Chap 16 - Chemical Kinetics

 Factors that Influence Reaction Rate

 Expressing the Reaction Rate
 Average, Instantaneous, Initial Reaction rates
 Rate & Concentration
 The Rate Law and its Components
 Determining the Initial Rate
 Reaction Order Terminology
 Determining Reaction Orders
 Determining the Rate Constant

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 Chap 16 - Chemical Kinetics
 Integrated Rate Laws: Concentration changes
over time
 First, Second, and Zero-Order Reactions
 Reaction Order
 Reaction Half-Life
 The Effect of Temperature on Reaction Rate
 Explaining the Effects of Concentration and
Temperature
 Collision Theory
 Transition State Theory

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 Chap 16 - Chemical Kinetics
 Reaction Mechanisms: Steps in the Overall
reaction
 Elementary Reactions
 The Rate-Determining Step
 The Mechanism and the Rate Law
 Catalysis: Speeding up a Chemical Reaction
 Homogeneous Catalysis
 Heterogeneous Catalysis

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 Chemical Kinetics
 Chemical Kinetics is the study of:
 Chemical Reaction Rates
 The changes in Chemical Concentration of
reactants as a function of time
 Chemical reactions range from very fast to very slow
 Under a given set of conditions each reaction has its
own rate
 Factors that influence reaction rate:
 Concentration
 Physical state (surface area)
 Temperature (frequency & energy of particle
collisions

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 Chemical Kinetics
 Factors That Influence Reaction Rate
 Concentration
 Molecule must Collide to React
 Reaction rate is proportional to the concentration
of the reactants
Rate ∝ collision frequency ∝ concentration
 Physical State
 Molecules must Mix to Collide
 The more finely divided a solid or liquid reactant:
 The greater its surface area per unit volume
 The more contact it makes with the other
reactant
 The faster the reaction occurs

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 Chemical Kinetics
 Temperature
 Molecules must collide with enough energy
to react
 At a higher temperature, more collisions
occur in a given time
 Raising the temperature increases the
reaction rate by increasing the number and
energy of the collisions
Rate ∝ Collision Energy ∝ Temperature

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 Chemical Kinetics
 A fundamental question addressed in chemical reactions
is “how fast does the reaction occur?”
 Kinetics is the study of the rate of chemical reactions;
rate is a time dependent process
 Rate units are concentration over time
 Consider the reaction A → B
 Reactant concentrations [A] decrease while product
concentrations [B] increase

conc
change in concentration of AΔ(conc A)A 2 - conc A1
Note:
 Rate Reaction
of Reaction = -rate is positive, but the = - concentration = - of
change in time t2 - tΔt
A at t2 (A2) is always less than the concentration of 1

A at t1 (A1), thus, the change in concentration

(final – initial) of reactant A is always negative

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 Chemical Kinetics
 Consider the reaction:
A + B → C
 Concentrations of both reactants ([A] & [B])
decrease at the same rate
change in concentration
Rate =
change in time
Δ [ A] Δ [ B]
Rate = - = -
Δt Δt
∆ Indicates “Change in”
Brackets [ ] indicate concentration

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 Chemical Kinetics
 Reaction - Butyl Chloride (C4H9Cl) and water (H2O)

CH3(CH2)2CH2-Cl(l) + H2O(l) → CH3(CH2)2CH2-OH(l) + HCl

ΔA  0.0905 mol / L - 0.1000 mol / L  -4

Ex. rate = - = -  = 1.9 × 10 mol / sec
Δt  50.0 s - 0.0 s 
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 Chemical Kinetics
Butyl Chloride (C4H9Cl)
 When plotting Concentration
versus Time for a chemical
reaction, the tangent at any
point on the curve (drawn
through the concentration
points) defines the
instantaneous rate of the
reaction
 The average rate of a
reaction over some time
interval is determined through
triangulation of concentration
plot (slope of hypotenuse of
right triangle)
 The rate of the reaction
decreases over time as the
reactants are consumed
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10
 Chemical Kinetics
 Rate of reaction of the Products
 The rate of reaction for the formation of the
products is the same as for the reactants, but
opposite, that is the concentrations are increasing
C 2 H 4 + O 3 → C 2 H 4O + O 2

Δ[C2H 4 ] Δ[O 3 ] Δ[C2H 4O] Δ[O 2 ]

Rate = - = - = + = +
Δt Δt Δt Δt
The rate of change of ethane (C2H4) and
Ozone (O3) is the same, but exactly opposite
for acetaldehyde (C2H4O) and oxygen (O2)
Product concentration increases at the same
rate that the reactant concentrations
decrease
The curves have the same shape, but are
inverted
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 Chemical Kinetics
 The Rate expression must be consistent with
stoichiometry
 When the stoichiometric molar ratios are not 1:1, the
reactants disappear and the products appear, but at
different rates

H 2 (g) + I 2 (g) = 2HI(g)

 For every molecule of H2 that disappears, one
molecule of I2 disappears and 2 molecules of HI
appear
 The rate of H2 decrease is the same as the rate
of I2 decrease, but both are only half the rate of
HI increase
Δ[H 2 ] Δ[ I2 ] 1 Δ [ HI ]
Rate = - = - =
Δt Δt 2 Δt
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 Chemical Kinetics
 Summary equation for any reaction
aA + bB = cC + dD
1 Δ [ A] 1 Δ[ B] 1 Δ[ C] 1 Δ[ D]
Rate = - = - = + = +
aΔt b Δt c Δt d Δt
 The rate of a reaction is dependent on the
concentration of reactants
 The average reaction rate is the change in
reactant (or) product concentration over a
change in time, ∆ t
 The instantaneous rate at a time, t, is obtained
from the slope of the tangent to a concentration
vs. time curve at a given time, t

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 Chemical Kinetics
 As reactant concentrations decrease, the reaction
rates decrease with time
 Product concentrations increase at the same rate
as the reactants relative to the stoichiometric
ratios
 The rate of a reaction depends on the following
variables:
 reactant concentration
 temperature
 presence and concentration of a catalyst
 surface area of solids, liquids or catalysts

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 Sample Problems
Write an expression defining equivalent rates for the
loss of NO2 and the formation of NO in the following
reaction with respect to the rate of formation of O2.

