Chapter 12, Chemical Kinetics

This chapter is about:

1. numerical descriptions of how fast rxns. occur

2. the intermediates that form during a rxn (re.
mechanism)
3. applying thermodynamics & the kinetic molecular
theory to go from the descriptive learning to
understanding.

Our focus will be on gas and liquid phase (soln.)

reactions.
Why care? Your health!
1
I. Reaction Rates
A. Defining rate: change per unit time

rate = concentration change

time change
B. Example:

2 N2O5 (g) ÷ 4 NO2 (g) + O2 (g)

How could you measure the rate?

1. Measure [N2O5], [NO2], or [O2] at various times.

2. Method: Pressure change, color change, etc.

2
 C. Define rate as increase in product conc. per unit
time or decrease in reactant conc./unit time.

D. Let’s try O2 using data in Table 12.1, p. 430.

rate O2 formation = Δ O2 = [O2] at t2 ! [O2] at t1
Δt t2 ! t1

Your text uses the 300-400 s interval, rate = 9 x 10!6 M/s.

You should try a different time interval. (Pick one!)

Re. Fig. 12.1, does your answer seem reasonable relative

to the value at t = 300-400s?
3
E. Is rate of NO2 formation equal to the rate of O2
formation (or the rate of N2O5 decomposition)?

1. Look at Fig. 12.1. (& Instructor animation: N2O5)

2. The balanced equation gives us the mole ratios.

a) Stoichiometry: 1 O2, : 4 NO2 : !2 N2O5
b) Therefore equivalent rates (on M/s basis) are:

Δ [O2] = ¼ Δ [NO2] = !½ Δ [N2O5]

Δt Δt Δt

As Δ t approaches zero, Δ[X]'Δ t becomes the slope.

4
 So, if the O2 formation rate was 0.80 M/s, the NO2
formation rate should be , and the N2O5
decomposition rate should be .

(Remember, these rates are always positive numbers.)

F. Does the rxn. rate change with time?

Would you have predicted this? Logic?
Try problem 12.2, p. 434.

5
II. Rate Laws & Rxn. Order (Demolition derby?)
A. We are going to relate our numerical analysis of
the rxn. rate to a mental picture (model) of what
sort of collisions are occurring during the rxn.

B. Consider the following general rxn.:

a A + b B ÷ Products
1. I can write a rate law for this reaction in the form:

Rate = k [A] [B]

m n
k: rate constant specific for
this rxn., T, etc.
6
 2. Why does this equation work? (Collision-theory)
a) Why does a k value have to be included?
b) Why [A] times [B]? (Boltzmann?)
c) Why is [A] raised to the m power? (Aside: Is a
sometimes equal to m [and b to n]?)

C. Reaction order
1. The overall reaction order = the sum of all the
exponents in the rate law.

2. The reaction order “with respect to a specific

reactant” = the exponent for that reactant. Do
prob. 12.3, p. 436 to illustrate.

7
 D. If you have a balanced chemical rxn., you do
not necessarily know the rate law.

The rate law must be determined

experimentally!!!

How can we do that?

8
III. Experimental Determination of a Rate Law
One method is to measure initial rate at different [reactant]. Then
see what exponent (remember m and n?) best fits the data.

Rxn.: 2 NO (g) + O2 (g) ÿ 2 NO2 (g)

General Rate law: rate = k [NO]m [O2]n

Use Table 12.3 data, p. 436, to get values for variables.

9
A. To get m, compare exp. #1 & #2, where [O2] is
constant, but [NO] changes by a factor of 2
(0.015 M vs. 0.030 M). (Do math on board!)

If m = 1, the rate should double,

if m = 2, the rate should quadruple,
if m = 3, the rate should go up by factor of 8, etc.
1 2 3
Logic 2 = 2, 2 = 4, 2 = 8, etc.

From the data, we see that the rate quadrupled:

0.192 / 0.048 = 4, therefore, m = 2.
10
B. Following same logic, we can determine value
of n.

What exps. should we compare in Table 12.3 to

accomplish this? Exp. # and exp. # .

Note: In this case we want [NO] to be constant.

