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Kinetics PDF
Kinetics PDF
Reaction Rates:
Reaction Rate: The change in the concentration of a reactant or a
product with time (M/s).
Reactant Products
A B
( moles of B ) [B]
= =
t t
[A]
Since reactants go away with time: Rate =
t
1
Consider the decomposition of N2O5 to give NO2 and O2:
2N2O5(g) 4NO2(g) + O2(g)
reactants products
decrease with increase with
time time
2
From the graph looking at t = 300 to 400 s
0.0009M
Rate O 2 = = 9 106 Ms 1 Why do they differ?
100s
0.0037M
Rate NO 2 = = 3.7 105 Ms 1 Recall:
100s
0.0019M 2N2O5(g) 4NO2(g) + O2(g)
Rate N 2 O5 = = 1.9 105 Ms 1
100s
aA + bB cC + dD
1 [A] 1 [ B] 1 [C] 1 [ D]
Rate = = = =
a t b t c t d t
3
Rate Law & Reaction Order
The reaction rate law expression relates the rate of a reaction to
the concentrations of the reactants.
Each concentration is expressed with an order (exponent).
The rate constant converts the concentration expression into the
correct units of rate (Ms1). (It also has deeper significance,
which will be discussed later)
For the general reaction: aA + bB cC + dD
4
The Overall Order of a reaction is the sum of the individual
orders:
Rate (Ms1) = k[A][B]1/2[C]2
or sevenhalves order
To find the units of a rate constant for a particular rate law, simply divide
the units of rate by the units of molarity in the concentration term of the
rate law.
Ms 1
k(units) = = s 1
M
5
Reaction Rates
Y [concentration]
Average Rate =
X time
time (s)
Rules of logarithms
x
Ax A A
log x = log = x log
B B B
A
log(AB) = log A + log B log = log A log B
B
6
Determining Reaction Order: The Method of Initial Rates
From the following data, determine the rate law and rate constant.
Initial Rate
Run [NO]o (M) [H2]o (M)
(M/min)
1 0.0100 0.0100 0.00600
Rate(M/min) = k [NO]x[H2]y
Taking the ratio of the rates of runs 3 and 1 one finds:
x y
Rate(3) k [NO](3) [H 2 ](3)
= x y
Rate(1) k [NO](1) [H 2 ](1)
y
[0.0200]y 0.0200
=
[0.0100]y 0.0100
7
x y
Rate(1) k [NO](1) [H 2 ](1)
0.0200
y
=
= 2
x y
log Rate(2) k [NO](2) [H 2 ](2)
0.0100
x
y 0.00600 k [0.0100] [0.0100]
0.0200 =
log = log 2 0.144 k [0.0200]x [0.0300]
0.0100
x
1 1 1
=
y log ( 2 ) = log 2 24 2 3
x
y=1 1 1
=
2 8
Now that y is known, we 1 1
x log = log
may solve for x in a similar 2 8
manner:
x=3
Rate(M/min) = k [NO]3[H2]
To find the rate constant, choose one set of data and solve:
M
= k ( 0.0100M ) ( 0.0200M )
3
0.0120
min
M M
0.0120 0.0120
k= min = min
( 0.0100M ) ( 0.0200M ) ( )( ) M4
3 3
0.0100 0.0200
M 3
k = 6.00 105
min
8
Integrated Rate Laws: time dependence of concentration
For a first order process, the
A products
rate law can be written:
[A]
Rate(Ms 1 ) = = k[A] This is the average rate
t
If one considers the infinitesimal changes in concentration and time the rate
law equation becomes:
d[A]
Rate(Ms 1 ) = = k[A] This is the instantaneous rate
dt
Integrating in terms of d[A] and dt:
[A] d[A] t
[A]o [A] 0 dt
where [A] = [A]o at time t = 0
= k
and [A] = [A] at time t = t
d[A]
[A] t [A]
[A]o [A]
= k dt
0
ln = kt
[A]o
Taking the exponent to each side of the equation:
[A]
= e kt or [A] = [A]o e kt
[A]o
9
Recognizing a first order process: Aproducts
[A] = [A]o e kt
Taking the log of the integrated rate law for a first order process we find:
10
Example: The rate of decomposition of azomethane (C2H6N2) was
studied by monitoring the partial pressure of the reactant as a function of
time.
