How do we monitor the progress of a reaction?

How do we monitor the progress of a reaction?

Monitor quantities that change during the reaction
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
Example:
2N2 O5 (g) → 4NO2 (g)+O2 (g)
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
Example:
2N2 O5 (g) → 4NO2 (g)+O2 (g)
Let initial pressure=p0
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
Example:
2N2 O5 (g) → 4NO2 (g)+O2 (g)
Let initial pressure=p0
initial amount of N2 O5 = n mols
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
Example:
2N2 O5 (g) → 4NO2 (g)+O2 (g)
Let initial pressure=p0
initial amount of N2 O5 = n mols
at time t , degree of dissociation =α

N2 O5 NO2 O2 total

amount n(1 − α) 2αn 1
2αn n 1 + 32 α
 How do we monitor the progress of a reaction?
Monitor quantities that change during the reaction
If at least one component is a gas, we can monitor the change in pressure.
Example:
2N2 O5 (g) → 4NO2 (g)+O2 (g)
Let initial pressure=p0
initial amount of N2 O5 = n mols
at time t , degree of dissociation =α

N2 O5 NO2 O2 total

amount n(1 − α) 2αn 1
2α n n 1 + 32 α

When α = 0, p = p0 ∴ at time t , p (t ) = 1 + 32 α p0


real-time-analysis: ow technique

location of the spectrometer corresponds to dierent times after initiation

real-time-analysis: ow technique

location of the spectrometer corresponds to dierent times after initiation

e.g., progress of the reaction H2 (g)+Br2 (g) → 2HBr(g)
can be followed by measuring amount of visible light absorbed by Br2 (g)
Similarly, changes in conductivity and pH can be used as means of monitoring the
progress of a reaction
Similarly, changes in conductivity and pH can be used as means of monitoring the
progress of a reaction
e.g., the reaction (CH3 )3 CCl(aq)+H2 O(l)→(CH3 )3 COH(aq)+H+ (aq)+Cl− (aq)
Similarly, changes in conductivity and pH can be used as means of monitoring the
progress of a reaction
e.g., the reaction (CH3 )3 CCl(aq)+H2 O(l)→(CH3 )3 COH(aq)+H+ (aq)+Cl− (aq)
can be monitored by measuring either conductivity or pH
stopped-ow technique
instantaneous rate
instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
v = V1 ddtξ ; V = vol. of reaction mix.
instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
v = V1 ddtξ ; V = vol. of reaction mix.
= V1 ν1J dn
dt
J
instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
v = V1 ddtξ ; V = vol. of reaction mix.
= V1 ν1J dn
dt
J

or, v = ν1J ddt[J ] (mol.dm−3 s−1 )

for gas phase, (molecules.cm−3 s−1 )
 instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
v = V1 ddtξ ; V = vol. of reaction mix.
= V1 ν1J dn
dt
J

or, v = ν1J ddt[J ] (mol.dm−3 s−1 )

for gas phase, (molecules.cm−3 s−1 )
For a reactionaA+bB→ cC+dD, v = −1a ddt[A] = −b1 ddt[B ] = c1 ddt[C ] = · · ·
e.g., for 2H2+O2 → 2H2O,
 instantaneous rate
extent of reaction ξ = n −ν n
J

J
J,0

J refers to species in a reaction mixture

nJ =amount of J at some time
nJ,0 =amount of J at initial time
νJ =stoichiometric number of species J
< 0 for reactants and > 0 for products
v = V1 ddtξ ; V = vol. of reaction mix.
= V1 ν1J dn
dt
J

or, v = ν1J ddt[J ] (mol.dm−3 s−1 )