(Do math on board!)
C. Now that we know m = 2 and n = , do we
have enough information to determine k?

Solve for k in the space below:(Do math on board!)

11
 Should we do Worked Key Concept Ex. 12.4 (p.
439) in class? Comment on Key Concept problems!!!

IV. Integrated Rate Law: 1st-order Reaction

st
A. For rxn, A ÿ products, that is 1 order overall:
rate = !ΔA / Δt = k [A] (m = 1)

Recall from your calculus:

!ΔA / Δt = k [A] is ~same as:!dA / dt = k [A]
which we can rearrange to get: dA / [A] = !k dt
which we can integrate to get: ln [A]t /[A]0 = !k t
12
 st
This is the integrated 1 order rate equation.

If you prefer base 10: log [A]t /[A]0 = !k t /2.303

B. Because [A]0 means [A] at time = 0, it is a

constant, we can simplify to:
log [A]t = !k t /2.303 + log [A]0
1. This should remind you of the equation for a straight
line: y = m x + b (See Fig. 12.6, p. 441, next page.)

Not the same m as the exponent in the general rate law.

13
 2. Can you do a linear regression on your calculator to
solve for m & b? (You do Probs. 12.6 & 12.7.)

V. Half-life of a First-order Reaction

st
A. A number of interesting rxns follow 1 order
3
decay kinetics. Example: decay of H (tritium,
t½ = 12.3 yr), re. SRS (Savanna River Site).

B. Because of the nature of this type of rxn. the

half-life is a constant. (What is half-life?) (1st
order CD animation)

14
C. Rxn. half-life: time required for amount of
reactant to decrease to ½ of its original value.
(Fig. 12.7, p. 445)

D. Mathematically: log [A]t /[A]0 = !k t /2.303

log (½) = !k t½
/2.303
1/k
!0.3010 = !k t½ /2.303

So, t½ = (!0.3010 × !2.303)/ k = 0.693/ k

15
 E. This means that: t½ % 1'k
Surprising? (Do Prob.12.9, p 446, Key Concept Prob 12.10)

VI. Radioactive Decay Rates

A. Applications:
1. Medicine, particularly internal exposure.
14
2. Archeology, etc. C dating
3. Geology: How old are rocks, age of the earth?

B. Try an application with 14C dating: prob. 12.13,

p. 449.
16
VII. Second-order Reactions
Many reactions do not fit 1st order kinetics. Of these, many do
fit 2nd order kinetics.

nd
A. For rxn that is 2 order in A:
ΔA / Δt = k [A]2

Example: 2 NO2 (g) ÿ 2 NO (g) + O2 (g)

B. The integrated rate law is: 1/[A]t = k t + 1/ [A]0

C. Does this look like y = m x + b? Look at

Figure 12.8 & the figure on p. 452 in Ex. 12.12.
17
Worked Example 12.8 (Graphical determination of rate law)
Left-hand graph should give a straight line if rxn is 1st order.
Right-hand graph should give a straight line if rxn is 2nd order.
What is the order of this rxn with respect to NO2?

A copy of Table 12.4 will be provided w/Exam I.

1. Fig. 12.8: plot of [A] vs. t for a 2nd order rxn.

2. Which of the figures on p. 452 is a better fit to a

straight line? What does this tell you about the
kinetics of NO2 decomposition?

D. Try prob. 12.15 outside of class.

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VIII. Zeroth- Order Reactions (See Fig. 12.9, p. 453)

Rare. Text example notes Pt catalyzed decomposition

of NH3. Collisions appear to be unimportant. This is
zeroth order (with respect to ?) under the conditions given:

1. Relatively large amount of NH3

2. Relatively small Pt surface

See CD animation for Surface Reaction-hydrogenation

Can you imagine conditions where [NH3] & collisions

would become important re. rate?

19
 3. Enzymes can sometimes be viewed as surface
catalysts. Assays to determine the amount of a
given enzyme (ex.: the enzyme PAH for PKU
diagnosis) are often set up to be zeroeth order
with respect to the reactants.

Would the slope change if we changed [A]0?

