12 - Kinetics

Chapter Twelve:
CHEMICAL
KINETICS
Copyright Houghton Mifflin Company. All rights reserved. Chapter 12 | Slide 2
Chemical Kinetics
Once thermodynamics determines that a
reaction will occur
Chemical kinetics is the study of the
rates of spontaneous reactions.

12.1
Reaction Rate
Usually defined as the change in
concentration (mol/L) of a given reactant
or product per unit time.
12.1
Reaction Rate
For 2A + B C + 3D
the rate with respect to A is:

= - [A]
t (reaction rates are shown as positive values)
12.1
Rate =
conc of A at time conc of A at time
2 1
2 1
t t
t t
-
-
Reaction Rate
Graphical
view of the
decrease in
concentration
of reactants
over time:
12.1
Instantaneous Reaction Rate
strike a
tangent at a
given time to
find the rate at
that point
12.1
Instantaneous Reaction Rate

Rate= D[N2O5] = slope
Dtime
(find slope the old
school way)
12.1
Homework
A reactant concentration vs. time graph was plotted for a
certain reaction. Determine the instantaneous rate of the
reaction at 10 seconds elapsed time (do your best to
estimate values on the axes)
12.2
Ambiguous Reaction Rate Values
For 2A + B C + 3D
If = 0.24 mol L
-1
min
-1
, then

= 0.12 mol L
-1
min
-1

12.1
[ ]
D
D
A
t
[ ]
D
D
B
t
Reaction Rate Per Mole of Reaction
Reaction Rates can also be defined as
the rate per mole of reaction.
In this case, there is only one value for
the reaction rate
Which is equal to any of the individual
reaction rates divided by its coefficient
12.1
Reaction Rate Per Mole of Reaction
For 2A + B C + 3 D

Rxn rate = - 1 [A] = - [B] = [C] = 1 [D]
2 t t t 3 t

12.1
Note how the
stoichiometry is
apparent in this
graph of
2NO
2
2NO + O
2

12.1
Differential Rate Laws
For the decomposition of nitrogen dioxide:
2NO
2
(g) 2NO(g) + O
2
(g)
Rate = k[NO
2
]
n
:
k = rate constant
n = order of the reactant
it is the power by which a change in
reactant concentration affects the reaction
rate
if n=2, then tripling the reactant
concentration will increase the reaction rate
by 9 times

12.2
Rate = k[NO
2
]
n
The exponent (n) of a given reactant is
called its order. So a reactant with an
exponent of 2 is said to be a second
order reactant.
The value of the exponent n must be
determined by experiment; it cannot be
determined from the balanced equation

12.2
Determining Differential Rate Equation Values:
Method of Initial Rates
The basic idea is to look at how the initial
rate of a reaction changes due to a
change in a reactant concentration.
If the concentration is doubled, and the
rate increases by 4x, then the exponent for
that reactant is 2 (since 2
2
=4)
12.2
Example: Using the following data table,
determine the exponents for the reactants NH
4
+

and NO
2
-
(theres a typo in the chart should be NO
2
-
not NH
2
-
).
12.2
Note that between trials 1 and 2, NH
4
+
remains
constant and NO
2
-
doubles and the rate doubles.
The exponent for NO
2
-
must therefore be 1.
12.2
Note that between trials 2 and 3, NO
2
-
remains
constant and NH
4
+
doubles and the rate doubles.
The exponent for NH
4
+
also must be 1.
12.2
So far, we have the differential rate law as:
rate = k[NH
4
+
][NO
2
-
]
All thats left is to determine the rate constant, k

12.2
This is done by picking a trial (several, if this is
actual lab data and not book data) and plugging
in the concentration and rate values, along with
the determined exponents.

12.2
Using trial 1:
1.25x10
-7
mol/Ls = k(0.100mol/L)
1
(0.0050mol/L)
1

2.50x10
-4
L/mols = k (Take note of the units!)
12.2
Rate = k[NO
2
]
n
If the concentration is doubled
And as a result, the reaction rate remains
the same
n must = 0
NO
2
is a zero order reactant
12.2
1/2 Orders are also possible, though
somewhat rare.

(The mathematics for calculating non-integer
orders is covered in the Flooding notes)
12.2
The problem, though, with a
differential rate laws like
rate = k[A]
2

they cannot relate time elapsed to
concentration remaining.
12.4
The Problem with Differential Rate Laws
In other words, for A Products
rate current x time elapsed conc. A reacted away

Why????

