Chapter 14

Chemical Kinetics
Overview:
Reaction Rates
Stoichiometry, Conditions, Concentration
Rate Equations
Order
Initial Rate
Concentration vs. Time
First Order Rxns.
Second Order Rxns.
Graphical Methods

Contd
Molecular Theory
Activation Energy
Concentration
Molecular Orientation
Temperature
Arrhenius Equation
Reaction Mechanisms
Elementary Steps, Reaction Order, Intermediates
Catalysts

Reaction Rates
What Affects Rates of Reactions?

Concentration of the Reactants
Temperature of Reaction
Presence of a Catalyst
Surface Area of Solid or Liquid Reactants
[M]
time
D[M]
Dt
for reaction A B
Reaction Rates (graphical):

Average Rate = D[M]
Dt

Rates
for A B

- D[A] = D[B]
Dt Dt

Rate of the disappearance of A is equal in
magnitude but opposite in sign to the rate
of the appearance of B
[M]
time
tangent at time, t
t
Average Rate--D mol (or concentration) over a
period of time, Dt
Instantaneous Rate-- slope of the tangent at a
specific time, t
Initial Rate-- instantaneous rate at t = 0

Average Rate =
[A]
final time
- [A]
initial time

Dt
final
- Dt
initial

for A B
[M]
time
tangent at time, t
t
Instantaneous Rate
time, t
= slope of the tangent at time = t
Stoichiometry

4PH
3
=> P
4
+ 6H
2


- 1D[PH
3
] = + 1 D[P
4
] = + 1 D[H
2
]
4 Dt 1 Dt 6 Dt

- D[PH
3
] = + 4 D[P
4
] = + 2 D[H
2
]
Dt Dt 3 Dt


General Relationship

Rate =

- 1 D[A] = - 1 D[B] = + 1 D[C] = + 1 D[D]
a D t b D t c D t d D t


aA + bB cC + dD


Conditions which affect rates
Concentration
concentration rate
Temperature
temperature rate
Catalyst
substance which increases rate but itself remains
unchanged




aA + bB xX rate law



rate = k[A]
m
[B]
n


m, n are orders of the reactants
extent to which rate depends on concentration
m + n = overall rxn order
k is the rate constant for the reaction

Rate Equations:

Examples:

2N
2
O
5
=> 4NO
2
+ O
2

rate = k[N
2
O
5
] 1
st
order
2NO + Cl
2
=> 2NOCl
rate = k[NO]
2
[Cl
2
] 3
rd
order
2NH
3
=> N
2
+ 3H
2

rate = k[NH
3
]
0
= k 0
th
order

Determination of Rate Equations:
Data for: A + B => C
Expt. # [A] [B] initial rate
1 0.10 0.10 4.0
2 0.10 0.20 4.0
3 0.20 0.10 16.0

rate = k[A]
2
[B]
0
= k[A]
2

k = 4.0 Ms
-1
= 400 M
-1
s
-1

(0.10)
2
M
2

Exponent Values Relative to DRate
Exponent Value [conc] rate
0 double same
1 double double
2 double x 4
3 double x 8
4 double x 16


Problem:
Data for: 2NO + H
2
=> N
2
O + H
2
O

Expt. # [NO] [H
2
] rate
1 6.4x10
-3
2.2x10
-3
2.6x10
-5

2 12.8x10
-3
2.2x10
-3
1.0x10
-4

3 6.4x10
-3
4.5x10
-3
5.0x10
-5



rate = k[NO]
2
[H
2
]
Units of Rate Constants

units of rates M/s
units of rate constants will vary depending
on order of rxn

M = 1 (M)
2
(M) for
s sM
2


rate = k [A]
2
[B]

rate constants are independent of the
concentration

Concentration vs. Time
1st and 2nd order integrated rate equations
First Order: rate = - D[A] = k [A]
D t
ln [A]
t
= - kt A = reactant
[A]
0

or ln [A]
t
- ln [A]
0
= - kt
Conversion to base-10 logarithms:

