CHEM

6. CHEMICAL
18 KINETICS
6.1. The rate of reaction
6.2. Rate laws
6.3. Order of Reaction
6.4. Factors affecting rate
of reaction
6.5. Collision Theory

CHEM 18 UNIVERSITY CHEMISTRY

RHEA M. YANOS, M. Sc., R. Ch.
 CHEMICAL KINETICS
 branch of chemistry concerned with the rate of
reaction and the mechanism responsible for the
conversion of reactants to products

REACTION RATE How fast will the

reaction proceed?

REACTION Which bonds are

broken/formed? In what
MECHANISM sequence?
REACTION RATE, ʋ
a measure of how quickly a reactant is being consumed or how quickly a
product is being produced

As the reaction
progresses, the
amount of
reactant A
diminishes
while the
amount of
product B
increases.

REACTION PROGRESS
 REACTION RATE, ʋ
the change in the concentration of a species per unit time

 unit of rate: M/s or mol/L-s

 rate can be written as:
o change in concentration
of reactant A ([A]) over D[A] (-) since [A]
rate = -
time (t) Dt decreases with time

o change in concentration
D[B] (+) since [B]
of product B ([B]) over rate = increases with time
time (t) Dt
 REACTION RATE & STOICHIOMETRY

 Consider the reaction: note:

 a, b, c, and d are stoichiometric
aA + bB → cC + dD coefficients in a balanced equation
 A, B, C, and D are chemical species

 the rate of reaction can be written based on the:

o disappearance 1 ∆A 1 ∆B
of the reactants: ʋ=− =−
a ∆t b ∆t

o appearance of 1 ∆C 1 ∆D
the products: ʋ = =
c ∆t d ∆t
 REACTION RATE & STOICHIOMETRY

aA + bB → cC + dD
1 ∆A 1 ∆B 1 ∆C 1 ∆D
ʋ=− =− = =
a ∆t b ∆t c ∆t d ∆t
 the rate of disappearance (consumption) of reactants can be
expressed as:
∆A ∆B
− = aʋ − = bʋ
∆t ∆t
 the rate of appearance (production) of products can be
expressed as:
∆C ∆D
= cʋ = dʋ
∆t ∆t
 REACTION RATE & STOCHIOMETRY
 Examples: 1 ∆A ∆B
1. 2A → B ʋ=− =
2 ∆t ∆t
∆A ∆B
− = 2ʋ =ʋ
∆t ∆t
2. 2NOBr → 2NO + Br2
1 ∆ NOBr 1 ∆ NO ∆ Br
ʋ=− = =
2 ∆t 2 ∆t ∆t

∆ NOBr ∆ NO ∆ Br
− = 2ʋ = 2ʋ =ʋ
∆t ∆t ∆t
 PRACTICE!
Write the reaction rate expression and the rate
of appearance/disappearance of each
species:
Br2 + HCOOH → 2Br- + 2H+ + CO2
∆ Br2 ∆ HCOOH 1 ∆ Br− 1 ∆H ∆ CO2
ʋ=− =− = = =
∆t ∆t 2 ∆t 2 ∆t ∆t

∆ Br2 ∆ Br− ∆ CO2

− =ʋ = 2ʋ = 2ʋ
∆t ∆t ∆t
∆ HCOOH ∆H
− =ʋ = 2ʋ
∆t ∆t
 SOLVED PROBLEM
If the rate of decomposition of N2O5 in the reaction:
2 N2O5(g) → 4 NO2(g) + O2(g)
at a particular instant is 4.2 × 10–7 M/s, what is the rate
of appearance of (a) NO2 and (b) O2 at that instant?
1 ∆ N2O5 1 M M
ʋ=− =− −4.2 × 10–7 = 2.1×10–7
2 ∆t 2 s s
1 ∆ NO2 ∆ O2
ʋ= ʋ=
4 ∆t ∆t
∆ NO2 M ∆ O2 M
= 4ʋ = 4 2.1×10 –7
= ʋ = 2.1×10–7
∆t s ∆t s
= 8.4 × 10–7 M/s
 PRACTICE!
The rate of formation of NO in the reaction below
2NOBr → 2NO + Br2
was reported as 1.6×10-4 mol/L-s. What is the rate of reaction
and the rate of consumption of NOBr?
∆ NO M
= 1.6×10 –4
∆t s
1 ∆ NO 1 M M
ʋ= = 1.6×10–4 = 8.0×10 –5
2 ∆t 2 s s

