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Module in 2: General Chemistry

1. The document discusses chemical kinetics, specifically rate laws and order of reaction. It defines rate laws and explains how they are determined experimentally based on how reaction rates change with changing reactant concentrations. 2. Methods for determining the order of a reaction are described, including using initial rate data from multiple experiments where concentrations of one reactant are varied while others are held constant. This allows calculating the order of each reactant. 3. First-order reactions have a characteristic half-life, defined as the time for half the starting material to react. The half-life of a first-order reaction is calculated to be 0.693/k, where k is the rate constant.

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201 views

Module in 2: General Chemistry

1. The document discusses chemical kinetics, specifically rate laws and order of reaction. It defines rate laws and explains how they are determined experimentally based on how reaction rates change with changing reactant concentrations. 2. Methods for determining the order of a reaction are described, including using initial rate data from multiple experiments where concentrations of one reactant are varied while others are held constant. This allows calculating the order of each reactant. 3. First-order reactions have a characteristic half-life, defined as the time for half the starting material to react. The half-life of a first-order reaction is calculated to be 0.693/k, where k is the rate constant.

Uploaded by

riza amores
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© © All Rights Reserved
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MODULE in

GENERAL CHEMISTRY 2
CHEMICAL KINETICS
Rate Law and Order of Reaction

(GRADE 12)

WEEK 3
MARCH 23 - MARCH 27, 2020
CHEMICAL KINETICS
At the end of the lesson the learner should be able to:
1. State and explain rate law
2. Identify the order of chemical reaction.

What is a Rate Law?


 It is an equation derived from a reaction which gives its rate as a function of reactant
concentration
 To determine the rate law we measure the rate at different starting concentrations
 Rate laws are always determined experimentally
 Reaction order is always defined regarding reactant (not product) concentrations
 The order of a reactant is not related to the stoichiometric coefficient of the reactant in the
balanced chemical equation

TYPES OF RATE LAW:


1. Differential rate law (simply called rate law)
 Shows hiw the rate of a reaction depends on concentration
2. Integrated rate law
 Shows how the concentration of species in the reaction depend on time
Example:
F2 (g) + 2ClO2 (g) -----> 2FClO2 (g)
rate = k [F2][ClO2]
 In general, rates of reactions increase as concentrations increase since there are more
collisions occuring between reactants
 The overall concentration dependence of reaction rate is given in a rate law or rate
expression
The general rate law for a reaction
Rate = k [A]m [B]n
Where:
[A] & [B] represent the reactants
The exponents m and n are called "reaction orders"
The proportionality constant k is called the rate constant
The overall reaction order is the sum of the reaction orders = m + n

Example:
Consider the following reaction: NH4+ (aq) + NO2- (aq) -----> N2 (g) + 2H2O (l)
The following observations were made:
as [NH4+] doubles the rate doubles with [NO2-] constant
as [NO2-] doubles the rate doubles with [NH4+] constant
The rate of reaction can be written as:
Rate = k[NH4+][NO2-]
The overall order of the reaction is m + n = 1 + 1 = 2, second order reaction

How to determine the Order of Reaction


Order of reaction involving single reactant
A -----> products
The general form of the rate expression
Rate = k[A]m
The power of the concentration of A is called order of the reaction
If m =0 zero order reaction
m =1 first order reaction
m =2 second order reaction
 Coefficients in the balancen equation cannot be used to determine the order of reaction
becaise there are any different ways a reaction can be balanced.
Method of Initial Rates
 One method to find the order of reaction is to measure the initial rate at t = 0 as a function
of the concentration of reactant
 You will be given a series of varying concentrations, and a rate and from this asked to
determine the individual reaction rates
Example:
C3H6O + Br2 -----> C3H5OBr + HBr
Rate = [C3H6O]m [Br2]n
Using the following initial rates data, it is possible to calculate the order of the reaction
for baoth bromine and acetone:
Experiment [C3H6O] [Br2] Initial rate (M/s)
1 0.1 M 0.1 M 1.64 × 10-5
2 0.2 M 0.1 M 1.64 × 10-5
3 0.1 M 0.2 M 3.29 × 10-5
To calculate the order of the reaction for bromine, notice that experiments 1 and 2 hold the
concentration of acetone constant while doubling the concentration of bromine.
The initial rate of the reaction is unaffected by the increase in bromine concentratio , so the
reaction is zero order in bromine.
We can prove this mathematically by taking the ratio of the rates from experiments 1 & 2:
Rate 1 = k [C3H6O]m[Br2]n = k (0.1 M)m (0.1 M)n
Rate 2 = k [C3H6O]m[Br2]n = k (0.2 M)m (0.1 M)n
1.64 × 10-5 = [0.1 M]m 1= 2 m = In 1/2 = 0
1.64 × 10-5 [0.2 M]m

 As you can see in the above equations, by holding the concentrations of all but one
soecies constant between two experiments, you can calculate the order of the reaction
with a single reactant at a time.
 By similar reasoning, we can conclude that because the rate of reaction doubled when the
concentration of acetone was doubled (cf. experiments 1 and 3), the reaction must be first
order in acetone.
 However, had the rate quadrupled or octuplet with a doubling of the acetone
concentration, the reaction would have been second or third order in acrtone,
respectively.
 In practice, you will likely never see a reaction with an irder higher than 3.
 If you calculate an order higher than 3 for a reaction, double check your math because
that is highly unusual.
 If you compute a fractional power for a reactants order, do not be discouraged; they are
quite common (especially half-order reactions).
 To calculate the value of k, the rate constant, you simply plug into the rate law the values
of the concentrations, the orders, and the rate of the reaction from any one of the three
experiments.
 All thr three experiments should give a value of 1.64 × 10-4 /s.

Half-life of a First-Order Reaction

 A half-life is a time it takes for one-half of the starting material to be transformed into
its products.
 You will hear half-life associated with radioactive decay phenomena (which follows the
first order kinetics), but the term can be applied to any reaction
 The half-life of a reaction not only depends on the rate constant of the reaction (those
with larger k's have shorter half-lives) but also on the integrated rate law for the reaction
 To derive the form of the half-life expression for a first order reaction, we start with its
integrated rate law, and then substitute the value 0.5 for the ratio of [A] to [A]o
In [A] = kt + In [A]o or In [A] / [A]o = -kt
In 0.5 = -kt1/2 therefore: t1/2 = In 2/ k = 0.693/ k
Example:
A certain first-order reaction has a half-life of 10.0 minutes.
a. Calculate the rate constant for the reaction
b. How much time is required for this reaction to be 80% complete

Solution:
a. Using the equation: t1/2 = 0.693/ k k= 0.693/t1/2 = 0.693/10 min. = 0.0693/min
b. Use the integrated rate law:
In [A]o / [A] = kt

If the reaction is 80% complete, 80% of the reactant has been consumed, leaving 20% in the
original form:
[A]o/ [A] = 1/20 = 5
In (5) = 0.0693/min
(t) t= 23.22 minutes
Therfore: It takes 23.22 minutes for this reaction to reach 80% cimpletion

Second-Order Rate Laws:


aA -----> products
Rate law in second order is:
Rate = ∆[A] / ∆t = k[A]2
The integrated second-order rate law is :
1/[A] = kt + 1/ [A]o
Half-life of second-order reaction has elapsed (t = t1/2)
[A] = [A]o / 2 substitute this equation to the integrated second-order rate law
t1/2 = 1/ k[A]o

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