Kinetics

The speed with which reactions

proceed.
Chemists make things. Chemistry is the study of how
to make things, how to measure the things we make,
and the principles that govern these syntheses.

If a reaction can go, then kinetics is the study of the

speed with which it goes and the construction of a
plausible mechanism of the reaction.

Overarching Goal: the design of a mechanism for a

reaction.

In Chem 104 we learn pieces of this big goal.

 STEP ONE
The Rate
Need to be able to express the speed of a reaction
mathematically and relate it to the stoichiometric
equation. We need to understand what the rate of reaction
means conceptually.

Consider the reaction:

2NO2  2NO(g) + O2(g)

Balanced?
Look at these data. Now we are really thinking about how long (time) it
takes for a reaction to take place – this differs from CHEM 102 when we
computed endpoints.
Seconds MOLES Reaction:
Time NO2 NO O2
0 0.02 ___ ___
2NO2(g) 
100 0.013 ___ ___
200 0.0096 ___ ___ 2NO(g) + O2(g)

Spend a moment understanding these data. Fill in the

blanks.
Go back to the original
data and now let’s graph
the concentrations:
Huge amount of mathematical
information in these plots.

Notice
1) The concentration of
reactants and products
change with time consistent
with the stoichiometry of
the reaction.
2) The RATE of the reaction is
defined as the change in
concentration with change
in time.
3) The instantaneous rate is
the slope of the tangent to
the curve at a given time –
this is the derivative from
calculus.
Notice
4) The slope of the tangent
line changes with time!
5) This means the rate of the
reaction changes with time.
6) Reactants --Rate is
NEGATIVE
7) PRODUCTS – Rate is
POSITIVE
8) Magnitude of the rate
DECREASES with time –
that is reactions slow down
Mathematically:

The rate of the reaction

can be written as

D[species]/Dt

In this example we have:

D[NO2]/Dt
D[NO]/Dt
D[O2]/Dt

Here’s the rub: these

rates are not equal
However, not so grim:

For: 2NO2  2NO(g) + O2(g)

We have

1 [ NO2] 1 [ NO] [O2]

R  
2 t 2 t t
Where R means “rate of reaction”. Notice that by convention the
rate of the reaction is taken to be POSITIVE.
For: 2NO2  2NO(g) + O2(g)

1 [ NO2] 1 [ NO] [O2]

R  
2 t 2 t t
If the rate of this reaction at 100 s was measured to be 0.1M/s, then
what is the rate of loss of nitrogen dioxide, the rate of production of
nitrogen monoxide and the rate of production of oxygen at this
time?
Consider the Reaction:

2N2O5 (soln)→4NO2(soln) + O2(g)

If the rate of the reaction is 10M/min, what is [NO2 ] ?

t
A) 10M/min B) 40M/min C) 2.5M/min D) 5M/min
Consider the Reaction:

2N2O5 (soln)→4NO2(soln) + O2(g)

Which rate (absolute value) has the largest number?

A)Rate of loss of N2O5

B) Rate of production of NO2
C) Rate of production of O2
Consider the Reaction:

2N2O5 (soln)→4NO2(soln) + O2(g)

[N2O5 ] [NO2 ]
If = -5M/s, then what is
t t

A) -10M/s B) 10M/s C) -5M/s D) 5M/s

 STEP TWO
The Rate Law

What influences the rate of a reaction?

Following the logic flow (which is all it is, this is not

a derivation)

1) For a reaction to go, the reacting species must

collide. That means that the particles have to be in the
same place at the same time (or near enough) to react.
Thus the rate of the reaction must be proportional to
the probability of the species being at the specific
place.
2) The probability that the reacting species are
present at a particular place, will be proportional to
the concentration of the reacting species.

3) All the reacting species have to be present at the

same place (or near enough) at the same time. This
is like the following probability problem: suppose
you have 3 dice. What is the probability that you
will throw a 3 with one dice and then another 3 and
then another 3? 1/6 x 1/6 x 1/6 (AND probability)
Putting this altogether

Rate  [Reactant 1]x[Reactant 2]y [Reactant 3]z …

Or, creating an equation,

Rate = k(T) [Reactant 1]x[Reactant 2]y [Reactant 3]z

Where k is called the “rate constant” and is

dependent upon T but
independent upon concentration
Here’s where you need to think about the form of this
equation. It actually doesn’t give us a lot of
information – yet.

The details have to be determined – and the details

mean

Determine:

x, y, z, and k
Go over some language

1) Rate law – you can be asked to determine the rate law.

