UNIT FOUR: CHEMICAL KINETICS

CHEMICAL KINETICS: is the study of rate or speed of a chemical reaction.

-speed of reaction means the rate at which the concentrations of reactants and products change.
Example: A + 2B 3C

RATE OF REACTION:
 Measures the decrease in concentration of reactants or the increase in concentration of products.
 Measures how fast a reactant is consumed/used up or how fast a product is formed.
 Measures the speed at which reactants disappear or products appear during a chemical reaction.
 The rate at which the reactants are transferred in to products.
 Rate of reaction is the change in concentration of a reactants or products per unit time.
∆C Cf −Ci
Rate = =
∆t tf −ti

For the reaction: A + B C + D,

The rate of reaction in terms of disappearance of reactants expressed as:

−∆ A −∆ B
Rate = =
△t △t

The minus sign indicates a decrease in concentration of Aor B with time. Since the concentration of A
or B decreases with timeinterval,the value of ∆Aor ∆Bare all negativequantity.Af<Ai OR
Bf<Bi

The rate of reaction is always positive quantity,so a minus sign is needed in the rate expression to make
the rate positive.

The rate of reaction in terms of appearance of products expressed as:

The rate of product formation does not require a minus sign because Δ[C] or Δ[D]is a positive
quantity (the concentration of C or Dincreases with time).

∆C ∆ D
Rate= = , since the concentration of C or D increases with time, the value of ∆C or ∆D
△t △t
are all positive. Since Cf>Ci OR Df>Di
−1
The units of rate aremol L−1 S−1 or mol dm 3−¿ S ¿

The graph below show how the concentrations of A and B change during the course of the reaction:
A B
A is used up and its concentration falls (decreases) while B is formed and its concentration increases.

B

A

Time, t

Rate A and Rate B have opposite signs because B increases over time while A decrease over time. But the
rate of reaction is always positive quantity.

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 UNIT FOUR: CHEMICAL KINETICS

Example:The following data was obtained during an experiment:

A B
Time(s) B(molL-1)
0 0
300 0.02304
900 0.03948
1500 0.0472
a) Plot a graph, showing the B vs time
b) Calculate the average rate of appearance of B from 0 to 300 second
c) Calculate the average rate of appearance of B from 300 to 900 second
d) Suggest reason, why there are changes in the concentration as time increases?

Reaction Rate and stoichiometry:

For the reaction: aA + bB cC + dD, where a, b, c and d are coefficients of A, B, C and D respectively.
−1 Δ [ A ] −1 Δ [ B ] 1 Δ [ C ] 1 Δ [ D ]
Rate = = = =
a Δt b Δt c Δt d Δt

EXAMPLES:Write the rate expressions for the following reactions in terms of the disappearance of the
reactants and the appearance of the products:

(a) I2(aq) + OCl2(aq) l2(aq) + OI2(aq)

(b) 3O2(g) 2O3(g)
(c) 4NH3(g) +5O2(g) 4NO(g) + 6H2O(g)
Solution
(a) Because each of the stoichiometric coefficients equals 1,
Rate = - Δ[I2] = - Δ[OCl2] = Δ[Cl2] = Δ[OI2]
Δt Δt Δt Δt
(b) Here the coefficients are 3 and 2, so
Rate = -1 Δ[O2] = 1 Δ[O3]
3Δt 2Δt
(c) In this reaction
Rate = -1 Δ[NH3] = -1 Δ[O2] = 1Δ[NO] = 1Δ[H2O]
4Δ t 5Δ t4Δ t6Δ t
Practice Exercise: 1. Write the rate expression for the following reaction:
a) CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
b) 4NO2(g) + O2(g) 2N2O5(g)
c) 5Br (aq) + BrO3 (aq) + 6H+ (aq)
- -
3Br2(aq) + 3H2O(l)
d) 2C2H6(g)+ 7O2(g) 4CO2(g) + 6H2O(g)
2. Write a balanced equation for a gas-phase reaction whose rate is given by:
Rate = -[SO2] = -1/3 [CO] = 1/2[CO2] = [COS]
t t t t

EXAMPLE: 1.Consider the reaction of nitrogen dioxide with fluorine to give nitryl fluoride, NO 2F.
2NO2(g) + F2 (g) 2NO2F(g)
How is the rate of formation of NO2F related to the rate of reaction of fluorine and NO2?

