Chemical kinetics, also called

reaction kinetics, is the study of

the rates and mechanisms of
1. Rates of consumption and formation
chemical reactions.
2. Rate of reaction
3. Rate laws and rate constants
4. Order of reaction
5. Integrated rate laws
6. Determination of rate laws
7. Effect of temperature on rate of reactions
8. Complex reactions
9. Mechanism of reactions
10. Chain reactions
11. Relaxation methods
1. Rates of Consumption and Formation
▪ Kinetic investigation are concerned with rates of change of

concentrations of reactants and products.

▪ Consider, a reaction :

A + 3B → 2Y
The rate of consumption of A at time t is

𝒅[𝑨]
𝒗𝑨 = − (1)
𝒅𝒕
The rate of formation of Y at time t is

𝒅[𝒀]
𝒗𝒀 = + (2)
𝒅𝒕
 A + 3B → 2Y

▪ In this particular reaction, the stoichiometric coefficients are different

for the three species, A, B and Y, and the rates of change of their
concentrations are correspondingly different.

▪ Thus,

1 1
𝑣𝐴 = 𝑣 = 𝑣 (3)
3 𝐵 2 𝑌
2. Rate of Reaction, ν
▪ Reaction rates depend on the composition and the temperature of the reaction

mixture.

▪ The extent of the reaction, ξ (xi), is the same for every reactant and product.

𝑛𝑖 = 𝑛𝑖,𝑜 + ν𝑖 ξ (4)

where 𝑛𝑖 = the amount of substrate i at any time

𝑛𝑖,𝑜 = the initial amount of the substrate I

ν𝑖 = the stoichiometric coefficient

▪ Taking the time derivative of ni yield

dni d Rate of conversion (5)

= vi
dt dt

▪ The concept of the extent of reaction forms the basis of the definition of rate of

reaction.
▪ The rate of reaction, v, is defined as the change of the extent of

reaction divided by the volume:

1 𝑑ξ 1 𝑑𝑛𝑖
𝑣= = (6)
𝑉 𝑑𝑡 𝑉ν𝑖 𝑑𝑡
𝑑𝑛𝑖
If the volume is constant, can be replaced by the concentration change,
𝑑𝑡

and the rate of reaction is:

1 𝑑[𝐶𝑖 ]
𝑣= (7)
ν𝑖 𝑑𝑡
This quantity is independent of which reactant or product species is chosen.
▪ For a reaction

aA + bB → yY + zZ
occurring at constant volume, the rate of reaction is:

1 d A 1 d B  1 d Y  1 d Z 
v=− =− = =
a dt b dt y dt z dt (8)
Example:
The reaction H2 + Br2 → 2HBr is carried out in a 0.250-L reaction vessel.
The change in the amount of Br2 in 0.01 s is – 0.001 mol.
(a) What is the rate of conversion dξ/dt? (b) What is the rate of reaction,
υ? (c) What are the values of d[H2]/dt, d[Br2]/dt and d[HBr]/dt?
Solution:

d 0.001 mol
(a ) = = 0.1 mol s −1
dt 0.01 s
1 d 0.1 mol s −1
( b)  = = = 0.40 mol L−1 s −1
V dt 0.25 L ;
d[H 2 ] d[Br2 ]
( c) = −0.40 mol L−1 s −1 = −0.40 mol L−1 s −1
dt dt

d[HBr]
= 0.80 mol L−1 s −1
dt
3. Rate laws and Rate Constants
▪ The rate of reaction is often found to be proportional to the
concentrations of the reactants raised to a power.
▪ Consider the reaction

A+ B →C

The rate of reaction is

v = k AB  (9)

where each concentration is raised to the first power. The coefficient k

is called the rate constant.
▪ The rate constant is independent of the concentrations but depends on
the temperature. An experimentally determined equation of this kind is
called the rate law of the reaction.
▪ A rate law is an equation of the concentration of all the species present
in the overall chemical equation for the reaction at some time.

v = f ( A , B  , .....)
(10)

▪ For homogenous gas- phase reaction, it is often more convenient to

express the rate laws in terms of partial pressures
v = f ( PA , PB , .....) (11)

▪ The rate law of a reaction is determined experimentally, and cannot in

general be inferred from the chemical equation for the reaction.
For example:
H 2 ( g ) + Br2 ( g ) → 2 HBr ( g )

The rate law is: k H 2 Br2  (12)

3/ 2
v=
Br2  + k ' HBr 
▪ Once we know the rate law and the value of the rate constant, we
can predict the rate of reaction from the composition of the
mixture.

▪ By knowing the rate law, we can predict the composition of the

reaction mixture at a later stage of the reaction.

▪ A rate law is a guide to the mechanism of the reaction, for any

proposed mechanism must be consistent with the observed rate
law.
4. Order of Reaction
▪ Many reactions are found to have rate laws of the form

v = k A B  ....
 
(13)
where
 and  = the order of the reaction with respect to reactants A and B,
respectively. (they are not the stoichiometric numbers but have to be
determined from the rate experiments)
▪ Overall order of the reaction =  +  + .....
▪ The order is not necessarily an integer.
➢ Example 1: a reaction having the rate law,

v = k A B
1/ 2

is half-order in A, first-order in B and three-halves-order overall.

➢ Example 2 (Eq. 9)
▪ Some reactions obey a zero-order rate law, and therefore have a rate
that is independent of the concentration of the reactant.

Example: The catalytic decomposition of phosphorene (PH3) on hot

tungsten at high pressure.

v=k
constant rate

Recap: the value of rate constant, k, is affected by temperature.

5. Integrated Rate Laws
▪ The rate law that governs a reaction is a differential equation that gives
the rates of change in the concentrations of the reacting species.

▪ To obtain the concentrations versus time predicted by a rate law, one

must integrate the rate law.

