Chemical Kinetics

Rates of chemical reactions

Every chemical reaction has its own
signature rate
• Diamonds are made • the chemical reaction
by converting Carbon of photosynthesis (a
from its graphite state. plants ability to make
• takes millions years to its own food, which is
consume the graphite the reaction's product
(the reactant) to form along with Oxygen)
a diamond (the takes place on a time
product). scale as short as...
• this is why we place ...10^-12 seconds
such a high value on (0.000000000001 s)
diamonds
 Chemical Kinetics
• We can think of reaction rate in terms of
the change of concentration with time.
• IF A→B, then...

rate = - ΔA/Δt or rate = ΔB/Δt

...wherein ΔA and ΔB are changes in the

concentration (the molarity) over a time
period.
• The rate of reaction A→B, represented as the
decrease of A molecules with time and as the
increase of B molecules with time.
B molecules

A molecules
 Deriving rates of reactions:
you must first determine the
concentration of the reactant at
different intervals of time
• Instantaneous rate
Reactant concentration is
proportional to the reaction rate...
• Average rate
– the mean rate of
change in the
concentration of the
reactant over the
whole duration of the
reaction
- ΔA/Δt
– a specific rate at a
particular moment in
time
– If temperature is the
same and the initial
concentration of the
reactant used in the
reaction is the same,
the rate will always be
the same at that
moment in time every
time you perform the
reaction
Instanteous Rate
 rate is directly proportional to Br2
concentration...
 
Br2 ( aq )  HCOOH ( aq )  2 Br ( aq )  2H ( aq )  CO2 ( g )

rate α Br2
to make proportionality into
an equation (), we must
provide a constant
rate  kBr2 
 rate constant (k)
• a constant of
proportionality between reaction
the reaction rate and the time (s) Br2 M
rate (M/s)
concentration of reactant.
• plot the data in a graph: 0.0 0.0120 4.2 x 10^-5
rate vs. Br2 concentration
• Is it a straight line or 50.0 0.0101 3.52 x 10^-5
a curved line?
The fact that the graph 100.0 0.00846 2.96 x 10^-5
is a straight line shows
that the rate is directly
proportional to 150.0 0.00710 2.49 x 10^-5
concentration.
 units for rate constant
• Because reaction rate has the units M/s,
and Br2 is in M, the unit of k is...
1/s or s^-1
• k is not affected by the concentration of
Br2.
• To be sure, the rate is greater at a higher
concentration and smaller at a lower
concentration of Br2, but the ratio of
rate/Br2 remains the same provided the
temp. remains constant.
 Find the rate constant for the
following reaction
 
Br2 ( aq )  HCOOH ( aq )  2 Br ( aq )  2H ( aq )  CO2 ( g )
reaction
k = rate/Br2 time (s) Br2 M
rate (M/s)

0.0 0.0120 4.2 x 10^-5

Use the chart to
determine the rate 50.0 0.0101 3.52 x 10^-5

constant
100.0 0.00846 2.96 x 10^-5

3.49 x 10^-3 s^-1 150.0 0.00710 2.49 x 10^-5

Reaction Rates and Stoichiometry
• STOICHIOMETRY - The quantitative
study of reactants and products in a
chemical reaction
– Balancing equations and using molar masses
to figure the amount of each substance being
used as reactants to determine how much
product is being converted during a reaction
– Unbeknownst to you, we have been operating
this concept, but we have yet to define it...
 Reaction Rates and Stoichiometry
• I have introduced to you simple situations...
A→B
• what if...
2A→B
• Uh-ohhhh... What to do? What to do?
• Well, this expression is stating that 2 moles of A
disappear for each mole of B that forms.
• The rate of disappearance of A is twice as fast
as the rate of appearance of B.
• How could we express this rate?
 Reaction Rates and Stoichiometry
How about like this...