∆ NOBr M M
− = 2ʋ = 2 8.0×10–5 = 1.6×10–4
∆t s s
 RATE LAW/RATE EQUATION
also called differential rate law
 mathematical expression describing the dependency of
reaction rate to the reactant concentration (or pressure)
 cannot be predicted from the overall balanced chemical
reaction; rate laws must be determined experimentally
 Consider a hypothetical reaction: aA + bB → cC + dD
𝐦 𝐧
RATE LAW/EQUATION: ʋ = 𝐤[𝐀] [𝐁]
where k = rate constant (independent of concentration
but dependent on T)
m = reaction order wrt A (power to which [A] is raised)
n = reaction order wrt B (power to which [B] is raised)
overall order of the reaction = m+n
 REACTION ORDER
describes the effect of the reactant concentration on the reaction rate

 experimentally determined
 not related to the stoichiometric coefficient of the reactant
in the balanced chemical equation (unless the reaction is a
one-step reaction)
 usually a positive number, but can also be a fraction or a
negative number
 Example: F2 + 2ClO2 → 2FClO2
experimentally determined rate law: ʋ = k F [ClO ]
1st order wrt F2
1st order wrt ClO2
2nd order overall
 1st ORDER REACTION

ʋ = 𝐤[𝐀]

 reaction rate depends linearly on only one reactant

concentration (if [A] is doubled, rate will be doubled)
 other reactants can be present, but each will be zero order
 the reactant concentration decreases exponentially with time
 2nd ORDER REACTION

ʋ= 𝐤[𝐀]𝟐

 rate depends on the concentration of a 2nd order reactant (or

two 1st-order reactants)
 the reaction rate is proportional to the square of the
concentration of the reactant(if [A] is doubled, rate will be
quadrupled)
 the reactant concentration decreases exponentially with time
 DETERMINATION OF REACTION
ORDER
1. Method of Initial Rates
 initial rate (rate just after the reaction
begins, after t =0) of a reaction is
determined at different concentrations of
a certain reactant while keeping the
concentration of other reactants constant
2. Comparison with Integrated
Rate Law
 concentration of the reactant is
determined at the initial and specific
time intervals
 INTEGRATED RATE LAW
shows how the concentration of species changes over time
 the order of the reaction
is hard to tell from the
concentration-time graph
since 1st order and 2nd [A],
order reactions have M
similar plots
Time, min
 Rate laws are
transformed into a
linear form
 the plot that is more
linear (r ≈ ±1)
corresponds to the
correct order
 INTEGRATED RATE LAW
 rate laws are integrated and transformed into a linear form
(y = mx + b):

Order Rate Law Integrated Rate Integrated Rate Law

Law in Linear Form
1st ʋ = 𝐤[𝐀] [A] = [A] e 𝐥𝐧[𝐀]𝐭 = −𝐤𝐭 + 𝐥𝐧 𝐀 𝐨

1 1 𝟏 𝟏
2nd ʋ = 𝐤[𝐀] 𝟐 = kt + = 𝐤𝐭 +
[A] [A] [𝐀]𝐭 [𝐀]𝐨

 plot is prepared for a given set of data; the plot that is more
linear (r ≈ ±1) corresponds to the correct order
 SOLVED PROBLEM 1

The following data were obtained for Time, s [NO2], M

the gas-phase decomposition of NO2
0.0 0.01000
at 300°C:
50.0 0.00787
NO2(g) → NO(g) + ½ O2(g) 100.0 0.00649
200.0 0.00481
A. Determine the order of the reaction. 300.0 0.00380
B. What is the value of the rate
constant?
C. Write the integrated rate law in
linear form
D. Calculate [NO2] at t = 60 seconds
 SOLVED PROBLEM 1 Time, s [NO2], M
0.0 0.01000
𝟏 𝟎. 𝟓𝟒𝟑𝟏 50.0 0.00787
= 𝐭 + 𝟗𝟗. 𝟖
[𝐍𝐎𝟐 ]𝐭 𝐌𝐬 100.0 0.00649
200.0 0.00481
Note: the unit of rate constant (k)
depends on the order of the reaction. 300.0 0.00380
Order Integrated Rate Law x y slope r y-int
in Linear Form

-k = -3.17 x10-3 ln 𝐴
1st 𝐥𝐧[𝐀]𝐭 = −𝐤𝐭 + 𝐥𝐧 𝐀 𝐨 t ln [A] -0.99117
s-1 = -4.67

𝟏 𝟏 k = 0.5431 =
2nd = 𝐤𝐭 + t 1/[A] 0.99999 [ ]
[𝐀]𝐭 [𝐀]𝐨 M-1s-1 99.8 M-1
 SOLVED PROBLEM 1

