Pick Up a

Good Morning Clicker!

Schedule
8-9 Discussion Kinetics
9-9:30 Test 2 on Kinetics Part 1
9:30-12:00 Lecture on Kinetics Part 2
 Kinetics Continued

Last time:
Have acquired experience finding and
using the rate law
 Study First Order Rxns

First order reactions have rate law: R=k[A]; where A is the or

one of the reactants.

A very important class of 1st order reactions are radionuclide

decay reactions. We will study the kinetics of 1st order decay
reactions in general and then apply our knowledge to
radiochemistry in specific (next week).
How do we know a reaction has 1st order kinetics?
• You are told
• It is a nuclear decay (synonyms: radiochemistry,
radionuclide) (all nuclear reactions are 1st order)
• You measure the kinetics and discover it is 1st order
 by something like the method of initial rates
 by appropriately graphing concentration(t) data
 by knowing the mechanisms is unimolecular

We will study the last two bullets today.

 Graphing Conc(time)
The title is to be read
“graphing concentration as a
function of time”. For all
reactions we can measure the
concentration of a reactant as
a function of time. And we
can graph it. In fact, one of
the first slides, shown here
again, is nothing more than a
concentration(time) graph.
A graph of Conc(t)
yields the characteristic
decay curve. But a
graph of the ln of the
concentration yields a
characteristic straight
line graph.

If the ln(conc) vs t
graph is linear, then
first order kinetics
applies.
 t c
So a question type: 0 1
100 0.904837
200 0.818731
400 0.67032
Given a set of data, 500 0.606531

such as that on the 800

1000
0.449329
0.367879

right, determine if 1500 0.22313

2000 0.135335
the rate law is first 3000 0.049787

order.
To check if the data is first order, compute ln(conc) and
then graph ln(conc) vs t.

t c ln(conc)
0 1 0
100 0.90483 -0.1
7
200 0.81873 -0.2
1
400 0.67032 -0.4
500 0.60653 -0.5
1
800 0.44932 -0.8
9
1000 0.36787 -1
9
1500 0.22313 -1.5
2000 0.13533 -2
5
3000 0.04978 -3
7

Conclusion: Yes, first order behavior, therefore the rate law is R=k[A]
To check if the data is first order, compute ln(conc) and
then graph ln(conc) vs t.

t c lnc
0 1 0
100 0.90909 -
1 0.09531
200 0.83333 -
3 0.18232
400 0.71428 -
6 0.33647
500 0.66666 -
7 0.40547
800 0.55555 -
6 0.58779
1000 0.5 -
0.69315
1500 0.4 -
0.91629
2000 0.33333 -
3 1.09861
3000 0.25 -
Conclusion: No, a ln(conc) vs time plot is NOT linear and therefore these
1.38629
data do not exhibit 1st order behavior. We will not go beyond this
reasoning – you do not need to figure out what order this is – just note
that it is not 1st order.
So now we know that if we have a linear plot of
ln(conc) vs time, then the reaction is first order.

What do we do with this information?

1) read the rate constant from the linear plot of
ln(conc) vs. time
2) use the equation that describes the straight line to
solve for concentrations or time
 For Folks who know Calc

Let’s see where a ln(A) vs t graph comes from. First

start with the rate equation:

R = k[A] Rate law corresponding to first order

∆[ A]
= −kt Rewriting the rate law into explicit math
∆t terminology

d [ A]
= − kA Switching to more appropriate calculus notation
dt

d [ A]
= − kdt Setting up the differential equation
[ A]
A t Setting up the integral
d [ A]
∫A [ A] = ∫0 d t
0
And then integrating.

ln[ A] − ln[ A]0 = −kt

You do not need to know how this was derived – you need the equation in
the box above.
Rearranging the equation gives:

ln[A] = ln[A]0 – kt

Compare this with the equation for a line

y = mx +b
And equate the following:
y = ln[A]
x=t
The Slope of a ln[conc] vs time graph
b= ln[A]0 gives the negative of the rate constant.
m= -k
How else might we use the equation? Let’s reproduce it
here: ln[A] = ln[A]0 – kt

There are four “variables”. In addition, the rules of

logarithms can be used to rewrite the equation as:

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

Where [A]/[A]0 is the fraction remaining.

Thus, now think about all the possible combinations.