▪ In the following discussion, it is assumed unless stated otherwise that:

a) The reaction is carried out at constant temperature (k constant).
b) The volume is constant.
c) The reaction is ‘irreversible’, meaning that no significant amount of
reverse reaction occurs. This will be true if the equilibrium constant
is very large or if one studies only the initial rate.
5a. First-order reactions
Suppose the reaction
aA → products
is first-order, then the rate equation is:
1𝑑 𝐴 Unit: mol L-1
Unit: mol L-1s-1 𝑣=− = 𝑘[𝐴]
𝑎 𝑑𝑡 (14)
Defining k A as k A  ak : Unit: s-1

d A
− = k A [ A]
dt (15)
Rearranging Eq. (15):

d A
− = k A dt
[ A] (16)
If the concentration of A is [A] 1, at t1 and [A] 2 at t2, then

[ A ]2 d A 2
− = k A  dt
[ A ]1 [ A] 1

In
 A1
= k A (t 2 − t1 )
A2 (17)

If state 1 is the initial state at the start of the reaction when t = 0 and
[A]1 = [A]o , then eq. (17) becomes

For a first-
In
 Ao
= k At
A
order (18)
reaction, [A]
decreases
exponentially
Integrated
A = Ao e − k t
or
with time. A rate law
(19)

InA = InAo − k A t (20)

 InA = InAo − k At (20)

y c mx

A plot of In ([A]o/ [A]) versus t gives a straight line of slope -kA.

slope = − k A
The time needed for [A] to drop to half its value is called the
reaction’s half life, t1/2.

 
Substitute A = 1 / 2 A  o and t = t1/ 2 in eq. (18):
[ A]
In = k At1/ 2
1 / 2[ A]

ln 2 0.693
or t1/ 2 = = (21)
kA kA
For a first- order 1
reaction, the half-
life of a reactant is First-order
[A] 0.5
independent of its [A]o
initial
concentration. 0.25

00
1 2
t/t1
/2
Another indication of the rate of a first-order reaction is the relaxation
1
time, τ, the time required for [A] to fall to of its initial value.
𝑒

Substitute A = 1 / eAo and t=τ in eq. (18):

[ A]
In = kAτ
1 / e[ A]
1
or τ= (22)
kA

Thus, Eq. (19) becomes

A = Ao e −t / τ (23)

First-order reaction In
 Ao
= k At
k = 5.12 × 10-3 s-1 A UNITS!
P(N2O5)o = 0.500 atm
A = Ao e − k t
A

P(N2O5)t at t = 60.0 s ?
InA = InAo − k A t
First-order reaction ln 2 0.693
t1/ 2 = =
t1/2 = 7.1 × 108 year k k

k and τ ?
τ =
1
k
5b. Second-order reactions
The most commons of second-order rate laws are:

 = k[ A]2
and  = k[ A][ B]
where A and B are two different reactants.
5b. Second order (case 1)
Suppose the reaction

aA → products
is second-order, then the rate equation is:

1 d A
Unit: mol L-1 s-1 v=− = k[ A]2 Unit: (24)
a dt mol2 L-2

Unit: mol-1 L s-1

d A
or − = k A [ A]2 (25)
dt

where k A  ak
5b. Second order (case 1)
Rearrange Eq. (25) and integrate:
1
−
[ A ]2
d [ A] = k A  dt
t2
2
[ A ]1 [ A] t1

1 1
− = k A (t 2 − t1 )
[ A]2 [ A]1 (26)

1 1
or − = k At (27)
[ A] [ A]o

1
[ A] =
1 + k A t[ A]o (28)
Rearranging eq. (27):

1 1
= k At +
[ A] [ A]o

y mx c

A plot of 1/[A] versus t gives a straight line of slope kA.

1
[ A]

1 slope = k A
[ A]o
The half-life of a second-order reaction is

1
t1/ 2 = (29)
k A [ A]0
second-order reaction
1 1
[NO3]o = 0.0500 mol L-1
− =k t
[ A] [ A]o
UNITS!
[NO3] at t = 60.0 min = 0.0358 mol L-1
k?
5b. Second order (case 2)
Consider aA + bB → products
The rate equation is:
1 𝑑[𝐴] 1 𝑑[𝐵]
ν=− =− = 𝑘[𝐴][𝐵] (30)
𝑎 𝑑𝑡 𝑏 𝑑𝑡

Suppose, the initial concentrations of A and B are [A]o and [B]o

([A]o ≠ [B]o ), the rate after an amount x (per unit volume) has reacted
is
 b 
= k ([ A]o − x ) B o − x 
1 d[A]
−
a dt  a 
d [ A] dx
Since − =
dt dt

 b 
= k ([ A]o − x ) B o − x 
1 dx
a dt  a 
Rearranging the equation:

dx
= k A dt
b
([ A]o − x)([ B]o − x)
a
where k A = ak.
To solve an integral of this form, we use the method of partial fractions

1 x adx x bdx t

(a[ B]o − b[ B]o ) 0 ([ A]o − x)

−
0 b
=  k A dt
0
([ B]o − x)
a

The integrated raw law is:

1 [B][ A]o 1 [ A][ B]o

= kt or ln = kt
In
(a[ B]o − b[ A]o ) [A][ B]o (b[ A]o − aBo ) [ B][ A]o (31)
Example:
The reaction
n-C3H7Br + S2O32- → C3H7S2O3- + Br-
in aqueous solution is first-order in S2O32-. The following data were
obtained at 37.5 oC:
103 [S2O32-]/mol dm-3 96.6 90.4 86.3 76.6 66.8
t/103 s 0 1.110 2.010 5.052 11.232

The initial C3H7Br concentration was 39.5 mmol dm-3. Determine the
rate constant.
This is a second-order reaction.

Solution:
1 [B][ A]o
In = kt [𝐵]
Plot ln [𝐴] vs t
(a[ B]o − b[ A]o ) [A][ B]o

= (a[B]o − b[A]o )kt + ln

[B] [B]o Determine k from the
ln
[A] [A]o slope.
 a=b=1
Let A C3H7Br and B  S2O32- .