D. Calculate [NO2] at t = 60 seconds

𝟏 𝟎. 𝟓𝟒𝟑𝟏
= 𝐭 + 𝟗𝟗. 𝟖
[𝐍𝐎𝟐 ]𝐭 𝐌𝐬
𝟎. 𝟓𝟒𝟑𝟏
= (𝟔𝟎 𝐬) + 𝟗𝟗. 𝟖
𝐌𝐬
𝟏 𝟏
= 𝟏𝟑𝟐. 𝟒𝟐 𝐌
[𝐍𝐎𝟐 ]𝐭

𝟑
𝐍𝐎𝟐 𝐭 = 𝟕. 𝟓𝟓 𝐱 𝟏𝟎 𝐌
 SOLVED PROBLEM 2

Using the data for the reaction: Time, s [N2O5], M

2N2O5(g) → 4NO2(g) + O2(g) 0.0 0.1000
A. Determine the order of the reaction 50.0 0.0707
B. Write the integrated rate law in 100.0 0.0500
linear form 200.0 0.0250
C. Calculate [N2O5] at 150s after the 300.0 0.0125
start of the reaction.
400.0 0.00625
 SOLVED PROBLEM 2 Time, s [N2O5], M
0.0 0.1000
50.0 0.0707
−6.93 x10−3
𝐥𝐧[𝐍𝟐 𝐎𝟓 ]𝐭 = 𝐭 − 𝟐. 𝟑𝟎 100.0 0.0500
𝐬
6.93 x10−3 200.0 0.0250
𝐥𝐧[𝐍𝟐 𝐎𝟓 ]𝐭 = (𝟏𝟓𝟎𝐬) − 𝟐. 𝟑𝟎 = -3.34
𝐬
300.0 0.0125
[𝐍𝟐 𝐎𝟓 ] = 0.03535 M 400.0 0.00625
Order Integrated Rate Law x y slope r y-int
in Linear Form
-k = -6.93 x10-3 - ln 𝐴
1st 𝐥𝐧[𝐀]𝐭 = −𝐤𝐭 + 𝐥𝐧 𝐀 𝐨 t ln [A] -0.99999
s-1 = -2.30

𝟏 𝟏 k = 0.3535 =
2nd = 𝐤𝐭 + t 1/[A] 0.94024 [ ]
[𝐀]𝐭 [𝐀]𝐨 M-1s-1 -7.84 M-1
PRACTICE!
Given the following kinetics data,
determine the order of the reaction,
write the integrated rate law in linear form,
and predict the concentration of A at 450 s.
A→B+C
Order x y slope r y-int
ln ln 𝐴
1st t -k = -2.17 x10-3 s-1 -0.94595
[A] = 0.49

k = 3.75x10-3 =
2nd t 1/[A] 0.999996 [ ]
M-1s-1 0.35 M-1
𝟏 3.75x10−3
= 𝐭 + 𝟎. 𝟑𝟓
[𝐀]𝐭 𝐌𝐬 𝐀 𝐚𝐭 𝟒𝟓𝟎 𝐬 = 0.49 M
HALF LIFE, 𝐭 𝟏 𝟐 time required for the concentration of
a reactant to decrease to half of its
initial concentration
 a convenient way to
describe how fast a
reaction occurs:
faster reactions have
short half-lives
 1st order reaction:
𝐥𝐧 𝟐
𝐭𝟏 𝟐 =
𝐤
 2nd order reaction:
𝟏
𝐭𝟏 𝟐 =
𝐤[𝐀]𝟎
 SOLVED PROBLEM 1

The reaction 2A →B is 1st order with a rate constant of 2.8 x

10-2 s-1 at 800C.
a. If the initial concentration of A is 0.88 M, what is the
concentration after 2.0 min? ans. 0.0306 M
𝐥𝐧[𝐀]𝐭 = −𝐤𝐭 + 𝐥𝐧 𝐀 𝐨

ln[A] = −2.8 x 10−2 s−1(120 s) + ln (0.88)

[𝐀]𝐭 = 0.0306 M
b. What is the half-life of the reaction? Ans. 24. 76 s
𝐭𝟏 𝟐 = = = 𝟐𝟒. 𝟕𝟔 𝐬
.
 SOLVED PROBLEM 2