Example questions:
1) How much A remains after 10 seconds if I start with
1M of A and the system has a rate constant of 0.01 min-
1
. (given A0, k, t  find A)
2) Now consider every permutation: given A, k, t, find A0;
given A, A0, t, find k; given A, A0, k, find t
3) Realize that the ratio of A/A0 can also be thought of as
a variable (a fraction). So you can have questions like
what fraction remains after some time has passed. You
can answer this even though you have neither A or A0.
Another characteristic features of the 1st order
reaction: Half life is independent of amount

Define Half Life: this is the time it takes for ½ of the

amount of stuff you have to react or decay.

In the special case of 1st order kinetics, the time it takes

for half the stuff to decay does not depend upon how
much stuff you have.
Example:

The half life of carbon 14 – a radioactive isotope of carbon

typically used in dating materials, is 5730 years.
How many years will it take:
1) 10 grams of carbon -14 to decay to 5 grams? 5730 yrs
2) 5 grams of carbon-14 to decay to 2.5 grams? 5730 years
3) 100 grams of carbon-14 to decay to 50 grams? 5730
years

You see the point.

The half life is an important parameter because it is
often measured and thus known and tabulated. The
half life is related to the rate constant:

Let’s say [A]=1/2[A]0. that is A has decayed to half its

initial value. Therefore

Using ln[A]/[A]0=ln(1/2) = -kt

0.693 = kt1/2
If we know the half life, we know the rate constant and
vice versa.

ln 2 ln 2
= t1/ 2 =k
k t1/ 2

ln 2 = kt1/ 2
Clicker Time

Fire up your calculator

 ln[A] = -kt +ln[A]o t½ = ln2/k

The slope of this graph is

a) -2.0/100 b) 0.693/100 c) -0.693/100 d) 3.0/400

12–21
 ln[A] = -kt +ln[A]o t½ = ln2/k

The half life for the decay of N2O5 is approximately

a) 50 s b) 100s c) 200s d) 400s

12–22
The decomposition of N2O5(g) to NO2(g) and O2(g) obeys first-order
kinetics. Assuming the form of the rate law is:

∆[N 2 O5 ]
Rate = − = k[N 2O 5 ]
∆t

where k = 3.4 × 10–5 s–1 at 25°C, what is the initial rate of

reaction at 25°C where [N2O5]0 = 9.4 × 10–2 M?

a) 3.4 × 10–5 mol/L·s b) 3.2 × 10-6 mol/L·s

c) 3.6 × 10–4 mol/L·s d) 9.4 × 10–2 mol/L·s
e) none of these
In 6 M HCl, the complex ion Ru(NH3)63+ decomposes to a variety of
products. The reaction is first order in Ru(NH3)63+ and has a half-life
of 14 hours at 25°C. Under these conditions, how long will it take
for the [Ru(NH3)63+ ] to decrease to 14.7% of its initial value?
a) 3.2 hours b) 9.7 hours
c) 2.1 hours d) 14 hours
e) 39 hours
 Ahrenius Theory

A simple model for chemical

reactions
Consider ClNO2(g) +NO(g) NO2(g) + ClNO(g)
If total pressure is 1 atm, average distance a molecule travels between
collisions is

WHY? 1x10-5 cm

The average molecule would have about how many

collisions per second at 298 K?

1,000,000,000!

Only about 1 in 10,000,000 of these leads to reaction!!

Molecules must collide to react. But most
collisions don’t lead to reaction. Why?

1.Orientation
2.Energy
 2BrNO  2NO + Br2

1. Orientation – Figure 12.12

This orientation works! Notice how different this is from what you
learned in CHEM 102. We are no longer talking about how much is
made but actually talking about how it is made.
 2BrNO  2NO + Br2

1. Now consider this Orientation –

still Figure 12.12

Notice how the orientation in (c ) doesn’t work. So while there are

lots of collisions they are not all effective.
2. Second Reason – Energy

Molecules may need significant energy to overcome a

potential energy barrier – and some collisions may
be in the right orientation but not have energy.

We can represent this using a reaction path diagram.

 Reaction Path Diagram –Figure 12.10

You need to deeply understand this diagram.

