction Mechanisms
Elementary reactions
------ a series of steps in a reaction ------ which involves only one or
two molecules or ions
--------- writing chemical equations without displaying the physical
state of the species

Molecularity of an elementary reaction is the number of molecules

coming together to react.

Unimolecular reaction ----- a single molecule shakes itself apart

or shakes its atoms into a new arrangement (isomerization of
cyclopropane to propene)

Bimolecular reaction – two molecules collide and exchange

energy, atoms or group of atoms (Reaction between H and Br2)
Order of a reaction is an empirical quantity ------ obtained by the inspection of the
experimentally determined rate law

Molecularity of a reaction refers to an individual elementary reaction that has been

postulated as a step in a proposed mechanism
 FORMULATION OF RATE LAWS – STEADY STATE APPROXIMATION

If it is proposed that a particular reaction is the outcome of a sequence of

elementary steps, how to arrive at the overall rate law implied by the
mechanism?
2NO(g) + O2 (g)  2 NO2(g) v = kr[NO]2[O2]

Termolecular reaction in a single step is rare

Proposed reaction mechanism

STEP 1: Two NO molecules combine to form a dimer

NO + NO  N2O2 Rate of formation of N2O2 = ka[NO]2

Each step in a proposed mechanism in principle has its reverse

N2O2  NO + NO Rate of decomposition of N2O2 = ka’[N2O2]

STEP 2: An O2 molecule collide with the dimer and results in the formation of
NO2
N2O2 + O2  NO2 + NO2 Rate of consumption of N2O2 = kb[N2O2][O2]

Reverse of this reaction is likely to be very slow and can be ignored

Rate law for the formation of product (directly from step 2)

Rate of formation of NO2 = 2 kb[N2O2][O2]

because two NO2 is formed in each reaction event

not the final acceptable overall rate as it involves intermediates

(an intermediate is any species that does not appear in the overall reaction
but which has been invoked in the mechanism)

Acceptable rate law for an overall reaction ------- solely in terms of the species
that appear in the overall reaction

Net rate of formation of N2O2 = ka[NO]2 - ka‘[N2O2] - kb[N2O2][O2]

Formation term occurs with positive sign

Steady state approximation

Concentration of all intermediates remain constant and small throughout the
reaction

Net rate of formation of the intermediate species N2O2 = 0

0 = ka[NO]2 - ka‘[N2O2] - kb[N2O2][O2] [N2O2] = ka[NO]2 / (ka’ + kb[O2])

[N2O2] = ka[NO]2/(ka’ + kb[O2])

Rate of formation of NO2 = 2kb[N2O2][O2] = 2kakb[NO]2[O2]/(ka’+ kb[O2])

If rate of decomposition of dimer N2O2 is more than its rate of reaction with O2,
ka’[N2O2] >> kb[N2O2][O2] ka’ >> kb[O2]

Rate of formation of NO2 = (2kakb/ka’)[NO]2[O2]

v = kr[NO]2[O2] (third order form) kr = (2kakb/ka’)

each of the rate constants may increase with temperature, but may not be true
for kr itself

ka’ >> kakb, the kr will decrease and the reaction go slowly as temperature is raised

N2O2 dimer shakes itself apart so quickly at the higher temperature

Opportunity for it to react with O2 is reduced and products are formed slowly
 RATE DETERMINING STEP
Rate of formation of NO2 = 2kakb[NO]2[O2]/(ka’ + kb[O2])

suppose
step 2 is faster: ka’ << kb[O2] (to achieve this, increase [O2])

Rate of formation of NO2 = 2kakb[NO]2[O2]/kb[O2] = 2ka[NO]2

second order in NO concentration of O2 does not appear in the rate law

N2O2 reacts with O2 (high concentration) as soon as it is formed

under these conditions, the rate of formation of NO2 is determined by

the rate at which N2O2 is formed ---- rate determining step ----- the slowest step
in a reaction mechanism and which controls the rate of the overall reaction