Solution: Rate of formation of NO2F= 1Δ[NO2F]= -Δ[F2]Δ[NO2F] = -2Δ[F2]

2Δt sΔt Δt Δt

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 UNIT FOUR: CHEMICAL KINETICS

Rate required=coefficient required/

Coefficient given

FACTORS THAT AFFECTING THE RATE OF REACTION

The rate depends on the characteristics of the reactants in a particular reaction. Some reactions are fast and
others are slow, but the rate of any given reaction may be affected by the following factors:

1. Concentration of the reactants:

When the concentration of one or more reactants increases, the rate of reaction also increases.
Because increasing the concentration produces more contact (collision frequency) between the
reacting particles, which results in increasing the rate of reaction.
Example: a) 2HCl(6M) + Mg(s) MgCl2(aq) + H2(g)
b) 2HCl(1M) + Mg(s) MgCl2(aq) + H2(g)
Which of the reactions is fast?
 Reaction a, because this reaction is more concentrated

If you take the same volume of 6M HCl and 1MHCl, there will be more HCl molecules in the 6M HCl.
Therefore, there will be more collision between these molecules and the Mg metal.

2. Temperature of the reactants:

As the temperature of a system increases, the reaction rate increases.
Temperature is a measure of the average kinetic energy of the particles of the substance. As this
result the temperature of the reaction mixture increases, the average kinetic energy of the reacting
particles increases. So, they collide more frequently and with greater energy.
Example: Foods cook faster at higher temperatures than lower ones.
3. Nature of the reactants:
The rate of a reaction depends on the nature of the participating substances. The chemical properties
of a pure substance (reactivity) can affect reaction rate. The substances have more reactive the
reactants, the faster the rate of reaction.
Example:Na + O2 fast reaction
Fe + O2slow reaction

The reactions between covalent compounds are slower than reactions between ionic compounds. Ions are
not present in covalent compounds but characterize ionic compounds. In solutions, ions have a greater
freedom of movement than uncharged molecules. Therefore, reactions between ions are faster than reaction
between covalent molecules.

Example: H2(g) + I2(g) 2HI(g)-------slower

NaOH(aq) + HCl(aq) NaCl(aq) + H2O(aq)-----faster

4. Surface area of solid reactants:

As surface area of solid reactant increases, the rate of a reaction also increases. The smaller the
particle sizes the faster the rate of a reaction.
Example: CaCO3(powder) + 2HCl faster
CaCO3(crystal) + 2HCl slower

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 UNIT FOUR: CHEMICAL KINETICS

Increasing the surface area of the reactants has a higher number of reaction sites. Increasing the
number of site increases the total number of collisions. The greater the frequency of total collisions,
have the greater the frequency of effective collisions. If the frequency of effective collisions increases,
so does the reaction rate.
5. Presence of catalyst:
Catalyst is a substance that speeds up the rate of a reaction but it is not consumed in the reaction.
Catalyst will appear in the reaction mechanism, but it will not appear in the overall chemical reaction
as reactants or products.
Presence of catalyst increases the rate of reaction by lowering the activation energy (Ea).

Ea without a catalyst

Ea with a catalyst

Catalysts are classified as homogeneous or heterogeneous.

A homogeneous catalyst exists in the same phase as the reacting molecules
Example: C2H5OH (l) + CH3COOH (l) H 2 SO 4 (l)CH3COOC2H5 (l) + H2O (l),
→

A heterogeneous catalyst exists in a different phase, usually as a solid.

Example: 2SO2 (g) + O2 (g) V 2O 5(s)2SO3 (g)
→

Chemical catalysts can be also classified as positive or negative:

Positive catalyst: speed up the rate of reaction by lowering the activation energy.
2SO2 (g) + O2 (g) V 2O 5(s) 2SO3 (g)
→
Negative catalyst or Inhibitors: slow down the rate of reaction by increasing the activation energy.
−¿(aq)
OCl
−¿¿
(aq) + I
−¿¿
(aq)OH ¿O I −¿¿ (aq) + Cl−¿¿(aq)
→
Enzyme catalyst:Enzymes are biological catalysts that catalyze biochemical reactions in the human body and
other living things.