1) What do the axes represent? What does reaction progress mean?
The x axis represents a physical coordinate – it could be distance between
atoms and reflects a specific geometric arrangement.
The y axis represents potential energy
2) Potential Energy. The actual value of the potential energy is not important.
The reactants are located at an unspecified PE. The products are then
located relative to the reactants. The products could end at a lower PE or
higher PE.
3) The barrier. As the reaction proceeds, two molecules of BrNO interact.
Generally these molecules have to get very close together than thus their
interaction is generally repulsive. The total potential energy of these two
molecules goes up. It would be like a carbon molecule having a temporary 5
bond complex – not a stable state. The molecular arrangement at the
maximum of the hump is called the transition complex.
4) The energy of the barrier. The PE of the barrier is called the activation
energy and given the notation Ea (read “E sub a”). The energy of activation
is the energy needed for the reaction to proceed. So now it should be clear
that if the molecules do not have enough energy when they collide, they will
not be able to surmount the barrier.
An Example of an ENDOTHERMIC reaction.
Only some molecules have enough energy to reach the
energy of the transition state.
And the number
that does
increases with
temperature.
So we expect that:

As T the speed of the reaction will go up and thus k

As Ea the speed of the reaction will go down and thus k

 Svante Arrhenius showed
that the relationship
between k and temperature
could be mathematically
modeled by

Ea
− RT
k = Ae
•k is the rate constant
•Ea is the activation energy
(the energy of the transition
state complex)
•A is the orientation factor
•R is the gas constant –
0.0083kJ/mol

Ea
− RT
k = Ae
 Ea
− RT
k = Ae
Ea
ln k = − + ln A
RT
k1 Ea 1 1
ln = − [ − ]
k2 R T1 T2
A plot of ln k vs 1/T is linear.

Slope = -Ea/R
Intercept = ln A
Vocabulary: A catalyst is something that speeds a reaction
without being consumed itself. Biological catalysts are called
enzymes.

A catalyst lowers the

activation energy by
providing a new
reaction pathway.
Because Ea is lowered,
more of the collisions
lead to reaction.
Vocabulary: A homogeneous catalyst is one that is present in the same
phase as the reacting molecules.

Ex: the destruction of ozone (O3(g)) in the upper atmosphere by freons

(most common one is CCl2F2(g)).

In the upper atmosphere light causes the freon to decompose:

CCl2F2(g) + hf  CClF2(g) + Cl(g)

The free chlorine atom now acts as a catalyst to decompose ozone:

Cl(g) + O3(g)  ClO(g) + O2(g)

O(g) + ClO(g)  Cl(g) + O2(g)
O(g) + O3(g)  2O2(g)
Vocabulary: A heterogeneous catalyst is in a different phase
(usually solid) from the reacting molecules.

Heterogeneous catalysis usually involved adsorption of the

reacting molecules onto the solid surface of the catalyst.

For example, platinum metal speeds the reaction of hydrogen gas

with many double bonded hydrocarbon gases by adsorbing them
onto the metal surface, weakening the bond between the atoms in
H2.
Clicker Time

Fire up your calculator

 This diagram shows
Arrhenius plots for data
A
gathered when a reaction
was run two ways: in the B
presence and in the
absence of a catalyst.
Which line represents data
for the catalyzed reaction? 1/temp

1. A
2. B
3. Need to know mechanism of catalysis
4. I’m not sure
The forward reaction is _____ and the reverse reaction is ________.
a) endothermic; exothermic
b) endothermic; endothermic
c) exothermic; endothermic
d) exothermic; exothermic
The energy of activation of the reverse reaction is
a) EA + EC
b) EA
c) EC
 − Ea
k = Ae RT

Use the following information to determine the activation

energy for the reaction shown here:
2NO N2 + O2
Temperature (K) Rate Constant (L/mol·s)
1400 0.143
1500 0.624

a) 8.2 x 104 J/mol b) 1.2 x 101 J/mol

c) 8.9 x 103 J/mol d) 3.1 x 104 J/mol
e) 2.6 x 105 J/mol
Reaction Mechanisms
Reaction Mechanisms

A reaction mechanism is a series of steps that reflects

the actual process by which the overall reaction of
interest proceeds.
 A+BC+D

For two molecules to react they must collide. If it

is a single step reaction then the rate law will be

rate = k[A][B]
Note that this is the source of great confusion. IF, IF, IF, the
reaction proceeds in a single step, then the reaction is said to
reflect the actual molecularity of the process. So If the
reaction is elementary, then by definition it is a single step.

In this case, then, the reaction will proceed when A reacts

with B and thus the rate is proportional to the probability that
A and B are in the same place at the same time.
 Vocabulary: Single step reactions are also called elementary
reactions.

2NO + O2  2NO2

If this is an elementary reaction, then

Rate = k[NO]2[O2]
STUDY THIS!!

When reactions are elementary, the rate law can be

obtained from the stoichiometry. NOTE THAT: when
reactions are NOT elementary, the rate law CANNOT be
obtained from the stoichiometry.
 However the chances of three molecules colliding
simultaneously is very small. What if the reaction below
occurs in more than one step?