for gas phase, (molecules.cm−3 s−1 )
For a reaction aA+bB→ cC+dD, v = −1a ddt[A] = −b1 ddt[B ] = c1 ddt[C ] = · · ·
e.g., for 2H2+O2 → 2H2O, v = −12 d [dtH2] = −d [dtO2] = 12 d [Hdt2O]
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
v = f (pA pB · · · ) : Rate law in terms of pressures
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
v = f (pA pB · · · ) : Rate law in terms of pressures
N n
generally, v = k ci i ; ni =order w.r.t. componet i of N
Q
i =1
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
v = f (pA pB · · · ) : Rate law in terms of pressures
N n
generally, v = k ci i ; ni =order w.r.t. componet i of N
Q
i =1
an overall reaction may contain a set of elementary reactions
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
v = f (pA pB · · · ) : Rate law in terms of pressures
N n
generally, v = k ci i ; ni =order w.r.t. componet i of N
Q
i =1
an overall reaction may contain a set of elementary reactions
molecularity : # reactant molecules involved in an elementary step ∈ Z+
 Typical rate expression, v = k [A]m [B ]n ; k = rate constant
order w.r.t. A= m ∈ R; order w.r.t. B= n ∈ R; overall order= m + n ∈ R
v = f ([A] , [B ] , · · · ) : Rate law in terms of concentrations
v = f (pA pB · · · ) : Rate law in terms of pressures
N n
generally, v = k ci i ; ni =order w.r.t. componet i of N
Q
i =1
an overall reaction may contain a set of elementary reactions
molecularity : # reactant molecules involved in an elementary step ∈ Z+
example : unimolecular, N2 O4 → 2NO2
bimolecular, O+ H2 →OH+H
Method of initial rates:
Method of initial rates:
Recombination of I atoms in the gas phase in the presence of Ar,
2 I(g) + Ar(g)→ I2 (g) + Ar(g); v0 = k [A]a0 =⇒ log v0 = log k + a log [A]0

[Ar] : (a) 1 mmol dm−3 (b) 5 mmol dm−3 and (c) 10 mmol dm−3
Method of initial rates:
Recombination of I atoms in the gas phase in the presence of Ar,
2 I(g) + Ar(g)→ I2 (g) + Ar(g); v0 = k [A]a0 =⇒ log v0 = log k + a log [A]0

[Ar] : (a) 1 mmol dm−3 (b) 5 mmol dm−3 and (c) 10 mmol dm−3

intercept, k = 9 × 109 mol−2 dm6 s−1

Method of initial rates:
Recombination of I atoms in the gas phase in the presence of Ar,
2 I(g) + Ar(g)→ I2 (g) + Ar(g); v0 = k [A]a0 =⇒ log v0 = log k + a log [A]0

[Ar] : (a) 1 mmol dm−3 (b) 5 mmol dm−3 and (c) 10 mmol dm−3

intercept, k = 9 × 109 mol−2 dm6 s−1

slope=2 slope=1 v0 = k [I]20 [Ar]0
▶ method of initial rates might not reveal full rate law
▶ method of initial rates might not reveal full rate law
▶ once products are generated they might participate in reaction and aect its
rate
▶ method of initial rates might not reveal full rate law
▶ once products are generated they might participate in reaction and aect its
rate
▶ e.g., products participate in the synthesis of HBr, H2 +Br2 →HBr
▶ method of initial rates might not reveal full rate law
▶ once products are generated they might participate in reaction and aect its
rate
▶ e.g., products participate in the synthesis of HBr, H2 +Br2 →HBr
▶ full rate law depends on [HBr]
half-life
half-life
1st order reaction: t = lnk2
1
2

time constant, τ = k1
integrated rate law: Zero- order rxn
integrated rate law: Zero- order rxn
d [A] = −k [A]0 = −k
dt
integrated rate law: Zero- order rxn
d [A] = −k [A]0 = −k
dt

[A] = [A]0 − kt
1st order rxn
1st order rxn

d [A] = −k [A]
dt
1st order rxn

d [A] = −k [A]
dt
[A] = [A]0 e −kt
CH3 N2 CH3 (g)→ CH3 CH3 (g)+N2 (g)
t/s 0 1000 2000 3000 4000
p/Pa 10.9 7.63 5.32 3.71 2.59
second-order:
second-order:

d [A] = −k [A]2
dt
second-order:

d [A] = −k [A]2
dt
[A] − [A]0 = kt
1 1
second-order:

d [A] = −k [A]2
dt
[A] − [A]0 = kt
1 1

[A]0
[ A] = 1+kt [A]0
klarge = 3ksmall
(grey lines for rst order)
half life for second order reaction: t = k [A1 ]
1
2 0
half life for second order reaction: t = k [A1 ]
1
2 0