At time t, [A] – [A]o = [B] – [B]o [B]

Using these information, [A] and so ln
[A]
can be calculated.
t/s 0 1110 2010 5052 11232
[B]/mmol dm-3 96.6 90.4 86.3 76.6 66.8
[A]/mmol dm-3 39.5 33.3 29.2 19.5 9.7
0.894 0.999 1.084 1.368 1.930
ln [B]
[A]
slope = 9.2 x 10-5 s-1
slope = 𝑎[𝐴]0 − 𝑏[𝐵]0 𝑘

a[B]o – b[A]o = (96.6 – 39.5) mmol dm-3

= 57.1 mmol dm-3
ln [B]
[A]
∴ k = 9.2 x 10-5 s-1/0.0571 mol dm-3
= 1.61 x 10-3 dm3 mol-1 s-1

t/s
Pseudo-first-order
aA + bB → products
ν = k[A][B]
(32)
If reactant B is in large excess, then

[ B] = [ B]o − x  [ B]o

Eq. (32) becomes

ν = k[A][B]o
Pseudo-first-order
= k [A]
'
rate law (33)
(the true rate law is
where k ' = k[B]o forced into first-
order form by
assuming that the
[B] is constant.
 5c. Simple third-order reactions
Consider aA → product
The rate equation for a simple third-order reaction is:
d[A]
Unit: mol L-1 s-1 ν=− = k A [A] 3 Unit: mol3 L-3
dt (34)
Unit: : mol-2 L2 s-1
Rearrange the equation and integrate:
[𝐴] 𝑡
𝑑[𝐴]
−න 3
= 𝑘𝐴 න 𝑑𝑡
[𝐴]𝑜 [𝐴] 0

1 1
− (− 2
+ 2
) = k At
2[ A] 2[ A]o
1 1
or
2
− 2
= 2 k At (35)
[ A] [ A]o
As usual we define half-life as the time when [A] = ½ [A]o, which gives,

1 1
2
− 2
= 2 k At 1
 [A]0  [A]0
 
2

 2 
3
2
= 2 k At 1
[ A]0 2

3
t1 = 2
2 2k A [ A]o (36)
 5d. Zeroth-order reactions
A reaction is zero order if the rate is independent of the concentration of
the reactant.
The rate equation is:
d[A]
Unit: mol L-1s-1 ν=− =k (37)
dt Unit: mol-1 L s-1

Rearrange the equation and integrate:

[ A] t
− d[A] = k  dt
[ A ]o 0 (38)

[ A]o − [ A] = kt (39)

[ A]o
The half life: t1 / 2 = (40)
2k
 5e. nth-order reactions
Of the many nth- order laws, we consider
d[A] (41)
ν=− = k A [ A]n
dt
Integration gives:
[A] d[A] t
[A]o [A] n
= −k A  dt
o (42)

- n +1
[A] − n +1 − [A] o
The integrated = −k A t for n  1 (43)
− n +1
rate law:
n −1
Multiply both sides by (1 − n)[A]o
[A] 1− n n −1
( ) = 1 + [A]o (n − 1 ) k At for n  1
[A]o (44)
 Summary
Reaction Differentiate Integrated rate Linear plot Slope of Units of rate
order rate law law linear plot constant

d[A]
0 − =k [A] = −kt + [A]0 [A] vs t −k mol.L−1.s −1
dt

= k[A] ln[ A] = −kt + ln[ A]0

d[A]
1 − ln[A] vs t −k s −1
dt
1 1 1
2 d[A] = kt + vs t mol −1.L.s −1
− = k[A]2 [A] [A]0 [A]
k
dt
1 1 1
3 −
d[A]
= k[A]3 = 2 kt + 2
vs t 2k mol −2 .L2 .s −1
dt [A]2 [A]02 [A]
6. Determination of the Rate Law
▪ Experimental data give species concentrations at various times
during the reaction.
▪ The discussion is restricted to cases where the rate law has the
form

v = k[ A] [ B]  ......[ L]

▪ It is usually best to find the orders , , ….. first and then find the
rate constant k.
Techniques for finding rate laws
(NOT from the balanced equation)

a) Fitting data to rate laws (integrated form)

b) Isolation method
c) Differential method
d) Half-lives
 6a. Data fitting into rate laws

• Try and error.

• Errors < 5 %, the proposed rate law is consistent with the data.
• Expect to get a straight line.
• If the fit is not good enough, another law will have to be proposed
and tested against the data.

1 1
ln[ A] = ln[ A]0 − kt kt = −
[ A] [ A]0 [ A]0 − [ A] = kt
First-order Second-order Zero-order
 6b. Isolation method
• The determination of a rate law is simplified by the isolation method in
which the concentrations of all reactants except one are in large excess.
• Consider A + B → products
The true rate law is

d [ B]
− = k3rd [ A]2 [ B] (45)
dt
Make A in large excess that [A]>>[B], (eg. 50x) so that [A] concentration
is assumed to remain constant throughout the reaction.
Eq. (45) becomes
Pseudo-first- 𝑑[𝐵]
order rate − = 𝑘𝑒𝑓𝑓 [𝐵] where 𝑘𝑒𝑓𝑓 = 𝑘3𝑟𝑑 [𝐴]𝑜 2
𝑑𝑡 (46)
law

Several measurements made at different excess [A], the value of k3rd

can be found from a plot of keff against [A]02
6c. Differential method
Consider
A → products

The rate law is:

ν = k[ A] n
(47)

or ln ν = ln k + n ln[ A] (48)

Determine n by plotting ln [ν] vs ln [A] where n is the slope.

6d. Half-life method
This method applies when the rate law has the form
d[A]
ν=− = k A [ A]n (41)
dt
The integrated rate law is:
[A] 1− n n −1
( ) = 1 + [A]o (n − 1 ) k At for n  1 (44)
[A]o
The half-life is:
2 n −1 − 1
t1 / 2 = n −1
n 1
(n − 1 )[A]o k A

2 n −1 − 1
or log t1 / 2 = −(n − 1) log[ A]o + log n 1 (49)
(n − 1)k A
A plot of log t1/2 versus log [A]o gives a straight line of slope (1-n).
Example:

The data for the dimerization reaction 2A → A2 of a certain nitrile oxide (compound A)
in ethanol solution at 40 oC are as follows:

[A]/mmol dm-3 68.0 50.2 40.3 33.1 28.4 22.3 18.7 14.5
t/min 0 40 80 120 160 240 300 420

Determine the reaction order using the half-life method.

Solution:

1) Plot [A] versus t :

2) Determine half-lives

34
 [A]/mmol dm-3 68→34 60→30 50→25 40→20 30→15
t/min 0→114 14→146 42→205 82→280 146→ 412

(The fact that the half-life is not constant indicates that the reaction is not first
order.)