2NO + O2  2NO2
 2NO + O2  2NO2

A possible (but incomplete) reaction mechanism:

Reaction mechanisms
Step 1: 2NO  N2O2 MUST BE composed
of elementary steps
Step 2: N2O2 + O2  2NO2

Each step shown is an elementary reaction.

1. The sum of Steps 1 and 2 must yield the overall
reaction.

2. N2O2 is called a reaction intermediate. It is not a

reactant nor a product.
 2NO + O2  2NO2
A possible (but incomplete) reaction mechanism:

Step 1: 2NO  N2O2

Step 2: N2O2 + O2  2NO2

These two steps are very unlikely to proceed at the same

rate. One will be much slower than the other. The
slow step is the
RATE DETERMINING STEP.

That is what was missing from the mechanism –

which step is slow.
 Below is a complete possible mechanism for this reaction.

2NO + O2  2NO2
Step 1: 2NO  N2O2 slow
Step 2: N2O2 + O2  2NO2 fast

It is possible to predict rates based on a proposed

mechanism.

If the experimentally observed rate matched the predicted

rate, then the mechanism is possibly correct.
 Either step could, in principle, be slow. In this mechanism, the
first step is slow.

2NO + O2  2NO2
Step 1: 2NO  N2O2 slow
Step 2: N2O2 + O2  2NO2 fast

• Because the first step is slow, it determines the rate.

• Because it is an elementary reaction, the rate equation
can be written directly:

Predicted rate = k[NO]2

 2NO + O2  2NO2
second step slow:

Step 1: 2NO ⇄ N2O2 fast

Step 2: N2O2 + O2  2NO2 slow

rate = k[N2O2][O2]

Rate equations CANNOT include intermediates such as

N2O2.

Can use the first step to fix this.

 An alternate mechanism, second step slow:
Step 1: 2NO ⇄ N2O2 fast
Step 2: N2O2 + O2  2NO2 slow
In Step 1 the forward rate = k1[NO]2
the back rate = k-1 [N2O2]

As step 1 proceeds, [N2O2] increases and [NO]

decreases, until the rates become equal.

This is called the steady-state approximation.

 An alternate mechanism, second step slow:
Step 1: 2NO ⇄ N2O2 fast
Step 2: N2O2 + O2  2NO2 slow
A note on the steady-state assumption:
forward rate = back rate
k1[NO]2 = k-1 [N2O2]

[ N 2O2 ]
k1/k-1 = K = 2
[ NO ]
K is called the equilibrium constant, and will be the subject of
the next chapter. K is just a number, it equals the ratio of
forward to back rate constants:
K = k1/k-1
 second step slow:

Step 1: 2NO ⇄ N2O2 fast

Step 2: N2O2 + O2  2NO2 slow
From step 1,
rate fwd = rate back
k1[NO]2=k-1 [N2O2]

So [N2O2] = (k1/k-1 )[NO]2 = K[NO]2

From second step, rate = k2[N2O2][O2]

predicted rate = k2{K[NO]2}[O2]

predicted rate = k’ [NO]2[O2]

 2NO + O2  2NO2

Step 1: 2NO ⇄ N2O2

Step 2: N2O2 + O2  2NO2
First step slow, predict rate = k[NO]2
Second step slow, predict rate = k[NO]2[O2]

Can use experiment to tell these two possibilities apart.

Consolidate

•collision required for reaction

•only small fraction of collisions actually leads to reaction

•for an elementary reaction aA + bB  cC + dD, the rate law is: rate =

k[A]a[B]b

•for multi‑step reactions, the rate law will depend on the reaction
mechanism ‑

•the slow step in a multi‑step reaction is rate determining for the

overall reaction

•mechanisms can be tested by experimental determination of the rate

law.
General Observations about reaction
mechanisms:
1.Finding a mechanism that yields a prediction that is
consistent with experiment does NOT prove the
mechanism.

