Chapter 7:
Chemical Kinetic
Thermodynamics and Kinetics
Chemical Thermodynamics: prediction
whether or not a chemical reaction will take place
Chemical Kinetic: once the reaction started, it
indicates how fast does the reaction proceeds and
how far will this reaction go before it stops
The branch of chemistry which is concerned with the rates of
chemical reactions and the mechanisms by which they occur
• Speed of chemical reaction is measured as a change in the
amount of some reactant or product per unit time
• H2 (g) + I2 (g) 2 HI (g)
• We can measure the disappearance of reactants or the
appearance of products
Chemical Kinetics
Classification of reaction:
Fast (few seconds) : 2H2 + O2 2H2O
Slowly (few minutes) : 2Fe(s) + O2 2FeO
Very slowly : C(diamond) C(graphite)
Reactants → Products (complete)
► Change in amount or concentration per unit time
(in one direction)
Reactants ⇌ Products
► Reaction in two directions. In each direction
(forward or backward), there is a definite rate. At
equilibrium, the two rates are equal
Rate of reaction
The rate of a chemical reaction is generally measured
in terms of how much the concentration of a
reactant decreases in a given period of time
or product concentration increases
For reactants, a negative sign is placed in front of the
definition
For reaction: A B: instantaneous rate of
disappearance of A or rate of formation of B
d[ A ] d[B]
r r ( B)
dt t dt t
[A] decreases with time, [B] increases
The rate decreases generally with time and it can be
constant but never increases
Rate Calculation
The instantaneous rate of the
reaction:
Rate at any single point
Rate is determined by
calculating the slope of the
tangent to the curve
The average rate is the change in measured
concentrations in any particular time period
The larger the time interval, the more the average rate
deviates from the instantaneous rate
Relative Rates: Relation
aA + bB → cC + dD
Stoichiometric Coefficients
1 [ A] 1 [ B] 1 [C ] 1 [ D]
r ( ) ( ) ( ) ( )
a t b t c t d t
r(A) r ( B) r (C ) r ( D)
Instantaneous rates : r (at same time t)
a b c d
r ( A) r ( B) r (C ) r ( D)
Average rates : r (at same t)
a b c d
Reaction: 2H2O2 2H2O + O2
1 d[H2 O2 ] 1 d[O2 ] d[H2 O2 ] d[O2 ]
2
2 dt 1 dt dt dt
Example 7.1
For the reaction given, the [I] changes from
1.000 M to 0.868 M in the first 10 s. Calculate
the average rate in the first 10 s and the [H+].
H2O2(aq) + 3 I(aq) + 2 H+(aq) I3(aq) + 2 H2O(l)
Factors influence the rate of reaction
Temperature: At higher temperatures, reactant molecules have
more kinetic energy, move faster, and collide with greater energy
Collision Theory: When two chemicals react, their molecules have to
collide in a particular orientation with sufficient energy for the reaction
to take place.
Kinetic Theory: Increasing temperature means the molecules move
faster
Concentrations of reactants
Concentration of reactants increases, molecules will collide
better, rate increases
Catalysts
Speed up reactions by lowering activation energy
Surface area of a solid reactant
More area for reactants to be in contact
Pressure of gaseous reactants or products
Increased number of collisions
Objectives
Reaction Rates How we measure rates
How the rate depends on amounts
Rate Laws
of reactants
How to calculate amount left or
Integrated Rate Laws
time to reach a given amount
How long it takes to react 50% of
Half-life
reactants
How rate constant changes with
Arrhenius Equation
temperature
Link between rate and molecular
Mechanisms
scale processes
Rate Law
aA + bB → cC + dD r = k [A]m [B]n
k: rate constant (T dependant)
m: partial order of the reaction with respect to A
n: partial order of the reaction with respect to B
m+n: global or total order of the reaction
For the same reaction, m and n are constants ( T and
concentrations are variables)
r, [A] and [B] are at the same time t in the rate law
expression
Partial order may be integer number or fraction (mostly 0, 1
or 2)
Rate Law
Rates laws are also determined experimentally. There
is no necessary relationship between the form of
the rate law and the form of the balanced chemical
equation CH3CN CH3NC Rate = k[CH3CN]
CH3CHO CH4 + CO Rate = k[CH3CHO]3/2
2 N2O5 4 NO2 + O2 Rate = k[N2O5]
Reaction order is always defined in terms of reactant
(not product) concentrations
The value of k depends on temperature,
but not on the value of any concentration. The units of
k depend on the form of the rate law.
