Experiment 4:

Chemical Kinetics
& Factors
Affecting Reaction
Rates
Purpose
To introduce the basic principles of Chemical
Kinetics.
To study the various factors affecting the rates
of chemical reactions.
To determine the order of two different
reactions with respect to each reactant, and
then deduce the overall order.
To determine the rate, and the rate constant for
one reaction at a given temperature.
Thermodynamics does a reaction take place?
Kinetics how fast does a reaction proceed?
Chemical Kinetics: is the area of chemistry concerned with the speeds,
or rates, at which a chemical reaction occurs.
Reaction rate is the change in the concentration of a reactant or a
product with time (M/s).

A B
rate = -
[]

[A] = change in concentration of A over time period t

rate =
[]

[B] = change in concentration of B over time period t

Because [A] decreases with time, [A] is negative.
Chemical Kinetics
A B
Chemical Kinetics
rate = -
[]

rate =
[]

time





In general, the rate of a chemical reaction depends on
several factors:
The nature of the reaction
The concentrations of reactants
The surface area
The temperature
The presence of a catalyst

In this experiment, the first three listed factors will be
investigated.
The effect of temperature on a reaction will be
investigated in a later experiment.
Chemical Kinetics
Two moles of A disappear for each mole of B that is formed:

2A B rate = -

rate =
[]

The rate of product formation does not require the minus
sign because [C] and [D] are positive quantities.
In addition, a moles of A and b moles of B must be
destroyed for the formation of c moles of C and d moles
of D.
Reaction Rates and
Stoichiometry
Rate of a chemical reaction
aA + bB cC + dD





slope
a
rate =
1
slope = initial rate
[A]
0

rate = -

Rate Law
Rate Law equation that gives the dependence of
the reaction rate on the rate constant
and concentrations of the reactants.
aA + bB cC + dD



Rate = k [A]
m
[B]
n
General form

Sum of all the exponents
ally experiment determined are n & m
order overall n m
B in reaction the of order n
A in reaction the of order m
constant rate k
= +
)
`

Rate Law
Rate laws are always determined experimentally.
Reaction order is always defined in terms of
reactant (not product) concentrations.
The order of a reactant is not related to the
stoichiometric coefficient of the reactant in the
balanced chemical equation.

F
2
(g) + 2 ClO
2
(g) 2 FClO
2
(g)

Rate = k [F
2
][ClO
2
]
1

Rate Law
Types of rate laws:
a) Differential rate law shows how the rate of a reaction
depends on concentration, called rate law.
b) Integrated rate law shows how the concentrations of
species in the reaction depend on time.







The rate of a reaction most of the time, increases with
temperature.

Order Rate Law Integrated Rate Law


=

=

=

=

= []

+
Zero-Order Reactions

=

= /

=
=

= []

Integrated Rate Law

The half-life, t, is the time required for the concentration
of a reactant to decrease to half of its initial concentration.
t = t when =
[]

/
=
[]

A product
First-Order Reactions

A product =

[]
=
/

= /

d A
A
=

= []

Integrated Rate Law

t = t when =
[]

/
=
[]

[]

/
=

Second-Order Reactions

A product =

[]

=
/

= /

[A]
2
=

[]

[]
=

[]

+ Integrated Rate Law

t = t when =
[]

/
=
/[]

/[]

/
=

[]

Dependence of the rate on temperature
A + B C + D

Exothermic Reaction Endothermic Reaction
Dependence of the rate on temperature
Can get very complicated. Simplest form is:



If A independent of T:




RT E
a
e A k

=
|
.
|

\
|
= =
T R
E
A
RT
E
A k
a a
1
ln ln ln
Arrhenius
Equation

Vant Hoff plot: determine E
a







K J/mol 314 . 8
determine : slope
1
vs ln Plot
=

=
|
.
|

\
|
R
E
R
E
T
k
a
a
constant
1
ln +
|
.
|

\
|
=
T R
E
k
a Equation of a
straight line
Physical significance of E
a
:
the activation energy




Minimum energy that system of colliding reactants
must have in order for a chemical reaction to occur
and lead to products.