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


to

log [A]
t
= - kt
[A]
0
2.303

Problem:
The rate equation for the reaction of sucrose in
water is, rate = k[C
12
H
22
O
11
]. After 2.57 h at
27C, 5.00 g/L of sucrose has decreased to 4.50
g/L. Find k.
C
12
H
22
O
11(aq)
+ H
2
O
(l)
=> 2C
6
H
12
O
6


ln 4.50g/L = - k (2.57 h)
5.00g/L

k = 0.0410 h
-1
Concentration vs. Time

Second Order: rate = - D[A] = k[A]
2

Dt
1 - 1 = kt
[A]
t
[A]
0


second order rxn with one reactant:

rate = k [A]
2

Problem:
Ammonium cyanate, NH
4
NCO, rearranges in water to
give urea, (NH
2
)
2
CO. If the original concentration of
NH
4
NCO is 0.458 mol/L and k = 0.0113 L/mol min,
how much time elapses before the concentration is
reduced to 0.300 mol/L?
NH
4
NCO
(aq)
=> (NH
2
)
2
CO
(aq)
rate = k[NH
4
NCO]

1 - 1 = (0.0113) t
(0.300) (0.458)
t = 102 min
b = slope
a = y intercept
x = time
Graphical Methods
Equation for a Straight Line

y = bx + a

ln[A]
t
= - kt + ln[A]
0
1
st
order

1 = kt + 1 2
nd
order
[A]
t
[A]
0

time
[H2O2]
First Order: 2H
2
O
2(aq)
2H
2
O
(l)

+ O
2(g)

ln [H2O2]
time
slope, b = -1.06 x 10
-3
min
-1
= - k
First Order: 2H
2
O
2(aq)
2H
2
O
(l)
+ O
2(g)

1/[NO
2
]
time
slope, b = +k
Second Order: 2NO
2
2NO + O
2

0.020 M
0.010 M
t
1/2
[M]
time
t
1/2
= 0.693
k
0.005 M
t
1/2
Half-Life of a 1
st
order process:

Problem:
The decomposition of SO
2
Cl
2
is first order in
SO
2
Cl
2
and has a half-life of 4.1 hr. If you
begin with 1.6 x 10
-3
mol of SO
2
Cl
2
in a flask,
how many hours elapse before the quantity of
SO
2
Cl
2
has decreased to 2.00 x 10
-4
mol?

SO
2
Cl
2(g)
=> SO
2(g)
+ Cl
2(g)


Temperature Effects
Rates typically increase with T increase
Collisions between molecules increase
Energy of collisions increase
Even though only a small fraction of
collisions lead to reaction
Minimum Energy necessary for reaction
is the Activation Energy
Activation Energy, Ea
E
n
e
r
g
y

Reaction Progress
Reactant
Product
DH reaction
Ea forward rxn.
Ea reverse rxn.
Molecular Theory
(Collision Theory)
Activation Energy
Activation Energy varies greatly
almost zero to hundreds of kJ
size of E
a
affects reaction rates
Concentration
more molecules, more collisions
Molecular Orientation
collisions must occur sterically


The Arrhenius Equation
increase temperature, inc. reaction rates
rxn rates are a to energy, collisions,
temp. & orient
k = Ae
-Ea/RT

k = rxn rate constant
A = frequency of collisions
-Ea/RT = fraction of molecules with energy necessary
for reaction

1/T
l
n

k

slope = -Ea/R
Graphical Determination of Ea
rearrange eqtn to give straight-line eqtn
y = bx + a
ln k = -E
a
1 + ln A
R T
Problem:
Data for the following rxn are listed in the
table. Calculate E
a
graphically, calculate A
and find k at 311 K.
Mn(CO)
5
(CH
3
CN)
+
+ NC
5
H
5
=> Mn(CO)
5
(NC
5
H
5
)
+
+ CH
3
CN
ln k k, min
-1
T (K) 1/T x 10
-3

-3.20 0.0409 298 3.35
-2.50 0.0818 308 3.25
-1.85 0.157 318 3.14
slope = -6373 = -Ea/R

Ea = (-6373)(-8.31 x 10
-3
kJ/K mol)
= 53.0 kJ
l
n

k

1/T
3.14 3.25 3.35 x 10
-3
-
3
.
2
0






-
2
.
5
0







-
1
.
8
5

y intercept = 18.19 = ln A
A = 8.0 x 10
7

k = 0.0985 min
-1

Problem:
The energy of activation for
C
4
H
8(g)
=> 2C
2
H
4(g)

is 260 kJ/mol at 800 K and k = 0.0315 sec

Find k at 850 K.

ln k
2
= - E
a
(1/T
2
- 1/T
1
)
k
1
R
k at 850 K = 0.314 sec
-1

Reaction Mechanisms
Elementary Step
equation describing a single molecular event
Molecularity
unimolecular
bimolecular
termolecular
2O
3
=> 3O
2