Determine if the data below support a first order reaction.
Calculate the rate constant for the reaction.
Time P
ln (P)
(s) (mmHg Plot of lnP vs. time
0 284 5.65 5.70
100 220 5.39 5.60 y = -0.0026x + 5.6485
150 193 5.26 5.50
R2 = 1
200 170 5.14 5.40
ln P
250 150 5.01 5.30
5.20
5.10
5.00
k = 2.6x10-3s-1 4.90
0 50 100 150 200 250 300
time (s)
Reaction Half-Life
11
Reaction Half-life:
Half-life is the time taken for the concentration of a reactant to drop to
half its original value.
[A]o
[A] =
2
For a first order process the half life (t ) is found mathematically from:
(1) ln [ A ] = kt + ln [ A ]0
[ A ]0
(5) ln = kt
(2) ln [ A ] ln [ A ]0 = kt [A]0 1
2
2
[A]
(3) ln = kt
[A]0 ln 2 0.693
t1 = =
[ A ]0 k k
(4) ln = kt 2
[A]
Using the integrated rate law, substituting in the value of k and 900s we find:
[A] [A] 1
= e kt = e 0.00385 s 900 s = 0.0312
[A]o [A]o
Since the ratio of [A] to [A]0 represents the fraction of [A]o that remains, the
% is given by:
100 0.0312 = 3.12%
12
For a Second Order Process:
A Products
Rate = k[A]2
d[A]
Rate(Ms 1 ) = = k[A]2
dt
Integrating as before we find:
1 1
= kt +
[A] [ A ]0
A plot of 1/[A] versus t is a straight line with slope k and intercept 1/[A]0
For a second order reaction, a plot of ln[A] vs. t is not linear.
1 1
= kt +
[A] [ A ]0
Nonlinearity indicates
that the reaction
is not first order. Slope = k (rate constant)
13
Half-life for a second-order reaction
Unlike a first order reaction, the rate constant for a second order process
depends on and the initial concentration of a reactant.
1 1
= kt +
[ A ]t [ A ]0
1
at the halflife, [ A ]t = [ A ]0
2
1
Substituting and solving, t1/ 2 =
k [ A ]0
14
SOLUTION: One can solve for the amount of NOBr after 10 minutes by
substituting the given data into the integrated rate law for a second-order
reaction.
1 1
= kt + (Second Order)
[ NOBr ]t [ NOBr ]0
1 1
= (0.810 M -1 s -1 ) (600 s) +
[ NOBr ]t 7.5 103 M
1
= 6.19 102 M -1
[ NOBr ]t
1
t1/ 2 =
k [ A ]0
1
t1/ 2 = = 160 s
0.810 M s (7.5 103 M)
-1 1
15
The Arrhenius Equation:
Temperature dependence of the Rate Constant
k = f (T)
k(T) ef (T)
16
Why would k (along with the rate) increase with temperature?
Lets go back to Kinetic Molecular Theory to understand
Activation Energy
17
Consider the reaction:
N2O(g) + O2(g) N2(g) + NO2(g)
Reactants
Products
E < Ea E > Ea
18
Orientation factors into the equation
(2) The fraction of collisions that occur with the correct orientation.
19
Arrhenius equation
Ea
k = Ae RT
Ea Ea
ln k = Ae RT ln k = + ln A
RT
Golly
Gollygee, what do we
have once again
ln k
A plot of ln k vs 1/T will
have a slope of Ea/R
and a y-intercept of ln A.
1/T
20
Determining the Activation Energy
If one takes the natural log of the ratio of k2 over k1 we find that:
k
ln 2 = ln k 2 ln k1
k1
Ea Ea
ln k 2 ln k1 = RT + ln A RT + ln A
2 1
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Example: The activation energy of a first order reaction is 50.2 kJ/mol at
25oC. At what temperature will the rate constant double?
k 2k E 1 1
(1) k 2 = 2k1 (2) ln 2 =ln 1 = ln(2) = a
k1 k1 R T1 T2
103J
Ea 50.2 kJ/mol
(3) = 1kJ = 6.04 103 K
R J
8.314
mol K
1 A 10oC change of
1
(4) ln(2) = 0.693 = 6.04 10 K 3 temperature doubles
298K T2 the rate!!
1
(5) = 3.24 103 K 1 T2 = 308 K
T2
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