Example 7.2
The rate equation for the reaction of NO with
ozone is Rate = k[NO][O3]. If the rate is 6.60 ×
10−5 M/sec when [NO] = 1.00 × 10−6 M and [O3]
= 3.00 × 10−6 M, calculate the rate constant.
Rate = k[NO][O3]
Determination of the reaction order
To find the order (m+n) of a reaction, several methods
can be used. The choice of the method depends on the
type of the date given
Direct Methods (1, 2 and 3):
Method 1: Logarithmic plots
Method 2: Ratio technique
Method 3: Expression of the variation of the
[reactant] with time (integrated rate
laws)
Direct Methods (4 and 5):
Method 4: From the unit of the rate constant k
Method 5: Expression of halt time t1/2
Method 1: Logarithmic Plots
aA + bB → cC + dD r = k [A]m [B]n
To find m, the following procedure is used:
Make an experiment where [B] is k[B]n = constant
hold constant with respect to time, r = k’ [A]m
While [A] varies with time
r(A):
[A] How? determined at
any time by the
[A]0 <<< [B]0 tangent rule
rt ( A )
rt
time a
Method 1: Logarithmic Plots
r = k’ [A]m ln r = lnk’ + m ln[A]
The slope of this
straight line is m
By the same method,
find n
rt
k m n
How to find k? [ A]t [B]t
Method 2: Ratio Technique
Repeat the same reaction at the same time but
with different initial concentrations of reactants
Each experiment allows to calculate the rate of
reaction at any time t, [A]t and [B]t
For each experiment, the expression of the rate
law is the same (same m and n because same
reaction, same k because same temperature)
r = k [A]m [B]n
Ratio Technique
aA + bB → cC + dD r = k [A]m [B]n
Given: r1 [A]1 [B]1 (at the same time t)
r2 [A]2 [B]2 (at the same time t’)
r3 [A]3 [B]3 (at the same time t”)
r1 = k[A]m1[B]n1
If [B1] = [B2]
r2 = k[A]m2[B]n2
r1 (A1)m
=
r2 (A2)m
Example 7.3
Determine the Rate Law Expression for:
r = k [A]m [B]n[C]p
Exp [A]0 (M) [B]0 (M) [C]0 (M) r0 (M/s)
1 0.1 0.1 0.1 0.5
2 0.2 0.1 0.1 2.0
3 0.2 0.2 0.1 16
4 0.2 0.1 0.2 4.0
1/2: calculation of the order w/respect to A
2/3: calculation of the order w/respect to B
2/4: calculation of the order w/respect to C
Method 3: Integrated Rate Laws
For any reaction of known order, the concentration
of reactants varies with time according a known
relation, for example (see prove later):
zero order, the relation 1: [A] = -kt + [A]0
First order, the relation 2: Ln [A]= -kt +Ln [A0]
Second order, the relation 3: 1/A = kt + 1/ A0
If given, the concentration of one reactant at any
time t, for example [A]t, plot [A]=f(t)
If a straight line is obtained zero order
If not, pass to relation 2 …………….