2 NO2(g) → 2 NO(g) + O2(g)

Δ [ O2 ] 1 Δ [ NO ] 1 Δ [ NO2 ]
Rate = = = -
Δt 2 Δt 2 Δt

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 Chemical Kinetics –The Rate
Law
 The dependence of reaction rate on concentrations is
expressed mathematically by the rate law
 The rate law expresses the rate as a function of reactant
concentrations, product concentrations, and temperature
 In the following development, only the reactants appear in
the rate law
 For a general reaction at a fixed temperature:
aA + bB + … → cC + dD + …
the rate law has the form:
Rate = k[A]m[B]n ...
Note: The Stoichiometric Coefficients – a, b, c – are not
used in the rate equation and are not related to the
reaction order terms – m, n, p, etc.

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 Rate Law
 Components of the rate law

 aA + bB + …→ products
m n p
Rate = -∆ [A]/∆ t = k[A] [B] [C]

 [A] & [B] = concentrations of reactants (M)

 [C] = concentration of catalyst (M), if used

 k = rate constant

 m, n, & p = Reaction Orders

Note: Reaction Orders are not related to the

Stoichiometric coefficients in chemical
equation)
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 Chemical Kinetics
 The Rate Law
 The rate constant “k” is a proportionality constant
 “k” changes with temperature; thus it determines how
temperature affects the rate of the reaction
 The exponents (m, n, p, etc.) are called reaction orders,
which must be determined experimentally
 Reaction orders define how the rate is affected by the
reactant concentration
 If the rate doubles when [A] doubles, the rate depends
on [A] raised to the first power, i.e., m =1 (a 1st order
reaction)
 If the rate Quadruples when [B] doubles, the rate
depends on [B] raised to the second power, i.e., n = 2
(a 2nd order reaction)

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 Rate Constant - Units
 Units of the Rate Constant k change depending
on the overall Reaction Order
Overall Reaction Order Units of k (t in seconds)

0 mol/Ls (or mol L-1 s-1 )

1 1/s (or s-1 )
2 L/mols (or L mol -1 s-1 )
3 L2 / mol2 s (or L2 mol-2 s-1 )

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 The Rate Law
 The Rate Law
 If the rate does not change even though [A]
doubles, the rate does not depend on the
concentration of A and m = 0.
 The Stoichiometric coefficients, a, b, c, etc. in the
general balanced equation are not necessarily
related in any way to the reaction orders m, n,
etc.
 The components of the Rate Law – rate, reaction
orders, rate constant – must be determined
experimentally; they cannot be deduced or
inferred from the balanced stoichiometric
equation

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 Rate Law
 The Rate Law - Examples
NO(g) + O3(g) → NO2(g) + O(g)
Rate = k[NO]1[O3]1
Reaction is 1st order with respect to NO, m=1
Rate depends on [NO] raised to 1st power
Reaction is 1st order with respect to O3, n=1
The overall reaction is 2nd order, m + n = 1 + 1 =
2
2NO(g) + 2H2(g) → N2(g) + 2H2O(g)
Rate = k[NO]2[H2]1
Reaction is 2nd order in NO and 1st order in H2
Overall reaction is 2 + 1 = 3rd order
Note: [NO] coefficient (2) is not related to the
[NO] reaction order (2)
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 Rate Law
 The rate law – Examples
(CH3)3C–Br(l) + H2O(l) → (CH3)C–OH(l) + H+(aq) + Br-(aq)

Rate = k[(CH3)3CBr]1[H2O]0 or

Rate = k[(CH3)3CBr]1
Reaction is first order in 2-bromo-2-methyl propane
Reaction is zero order (n=0) in water [H2O]0

Note: zero order reaction order terms, ex. [H2O]0 can be

eliminated from the overall rate equation, i.e. any term
raised to the “0” power is equal to 1
[H2O]0 = 1

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 Rate Law
 The Rate Law
CHCl3(g) + Cl2(g) → CCl4(g) + HCl(g)
Rate = k[CHCL3][Cl2]1/2
The reaction order means that the rate depends
on the square root of the Chlorine (CL2)
concentration
If the initial Cl2 concentration is increased by a
factor of 4, while the initial concentration of
CHCl3 is kept the same, the rate increases by a
factor of 2, the square root of the change in Cl2

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 Rate Law
 The Rate Law

2O 3 (g) € 3O2 (g)

2
2 -1 [O 3 ]
Rate = k[O 3 ] [O 2 ] = k
[O 2 ]1
Negative reaction orders are used when the law includes the product(s)
If the O2 concentration doubles, the reaction proceeds at one half (1/2)
the rate

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 Rate Law – Reaction Order
 Overall reaction order = sum of exponents in
rate equation
Order of Rxn Possible Expression of Rate Law
1 k[A]
2 k[A]2
2 k[A][B]
3 k[A]2[B]
3 k[A][B][C]

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 Practice Problem
 What is the reaction order of acetaldehyde and
the overall order in the following reaction
CH3CHO(g) → CH4(g) + CO(g)

Rate = k[CH3CHO]3/2
Ans:
3/2 order in CH3CHO
Overall order: 3/2

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 Practice Problem
Experiments are performed for the reaction
A →B + C
and the rate law has the been determined to be of the form
Rate = k[A]x
Determine the value of the exponent “x” for each of the
following:
a. [A] is tripled and you observe no rate change
Ans: x = 0 k[3A]0
b. [A] is doubled and the rate doubles
Ans: x = 1 k[2A]1
c. [A] is tripled and the rate increases by a factor of 27
Ans: x = 3 k[3A]3