K J/molec 10 381 . 1
J/mol
J/molec
23

= =

>
A
/RT E
/kT E
a collision
N
R
k
e A
e A
E E
a
a
Boltzmann constant
Catalyst




A catalyst is a substance that increases the rate of a
chemical reaction without itself being consumed.

Rate catalyzed > rate uncatalyzed Ea< Ea
Nature of Reactants

Reactivity of different acids (hydrochloric
acid, sulfuric acid, acetic acid and
phosphoric acid), with Magnesium metal.

Reactivity of different metals ( zinc,
magnesium and copper with the same
acid (HCl).





Surface Area


The larger the surface area of a solid, the more
atoms is available to react.
The reaction rate of two different forms of
marble chips (CaCO
3
) will be investigated.

glass tubing
collected
gas
water beaker
Setup for the gas collection
Concentration of Reactants

Reaction of Mg with HCl:

Mg (aq) + 2H
+
(aq) Mg
2+
(aq)+ H
2
(g)

The general rate law expression for this reaction
is:
rate = k [H
+
]
n
, n is the order of the reaction.

Concentration of Reactants

The rate can be expressed in terms of reciprocal
time since the concentration of the magnesium is a
constant. Thus, rate is directly proportional to 1/t

1/t = k [H
+
]
n
=> ln (1/t) = n ln[H
+
] + ln k

By measuring the time required for magnesium
metal to react with HCl solutions of different
concentrations and plotting ln(1/t) versus ln[H
+
],
the linear curve will give you the slope as the order
of the reaction.


Our chemical reaction




Rate = k [Ace.]
m
[I
2
]
n
[H
+
]
p

H
+
catalyses the reaction

Rate analysis
rate
t
] [I ] I [
k
kt ] [I ] [I
dt k ] [I d kdt ] [I d
k
dt
] [I d
k ] I [ k
dt
] [I d
: I (0) zero order of is reaction that know We
0 2 2
0 2 2
t
0
] [I
] [I
2 2
2
0
2
2
2
t 2
0 2
=

=
=
= =
= = =
} }
wrt




t
I
t
I
slope Rate
0 2 0 2
] [
) 0 (
) ] [ 0 (
=

= =
Tremendously easy measurement of rate
We know that the reaction is zero order w.r.t. I
2
:
Visual determination of I
2
In the lab, determine time of reaction by visual
observation of color of I
2
in the tube.

When the brown color disappears, it means that
the reactant (I
2
) is completely consumed.

Then: [I
2
]
t
= 0 determine the corresponding
time.






Procedure
Procedure
Report
Assigned questions 1, 2, and 3
Data and calculations/Report
[Ace.] = 4.00 M [I
2
] = 0.00500 M
[H
+
] = 1.00 M

Iodine Acetone H
+
Water Rate
I
10.00 10.00 10.00 20.00

II
10.00 20.00 10.00 10.00
III
10.00 10.00 20.00

10.00
Method of initial rates








)
`

=
=
M 1.60 [Ace.]
M 0.800 [Ace.]
II
I
m
m
I
II
p
I
n
I 2
m
I
p
II
n
II 2
m
II
(2.00)
[Ace.]
[Ace.]
] H [ ] I [ [Ace.]
] H [ ] I [ [Ace.]
I Rate
II Rate
=
|
|
.
|

\
|
=
=
+
+
= = m 2.00 ln m ln x
x
Rate constant
Similarly, [HCl]
I
= 0.200 M [HCl]
III
= 0.400M



lny = pln 2.00 p


k
I
= ..
Take average of 4 runs OR 3 runs

p
I
n
I 2
m
I I
] [H ] [I [Ac] k Rate
+
=
=
p
p
2.00
0.200
0.400
I Rate
III Rate
=
|
.
|

\
|
=
y