12.4
For most reactions,
the rate decreases
as the reaction
proceeds
12.4
First-Order Reactant Integrated Rate Law
Differential rate law:
Rate = k[A]

Integrated rate law:
ln[A]
remaining
- ln[A]
initial
= -k t
elapsed

or
ln [A]rem = -k t
elapsed

[A]
I

1
st
order is MOST common reactant order!!

12.4
Exercise
A first order reaction is 35% complete at the
end of 55 minutes. What is the value of k?
12.4
ln [A]rem = - k t
elapsed
[A]initial
Second-Order Integrated Rate Law
Differential Rate Law:
rate = k[A]
2

Integrated Rate Law:
1 - 1 = kt
[A]
rem
[A]
i

12.4
Zero-Order
Rate = k[A]
0
= k

Integrated:
[A]
rem
- [A]
i
= -kt
elapsed

12.4
Another Method (Besides Initial Rates)
to Determine Reactant Order:
Graphical Technique
Given experimental concentrations at
given times, we can use graphing as a
diagnostic tool to determine reactant
order.

12.4
Graphing Technique to Determine IF a
reactant is 1
st
order
1
st
order Integrated rate law:
ln[A]
remaining
- ln[A]
initial
= -k t
elapsed

Rearranged:
ln[A]
remaining
= -k t
elapsed
+ ln[A]
initial

y = mx + b

12.4
reactant is 1
st
order
ln[A]
remaining
= -k t
elapsed
+ ln[A]
initial

y = mx + b

So IF a graph of the ln[A] vs. time is
linear, THEN the reactant is first
order.
12.4
reactant is 1
st
order
ln[A]
remaining
= -k t
elapsed
+ ln[A]
initial

y = mx + b

And if it is linear what does the slope
give us??

The rate constant, k k = |m|

12.4
reactant is 2
nd
order
2
nd
order Integrated rate law:
1 - 1 = kt
[A]
rem
[A]
i

Rearranged:
1 = kt + 1
[A]
rem
[A]
i

y = mx + b
12.4
reactant is 2
nd
order
1 = kt + 1
[A]
rem
[A]
i

y = mx + b

So IF a graph of 1/[A] vs. time is linear,
THEN the reactant is 2nd order,
with k = |m|
If its not linear, then it will be zero or 1
st
order
12.4
Zero-Order
Rate = k[A]
0
= k

Integrated:
[A]
rem
- [A]
i
= -kt
elapsed

Graphical diagnostic:
If zero order, a graph of [A] vs. time will
be linear, and k = |m|

12.4
The Problem with Integrated Rate Laws
They only work for one-reactant
systems.
For two-reactant systems, either one
reactant must already be zero order,
Or we must trick the reaction into
behaving like one of the reactants is
zero order.

12.6
Flooding
This is done by flooding the reaction
with such a high concentration of that
reactant that its concentration changes
negligibly during the course of the
reaction.
This will result in a negligible change to
the rate due to the flooded reactant it
will appear zero order!

12.6
Flooding
Only one reactant affects the rate,
now, so the integrated rate laws will
work for that reactant.
The actual order of the flooded
reactant will be found afterward by
method similar to method of initial rates
once the rate constant is known.
12.6
Flooding Mathematics
For A + F Products
Where F will be the flooded reactant and A is the reactant
affecting the rate

Rate = k
real
[A]
x
[F]
y
= k[A]
x

Where k = k
real
[F]
y

x is determined by graphical diagnostic,
and k = |m| linear graph
12.6
To determine the order of reactant F, do
the experiment twice, each with different
initial concentrations of F.
You will get different k values
corresponding to the different [F]initial values
krxn 1 = kreal [F]
y
rxn 1 and
krxn 2 = kreal [F]
y
rxn 2

Where the [F] values are known
12.6
Substituting, rearranging
krxn 1 = [F]
y
rxn 1
krxn 2 = [F]
y
rxn 2

Taking the log10 of both sides:

log krxn 1 = y log [F]rxn 1
krxn 2 [F]rxn 2

12.6
Solving for y gives the order of reactant
F
Substitute back into
krxn 1 = kreal [F]
y
rxn 1 and
krxn 2 = kreal [F]
y
rxn 2
to determine kreal for each trial, and average
them.

