Chemical Kinetics

What is chemical kinetics?

It is the study of how fast reactions take place.

• Some reactions are fast (photosynthesis).

• Some reactions are slow (conversion of diamond to graphite).

Importance of Studying Reaction Rates

• Speed up desirable reactions.
• Minimize damage by undesirable reactions.
• Useful in drug design, pollution control, and food processing.

Rate of Reaction
• Expressed as either:
– Rate of disappearance of reactants (decrease or negative)
– OR Rate of appearance of products (increase or positive)

  [A] or  [B]
t t
Average Reaction Rate
Br2(aq) + HCOOH(aq)→2Br(aq) + 2H+(aq) + CO2(g)
Note: Br2 disappears over time

[Br2 ]  [Br2 ]
final initial
• Avg. rate = t  t
final initial

0.0101 M  0.0120 M
• Avg. rate = = 3.80  M /s
50 s  0 s

• Average rate depends on time interval.

• Plot of [Br2] vs time = curve.
• Plot of Rate vs [Br2] = straight line.
Instantaneous Rate
• Instantaneous: rate at a specific instance in time (slope of a tangent to the curve)

Rate Constant

From the data of the table we can conclude—

• When the [Br2] is halved; the rate is halved
• Rate is directly proportional to [Br2]
• rate = k [Br2]
• k = proportionality constant and is constant as long as temp remains constant
• Calculate the value of the rate constant for any set of data and get basically the same
answer!
• k = rate / [Br2]

3.52 x 105 M/s

k   3.5 x 103 /s
0.0101 M
Stoichiometry and Reaction Rate

• When stoichiometric ratios are not 1:1 rate of reaction is expressed as follows

General equation:

aA + bB →cC + dD
1  [A] 1  [B] 1  [C] 1  [D]
rate =    
a t b t c t d t
• Write the rate expression for the following reaction

2NO(g) + O2(g) →2NO2(g)

--------------------------------------------------------------------------------------------------------------

4PH3(g) → P4(g) + 6H2(g)

If molecular hydrogen is formed at a rate of 0.168 M/s, at what rate is P4 being produced?

1  [PH3] 1  [P4] 1  [H2]

  
4 t 1 t 6 t
Answer
1  [H2] 1
 (0.168 M /s)  0.028 M /s
6 t 6
1  [P4]
 0.028 M /s
1 t
Dependence of Reaction Rate on Reactant Concentration

Rate law expression

For the general equation:

aA + bB → cC + dD

rate law = k[A]x[B]y

k = proportionality constant

x and y = the order of the reaction with respect to each reactant

Order of a reaction:

• Exponents represent order.

• Only determined via experimental data.

 – 1st order - rate directly proportional to concentration

– 2nd order - exponential relationship

– 0 order - no relationship

• Sum of exponents (order) indicates overall reaction order

Experimental Determination of Rate Law

• Method of initial rates - examine instantaneous rate data at beginning of reaction

rate = k[F2]x [ClO2]y

Find order (exponents) by comparing data

Exp. 1 and 3: [ClO2] is held constant

[F2] [rate] 3
3  0.20 M  2 3  2.4 10 M /s  2
[F2] 0.10 M [rate] 1.2  103 M /s
1 1

1st order with respect to [F2] (rate and M directly related)

rate = k[F2]1[ClO2]y

Find order (exponents) by comparing data

Exp. 1 and 2: [F2] is held constant

[rate] 3
[ClO2] 2  4.8 10 M /s  4
2  0.040 M  4
[ClO2] 0.010 M
[rate] 1.2  103 M /s
1
1
1st order with respect to [ClO2] (rate and M directly related)

rate = k[F2]1[ClO2]1 overall order = 2

Find k (use any set of data)

Therefore, k= rate/[F2][ClO2]

Determining Rate Law second example:

• In experiment 1 and 2; [B] is constant; [A] doubles and rate doubles - the reaction is 1st
order with respect to [A]

• In experiment 1 and 3; [A] is constant; [B] doubles but the rate quadruples! This means
that the reaction is 2nd order with respect to [B]

• Rate = k[A] [B]2

• The rxn is 1st order w/ respect to [A]

• The rxn is 2nd order w/ respect to [B]

• The rxn is 3rd order overall (1 + 2)

[rate] 2.1  104 M /s

k   9.3 M 2  s1
[A] [B]2 (0.10 M ) (0.015 M ) 2
First Order Reaction:

• First-Order reactions may be expressed in several ways

• Example: A →products
 [A]
rate = k[A] rate  
t
Integrated First Order Rate Law:

When the two expressions are set equal to each other, we get an expression that can be
rearranged in the form of a straight line
ln  A   kt  ln  A0

y = mx + b

• Given concentration and time data, graphing can determine order

• For a 1st order reaction, a plot of ln [A] vs time yields a straight line

• The slope = k (the rate constant)

Try Graphing
 • Plot ln [Pressure] on y-axis and time on x-axis.

• If the plot is a straight line, then the integrated rate law equation can be used to find the
rate constant, k, or the slope of the line can be calculated for the rate constant.

• The rate constant for the reaction 2A → B is 7.5 x 10 3 s1 at 110°C. The reaction is 1st
order in A. How long (in seconds) will it take for [A] to decrease from 1.25 M to 0.71 M?

