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Chemical Kine1cs
We have discussed T. Now it is 1me
to give a<en1on to t.

What we do with kine1cs

1) First, we measure rates of reac1ons.
2) Next, we use the rates to propose a reac*on
mechanism.
3) We check the reac1on mechanism vs. the
observed kine*cs.

We shall deviate a li<le at the start from the
book in order to look at molecules rst.

ALL chemical reac1ons can be broken

down into elementary steps
The elementary steps are

1) Unimolecular
2) Bimolecular
3) Termolecular

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Unimolecular:

Bimolecular:

Termolecular:

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Let us look at a typical mechanism

The rules:

1) The reac1on must proceed via elementary
steps.
2) These elementary steps must sum up to give
the total reac1on.
3) Some steps may be reversible.

Consider this reac1on

A possible mechanism

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Points to note
1)
2)
3)
4)

Each step is an elementary step.

They do indeed add up to the total reac1on.
The species in RED are called intermediates.
The rst step is reversible.

The steps can go at dierent rates

The slow step

is called the rate limi*ng or rate determing
step.
We shall talk more about this later.
Note that this is just a proposed mechanism.
We can not actually prove a mechanism.
We can only denitely disprove a mechanism.
All accepted mechanisms simply must make sense
and be based upon a preponderance of evidence.

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Now
LETS SEE HOW WE DO KINETICS!

AND, LETS LOOK AT THE BASIC RULES AND
DEFINITIONS.

FOR MOST OF THE DISCUSSION, WE SHALL
CONCENTRATE JUST ON FORWARD REACTIONS.

In discussing rates, I shall deviate a

li<le from the book.

We can visualize this by discussing this

graph:

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Special point:

REACTION RATES ARE
ALWAYS DEFINED AS
POSITIVE.

The General Case (assuming

intermediates to be short-lived)

Now comes the math

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And here it is!

What does this entail?

These rela1ons are true, provided

there are no long-lived intermediates.

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Units of reac1on rates:

Rate = (conc. change)/1me
Usual units: M/s (or Ms-1)
But we can change the 1me unit to hours,
days, years, or whatever.
And, some1mes, we might monitor pressure
in which case typical units might be Atm/s.

Major point!
To get the reac1on rate,
all you need to do is
monitor any one product
or reactant.
Of course, if you monitor
more, you will have more
data.
Looking at reactant and
product helps you
determine if there is a
love-lived intermediate!

Status at this point.

Right now, we are
expressing rates as, for
instance,

d[A]/dt =

AND EVERY EQUATION
NEEDS A RIGHT SIDE!

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Let us look at a simple reac1on:

For this, we could write

Units of k:
Let the rate have units of M/s (Ms-1)
Thus, must have the units M1-(n+m)s-1.
(Of course, we could use other concentra1on
units and 1me units but molarity and s-1 are
by far the most common.)

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More about m and n

m and n are usually integers.
The most common values are 0, 1, and 2.
Some1mes, they can be frac1ons such as .
m + n is termed the overall order of the reac1on.
m and n can be related to the reac1on
stoichiometry but quite ouen are NOT.
But they ARE related for ELEMENTARY
REACTIONS!

Example:
Rate = k [A][B]2.
The reac1on is rst order wrt [A],
second order wrt [B],
and third order overall.

Determining Rates & Rate Laws

We 1st look at rates vs t.
Since we stress forward
reac1ons, these are
most ouen ini*al rates.
Experimental
techniques for rates will
be skipped here.
We look at rates for the
common orders in the
slide to the right.

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An alternate look at rates

Rates vs. concentra1on
are also of interest.
These graphs look a lot
dierent.
Note that we have yet
to discuss [conc] vs. t.

What we shall be doing next

Repor1ng rates vs. concentra1on.
Determining the ORDERS of the various
reactants to put together the RATE LAW.
NOTE THAT WE ARE GOING TO BE DEFINED
TO JUST INITIAL RATES!

Rates vs. Concentra1on

To the right we see a
table of ini1al rate vs.
concentra1on for a
rst-order reac*on.
The rate is directly
propor1onal to the
concentra1on..

[A] {M}

In1al Rate {M/s}

0.10

0.015

0.20

0.030

0.40

0.060

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Rates vs. Concentra1on

To the right we see a
table of ini1al rate vs.
concentra1on for a
zero-order reac*on.
The rate stays
constant...
Special point here: This
would break down near
the end of the reac*on.

[A] {M}

In1al Rate {M/s}

0.10

0.015

0.20

0.015

0.40

0.015

Rates vs. Concentra1on

To the right we see a
table of ini1al rate vs.
concentra1on for a
second-order reac*on.
The rate is directly
propor1onal to the
square of the
concentra1on..

[A] {M}

In1al Rate {M/s}

0.10

0.015

0.20

0.060

0.40

0.240

Mul1ple reactants

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Example: NO2(g) + CO(g) NO(g) + CO2(g)

We give the results here

Thought ques1on

Would it make any

dierence which pair of
[NO2] and ini1al rate
were used?

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Integrated Rate Laws

[conc] vs. t plots show the course of the en1re
reac1on.
Each plot has a given shape that can be
converted to a straight line by an appropriate
change of variable.
The book leaves out some calculus. Ill do it at
the board in passim but you are not
responsible for the deriva1on!

First Order Basics: A Product(s)

Second Order Basics: A Product(s)

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Zero Order Basics: A Product(s)

We can look at plots to determine reac1on orders:

NO2(g)NO(g)+ O(g)
First order?

Second Order?

