Chemical Kinetics

The Rates of Reactions

CHM172 1st Sem, 2022-2023

Marvin Jose F. Fernandez

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Brief Illustration 1

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Brief Illustration 2

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Experimental techniques
 real-time analysis, a procedure in which the composition of a system is analysed while the
reaction is in progress.
(1) flow method, a procedure in which the composition of a system is analysed as the reactants
flow into a mixing chamber.
(2) stopped-flow technique, a procedure in which the reagents are mixed very quickly in a small
chamber fitted with a syringe instead of an outlet tube.
(3) flash photolysis, a procedure in which the reaction is initiated by a brief flash of light.

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 quenching methods, techniques based on stopping the reaction after it has been allowed
to proceed for a certain time.
(1)chemical quench flow method, a technique in which the reactants are mixed as in the
flow method but the reaction is quenched by another reagent.
(2)freeze quench method, a technique in which the reaction is quenched by cooling the
mixture.

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 method of initial rates, a procedure in which the rate is measured at the beginning of
the reaction for several different initial concentrations of reactants; v0 = kr [A]0a
log v0 = log kr + a log [A]0.

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Integrated rate laws
(a) First-order reactions
 first-order integrated rate law, -d[A]/dt= kr[A]→ ln([A]/[A]0) = –krt,
[A] = [A]0𝑒 −𝑘𝑟 𝑡 .
 half life, t1/2 = (ln 2)/kr.
 time constant, the time required for the concentration of a reactant to fall to 1/e of its
initial value,τ = 1/kr.

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Second-order reactions
 second-order integrated rate law, -d[A]/dt= kr[A]2 → 1/[A] – 1/[A]0 = krt
[A] = [A]0/(1 + krt[A]0).
 half life, t1/2 = 1/kr[A]0.
 half life for nth-order reaction (n>1), t1/2 = 2n-1-1/(n-1)kr[A]0n-1.
d [ A]
A + B → P; = −k r [ A][ B ]
dt
d [ A] A ]=[ A ]0 − x → d [ A ] / dt = − dx / dt dx
= −k r ([ A]0 − x)([B ]0 − x) ⎯[⎯ ⎯ ⎯ ⎯ ⎯ ⎯ ⎯⎯→ = k r ([ A]0 − x)([B]0 − x)
dt dt
x dx t
0 ([ A]0 − x)([B]0 − x) = kr 0 dt = kr t
1 1  1 1 
=  − 
(a − x)(b − x) b − a  a − x b − x 
dx 1  dx dx  1  1 1 
 =   −  =  ln − ln + constant
(a − x)(b − x) b − a  a − x b − x b − a  a − x b − x 
x dx 1   [ A]0   [ B]0 
 =
([ A]0 − x)([B]0 − x) [ B]0 − [ A]0
ln
 [ A] − x
 − ln
  [ B ] − x



0
0 0

 [ B] /[ B]0 
ln  = ([ B ]0 − [ A]0 )k r t
 [ A] /[ A]0 

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Brief Illustration 3

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End of Class

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