The [A]o and corresponding t1/2values can be determined from the graph and
their log values are:

[A]/mmol dm-3 68 60 50 40 30
t1/2/min 114 132 163 198 266
log (t1/2 /min) 2.057 2.121 2.212 2.297 2.425
log ([A]o/mmol dm-3) 1.833 1.778 1.699 1.602 1.477

2 n −1 − 1
log t1 / 2 = −(n − 1) log[ A]o + log n 1
(n − 1)k A
 3) Plot of log t1/2 vs log [A]o : 2 n −1 − 1
log t1 / 2 = −(n − 1) log[ A]o + log
(n − 1)k A

The slope = -1.06 = 1-n

Hence, n = 2.06
log t 1/2
The reaction is therefore second-
order.

0 1.4 1.6 1.8 Intercept = 3.937

log[A]o = log (2n-1-1)/(n-1)kA
1
k = 8649.7
A

kA = 1.156 x 10-4 dm3 mmol-1 min-1

k = 5.78 x 10-5 dm3 mmol-1 min-1

7. Temperature dependence of reaction rates
The dependence of rate constants on temperatures over a limited range
can be represented by Arrhenius equation:
− Ea
k = Ae RT (50)

or in linear form:
Ea
ln k = ln A − (51)
RT

A is the pre- exponential factor or the frequency factor and Ea is the

activation energy.

1
If the Arrhenius equation is obeyed a plot of In k versus is a straight line
𝑇
𝐸𝑎
with slope - and intercept ln A.
𝑅
Activation energy

➢ In a chemical reaction, bonds are

broken and new bonds are formed.

➢ Reactant molecules must collide with

correct orientation and with enough
energy to cause bond breakages and
formations.

➢ Ea = the minimum kinetic energy that

reactant mush have in order to form
products.
Maxwell-Boltzmann distributions

➢ In a gas-phase reaction, there are numerous collisions each second, but

only a tiny proportion are sufficiently energetic to lead to reaction.
The pre-exponential factor is a The fraction of
measure of the rate at which collisions with a kinetic
collisions occur irrespective of their energy in excess of an
energy. − Ea energy Ea.
k= A e RT

Rate of successful collisions.

The temperature dependence of some reaction is not Arrhenius-
like in the sense that a straight line is not obtained when In k versus
1
.
𝑇

However, it is still possible to define activation energy as:

 d ln k 
Ea = RT  2
 (52)
 dT 

Integration of (51) yields:

k 2 Ea  T2 − T1 
ln =   (53)
k1 R  T1T2 
Example:
The reaction: 2 NO2(g) → 2NO(g) + O2(g)
The rate constant k = 10-10 s-1 at 300 K and the Ea = 111 kJ mol-1.
What are (i) A at 300 K; (ii) k at 273 K; and (iii)T when k = 10-11 s-1.

Solution:
111000 J mol −1

( )
Ea
(i) A = ke RT
= 110 −10 s −1 e 8 .314 J mol −1 K −1 300 K
= 2.13 109 s −1
−111000 J mol −1

( )
E
− a
(ii) k = Ae RT
= 2.13 109 s −1 e 8 .314 J mol −1 K −1 273 K
= 1.23 10 −12 s −1

𝐸𝑎 111000 𝐽 𝑚𝑜𝑙 −1
(iii) 𝑇 = = 9 𝑠 −1 = 285𝐾
𝐴 −1 −1 2.13 × 10
𝑅 ln
𝑘 8.314 𝐽 𝑚𝑜𝑙 𝐾 × ln 10−11 𝑠 −1
8. Elementary Reactions and Mechanism
Elementary reactions are steps of molecular events showing how
reactions proceed.
The sequence of elementary reactions that add up to give the overall
reaction is called the mechanism of the reaction.
Example: The mechanism for the reaction between CO and NO2 is
proposed to be
Step 1 NO2 + NO2 → NO3 + NO (an elementary reaction)
Step 2 NO3 + CO → NO2 + CO2 (an elementary reaction)

Add these two equations led to the overall reaction

NO2 + CO → NO + CO2 (overall reaction)

A mechanism is a proposal to explain the rate law, and it has to satisfy

the rate law.
 Molecularity of Elementary Reactions
the number of reactant
Molecularity molecules in an
elementary step.

Unimolecular Bimolecular Trimolecular

reaction reaction reaction

Number of 1 2 3
reactant?

Example. O3 → O2 + O NO2 + NO2 → NO3 + NO 2Br• + Ar → Br2 + Ar*

Order of
First order. Second order. Third order.
reaction
rate = k [O3] rate = k [NO2]2 rate = k [Br•]2[Ar]
and rate
law * The rate law of an elementary step can be obtained directly
from its chemical equation step.
Example:
Some elementary reactions for the reaction between CH4 and Cl2 are:
Cl2 → 2 Cl•
2 Cl• → Cl2
Cl• + CH4 → HCl + CH3•
CH3• + Cl• → CH3Cl
CH3• + CH3• → CH3-CH3
CH3Cl + Cl• → HCl + CH2Cl•
CH2Cl• + Cl• → CH2Cl2
* * * (more)
rate = k [Cl2]
rate = k [Cl•]2
rate = k [Cl•][CH4]
rate = k [CH3•][Cl•]
rate = k [CH3•]2
rate = k [CH3Cl][Cl•]
rate = k [CH2Cl•][Cl•]
9. Complex Reactions
(combinations of elementary steps)

Reversible unimolecular
K = k1/k-1 ; “principle of microscopic
k-1 reversibility”

Parallel unimolecular

Consecutive unimolecular

C Consecutive reversible unimolecular

k-1
10. Approximation Methods for Reaction
Mechanism

The observed rate law provides information on the mechanism of a

reaction in that any proposed mechanism must yield the observed
rate law.

Usually an exact deduction of the rate law from the differential rate
equations of a multi-step mechanism is not possible because of
mathematical difficulties.

Therefore one of the two approximation methods is generally used:

a. Rate Determining Step

b. Pre-equilibrium
c. Steady-state Approximation
10a. Rate-determining Step
The rate- determining step is the slowest step in a mechanism and
controls the overall rate of the reaction.

Example 1:
The observed rate law for the reaction,

2 NO2 (g) + F2 (g) → 2 NO2F (g)

is rate = k [NO2] [F2].