In general, for n−th order reaction: t = k [A1]n−

1
2
1
0
General second-order reaction:
General second-order reaction:
A+B→products
General second-order reaction:
A+B→products
d [A] = −k [A][B ] = −k ([A] − x ) ([B ] − x ) = − dx
dt 0 0 dt
General second-order reaction:
A+B→products
d [A] = −k [A][B ] = −k ([A] − x ) ([B ] − x ) = − dx
dt 0 0 dt
 [B ] 
ln [B[A]] = ([B ]0 − [A]0 ) kt
0

A
[ ]0
Statistics of Birth-Death processes applied to chemical kinetics :
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
and the state of n molecules may become the state of n − 1 molecules with
probability Pn (t )Wn,n−1
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
and the state of n molecules may become the state of n − 1 molecules with
probability Pn (t )Wn,n−1
∴ Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )Wn+1,n − Pn (t )Wn,n−1 (no term containing
Wn,n+1 because it is a decay, n → n + 1not possible)
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
and the state of n molecules may become the state of n − 1 molecules with
probability Pn (t )Wn,n−1
∴ Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )Wn+1,n − Pn (t )Wn,n−1 (no term containing
Wn,n+1 because it is a decay, n → n + 1not possible)
or, Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )k (n + 1)∆t − Pn (t )kn∆t
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
and the state of n molecules may become the state of n − 1 molecules with
probability Pn (t )Wn,n−1
∴ Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )Wn+1,n − Pn (t )Wn,n−1 (no term containing
Wn,n+1 because it is a decay, n → n + 1not possible)
or, Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )k (n + 1)∆t − Pn (t )kn∆t
or, P˙n = Pn (t +∆∆tt)−Pn (t ) = k (n + 1)Pn+1 (t ) − knPn (t ) ∀ n = 1, · · · , n0 − 1
Statistics of Birth-Death processes applied to chemical kinetics :
Consider a rst order decay process,
probability that at time we have n molecules at time t : Pn (t )
Transition probability of going from n to n − 1 molecules in time ∆t :
Wn,n−1 = kn∆t
In time ∆t , the state of n + 1 molecules may become the state of n molecules with
probability Pn+1 (t )Wn+1,n
and the state of n molecules may become the state of n − 1 molecules with
probability Pn (t )Wn,n−1
∴ Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )Wn+1,n − Pn (t )Wn,n−1 (no term containing
Wn,n+1 because it is a decay, n → n + 1not possible)
or, Pn (t + ∆t ) = Pn (t ) + Pn+1 (t )k (n + 1)∆t − Pn (t )kn∆t
or, P˙n = Pn (t +∆∆tt)−Pn (t ) = k (n + 1)Pn+1 (t ) − knPn (t ) ∀ n = 1, · · · , n0 − 1
This is a dierential-dierence equation (also called a master equation) with the
1 if n = n0
initial condition Pn (0) =
0 if n ̸= n0
For n = n0 ,
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
0 0 0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

0 0 0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0

This is an equation of the kind ẏ (t ) = −ay (t ) + f (t )

For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0

This is an equation of the kind ẏ (t ) = −ay (t ) + f (t )

use, the method of integrating factors, multiply both sides by e adt = e at ,
R

e at ẏ (t ) = −ay (t )e at + f (t )e at
or dtd (e at y ) = f (t )e at
Rt
∴ e at y (t ) − y (0) = f (t )e at dt
0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0

This is an equation of the kind ẏ (t ) = −ay (t ) + f (t )

use, the method of integrating factors, multiply both sides by e adt = e at ,
R

e at ẏ (t ) = −ay (t )e at + f (t )e at
or dtd (e at y ) = f (t )e at
Rt
∴ e at y (t ) − y (0) = f (t )e at dt
0
e at ≡ e k (n −1)t andt
0