THEORIES OF REACTION RATE

1.Collision theoryof reaction rates is a theory that assumes that, for reaction to occur,reactant molecules
must collide with energy greater than some minimum value andwith the proper orientation.
The rate of a reaction to be directly proportional to the number of molecular collisions per second, or to the frequency of
molecular collisions:
Rate α number of collisions,
Second
According to collision theory, the more collisions there are, the faster the rate of reaction. This simple
relationship explains the dependence of reaction rate on concentration.
The minimum energy of collision required for two moleculesto react is called the activation energy, Ea. The
value of Ea depends on the particular reaction.

2.Transition-state theory: explains the reaction resulting from the collision of two molecules in terms
of an activated complex. An activated complex (transition state) is a short- lived, high energy state species
that is temporarily formed by the collision of reactant molecules before they form products.

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 UNIT FOUR: CHEMICAL KINETICS

We can represent the formation of the activated complex this way:

O=N + Cl-Cl [O=N----Cl---Cl]
Activated complex
O=N + Cl2 ← [O=N----Cl---Cl] → O=N-Cl + Cl
Reactants Activated complex Products

RATE LAW OR RATE EQUATION

It expressesthe relationship between the rate of reaction and concentration of reactants.
It cannot be determined by examining its balanced equation for the reaction.
It can only be determined by experiments.

ORDER OF REACTION AND RATE CONSTANT

 The rate is directly proportional to the concentration of the reactants to a certain power.
 The order of a reaction is determined from the exponent found in its rate equation.
 The order of a reaction is equal to the power to which the concentration of that reactant is raised to
the rate equation.

For the reaction; Aa + bB cD + dD

Rate α[A]x[B]y, Rate= k[A]x[B]y
Where: [A]&[B]- are reactant concentrations
X & y- are order of the reaction with respect to A & B
K- is proportionality constant or rate constant

 The overall order of reaction is the sum of the orders with respect to each reactant
Overall order= x+y
 The order of reaction values may be small (0), positive, negative or fraction.
 If x= 1, the reaction is first-order in A
 If x= 2, the reaction is second-order in A
 If x= 3, the reaction is third-order in A
 If x= 0, the reaction is zeros-order in A
 If x= 1/2, the reaction is half-order in A, etc

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 UNIT FOUR: CHEMICAL KINETICS

 Zero-order: indicates that the concentration of those reactants does not affect the rate of a
reaction.
 Positive order: indicates that the concentration of that reactants directly affect the rate of a
reaction.
 Negative order: indicates that the concentration of that reactants inversely affect the rate of a
reaction.

Identifying the Order of a Reaction

1. Zero-orderReaction:has a constant rate that is independent of the reactants concentration.
A product
Rate= k [A] ,
0
a0= 1, a≠0
Rate = K
 The unit of rate constant(k) in zero order rate equations are mol L−1 S−1
If the rate is zero-order with respect to a reactant, the rate of the reaction
does not change as the concentration of the reactant changes.

2. First-order Reaction:in the first-order reaction the rate is proportional to the first power of the
concentration.
A product
Rate = k [A]1
 Doubling the concentration of a reactant in the first-order reaction doubles the reaction
rate.
Let the concentration of A be ‘a’
Rate1 = k [a]1
Rate2 = k [2a]1 = 2k [a]1
Rate2=2 x Rate1; because Rate1= k [a]1
 The unit of rate constant in first-order rate equations are the reciprocal time, 1/S or S−1

If the concentration of a reactants doubled, the rate of the reaction also

doubled the order with respect to that reactant is first.

3. Second Order Reaction:In the second-order reaction, the rate is proportional to the
second power (the square) of the concentration of a substance.

A product or A + B product
Rate=k [A] 2
Rate= k [A][B]

In other words, second-order reaction has a rate law in which the sum of the exponents is equal to 2.

Doubling the concentration of the reactants in any second order reaction increases the
reaction rate by a factor of four.
Let the concentration of A is ‘a’
Rate1 = k [a]2
Rate2 = k [2a]2 = 4k [a]2
 Rate2= 4 x Rate1; because Rate1= k [a]2
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 UNIT FOUR: CHEMICAL KINETICS

Similarly, for the rate equation: Rate= k [A] [B]; if we double the concentration of both A & B, the reaction
rate increases by 4 factors. Let the concentrations of A& Bare ‘a’& ‘b’ respectively.