2.Reaction stoichiometry does not give you the rate law

unless you know it proceeds with a single step
mechanism.
It is very difficult to prove a reaction mechanism.
Need strong circumstantial evidence, such as:

1.Experimental detection of an intermediate

2.Calculations supporting the mechanism as a low
energy pathway.
3.Chemical precedent.
Practice Problems
Consider this reaction:
H2 + 2 ICl  I2 + 2 HCl

The rate law for this reaction is:

1.Rate = k [H2][ICl]
2.Rate = k[H2][ICl]2
3.Neither of the above
4.It is not possible to determine the rate law without
more information.
 0

Consider a gas phase reaction for which the

overall balanced reaction is: A + 2B  C
The rate equation for this reaction will be:

1. Rate = k[A][B]
2. Rate = k[A][2B]
3. Rate = k[A][B]2
4. Can’t tell without
more information
5. I’m not sure
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 0

Consider a gas phase reaction for which the

overall balanced reaction is: A + 2B  C
If the rate is defined –d[A]/dt, you find at 298 K
rate = 2.2x10-3 M/s. If you were to change the
definition to rate = -d[B]/dt, the rate would then be
1. 2.2x10-3 M/s
2. 1.1x10-3 M/s
3. 4.4x10-3 M/s
4. I’m not sure

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 0

The experimental determined rate law for the

reaction of H2 with NO to produce N2 and H2O is
second order in NO and first order in H2. The
rate law for this reaction is
1. Rate = k[H2][NO]
2. Rate = k[H2][NO]2
3. Can’t tell without
more information
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3
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 0
The experimentally determined rate law for the
reaction H2 + NO  ½N2 + H2O is
rate = k[H2][NO]2.
Is the mechanism below consistent with the
observed rate law?
Step 1: H2 + NO  N + H2O Slow
Step 2: N + NO  N2 + O Fast
Step 3: O + H2  H2O Fast
1. Yes, because the slow step reactants are the same as
for the reaction in question.
2. Yes, because it is consistent with the rate law.
1 3. 2 No,
3 because
4 5 6 it7 isn’t
8 9consistent
10 11 12 with
13 14the
15 rate
16 law
17 18 19 20
21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40
41 4.42 I’m
43 not45sure
44 46 47 48 49 50 51 52 53 54 55 56 57 58 59 0
60
Here is data collected at 356
K for the reaction below.
C4H8 (g)  2C2H4 (g)
What is the rate law for this
reaction?
1. Rate = k[C4H8]
2. Rate = k[C4H8]2
3. Need more information to tell
4. I’m not sure
 Here is data collected at
356 K for the decomposition
reaction of C4H8. What is the
starting concentration of
C4H8?

1. 1.0 M
2. 0.7 M
3. 0.5 M
4. Need more information to tell
5. I’m not sure
 Here is data
collected at 356 K for
the decomposition
reaction of C4H8.
What is the value of
k for this reaction?
1. 0.007 s-1
2. 0.004 s-1
3. 0.011 s-1
4. Need more information to tell
5. I’m not sure
 Here is data collected
at 356 K for the
decomposition reaction
of C4H8. What is the
value of the rate at time
zero?
1. 0.007 M/s-1
2. 0.004 M/s-1
3. 0.002 M/s-1
4. Need more information to tell
5. I’m not sure
 A catalyst increases the rate of a reaction but doesn’t
affect the yield. In view of the relationship between
the rate constants and the equilibrium constant, how
is this possible?
1. The catalyst increases kf, but since K only depends on
temperature the yield is unaffected.
2. The catalyst speeds both the back and forward reactions, so
the ratio of rate constants remains the same.
3. A catalyst doesn’t affect ΔH° or ΔS°, so K is unchanged.
4. I’m not sure
 0
-2.5 -2 -1.5 -1 -0.5 0

Y = 2x – 1.8 -1

What is the value -2

of the rate

Ln(initial rate)
-3

constant for this -4

reaction? -5

-6

-7

Ln[A]

1. 0.0033 M-1s-1
2. 1.8 M-1s-1
3. 0.165 M-1s-1
4. I’m not sure
 0
The experimentally determined rate law for the reaction
H2 + NO  ½N2 + H2O is rate = k[H2][NO]2.
Is the mechanism below consistent with the observed rate
law?

Step 1: 2NO ⇄ N2O2 Fast

Step 2: H2 + N2O2  N2O + H2O Slow
Step 3: N2O + H2  N2 + H2O Fast

1. No, because the sum of the three steps is double

the reaction in question.
2. Yes, because it is consistent with the rate law.
3. No, because it isn’t consistent with the rate law
1
4.
2 3
I’m
4
not
5
sure
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
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The decomposition of ozone, 2O3  3O2, is known to proceed
0

according to the following two step mechanism:

Step 1: O3(g)  O2 (g) + O (g) Fast

Step 2: O3(g) + O (g)  2O2(g) Slow

The rate equation for the overall reaction is best expressed as

1. Rate = k[O3(g)][O(g)]
2. Rate = k[O3(g)]2
3. Rate = k[O3(g)]2[O2(g)]-1
4. I’m not sure

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