Rt Rt
f (t )e at dt ≡ kn0 e −kn t e k (n −1)t dt = kn0 e −kt dt = n0 1 − e −kt
R

0 0

0 0 0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0

This is an equation of the kind ẏ (t ) = −ay (t ) + f (t )

use, the method of integrating factors, multiply both sides by e adt = e at ,
R

e at ẏ (t ) = −ay (t )e at + f (t )e at
or dtd (e at y ) = f (t )e at
Rt
∴ e at y (t ) − y (0) = f (t )e at dt
0
e at ≡ e k (n −1)t andt
0

Rt Rt
f (t )e at dt ≡ kn0 e −kn t e k (n −1)t dt = kn0 e −kt dt = n0 1 − e −kt
R

0 0

0 0 0
∴ e k (n −1)t Pn t ) − Pn −1 (0) = n0 1 − e −kt with the initial condition


−1 (
0
0 0

Pn −1 (0) = 0
0
For n = n0 ,
eqn. becomes, Ṗn = −kn0 Pn (t ) with the initial condition Pn (0) = 1
soln. : Pn (t ) = e −kn t Pn (0) = e −kn t
0 0 0
0 0
0 0

For n = n0 − 1, Ṗn −1 = kn0 Pn (t ) − k (n0 − 1)Pn −1 (t )

or, Ṗn −1 = −k (n0 − 1)Pn −1 (t ) + kn0 e −kn t with the initial condition
0 0 0
0
0 0

Pn −1 (0) = 0
0

This is an equation of the kind ẏ (t ) = −ay (t ) + f (t )

use, the method of integrating factors, multiply both sides by e adt = e at ,
R

e at ẏ (t ) = −ay (t )e at + f (t )e at
or dtd (e at y ) = f (t )e at
Rt
∴ e at y (t ) − y (0) = f (t )e at dt
0
e at ≡ e k (n −1)t andt
0

Rt Rt
f (t )e at dt ≡ kn0 e −kn t e k (n −1)t dt = kn0 e −kt dt = n0 1 − e −kt
R

0 0

0 0 0
∴ e k (n −1)t Pn −1 (t ) − Pn −1 (0) = n0 1 − e −kt with the initial condition


0
0 0

Pn −1 (0) = 0
0

n −1
or, Pn −1 (t ) = n0 e −kt 1 − e −kt
0


0
Similarly, for n = n0 − 2, Ṗn 0 −2 = k (n0 − 1)Pn 0 −1 ( t ) − k (n0 − 2)Pn −2 (t )
0
Similarly, for n = n0 − 2, Ṗn −2 = k (n0 − 1)Pn −1 (t ) − k (n0 − 2)Pn −2 (t )
0 0

n −1 0

or, Ṗn −2 = −k (n0 − 2)Pn −2 (t ) − k (n0 − 1)n0 e −kt 1 − e −kt

0


0 0

with initial condition Pn −2 (0) = 0

0
Similarly, for n = n0 − 2, Ṗn −2 = k (n0 − 1)Pn −1 (t ) − k (n0 − 2)Pn −2 (t )
0 0

n −1 0

or, Ṗn −2 = −k (n0 − 2)Pn −2 (t ) − k (n0 − 1)n0 e −kt 1 − e −kt

0


0 0

with initial condition Pn −2 (0) = 0

0

This can be solved as before and we get,

Pn −2 (t ) = n (n2 −1) e −kt n −2 1 − e −kt 2
0 0

0


0
Similarly, for n = n0 − 2, Ṗn −2 = k (n0 − 1)Pn −1 (t ) − k (n0 − 2)Pn −2 (t )
0 0

n −1 0

or, Ṗn −2 = −k (n0 − 2)Pn −2 (t ) − k (n0 − 1)n0 e −kt 1 − e −kt

0


0 0

with initial condition Pn −2 (0) = 0

0

This can be solved as before and we get,

Pn −2 (t ) = n (n2 −1) e −kt n −2 1 − e −kt 2
0 0

0


0

continuing like this, we get, Pn (t ) =

n0 e −kt

n
1 − e −kt

n −n
0

n
Similarly, for n = n0 − 2, Ṗn −2 = k (n0 − 1)Pn −1 (t ) − k (n0 − 2)Pn −2 (t )
0

