C6H6(l)+Br2(l)→FeBr3C6H5Br(l)+HBr(g)C6H6(l)+Br2(l)→FeBr3C6H5Br(l)

+HBr(g)

Alkyl groups can be introduced onto a benzene ring by the reaction of bgenzene with an alkyl
halide, using aluminum chloride as the catalyst. In the reaction below, benzene reacts with
chloroethane to produce ethylbenzene.

C6H6(l)+CH3CH2Cl(g)→AlCl3C6H5CH2CH3(l)+HCl(g)C6H6(l)
+CH3CH2Cl(g)→AlCl3C6H5CH2CH3(l)+HCl(g)

The reaction of an alkyl halide with an inorganic hydroxide base at elevated temperature
produces an alcohol. The molecular reaction to produce methanol from iodomethane and sodium
hydroxide is shown below.

CH3I(l)+NaOH(aq)→100oCCH3OH(l)+NaI(aq)

Addition Reaction :
An addition reaction is a chemical reaction wherein two or more reactants come together to form
a larger single product.
Addition Reaction Explanation

But only chemical compounds containing multiple bond character can undergo an addition
reaction as a double or triple bond is usually broken to form the required single bonds. An
addition reaction is essentially a reverse of a decomposition reaction wherein a decomposition
reaction is a reaction where one compound decomposes into one or more elements or
compounds. Looking at an example of an addition reaction, hydrochlorination of propane (an
alkene), for which the equation is

CH3CH = CH2 + HCl → CH3C+HCH3 + Cl− → CH3CHClCH3

Types of Addition Reactions
For polar addition reactions there are two classifications, namely:

1. Electrophilic Addition reactions

2. Nucleophilic Addition reactions
For non-polar addition reactions, we have two classifications, namely:

1. Free radical addition reactions

2. Cycloadditions reactions

Electrophilic addition:

An electrophilic addition reaction can be described as an addition reaction in which a reactant

with multiple bonds as in a double or triple bond undergoes its π bond broken and two new σ
bonds are formed.

Nucleophilic addition:

A nucleophilic addition reaction is an addition reaction where a chemical compound with an

electron-deficient or electrophilic double or triple bond, a π bond, reacts with a nucleophile
which is an electron-rich reactant with the disappearance of the double bond and creation of two
new single, or σ, bonds.
A typical addition reaction may be illustrated by the hydrochlorination of propene (an alkene),
for which the equation is CH3CH = CH2 + HCl → CH3C+HCH3 + Cl− → CH3CHClCH3.

Addition of Hydrogen Halides to Alkenes

All alkenes undergo addition reactions with the hydrogen halides. A hydrogen atom
joins to one of the carbon atoms originally in the double bond, and a halogen atom to
the other. For example, with ethene and hydrogen chloride, you get chloroethane:

With but-2-ene you get 2-chlorobutane:

Reaction rates increase as the alkene gets more complicated - in the sense of the number of alkyl
groups (such as methyl groups) attached to the carbon atoms at either end of the double bond.
For example:
Addition to unsymmetrical alkenes

Addition of Halogens: Halogenation of Alkenes

R2C=CR2+X2→R2CX−CR2X

Step 1: In the first step of the addition the Br-Br bond polarizes, heterolytic cleavage occurs and
Br with the positive charge forms a intermediate cycle with the double bond.

Step 2: In the second step, bromide anion attacks any carbon of the bridged bromonium ion from
the back side of the cycle. Cycle opens up and two halogens are in the position anti.

Elimination Reaction
An elimination reaction is a reaction in which atoms are removed as molecules or compounds.
Elimination is generally catalysed by a metal, an acid or base.

Elimination reactions often compete with substitution reactions. In this reaction, a substrate
(typically an alkyl halide) eliminates one equivalent (unit) of acid to form an alkene. Two
possible mechanisms are available for this elimination reaction – E1 and E2 mechanisms.
What is Elimination Reaction?
Elimination reaction is a type of reaction that is mainly used to transform saturated
compounds (organic compounds which contain single carbon-carbon bonds) to unsaturated
compounds (compounds which feature double or triple carbon-carbon bonds).

An elimination reaction is a type of chemical reaction where several atoms either in pairs or
groups are removed from a molecule. The removal usually takes place due to the action of acids
and bases or the action of metals. It can also happen through the process of heating at high
temperatures.