Half Lives
Some1mes, 1me is easier to imagine than is
rate.
The HALF LIFE of a reactant is the 1me it takes
for half of it to disappear.
Half lives are most useful with rst-order
kine1cs but are also useful for other orders.
Half-life is a constant ONLY for FIRST-ORDER
reac1ons.

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Half life of a rst-order reac1on.

This is for a rst-order
reac1on.
Note that we a really
plo{ng in terms of
constant half lives of
100 seconds.
We derive our
equa1ons now

Some math for rst-order t1/2

Some convenient forms

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Half-lives of second-order reac1ons

Special point
We just derived the
equa1on for the FIRST
HALF-LIFE of a second-
order reac1on.
The half-life DOUBLES
for each half-life period.
The general formula is
to the right

A grand summary

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Back to reac1on mechanisms

A mechanism must agree with the observed
kine1cs.
The overall stoichiometry does not have to
follow the rate law, however!
The mechanism must sum up to the actual
observed reac1on.
The mechanism can consist only of
elementary steps!

Elementary Steps: A Review

For elementary steps

the reac1on orders and stoichiometry DO
agree!!!
This is important since, quite ouen, the
SLOWEST ELEMENTARY STEP determines the
rate law of the reac1on!!!

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In addi1on: A decree!

Some hints about mechanisms and

observed kine1cs
If the rst step be the slow step, things are
usually quite simple!
If a later step be the slow step, then things can
be more complicated.
This is especially true if the rst step be fast
and reversible.
The next few slides will show some relevant
examples.

NO2(g) + CO(g) NO(g) + CO2(g)

The observed rate law is

Rate = k[NO2]2

The reac1on is 2nd order in [NO2] and 0th order
in CO.

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A possible mechanism

NO2 + NO2 NO3 + NO (SLOW)
NO3 + CO NO2 + CO2 (FAST)

(These sum to the total reac1on!)
(This is an example with a slow ini1al step.)

The rst step is slow

Thus, we see that this rate-determining step also
ensures the kine1cs!

Rate = kslow[NO2]2

In the next slide, we see what happens if the

rst step is fast AND reversible

2H2(g) + 2NO(g) 2H2O(g) + N2(g)

(Fast ini1al step example!)

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The math in this

CHCl3(g) + Cl2(g) CCl4(g) + HCl(g)

A very amusing case

2O3(g) 3O2(g)

Rate = k[O3]2[O2]-1

Deriva1on to the right

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A general procedure with these

Write out the rate law corresponding to the
SLOW step.
If necessary, solve for the intermediate from
another (usually reversible) step.
Put the intermediate in to complete the rate
law.
Remember: Intermediates cannot appear in
the completed rate law.

Temperature Eects: Arrhenius

The ac1va1on energy

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A more detailed example: The

isomeriza1on of CH3-NC

Some points about Ea

This represents an energy that must be
overcome for a reac1on to start. (Instructor
will give examples.)
When the ac1vated complex forms, the
reac1on can either go leu or right.
The ac1va1on energy of the reverse reac1on
E
is a + H rxn .

The exponen1al factor

This represents the frac1on of molecules with
sucient energy to overcome the ac1va1on
energy barrier.
This is simply derived from the Boltzmann
distribu1on.

Exponential Factor = e

Ea
RT

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Here is a typical representa1on

Some useful formulas

Arrhenius Plot: O3(g) O2(g) + O(g)

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The two-point formula is also useful

Example
Rxn: NO2(g) + CO(g) NO(g)+CO2(g)

T1 = 701K Rate = 2.57 M-1s-1
T2 = 895K Rate = 567 M-1s-1

Calculate Ea in kJ/mol.

Here is the answer (Math Whiz

version)

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Why does the equa1on usually work?

Usually, we have just one slow (rate-
determining) step.
Molecules get their energy from binary
collisions.
This is true even for unimolecular steps
(WHY?).
BUT, if there are two slow steps, we can
some1mes get non-Arrhenius behavior
Why would that be? (Explain!)

This slide shows a rate-determining

step in more detail

So far, for Arrhenius

we have explained the ac1va1on energy
and the exponen1al factor
BUT NOT the frequency factor, A.
It is this la<er factor that brings in the
COLLISION MODEL.

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Some ideas here

Only a certain frac1on of collisions have E > Ea.
But, it is not just the quan1ty, but also the
quality of a collision that is important.
Collisions require proper orienta*on.

An example: Look at this reac1on.

Now look at some possible collisions

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We modify the Arrhenius equa1on to

take all this into account

Usually, p < 1, but

Some1mes, reactants
can do extra things to
augment the
eec1veness of the
collision.
Look at K(g) + Br2(g)
KBr(g) + Br(g)
Here, p = 4.8
The K atom transfers an
electron rst and

Nothing more to say except

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Catalysis
Deni1on of a catalyst:
A regular (posi1ve) catalyst increases k at a given
temperature.
A nega1ve catalyst (inhibitor) decreases k at a
given temperature.

A catalyst can be
an extra reagent or
an acid or base or
one of the products of a reac1on.

Catalysts act
Either by changing the ac1va1on energy
OR
Altering the orienta1on factor, p.
Note this: A catalyst catalyzes BOTH the
forward and reverse reac1on.

A typical example

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Catalyst types

A common example of heterogeneous

catalysis

The fastestand most specialized

catalysts: Enzymes (sucrase here)

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A closer look

Most enzymes follow the same

mechanism

Some more detail about sucrase

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One last thing: Enzymes are usually

HUGE PROTEINS!

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