A two-step mechanism is proposed:
1. NO2 (g) + F2 (g) → NO2F (g) + F (g) (Slow)
2. NO2 (g) + F (g) → NO2F (g) (Fast)
Which is the rate determining step?
Answer:
The rate for step 1 is rate = k [NO2] [F2], which is the rate law, this
suggests that step 1 is the rate-determining or the slow step.
Example 2:
The decomposition of H2O2 in the presence of I– follow this mechanism:

k1
(i) H2O2 + I– → H2O + IO– slow
k2
(ii) H2O2 + IO– → H2O + O2 + I– fast
What is the rate law?
Energy
Solution
The slow step determines the rate, and
Eai
the rate law is:
rate = k1 [H2O2] [I–] Eai
i
Since both [H2O2] and [I–] are
measurable in the system, this is the
rate law. reaction
10b. Pre-equilibrium
Consider: kf
𝑎𝐴 + 𝑏𝐵 𝑐𝐶 + 𝑑𝐷
kr

Raw law for the elementary reactions:

v f = k f [A] a [B] b (54)

vr = k r [C] c [D] d (55)

At equilibrium, forward rate = reverse rate:

k f [A] a [B] b = k r [C] c [D] d (56)

The equilibrium constant, K:

kf 𝐶 𝑐
𝐷 𝑑
𝐾= = (57)
kr 𝐴 𝑎
𝐵 𝑏
Example 1:
The rate law for the Br- catalyzed aqueous reaction:
+ Br − +
H + HNO 2 + C 6 H 5 NH 2 ⎯⎯⎯→ C 6 H 5 N 2 + 2H 2 O

is observed to be:
v = k[H + ][HNO 2 ][Br - ]

A proposed mechanism is:

+ k2
H 2 NO 2 + Br − ⎯⎯→ ONBr + H 2 O slow
k3 +
ONBr + C 6 H 5 NH 2 ⎯⎯→ C 6 H 5 N 2 + H 2 O + Br - fast

Deduce the rate law for this mechanism and relate the observed rate
constant k to the rate constants in the assumed mechanism.
Solution:
The second step in the mechanism is the determining step. The
+
reaction rate is: v = k 2 [H 2 NO 2 ][Br − ]
The species H2NO2+ is a reaction intermediate and we need to
express v in terms of reactants and products.

Since step 1 is in near equilibrium,

+
k [H NO 2 ]
K = 1 = +2
k-1 [H ][HNO2 ]
+  k1  +
[H 2 NO 2 ] =  [H ][HNO2 ]
 k-1 
Substitute this equation into v:
 k 2 k1  + −
v =  [H ][HNO 2 ][Br ]
 k -1 
k 2 k1
k= = K k2
k -1
Example 2:
The observed rate law for the reaction:

2O3 (g) ⎯
⎯→ 2O 2 (g)

is observed to be:
[O3 ]2
v=k
[O2 ]
A proposed mechanism is:
k1
O3 O2 + O fast equilibrium
k-1
k2
O 3 + O ⎯⎯→ 2O 2 slow
Deduce the rate law for this mechanism using pre-equilibrium
calculation and relate the observed rate constant k to the rate
constants in the proposed mechanism.
Solution:
The second step in the mechanism is the determining step. The
reaction rate is: v = k 2 [O3 ][O]

The species O is a reaction intermediate.

Since step 1 is in near equilibrium,

k1 [O 2 ][O]
K= =
k-1 [O 3 ]
K [O 3 ]
[O] =
[O 2 ]
Substitute this equation into v:
[ O 3 ]2
v = k2 K
[O 2 ]

k = k2 K
Example 3:
Derive the rate law for the reaction, H2 + Br2 → 2 HBr.
From the proposed mechanism:

Br2 2Br fast equilibrium (k1, k-1 )

H 2 + Br ⎯⎯→
k2
HBr + H slow
H + Br ⎯⎯→k3
HBr fast
Solution:
The slow step determines the rate law,
rate = k2 [H2] [Br] where Br is an intermediate
The fast equilibrium condition simply says that
k1 [Br2] = k-1 [Br]2
and [Br] = (k1/k-1 [Br2])½

Therefore, rate = k2 [H2] (k1/k-1 [Br2])½

= k [H2] [Br2] ½
where k = k2 (k1/k-1)½ = k2K½ (Unit of k: M-½ s -1)
The total order is 1.5.
10c. Steady-state approximation
Multi- steps reaction mechanism usually involves one or more
intermediate species that do not appear in the overall equation.

The steady- state approximation assumes that, after initial induction

period, an interval during which the concentration of intermediates, I,
rise from zero, and during the major part of the reaction, the rates
of change of concentrations of all reaction intermediates are
negligibly small.

d[I ]
0
dt
(58)
 k1
Consider: 𝐴+𝐵 I
k-1
k2
I ⎯⎯→ P
The rate law for the production of P:

d [ P] (59)
= k2 [ I ]
dt
I is an intermediate.
Applying steady-state approximation, d [ I ] .
=0
dt
d[I ] (60)
= k1[ A][ B] − k −1[ I ] − k 2 [ I ] = 0
dt (61)
k1[ A][ B]
[ I ] =
k −1 + k 2
Substituting Rq. (61) into (59) yields:

d [ P] k1k 2 [ A][ B] (62)

=
dt k −1 + k 2
Example 1:
Consider 2NO + H 2 ⎯
⎯→ N 2 O + H 2 O

A proposed mechanism is:

k1
2NO N 2O 2
k-1
k2
N 2 O 2 + H 2 ⎯⎯→ N 2O + H 2O

Derive the rate law for this reaction using steady-state

approximation.

Solution:

Step 1: Write the raw law for the reaction.

d [ N 2O ]
ν= = k 2 [ N 2O2 ][ H 2 ] (i)
dt
 d [ N 2O ]
ν= = k 2 [ N 2O2 ][ H 2 ]
dt
Step 2: Identify intermediate and solve the equation using the apply
steady-state approximation.

N2O2 is an intermediate.