20
IX. Reaction Mechanisms (major shift in approach)
Time to see if there is more to the analysis that we have been doing than
meets the eye. A rxn mechanism describes the specific changes that occur
during a chemical rxn.
This stuff is massively useful in drug development!

A. Terms

1. A single step in mechanism is called an elementary

reaction or an elementary step.
2. The molecularity of a rxn refers to the # of separate
molecules/atoms on reactant side of elementary rxn.
a) unimolecular = one
b) bimolecular = two
c) termolecular = three (These are uncommon.)
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B. Let’s look at a mechanism for:

NO2 (g) + CO (g) ÿ NO (g) + CO2 (g)

1. Experiments have suggested a two step process:

1st step: NO2(g) + NO2(g) ÿ NO(g) + NO3(g)

2nd step: NO3(g) + CO(g) ÿ NO2(g) + CO2(g)

See Fig. 12.11, p. 454

(Think about molecules colliding and/or breaking apart!)

22
 st
The molecularity of the 1 step is .
The molecularity of the 2nd step is .

2.While a number of the components in the balanced

molecular equation are unstable, one component of
elementary rxns. is very unstable. That is NO3. A
component like NO3 that exists transiently (made &
then used up) in the mechanism is a reaction
intermediate.

3. Notice that the sum of the individual elementary

steps must add up to the overall, balanced molecular
equation:

23
 1st step: NO2(g) + NO2(g) ÿ NO(g) + NO3(g)
2nd step: NO3(g) + CO(g) ÿ NO2(g) + CO2(g)

NO2(g) +NO2(g) + NO3(g) + CO(g) ÿ NO(g) + NO3(g) + NO2(g) + CO2(g)

Net: NO2(g) + CO(g) ÿNO(g) + CO2(g)

The terms that occur on both reactant and products

sides of this summed equation are shown in bold.
When these terms are dropped, you must regenerate
the original, balanced overall rxn. for the mechanism
to have a chance of being correct.

Do Prob. 12.16, p. 457. a) Equation for overall rxn?

b) Molecularity of each step?
24
X. Rate Laws for Elementary Reactions (simple)
A. 1st order example, decay of O3: O3 ÿ O2 + O
st
If this is 1 order in O3, what is the rate law?

B. Second order example, rxn. of CH3Br w/ OH!:

See SN2 Molecular Movies animation. Also on 4th floor computers.

! !
CH3Br + OH ÿ CH3OH + Br
st !
If this is 1 order in both CH3Br & OH what is
the rate law?
25
Important: When the overall rxn. occurs in a
single step, then the rate law is determined by
the molecular equation.

Because this rxn. has a single step mechanism:

CH3Br(aq) + OH!(aq) ÿ CH3OH(aq) + Br!(aq)

!
rate = !Δ [CH3Br] / Δt = k [CH3Br] [OH ]

Do prob. 12.17, p. 459.

26
XI. Rate Laws for Overall Reactions
Back to the crossword puzzle analogy.
The balanced molecular equation for a rxn. only gives
information about stoichiometry, not necessarily about the
mechanism. However, the rate law for the rate limiting step in a
mechanism does define the rate law for the overall rxn.

A. Introductory comments:
1. Find an every day analogy of a multistep process with a clear
rate limiting step. The rate limiting step is the slowest step.
(Shopping?) Ever worked on or seen an assembly line?
When a rxn. occurs with more than one elementary step, usually
one of the elementary steps is much slower than the others. This is
the rate limiting step.

27
 B. Multi step Reactions with an Initial Slow Step
1. Let’s go back and look at the rxn. of NO2 with CO:

Balanced rxn.: NO2 (g) + CO (g) ÿ NO (g) + CO2 (g)

Proposed mechanism:
k1
st
1 step: NO2(g) + NO2(g) ÿ NO(g) + NO3(g)

nd
k2
2 step: NO3(g) + CO(g) ÿ NO2(g) + CO2(g)
The 1st step is the “slow” step in this sequence. By
slow, I mean slow relative to the 2nd step. That is, k1 << k2.