Rate1= k [a] [b]

Rate2 = k [2a] [2b] = 4k [a] [b]
 Rate2= 4 x Rate1; because Rate1= k [a][b]
In second-order reaction the unit of rate constant is L .mol−1 S−1

If the concentration of a reactant is doubled, the rate of the reaction is increased by

a factor of four; the reaction is second order with respect to that component.

Practice Exercise: what happens to the rate of second-order reaction if the concentration of reactant
increases by a factor of four?

4. Third-Order Reaction:in thethird-order reaction, the rate is proportional to the third power (the
cubic) of the concentration of a substance.
Rate=k [A]3 or
Rate= k [A]2[B] or Rate= k [A][B]2or
Rate= k [A][B][C]
In other words third-order reaction has a rate law in which the sum of the exponent is equal to 3.
Doubling the concentration of the reactants in any third order reaction increases reaction rate by a
factor of eight.
A Product
Rate= k [A] 3

Rate1= k [a]
If Rate1= a &Rate2= 2a
Rate1 = k [a]3
Rate2 = k [2a]3= 8k[a]3
 Rate2= 8 x Rate1; because Rate1= k [a]3
Similarly, for the rate equation: Rate= k [A]2[B]; if we double the concentration of both A & B, the reaction
rate increases by 8 factors.

The unit of rate constant in third-order reaction is L2 mol−2 S−1

If the rate is increased by a factor of eight, when the concentration of a reactant is

doubled, the reaction is third-order with respect to that component.

Arrhenius Equation
Rate constants for most chemical reactions closely follow an equation of the form:
k =Ae_Ea /RT
The mathematical equation k=Ae_Ea/RT, which expresses the dependence of the rate constant on temperature,
is called the Arrhenius equation, after its formulator,the Swedish chemist Svante Arrhenius.

Here eis the base of natural logarithms,2.718 . . . ; Eais the activation energy; Ris the gas constant,
(8.314J/(K.mol); and Tis the absolute temperature. The symbol A in the Arrhenius equation, which is assumed

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 UNIT FOUR: CHEMICAL KINETICS

to be a constant, is called the frequency factor. The frequency factor is related to the frequency of collisions
with proper orientation. (The frequency factor does have a slight dependence on temperature, as you see
from collision theory, but usually it can be ignored.)

It is useful to recast Arrhenius’s equation in logarithmic form. Taking the naturallogarithm of both sides of the
Arrhenius equation gives
−Ea
ln k = +ln A, (but ln x= 2.303log x)
RT
−Ea
OR log k= + log A
2.303 RT
Let us make the following identification of symbols:
−Ea 1
ln k =( )¿)+ ln A .This shows that if you plot ln k against , you should get a straight line. The slope of
R T
−Ea
this line is , from which you can obtain the activation energy Ea. The intercept is ln A.
R

lnk log k

You can put the previous equation into a form that is useful for computation.First you write the equation for two different
absolute temperatures T1 and T2. You write k1 for the rate constant at temperature T1 and k2 for the rate constant at
temperature T2.
−Ea −Ea −Ea −Ea
ln k2= ln A and ln k 1= ln A or log k2= log A and log k 1= log A
RT 2 RT 1 2.303 RT 2 2.303 RT 1
You eliminate ln A by subtracting the equations.
−Ea Ea −Ea Ea
ln k2−¿ ln k1 = + ORlogk2−¿ log k1 = + , but ln x = 2.303log x
RT 2 RT 1 2.303 RT 2 2.303 RT 1
lnk 2 Ea Ea logk 2 −Ea −Ea
= ¿) = ¿)or = ¿) = ¿) or
lnk 1 R R logk 1 2.303 R 2.303 R
lnk 2 −Ea −Ea
= ¿) = ¿) Logk 2 Ea Ea
lnk 1 R R = ¿) = ¿)
logk 1 2.303 R 2.303 R

Example

COCENTRATION-TIME EQUATION (Integrated Rate Equation)

1. Zero- order Reaction

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 UNIT FOUR: CHEMICAL KINETICS

The rate of the reaction is independent of the concentration of the reactants.