Important Methods of Elimination Reaction

Normally, elimination reactions are distinguished by the kind of atoms or groups of atoms that
leave the molecule. Due to this, there are two main methods involved in this type of reaction;

 Dehydration
 Dehydrohalogenation
In the dehydration method, there is the elimination of a water molecule mostly from compounds
such as alcohol. Sometimes, this method is also called a Beta elimination reaction where the
leaving group and H are placed at neighbouring carbon atoms. On the other hand, in
dehydrohalogenation, there is a removal of a hydrogen atom and a halogen atom.

Some other common types of elimination reactions are α-elimination and γ- and δ-elimination.

Mechanism Of Elimination Reaction

The elimination reaction consists of three fundamental events, and they are;

1. Proton removal.
2. Formation of C-C pi bond.
 3. Removal of the leaving group.
Depending on the reaction kinetics, elimination reactions can occur mostly by two mechanisms
namely E1 or E2 where E is referred to as elimination and the number represents the
molecularity.

E1 Reaction

 In the E1 mechanism which is also known as unimolecular elimination, there are usually
two steps involved – ionization and deprotonation.
 During ionization, there is a formation of carbocation as an intermediate. In
deprotonation, a proton is lost by the carbocation.
 This happens in the presence of a base which further leads to the formation of a pi-bond
in the molecule.
 In E1, the reaction rate is also proportional to the concentration of the substance to be
transformed.
 It exhibits first-order kinetics.

The E1 mechanism shares the features of the SN1 reaction. The initial step is the formation of a
carbocation intermediate through the loss of the leaving group. This slow step becomes the rate-
determining step for the whole reaction.

E2 Reaction

 In an E2 mechanism which refers to bimolecular elimination is basically a one-step

mechanism.
 Here, the carbon-hydrogen and carbon-halogen bonds mostly break off to form a new
double bond.
 However, in the E2 mechanism, a base is part of the rate-determining step and it has a
huge influence on the mechanism.
 The reaction rate is mostly proportional to the concentrations of both the eliminating
agent and the substrate.
 It exhibits second-order kinetics.
The E2 mechanism can generally be represented as below. In the below-mentioned
representation, B stands for base and X stands for halogen.

The rate of the E2 reaction is

Rate = k[RX][Base]

So the reaction rate depends on both the substrate (RX) and the base involved. In the elimination
reaction, the major product formed is the most stable alkene.

Elimination Reaction Example

One of the common examples of elimination reaction is the dehydration of alcohol. Here the
process takes place in the presence of a base such as an ethoxide ion (C2H5O–). It can be
represented as;

“E2 and E1 reactions differ significantly in the nature of the transition states that
determine the regiochemistry of the product”. The E2 pathway involves a transition state
leading from starting material directly to the product. The product forming step of an E1 reaction
is more exothermic than that of an E2 reaction. Thus, the E1 reaction has a relatively early
transition state, closely resembling the carbocation formed in the rate-determining step.

What happens in an elimination reaction?

An elimination reaction is a form of organic reaction in which in either a one- or two-step
process two substituents are separated from a molecule.
What is nucleophilic elimination reaction?
Nucleophilic substitution is a fundamental class of reactions in which an electron-rich
nucleophile selectively binds or attacks the positive or partially positive charge of an atom or
group of atoms as a substitute for a so-called leaving group.
Q3

What is the difference between substitution and elimination reactions?

Substitution reaction involves the replacement of a particular atom or group with another group.
An elimination reaction involves the removal of a group or atom.
What factors affect elimination reactions?
The stability of the carbocation, the form of the leaving group, and the solvent type are the three
essential factors that influence E1 elimination reactions.
Why is alcohol used in elimination reactions?
Most alcohols are weaker acids than water because of which equilibrium lies to the left.
Hydroxyl ions and a proton from alcohol are removed as water molecules here. Water is a better
leaving group than -OH.

Rearrangement Reaction

The term “rearrangement” is used to describe two different types of organic chemical reactions.
A rearrangement may involve the one -step migration of an H atom or of a larger molecular
fragment within a relatively short lived intermediate.

On the other hand, a rearrangement may be a multi-step reaction that includes the migration of
an H atom or of a larger molecular fragment as one of its steps.

In many rearrangements, the migrating group connects to one of the direct neighbours of the
atom to which it was originally attached. Rearrangements of this type are the so-called [1,2] –
rearrangements or [1,2] – shifts. These rearrangements can be considered as sigma-tropic
processes, the numbers 1 and 2 characterizing the subclass to which they belong.