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 Experimental Rate Law
 Concentration Exponents (reaction orders) must
be determined experimentally because the
stoichiometric balanced equation with its reaction
coefficients, does not indicate the mechanism of
the reaction
 Experimentally, the reaction is run with varying
concentrations of the reactants, while observing
the change in rate over time
 The initial rate of reaction is observed, where the
rate is linear with time (instantaneous rate =
average rate); usually just when the reaction
begins

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 Experimental Rate Law
Initial rates of reaction from experiments on the reaction:
O2(g) + 2NO) g) → 2 NO2)g)
Rate = k[O2] m[NO] n
Determine “m” & “n” from experimental data


Initial Reactant Concentration (mol/L)

Experiment O2 NO Initial Rate
Mol/Ls

1 1.10x10-2 1.30x10-2 3.21x10-3

2 2.20x10-2 1.30x10-2 6.40x10-3
3 1.10x10-2 2.60x10-2 12.8x10-3
4 3.30x10-2 1.30x10-2 9.60x10-3
5 1.10x10-2 3.90x10-2 28.8x10-3
Rate equations from two applicable experiments are combined,
depending on the reactant order to be determined
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 Experimental Rate Law
Select the 1st two experiments where the effect of doubling the concentration of O2 is observed at constant
temperature

Rate2 k[O2]m2 [NO] n

2
=
Rate1 k[O2]1m [NO]1n
K is constant and [NO] does not change
m
Rate2 [O2]m
 [O2]2 
2
=
= 
Rate1 [O2]1m
 [O2]1 
Substitute rate values and concentration values
m
-3
6.40 x 10 mol / l•s  2.20 x 10 mol / L  -2
= 
-3  -2
3.21 x 10 mol / l•s  1.10 x 10 mol / L 
1.99=2.00m
log(1.99) = m × log(2.00) Reaction is 1 st
order in O2:
m =1(rounded) When [O2] doubles, the rate doubles
12/12/10 30
 Experimental Rate Law
 Determining the Rate Constant (k)
 The rate data from any one of the experiments in the
previous table can be used to compute the rate
constant
 Using the first experiment:
-2 -2
[O2 ] =1.10 x 10 mol / L [NO] 0
=1.3
x 10 mol /L
-3
Rate 1 = 3.21 x 10 mol / L •s
m n
Rate 1 =k [O
2 ] [NO]
Rate 1
k =
[O2 ]m [NO]n
m =1; n = 2 (From previous calculation
s) (Overall reaction order = 1 +3)
2=
3.21 x 10-3 mol / L •s
k =
( 1.10 x 10 )( )
-2 1 -2 2
mol / L 1.30 x 10 mol / L
3 2 2
k =1.73 x 10 L / mol •s (Note unitsoverall
for reaction order = 3)
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 Integrated Rate Laws
 Concentration changes over time
 Previous notes assume that time is not a variable
and the rate or concentration for a reaction is at a
given instant in time
 By using time as a factor in the reaction, the rate
law can be integrated
“How long will it take
for x moles per liter of reactant ‘A’ to be used up?”

“What are the concentrations of ‘A’ after ‘y’ minutes

of the reaction”

12/12/10 32
 Integration of Rate Equation
First Order Reaction
Δ [ A]
= k [ A]
1
-
Δt
Rearrange Equation
Δ [ A] 1  1
- = kΔt  dx  = kdt ∫ dx = ln x
[ A] x  x
-ln [ A ] = kt + C (at t = 0, C = ln[Ao ])
-ln ( [ A ] t - [ A ] 0 ) = kt

( )
ln [ A ] 0 - [ A ] t = kt
[ A] 0 [ A] 0 kt
ln = kt or log =
[ A] t [ A] t 2.303

12/12/10 33
 Integration of Rate Equation
 Second Order Reaction

Δ [ A]
= k [ A]
2
-
Δt
Δ [ A]  1  1 xn+1 x-2+1 1
- = kΔt  2  = kdt
dx ∫ n dx = = = -
[ A] 2
x  x n +1 -2 + 1 x

 1   1 
--
 [ A ] 
= kt + C  a t = 0, C = 
 

 [ A ] 0 
 1   1 
--  = kt +  
 [ A]   [ A] 
 t   0

 1   1 
  -   = kt
 [ A]   [ A] 
 t   0
1
= kt
[ A] t - [ A] 0
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 Integration of Rate Equation
 Zero Order Reaction

Δ [ A]
= k [ A]
0
- = k ×1
Δt
Δ [ A]
- = k
At
-Δ [ A ] = kAt
-([ A ] t - [ A ] 0 ) = kt
[ A] t - [ A] 0 = - kt

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 Integrated Rate Law
 Integrated Rate Law – Straight Line Plot
For a 1st order reaction
ln[A]0 - ln[A]t = kt
Rearrange into equation for a straight line
ln[A]t = - kt + ln[A]0
y = mx + b (m = slope; b = y - axis intercept)
For a simple 2nd order reaction :
1 1
- = kt
[A]t [A]0
1 1
= kt +
[A]t [A]0
y = mx + b (m = slope; b = y - axis intercept)
For a zero - order reaction :
[A]t - [A]0 = - kt
[A]t = - kt + [A]0
y = mx + b
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 Integrated Rate Law

12/12/10
37
 First-Order Concentration vs.
Time Graphs

12/12/10 38
 Integrated Rate Law
 1st Order Reaction Half-Life
 The half-life of a reaction is the time required for the
reactant concentration to reach ½ its initial value
 At fixed conditions, the half-life of a 1st order reaction is
a constant, independent of reactant concentration

[A]0
ln = kt
[A]t

After one half - life, t = t1/ 2 , and [A]t = 1

2 [A]0

Substituting
[A]
ln 1 0 = kt1/ 2
2
[A]0

ln 2 = kt1/ 2 [Recall Radioactivity half-life (Chap 24)]

ln2 0.693
t1/ 2 = =
k k
12/12/10 39
 Integrated Rate Law – Half-LIfe

1 1
- = kt
[ A] 0 [ A] 0
After one half - life, t = t1/ 2 , and [A]t = 1
2 [A]0

1 1 1 1 2 1 1
- - -
[ A] t [ A] 0 1 / 2[ A] 0 [ A] 0 [ A] 0 [ A] 0 [ A] 0
t1/ 2 = = = =
k k k k
1
t1/ 2 =
k [ A] 0

