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Chemical Kinetics

• Slow reaction and its rate determination


• Molecularity of reactions
• Chain reaction and mechanism
Slow Reactions
Slow reaction: These are the reactions which proceed slowly and their
rates can be measured by conventional methods. An example is the
inversion of cane sugar in aqueous solution.
C12H22O11O → C6H12O6 + C6H12O
cane sugar Glucose Fructose

In slow reaction a large number of bonds have to be broken in reactant


molecules and a large number of new bonds have to be form in the
product molecules.
Measurement of Rate of Slow Reaction
There are several techniques, in general, to measure the rate of slow reactions. They are:
1. By Observing The Partial Pressure Change:
Reactions that occur in gaseous phase proceed by changing the partial pressures of the
reactant species. So, by observing how the partial pressure changes, rate of the reaction
can be observed.
.Conversation of CH3NC to CH3CN
2. By observing the change of concentration:
When the density measurements are restricted to dilute solutions, the change in
concentration of the sample is a function of the percentage completion of the
reaction.
3. By Colorimetric Method:
Colorimetry may be adopted to the study of reactions in which the disappearance
of a colored reactant results in the formation of a differently colored product. By
observing the change of color with time, the reaction rate can be calculated.
4.By Spectrophotometric method:
Every chemical species has an identical spectrum in UV-Vis or even IR
spectra. By observing the spectra of the whole chemical reaction, the
change of reactants’ absorption spectra with time the rate of the whole
chemical process can be calculated.
•5.By
  observing the conductance change:
Reactions that correspond with the formation of various ions, the rate of such reactions
can be observed by measuring the change of conductance with time. Not all the ions
contribute same in the conductance and hence, conduction changes as the reaction
proceeds.
The equation regarding this:
•6.Calorimetry
  method:
• Calorimetry is a unique among the methods used to determine
kinetics of slow reaction .
• Calorimetry directly measures the rate of heat generation which is
proportional to the rate of the process.
• The equation regarding this:

Here,
Rmd is the minimum detectable rate of the slow reaction
Ø is the minimum detectable heat rate of the calorimeter.
∆H is the enthalpy change for the reaction .
A plot of Ø×∆H versus kt to determine rate of slow reaction.
Molecularity of a Reaction
Molecularity of a reaction:
• The molecularity of a reaction is defined as the number of reactant
molecules which take part in an elementary reaction or rate determining
step.
• The reaction are said to be unimolecular , bimolecular or tri molecular
depending upon whether one ,two or three molecules are involved in a
chemical reaction.
For example, H2 + I2 →2HI
The molecularity and order of the reaction is two.
C12H22O11 + H2O → C6H12O6 + C6H12O6
Sucrose GLUCOSE FRUCTOSE
The molecularity of the reaction is two but order is one.
Order of a reaction:
• The order of a reaction is defined as the sum of powers of the concentration
terms in the rate equation.
• The molecularity and order of a reaction are generally different. But
sometimes they may be same.

Types of reaction with respect to their Order

Second-Order Pseudo-Order
First-Order Reaction Zero-Order Reaction
Reaction Reaction
The Steady-State Approximation
• The steady-state approximation is a method used to derive a rate law.
• The method is based on the assumption that one intermediate in the
reaction mechanism is consumed as quickly as it is generated.
• Intermediate’s concentration remains the same in a duration of the
reaction.
Chain Reaction
Chain reaction: A chain reaction is a sequence of reactions where the
Chain reaction: A chain reaction is a sequence of reactions where a
formation of free radicals initiate the reactions and the reactions proceed
reactive
untilproduct
the free or by-product
radicals causes additional reactions to take place.
terminate.

Steps of Chain Reaction

Initiation Propagation

Termination Retardation
The main types of steps in chain reaction are of the following types:
• Initiation: In which a reactive intermediate, which may be an atom, anion,
or a neutral molecular fragment is formed, usually through the action of an
agent such as light, heat or a catalyst. Formation of active particles or chain
carriers.
• Propagation: Whereby the intermediate reacts with the original
reactants, producing stable an another intermediate, whether of the same
or different kind; the new intermediate reacts as before, so a repetitive
cycle begins. In effect the active particle serves as a catalyst for the overall
reaction of the propagation cycle. Particular cases are:
• Termination: It is an elementary step in which the active particle loses its
activity; e. g. by recombination of two free radicals.
Mechanism of Formation of HBr
1. Initiation:
Br2 → 2Br• (thermal) or Br2 + hv → 2Br• (photochemical)
Each ‘Br’ atom is a free radical, indicated by the symbol ‘•’ representing an
unpaired electron.

2. Propagation:
Br• + H2 → HBr + H•
H• + Br2 → HBr + Br•
The sum of these two steps corresponds to the overall reaction H2 + Br2 →
2 HBr, with catalysis by Br• which participates in the first step and is
regenerated in the second step.
3) Retardation (inhibition):
H• + HBr → H2 + Br•
this step is specific to this example, and corresponds to the first propagation
step in reverse.