Curtius Rearrangement or Curtius Reaction

Curtius’ reaction involves the heating of an acyl azide which loses nitrogen and then rearranges
to an isocyanate.

RCON3 → R-N=C=O + N2

If the reaction is performed in an alcoholic or aqueous medium, the isocyanate further reacts to
form urethane, amine or substituted urea.

The conversion of acyl azides to isocyanates involves Curtius rearrangement whereas

Curtius reaction involves the conversion of acids to amines, urethane and substituted
urea via Curtius rearrangement.

Acyl azide required for the reaction is obtained as follows.

RCOCl + NaN3 (Sodium azide) → RCON3 (Acyl azide) + NaCl

RCOOC2H5 → RCONHNH2 (Acyl hydrazide) → RCON3 + 2H2O

Claisen Rearrangement

The classical Claisen rearrangement is the first and slow step of the isomerization of
allyl aryl ethers to ortho allylated phenols. A cyclohexadienone is formed in the actual
rearrangement step which is a [3,3]-sigmatropic rearrangement. Three valence electron
pairs are shifted simultaneously.

Cyclohexadienone, a non-aromatic compound, cannot be isolated and tautomerizes

immediately to the aromatic and consequently more stable phenol.
The Claisen rearrangement is a thermal rearrangement of allyl aryl ethers and allyl vinyl ethers
respectively. It may be regarded as the oxa-version of the closely related Cope rearrangement.
Claisen discovered this reaction first on allyl vinyl ethers and then extended to the rearrangement
of allyl aryl ethers to yield o-allylphenols.

Beckmann Rearrangement

In the Beckmann rearrangement , an oxime is converted to an amide . An oxime is easily

obtained by treatment of aldehyde or ketone with hydroxylamine. The OH group of ketoximes
can become a leaving group. The Beckmann rearrangement of cyclic oximes results in lactams.

The comparison of the structure of the starting ketone with those of the products reveals that the
combination of oxime formation and Beckmann rearrangement accomplishes the insertion of an
NH group between the carbonyl carbon and the alpha carbon.

Beckmann rearrangement of the oxime of cyclohexanone is carried out on a very large scale
industrially because the product, caprolactam, is the direct precursor of nylon 6, a versatile
polymer that has many applications: for example, the manufacture of fibres for carpeting and
other textiles. Concentrated sulphuric acid is used as both the acid catalyst and the solvent for the
reaction.
Hofmann Rearrangement

The Hofmann rearrangement results from the treatment of a primary amide with bromine and
hydroxide ion in water, ultimately forming an amine in which the carbonyl group of the starting
amide has been lost. Thus, the Hofmann rearrangement results in a shortening of the carbon
chain by one atom and a change in functional group from an amide to an amine. The Hofmann
rearrangement occurs through a pathway similar to that for the Beckmann rearrangement.

Pericyclic Rearrangement
Pericyclic reactions are defined as the reactions that occur by a concerted cyclic shift of
electrons. This definition states two key points that characterize a pericyclic reaction.

 First point is that reaction is concerted. In concerted reaction, reactant bonds are broken
and product bonds are formed at the same time without intermediates.
 Second key point in pericyclic reactions involves a cyclic shift of electrons. The word
pericyclic means around the circle. Pericyclic words come from the cyclic shift of
electrons. Pericyclic reactions thus are characterized by a cyclic transition state involving
the pi bonds.

The energy of activation of pericyclic reactions is supplied by heat or by UV light. Pericyclic

reactions are stereospecific and it is not uncommon that the two modes of induction yield
products of opposite stereochemistry.
Three features of any pericyclic reaction are intimately interrelated. These are

 Activation – Pericyclic reactions are activated either by thermal energy or by UV light.

However, many reactions that require heat are not initiated by light and vice versa.
 The number of pi bonds involved in the reaction.
 The stereochemistry of the reaction

Photochemical rearrangements

Many photoreactions are known to interconvert isomeric compounds. The term

“rearrangement” is more general than “isomerization” but for the reactions under photochemical
rearrangement will not be concerned with a distinction between these terms.

For convenience, we shall classify primary photochemical rearrangements as the following

types.

1. Cis trans isomerization

2. Sigmatropic rearrangements
3. Electrocyclic rearrangements
4. Structural rearrangements which result from intramolecular cycloadditions.
In a broad sense, all four of these classes are special cases of pericyclic rearrangements and for
concerted reactions, they all may be treated under a unifying framework guided by the rules
derived from orbital symmetry considerations.