Zero order: Integrated Rate Laws
Reaction type: A → products r = k[A]0 =k
r r ( A)
d [ A]
r k
dt
d [ A] kdt
At t
d [ A] k dt
A0 0
[ A ]t [ A ]0 kt
First order: Integrated Rate Laws
Reaction type: A → products r = k[A]1
d[ A ]
r k[ A ]
dt
d[ A ] k[ A ]dt
d[ A ]
kdt
[A]
At t
d[ A ]
A0
[A]
k dt
0
ln[A ]t ln[A ]0 kt
Second order: Integrated Rate Laws
Reaction type: A → products r = k[A]2
d[ A ]
r k[ A ]2
dt
d[ A ] k[ A ]2 dt
d[ A ]
2
kdt
[A]
At t
d[ A ]
A0
[A] 2
k dt
0
1 1
kt
[ A ]t [ A ]0
Example 7.4
Rate Data for: C4H9Cl + H2O C4H9OH + HCl
Time (sec) [C4H9Cl], M
0.0 0.1000
50.0 0.0905
100.0 0.0820
150.0 0.0741
200.0 0.0671
300.0 0.0549
400.0 0.0448
500.0 0.0368
800.0 0.0200
10000.0 0.0000
Find the order of the reaction
Example 7.4
Draw [C4H9Cl] = f(t)
No straight line: not zero order
Example 7.4
Draw Ln[C4H9Cl] = f(t)
Order 1
slope =
−2.01 × 10−3
k = 2.01 × 10−3 s–1
1st and 2nd Order Rate Laws: k[A] vs. k[A]2
For first or second order reaction, the variation
[A]=f(t) has practically the same shape
Method 4: From k units
According to the integrated law, k has definite units
Order Rate Eq Integrated Law k (units)
0 r=k [ A ]t [ A ]0 kt M / time
1 r = k[A] ln[A]t ln[A]0 kt 1 / time
2 r = k[A]2 1 1 1 / ([Link])
kt
[ A]t [ A]0
Gas Phase Reactions
► Ideal gas: P.V = n.R.T [A] = nA / V = PA / RT
At constant T, PA is proportional to [A]
Integrated law Integrated law
in terms of concentrations in terms of pressure
[ A ]t [ A ]0 kt ( PA )t ( PA )0
kt (PA )t (PA )0 kt(RT)
RT RT
( PA )t
ln[A]t ln[A]0 kt [ A ]t
ln
[ A ]0
kt ln RT kt
( PA )0 ln(PA )t ln(PA )0 kt
RT
1 1
kt RT
RT
kt
1
1
kt
[ A]t [ A]0 ( PA )t ( PA )0 ( PA )t ( PA )0 RT
Example 7.5
The reaction SO2Cl2(g) SO2(g) + Cl2(g) is first order with a rate
constant of 2.90 × 10–4 s–1 at a given set of conditions. Find the [SO 2Cl2]
at 865 s when [SO2Cl2]initial = 0.0225 M.
Given: [SO2Cl2]init = 0.0225 M, t = 865, k = 2.90 × 10–4 s−1
Find: [SO2Cl2]
Conceptual
Plan: [SO2Cl2]init, t, k [SO2Cl2]
Relationship
s:
Solution:
Check: The new concentration is less than the
original, as expected.
Half-Life
The half-life or half-time (t1/2) of a reaction is
the time required for the concentration of a
limiting reactant to fall to one-half of its initial
value (or to form the half of the final product)
If initial concentration = 1.0 M and the half-life is
100 seconds then the concentration will fall to 0.50
M in 100s
The half-life expression
– defines the dependence of half-life on rate
constant and initial concentration
– Is different for different reaction orders
Half life: Zero Order Rxns
t1/2= time for concentration to be ½ of the initial
[ A ]0
At t 1 2 : [A]t 1 2
2
For zero Order Rxn: [A]t – [A]o = -kt
[ A ]t 1 2 [ A ]0 kt 1 2
[ A ]0 [A0 ]
[ A ]0 kt 1 2
2 t1 2
[ A ]0
2k
kt 1 2
2
Half life: 1st Order Rxns
t1/2= time for concentration to be ½ of the initial
[ A ]0
At t 1 2 : [A]t 1 2
2
For 1st Order Rxn:
ln[A]t – ln[A]o = -kt
ln[ A ]t 1 2 ln[ A ]0 kt 1 2
[ A ]0
ln ln[ A ]0 kt 1 2
2
[ A ]0
ln 2
ln 2 kt 1 2 t1 2
[ A ]0 k
Half life: 2nd Order Rxns
[ A ]0
At t 1 2 : [A]t 1 2
2
1 1
For 2nd Order Rxn:
[ A ]t [ A ]0
kt
1 1
kt 1 2
[ A ]t 1 2 [ A ]0
1
1 1 t1 2
[ A ]0 [ A ]0
kt 1 2 k[ A ]0
2
2 1
kt 1 2 Length of t1/2 depends on
[ A ]0 [ A ]0
1 [A]0; successive half-lives
kt 1 2
[ A ]0 are longer by a factor of 2
Summary
Example 7.6
Molecular iodine dissociates at 625 K with a
first-order rate constant of 0.271 s−1. What is the
half-life of this reaction?
