`Part III: TEACHING-LEARNING ACTIVITIES (TLA)

TLA1: Reading Materials

Law of mass action

- The substances that influence the rate of reaction are usually one or more of
the reactants but can occasionally include products.

- Catalysts, which do not appear in the balanced overall chemical equation,

can also influence reaction rate.

- The rate law is experimentally determined and can be used to predict the
relationship between the rate of a reaction and the concentrations of reactants.

Differential and Integral Rate Laws

 Measuring instantaneous rates (particularly initial rates) is the most direct

way of determining the rate law of a reaction, but it is not always
convenient, and it may not be possible to do so with precision.

- If the reaction is very fast, its rate may change more rapidly than the
time required to measure it; the reaction may be finished before even
an initial rate can be observed.

- In the case of very slow reactions, observable changes in

concentrations occur so slowly that the observation of a truly
"instantaneous" rate becomes impractical.

 The ordinary rate law (more precisely known as

the instantaneous or differential rate law) shows how the rate of a reaction
depends on the concentrations of the reactants.

- However, for many practical purposes, it is more important to know

how the concentrations of reactants (and products) change with time.

- For example, when carrying out a reaction on an industrial scale, it is

important to know how long it will take for, as an example, 95% of
the reactants to be converted into products. This is the purpose of
an integrated rate law.

Rate law of General Equations

Some Reactions and their Experimental Rate Laws

Rate Law

- This expresses the rate of a reaction in terms of the concentrations of the reactants
raised to an Experimentally Determined Power.

- The exponent on each concentration term is called the order of the reaction with
respect to that particular reactant.

- The sum of the exponents in the rate law is called the order of the reaction.

- The powers on the concentration terms in a rate law are NOT the stoichiometric
coefficients from the balanced equation!
Rate Law

One can, therefore, conclude that

Rate ∝[NH4+] or first-order in terms of ammonium
Rate ∝[NO2−] or first-order in terms of nitrite

By combining the two relationships

Rate ∝[NH4+][NO2−]

Rate=k [NH4+][NO2−]
This equation is called the rate law, and k is the rate constant

Rate=k [NH4+][NO2−]

The sum of the exponents of the reactants is the overall order of the reaction
The reaction is second-order overall

- Although the exponents in the rate law are often the same as the coefficient in the
balanced reaction, this is not necessarily the case.

- The values of these exponents must be determined experimentally.

- Most reaction orders are 0, 1, or 2. However, they may also be in fractional orders.

- The rate of the reaction depends on the concentration but the rate constant, k, does
not.
k is only dependent on temperature

Sample Problem 1
Sample Problem 2
Sample Problem 3

Order of Reaction Rate

1. The reaction is first order in a reactant

- If the concentration of a particular component is doubled, the rate
doubles and triples when the concentration triples
2. If the reaction is second order with respect to a component
- If the rate is second order with respect to a particular component,
doubling its concentration increases the rate by a factor of 22 = 4
- Tripling its concentration increases the rate by a factor of 32 = 9
3. If a reaction is zero order with respect to a component
- If a reaction is zero order in a particular reactant, changing its
concentration will have no effect on the rate as long as the reactant is
present.

K, rate constant calculation

Sample Problem 1

Integrated Rate Law

Change of Concentration with time for the First-Order Reactions

Derivation of the integrated rate law for First order reactions

Sample Problem 1
Half-Life

- Another concept that is important to understand with respect to reaction rate

is the half-life. Half-life (t1/2) is defined as the time required for half of the
original amount of A to decay (or react). When the reaction has reached t =
half-life, t1/2, then [A] would be equal to ½ [A]0

- Note that with a first-order reaction, the half-life has a fixed value that is not
dependent on the concentration of the reactant. A first-order reaction is the
only reaction type where [A] is not included in the half-life expression.

- Radioactive decay is a first-order reaction.

Sample Problem 1
Zeroth-Order Reactions

- The integrated rate law for a zeroth-order reaction also produces a straight line and
has the general form
[A] t=[A]0−kt

- Although it may seem counterintuitive for the reaction rate to be independent of the
reactant concentration(s), such reactions are common. They occur most often when
the reaction rate is determined by available surface area.
- An example is the decomposition of N2O on a platinum (Pt) surface to produce
N2 and O2, which occurs at temperatures ranging from 200°C to 400°C.
Sample Problem
1. Using the integrated form of the rate law, determine the rate constant k of
a zero-order reaction if the initial concentration of substance A is 1.5 M and
after 120 seconds the concentration of substance A is 0.75 M.
Solution:
[A]t=[A]0−kt

0.75 = 1.5 - 120k

k = 0.75/120
k = 0.00635M/s

Second Order Reactions

Sample Problem 1
Sample Problem 2

Formula for Integrated Rate Law