Pericyclic Reaction:

Simply put, any concerted reactions featuring a cyclic flow of electrons via a single transition
state are referred to as “pericyclic.”
There are no ions, free radicals, or catalysts in these reactions. The reactions take place under
extreme temperature and photochemical conditions, making molecular orbital symmetry a major
consideration. Pericyclic reactions are stereospecific to a large extent.
In 1965, the scientists Hoffman and Woodward were the first to explain pericyclic reactions
(pericyclic meaning transferring electrons around a circle).

Classification of Pericyclic Reaction

The bond-forming or -breaking processes take place in a concerted way, without the formation of
any intermediate through a cyclic transition state.
There are four types of reactions that are considered as pericyclic reactions.

 Electrocyclic Reaction
 Cycloadditions Reaction
 Sigmatropic Reaction
 Group Transfer Reaction
Concerted reactions are pericyclic reactions. They are distinguished by the formation or
dissolution of bonds in a single coordinated step via a cyclic transition state involving x or an
electron. Heat is used to activate pericyclic processes in a thermally induced reaction, and
ultraviolet light is used in a photo induced reaction.

Because pericyclic reactions are extremely stereospecific, thermal and photochemical activities
frequently result in molecules with diverse but distinct stereochemistry. Solvents are not used in
pericyclic reactions since there are no ionic or free radical intermediates. Reagents that are
nucleophilic or electrophilic have no effect on the outcome of these reactions.

Electrocyclic Reaction

Electrocyclic reactions are reversible cyclisation processes involving a molecule having

conjugated double bonds. Two pi electrons are used to generate a sigma bond in this method. An
electrocyclic reaction is a reversible reaction in which a conjugated polyene’s ring closes to form
a cycloalkene, or a cycloalkene’s ring opens to form a conjugated polyene. Formation of a
(sigma) bond across the conjugated polyene.
Note: ring formation from an open-chain conjugated system.

Cycloaddition Reaction

Two molecules join to form a ring in a cycloaddition reaction, with two pi bonds being changed
to two sigma bonds in the process. The Diels-Alder reaction, shown below, is the most well-
known cycloaddition reaction.

Two components make a ring when they come together and form two new bonds, one at each
end of both components. This is the most widespread type of pericyclic reaction. It is defined by
two fragments coming together in a ring to produce two new sigma-bonds.

Sigmatropic Reaction

Sigmatropic rearrangements are intramolecular rearrangements in which an atom or a group of

atoms shift from one place to another in a coordinated manner. In organic chemistry, a
sigmatropic reaction is a pericyclic reaction via which one -bond is transformed into another -
bond in an uncatalyzed intramolecular reaction.
Group Transfer Reaction

A group transfer reaction is a pericyclic process in organic chemistry in which one or more
groups of atoms are transferred from one molecule to another. The ene reaction, in which allylic
hydrogen is transferred to an alkene, is the most well-known group transfer reaction.

Group transfer reactions, unlike other pericyclic reaction types, do not have a particular
conversion of pi bonds and sigma bonds or vice versa, and are hence less common. They must
follow the Woodward–Hoffmann laws, just as all pericyclic reactions.

Reaction mechanism:

Organic reactions are the chemical reactions that are undergone by organic compounds (the
chemical compounds containing carbon). A few important types of organic reactions are
illustrated below.

There are mainly five types of organic reactions:

1. Substitution reaction
2. Elimination reaction
3. Addition reaction
4. Radical reactions
5. Oxidation-Reduction Reactions.
Substitution Reactions

In a substitution reaction, one atom or a group of atoms is substituted by another atom or a group
of atoms to form a new substance.

For example, the conversion of methane to chloromethane is a substitution reaction as hydrogen

atoms are replaced by chlorine atoms.
CH4 + Cl2 → CH3Cl + HCl

Elimination reaction
There are some reactions which involve the elimination or removal of the adjacent atoms or
group of atoms. After this multiple bonds are formed and there is a release of small molecules as
products.
One of the examples of elimination reaction is the conversion of ethyl chloride to ethylene.
CH3CH2Cl → CH2=CH2 + HCl
In the above reaction, the eliminated molecule is HCl, which is formed by the combination of
H+ from the carbon atom which is on the left side and Cl– from the carbon atom which is on the
right side.

