RATES OF CHEMICAL

REACTIONS
kinetics 1
 rates of reaction
 reaction rate studies:

 help predict the speed of a reaction

 understand the reaction mechanism

@ therefore  we have to look into :


reaction rate measurements and interpretation
 rates of reaction
Recall: kinetic reaction studies -

= requirement: establish the stoichiometric reaction

and identify any side reactions

= basic data: concentrations of reactants and

products at different time after reaction

= temperature constant throughout the reaction time

- chemical reactions are sensitive to temperature
 rates of reaction
 Methods of monitoring
? how to measure the change in concentration?
 if at least one of the components is a gas
= total pressure of the system at constant volume
 spectrophotometry
- one substance has a strong characteristic
absorption in an accessible region
= measure the intensity of absorption
others: conductivity, pH, titration, mass spec., GC,
NMR, polarimetry
 rates of reaction
Composition may be analyzed while the reaction
is in progress

(a) withdrawal of a small sample

(b) bulk solution

 rates of reaction
 Techniques in measuring -
 quenching method - by dilution
- by sudden cooling
- by rapid neutralization
 flow method
- reactants are mixed as they flow together in a
chamber

monitor reaction along the tube
= movable spectrophotometer
 rates of reaction
 Techniques in measuring -
 stopped-flow technique
= solutions mixed rapidly in a chamber fitted
with a stopping syringe
 flash photolysis
= gaseous or liquid sample is exposed briefly
to a photolytic flash of light

the contents are monitored
 rates of reaction
 RATES OF REACTIONS

 Consider the reaction : A + B  C + D

assumptions: a. there is only one step

b. system is homogeneous
c. behaves ideally

= after mixing - at certain time, t,

- concentration of species are [A], [B], [C], and [D]
 rates of reaction
 the rate of reaction
= the rate of formation of product C or D
or the rate of decomposition of reactant A or B
 may be expressed as,
d[A]
rate of disappearance of A = 
dt
d[C]
rate of formation of C =
dt
 rates are positive values
 for this reaction - based on the stoichiometry
the rate of formation of C
= rate of disappearance of A
 rates of reaction
 Suppose the reaction is :
A + 2 B  3 C + D
* rate of formation of C
= 3 x rate of disappearance of A
d[A] 1 d[B] 1 d[C] d[D]
specifically,    
dt 2 dt 3 dt dt
in general rate 1 d[J]
nj dt
 there is only one rate for the entire reaction
 rates of reaction
 Factors affecting the rate of the reaction:

= Temperature and Pressure

= Presence of catalyst

= Concentration of reactants

= Nature of reactants
 rates of reaction
 RATE LAW AND RATE CONSTANT
rate law : expresses the rate of reaction as a
function of the concentrations of all the species
present in the overall chemical equation for the
reaction
 Rate Laws -
practical point of view: predict the rate of reaction
from the composition knowing the rate and rate
constants (or vice versa)
theoretical point of view: guide to the mechanism of
the reaction
 rates of reaction
 Consider the reaction: A + B  products
rate  [A][B]
or rate = k[A][B]
where k is the proportionality constant known as
RATE CONSTANT for the reaction
k : independent of concentration
dependent on temperature

 RATE LAW of the reaction

= experimentally determined equation
 rates of reaction
Reaction Order –
 power to which the concentration is raised in a
rate law
= ORDER of the reaction
@ example
experimental rate law for the reaction:
H2 + Br2 = 2 HBr
3/2
k[H2 ][Br 2 ]
rate 
[Br 2 ]  k' [HBr]
 rates of reaction 3/2
k[H2 ][Br 2 ]
rate 
 Reaction Order – [Br 2 ]  k' [HBr]

* such rate law may be simplified by modifying or

controlling the conditions, like suppose there is
a large amount of Br2

such that [Br2] >> k’[HBr]

 one-half order with respect to Br2

 rates of reaction
 Determination of the Rate Law
 isolation method -
= concentration of all reactant are in excess
except for one
* for the reaction : A + B  products
- if B is in excess  may be taken as constant
rate law : rate = k’[A] where k’ = k[B]

represents a first order reaction
= pseudo-first order rate law
 rates of reaction
 initial rate method
= rate is measured at the beginning of the reaction
for several different initial concentrations of the
reactants
* consider a reaction with a rate law: rate = k[A]a

(rate)0 = k[A0]a or log (rate)0 = log k + a log[A0]

= for several initial concentrations,

plot log [A0] against log (rate)0
 so that a is the slope
 rates of reaction
@ example