n −1
0 0

or, Ṗn −2 = −k (n0 − 2)Pn −2 (t ) − k (n0 − 1)n0 e −kt 1 − e −kt

0

0 0

with initial condition Pn −2 (0) = 0 0

This can be solved as before and we get,

Pn −2 (t ) = n (n2 −1) e −kt n −2 1 − e −kt 2
0 0

0


0

continuing like this, we get, Pn (t ) =

n0 e −kt

n
1 − e −kt

n −n
0

n
n n  n0


n
n −n
⟨n⟩(t ) = nPn = n e −kt 1 − e −kt = e −kt n0
0 0
0
P P
0 0 n
Similarly, for n = n0 − 2, Ṗn −2 = k (n0 − 1)Pn −1 (t ) − k (n0 − 2)Pn −2 (t )
0

n −1 0 0

or, Ṗn −2 = −k (n0 − 2)Pn −2 (t ) − k (n0 − 1)n0 e −kt 1 − e −kt

0

0 0

with initial condition Pn −2 (0) = 0 0

This can be solved as before and we get,

Pn −2 (t ) = n (n2 −1) e −kt n −2 1 − e −kt 2
0 0

0


0

continuing like this, we get, Pn (t ) =

n0 e −kt

n
1 − e −kt

n −n
0

n
n n  n0


n
n −n
⟨n⟩(t ) = nPn = n e −kt 1 − e −kt = e −kt n0
0 0
0
P P
0 0 n
m  m

[using p a p b m −p =
P
0 p
mP
−1
(m−1)!
ma (p −1)!{(m−1)−(p −1)})! ap−1 b{(m−1)−(p−1)} = ma(a + b)m−1 and a + b = 1]
p−1=0
Note : 1. The choice of the transition probability Wn,n−1 is a trick. When we
know it is a rst order reaction, we x it as kn∆t . What should it be for a zeroth
order or second order reaction?
Note : 1. The choice of the transition probability Wn,n−1 is a trick. When we
know it is a rst order reaction, we x it as kn∆t . What should it be for a zeroth
order or second order reaction?
2. We could have obtained the nal result above by starting from rst order decay,
such that the probability of a molecule remaining unreacted after time t is e −kt
and not reacting is 1 − e −kt
n
=⇒ the probability of n molecules remaining unreacted after time t is e −kt and

n −n
not reacting is 1 − e −kt 0
3. The variance = n0 e −kt (1 − e −kt )
m m ap bm−p a+==
b =1
 
[using p2 m(m − 1)a2 + ma
P
p=0 p
3. The variance = n0 e −kt (1 − e −kt )
m m ap bm−p a+==
b =1
 
[using p2 m(m − 1)a2 + ma
P
p=0 p
standard
√ deviation, ∆ = σt2 = n0 e −kt (1 − e −kt ) and
p p

∆ n0 e kt (1−e −kt )
−
√1
⟨n ⟩ = e −kt n0 ∝ n 0
3. The variance = n0 e −kt (1 − e −kt )
m m ap bm−p a+==
b =1
 
[using p2 m(m − 1)a2 + ma
P
p=0 p
standard
√ deviation, ∆ = σt2 = n0 e −kt (1 − e −kt ) and
p p

∆ n0 e kt (1−e −kt )
−
√1
⟨n ⟩ = e −kt n0 ∝ n 0

i.e., the larger the number of molecules, the relative deviation from the mean will
be smaller. This is why the phenomenological results work - at the macroscopic
level, the deviation is negligible.
4. The assumption that the transition is occurring in a single step from n to n − 1
and not to n − 2 is tantamount to Markovian statistics.