This means find the exponents x, y, z, etc and find k, the
rate constant.
2) The rate law will give us the “order” of the reaction. Be
careful with the language
1) The overall order of the reaction is the sum of the
exponents OR
2) You can talk about the order of a particular
reactant
3) If the exponent is 1 the reaction is first order; if 2
second order, etc.
Examples:

Consider reaction NH4+(aq)+NO2-(aq) → N2(g)+2H2O(l)

The rate law for this reaction was determined to be:

R = k[NH4+][NO2-]

A. zeroeth, B. first C. second D. third

The rate is 1st order in ammonium, 1st order in nitrite, and

2nd order overall.
Questions:

The reaction 2N2O5 (soln)→4NO2(soln) + O2(g) is first

order in N2O5 .
The rate law for the reaction is
A) R=k[N2O5] B) R=k[N2O5]2 C) R=k[N2O5]0
Questions:

The reaction 2N2O5 (soln)→4NO2(soln) + O2(g) is first

order in N2O5 .
The units of the rate constant are
A) M/sec B) sec-1 C) M2 sec-1
Questions:

The reaction 2N2O5 (soln)→4NO2(soln) + O2(g) is first

order in N2O5 . At 300 K the initial rate of the
reaction was found to be 2.5 millimolar (mM)/min
when the dinitrogen pentoxide concentration was
0.10 millimolar. The value of k is
The units of the rate constant are
A) 0.25 min-1 B) 2.5 min-1 C) 25 min-1
One more question:

The reaction 2N2O5 (soln)→4NO2(soln) + O2(g) is first order in

N2O5 . At 300 K the initial rate of the reaction was found to be
2.5 millimolar (mM)/min when the dinitrogen pentoxide
concentration was 0.10 millimolar. If the initial concentration
was quadrupoled in another experiment, the rate and the rate
constant are expected to
A) Remain the same
B) Quadruple
C) Double
D) The rate will quadruple and the rate constant will remain
the same
 STEP THREE
Determining the Rate Law by
the Method of Initial Rates
So we now know what the rate law is, but we need to figure out
(measure) the exponents.

Since the rate of the reaction depends on the concentration of

reacting species, we must pick a time to measure the rates. We
will pick the INITIAL TIME and measure the initial rates of the
reactions.
We do several experiments with different initial
conditions. I am going to obtain the exponents by
inspection.
First, if I compare expts 1 and 2 I see that I don’t change
the ammonium conc and I double the nitrite
concentration. When I double the nitrite, the rate
doubles.

THEREFORE: the rate law is FIRST ORDER in nitrite.

You must understand this logic.

Note the math:

Suppose I have an equation R = kx, where k is a

constant and x is the variable. If I double x, what
happens to R?
If the exponent is 1 and I double the concentration then
R will double.
So if I double the concentration and R doubles, then the
exponent must have been 1.
Let’s look at the case when the exponent is 2.

R=kx2.

If I double x, note that R quadruples (22=4).

So if I double x and R quadruples then the exponent

must be 2.
And one more case – suppose I double the
concentration and R doesn’t change?

Then the exponent has to be 0 because the rate doesn’t

dependent on the concentration. Recall that anything
to the power of 0 = 1.

So now, by judicious choice of experiments we can

determine the rate law.
Determine the rate law for the following reaction:

A) R=k[BrO3-][Br-][H+]
B) R=k[BrO3-][Br-]
C) R=k[BrO3-][Br-][H+]2
The rate law was found to be R=k[BrO3-][Br-][H+]2

The value of the rate constant is

A) 8.0 Ms-1
B) 8.0 M-2s-1
C) 8.0 M-3s-1
Determining the Rate Law for
Special Cases

First Order Reactions:

R = k[A] where A is the relevant species

First order reactions are very important. Nuclear
reactions (radiochemistry) are ALL first order
reactions.

First order reactions produce a very specific outcome –

the half lives of the reactant are independent of the
amount of reactant present.
Calculus Interlude (if you don’t know calc, don’t
worry, just realize that there is a mathematical way
to arrive at the answer)

See next page

R  k [ A] where [A] is the concentrat ion of the reactant " A"
d [ A]
  k [ A] where we have substitute d the expression for R
dt
d[A]
  kdt where the terms involving A are on the left
[ A]
and those involving t are on the right
Now integratin g
d[A]
 [A]   k  dt
ln[ A]   kt  C where C is the integratio n constant.
At t  0, [A]  initial concentrat ion of A, written [A] 0
Therefore C  ln[ A]0
Putting it all together
ln[ A]  ln[ A]0  kt
The final outcome is what matters and can be expressed
in several ways (called the integrated rate eqn):

ln[A] =ln[A]0-kt
ln[A]/[A]0 = -kt
[A]/[A] 0 = e-kt

Graphs of ln[A] vs t are linear and the slope = -k.