A Product

−∆ A
Rate = = k[A]0, ---------- [A]0 = 1
△t
The integrated rate law for a zero-order reaction is: [A]= -kt + [A]0
Y = mx + b

∆ [ A]
Slope= = -k
∆t
In this case a plot of [A] versus t gives a straight line of slope –k and intercept [A]0

Half-Life for Zero-Order Reactions

Definition:half-life, t1/2, is time requiredfor the concentration of the reactant A to decrease to half its initial
value.t t½

1
[A]t = [A]0 by definition
2

Integrated rate law for zero-order reactions:

[A] = -kt + [A]0

1
[A]0= -kt1/2 + [A]0 from the integrated rate law
----------
2
1
kt1/2 = [A]0- [A]0
2
[ A ]0
t1/2 =
2k
Therefore, for zero order reaction, the half-life (t1/2) is depend on initial concentration of reactant, [A]0

First-Order Reactions
A first-order reaction is a reaction whose rate depends on the reactant concentration raised to the first power. In a first-
order reaction of the type
A product

−∆ A
Rate= = k[A]and the integrated first-order rate law is: ln[A]t= -kt + ln [A]0
△t

−kt
or log[A]t = + log[A]0
2.303
There are several important things to note about Equation;
1. The equation shows how the concentration of A depends on time. If the initial concentrationof A and the
rate constantk are known, the concentration of A at any timecan be calculated.s

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 UNIT FOUR: CHEMICAL KINETICS

2. Equation is of the form y =mx +b, where a plot of y versus x is a straightline with slope m and intercept b. In
Equation:sln [A] = -kt + ln [A]0
y = mx + b

ln[A]0

∆[A]
ln [A]t slope= ln = -k
∆t

time (t)
Thus, for a first-order reaction, plotting the natural logarithm of concentration versustime always gives a
straight line. This fact is often used to test whether a reaction isfirst order. For the reactionthe reaction is first
order in A if a plot of ln[A] versus time is a straight line. Conversely,if this plot is not a straight line, the
reaction is not first order in A.
3. This integrated rate law for a first-order reaction also can be expressed in terms of aratio of [A] and [A]0 as
follows:
ln¿) = ktor ln¿)= -kt
HALF-LIFE FOR FIRST-ORDER REACTIONS
[ A ]t [ A ]0 kt
Integrated rate law in this form: ln = -kt or log =
[ A]0 [ A]t 2.303
Can be used for easy calculation of half-life
[ A ]t [ A]0 kt 1/2
From the integrated rate law:ln = -kt log =
[ A]0 1/2[ A ]0 2.303

1/2[ A ]0 kt 1/2
ln = -kt1/2 log2 =
[ A]0 2.303

-0.693 = -kt1/2 2.303log2 = kt1/2, (log2 = 0.301)

0.693 0.693
t1/2 = t1/2 t1/2 = t1/2
k k
Therefore, for a first order reaction,the half-life (t1/2) is independent of initial concentration of reactants,
[A]0(it is constant for a first-order reaction).

Second-Order Rate Laws

For a general reaction involving a single reactant, that is,
aA Product
that is second order in A, the rate law is;
−∆ A
Rate = = k[A]2
△t

The integrated second-order rate law has the form:

1 1
=kt +
At A0

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 UNIT FOUR: CHEMICAL KINETICS

Note the following characteristics of Equation;

1. A plot of 1/ [A] versus time will produce a straight line with a slope equal to k.
2. Equation shows how [A] depends on time and can be used to calculate [A] at any time t, provided k and [A]0 are
known.

1
Slope = k
At

1
A0

Time(t)

Half-Life for Second-Order Reactions

1 1 1 1
From the integrated rate law: = kt + or − = kt
At A0 At A0

1 1
From the of definition of t1/2 = − = kt1/2
1/2 A 0 A 0

A 0−1/2 A 0
= 1 /2 A 0 A 0 = kt1/2

1/2 A 0
= 1/2 A 0 A 0 = kt1/2

1
= A 0 = kt1/2

1
t1/2 =
kA0
Therefore, for second order reactions half-life depends on initial concentration of reactants, [A]0.
Note that the half-life of a second-order reaction is inversely proportional to the initial reactant
concentration. This result makes sense because the half-life should be shorter in the early stage of the
reaction when more reactant molecules are present to collide with each other. Measuring the half-lives at
different initial concentrations is one way to distinguish between a first-order and a second-order reaction.