Consider the second-order decomposition of dinitrogen

pentoxide at 335 K. N2O5(g) → 2 NO2(g) + ½ O2(g)
If we start with 0.025 M of N2O5 at 335 K and have 0.015 M
remaining after 109 s,
(a) What is the value of the rate constant k? (ans. 0.2446 M s )
𝟏 𝟏
= 𝐤𝐭 +
[𝐀]𝐭 [𝐀]𝐨
𝟏 𝟏 𝟏 𝟏
= 𝐤(𝟏𝟎𝟗𝐬) + 𝐤 = 𝟎. 𝟐𝟒𝟒𝟔 𝐌 𝐬
𝟎. 𝟎𝟏𝟓 𝐌 𝟎. 𝟎𝟐𝟓 𝐌
(b) What is the half-life of the reaction in min? (ans. 2.725 min)
1 1min
𝐭𝟏 𝟐 = = = 𝟐. 𝟕𝟐𝟓 𝐦𝐢𝐧
[ ] 0.2446 M s (0.025 M) 60 s
 SOLVED PROBLEM 3:
RADIOACTIVE DECAY follows 1st order kinetics

𝐥𝐧 𝟐
𝐥𝐧 𝐍𝐭 = −𝐤𝐭 + 𝐥𝐧 𝐍𝐨 𝐭𝟏 𝟐 =
𝐤

The half-life of Mo-99 is 67.0 h. How much of a 1.00-mg

sample of Mo-99 is left after 335 h? ans. 0.03125 mg

k= = = 0.010345 h−1

𝐥𝐧 𝐍𝐭 = −(0.010345 h−1)(335h) + ln(1mg)

𝐍𝐭 = 0.03125 mg
 PRACTICE!

The reaction 2A →B is 2nd order with a

rate constant of 51 M–1 min–1 at 24°C.
a. Starting with [A]0 = 0.0054 M, how long will it take for A to
be reduced to 0.0016 M?
1 1
= 51 M min (𝐭) +
0.0016 M 0.0054 M
1 1
−
𝐭= 0.0016 M 0.0054 M
= 𝟖. 𝟔𝟐 𝐦𝐢𝐧
51 M min
b. Calculate the half life of the reaction.
1
𝐭𝟏 𝟐 = = = 𝟑. 𝟔𝟑 𝐦𝐢𝐧
[ ] 51 M min (0.0054 M)
 PRACTICE!

The half-life of Co-60 is 5.26 yrs. How long does

it take for 87.5% of a sample to decay?

k= = = 0.1318 yrs−1
.

ln (100 − 87.5) = −(0.1318 yrs−1)𝐭 + ln (100)

𝐭 = 𝟏𝟓. 𝟕𝟖 𝐲𝐞𝐚𝐫𝐬
 SUMMARY

1ST Order 2ND Order

Rate law Rate = k[A] Rate = k[A]2
Unit of k s–1 M–1s–1
ln 2 1
Half life t ⁄ = t ⁄ =
k kA
Integrated 1 1
rate law in ln A = −kt + ln A = kt +
A A
linear form
Plot for 1
ln[A]t vs. t vs. t
straight line A
 REACTION ENERGY DIAGRAMS
shows the energy profile of a chemical reaction
 a graphical representation of  gives information on:
the energy changes that occur 1. number of steps
during a reaction 2. relative rates
3. thermodynamics
 REACTION ENERGY DIAGRAMS
Transition State

 highest energy state in a

molecular collision
 unstable and cannot be
isolated
 REACTION ENERGY DIAGRAMS
Activation Energy, Ea
 minimum amount of
energy needed to
break the bond of
the reactants
 energy barrier of the
reaction at a given
temperature
 The overall rate of
reaction depends on
the magnitude of Ea
 COLLISION THEORY
reaction rate is directly proportional to the frequency of effective collision

 For a reaction to occur, there must be

effective collisions between the
elementary particle (ions, atoms, or
molecules) involved in the reaction
 ↑frequency of collision, ↑probability of
effecting a reaction (successful/
effective collision)
Effective Collisions:
 have proper orientations toward one
another at the time of collision
 collisions must involve enough energy
to break existing bonds and form new Only a fraction of the total
bonds (collision energy>Ea) collisions are successful collisions
 FACTORS AFFECTING REACTION RATE

1. Concentration
 ↑concentration, ↑frequency of collision, ↑rate
 higher concentration means there are more particles moving
about in a given volume, increasing the frequency at which
particles collide
 FACTORS AFFECTING REACTION RATE

2. Pressure/Volume
 for gases, increasing the pressure increases the rate of
gaseous reactions
 gas particles are closer to each other, more frequent
collisions
 FACTORS AFFECTING REACTION RATE