28
 Rate of the overall process can’t be faster than rate of
step 1. Can we write a rate law for the 1st elementary rxn.?
2
Rate = !Δ [NO2] / Δt = k1 [NO2]

The experimentally determined rate law for this rxn.

does turn out to be:
Rate = !Δ [NO2] / Δt = k [NO2]2
Therefore, our mechanism predicted the correct rate law.

There is something of a mutually reinforcing relationship

between the mechanism and the rate law: The rate law
helps to confirm the mechanism and the mechanism gives
us insight into the rate law.

29
What is the order of the NO2-CO rxn.: Overall?
With respect to NO2?
With respect to CO?
Does this seem logical?

In other words: does it bother you that the rate law for
the rxn.:
NO2(g) + CO(g) ÿ NO(g) + CO2(g)

has no [CO] term in it?

Try Prob. 12.18, p. 463

30
 C. Multi step Reactions with Initial Fast Step New!
What if step 1 in the mechanism isn’t the rate limiting step?

1. Example: 2 NO(g) + 2 H2(g) ÿ N2(g) + 2 H2O(g)

2. Proposed mechanism:
k1
Step 1: 2 NO W 2 N2O2 fast, reversible
k !1
k2
Step 2: N2O2 + H2 ÿ N2O + H2O slow, rate limiting
k3
Step 3: N2O + H2 ÿ N2 + H2O fast

Do these steps sum to give the overall balanced equation?

31
3. Based on our previous logic, the rate law should be:

rate = k2 [N2O2] [H2] This isn’t practical or useful.

a) Not practical because we can’t measure [N2O2] easily.
b) Not useful because we can’t control [N2O2] easily.

4. Is there a way to cope?

a) Because the 1st rxn is fast, it is essentially at equilibrium.
(By definition: at equilibrium, rateforward = ratereverse)

b) Therefore ratef = k1[NO]2 and rater = k!1[N2O2]

c) Since ratef = rater then k1[NO]2 = k!1[N2O2]

d) Rearrange k1[NO]2 = k!1[N2O2] to solve for [N2O2]:

32
 k1
[N2O2] = )) [NO]2 & substitute this back into:
k!1

rate = k2 [N2O2] [H2] to get:

k1
rate = )) k2 [NO]2[H2] Practical and useful!
k!1

We usually combine all of the constant terms into a new

constant k.

33
XII. Rxn Rates & Temp: Arrhenius Equation
This equation will help us relate the rate constant, k, to other
chemical ideas (collision theory, steric hindrance, etc.). It helps to
unify our thoughts about kinetics.

A. Reaction rates tend to increase with increasing

temperature. Why?

1. Consider the rxn.: O(g) + HCl(g) ÿ OH(g) + Cl(g)

In this rxn. the H!Cl bond must be broken. Think
about overlap of electron clouds.
÷ ²
O H!Cl ÿ OþHþCl ÿ O!H Cl

34
 2. Do electrons normally repel each other? (Y or N?)

3. The intermediates in a rxn. are usually very unstable

& high in potential energy. (See Fig 12.15)
Important terms:
a) activation energy (Ea)
b) transition state (synonym: activated complex)

Try to relate the process of going from reactants to the

transition state to some human activity. (Mountain
climbing?)

35
 B. Some of the thoughts behind this part of kinetics
started with analysis of collision rates in the gas phase.

1. Air, at normal T & P: each gas molecule has about

109 collisions/sec. Imagine a reaction occurring with
each collision. While this does seem consistent with
the rates of chemical rxns. that cause explosions, it
clearly is not consistent with the rates of the majority
of chemical rxns.

Therefore, for most rxns., only a small percentage of the

collisions lead to a reaction occurring. These productive
collisions occur with appropriate energy and orientation.

36
 2. The fraction of collisions with enough energy (see
Fig. 12.15) to reach Ea is:
!Ea/RT
f=e (Units for T??)
At T= 298K, a rxn. with Ea = 75 kJ/mol has f = 7 x 10!14.
With a collision rate of 109 /s, how long (ave)would you
have to wait to get a collision with sufficient energy?

What would f be for this reaction at 373 K?

Can you see why T has such a large effect on rxn rate?