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 Integrated Rate Law – Half-LIfe
 Zero Order Reaction Half-Life

[A]t - [A]0 = - kt

After one half - life, t = t 1/ 2 , and [A]t = 1

2 [A]0

[A]t - [A]0 1 / 2[A]0 - [A]0 -0.5[A]0

t1/ 2 = = =
-k -k -k
[A]0
t1/ 2 =
2k

12/12/10 41
 Practice Problem
A reaction is first order with respect to A. The
first-order rate constant is 2.61 /min. How long
will it take the concentration of A to decrease from
0.100 M to 0.00812 M? What is the half-life of the
reaction? How long will it take for the
concentration
k = 2.61 / min
of A to decrease by 85%?
ln[A]0 - ln[A]t = kt

 [A] 
ln  0  ln  0.100 
ln[A]0 - ln[A]t [A]t  0.00812  ln ( 12.3152709 ) 2.51084
t= =  =  = =
k k 2.61 / min 2.61 2.61
t = 0.962min
ln2 0.693 0.693
t1/2 = = = = 0.266 min
k k 2.61 / min
 [A] 
ln  0  ln  0.1 
ln[A]0 - ln[A]t [A]t  0.1× 0.15  ln ( 6.66667 ) 1.89712
t= =  =  = = = 0.727 min
k k 2.61 2.61 2.61
12/12/10 42
 Practice Problem
A reaction is second order with respect to B.
The second-order rate constant is 1.5 L/molmin
How long will it take the concentration of B to
decrease from 0.100 M to 0.025 M?
k = 1.5 L / mol • min
1 1
- = kt
[A]t [A]0
1 1
-
[A]t [A]0
t=
k
1 1
-
t = 0.025 mol / L 0.100 mol / L
1.5 L / mol • min
40 - 10
t= = 20min
1.5
12/12/10 43
 Temperature Dependence of Reaction
Rate
 An increase in Temperature (T) generally
increases the reaction rate
 A 10 oC increase in T usually doubles rate
 Temperature affects the rate constant (K) of the
rate equation
 Temperature effect process is described by
Collision Theory
 Can calculate the effect of T on rate of a reaction
using the Arrhenius Equation

12/12/10 44
 Effects of Concentration &
Temperature
 Two major models explain the observed effects of
Concentration & Temperature on reaction rate
 Collision Theory
 Views the reaction rate as a result of
particles colliding with a certain frequency
and minimum energy
 Transition State Theory
 Close-up view of how the energy of a
collision converts reactant to product

12/12/10 45
 Collision Theory
 Why concentrations are “Multiplied” in the Rate Law
 Consider 2 particles of “A” & 2 particles of “B”
 Total A-B collisions = 4 (2 x 2)
A1B1 A1B2 A2B1 A2B2
 Add additional Particle of “A”
 Total A-B collisions = 6 (3 x 2)
A1B1 A1B2 A2B1 A2B2 A3B1 A3B2
 It is the product of the number of different particles, not the sum (6
vs 5), that determines the number of collisions (reactions) possible
 The number of particles of reactant A (concentration) must be
multiplied by the number of particles of Reactant B to account for
the total number of collisions (reactions) that occur.

12/12/10 46
 Collision Theory
 Increasing the temperature of a reaction increases the average
speed of particles; thus, the frequency of collision
 Most collisions do not result in a “reaction”
 Collision Theory assumes that, for a reaction to occur, reactant
molecules must collide with an energy greater than some minimum
value and with proper orientation
Activation Energy (Ea)
 The rate constant, k, for a reaction is a function of 3 collision
related factors:
 Z, collision frequency
 f, fraction of collisions => activation energy
 p, fraction of collisions in proper orientation
k = Zpf

12/12/10 47
 Collision Theory
 At a given temperature, the fraction of molecular
collisions, f, with energy greater than or equal to
the activation energy, Ea, is related to activation
energy by the expression:-E RT
f =e a

 An equation (Arrhenius) expressing the

dependence of the rate constant, k, on
temperature can be obtained by combining the
relationship between the rate constant and
fraction of collisions, f, that are >= to the
“activation energy”, Ea
k = Zpf
Let A = Zp = frequency factor
k = Af
-Ea RT
f =e
∴ k = Ae-Ea RT

12/12/10 48
 Arrhenius Equation
 Temperature dependence of reaction rate
-Ea/RT
k = Ae
K = rate constant
A = frequency factor (pZ)
Ea = activation energy (J)
R = gas constant (8.314 J/mol•K)
T = temperature (K)
 The negative exponential relationship between
temperature (T) and the rate constant k means
that as the temperature increases, the negative
exponent becomes smaller, so the value of k
becomes larger, which means that the rate of the
reaction increases
Higher T ⇒ large k ⇒ increased rate
12/12/10 49
 Arrhenius Equation
 The activation energy (Ea) can be calculated from
the Arrhenius equation by taking the natural
logarithm of both sides and rearranging the
equation into a “straight line (y=b+mx) form
-Ea / RT
k = Ae
ln k = ln A + ln e ( -Ea / RT
)
Ea  1 
ln k = ln A -  
R T
y = b + mx
 A plot of ln k (y) vs. 1/T (x) gives a straight line whose
slope (m) is -Ea/R and whose y intercept is Ln A (b)

12/12/10 50
 Arrhenius Equation
 Ea can be determined graphically from a
series of k values at different temperatures
 Determine the slope from the plot
 Use slope formula = -Ea/R