4) Termination:
2 Br• → Br2
recombination of two radicals, corresponding in this example to initiation in
reverse.
Determination of rate of a chain reaction
Let consider a reaction,
𝑘
H2 + Br2 ՜ 2HBr

Normally the reaction rate for the reaction is,

3
𝑘[𝐻2 ][𝐵𝑟2 ] ൗ
2
Ѵt = [𝐻𝐵𝑟 ]
1+ ൘𝑚 [𝐵𝑟 ]
2

Where k and m are constants; the value of m is about 10 and is


practically independent of temperature.
But the accepted mechanism for the reaction of Br2 and H2 is chain mechanism
.The mechanism have the following steps.
Initiation :
𝑘𝑖
Br2 + M ՜ 2Br▪ + M

Chain propagation:
𝑘𝑝
Br▪ + H2 ሱ
ሮ HBr + H▪

𝑘𝑝
Br2 + H▪ ሱ
ሮ HBr + Br▪

Retardation:
𝑘𝑟
H▪ + HBr ՜ H2 + Br▪

Termination:
𝑘𝑡
Br▪ + Br▪ + M ՜ Br2 + M

The steady state hypothesis must be applied to the two intermediates


Br▪ and H▪, both of which are present at very low concentrations. The
steady state equation for H is
𝑑 [𝐻▪] ′
= kp[Br▪][H2] – 𝑘𝑝 [H▪][Br2] - kr[H▪][HBr] = 0 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙(1)
𝑑𝑡

And for Br▪ is


𝑑 [𝐵𝑟 ▪] ′
=2ki[Br2][M] – kp[Br▪][H2] + 𝑘𝑝 [H▪][Br2] + kr[H▪][HBr] – 2kt[Br▪]2[M]
𝑑𝑡
= 0 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙(2)
1 1
𝑘𝑡
So, [Br▪] = ( ൗ)
𝑘𝑡 . [Br2] [H▪]
2 2 ∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙∙(3)

Substitution the value of [H▪] in equation (3),


𝑘 1 1
𝑘 𝑝 ( 𝑖൘𝑘 ) ൗ 2 [𝐻 2 ][𝐵 𝑟 2 ] ൗ2
𝑡
[H▪] =
𝑘 𝑝′ ሾ𝐵𝑟2 ሿ
+ 𝑘 𝑟 [𝐻𝐵𝑟 ]

So the rate of formation of [HBr] is ,


𝑑 [𝐻𝐵𝑟 ]
= kp[Br▪][H2] + 𝑘𝑝′ [H▪][Br2] – kr[H▪][HBr]
𝑑𝑡

Now substitution the value of [H▪] and [Br▪] we get,


𝑘 1ൗ 3
2 [𝐻2 ][𝐵𝑟2 ] ൗ
𝑑 [𝐻𝐵𝑟 ] 2𝑘 𝑝 ( 𝑖ൗ)
𝑘
2
𝑡
= 𝑘 [𝐻𝐵𝑟 ]
𝑑𝑡 1+ ( 𝑝൘ ′ ) ൘[𝐵𝑟 ]
𝑘𝑝 2

3
[𝐵𝑟2 ] ൗ
𝑘 ሾ𝐻2 ሿ 2
=
[𝐻𝐵𝑟]
1+ ൘𝑚[𝐵𝑟 ]
2

Where ,
1 𝑘𝑝
K = 2𝑘𝑝 (𝑘𝑖ൗ)
𝑘
1ൗ
2 and
𝑚
൘𝑘 ′
=
𝑡 𝑝
Determination the rate of thermal decomposition of acetaldehyde
To obtain three-halves – order kinetics, there can still be first order
initiation , but now the termination step must be combination of two
identical chain carriers. Moreover , they must be those carries that are
involved in a second order propagation reaction. A good example is the
mechanism originally proposed by Rice and Herzfeld for the thermal
decomposition of acetaldehyde:

It has involved the following steps:

Initiation:
𝑘𝑖
CH3CHO ՜ ▪𝐶𝐻 3 + ▪CHO

Chain propagation:
𝐾𝑃
CH3CHO + ▪CH3 ሱ
ሮ 𝐶𝐻 4 + ▪CH3CO

𝐾𝑃
▪CH3CHO ሱ
ሮ ▪CH3 + CO

Chain termination:
𝐾𝑡
▪CH3 + ▪CH3 ՜ 𝐶𝐻 3—CH3
The radical ▪CHO undergoes further reactions , but for simplicity they
are ignored here. For this reason the Rice and Herzfeld scheme is close
to the truth.

The steady state equation for the methyl radicals ,


𝑑[▪𝐶𝐻3 ]
=Ki[CH3CHO] – kp[CH3CHO][▪CH3] + 𝑘𝑝′ [▪CH3CO] –
𝑑𝑡
2kt[▪CH3]2 = 0 ……………(1)
And for the ▪CH3CO radicals ,
𝑑[▪CH 3CO ]
= kp[CH3CHO][▪CH3] - 𝑘𝑝′ [▪CH3CO] = 0
𝑑𝑡
………………………(2)
From the equation 1 and 2 , we get

Ki[CH3CHO] - 2kt[▪CH3]2 = 0
𝑘 1ൗ 1
2 [CH3CHO] ൗ
So, [▪CH3] = ( 𝑖ൗ
2𝑘𝑡 ) 2

Now the rate of formation of CH4 is ,


𝑑[𝐶𝐻4 ]
=[▪CH3] [CH3CHO]
𝑑𝑡

𝑘 1ൗ 1
2 [CH3CHO] ൗ
= kp [CH3CHO] ( 𝑖ൗ
2𝑘𝑡 ) 2

𝑘 1ൗ 3
2 [CH3CHO] ൗ
= 𝑘𝑝 ( 𝑖ൗ
2𝑘𝑡 ) 2

3ൗ 𝑘𝑖 1ൗ
=k [CH3CHO] 2 [where, k = 𝑘𝑝 ( ൗ 2𝑘 )
2
𝑡
Thanks for Your Patience

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