Let’s use excel to graph the decay of Mo-99. The half
life of Mo-99 is 66 hours.
HALF LIVES

When ½ of the amount of initial material has decayed

or reacted from its initial amount, then
[A] ½ = ½[A]0. Substituting this into the integrated rate
equations:

ln (½[A]0/[A]0) = -kt1/2
ln(0.5) = -kt1/2
ln2 = -kt - -kT , where T=t=t1/2
KEY EQUATIONS

R=k[A]x[B]y[C]z ….

ln[A]=ln[A]0 – kt

ln2=kt
In the context of radioactive decay the symbol t stands
for:

a) The time for the substance to decay

b) The time for ½ of the substance to decay
c) The amount of substance present at the half life
The decay of P-31, like all radioactive decay, exhibits
first order kinetics. It takes 14 days for 10 mg of P-
31 to decay to 5 mg. What is the rate constant for
this reaction?

A) 0.05 days-1
B) 0.02 days-1
C) 5 days
D) 2 days
The following data were obtained for the reaction of NO with O2. Concentrations are in
molecules/cm3 and rates are in molecules/cm3×s.
[NO]0 [O2]0 Initial Rate
1  1018 1  1018 2.0  1016
2  1018 1  1018 8.0  1016
3  1018 1  1018 18.0  1016
1  1018 2  1018 4.0  1016
1  1018 3  1018 6.0  1016

What is the rate law?

a)Rate = k[NO][O2]
b) Rate = k[NO][O2]2
c)Rate = k[NO]2[O2]
d) Rate = k[NO]2
e)Rate = k[NO]2[O2]2
For a reaction in which A and B react to form C, the following initial rate data
were obtained:
 
[A] [B] Initial Rate of
  (mol/L) (mol/L) Formation of C
  (mol/L·s)
  0.10 0.10 1.00
0.10 0.20 1.00
 
0.20 0.40 8.00
 
 What is the rate law?
a) Rate = k[A][B]
b) Rate = k[A]2[B]
c) Rate = k[A][B]2
d) Rate = k[A]2[B]2
e) Rate = k[A]3
For the reaction 2N2O5(g)  4NO2(g) + O2(g), the
following data were collected:
t (minutes) [N2O5] (mol/L)
0 1.24 x 10–2
10. 0.92 x 10–2
20. 0.68 x 10–2
30. 0.50 x 10–2
40. 0.37 x 10–2
50. 0.28 x 10–2
70. 0.15 x 10–2

The order of this reaction in N2O5 is

a) 0 b) 1 c) 2
d) 3 e) none of these
 2N2O5(g)  4NO2(g) + O2(g)
t (minutes) [N2O5] (mol/L)
0 1.24 x 10–2
10. 0.92 x 10–2
20. 0.68 x 10–2
30. 0.50 x 10–2
40. 0.37 x 10–2
50. 0.28 x 10–2
70. 0.15 x 10–2

The concentration of O2 at t = 10. minutes is

a) 2.0 x 10–4 mol/L b) 0.32 x 10–2 mol/L
c) 0.16 x 10–2 mol/L d) 0.64 ´x10–2 mol/L
e) none of these
 2N2O5(g)  4NO2(g) + O2(g)
t (minutes) [N2O5] (mol/L)
0 1.24 x 10–2
10. 0.92 x 10–2
20. 0.68 x 10–2
30. 0.50 x 10–2
40. 0.37 x 10–2
50. 0.28 x 10–2
70. 0.15 x 10–2

The half-life of this reaction is approximately

a) 15 minutes b) 18 minutes
c) 23 minutes d) 36 minutes
e) 45 minutes
 2N2O5(g)  4NO2(g) + O2(g)
t (minutes) [N2O5] (mol/L)
0 1.24 x 10–2
10. 0.92 x 10–2
20. 0.68 x 10–2
30. 0.50 x 10–2
40. 0.37 x 10–2
50. 0.28 x 10–2
70. 0.15 x 10–2

The initial rate of production of NO2 for this reaction is approximately

a) 7.4 x 10–4 mol/L·min b) 3.2 x 10–4 mol/L·min
c) 1.24 x 10–2 mol/L·min d) 1.6 x 10–4 mol/L·min
e) none of these
Technetium-99 is used as a radiographic agent in
medicine. If Tc-99 has a half-life of 6.0 hours, what
fraction of an administered dose of 100 mg remains
in a patient’s body after 2.0 days.

a) 1 b) 1 c) 1 d) 1
2 4 8 16
2 2 2 2
Here is a challenging radioactive decay problem. 99mTc is a common
radioisotope used to image soft tissue and bones. 99mTc has a half life of 6
hours. Therefore, the isotope is generated just before administration to the
patient.
 
A. How many millicuries of radiation is delivered to the patient if 2ml of 10-
8M of 99mTc is initially injected? 1 curie of radiation is defined as 3.7x1010
disintegrations/sec.
 
B. 99mTc decays to 99Tc with the production of a g ray. It is the number of
g photons that are counted in the medical imaging. After 2 days, how many
millicuries of radiation are present from the 99mTc? Assume none of the 99mTc
has been excreted.
 
C. 99Tc has a half life of 2x105 years and decays by emitting a beta
particle. How many curies of radiation are present in the body 2 days after initial
administration? Assume that all of the 99mTc has decayed to 99Tc.