Trial [A]0 [B]0 [C]0 [cat]0 Initial

Rate, M/s
1 1 1 1 1 2
2 1 2 1 1 4
3 2 1 1 1 8
rate = k[A]a[B]b[C]c[cat]d
r1 = 2 = k[1]a[1]b[1]c[1]d  2/4 = (1/2)b
r2 = 4 = k[1]a[2]b[1]c[1]d b= 1
Trial Initial Concentration Initial Concentration Rate
of A (mole L-1) of B (mole L-1) (mole L-1 sec-1)

1 0.100 0.100 2.73

2 0.150 0.100 6.14

3 0.100 0.200 2.71

A+ B → C

r = k [A]a [B]b

r1 = k [A]1a [B]1b
r2 k [A]2a [B]2b
 rates of reaction
 integration method

@ First Order Reaction - A  products

d[A]
rate of disappearance = 
dt
rate of reaction = k[A]
d[A] d[A]
 =  k[A]  =  kt
dt [A]

integrating . . . .

 ln [A]t  ln [A]0 =  kt
rates of reaction
 rates of reaction

 plot ln [A]t against t

[A]0
y-intercept = 0

 plot ln [A]t against t

y-intercept = ln [A]0

* half-life:
at t = t1/2 [A] t = ½ [A] 0
ln 2
t1/2 = k1
 rates of reaction
@ Second Order Reaction - 2 A  products

d[A]
rate of disappearance = 
dt
rate of reaction = k [A]2
d[A] d[A]
=  k [A]2  2 = kt
dt [A]

integrating . . . . .
1 1
 = kt
[A]t [A]0
 equation of a straight line
 rates of reaction
 plotting the equation
* 1  1 against t
[A]t [A]0
 y-intercept = 0 slope = m = k
1
* [A] against t
t
 y-intercept = 1/[A]0 slope = m = k
* half-life:
at t = t1/2 [A] t = ½ [A] 0
1
t1/2 =
k 2 [A]0
rates of reaction
 rates of reaction
 another type of 2nd order reaction -
A + B  products
d[A]
rate of decomposition of A = 
dt
rate law =  k [A][B]
d[A]
 =  k [A][B]
dt
at ant time, t, [A] = ([A] 0  x)
and [B] = ([B] 0  x)
so that, d[A] = k ([A]  x) ([B]  x)
 0 0
dt
rates of reaction
d[A] dx
since, 
dt dt

then,
dx
= k([A] 0  x) ([B] 0  x)
dt

on integration,
[B]
1 [B]0
tk 2  ln
[B]0  [A]0 [A]
[A]0
 rates of reaction
@ Higher-order reactions -
d[A]
 3 A  products  = k [A]3
dt
d[A]
 2A + B  products  = k [A]2 [B]
dt
d[A]
 A + 2 B  products  = k [A] [B]2
dt
d[A]
 A + B + C  products  = k [A] [B] [C]
dt
 rates of reaction
 General Approach -
= aim to determine the rate law and the value
of the rate constant
ideally,
- identify all products

- isolation method

- confirm  order and rate constant (k)

 rates of reaction
 Temperature Dependence of Reaction Rates -

= rate of most reaction increases as the

temperature is increased

= empirical observations show that many

reactions follow the relationship

k = A eEa/RT
E
 a
ln k = ln A
RT
 Arrhenius equation
 rates of reaction
alternate forms:
   G or ++G =  RT ln k
ke RT
= activation Gibb’s energy
 some systems show dependence on T = not
Arrhenius-like
2  lnk 
Ea  RT 
 T  V
- using d(1/T) = dT/T2  rearranges to . . . .
dlnk
Ea  R 1
d
T
 
integrating at constant Ea = Arrhenius equation
 rates of reaction
 in general,
k = A eEa/RT

 plot of ln k against 1/T = straight line

y-intercept  frequency factor (A)

slope  activation energy (Ea)

 rates of reaction

@ second stage in the analysis of kinetic data

= look at the rate laws as clues

to the reaction mechanism
 rates of reaction
 ACCOUNTING FOR THE RATE LAWS
= reaction mechanism
 elementary reactions
= single event reaction
 molecularity
= number of molecules reacting
 unimolecular reaction = single molecule
 bimolecular reaction = 2 molecules
 rates of reaction
 Reaction Order
= an empirical quantity, obtained from the
experimental rate law
@ Molecularity = refers to an elementary
(step) reaction proposed as an individual
step in a mechanism
 molecularity
= number of
molecules reacting
 unimolecular
reaction = single molecule
 bimolecular
reaction = 2 molecules
 rates of reaction
 SIMPLE REACTIONS

d[A]
 A  products : =  k1t
dt
 1st order rate law
 1st order in A
 unimolecular reaction

d[A]
 A + B  products :  =  k2 [A][B]
dt
 2nd order rate law
 1st order in A or in B
 bimolecular reaction
 rates of reaction
 A + B + C  product:
d[A]
 = k3[A][B][C]
dt
 3rd order rate law
 1st order in A or B or C
 termolecular reaction

