Professional Documents
Culture Documents
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.
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.
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
3
𝑘[𝐻2 ][𝐵𝑟2 ] ൗ
2
Ѵt = [𝐻𝐵𝑟 ]
1+ ൘𝑚 [𝐵𝑟 ]
2
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
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:
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.
Ki[CH3CHO] - 2kt[▪CH3]2 = 0
𝑘 1ൗ 1
2 [CH3CHO] ൗ
So, [▪CH3] = ( 𝑖ൗ
2𝑘𝑡 ) 2
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