Factors Affecting Reaction Rates

Chemical Kinetics:.
I-The study of the Rates of Chemical Reactions:

how fast do chemical reactions proceed to form products
II. The study of Reaction Mechanisms-
the steps involved in the change from reactants to products.
Factors affecting Reaction Rates: Concentration of Reactants, Presence of a
Catalyst, Temperature, Surface Area of Reactants
Definition of Reaction Rate

H2 (g) + I2 (g) → 2 HI (g)
Reaction Rate: increase in the molar concentration of a product per unit time OR
decrease in the molar concentration of reactant per unit time
The Reaction Rate decreases as the reaction proceeds. Reason: the concentration of
reactants decreases. Any substance in the reaction can be used to express the Rxn.Rate
H2 (g) + I2 (g) → 2 HI (g)
Where -a, -b, c, d are the stoichiometric coefficients and is negative for
reactants and positive for products
Q1. For the hypothetical reaction shown below, write a rate expression based on each
reactant and product: 3 A + B → 2 C + 4 D
Rate based on A =
Rate based on B =
Rate based on C =
Rate based on D =
Q2 Consider the following reaction:

H2O2 (aq) + 3 I– (aq) + 2 H+ (aq) → I3 – (aq) + 2 H2O(l)
In the first 10.0 seconds of the reaction, the concentration of I– dropped from 1.000
M to 0.868 M.
a) Calculate the average rate of this reaction in this time interval
b) Predict the rate of change in concentration of H+ during this time interval.
RATE DETERMINATION
Rate determination is done by monitoring the change in concentration of reactant or

product over time.
Method: Withdraw samples from the reaction vessel at various times and analyze
some of their physical or chemical properties that give information on the
concentrations present.
Properties appropriate and easy to monitor

1. Color (if product or reactant absorbs light)
3. Oxidation State (using an electrochemical cell)
5. Volume, at constant p and T
(useful, if: - gaseous reactants and/or products are present
and - number of moles of reactants not equal number of moles of products)
6. Pressure, at constant V and T (useful, if: - gaseous reactants and/or products are
present, and - number of moles of reactants not equal number of moles of products)
7. Density (useful if : d(reactants) not equal d(products)
Properties not appropriate to monitor
2. Flammability ( difficult to measure quantitatively)
4. Mass(mass is conserved in a chemical reaction)
Analyzing either concentration of reactants or products over a period of

time. by different techniques as : titrations, formation of acidic or basic
products or ppt. quenching quickly i.e cooling a sample of the reactant or
product, or spectrophotometry, measuring color changes, measuring
pressure increase of the formation of a gas (holding the volume and
temperature constant)
Rate Law
In 1864 Peter Waage and Cato Guldberg pioneered the development of Chemical
Kinetics by formulating the law of mass action.
Law of Mass Action
The rate of an elementary reaction (a reaction that proceeds through only one transition
state or one mechanistic step) is proportional to the product of the concentrations of the
participating molecules.
Peter Waage Guldberg
Rate Law Equation
Rate will always be proportional to the product of the concentrations

of the reactants, where these concentrations are raised to some exponential values
Rate Laws and Order of Reaction
Experimental evidence has shown that the rate of a reaction is exponentially proportional
to the product of the concentration of the reactants (other factors held constant)
k is the rate constant or proportionality constant that is determined

experimentally and valid only for the temperature specified
The exponents are also called the individual orders of reaction tthat show the
dependence of the rate on the initial concentration of a particular reactant
Order of a Reaction
➢ The sum of the powers of the concentration terms ( + )
in the rate equation is known as the overall order of the
reaction.
➢ ,  are called the partial orders w. r. t the reactants A and
B respectively.
➢ The order of a reaction generally has a value 0 to 3
➢ Order can also have fractional value e.g. decomposition
of acetaldehyde: CH3CHO → CH4 + CO,
➢rate = k [CH3CHO]3/2 order = 3/2 or 1.5
➢Order is different from the stoichiometric coefficient and
needs to be determined experimentally.
Unit of Rate Constants of Reaction
Rate units=Concentration . time-1
e.g. mol L-1 sec-1 or mol dm-3 sec-1
Gaseous reactions: Pressure time-1 e.g. torr sec-1
Units of rate constant k
For a 0th order reaction: Rate = k
k = rate = [conc.] time-1
For a 1st order reaction: Rate = k [conc.]
k = rate/[conc.] = [conc.] time-1/[conc.] = time-1
For a 2nd order reaction: Rate = k [conc.]2
k = rate/[conc.] 2 = [conc.] time-1/[conc.] 2 = [conc.]-1 time-1
For a nth order reaction: Rate = k [conc.]n

k = rate/[conc.] n = [conc.] time-1/[conc.] n = [conc.]1-n time-1
Overall Reaction Example Units of k Simplified
Order Units of k
1 Rate=k[A] M/s/M s–1
2 Rate=k[A]2 M/s/M2 M –1 s–1
3 Rate=k[A]3 M/s/M3 M–2 s–1

:
Rate can be expressed in three different ways
(i) Initial rate
(ii) Average rate
(iii) Instantaneous rate
Rate changes with time hence expressing
the rate as an instantaneous rate is preferable.
Instantaneous rate means rate at a particular
instant (infinitesimal change in time) i.e.
Concentration
 d[concentration]
Rate =
dt
Time
Instantaneous rate of reaction
It is the change in the concentration of reactants or products per
unit time at that particular instant
Average rate of reaction – the change in concentration of

a reactant or product over time; is the absolute value of the
slope of the secant (a line between two points on a curve)
Instantaneous rate of reaction – the speed at which a
reaction is proceeding at a particular point in time; is the
slope of the curve at that point (the slope of the tangent to
a curve at a particular point)
Initial Rate
The initial rate is the instantaneous rate when the reaction starts.
This is of interest experimentally because it is the easiest time for
us to know the exact concentrations of the different species in
solution.
If the quantity change is immeasurable …Rate or

Reaction = 1/Time Taken for the Reaction
Thank you

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Chemical Kinetics:.

I-The study of the Rates of Chemical Reactions:

Definition of Reaction Rate

Q2 Consider the following reaction:

Rate determination is done by monitoring the change in concentration of reactant or

Properties appropriate and easy to monitor

Analyzing either concentration of reactants or products over a period of

Peter Waage Guldberg

Rate Law Equation

Rate will always be proportional to the product of the concentrations

k is the rate constant or proportionality constant that is determined

For a nth order reaction: Rate = k [conc.]n

1 Rate=k[A] M/s/M s–1

2 Rate=k[A]2 M/s/M2 M –1 s–1

3 Rate=k[A]3 M/s/M3 M–2 s–1

Average rate of reaction – the change in concentration of

If the quantity change is immeasurable …Rate or

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