Addition reactions
An addition reaction occurs when two or more reactants combine to form a product without the
loss of any atoms present in the reactants. Addition reaction is common in compounds that have
unsaturated C-C bonds, like double (alkene) and triple (alkyne) bonds. The weaker π bond is
converted into two new stronger σ bonds.
HCl + CH2=CH2→ CH3CH2Cl
Radical reactions
Many of the organic reactions involve radicals. The addition of a halogen to a saturated
hydrocarbon involves a free radical mechanism. There are three stages involved in a radical
reaction i.e. initiation, propagation, and termination. Initially when the weak bond is broken
initiation of the reaction takes place with the formation of free radicals. After that when the
halogen is added to the hydrocarbon a radical is produced and finally, it gives alkyl halide.
Chemical Kinetics

Chemical kinetics, also called reaction kinetics, helps us understand the rates of reactions and
how it is influenced by certain conditions. It further helps to gather and analyse information
about the mechanism of the reaction and define the characteristics of a chemical reaction.
Rate of Formations and Disappearances

In any chemical reaction, as the reaction proceeds, the amount of reactants decreases, whereas
the amount of products increases. One has to understand that the rate of the overall reaction
depends on the rate at which reactants are consumed or the rate at which the products are formed.

If a graph is plotted between the concentration of reactants and products and time, the rate of
formation of products and the rate of disappearance of reactants can be easily calculated from the
slope of curves for products and reactants. The overall rate of the reaction may or may not be
equal to the rate of formations and disappearances.

(a) Product concentration is zero at time t = 0

(b) at time t = 0, both reactants and products are present.

From the graph, it is understood that the slope of the reactants curve is negative and that for
product curve is positive, indicating the concentration of reactants and products decreases and
increases, respectively. We will take a simple reaction as an example to illustrate how the rate of
overall reactions, rate of disappearances of reactants and rate of formation of products are
related.
Let us take the reaction of the formation of water.
2H2 + O2 → 2H2O
From the balanced equation, it is under that for one mole of O2 consumed, 2 moles of H2 will be
consumed, and 2 moles of H2O will be formed. Say, the reaction proceeds for 10 mins, taking 1
mole of H2 and O2 each in the reaction mixture.
2H2 + O2 → 2H2O
t=0110
t = 10 mins 1 – 0.5 1 – 0.25 0.5
Say after 10 minutes, 0.5 moles of H2 is consumed, and according to stoichiometry, 0.25 moles
of O2 is consumed, and 0.5 moles of H2O is formed. Now, let us calculate the rates for H2, O2 and
H2O for the first 10 minutes.
Rate of disappearance of H2
The unit of rate is Moll-1 s-1 because it is concentration/time, and concentration is expressed in
terms of Molarity/mol l-1). It can also be Nm -2/s if the active mass is used in terms of partial
pressures. Depending on other units of time, it can also be mol l-1 min-1 or mol l-1 hour-1 etc.

The Rate Determining Steps

• Chemical reactions can occur in multiple steps. Many reactions don’t actually occur all in
one go as it might look from a chemical equation, they often occur in multiple steps.

Usually the steps involve dependency. The reactant of one step is the product of the previous
step, so each new step can’t take place until the one before it has.

• Only the slowest step of the reaction limits reaction rate. The rate-determining step is the
slowest step of all of the steps of a reaction, it is also sometimes known as the rate-limiting step.
The rate-determining step governs the overall rate of the reaction as it is the slowest. Any step
that follows the rate-determining step will not affect the rate of the reaction, as long as it is faster
than the rate- determining step.

• The reaction mechanism can be used to derive the rate equation. The total number of
moles of the substances in the slowest step and preceding it, will be the same as the order of
reaction for each substance in the rate equation. Any reactant involved in a step that follows
the rate-determining step will not be involved in the rate equation.

• Intermediates are not part of the rate equation. They must be replaced by the reactants
which make it up.

• Catalysts can be part of the rate equation. They can therefore be part of the rate limiting
step.
Worked Example:

F+G+H→A+B

This reaction may occur in these separate steps:

1. F + G→C (first intermediate) FAST

2. C →D (second intermediate) SLOW

3. D + H → A + B

Determine the overall rate equation.

Answer:

• Step 2 is the slowest step, so it is the rate determining step.

• Step 1 is faster than step 2, the rate-determining step, however step 2 depends on the product
of step 1.

• This means that step 1 also has an effect on the rate of the reaction because the rate-determining
step depends on it.

• Therefore all of the reactants of both step 1 and step 2 will need to be included in the rate
equation.