Reaction Mechanisms
•Most reactions will not proceed in a single step
•The step-by-step pathway by which a reaction occurs is called the reaction mechanism
•A possible reaction mechanism must be consistent with the:
1) stoichiometry of the overall reaction
2) Experimentally determined rate law
•Each step in the mechanism is called an elementary reaction (or process)

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 UNIT FOUR: CHEMICAL KINETICS

Characteristics of Elementary Reactions

•Elementary reactions are classified according to their molecularity. The molecularity is the number of
molecules on the reactant side of an elementary reaction.
•Unimolecularreaction is an elementary reaction that involves one reactant molecule;
•Bimolecular reaction is an elementary reaction that involves two reactant molecules and
•Termolecular reaction is an elementary reaction that involves three reactant molecules.

s
Elementary Step Molecularity Rate Law

A products Unimolecular Rate = k[A]

A+A products Bimolecular Rate =k[A]2
(2A products)
A+ B products Rate = k[A][B]
A+A+Aproducts Termolecular Rate =k[A]3
(3A products)
A+A+Bproducts Rate = k[A]2[B]
(2A + B products)
A + B + C products Rate= k[A][B][C]

•Orders of reaction in the rate law for the elementary reaction are the same as the stoichiometric
coefficients in the balanced equation for the process nottrue for the overall rate law and the overall
balanced equation
•Elementary processes can be reversible reactions; sometimes rates of forward and reverse reactions are
equal (we say that the two reactions are at equilibrium)

Intermediate species can be produced in an elementary reaction which do not appear in either
the overall chemical reaction or the overall rate law; such species produced by one elementary
reaction must be consumed by another
•Sometimes the rate of the overall reaction depends on a single elementary step (a single rate constant);
such a step is called the rate-determining step. The rate-determining step is the slowest step in the reaction
mechanism. Often the reaction mechanism does not have a rate determining step that is the rate of the
overall reaction depends on more than 1 step (more than 1 rate constant).

Overall rate law = the rate of the slowest step

We can now define a reaction mechanism more precisely. It is a series of elementary steps that must satisfy
two requirements:
1. The sum of the elementary steps must give the overall balanced equation for thereaction.
2. The mechanism must agree with the experimentally determined rate law.

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 UNIT FOUR: CHEMICAL KINETICS

Work sheet vI

1. A reaction has rate law expression as,

Rate = k[A]3/2 [B]-1/2

If concentrations of both A and B are increased four times, by what factor does
the rate of the reaction increases?

2. Write the rate expressions for the following reactions in terms of the
disappearance of
the reactants and the appearance of the products:
(a) I2(aq) + OC2(aq) Cl2(aq) + OI2(aq)
(b) 4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

3. Consider the reaction, 4NO2(g) + O2(g) 2N2O5(g)

Suppose that, at a particular moment during the reaction, molecular oxygen is
reacting at the
rate of 0.024 M/s.

(a) At what rate is N2O5 being formed? (b) At what rate is NO2 reacting?

4. The reaction of nitric oxide with hydrogen at 1280°C is, 2NO (g) + 2H2 (g) N2 (g)+
2H2O (g)

From the following data collected at this temperature, determine (a) the rate law,(b)
the rate constant, and (c) the order with respect to each reactant

Exp`t [NO](M) [H 2] (Initial rate)o (Ms-1)

1. 5.o×10 -3 2.0×10-3 1.3× 10 -5

2. 1.0×10 -2 2.0×10-3 5.0 ×10 -5
3. 1.0×10 -2 4.0×10-3 10.0 ×10 -5

5. The decomposition of ethane (C 2H6) to methyl radicals is a first-order reaction

with a rate constant of 5.36×10-4 s-1 at 700°C: C2H6( g) 2CH3(g)
Calculate the half-life of the reaction in minutes.

6. Iodine atoms combine to form molecular iodine in the gas phase I(g) + I(g) I2(g)
This reaction follows second-order kinetics and has the high rate constant
7.0×109M -1s-1 at 23°C.
(a) If the initial concentration of I was 0.086 M, calculate the concentration after
2.0 min.

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 UNIT FOUR: CHEMICAL KINETICS

(b) Calculate the half-life of the reaction if the initial concentration of I is 0.60 M
and if it is 0.42 M.

7. The rate constant of a first-order reaction is 3.46×10 -2 s-1 at 298 K. What is the
rate constant at 350 K if the activation energy for the reaction is 50.2 kJ/mol?

8. Consider the reaction, N2 + 3H2 2NH3

If the rate of decrease in concentration of hydrogen is x mol-1 S-1, then what is the
rate of increase in the concentration of ammonia?