(1) O
3
=> O
2
+ O unimolecular
(2) O
3
+ O => 2 O
2
bimolecular

Rate Equations
Molecularity Rate Law
unimolecular rate = k[A]
bimolecular rate = k[A][B]
bimolecular rate = k[A]
2

termolecular rate = k[A]
2
[B]
notice that molecularity for an elementary step is the
same as the order

2O
3
=> 3O
2

O
3
=> O
2
+ O rate = k[O
3
]
O
3
+ O => 2O
2
rate = k[O
3
][O]
2O
3
+ O => 3O
2
+ O
O is an intermediate
Problem:
Write the rate equation and give the
molecularity of the following elementary
steps:
NO
(g)
+ NO
3(g)
=> 2NO
2(g)

rate = k[NO][NO
3
] bimolecular

(CH
3
)
3
CBr
(aq)
=> (CH
3
)
3
C
+
(aq)

+
Br
-
(aq)

rate = k[(CH
3
)
3
CBr] unimolecular
Mechanisms and Rate Equations
rate determining step is the slow step --
the overall rate is limited by the rate
determining step

step 1 NO
2
+ F
2
=> FNO
2
+ F rate = k
1
[NO
2
][F
2
]
k
1
slow
step 2 NO
2
+ F => FNO
2
rate = k
2
[NO
2
][F]
k
2
fast

overall 2NO
2
+ F
2
=> 2FNO
2
rate = k
1
[NO
2
][F
2
]
Problem:
Given the following reaction and rate law:
NO
2(g)
+ CO
(g)
=> CO
2(g)
+ NO
(g)
rate = k[NO
2
]
2


Does the reaction occur in a single step?
Given the two mechanisms, which is most
likely:

NO
2
+ NO
2
=>NO
3
+ NO NO
2
=> NO + O
NO
3
+ CO => NO
2
+ CO
2
CO + O => CO
2

2O
3(g)
3O
2(g)
overall rxn

1: O
3(g)
O
2(g)
+ O
(g)
fast
equil. rate1 = k
1
[O
3
]
rate2 = k
2
[O
2
][O]
2: O
(g)
+ O
3(g)
2O
2(g)
slow
rate3 = k
3
[O][O
3
]
rate 3 includes the conc. of an intermediate and
the exptl. rate law will include only species that
are present in measurable quantities
Reaction Mechanisms & Equilibria
k
3
k
1
k
2
Substitution Method
at equilibrium k
1
[O
3
] = k
2
[O
2
][O]

rate3 =k
3
[O][O
3
] [O] = k
1
[O
3
]
k
2
[O
2
]

rate3 = k
3
k
1
[O
3
]
2
or
k
2
[O
2
]

overall rate = k [O
3
]
2

[O
2
]
substitute
Problem:
Derive the rate law for the following
reaction given the mechanism step below:
OCl
-

(aq)
+ I
-
(aq)
OI
-
(aq)
+ Cl
-
(aq)


OCl
-
+ H
2
O HOCl + OH
-
fast
I
-
+ HOCl HOI + Cl
-
slow
HOI + OH
-
H
2
O + OI
-
fast

k
1

k
2

k
3

k
4

Contd
rate1 = k
1
[OCl
-
][H
2
O] =
rate 2 = k
2
[HOCl][OH
-
]
[HOCl] = k
1
[OCl
-
][H
2
O]
k
2
[OH
-
]
rate 3 = k
3
[HOCl][I
-
]
rate 3 = k
3
k
1
[OCl
-
][H
2
O][I
-
]
k
2
[OH
-
]

overall rate = k [OCl
-
][I
-
]
[OH
-
]
solvent
Catalyst
Facilitates the progress of a reaction by
lowering the overall activation energy
homogeneous
heterogeneous
E
n
e
r
g
y

Reaction Progress
Ea
Ea
DHrxn
catalysts are used in an early rxn step but
regenerated in a later rxn step
Step 1: Cl
(g)
+ O
3(g)
+ O
(g)
=> ClO
(g)
+ O
2(g)
+ O
(g)

Step 2: ClO
(g)
+ O
2(g)
+

O
(g)
=> Cl
(g)
+ 2O
2(g)

Overall rxn: O
3(g)
+ O
(g)
=> 2O
2(g)

Catalyzed Reaction:
Uncatalyzed Reaction:
O
3(g)
<=> O
2(g)
+ O
(g)
O
(g)
+ O
3(g)
=> 2O
2(g)
E
a
uncatalyzed rxn
E
a
catalyzed rxn
ClO + O
2
+ O
Cl + O
3
+ O
Cl + O
2
+ O
2