12.6
Half Life
Amt. of time for of the reactants to
react away.
So [A]
remaining
= [A]
initial

Substituting [A]
initial
in for [A]
remaining

each of the integrated rate laws gives
an integrated rate law specifically for a
half-life situation.
Most important one is 1
st
order
All radioactive decay is 1
st
order!!
12.6
1
st
Order Half Life Equation
ln [A]initial = -kt

[A]initial

So ln 0.5 = -kt

- 0.693 = -kt

0.693 = kt

NOTE that for 1
st
order, the half-life is
independent of concentration!
12.6
Half Life
The Half-life equations of the other
orders can be derived in the same
fashion, but they are rarely used their
half-lives are concentration dependent.
For example:
2
nd
Order Half-life equation:
1 = kt

[A]
initial

12.6
Half Life
You will often be presented with the
half-life of a 1
st
order reactant as a
means to determine the rate constant,
k, to use in a related problem.
12.6
Reaction Mechanism
Most chemical reactions occur by a
series of steps.
A Reaction Mechanism is a listing of
these steps.
Each step is called an elementary
reaction and occurs literally as the
reaction equation states.
12.6
Reaction Mechanism
Each step is a literal reaction:
the reactants of a given step collide
an old bond breaks while a new bond
simultaneously is formed.
A-B
C A--B--C A + B-C
This in-between substance is called the
activated complex
It is also known as the transition state of the
reaction

12.6
Reaction Mechanism
An intermediate is formed in one step
and used up in a subsequent step and
thus is never seen as a product.
Catalysts are substances that are
reacted away, but subsequently are
reformed.
12.6
A Molecular Representation of the Elementary
Steps in the Reaction of NO
2
and CO

NO
2
+ CO NO +CO
2

12.6
Elementary Steps (Molecularity)
Unimolecular reaction involving one
molecule ; first order (no collision just a
decomposition often initiated by some form of energy (hn))
Bimolecular reaction involving the
collision of two molecules could be the
same type of molecule; second order
Termolecular reaction involving the
simultaneous collision of three species;
third order (rare)
12.6
Rate-Determining Step
A reaction is only as fast as its slowest
step.
So the slow step in a reaction
mechanism is called the rate-
determining step
The rate-determining step, therefore, is
the step that determines the differential
rate law!
This is yet ANOTHER way to determine
a rate law.
12.6
Using the Slow Step to Determine the
Differential Rate Law
For a given OVERALL reaction
mA + nB Products
The general form of the Differential Rate law
would be
Rate = k[A]
x
[B]
y

Recall that the differential rate law exponents
(x and y) are NOT determined from the
balanced equation coefficients (m and n)
12.6
That is because the rate relationship
between reactants and rate is not
determined by the overall equation, but by
the slow step of the reaction.
So the coefficients of the slow step
reactants ARE the exponents in the rate
law!
12.6

If you know the mechanism you know the
rate law!
12.6
Example:
for the Reaction 2A + B C + D

Proposed Mechanism
A + B C + E slow
A + E D fast

The rate law would be rate = k[A][B]
Since 1 A and 1 B appear as reactants in the slow
step.
12.6
Different Example:
for the Reaction 2A + B C + D

Proposed Mechanism
A + A C + E slow
B + E D fast

The rate law would be rate = k[A]
2
since 2 As
appear as reactants in the slow step. Note that
B is a zero order reactant because it doesnt
appear in the slow step!
12.6
So. If you were asked to predict which of
the previous 2 proposed mechanisms was
most likely, you would have to compare
the PREDICTED rate laws (from the
mechanisms) to the REAL rate law
(determined by experiment)
12.6
Reaction Mechanism Requirements
The sum of the elementary steps must
give the overall balanced equation for
the reaction.
The mechanism must agree with the
experimentally determined rate law.
It must not include more than 3
species colliding and its even
suspect if 3 species collide.
12.6
Back to Using Reaction Mechanisms to
determine Differential Rate laws
Many mechanisms contain at least one
step that is reversible.
This, of course, will affect the
subsequent steps.
Many of these mechanisms end up with
Intermediates in the slow step of the
mechanism

12.6
Intermediates are NOT allowed to be
included in rate laws, though, and must
be substituted out in terms of actual
reactants.
This process of substitution can get
rather messy, but we will only work
with relatively simple cases in AP Chem
12.6
A VAST majority of the time, when an
intermediate appears in the slow step,
this is the look that you will see in the
mechanism:
A + B I fast equilibrium
I + A C + D slow

NOTE: the intermediate, I (that must be
substituted out), is the ONLY product of a fast
equilibrium.
12.6
I + A C + D slow
The unofficial rate law would therefore be
Rate = k[I][A]