@ not simple reactions

 evaluate rate laws = k
 rates of reaction
 REACTIONS APPROACHING EQUILIBRIUM

* consider a reaction : A produces B

B decomposes to A
k


A k'
B



forward reaction = (rate)f =  k [A]

backward reaction = (rate)r = k’ [B]

 forward reaction reduces [A] while backward

reaction increases [A]
rates of reaction
net rate of change :
d[A]
= k[A] + k’ [B]
dt
* initially: concentration of A is [A] 0 and no B
* at any time t, [A] + [B] = [A] 0

thus,
d[A]
=  k[A] + k’([A]o  [A])
dt
=  (k + k’)[A] + k’ [A]o
rates of reaction
= first order differential equation

k'  ke(kk')t
[A]  [A]0
k  k'
at t  ke (k + k’)t  0
so,
k'
[A]  [A]0
k  k'
k
[B]  [A]o  [A]  [A]0
k  k'
 rates of reaction
 ratio of equilibrium concentration = equilibrium
constant
[B] k
Keq  
[A] k'
another way to look at it is to note that at
equilibrium,

net rate of change of [A] = 0 or d[A] = 0

therefore, dt
k[A] = k’[B]
k [B]
 K
k' [A]
 rates of reaction

= the importance of the equation is:

 it relates the thermodynamic quantity, K

to the rates, k

= if one of the rate constant can be

measured , the other may be
obtained from the known K
 rates of reaction
 Similar calculations may be done for other types of
equilibria -
A B C D
k


k'


 simple bimolecular and therefore 2nd order in
both directions

forward reaction: (rate)f =  k [A][B]

backward reaction: (rate)r = k’ [C][D]

 rates of reaction
* at equilibrium, net rate change = 0

 d[A] = 0
dt
therefore,

d[A]
=  k [A] [B] + k’ [C] [D] = 0
dt

k [C][D]
 K
k' [A][B]
 rates of reaction
 sequence of simple reactions :

A + B = C + D (rate)f =  ka [A][B]
(rate)b = ka’ [C][D]

C = E + F (rate)f =  kb [C]
(rate)b = kb’ [C][D]
 rates of reaction
 at equilibrium
ka  [C][D] kb  [E][F]
and
k'a [A][B] k'b [C]
* Overall reaction : A + B = D + E + F

[D][E][F] [C][D] [E][F] ka kb

K  x  x
[A][B] [A][B] [C] k'a k'b
 K  k a kb
k'a k'b
= results when the overall reaction is the sum of a
sequence of steps
 rates of reaction
@ in general,

k a kb ....
K
k'a k'b ....

where k = rate constants of the individual steps

k’ = rate constant of the corresponding

reverse step
 rates of reaction
 OPPOSING REACTIONS

 Consider the H2 - I2 reaction

 mechanism = simple with two elementary reaction
H2 + I2 = 2 HI
= since both are elementary reactions:
the net rate (formation of HI)
d[HI]
= k1 [H2] [I2]  k1[HI]2
dt
rates of reaction
= at equilibrium: [H2] = [H2]0  ½ x
[I2] = [I2]0  ½ x
[HI] = x
 substituting,
d[HI] dx
 = k1([H2]o ½ x)([I2]o  ½ x)  k1[x]2
dt dt
 at equilibrium, dx/dt = 0
x2 k
 K
 x  x  k 1 or
 [H2 ]0   [I2 ]0  k 1  k 1
 2  2 K
 rates of reaction
 multiplying out:  
dx k1  4   2 2[H2 ]0  [I2 ]0 x 4[H2 ]0 [I2 ]0 
  1  x   
dt 4  K    4   4 
1   1   
 K  K  
= expressions in the bracket can be written as
(x  x1)(x - x2)  x1 and x2 roots (FACTORING)
[H2 ]0  [I2 ]0  m [ ] + [I2] - m
x1  H 2
1
4 x 2
= 0
4
0