3. Surface area of solid reactants

 greater surface area of contact between reactant particles
entail higher chances of collisions and faster rate of reaction

vs.
 FACTORS AFFECTING REACTION RATE

4. Catalyst
 speeds up a chemical
reaction by providing an
alternative path with a
lower Ea (the lower the
Ea, the faster the
reaction)
 consumed then
regenerated in a reaction
 ex. acids, bases, metals,
enzymes, etc
 FACTORS AFFECTING REACTION RATE

4. Catalyst: Enzymes
 reaction between bound
molecules does not require an
improbable collision of two
molecules -- they're already in
“contact”

 reactants are not only near

each other on enzyme, they're
oriented in optimal position to
react, so the improbability of
colliding in correct orientation
is taken care of
 FACTORS AFFECTING REACTION RATE

5. Temperature
 ↑T, ↑KE, more
frequent collisions,
↑ rate of reaction
 at a higher
temperature, more
molecules have
enough energy
(greater than the
↑ KE, ↑ T ↓ KE, ↓ T
activation energy)
to react
 THE ARRHENIUS EQUATION
describes the dependence of the rate constant k with T

𝐄𝐚
𝐤 = 𝐀𝐞 𝐑𝐓
where:
k = rate constant T = temp. in K
Ea = activation energy (J) R = 8.314 J/mol-K
A = Arrhenius constant/collision frequency factor (same unit as k)
- reflects the frequency effective/successful collision
 The Arrhenius eqn also takes the following form:
𝑬𝒂 𝒌𝟏 𝑬𝒂 𝟏 𝟏
𝐥𝐧 𝒌 = − + 𝐥𝐧 𝑨 𝒍𝒏
𝒌𝟐
= −
𝑹 𝑻𝟐 𝑻𝟏
𝑹𝑻
For numerous data points For two data points
 SOLVED PROBLEM 1
For reaction: 2NO2(g)→2NO(g)+ O2(g)
the rate constant is 1.00x10-10 s-1at 300K and the activation
energy is 111 kJ/mol. Calculate the following:
1. frequency factor, A (ans. 2.13x109 s-1)
k = Ae
k 1x10 s−1
𝐀= = = 2.13x109 s-1
J/mol
e . / ( )
e
2. rate constant at 273 K (ans. 1.23 x 10-12 s-1)
J/mol
𝐤 = Ae = 2.13x109 s e−1 . / ( ) = 1.23x10 -12 s-1
 SOLVED PROBLEM 2
The rate constants for the T (K) k (1/M1/2-s)
decomposition of acetaldehyde was 700 0.011
measured at different temperatures 730 0.035
as shown. Determine the Ea for the
760 0.105
reaction. CH3CHO(g) → CH4(g) + CO(g)
790 0.343
𝐄𝐚 𝟏
𝐥𝐧 𝐤 = − + 𝐥𝐧 𝐀 810 0.789
𝐑 𝐓
𝐄𝐚
− = -21880 K
x y slope y-int 𝐑

Ea = 21880 (R)
𝟏 𝐄𝐚 = -21880 K ln A = 21880 K (8.314 J/molK)
𝐥𝐧 𝐤 −
𝐓 𝐑 = 26.66
Ea = 𝟏. 𝟖 𝐱 𝟏𝟎𝟓 J/mol
 SOLVED PROBLEM 3

Using the experimental data T (K) k (L/mol/s)

presented, determine the activation 555 3.52 x 10-7
energy. (ans. 1.85 × 105 J/mol) 781 3.95 x 10-2
k E 1 1
ln = −
k R T T

k 3.52 x 10−7
ln (R) ln (8.314 J/molK)
k 3.95 x 10−2
E = =
1 1 1 1
− −
T T 781K 555K

Ea = 1.85 × 105 J/mol

 PRACTICE!
Determine A and Ea from the following data:
T (K) k (L/mol-s)
x y slope y-int
300 7.9 x 106
350 3.0 x 107
𝟏 𝐄𝐚 = -2767 K ln A
400 7.9 x 107 𝐥𝐧 𝐤 −
𝐓 𝐑 = 25.1
450 1.7 x 108
500 3.2 x 108

A = 8.04 × 1010 L/mol-s

Ea = 2.3 × 104 J/mol
 PRACTICE!
Rate constants for the first-order decomposition of
acetonedicarboxylic acid are k = 4.75 ×10–4 s–1 at 293
K and k = 1.63 ×10–3 at 303 K. What is the activation
energy, Ea, for this reaction?
Ea = 9.1 × 104 J/mol
Any Question?