Another form of the integrated rate law

  7.5  103 s1 (t )

[A] (0.71 M)
t   kt ln
ln (1.25 M)
[A]
0
t  75 s

• Consider the same first order reaction 2A → B, for which k = 7.5 x 103 s1 at 110°C.
With a starting concentration of [A] = 2.25 M, what will [A] be after 2.0 minutes?

Half-Life (1st order)

• Half-life: the time that it takes for the reactant concentration to drop to half of its original
value.
• Half-life is the time that it takes for the reactant concentration to drop to half of its
original value.
.693
• The expression for half-life is simplified as t1/ 2 
k
• The decomposition of ethane (C2H6) to methyl radicals (CH3) is a first order reaction
with a rate constant of 5.36 x 104 s1 at 700 °C. C2H6 → 2CH3. Calculate the half-life in
minutes.
0.693
t1/2   1293 s
5.36  104 s 1

1 min
1293 s   21.5 min
60 s
Summary Table of First, Second and Zero Order Kinetics
Molecularity of Reaction (Molecularity and order of a reaction are not identical):

Molecularity is the number of molecules, atoms, or ions reacting in an elementary process. In the
reaction Br2 → 2Br

the process is unimolecular because the single molecule, Br2, decomposes to form two bromine
atoms.

In the single-step reaction H2 + I2 → 2HI

the process is bimolecular because two molecules, one of H2 and one of I2, must come together
to form the product HI.

Termolecular reactions, that is, processes in which three molecules must come together
simultaneously, are rare.

Chemical Reactions that proceed through single step are known as elementary reactions.
Chemical reactions that proceed through more than one step are known as complex reactions.
The overall order determined kinetically may not be identical with the molecularity because the
reaction consists of several steps, each with its own molecularity.

For the overall reaction, 2NO+O2→2NO2 the order has been found experimentally to be 2. The
reaction is not termolecular, in which two molecules of NO would collide simultaneously with
one molecule of O2. Instead, the mechanism is postulated to consist of two elementary steps,
each being bimolecular:

2NO→N2O2

N2O2+O2→2NO2
Difference between order and molecularity

Apparent or Pseudo-Order

“Apparent” or “pseudo”-order describes a situation where one of the reactants is present in large
excess or does not affect the overall reaction and can be held constant. For example, many
hydrolysis decomposition reactions of drug molecules are second order. Usually the amount of
water present is in excess of what is needed for the reaction to proceed. In other words, the
concentration of water is essentially constant throughout the reaction. In this case, the second-
order reaction behaves like a first-order reaction and is called an apparent or pseudo–first-order
reaction.
Reaction Mechanism:
Accelerated Stability Testing:
 In accelerated stability testing, a product is stressed at several high (warmer than
ambient) temperatures and the amount of heat input required to cause product failure is
determined.
 This is done to subject the product to a condition that accelerates degradation.
 This information is then projected to predict shelf life or used to compare the relative
stability of alternative formulations.
 This usually provides an early indication of the product shelf life and thus shortening the
development schedule.
 In addition to temperature, stress conditions applied during accelerated stability testing
are moisture, light, agitation, gravity, pH, and package.

The concept of accelerated stability testing in high temperature is bases on Arrhenius equation

ln K = -∆E/RT+lnA
K = degradation rate/s
A= frequency factors/s, (Specifically relates to molecular collision, deals with the frequency of
molecules that collide in the correct orientation and with enough energy to initiate a reaction. It
is a factor that is determined experimentally, as it varies with different reactions.
∆E=activation energy (kJ/mole)
R = universal gas constant (0.00831 kJ/mol)
T = absolute temperature (K)

This equation describes the relationship between storage temperatures and degradation rate.
Using Arrhenius equation, projection of stability from the degradation rates observed at high
temperatures for some degradation processes can be determined.

When the activation energy is known, the degradation rate at low temperatures may be projected
from those observed at “stress” temperatures.

Expiration Dating

The initial concentration of a drug decomposing according to first-order kinetics is 94 units/mL.

The specific decomposition rate, k, obtained from an Arrhenius plot is 2.09 × 10-5 hr-1 at room
temperature, 25°C. Previous experimentation has shown that when the concentration of the drug
falls below 45 units/mL it is not sufficiently potent for use and should be removed from the
market. What expiration date should be assigned to this product?
Shelf Life and Expiration Dating

Shelf life (also referred to as the expiration dating period) is the time period during which a drug
product is expected to remain within the approved specification for use, provided that it is stored
under the conditions defined on the container label.

Expiration date is the date placed on the container label of a drug product designating the time
prior to which a batch of the product is expected to remain within the approved shelf-life
specification if stored under defined conditions and after which it must not be used.
Important graphs related to the accelerated stability testing:

Fig. Accelerated breakdown of a drug in aqueous solution at elevated

temperature.

Fig. Arrhenius plot for predicting drug stability at room temperatures.

Fig. Time in days required for drug potency to fall to 90% of original value.
These times, designated t90, are then plotted on a log scale.

Fig. A log plot of t90 (i.e., time to 90% potency) on the vertical axis against
reciprocal temperature (both Kelvin and centigrade scales are shown) on the
horizontal axis.