𝑑[𝑁2 𝑂2]
= 𝑘1 [𝑁𝑂]2 − 𝑘−1 [𝑁2 𝑂2 ] − 𝑘2 [𝑁2 𝑂2 ][𝐻2 ] ≈ 0 (ii)
𝑑𝑡
𝑘1 [𝑁𝑂]2
∴ [𝑁2 𝑂2 ] = (iii)
𝑘−1 + 𝑘2 [𝐻2 ]

Step 3: Substitute Eq. (iii) into the Eq. (i)

d [ N 2O] k1k 2 [ NO]2 [ H 2 ]

ν= =
dt k −1 + k 2 [ H 2 ]
Example 2:
Derive the rate law for the formation of HI :

H 2 + I2 ⎯
⎯→ 2HI
The mechanism as follow:
k1
I 2 ⎯⎯→ 2I
k −1
2I ⎯⎯→
⎯ I2
k2
H 2 + 2 I ⎯⎯→ 2HI
Solution:

The rate law:

d [ HI ]
= 2k 2 [ H 2 ][ I ]2 (i)
dt

Steady-state approximation:

d[I ]
= 2k1[ I 2 ] − 2k −1[ I ]2 − 2k 2 [ H 2 ][ I ]2 = 0 (ii)
dt
k1[ I 2 ]
[ I ] =
2
(iii)
k −1 + k 2 [ H 2 ]

Substitute eq. (iii) into eq. (i):

d [ HI ] 2k1k 2 [ H 2 ][ I 2 ]
=
dt k −1 + k 2 [ H 2 ]
Example 3:
Derive the rate law for the reaction below:

H 2 + I2 ⎯
⎯→ 2HI
The mechanism as follow:
k1
I 2 ⎯⎯→ 2I
k −1
2I ⎯⎯→
⎯ I2
k2
H 2 + 2 I ⎯⎯→ 2HI
Solution:

The rate law:

1 d [ HI ] d[H 2 ] d[I 2 ]
rate = =− =−
2 dt dt dt

From the previous solution :

d [ HI ] 2k1k 2 [ H 2 ][ I 2 ]
=
dt k −1 + k 2 [ H 2 ]
1 d [ HI ] k1k 2 [ H 2 ][ I 2 ]
Rate = =
2 dt k −1 + k 2 [ H 2 ]
Solution (alternative):

The rate law:

1 d [ HI ] d[H 2 ] d[I 2 ]
rate = =− =−
2 dt dt dt (i)

d[H 2 ] (ii)
= −k 2 [ H 2 ][ I ]2
dt
Steady - state approximation(from previous solution) :
k1[ I 2 ]
[ I ]2 =
k −1 + k 2 [ H 2 ] (iii)
d[H 2 ] k1k 2 [ H 2 ][ I 2 ] (iv)
 =−
dt k −1 + k 2 [ H 2 ]
Therefore,
d[H 2 ] k1k 2 [ H 2 ][ I 2 ]
rate = − =+
dt k −1 + k 2 [ H 2 ]
11. Chain Reactions
Many gas- phase reactions and liquid- phase polymerization reactions
are chain reactions.

Example 1:

Consider hydroge-bromine reactions:

H 2 (g) + Br2 (g) → 2HBr(g)

The experimental rate law is:

1
d[HBr] 𝑘′ 𝐻2 𝐵𝑟2 2
=
dt 𝐻𝐵𝑟 (63)
1 + 𝑘 ′′
𝐵𝑟2
The postulated mechanism:

(64)
(65)
(66)
(67)
(68)

The net rate of formation of the product, HBr, is:

d[HBr]
=𝑘𝑏 [Br∙] 𝐻2 + 𝑘𝑐 H∙ 𝐵𝑟2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 (69)
dt

Intermediate?
Br∙ and H∙
The postulated mechanism:

(64)
(65)
(66)
(67)
(68)

d[Br∙]
=2𝑘𝑎 𝐵𝑟2 − 𝑘𝑏 [Br∙] 𝐻2 + 𝑘𝑐 H∙ 𝐵𝑟2 + 𝑘𝑑 H∙ 𝐻𝐵𝑟 -2𝑘𝑒 [Br∙]2 ≈ 0
dt
(70)
d[H ∙ ]
=𝑘𝑏 [Br∙] 𝐻2 − 𝑘𝑐 H∙ 𝐵𝑟2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 ≈ 0 (71)
dt

d[HBr]
=𝑘𝑏 [Br∙] 𝐻2 + 𝑘𝑐 H∙ 𝐵𝑟2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 (69)
dt
Eq. (70) + (71):

2𝑘𝑎 𝐵𝑟2 -2𝑘𝑒 [Br∙]2 ≈ 0 (72)

1
𝑘𝑎 2
𝐵𝑟 ∙ = 𝐵𝑟2 (73)
𝑘𝑒

From eq. (71):

𝑘𝑏 [Br∙] 𝐻2
[H ∙ ]= (74)
𝑘𝑐 𝐵𝑟2 + 𝑘𝑑 𝐻𝐵𝑟

substituting eq. (73) into (74):

1
𝑘𝑎 2
𝑘𝑏 𝐵𝑟2 𝐻2
𝑘𝑒
[H ∙ ]= (75)
𝑘𝑐 𝐵𝑟2 + 𝑘𝑑 𝐻𝐵𝑟
 d[HBr]
=𝑘𝑏 [Br∙] 𝐻2 + 𝑘𝑐 H∙ 𝐵𝑟2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 (69)
dt
d[H ∙ ] (71)
=𝑘𝑏 [Br∙] 𝐻2 − 𝑘𝑐 H∙ 𝐵𝑟2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 ≈ 0
dt
Rearrange eq. (71):

𝑘𝑏 [Br∙] 𝐻2 − 𝑘𝑑 H∙ 𝐻𝐵𝑟 = 𝑘𝑐 H∙ 𝐵𝑟2 (71a)

Substituting eq. (71a) into (69):

d[HBr]
=2𝑘𝑐 H∙ 𝐵𝑟2 (76)
dt

Substituting eq. (75) into (76):

1
𝑘𝑎 2
d[HBr] 𝑘𝑏 𝐵𝑟2 𝐻2
𝑘𝑒 (77)
=2𝑘𝑐 𝐵𝑟2
dt 𝑘𝑐 𝐵𝑟2 + 𝑘𝑑 𝐻𝐵𝑟
 1
𝑘𝑎 2
d[HBr] 𝑘𝑏 𝐵𝑟2 𝐻2
𝑘𝑒 (77)
=2𝑘𝑐 𝐵𝑟2
dt 𝑘𝑐 𝐵𝑟2 + 𝑘𝑑 𝐻𝐵𝑟

Rearrange eq. (77):

1
𝑘𝑎 2 1
d[HBr] 𝑘𝑏 𝐻2 𝐵𝑟2 2
𝑘𝑒 (77a)
=2
dt 𝑘 𝐻𝐵𝑟
1+ 𝑑
𝑘𝑐 𝐵𝑟2

Compare with experimental rate law (eq. (63)):

1
d[HBr] 𝑘 𝐻2 ′
𝐵𝑟2 2
=
dt 𝐻𝐵𝑟
1 + 𝑘 ′′
𝐵𝑟2

Eq. (77a) has the same form as Eq. (63), with:

1
𝑘 2 𝑘𝑑
𝑘 ′= 2𝑘𝑏 𝑘𝑎 and 𝑘 ′′ =
𝑒 𝑘𝑐
Example 2:

This reaction (gas phase) is a very important commercial reaction because

ethylene is a precursor to many important products.