 Alternate Approach - Compute Ea

mathematically if the rate constants
at two temperatures are known
Ea  1  Ea  1 
ln k 2 = ln A -   ln k 1 = ln A -  
R  T2  R  T1 
Ea  1   Ea  1   Ea  1  Ea  1  “ln A” term
ln k 2 - ln k 1 = ln A - -
   ln A -    = -  +  
R  T2   R  T1   R  T2  R  T1  drops out

k2 E  1 1  E T 1 T 1  E T -T 
ln =- a - =- a 1× - 2× =- a 1 2
k1 R  T2 T1  R  T1 T2 T2 T1  R  T1T2 
 k 2   T1T2 
Ea = -R × ln   ×  
k T
 1  1 2 - T
12/12/10 51
 Practice Problem
 Find the Activation Energy (Ea) for the decomposition of
Hydrogen Iodide (HI)
2HI(g) → H2(g) + I2(g)
The rate constants are:
9.51x10-9 L/mols at 500oK
1.10x10-5 L/mols at 600oK

k   TT 
Ea = -R × ln  2  ×  1 2 
 k 1   T1 - T2 
 1.10 x 10-5 L / mol • s   500o K × 600o K 
Ea = - ( 8.314J / mol • K ) × ln  ×
 9.51 x 10-9 L / mol • s   500o K - 600o K 
   
( ) (
Ea = - ( 8.314J / mol • K ) × ln 1.156677 x 10 3 × -3.00 x 103 )
(
Ea = - ( 8.314J / mol • K ) ×(7.053307)× -3.00 x 10 3 )
1kJ
Ea = 1.76 x 105 J / mol × 3
2
1 x 10 J
Ea = 1.76x10 kJ / mol
12/12/10 52
 Rate – Affects of Temperature
ACTIVATED STATE

Ea(forward)
Collision Energy

Collision Energy
Ea(reverse)

REACTANTS

PRODUCTS

 Molecules must collide with sufficient energy to reach “activation” status

 Minimum collision energy is “energy of activation, Ea”
 The forward reaction is exothermic because the reactants have more
energy than the products.
12/12/10
53
 Collision Theory: Proper Orientation (p)

12/12/10 54
 Transition-State Theory
 Transition-state theory explains the reaction in
terms of the collision of two high energy species –
activated complexes
 An activated complex (transition state) is an
unstable grouping of atoms that can break up
to form products.
 A simple analogy would be the collision of
three billiard balls on a billiard table.
 Suppose two balls are coated with a slightly
stick adhesive.
 We’ll take a third ball covered with an
extremely sticky adhesive and collide it with
our joined pair.

12/12/10 55
 Transition-State Theory
 Transition-state theory (cont’)
 At the instant of impact, when all three
spheres are joined, we have an unstable
transition-state complex
 The “incoming” billiard ball would likely
stick to one of the joined spheres and
provide sufficient energy to dislodge the
other, resulting in a new “pairing”
 If we repeated this scenario several times,
some collisions would be successful and
others (because of either insufficient
energy or improper orientation) would not
be successful.
 We could compare the energy we provided
to the billiard balls to the activation
energy, Ea
12/12/10 56
 Transition State Theory
 Reaction of Methyl Bromide & OH-
 Reaction is exothermic – reactants are higher in
energy than products
 Forward activation energy Ea(fwd) is less than
reverse Ea(rev)
 Difference in activation energies is “Heat of
Reaction”
∆ Hrxn = Ea(fwd) - Ea(rev)
Note the partial
elongated C-O and C-Br
bonds and the trigonal
bipyramidal shape of the
transition state

12/12/10 57
 Exothermic Reaction Pathway

Transition State

Ea(fwd) < Ea(rev)

∆ Hrxn = Ea(fwd) - Ea(rev)

12/12/10 58
 Endothermic Reaction Pathway

Ea(fwd) > Ea(rev)

12/12/10 59
 Reaction Mechanisms
 Steps in the overall reaction that detail how
reactants change into products
 Reaction Mechanism – set of elementary
reactions that leads to overall chemical equation
 Reaction Intermediate – species produced
during a chemical reaction that do not appear in
chemical equation
 Elementary Reactions – single molecular event
resulting in a reaction
 Molecularity – number of molecules on the
reactant side of elementary reaction
 Rate Determining Step (RDS) – slowest step in
the reaction mechanism
This is the reaction used to construct the rate law;
it is not necessarily the overall reaction

12/12/10 60
 Reaction Mechanisms
Proposed Overall Reaction
2 NO2(g) + 2 H2(g) → 2 H2O(g) + N2(g)

A mechanism in 3 elementary reactions:

2 NO2 → N2O2 (slow) (RDS)
H 2 + N 2O 2 → H 2O + N 2O (fast)
H 2 + N 2O → H 2O + N 2 (fast)
The Overall Reaction from Elementary Reactions:
2 NO2(g) + 2 H2(g) → 2 H2O(g) + N2(g)
 N2O2 and N2O are reaction intermediates
 Develop “Rate Law” from the “Rate Determining Step” (RDS)
 Rate law = Rate = k[NO2]2
 Note: The reaction order in an elementary reaction comes from the
stoichiometric coefficient, i.e., 2
 Adding together the reactions in the mechanism provides the
overall chemical equation

12/12/10 61
 Reaction Mechanisms
 Elementary Reactions (Steps) – The individual
steps, which together make up a proposed
reaction mechanism
 Each elementary reaction describes a single
molecular event, such as one particle
decomposing or two particles colliding and
combining.

