A faster reaction (top) and a slower reaction

Section II – Kinetics (bottom).

Lesson 12.4: A model for
Reaction Rate

Kinetics: Rates
and Mechanisms
of Chemical
Reactions

Expressing Reaction Rates Expressing the Reaction Rate

The reaction rate of a chemical reaction is the For the general reaction A → B, we measure the
change in concentration of a reactant or product concentration of A at t1 and at t2:
per unit of time.
change in concentration of A conc A2 - conc A1  [A]
Rate = =- =-
change in time t2 - t1 t

Square brackets indicate a concentration in moles per liter.

The negative sign is used because the concentration

of A is decreasing. This gives the rate a positive
value.

Concentration of O3 at Various Times in its

Reaction with C2H4 at 303 K

Concentration of O3
Time (s) (mol/L)

0.0 3.20x10-5  [C2H4]

10 0
10.0 rate = -
2 42 10-55
2.42x10 t
20.0 1.95x10-5  [O3]
=-
30.0 1.63x10-5 t
40.0 1.40x10-5
50.0 1.23x10-5
60.0 1.10x10-5

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 Plots of [reactant] and [product] vs. time. Plots of [reactant] and [product] vs. time.
C2 H4 + O 3 → C2 H4 O + O2 H2 + I2 → 2HI [HI] increases twice as fast
as [H2] decreases.
[O2] increases just as fast as
[C2H4] decreases.
[H2] [I2] [HI]
 [C2H4] [O3] Rate = - =- = 1
Rate = - =- t t 2 t
t t
[C2H4O] [O2] [IH] [H2] [I2]
= Rate = = -2 =-2
= t t t
t t
The expression for the rate of a
reaction and its numerical value
depend on which substance serves
as the reference.

Expressing Rate in Terms of Changes in

In general, for the reaction
aA + bB → cC + dD
where a, b, c, and d are the coefficients for the
balanced equation, the rate is expressed as:
Sample Problem
Concentration with Time
PROBLEM: Hydrogen gas has a nonpolluting combustion product
(water vapor). It is used as a fuel abord the space shuttle
and in earthbound cars with prototype engines:
2H2(g) + O2(g) → 2H2O(g)
(a) Express the rate in terms of changes in [H2], [O2], and
[H2O] with time.

1 [A] 1 [B] = 1
[C]
= 1
[D] (b) When [O2] is decreasing at 0.23 mol/L·s, at what rate is
rate = - =- [H2O] increasing?
a t b t c t d t
PLAN: We choose O2 as the reference because its coefficient is 1. For
every molecule of O2 that disappears, two molecules of H2
disappear, so the rate of [O2] decrease is ½ the rate of [H2]
decrease. Similarly, the rate at which [O2] decreases is ½ the rate
at which [H2O] increases.

Sample Problem
Collision Theory
SOLUTION:
[O2] 1 [H2] 1 [H2O]
 Reaction rate depends on the collisions
(a) Rate = - =- =
t 2 t 2 t between reacting particles.

(b) Calculating the rate of change of [H2O]: The Collision Theory states that in order for reactants to
yield products
1 [H2O] [O2]
=- = - (-0.23 mol/L·s)
2 t t 1. They must collide with each other
[H2O] 2. The collisions must have enough kinetic energy
= 2(0.23 mol/L·s) = 0.46 mol/L·s 3. The molecules must have the proper orientation
t

Effective Collisions:
Collisions of reactant that cause them to react – lead to
products.

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 Collision Theory (cont.)
The Collision Theory
An activated complex is a temporary, unstable
arrangement of atoms in which old bonds are
breaking and new bonds are forming.

Collision Theory (cont.) Reaction Mechanisms

The minimum amount of energy that reacting
particles must have to form the activated complex Can be very complex. Here’s an easy one:
and lead to a reaction is called the
activation energy.
energy Theoretical Reaction:

High activation energy means that few collisions 2A + B  A2B

have the required energy and the reaction rate is
slow.
Reaction Mechanism:
A + B  AB + A A2B

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Here’s a Real One: All Road Lead To Rome

Reaction:
H2 + I2  2HI Reactions can have different pathways
Step 1: depending on local conditions.
H2  2H – Absorbs energy Experimentation is needed to determine
Step 2: the reaction pathway.
pathway
I2  2I – Absorbs energy
Step 3: Rate-determining Step:
2H + 2I  2HI — Releases energy The slowest step in the reaction
Net Equation: pathway. It determines the overall rate of
H2 + I2  2HI
the reaction.

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Factors that Affect Reaction Rate
Reaction Rate:
How many reactions happen/Unit of time

NOT HOW FAST/SLOW THE REACTION

IS!!!

Reaction Rate can be affected in 2 ways:

1. Changing the reaction mechanism.
2. Changing the number of collisions
between reactants

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1. Nature of Reactants 2. Temperature

Different substances react at different rates. high temp = fast rxn rate
Has to do with how much energy those substances
need to react. Why?
Hotter the substance = higher the average KE.
Ionic reactions happen much faster than covalent g
Higher the average
g KE = higher
g the rate of effective
reactions.
reactions
collisions. (more collision and more force )
Examples:
Why?
 Putting batteries in the fridge.
In solution, ionic bonds are broken, covalent
 Heating up your food to cook it.
bonds aren’t.
It takes more energy to break the covalent
bonds.
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Temperature 3. Concentration
Analogy: 2-car high conc = fast rxn rate
collision Why?

Which has a higher Higher concentration = more of a substance per unit

rate of collisions? A 5 mph “fender
fender bender”
bender of area.
area
car going 5 mph or a More substance present = higher rate of effective
car going 50 mph? collisions
Increasing pressure on gases is the same thing as
increasing concentration.
50 mph “high-speed crash”
Examples:
 Dilute vs. Concentrated Acids.
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The number of possible collisions is the product, not 4. Surface area
the sum, of reactant concentrations.
Reaction rate increases with increasing surface area.
Why?
add another
6 collisions Higher surface area = more surface to collide with other
reactants = higher rate of effective collisions.
4 collisions
Only effects solids.

add another Examples:

 Dissolving a sugar cube vs. dissolving powdered
sugar.
 Using a shotgun vs. using a bb gun.
 Crushed garlic flavors more than a whole clove.
9 collisions
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1. Use of a catalyst
Catalyst:
1. Changes one or more steps in a reaction
(usually lowers the activation energy by
providing an alternative pathway).
2 Shortens
2. Sh t th
the reaction
ti mechanism.
h i
3. Is not consumed during the reaction.
Examples:
 Biological enzymes
 Catalytic converter in your car
 Dissolving substances in water.
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2. Use of an Inhibitor
Inhibitor:
1. Changes one or more steps in a reaction (usually
increases the activation energy).
2. Lengthens the reaction mechanism.
3 Is
3. I nott consumedd in
i th
the reaction
ti
Examples:
 Patina on the surface of a metal preventing
oxidation of the rest of the metal
 Painting your car

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To Review:
Reactions depend upon effective collisions. Any
Effective collisions require the proper orientation Questions
and energy of reactants.
?
Reactions happen according to reaction
pathways.
Anything that affects the number of effective
collisions or the pathway of the reaction will
effect the rate of the reaction.

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