C2H6 → C2H4 + H2

At 700-900 K, and pressure above ~0.2 bar, this reaction is first order in its
early stages.
The stages of the reaction appear as follows:

(78)

(79)

(80)

(81)

(82)
 (78)

(79)

(80)

(81)

(82)

Define the rate as the rate of production of C2H4:

d[𝐶2 𝐻4 ]
=𝑘3 [𝐶2 𝐻5 ∙] (83)
dt
d[𝐶2 𝐻5 ∙]
= 𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 − 𝑘3 [𝐶2 𝐻5 ∙] + 𝑘4 [𝐻∙] 𝐶2 𝐻6 − 𝑘5 [𝐶2 𝐻5 ∙] 𝐻∙ ≈ 0 (84)
dt Identify intermediates and apply steady-state approximation.
d[𝐻∙]
2 𝐻𝑘55∙ [𝐶2 𝐻5 ∙] 𝐻∙ ≈ 0
= 𝑘3 [𝐶2 𝐻5 ∙] − 𝑘4 [𝐻∙] 𝐶2 𝐻6 𝐶− (85)
dt 𝐻∙
d[𝐶𝐻3 ∙] 𝐶𝐻3 ∙
= 2𝑘1 [𝐶2 𝐻6 ] − 𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 ≈ 0 (86)
dt
 d[𝐶2 𝐻5 ∙]
= 𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 − 𝑘3 [𝐶2 𝐻5 ∙] + 𝑘4 [𝐻∙] 𝐶2 𝐻6 − 𝑘5 [𝐶2 𝐻5 ∙] 𝐻∙ ≈ 0 (84)
dt

d[𝐻∙]
= 𝑘3 [𝐶2 𝐻5 ∙] − 𝑘4 [𝐻∙] 𝐶2 𝐻6 − 𝑘5 [𝐶2 𝐻5 ∙] 𝐻∙ ≈ 0 (85)
dt
d[𝐶𝐻3 ∙]
= 2𝑘1 [𝐶2 𝐻6 ] − 𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 ≈ 0 (86)
dt

Eq. (84) + (85) and rearrange:

𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 − 2𝑘5 [𝐶2 𝐻5 ∙] 𝐻∙ = 0

𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6
∴ [𝐶2 𝐻5 ∙]=
2𝑘5 𝐻∙ (87)
Rearranging eq. (86):
2𝑘1
[𝐶𝐻3 ∙]= (88)
𝑘2

Substituting eq. (88) into (87):

𝑘1 𝐶2 𝐻6
[𝐶2 𝐻5 ∙]= (89)
𝑘5 𝐻∙
 𝑘1 𝐶2 𝐻6
[𝐶2 𝐻5 ∙]= (89)
𝑘5 𝐻∙
d[𝐶2 𝐻5 ∙]
= 𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 − 𝑘3 [𝐶2 𝐻5 ∙] + 𝑘4 [𝐻∙] 𝐶2 𝐻6 − 𝑘5 [𝐶2 𝐻5 ∙] 𝐻∙ ≈ 0 (84)
dt
Rearranging eq. (84), with :
𝑘2 [𝐶𝐻3 ∙] 𝐶2 𝐻6 + 𝑘4 [𝐻∙] 𝐶2 𝐻6 (90)
[𝐶2 𝐻5 ∙] =
𝑘3 + 𝑘5 𝐻∙
Substituting eq. (88) into (90):

2𝑘1 𝐶2 𝐻6 + 𝑘4 [𝐻∙] 𝐶2 𝐻6
[𝐶2 𝐻5 ∙] = (91)
𝑘3 + 𝑘5 𝐻∙

Eq. (89)= (91):

𝑘1 𝐶2 𝐻6 2𝑘1 𝐶2 𝐻6 + 𝑘4 [𝐻∙] 𝐶2 𝐻6
=
𝑘5 𝐻∙ 𝑘3 + 𝑘5 𝐻∙

Rearranging:
𝑘1 2𝑘1 + 𝑘4 [𝐻∙]
= (92)
𝑘5 𝐻∙ 𝑘3 + 𝑘5 𝐻∙
Rearranging eq. (92) and solve for 𝐻∙ :

𝑘4 𝑘5 [𝐻∙]2 + 𝑘1 𝑘5 𝐻∙ − 𝑘1 𝑘3 = 0

−𝑘1 𝑘5 ± 𝑘1 𝑘5 𝑘1 𝑘5 + 4𝑘3 𝑘4
[𝐻∙] = = 𝑘′ (93)
2𝑘4 𝑘5

Substituting eq. (93) into (89):

𝑘1 𝐶2 𝐻6
[𝐶2 𝐻5 ∙]= (94)
𝑘5 𝑘′

Substituting eq. (94) into (83), the rate law becomes:

d[𝐶2 𝐻4 ] 𝑘3 𝑘1 𝐶2 𝐻6
= (95)
dt 𝑘5 𝑘′

The reaction is first order in ethane.

12. Relaxation Method
• The essential feature of all methods of studying the kinetics of a
reaction is to determine the time dependence of concentrations of
reactants or products.
• Some reactions are so fast that special techniques have to be
employed in order for this to be possible.
H+ + OH− → H2O
Ba2+(aq) + SO42− (aq) → BaSO4(s).
• The term relaxation denotes the return of a system to equilibrium.
• A system in equilibrium is disturbed by a sudden change of one of
the independent variables (usually temperature (temperature-jump
method) or pressure (pressure-jump)) and the change of the
system to the new equilibrium is followed.
(a) Suppose that the reaction is of the simple type:

(96)

The reaction is first-order in each direction.