12/12/10 62
 Reaction Mechanisms
 An elementary step is characterized by its
“Molecularity – the number of reactant
particles involved in the step
2O3(g) → 3O2(g)
Proposed mechanism – 2 steps
1st step – Unimolecular reaction
(decomposition)
O3(g) → O2(g) + O(g)
2nd step – Bimolecular reaction (2 particles
react)
O3(g) + O(g) → O2(g)

12/12/10 63
 Rate Law & Reaction
Mechanisms
 Rate law for an elementary reaction can be
deduced directly from molecularity of reaction
(w/o experimentation)
 An elementary reaction occurs in one step
 Its rate must be proportional to the product of the
reactant concentrations
 The stoichiometric coefficients are used as the
reaction orders in the rate law for an elementary
step
 The above statement holds only for an
elementary reaction
 In an overall reaction the reaction orders must be
determined experimentally

12/12/10 64
 Rate Law & Reaction
Mechanisms
 Steps in determining rate law from reaction
mechanism
 Identify the rate determining step (RDS) of the
mechanism
 Write out the preliminary rate law from RDS
 Remove expressions for intermediates
algebraically
 Substitute into preliminary rate law to obtain
final rate law expression

12/12/10 65
 Practice Problem
The following two reactions are proposed as elementary
steps in the mechanism of an overall reaction:
(1) NO2Cl(g) NO2(g) + Cl(g)
(2) NO2Cl(g) + Cl(g) NO2(g) + Cl2(g)
(a) Write the overall balanced equation
(b) Determine the molecularity of each step
(c) What are the reaction intermediates
(d) Write the rate law for each step

PLAN: (a) The overall equation is the sum of the steps

(b) Molecularity is the sum of the reactant particles in the step.

SOLUTION: (b) Step(1) is unimolecular.

(a) (1) NO2Cl(g) NO2(g) + Cl (g) Step(2) is bimolecular.

(2) NO2Cl(g) + Cl (g) NO2(g) + Cl2(g) (c) Cl(g) is reaction intermediate

(d) rate1 = k1[NO2Cl]
2NO2Cl(g) 2NO2(g) + Cl2(g)
rate2 = k2[NO2Cl][Cl]
12/12/10 66
 Correlating Rate Law &
Mechanism
 Criteria required for proposed reaction
mechanism
 The elementary steps must add up to the
overall balanced equation
 The number of reactants and products
in the elementary reactions must be
consistent with the overall reaction
 The elementary steps must be physically
reasonable – they should involve one reactant
(unimolecular) or at most two reactant
particles (bimolecular)
 The mechanism must correlate with the “rate
law” – The mechanism must support the
experimental facts shown by the rate law, not
the other way around

12/12/10 67
 Practice Problem
If a slow step precedes a fast step in a two-step mechanism, do the
substances in the fast step appear in the rate law?
Ans: No, the overall rate law must contain reactants only (no
intermediates) and is determined by the slow step
If the first step in a reaction mechanism is slow, the rate law
for that step is the overall rate law
If a fast step precedes a slow step in a two-step mechanism, how is
the fast step affected?
Ans: If the slow step is not the first one, the faster preceding step
produces intermediates that accumulate before being consumed in
the slow step
How is this effect used to determine the validity of the mechanism?
Ans: Substitution of the intermediates into the rate law for the
slow step will produce the overall rate law.

12/12/10 68
 Mechanism with a Slow Initial
Step
Reaction between nitrogen dioxide & chlorine gas
Overall reaction
2NO2(g) + F2(g) → 2NO2F(g)
Experimental Rate Law
Rate = k[NO2][F2] (1st order)
Mechanism
(1) NO2(g) + F2(g) → NO2F(g) + F(g) [slow, rds]
(2) NO2(g) + F(g) → NO2F(g) [fast]
Overall: 2NO2(g) + F2(g) → 2NO2F(g)
Criteria 1: Elementary steps add up to experimental
Criteria 2: Both steps “Bimolecular”

Con’t on next Slide

12/12/10 69
 Mechanism with a Slow Initial
Step
 Criteria 3:
Experimental Rate Law: k[NO2][F2]
Elementary Reaction Rate Laws
Rate1 = k1[NO2][F2] (from rds)
Rate2 = k2[NO2][F]
Rate 1 (k1) from rds is same as overall k
The 2nd [NO2] term (in Rate2) does not appear in
the overall rate law

Each step in mechanism has its own transition state

Proposed transition state is shown in step 1
Reactants for 2nd step are the F atom intermediate
and the 2nd molecule of NO2
First step is slower – Higher Ea
Overall reaction is exothermic - ∆ Hrxn < 0

12/12/10 70
 Mechanism with a Fast Initial Step
 Nitric oxide, NO, is believed to react with chlorine
(Cl2) according to the following mechanism
NO + Cl2 ↔ NOCl2 (Fast, equilibrium)
NOCl2 + NO → 2 NOCl (slow, RDS)
1. What is the overall chemical equation for the
reaction?
2. Identify the reaction intermediates.
3. Propose a viable rateReactant
Intermediate law from
- NOCl 2 the mechanism.
RDS = NOCl 2 + NO → 2NOCl

The rate law cannot be directly determined from the RDS

NO+Cl 2 € NOCl 2 because of the presence of NOCl 2 , an"Intermediate Reactant"
NOCl 2+NO →2NOCl
k 1(fwd) [NO][CL 2 ] = k 1(rev)[NOCl 2 ]
2NO+Cl 2 →2NOCl
k 1(fwd)
[NOCl 2 ] = [NO][Cl 2 ]
k 1(rev)
Substituting in RDS gives :
k 1(fwd)
[NO][Cl 2 ][NO] = k [ NO ] [ Cl 2 ]
2
Rate =
k 1(rev)
12/12/10 71
 Catalysis – Speeding Up
Reaction
 It is often necessary to “Speed up” a reaction in
order to make it useful and in the case of
industry, profitable
 Approaches
 More energy (heat) – could be expensive!!
 Catalyst – Stoichiometrically small amount of a
substance that increases the rate of a reaction;
it is involved in the reaction, but ultimately is
not consumed

12/12/10 72
 Catalysis – Speeding Up
Reaction
 Catalyst:
 Causes lower “activation energy”, (Ea)
 Lower activation energy is provided by a
change in the reaction mechanism
 Makes Rate constant larger
 Promotes higher reaction rate
 Speeds up forward & reverse reactions
 Does not improve yield – just makes it faster