The rate equation for the reaction of F + G + H→ A + B is:

Using the Order of a Reaction to find the Rate Determining Step

The overall reaction for C4H9Br reacting with alkali is:

But there are two possible mechanisms for this reaction:

• A two-step mechanism – The C-Br is broken in the slow step and the fast step is two
oppositely charged ions interacting.
• A one-step mechanism – The C-Br bond is broken while the C-OH is formed.

C4H9Br exists as 3 different isomers and experiments have found that the isomer 1-
bromobutane has a second order mechanism when involved in this reaction. The rate equation is:

This shows that the rate is dependent upon the concentration of bromobutane and the hydroxide
ions, which suggests the mechanism is the second one we looked at, the one step reaction, as this
contains both the bromobutane and the hydroxide ions in the slow step, the rate-determining
step.

Worked example:

The rate equation for a reaction is:

r = k [NO]2[H2]

The overall reaction is:

2NO(g) + 2H2(g) →N2(g) + 2H2O(g)

The following three step mechanism is suggested for the reaction.

Determine the rate-determining step.

Step 1: 2NO → X

Step 2: X + H2 → Y

Step 3: Y + H2 → N2 + 2H2O

Answer:

As the rate equation contains NO and is second order, this suggests that two moles of NO are
used. This means that rate determining step could be step 1.

However, H2 is also included. This means the rate determining step is step 2.

It can’t be step three, as the reaction is first order with respect to hydrogen, but not second order.
If step 3 were involved, then there would be 2 moles of hydrogen.

 If a reactant appears in the rate-determining step, then the concentration of that reactant
will also appear in the rate equation
 For example, the rate equation for the reaction below is rate = k [CH3Br] [OH-]
CH3Br + OH- → CH3OH + Br-

o This suggests that both CH3Br and OH- take part in the slow rate-determining
step
 This reaction is a bimolecular reaction
o Unimolecular: one species involved in the rate-determining step
o Bimolecular: two species involved in the rate-determining step
 The intermediate is derived from substances that react together to form it in the rate-
determining step
o For example, for the reaction above the intermediate would consist of CH 3Br and
OH-

The intermediate is formed from the species that are involved in the rate-determining step
(and thus appear in the rate equation)

Predicting the reaction mechanism

 The overall reaction equation and rate equation can be used to predict a possible
reaction mechanism of a reaction
o This shows the individual reaction steps which are taking place
 For example, nitrogen dioxide (NO2) and carbon monoxide (CO) react to form nitrogen
monoxide (NO) and carbon dioxide (CO2)
o The overall reaction equation is:

NO2 (g) + CO (g) → NO (g) + CO2 (g)


o The rate equation is:

Rate = k [NO2]2

 From the rate equation it can be concluded that the reaction is zero order with respect to
CO (g) and second order with respect to NO2 (g)
  This means that there are two molecules of NO2 (g) involved in the rate-determining
step and zero molecules of CO (g)
 A possible reaction mechanism could therefore be:

Step 1:

2NO2 (g) → NO (g) + NO3 (g) slow (rate-determining step)

Step 2:

NO3 (g) + CO (g) → NO2 (g) + CO2 (g) fast

Overall:

2NO2 (g) + NO3 (g) + CO (g) → NO (g) + NO3 (g) + NO2 (g) + CO2 (g)

= NO2 (g) + CO (g) → NO (g) + CO2 (g)

Predicting the reaction order & deducing the rate equation

 The order of a reactant and thus the rate equation can be deduced from a reaction
mechanism if the rate-determining step is known
 For example, the reaction of nitrogen oxide (NO) with hydrogen (H2) to form nitrogen
(N2) and water

2NO (g) + 2H2 (g) → N2 (g) + 2H2O (l)

 The reaction mechanism for this reaction is:

Step 1:

NO (g) + NO (g) → N2O2 (g) fast

Step 2:

N2O2 (g) + H2 (g) → H2O (l) + N2O (g) slow (rate-determining step)

Step 3:

N2O (g) + H2 (g) → N2 (g) + H2O (l) fast

 The second step in this reaction mechanism is the rate-determining step

 The rate-determining step consists of:
o N2O2 which is formed from the reaction of two NO molecules
o One H2 molecule
  The reaction is, therefore, second order with respect to NO and first order with respect
to H2
 So, the rate equation becomes:

Rate = k [NO]2 [H2]