This takes care of part of the energy consideration

mentioned before. What about orientation?
37
C. Back to our previous example w/gas phase rxn.:
O(g) + HCl(g) ÿ OH(g) + Cl(g)
1. What if O collides with the Cl side of the HCl
molecule, instead of the H side?
÷ ²
H!Cl O ÿ No H to O bonding can occur.

2. Define a steric factor, p: fraction of collisions w/

appropriate orientation for the rxn. to occur. If two
atoms of a diatomic reactant are about the same size,
p . 0.5. (Electrostatics?)

38
 3. For the example above with HCl reacting w/ O,
would p be < 0.5 or > 0.5? Review molecular modeling:

3 representations of HCl

cylinder

ball and stick

All to same scale. Align atom centers.

space filling (geometrically

more accurate than the 2
above)

39
 º »

a) Recall the O (red) has to hit the H (white)

b) Is the surface area of the H greater than the surface area
of the Cl (green)?

40
 D. We can now try to set up an equation predicting
rxn. rates w/ the collision theory described here:
9
1. collision rate = Z [A] [B] (This was 10 above.)
2. rxn rate = p × f × collision rate = p × f × Z [A][B]

Remind you of our general rate law? rate = k [A][B]

Clearly, p × f × Z = k. Therefore: k = p Z e!Ea'RT

We now can relate structure, velocity, energy, etc. to

understanding & predicting rxn rates. Thanks Arrhenius!

p Z is sometimes called A, the frequency factor.

41
XIII. Using the Arrhenius equation

!Ea/RT
A. Rearrange k = A e to: ln k = ! Ea/RT + lnA
Can you see y = mx + b ?

By measuring k a range of different T values we can get a good

estimate of Ea. (Do prob. 12.21 on your own.)

B. Why would anyone want to do this?

42
 Knowledge is power!
1. If you understand a rxn., you can modify it to change
the rate, improve efficiency, and so on.
2. Enzyme inhibitors based on transition-state analogs.
By Baldwin et al., 1995
Green & blue represent the
A & B subunits of HIV
protease. The red molecule
(KNI-272) is a transition
state analog that is an
effective inhibitor of the
enzyme. From PDBSum
accession code 1hpx.
http://www.ebi.ac.uk/pdbsum/

43
2-dimensional map of inhibitor-enzyme interactions:
(From PDBSum code 1hpx)

Covalent bonds of
the inhibitor are shown
in purple. Everything
else is part of the
enzyme. (Ex.: Val 82(A)
is the valine residue at
position 82 of the A
subunit.)
Green dotted lines
are ionic interactions or
Hydrogen Bonds.
Red eyelashes
represent Hydrophobic
Interactions.
44
3-D view of inhibitor-enzyme interactions:

(From PDBSum code 1hpx)

The thicker tube structure

represents the inhibitor (KNI-272).
The thinner tubes represent those
parts of the enzyme that interact
directly with the inhibitor.
Standard CPK color-coding for
elements.
grey: carbon red: oxygen
blue: nitrogen yellow: sulfur
What element appears to be strangely
absent?
45
 The active site of the enzyme is a different environment
than bulk solvent. Hence, different energy pathway.
3. Catalytic antibodies = made-to-order catalysts.

XIV. Catalysis (PKU & PAH? HIV protease?)

A. Catalysts work by decreasing activation energy. (See
Fig. 12.18)

B. Enzymes (and catalysts in general) do this by creating

a different environment (different from what?), which
allows for a different (lower energy) reaction pathway.

46
 For some enzymes, the environment and pathway is
very well understood. See HIV protease.

C. Do catalysts speed up the rate of the reverse rxn. too?

Do Key Concept Prob. 12.22, p. 473-4

rxn: 2 A + C2 ÿ 2 AC A = red B = blue C = yellow

Relatives rates: 1 1 2 3
a) What is the order of the rxn in A, B, C?
b) Write the rate law.
c) Write a mechanism that agrees with the rate law.
d) Identify all catalysts & intermediates in mechanism.

47
XIII. Homogeneous & Heterogeneous
Catalysis (Read on your own.)

The Interlude on pp. 477-478 gives you a nice, brief

introduction into an important part of biochemistry.

48