12/12/10 73
 Homogeneous Catalysts
 Homegeneous Catalysts
 Exist in “Solution” with the reactant mixture
 All homogenous catalysts are gases, liquids, or
“soluble” solids
Mechanism for the catalyzed hydrolysis of an organic ester.
H+ , the catalyst, is a resonance forms
O fast H O proton supplied by a H O H O
H+ + R C R C strong acid
R C R C
O O +
Step 1: Catalytic H ion H O
O O
R' Step R' bonds to electron rich R C
1 oxygen. R' R'
O
Step 2: Slow, rate R'
determining step. resonance hybrid
Step
H O H O The increased positive
2
R C O H R C O H charge on the Carbon
attracts the partially H+ O
O H O H negative oxygen of the
slow, rate- all fast R C O H
R' determining R' water more strongly, OH
step increasing the fraction of
effective collisions, R'
Steps 3-6
speeding up this rate
determining step
12/12/10 74
 Heterogeneous Catalysts
 Heterogeneous Catalysts
 Speeds up a reaction that occurs in a separate
phase
 Ex. A solid interacting with gaseous or liquid
reactants
 The solid would have extremely large surface
area for contact
 If the rate-determining step occurs on the
surface of the catalyst, many reactions are
zero order, because once the surface area is
covered by the reactant, increasing the
concentration has no effect on the rate

12/12/10 75
 Heterogeneous Catalysts
 Hydrogenation of Ethylene (Ethene) to Ethane
catalyzed by Nickel (Ni), Palladium (Pd), or Platinum
(Pt) Ni, Pd, Pt
H2C=CH2(g) + H2(g) → H3C – CH3
 Finely divided Group 8B metals catalyze by adsorbing
the reactants onto their surface
 H2 lands and splits into separate H atoms chemically
bound to solid catalyst’s metal atoms
H – H + 1catM(s) → 2catM – H
 Then C2H4 absorbs and reacts with two H atoms, one
at a time, to form H3C–CH3
 The H-H split is the rate determining step providing a
lower energy of activation

12/12/10 76
 Effect of A Catalyst
Comparison of Activation Energies in the Uncatalyzed and
Catalyzed Decompositions of Ozone

Catalyst: provides alternative

mechanism for a reaction that
has a lower activation energy

12/12/10 77
 Practice Problem
Ethyl Chloride, CH3CH2Cl2, used to produce
tetraethyllead gasoline additive, decomposes, when
heated, to give ethylene and hydrogen chloride.
The reaction is first order. In an experiment, the
initial concentration of ethyl chloride was 0.00100
M. After heating at 500 C for 155 s, this was
reduced to 0.00067 M. What was the concentration
of ethyl
[A]o chloride after a total of 256 s?
ln = kt (1st order reaction)
[A]t
[A]o 0.00100M
ln ln
[A]t 0.00067M ln ( 1.492537 ) 0.400478
k= = = = = 0.0026 / s
t 155s 155 155
Determine concentration after t = 256 seconds
ln[A]t - ln[A]0 = - kt
ln[A]t = ln[A]0 - k t
ln[A]t = ln(0.00100 M) - 0.0026 / s × 256 s
ln[A]t = - 6.90776 - 0.6656 = - 7.57336
12/12/10 [A]t = 0.00052 M 78
 Practice Problem
The rate of a reaction increases by a factor of 2.4
when the temperature is increased from 275 K to
300 K. What is the activation energy of the
reaction?

k 2 T1 × T2
Ea = -R × ln ×
k 1 T1 - T2
 2.4 k 1   275o K × 300o K 
Ea = - ( 8.314J / mol • K ) × ln   × o o 
 k 1   275 K - 300 K 
Ea = 65, 846.88J / mol
Ea = 65 kJ / mol

12/12/10 79
 Practice Problem
The rate constant of a reaction at 250 oC is 2.69 x
10-3 1/M-s (L/mols). Given the activation energy for
the reaction is 250 kJ, what is the rate constant for
the reaction at 100 oC, assuming activation energy
is independent of temperature?
k 2 T1 × T2
Ea = -R × ln ×
k 1 T1 - T2
Ea T1 - T2
lnk2 = lnk1 + ×
-R T2 × T1
kJ 1000J
250  (250o C + 273.15)K - (100o C + 273.15)K 
-3
lnk 2 = ln(2.69x10 L / mol • s + mol kJ × 
-8.314J / mol • K  (250o C + 273.1)K ×(100o C + 273.15)K 
250, 000J / mol 150o K
lnk 2 = 1.002694 L / mol • s + ×
-8.314J / mol • K 195, 213.4225o K 2
37, 500, 000
lnk 2 = 1.002694L / mol • s -
1, 623, 004.395
lnk 2 = 1.002694L / mol • s - 23.105298 = -22.102604
k 2 = 2.52x10-10 L / mol • s
12/12/10 80
 Practice Problem
If the half-life of a first-order reaction is 25 min, how
long will it take for 20% of the reactant to be
consumed?
ln2 0.693
t1/ 2 = =
k k
0.693 0.693 0.693
k= = =
t1/ 2 t1/ 2 25min

k = 0.02772 / min
[A]o
ln = kt
[A]t

[A]t at time, t = 0.8[A]0

[A]o  [A]o   1.00 

ln ln   ln  
[A]t  0.8[A]0   0.80  ln ( 1.25 ) 0.223143551
t= = = =
k 0.02772 0.02772 0.02772 0.02772
t = 8.0 min
12/12/10 81
 Practice Problem
For a reaction with the rate law given as rate =
k[A]2, [A] decreases from 0.10 to 0.036 M in 161
min. What is the half-life of the reaction?
k[A]2 represents the rate of a second order reaction
1 1
- = kt
[ A] t [ A] 0
1 1 1 1
-
[ A] t [ A] 0 -
27.7778L / mol - 10L / mol 17.7778L / mol
k= = 0.036M 0.10M = =
t 161min 161min 161min
k = 0.11L / mol • min
Half - Life for 2nd order reaction
1
t1/ 2 = (See slide # 41)
k [ A] 0
1
t1/ 2 =
0.11 ( L / mol • min ) x 0.10 mol / L
t1/ 2 = 91min
12/12/10 82
 Practice Problem
The decomposition of the herbicide atrazine in the atmosphere by
sunlight is first order, with a rate constant of 1.1 x 10-3 1/s.
Following field application by spaying it is found that the
atmospheric concentration of atrazine is 2.5 x 10-6 ppm at mid-day.
How long (in hours) will it take for the atmospheric concentration of
atrazine to reach the air quality standard of 1.0 x 10-9 ppm?