 The reaction is, therefore, third order overall

Identifying the rate-determining step

 The rate-determining step can be identified from a rate equation given that the reaction
mechanism is known
 For example, propane (CH3CH2CH3) undergoes bromination under alkaline solutions
 The overall reaction is:

CH3CH2CH3 + Br2 + OH- → CH3CH2CH2Br + H2O + Br-

 The reaction mechanism is:

Reaction mechanism for the bromination of propane under alkaline conditions

 The rate equation is:

Rate = k [CH3CH2CH3] [OH-]

 From the rate equation, it can be deduced that only CH3CH2CH3 and OH- are involved in
the rate-determining step and not bromine (Br2)
 CH3CH2CH3 and OH- are only involved in the first step of the reaction mechanism,
therefore the rate-determining step is:
o CH3CH2CH3 + OH- → CH3CH2CH2- + H2O
Identifying intermediates & catalyst

 When a rate equation includes a species that is not part of the chemical reaction
equation then this species is a catalyst
 For example, the halogenation of butanone under acidic conditions
 The reaction mechanism is:

 The reaction mechanism is:

Reaction mechanism of the halogenation of butanone under acidic conditions

 The rate equation is:

Rate = k [CH3CH2COCH3] [H+]

 The H+ is not a reactant in the chemical reaction equation but does appear in the rate
equation
o H+ must, therefore, be a catalyst
 Furthermore, the rate equation suggest that CH3CH2COCH3 and H+ must be involved in
the rate-determining (slowest) step
 The CH3CH2COCH3 and H+ appear in the rate-determining step in the form of
an intermediate (which is a combination of the two species)
 Intermediate is formed in the rate-determining step from the reaction of
CH3CH2COCH3 and H+

Correlating Mechanism With Rate Law

Rate Law The rate law (also known as the rate equation) for a chemical reaction is an
expression that provides a relationship between the rate of the reaction and the concentrations of
the reactants participating in it.

Expression
For a reaction given by:
aA + bB → cC + dD
where a, b, c, and d are the stoichiometric coefficients of the reactants or products, the rate

Rate ∝ [A]x[B]y ⇒ Rate = k[A]x[B]y

equation for the reaction is given by:

 [A] & [B] denote the concentrations of the reactants A and B.

 x & y denote the partial reaction orders for reactants A & B (which
may or may not be equal to their stoichiometric coefficients a & b).
 The proportionality constant ‘k’ is the rate constant of the reaction.
It is important to note that the expression of the rate law for a specific reaction can only be
determined experimentally. The rate law expression cannot be obtained from the balanced
chemical equation (since the partial orders of the reactants are not necessarily equal to the
stoichiometric coefficients).

Reaction Orders
The sum of the partial orders of the reactants in the rate law expression gives the overall order of
the reaction.
If Rate = k[A]x[B]y; overall order of the reaction (n) = x+y
The order of a reaction provides insight into the change in the rate of the reaction that can be
expected by increasing the concentration of the reactants. For example:
  If the reaction is a zero-order reaction, doubling the reactant
concentration will have no effect on the reaction rate.
 If the reaction is of the first order, doubling the reactant
concentration will double the reaction rate.
 In second-order reactions, doubling the concentration of the
reactants will quadruple the overall reaction rate.
 For third-order reactions, the overall rate increases by eight times
when the reactant concentration is doubled.

Rate Constants
Rearranging the rate equation, the value of the rate constant ‘k’ is given by:
k = Rate/[A]x[B]y
Therefore, the units of k (assuming that concentration is represented in mol L-1 or M and time is
represented in seconds) can be calculated via the following equation.
k = (M s-1)*(M-n) = M(1-n) s-1
The units of the rate constants for zero, first, second, and nth-order reactions are tabulated below.
Reaction Order Units of Rate Constant
0 M s-1 (or) mol L-1.s-1
1 s-1
2 M-1 s-1 (or) L mol-1 s-1
N M1-n s-1 (or) L(-1+n) mol(1-n).s-1

Differential Rate Equations

Differential rate laws are used to express the rate of a reaction in terms of change in the
concentration of reactants (d[R]) over a small interval of time (dt). Therefore, the differential
form of the rate expression provided in the previous subsection is given by:
-d[R]/dt = k[A]x[B]y
Differential rate equations can be used to calculate the instantaneous rate of a reaction, which is
the reaction rate under a very small-time interval. It can be noted that the ordinary rate law is a
differential rate equation since it offers insight into the instantaneous rate of the reaction.