1-
where K K
m [H2]0[I2]0 2  4 [H2]0 [I2]0 1  4 K 
 rates of reaction
 rate expression becomes,
dx k 1 4
  1  dt
x  x1x  x2  4  K 
by partial-fraction method and
then integrating,
 x  x1  1
ln   k1mt  C


 x x2  2
 rates of reaction
* since x = 0 at t = 0 then, C = ln(x1/x2)

thus,  x1  x  x2  1
  k1mt
ln   2
 x1  x2  x 

plot the left term against time, t

= slope will give the value of k1

 rates of reaction
@ for comparison, the ordinary rate expression
without the reverse reaction,

 [I2 ]0  x  [H2 ]0 
ln    k [I2 ]0  [H2 ]0 t

 [I2 ]0  [H2 ]0  x 

 expressions are very similar

 x1  x  x2  1
  k1mt
ln   2
 x1  x2  x 
 rates of reaction
 CONSECUTIVE REACTIONS

 some reactions take place through the formation

of an intermediate
- as in a consecutive 1st order reaction
A  B  C
ex. decay of a radioactive family

239U  23.5 min  239Np  235 days  239Pu

? how do we set up the rate laws ?

 rates of reaction
 consider the reaction :
A  ka  B  kb  C
- rate of decay of A :
d[A]
=  ka[A]  not replenished
dt
- intermediate B is formed from A (at a rate ka[A])
but decays to C (at a rate kb[B] )
d[B]
= ka[A]  kb[B]
dt
- C is formed by a unimolecular, 1st order decay of B
d[C]
= kb[B]
dt
 rates of reaction
@ initially only A is present at a concentration [A]0
therefore: rate law  ordinary 1st order
[A]  [A]0 etka
 substituting for [A] in equation (2)
and that initially [B]0 = 0

 etk a  etkb 
[B]  ka [A]0  
kb + [B]
 since at any timet, [A] ka + [C] = [A] it follows,
0

  ka etkb  kb etk a 
[C]  [A]0 1   
  kb  k a 
rates of reaction
 rates of reaction   k a e  tkb  kb e  tka 
[C]  [A] 1   
  
0
kb  k a 
 suppose kb >> ka
= on formation of B, decays rapidly to C

- since etkb << etka

and kbka  close to kb

equation reduces to ,

[C] = [A]o[1  etka ]

* the rate determining step is the one with the

smallest rate coefficient  slow step
 rates of reaction
 Unimolecular reactions

= gas phase reaction

- following a 1st order kinetics and
proceeds through a unimolecular rate-
determining stage

= are called - presumably a molecule acquires

enough energy to react
– as a result of collisions with other molecules
 rates of reaction
 Consider: Unimolecular Decomposition
 Lindemann - Hinshelwood Mechanism

@ Proposed mechanism involves:

= the activation of molecules by collision
with a 1st order reaction

A + M  k1  A* + M
 rates of reaction
 the activated molecule reacts in two (2) ways:

(1) deactivation by collision

A* + M  k1  A + M

(2) decomposition into products

A*  k2  products
 rates of reaction
 rate of disappearance of A
= rate of the last reaction
d[A]
=  k2[A*]
dt
* assumption: once the reaction starts
- a steady-state is reached in which the
concentration of the activated species
does not change very much so that
d[A*]
= 0
dt
 rates of reaction
@ “ steady-state approximation “
d[A*]
 k1[ A ][M ]  k 1[ A * ][M ]  k 2 [ A * ]  0
dt
= therefore, we can express [A*] in terms of [A]
k 1[A][M]
[A*] 
k 1[M]  k 2
= substituting into the rate law,

d[A] k 2 k1[A][M]

dt k 1[M]  k 2
 rates of reaction d[A] k 2 k1[A][M]

 2 limiting forms: dt k 1[M]  k 2

(a) suppose the rate of decomposition is extremely

fast

= that is when k1[M][A*] << k2[A*]

then k1[M] << k2

therefore, k1[M] + k2  k2
d[A]
@ rate law : =  k1[A][M]
dt
 kinetics is second order
 rates of reaction
 2 limiting forms:
(b) - after activation there is an appreciable time lag
before the molecules falls apart
- if time lag is long, rate of deactivation ,
k1[M][A*] >> rate of decomposition, k2[A*]
= that is when k1[M] >> k2 then k1[M] >> k2
therefore, k1[M] + k2  k1[M]
@ rate law : d[A] / dt =  (k2k1/k 1)[A]
 kinetics is first order
rates of reaction

 Lindemann - Hinshelwood Mechanism

* reactions with this mechanism

= can switch from first order to

second order
thank you!

jose s. solis, ph.d

imee su martinez, ph.d
institute of chemistry
university of the philippines
diliman, quezon city