In THIS case : [I] = [A][B]
12.6
I + A C + D slow
The unofficial rate law would therefore be
Rate = k[I][A]

so the official rate law is

rate = k[A][B][A] = k[A]
2
[B]
12.6
I + A C + D slow rate = k[A]
2
[B]

A couple of things to note:
1. B is NOT in the slow step, but it is not zero order
because it is in an equilibrium reaction prior to the slow
step.
2. Even though the rate law has 2 As and 1 B in it, it does
NOT mean that 2As and 1 B are colliding simultaneously
that can be clearly seen from the mechanism. SO you
cant always tell what is actually colliding by just looking at
the rate law.
12.6
Requirements for an Effective
Collision
#1: The correct molecules must collide
#2: Activation Energy Consideration

12.7
Molecules must collide with enough
energy
Sufficient collision energy is necessary to disrupt
the bonds of the reactants to form the activated
complex ( A---B---C)
There is a threshold energy of collision that
must be met in order for that collision to have a
chance at reacting called the activation
energy.

12.7
Activation Energy
Change in Potential Energy
12.7
Maxwell Boltzman Distribution
12.7
Molecules must collide with enough
energy
Temperature of the reaction is the most
important variable regarding collision
energy more on this to come

12.7
Activation Energy
#3: Collision Orientation Considerations
12.7
Requirements for an Effective
Collision
The molecules must be oriented
correctly in space
If the transition state must be A--B--C,
then the reaction will not proceed if C
collides with A instead of B
C
A-B No Rxn.

12.7
Orientation of Colliding Species
12.7
Orientation of Colliding Species
Collision Model - Effective Collisions
So
not only do the correct molecules
need to collide.
They need to collide with
sufficient energy
And they need to be oriented
just right

12.7
Or there will be no reaction the
collision would not have been
effective

12.7
The rate constant, k, is the number of
effective slow step collisions per
mol/L of each reactant per time

12.7
Factors Affecting the
Rate Constant, k
12.7
The only factors that affect the
rate constant, k, are
temperature and the
presence of a catalyst.

The Effect of Temperature on Effective
Collisions (and the Rate Constant)
12.7
The equation that relates
temperature to the rate constant
(and therefore, the rate) is the
Arrhenius Equation.

The Arrhenius Equation
The fraction of
collisions
exceeding
the activation
energy is
given by
e
-E
a
/RT

12.7
The rate constant, k, is the number of
effective slow step collisions per
mol/L of each reactant per time

12.7
k = zr e
-E
A
/RT

total collisions per mol/L per time

fraction of collisions of correct orientation

fraction of collisions w/ sufficient
energy of collision (Ea)

12.7
Let zr = A
(collision frequency factor)

k = A e
-E
A
/RT

12.7
ln k = -EA 1 + ln A
R T
Looks like a graphing situation to me!!!

12.7
Two-Point Version
ln k2 = - EA ( 1 - 1 )
k1 R ( T
2
T
1
)

12.7
Catalyst
A substance that speeds up a
reaction without being (net)
consumed itself.
12.8
Catalyst
The main effect that a catalyst has is to
weaken (or even break) a bond in one
of the reactants.
This lowers the activation energy
needed to initiate the reaction.
This lower energy pathway leads to a
faster reaction rate.
Catalyst addition and temperature
increase are the only factors that
increase the rate constant, k.
12.8
Potential Energy Plots for a Catalyzed and
an Uncatalyzed Pathway for a Given
Reaction
12.8
A Maxwell-Boltzman Look at the Effect of
Catalyst Addition on Reaction Rate
12.8
A Maxwell-Boltzman Look at the Effect of
Catalyst Addition on Reaction Rate
12.8
Factors Affecting Reaction Rates
Reactant Concentration
Higher concentration, more collisions,
greater statistical chance of reaction
Reaction Temperature
Higher temperature, greater average
collision energy, greater number of
collisions with sufficient activation energy
Catalyst Addition
Provides a lower energy pathway for the
reaction to occur, resulting in more of the
collisions being effective
12.8
Factors Affecting Reaction Rates
Reactant Surface area (for solid
reactants only)
Increased surface area leads to more of
that reactant being exposed to the other
reactant, thus increasing the reaction rate.
(Physical Mixing)
(it is assumed that all reactions are done
with physical mixing, which assures that
there is not a depletion of reactant in one
part of the reaction vessel)
12.8

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