Integrated Rate Equations

Integrated rate equations express the concentration of the reactants in a chemical reaction as a
function of time. Therefore, such rate equations can be employed to check how long it would
take for a given percentage of the reactants to be consumed in a chemical reaction. It is important
to note that reactions of different orders have different integrated rate equations.
Integrated Rate Equation for Zero-Order Reactions
The integrated rate equation for a zero-order reaction is given by:
kt = [R0] – [R] (or) k = ([R0] – [R])/t
 [R0] is the initial concentration of the reactant (when t = 0)
 [R] is the concentration of the reactant at time ‘t’
 k is the rate constant

Integrated Rate Equation for First-Order Reactions

The integrated rate law for first-order reactions is:
kt = 2.303 log([R0]/[R]) (or) k = (2.303/t) log([R0]/[R])

Integrated Rate Equation for Second-Order Reactions

For second-order reactions, the integrated rate equation is:
kt = (1/[R]) – (1/[R0])

Solved Examples on the Rate Law

Example 1
For the reaction given by 2NO + O2 → 2NO2, The rate equation is:
Rate = k[NO]2[O2]
Find the overall order of the reaction and the units of the rate constant.
The overall order of the reaction = sum of exponents of reactants in the rate equation = 2+1 = 3
The reaction is a third-order reaction. Units of rate constant for ‘nth’ order reaction = M(1-n) s-1
Therefore, units of rate constant for the third-order reaction = M(1-3) s-1 = M-2 s-1 = L2 mol-2 s-1
Example 2
For the first-order reaction given by 2N2O5 → 4NO2 + O2 the initial concentration of
N2O5 was 0.1M (at a constant temperature of 300K). After 10 minutes, the concentration of
N2O5 was found to be 0.01M. Find the rate constant of this reaction (at 300K).
From the integral rate equation of first-order reactions:
k = (2.303/t)log([R0]/[R])
Given, t = 10 mins = 600 s
Initial concentration, [R0] = 0.1M
Final concentration, [R] = 0.01M
Therefore, rate constant, k = (2.303/600s)log(0.1M/0.01M) = 0.0038 s-1
The rate constant of this equation is 0.0038 s-1
thermodynamic reaction kinetics and thermodynamic control of reaction :

The potential outcome of a reaction is usually influenced by two factors:

1. the relative stability of the products (i.e. thermodynamic factors)

2. the rate of product formation (i.e. kinetic factors)

The following simple reaction coordinate diagram provides a basis for the key
issues about kinetic and thermodynamic control:

Consider the case where a starting

material, SM, can react in a similar
manner to give two different
products, P1 and P2 via different
(competing) pathways represented
by green and blue curves.

Reaction 1 via pathway 1 (green)

generates product 1 (P1) via
transition state 1 (TS1).
This will be the faster reaction since
it has a lower energy (more stable)
transition state, and therefore a
lower activation barrier. Therefore,
product 1, P1 is the kinetic
product (the product that forms the
fastest).

Reaction 2 via pathway 2 (blue)

generates product 2 (P2)
via transition state 2 (TS2).
P2 is the more stable product
since P2 is at a lower energy
than P1. Therefore, P2 is
the thermodynamic product (the
more stable product).

We now need to consider how the outcome of this situation changes with the
competing reactions of the starting material as we alter the reaction
temperature and therefore the average energy of the molecules changes.

1. At low temperature, the average energy of the molecules is low and more
molecules have enough sufficient energy cross activation energy EA1 than
EA2. Therefore the reaction preferentially proceeds along the green path
to P1. The reaction is not reversible since the molecules lack sufficient energy
to reverse to SM, i.e. it is irreversible, so the product ratio of the reaction is
dictated by the rates of formation of P1 and P2, k1: k2.

2. At some slightly higher temperature, reaction 1 will become reversible when

sufficient molecules have enough energy to cross the reverse reaction barrier
for reaction 1, while reaction 2 remains irreversible. So although P1 may form
initially, over time it will revert to SM and react to give the more stable P2.

3. At high temperature, both reaction 1 and 2 are reversible and the product
ratio of the reaction is dictated by the equilibrium constants for P1 and P2, K1 :
K2 .

Summary

 At low temperature, the reaction is under kinetic control (rate,

irreversible conditions) and the major product is that from the fastest
reaction.
 At high temperature, the reaction is under thermodynamic
control (equilibrium, reversible conditions) and the major product is the
more stable system