9. A gaseous reaction, 2A(g) + B(g) 2C(g) shows a decrease in pressure from

120 mm to 100 mm Hg in 10 minutes. What is the rate of appearance of C?

10. Consider a reaction, 2A B+C

If the initial concentration of A was reduced from 10 mol L -1 to 8 mol L-1 in 2

hours and then was reduced from 8 mol L -1 to 4 mol L-1 in 4 hours. What is the
order of the reaction?

11. For the reaction, 2SO2(g) + O2(g) 2SO 3(g) the rate of disappearance of
O2 is 2.0x10-4 mol L-1S-1.

a) What is the rate of appearance of SO3?

b) Calculate the rate at which SO2 is used.

12. From the following

a) 1 mol of A and 1 mol of B in a 1L vessel.

b) 2 mol of A and 2 mol of B in a 2L vessel.

c) 0.2 mol of A and 0.2 mol of B in a 0.1L vessel.

I. Which one of the above will produce more products in a given time?

II. Which one will react with the highest rate?

13. Consider the hypothetical reaction,

A2+ B + C AB + AC

it is found that doubling the concentration of A 2 doubles the reaction rate,

tripling the concentration of B triples the reaction rate and doubling the
concentration of C keeps the reaction rate to remain the same.

a) What is the rate law for the reaction?

b) Why concentration of C keeps the reaction rate the same?

14. Given the reaction,

2N2O(g) 2N2(g) + O2(g)

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 UNIT FOUR: CHEMICAL KINETICS

If the rate of decomposition of N2O falls by a factor of three when the concentration
of N2O reduced from 6.0x10-3 mol L-1 to 2.0 x 10-3 mol L-1. What is the reaction
order with respect to N2O?

15. The rate of a second order reaction,

2A products, is 8.0x10 -4 mol L-1 S-1 when the concentration of A is

2.0 mol L-1.

Determine the rate constant of the reaction.

16. Given the following experimental data for the reaction,

NO(g) + NO2(g) + O2(g) N2O5(g)

Exp’t [NO]0,M [NO2]0,M [O2]0,M Initial Rate, MS-1

1 0.10 0.10 0.10 2.1 x 10-2

2 0.20 0.10 0.10 4.2 x 10-2

3 0.20 0.30 0.20 1.26 x 10-1

4 0.10 0.10` 0.20 2.1 x 10-2

a) What is the order with respect to each reactant and the overall order of
the reaction?
b) Determine the rate law for the reaction.

c) Calculate the value of rate constant.

17. The decomposition of N2O5 is given by the equation,

2N2O5(g) 4NO2(g) + O2(g)

The initial concentration of N2O5 is 3.15M when the initial rate of reaction is
5.45x10-5 MS-1 and when the initial concentration of N2O5 is 0.75M the initial rate is
1.35x10-5 MS-1.

a) What is the rate law for this reaction?

b) Calculate the rate constant

18. For the reaction, A C

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 UNIT FOUR: CHEMICAL KINETICS

Use the data given below and calculate the average rate of reaction of A
between the time interval 5 seconds to 20 seconds.

[A], mol 0.20 0.14 0.10 0.071 0.05

L-1

Time (s) 0 5 10 15 20

19. For a chemical reaction, x y,

it is found that the rate of reaction doubles when the concentration of X is

increased four times. What is the order of the reaction?

20. The decomposition of NOCl to NO and Cl 2 has the rate constant of 9.3x10 -5 M-
1 -1
S at 1000C and 1.0x10-3 M-1 S-1at 1300C. What is the activation energy of this
reaction?

21. A second order reaction whose rate constant at 800 0C was found to be 5.0x10-3
L. mol-1S-1 has activation energy of 45 KJ. mol -1. What is the value of rate
constant at 8750C?

22. For a first order reaction, A B,t 1/2 = 1 hr, what fraction of the initial
concentration of Areacts in 4 hrs.

23. 75% of a first order reaction has completed in 32 minutes. What is the half-life
of the reaction?

24. At 250C, the second order rate constant for the reaction,

I- (aq) + ClO- (aq) IO-(aq) + Cl- (aq),

is 6.06x10-2 M-1 S-1. If a solution is initially 3.50x10-3M with respect of each

reactant, what will be the concentration of each reactant present after 300 S?

25. The half-life of a first order reaction is 2.50 hrs. Calculate the value of rate
constant in S-

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