1 A B
rate   or rate 
2 t t
THE RULE:
take the reciprocal of every product's coefficient and
every negative reciprocal of every reactant's coefficient
 FOR EXAMPLE

3O2 ( g )  2O3( g )
1 O2 1 O3
rate   
3 t 2 t
 YOUR TURN...
Write the rate expressions for these
following reactions in terms of
disappearance of reactants and
appearance of products...
4NH 3(g)  5O 2(g)  4 NO (g)  6H 2 O (g)

CH 4(g)  2O 2(g)  CO 2(g)  2H 2 O ( g )

The next step is to find the actual rate
2 H 2O(l )  O2 ( g )  2 H 2O2 ( aq )
Molecular oxygen is reacting at the rate of
0.024 M/s. At what rate is H2O2?
1 H 2O O2 1 H 2O2
rate    
2 t t 2 t
O2
 0.024 M / s
t
O2 1 H 2O2
 
t 2 t
H 2O2
 ()2(0.024 M / s )
t
H 2O2
 0.0048M / s
t
 HOMEWORK CHECK!
• 13.7
• 2NO + O2 → 2NO2
• Suppose that at a particular moment
during the reaction nitric oxide (NO) is
reacting at the rate of 0.066 M/s.
a) At what rate is NO2 being formed?
b)At what rate is molecular oxygen reacting?
 2NO + O2 → 2NO2
NO is reacting at the rate of 0.066 M/s
• To express the rate of reaction we need to do three
things...
– Use proper sign (- or +)
– Determine the reciprocal of the stoichiometric
coefficient for each molecule in the reaction
– Make all molecular rates equal to one another

 1  NO  1  O2  1  NO2

      
 2  t  1  t  2  t
 2NO + O → 2NO 2 2

NO is reacting at the rate of 0.066 M/s

• At what rate is NO2 being formed? NO -

 0.066 Ms
 1  NO  1  O2  1  NO2 t
      
 2  t  1  t  2  t GIVEN

 1  NO  1  NO2
    NO2
 2  t  2  t 0.066 M

_ 1  1  NO2
  0.066 s   
M
s
t
 2  2  t
 2NO + O → 2NO 2 2

NO is reacting at the rate of 0.066 M/s

• At what rate is molecular oxygen reacting? NO -
 0.066 Ms
 1  NO  1  O2  1  NO2 t
      
 2  t  1  t  2  t GIVEN

 1  NO  1  O2 _  1  O2

        0.066 s 
M
 2  t  1  t  2 t
_   1 0.066 M    1  O2 _0.033 M  O2
 1  t
s
 2  s
t
 N2 + 3H2 → 2NH3
Molecular hydrogen reacts at a rate of 0.074 M/s
• 13.8
• Suppose that at a particular moment during the
reaction molecular hydrogen is reacting at the
rate of 0.074 M/s.
a) At what rate is ammonia being formed?
b) At what rate is molecular nitrogen reacting?

 1  N 2  1  H 2  1  NH 3
      
 1  t  3  t  2  t
 N2 + 3H2 → 2NH3
Molecular hydrogen reacts at a rate of 0.074 M/s
H 2 -
• At what rate is  0.074 Ms
ammonia being formed? t GIVEN

 1  N 2  1  H 2  1  NH 3
      
 1  t  3  t  2  t
 1  H 2  1  NH 3  2  NH
      _    0.074 M
 3

 3  t  2  t  3 
s
t
_  1  1  NH 3
  0.074 s    NH 3
0.049 s 
M
M
 3  2  t
t
 N2 + 3H2 → 2NH3
Molecular hydrogen reacts at a rate of 0.074 M/s
H 2 -
• At what rate is molecular  0.074 Ms
nitrogen reacting? t GIVEN

 1  N 2  1  H 2  1  NH 3
      
 1  t  3  t  2  t
 1  H 2  1  N 2  1 N 2
     -  (1)  0.074 s 
M
 3  t  1  t 3 t
 1  1  N 2
    0.074 s    
M
N
 3  1  t  0.025 M
 2
s
t
HERE ARE YOUR TESTS