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Reaction
Chemical Kinetics
The area of chemistry concerned with the speeds, or rates at which a
chemical reaction occurs
Kinetic = movement/ change
Reaction rate is the change of concentration of a reactant or a
product with time (M/s)
Reactants [A] products [B]
The reactants are consumed while products are formed
Rate = -[A]
t
Rate = [B]
t
Example
In aqueous solution, molecular bromine reacts with formic acid (HCOOH) as follows:
Br2 (aq) + HCOOH (aq) 2Br- (aq) + 2H+ (aq) + CO2 (g)
Measuring the change (decrease) in bromine concentration at some initial time and then at some
final time enables us to determine the average rate of the reaction during that interval
Average rate = - [Br2]
t
= - [Br2]final [Br2]initial
tfinal - tinitial
The instantaneous rates of the reaction between molecular bromine and formic
acid at t = 100 s. 200 s and 300 s are given by the slopes of the tangents at these
times
From the graph, we can conclude that the rate of reaction is directly proportional to Br2
concentration, rate = k[Br2], where k is known as the rate constant (a constant of proportionality
between the reaction rate and the reaction of reactant)
Rearranging the equation, we get k = rate, where k is in 1/s or s-1
[Br2]
Instantaneous Rate: The rate at a single moment, and it is given by the slope of a line tangent to the curve
defined by the change in concentration versus time
Example
Consider the following data for the kinetics of this reaction. Determine the rate law and rate
constant for this reaction of these experiments.
Experiment
3.0 x 10-3
9.0 x 10-7
9.0 x 10-3
2.7 x 10-6
From the data, the initial concentration triples from the first to the second exp:
The rate of reaction will not change as the reactants are consumed. The integrated rate law for
this type of kinetics is given by [A]t = [A]0 kt
Rearrange this equation slightly and compare to the equation for a straight line with the form
y = mx + b
or
[A]t = [A]0e-kt
[A]0
[A]0 represents the initial concentration of the reactant at time t = 0. With these equations, if
we know the rate constant and the initial concentration, we can predict the concentration
at any subsequent time.
Example
The photodissociation of ozone by ultraviolet light in the upper atmosphere is a first- order reaction with a rate
constant of 1.0 x 10-5 s-1 at 10 km above the planets surface.
O3 + hv O + O2
Consider a laboratory exp in which a vessel of ozone is exposed to UV radiation at an intensity chosen to mimic
the conditions at that altitude. If the initial O3 concentration is 5.0 mM, what will the concentration be after 1.0
day?
Solution:
24
1.0 day x 1 x
60
1
60
x 1 = 8.6 x 104 s
[O3] = [O3]0e-kt
= 5.0 mM (e-(1.0 x 10-5)(8.6 x 104))
= 2.1 mM
1
[X]t
1 = kt
[X]0
where, [X]t is the concentration of X at time t and [X]0 is the initial concentration
Second- order reaction is a reaction whose rate depends on the concentration of one reactant
raised to the second power or on the concentrations of two different reactants, each raised to the
first power.
Half- Life
The half- life of a reactant is the time it takes for its concentration to fall to one- half its original
value. Although this quantity can be defined for any reaction, it is particularly meaningful for firstorder reactions
1
t1/2 = ln
0
0/2
or
t1/2 = ln 2 =
0.693
Half- life of a first- order reaction is independent of the initial concentration of the reactant. Thus,
it takes the same time for the concentration of the reactant to decrease from 1.0 M to 0.50 M,
say as it does for a decrease in concentration from 0.10 M to 0.050 M
A plot of [A]t vs time for the first- order reaction A products. The half- life of the reaction is 1 min. After the
elapse of each half- life, the concentration of A is halved
Example
The rate constant, k, for the thermal decomposition of ozone in the dark at 25C is just
3 x 10-26 s-1. What is the half life of ozone under these conditions?
Solution:
From the units of the rate constant, this is a first- order reaction.
t1/2 = 0.693 = 0.693
3 x 10-26 s-1
2 x 1025 s
Summary of the Kinetics of Zero- Order, First- Order, and Second- Order
Reactions
Any molecule in motion possesses kinetic energy; the faster it moves, the greater the kinetic
energy. But a fast- moving molecule will not break up into fragments on its own. To react, it must
collide with another molecule. When molecules collide, part of their kinetic energy is converted
to vibrational energy.
If the initial kinetic energies are large, then the colliding molecules will vibrate so strongly as to
break some of the chemical bonds. This bond fracture is the first step toward product formation.
If the initial kinetic energies are small, the molecules will merely bounce off each other intact.
There is some minimum collision energy below which no reaction occurs. Lacking this energy, the
molecules remain intact and no change results from the collision
a) Exothermic process
b) Endothermic process
Ae-Ea/RT
ln k = ln A Ea
RT
Ea is the activation energy of the reaction (in kJ/mol), R is the gas constant (8.314 J/K.mol). The
quantity A represents the collision frequency and is called the frequency factor
For example, 2SO2 + O2 2SO3 indicates that for every two molecules (g-moles, lb-mole) of O2
reacts to produce two molecules (g-moles, lb-moles) of SO3. A valid stoichiometric must be
balanced.
The stoichiometric ratio of two molecular species participating in a reaction is the ratio of their
stoichiometric coefficients in the balanced reaction. This ratio can be used as a conversion factor
to calculate the amount of a particular reactant (or product) that was consumed (or produced),
given a quantity of another reactant of product that participated in the reaction
For 2SO2 + O2 2SO3, you can write the stoichiometric ratios
or
Example
Consider the hydrogenation of acetylene to form ethane:
C2H2 + 2H2 C2H6
and suppose that 20.0 kmol/h of acetylene and 50.0 kmol/h of hydrogen are fed to a reactor. The
stoichiometric ratio of hydrogen to acetylene is 2:1 and since the ratio of H2 to C2H2 in the feed is
2.5:1 (50:20), hydrogen is fed in a greater-than-stoichiometric proportion to acetylene. Acetylene is
therefore the limiting reactant. Since it would take 40.0 kmol H2/h to react completely with all the
acetylene fed to the reactor, (nH2)stoich = 40.0 kmol/h
Thus, fractional excess of H2 = (50.00 40.0) kmol/h
40.0 kmol/h
= 0.25 (25% excess hydrogen in the feed)
f = moles reacted
moles fed
The fraction unreacted is accordingly 1- f. If 100 moles of a reactant are fed and 90 moles react, the
fractional conversion is 0.90 (the percentage conversion is 90%) and the fraction unreacted is 0.10.
If 20 mol/min of a reactant is fed and the percentage conversion is 80%, then (20)(0.80) = 16
mol/min has reacted and (20)(1-0.80) = 4 mol/min remains unreacted.