Rate Law for 1st order reaction

[ A] 0
ln = kt
[ A] t
[ A] 0  2.5x10-6 mol / L 

t=
ln
[ A] t
ln 
=  = (
 1.0x10-9 mol / L  ln 2.5x103) =
7.82405
k 1hr 3.9600 / hr 3.96 / hr
1.1x10-3 / s
3600s
t = 2.0 hr
12/12/10 83
 Practice Problem
The indirect photolysis of the pesticide atrazine (Atr,
C8H14 ClN5) in air by hydroxyl radical (OH) is shown below
C8H14 ClN5 + OH → C8H13 ClN5 + H2O

The reaction is second order and follows the rate law

∆ [Atr]/∆ t = kph [Atr][OH]. The concentration of OH is at
steady-state during daylight hours at ~1.0e-18 M, and kph
is 5.0e15 1/M-s. How long (in min) will it take for Atr to
decrease from 2.5e-15 M to 1.0e-18 M (the air quality
criteria) following application to a golf course assuming
pseudo-first-order kinetics during daylight?

a. 26 b. 1.8 c. 527 d. 4,218 e. 119

12/12/10
Solution on next Slide 84
 Practice Problem
 Photolysis of Atrazine (con’t)
 The 2nd order rate law (∆ [Atr]/∆ t = kph[Atr][OH]) is stated
in terms of two reactants
 This would result in a different integrated form of the 2nd
order reaction, more complicated math
 Since the concentration of hydroxyl, [OH], is constant,
the rate law can be reduced to a pseudo 1st order
reaction by combining the Kph & [OH] terms (both
constants) into a new15
rate constant:
-18 -3
k = k ph ×[OH] = 5.0 x 10 L / mol • s ×1.0 x 10 mol / L = 5.0 x 10 / s

Δ[Atr]
= k[Atr] (Restatement of 2nd order rate law into pseudo 1st order)
Δt
[A]o
ln = kt (Integrated 1st order Rate Law))
[A]t

[A]o -15
ln 2.5 x 10 mol / L
ln
[A]t 1.0 x 10 -18
mol / L ln(2.5 x 103 ) 7.824046
t= = = =
k 5.0 x 10-3 / s 5.0 x 10-3 / s 5.0 x 10 -3 / s
1min
t = 1.5648 x 103 s × = 26 min
60s
12/12/10 85
 Practice Problem
A convenient rule of thumb is that the rate of a
reaction doubles for a 10 oC change in temperature.
What is the activation energy for a reaction whose
rate doubles from 10.0 oC to 20.0 oC?
a. 47.8 kJ b. 19.5 kJ c. 24.3 kJ d. 10.1 kJ e. 69.2
kJ k   TT 
Ea = - R × ln  2  ×  1 2 
 k1   T1 - T2 
At 20o C the rate constant k 2 = 2 k1

( ) ( ) 
o
o o o
 2k1   10 C + 273.15 K × 20 C + 273.15) K
Ea = -8.314J / mol • K × ln  × 
( ) ( ) 
k o
 1   10o C + 273.15 K 1 - 20o C + 273.15)o K

8.30054 x 104o K 2
Ea = -8.314J / mol • K × ln ( 2 ) ×
-10o K
Ea = -8.314J / mol • K × 0.693147 × 8.30054 x 103o K
kJ
Ea = 4.783455 x 104 J / mol × = 47.8kJ / mol
1000J
12/12/10 86
 Rate Equations - Summary
Integrated Rate Laws
Δ [ A]
rate = - = k[A]0 = k Zero Order Rate Reaction
Δt
[ A] 0
Rate Law : [ A ] t - [ A ] 0 = -kt Half - Life t1/ 2 =
2k

Δ [ A]
rate = - = k[A] First Order Reaction
Δt
ln2 0.693
Rate Law : ln[A]0 - ln[A]t = kt Half - Life t1/ 2 = =
k k

Δ [ A]
rate = - = k[A]2 Second Order Reaction
Δt
1 1 1
Rate Law : - = kt Half - Life t1/ 2 =
ln[A]t ln[A]0 k [A]0

12/12/10 87
 Rate Equations - Summary
An Overview of Zero-Order, First-Order, and Simple
Second-Order Reactions

Zero Order First Order Second Order

Rate law rate = k rate = k[A] rate = k[A]2
Units for k mol/L*s 1/s L/mol*s

Integrated rate law [A] = -kt + [A] ln [A] = -kt + ln [A] 1/[A] = kt + 1/[A]
t 0 t 0 t 0
in straight-line form

Plot for straight line [A]t vs. t ln [A]t vs. t 1/[A]t = t

Slope, y intercept k, [A]0 -k, ln [A]0 k, 1/[A]0

Half-life [A]0/2k ln 2/k 1/k[A]0

12/12/10 88
 Rate Equations - Summary
Activation Energy (Ea)
k = Zpf
f = e -Ea/RT
k = Zpe -Ea/RT = Ae -Ea/RT
k, rate constant
Z, collision frequency
f, fraction of collisions that are => activation
energy
p, fraction of collisions in proper orientation
A = frequency factor (pZ)
Ea = activation energy (J)
R = gas constant (8.314 J/molK)
T = temperature (K)
Arrhenius Equation
k   TT 
Ea = -R × ln  2  ×  1 2 
 k 1   T1 - T2 
12/12/10 89