Given: k = 0.271 s−1
Find: t1/2
Conceptual
Plan: k t1/2
Relationship
s:
Solution:
Relation between k and T
Rate of chemical reactions are highly sensitive to
temperature
When T increases Molecules move faster
More collisions between molecules
Most reactions go faster at higher temperature
The rate constant k almost always increases with
r k[ A]m [B]n
For the same reaction, k is related to Ea
the temperature according to k Ae RT
Arrhenius Equation:
E
RT
a
r ( Ae )[ A]m [B]n
Arrhenius Equation
Ea
k Ae RT
Ea: activation energy is the minimum amount of
energy required to initiate an chemical reaction
(in kJ/mol)
A: frequency factor (steric factor) in (M-1s-1):
frequency of collisions with proper orientation
when reactant concentrations = 1M. For the same
reaction at different temperatures, A is constant
T: absolute temperature (in kelvin)
R: ideal gas constant (8.314 [Link]-1)
Activation Energy and the Activated Complex
Eproducts < Ereactants
products are more stable
exothermic
Eproducts > Ereactants
reactants are more stable
endothermic
The activated complex is a
highly unstable species with
high potential energy
• The activation energy is the amount of energy needed to
convert reactants into the activated complex.
• The activated complex is a chemical species with partially
broken and partially formed bonds.
Activation Energy Calculation
Ea
Ea
k Ae RT ln k ln A
RT
To calculate the
activation of a
ln k
reaction: Slope of the
line: -Ea/R
► Realize the reaction at ln A
different temperature
► At each temperature,
calculate the rate 1/T
constant k of the reaction
Example 7.7
Determine the activation energy and
frequency factor for the reaction given the
following data. O3(g) O2(g) + O(g)
Temp, K k, M–1∙s–1 Temp, K k, M–1∙s–1
600 3.37 × 103 1300 7.83 × 107
700 4.83 × 104 1400 1.45 × 108
800 3.58 × 105 1500 2.46 × 108
900 1.70 × 106 1600 3.93 × 108
1000 5.90 × 106 1700 5.93 × 108
1100 1.63 × 107 1800 8.55 × 108
1200 3.81 × 107 1900 1.19 × 109
Example 7.7
Example 7.7
Slope= -Ea/R
For 1/T = 0: LnK = LnA
Relation: rate constant k & temperature T
For the same reaction, knowing k at one T, find
it at another T:
Ea
Arrhenius Equation: k Ae RT
For the same reaction: Ea and A are constant
Ea T1 T2
( TT )
E
RTa k 1 k 2e R 1 2
k1 e 1
Ea k1 Ea 1 1
k2 e RT2 ln
k2 R T2 T1
k2 Ea 1 1
ln
k1 R T2 T1
Example 7.8
The reaction NO2(g) + CO(g) CO2(g) + NO(g) has a
rate constant of 2.57 M–1∙s–1 at 701 K and 567 M–1∙s–1
at 895 K. Find the activation energy in kJ/mol.
Given: T1 = 701 K, k1 = 2.57 M–1∙s–1, T2 = 895 K, k2 = 567 M–1∙s–1
Find: Ea, kJ/mol
Conceptual
Plan: T1, k1, T2, k2 Ea
Relationships:
Solution:
Check: Most activation energies are tens to hundreds
of kJ/mol, so the answer is reasonable.
Catalysts
Speed up rates of reaction
They are not consumed in a reaction
They are involved in intermediate steps of a reaction
Lower Activation Energy
There are two types of catalysts:
Homogeneous catalyst: same phase as reactants
Heterogeneous catalyst: different phase than reactants
Neither appears in the balanced reaction
Properties
A catalyst appears first as a reactant
An intermediate appears first as a product
It is not usually possible for a chemist to
identify (to characterize) an intermediate
Catalysts
Catalysts lower Ea by making a different
reaction mechanism possible
Non catalyzed reaction
Ea
Potential Energy
Catalyzed reaction
reactants
E’a
products
Reaction
Heterogeneous Catalyst
Acting on its surface: presence of the active site
As number of sites increases: better catalytic activity
Heterogeneous catalyst does intervene in the rate law
expression
How can the efficiency of a By increasing the
heterogeneous catalyst be increased? surface area
Homogeneous Catalyst
They appear in the rate law expression
The higher the concentration the more effective
Br2
2 H2O2 2 H2O + O2
catalyst intermediate
Br2 + H2O2 → 2 Br + 2H+ + O2
2 Br + H2O2 + 2H+ → Br2 + 2H2O
2 H2O2 → 2 H2O + O2
r = k[Br2][H2O2]