When a T-jump is applied to the the equilibrium, the composition
relaxes exponentially to the new equilibrium composition:
t
−τ
x= xo e (97)

1
= k1 + k −1 (98)
τ

where x is the deviation of concentration from new equilibrium and xo is

the deviation immediately after the temperature jump (at t =0).
Suppose that the reaction is of the simple type:

(96)

At the initial state of equilibrium, the product B is at a certain

concentration and it stays at this concentration until the temperature
jump occurs, when the concentration changes to another value.

At the initial temperature, when the rate constants are k’1 and k’-1, the
net rate of change of [A] is

d[A]
= −k'1 [A] + k'-1 [B] (97)
dt
At equilibrium under these conditions:

d[A]
=0
dt
and the concentrations are [A]′𝑒 and [B]′𝑒 .
Therefore,

k1 ′ A ′e = k −1 ′[B]′e (98)

When the temperature is increased suddenly, the rate constants change

to k1 and k-1 but the concentration of A and B remain for an instant at
their old equilibrium values. As the system is no longer at equilibrium, it
readjust to the new equilibrium concentrations.

k1 A e= k −1 B e
(99)
Let x be the deviation of [𝐴] from its new equilibrium value at time t,

[A] = x + A (100)
e

B = −x + B (101)
e

d[A]
= −k 1 [A] + k -1 [B]
dt
= −k 1 ( x + [A]e ) + k -1 (- x + [B]e )
= −(k 1 + k -1 ) x

dx
= −(k1 + k -1 ) x (102)
dt
Integration gives:

𝑥 𝑡
𝑑𝑥
න = − k1 + k −1 න 𝑑𝑡
𝑥𝑜 𝑥 0

ln x − ln xo = − k1 + k −1 t

x = x o e− k1 +k−1 t

t
−τ
x = xo e (97)

1
= k1 + k −1 (98)
τ

t 𝑥𝑜
or = ln (103)
τ 𝑥
 ′=
𝐭=𝟎
k1 ′ A e k −1 ′[B]′e

t
−τ
x = xo e
Concentration, [A]

𝐱𝐨 [A] = x + A e

Exponential
relaxation
𝐱
k1 A e= k −1 B e

T1 T2

Time, t
The relaxation to the new equilibrium composition when a reaction
initially at equilibrium at temperature T1 is subjected to a sudden
change of temperature to T2.
(b) Consider the reversible elementary reaction:

(104)

At the new temperature,

d[A]
= −k 1 [A][B] + k 2 [C]
dt
let x = [A] − [A]e
Then [A] = x + [A]e (105)
[B] = x + [B]e (106)
[C] = − x + [C]e (107)

where [A]e, [B]e, [C]e are the equilibrium concentrations at the new
temperature.
 dx
= −k 1 ( x + [A]e )( x + [B]e ) + k 2 (− x + [C]e )
dt
= −k 1 ( x 2 + x[A]e + x[B]e + [A]e [B]e ) + k 2 [C]e − k 2 x
= −k 1 [A]e [B]e + k 2 [C]e − x{k 1 ( x + [A]e + [B]e ) + k 2 }
(108)
At equilibrium,
d[A] ;
=0 k1[A]e [B]e = k 2 [C]e
dt
Since the perturbation is small, the deviation x of [A] from its
equilibrium value is small and

x  [A]e + [B]e
Eq. (108) becomes,

dx
= -{k1 ([A]e + [B]e ) + k 2 }x (109)
dt
 dx
= -{k1 ([A]e + [B]e ) + k 2 }x (109)
dt
dx 1
=− x (110)
dt 

where
τ = {k 1 ([A] e + [B] e ) + k 2 }−1

This integrates to
t
−τ
x = xo e (111)

where xo is the value of x, the instant after the T jump is applied at t =0.
The constant τ is called the relaxation time.

τ is the time it takes the deviation [A]−[A]e to drop to 1𝑒 of its initial value.
𝑥𝑜
t 𝑥𝑜 τ = t when =𝑒
= ln 𝑥
τ 𝑥
Example:
For the elementary reaction
k1

k2

The relaxation time has been measured as 36 s at 25 ˚C and pH = 7,

and pKw = 14.0. Find k1 and k2.

Solution:
d[H2O] + −
=k1 H OH − k 2 [H2O] (1)
dt
Let
H2O = H2O e + x
+ +
H = H 𝑒−𝑥
− −
OH = OH e − x
dx + −
= k1 ( H 𝑒 − 𝑥 )( OH e − x) − k 2 ( H2O e + x)
dt
+ − + −
= k1 H 𝑒 OH e − H 𝑒𝑥 − OH ex + x2 − k 2 H2O e − k 2 x (2)

At equilibrium,
+ −
k1 H 𝑒 OH e = k 2 H2O e (3)
Also, the term x2 is negligible.

Eq. (2) becomes

dx + −
= −{k1 H e + OH e + k2}x
dt
1
=− x
τ

1 + −
= {k1 H e + OH e + k2 (4)
τ
 1 + −
= −{k1 H e + OH e + k2 (4)
τ

At equilibrium,
+ −
k1 H 𝑒 OH e = k 2 H2O e

+ −
k1 H 𝑒 OH e
k2 = (5)
H2O e

Substituting Eq. (5) into (4):

+ −
1 + − H 𝑒 OH e
= −k1 H e + OH e +
τ H2O e (6)

+ −
H e = OH e , equation 6 becomes
+
1 + H 𝑒2
= −k1 2 H e + (7)
τ H2O e
 + − +
𝐾𝑤 = 10−14.0 = H e= H
OH 2
𝑒 𝑒
+
∴ H 𝑒 = 10−7.0 (8)
For 1 L of pure water,
m 1000 g
n= = = 55.6 mol
M 18 gmol−1
n (9)
∴ H2O e = 1 L = 55.6 molL−1

Substitute Eqs. (8) and (9) into (7):

1  1  10 −14 
 10 = k1  2.0  10 +
6 −7

36  55 .5 

k1 = 1.4 x 1011 L mol-1 s-1

Using Eq. (5):

1.4  1011  1  10 −14
k2 =
55.5
= 2.5  10 −5 s −1