Chlorination

Subject : Heavy Metal Toxin
Unit : I
Title : Chlorination
Lecturer N.Muthukrishnan, CARISM, SASTRA University
Unit : I
Valence
The normal valency of an atom is equal to the
number of outer electrons if that number is four or less.
Otherwise, the valency is equal to 8 minus the number of
outer electrons.
Finally, Fluorine and Chlorine - seven outer
electrons. This is one short of a full shell. They both
combine with a single Hydrogen atom and their normal
valences are 1.
As a side note, Chlorine can also have valences of 3, 5

and 7.
Unit : I
The atoms with full electron shells (Helium, Neon,

Argon) are chemically inert forming few compounds.
The atoms with a single outer electron or a single
missing electron are all highly reactive.
Both are highly reactive gases not found as elements in
the natural state and forming crystaline salt-like compounds
with metals and are one electron short of a complete outer
shell. This makes them reactive.
Atom
Symbol
Atomic Number
s Shell
p Shell
d Shell
Chlorine
Cl
17
f Shell
Unit : I
Sodium Chloride (NaCl, common salt) involve the transfer

of a single electron from one atom to another.
sodium metal
chlorine gas
table salt
Unit : I
Two electrons can also be transferred as in the compounds

Calcium Fluoride (CaF2) and Magnesium Chloride (MgCl2).
In these compounds, the outer two electrons of the Calcium or
Magnesium are transferred to two Fluorine or Chlorine atoms.
Unit : I
Ionic bonds are produced when the outermost electrons are

removed from one atom, the electron donor, and reside in the
electron orbitals of another atom, the electron acceptor.
The electron donors then produce cations, Whereas the
electron acceptors are referred to as anions. The bonding in
the mineral halite (NaCl) is the classic example.
There is almost complete removal of the outermost electron
form Na to produce the cation Na+ and its incorporation into
the outer electron orbital of Cl+ to give the anion Cl-.
Na
e-
Cation (electron donar)
Cl
Anion (electron acceptor)
Unit : I
Covalent bonds form where a pair of electrons of equivalent

energy and opposite spins are shared between atoms.
These bonds are quite stable because the sharing allows the stable
electronic configuration for both elements to occur.
Covalent bonds exist in the gases H2, N2, O2 and Cl2.
single - one shared pair of electrons - Cl - Cl, C - C
double - two shared pairs of electrons - O = O, C = C
triple - three shared pairs of electrons - N N, C C
Two nonmetal atoms form a covalent bond because they have less energy after they bonded
H +
H : H = HH = H2
hydrogen molecule
Unit : I
Covalent Bond Strength
Most simply, the strength of a bond is measured

by determining how much energy is required to
break the bond.
This is the bond enthalpy.
The bond enthalpy for a ClCl bond,
D(ClCl), is measured to be 242 kJ/mol.
Unit : I
As atoms approach
The attraction for electrons is not
limited to free electrons, but also
involves electrons that are part of
other atoms.
Thus, atoms are pulled toward each other

How far they are pulled together will depend
on a balance of attraction (nucleus to
electrons) and repulsion (nucleus to nucleus
and electrons to electrons)
Unit : I
Enthalpy
If a process takes place at constant pressure
(as the majority of processes we study do) and
the only work done is this pressure-volume
work, we can account for heat flow during the
process by measuring the enthalpy of the
system.
Enthalpy is the internal energy plus the
product of pressure and volume:
H = E + PV
Unit : I
Enthalpy
When the system changes at constant
pressure, the change in enthalpy, H, is
H = (E + PV)
This can be written
H = E + PV
Unit : I
Enthalpy
Since E = q + w and w = PV, we can
substitute these into the enthalpy
expression:
H = E + PV
H = (q+w) w
H = q
So, at constant pressure the change in
enthalpy is the heat gained or lost.
Unit : I
Bond Enthalpy and Bond Length
We can also measure an average bond length for

different bond types.
As the number of bonds between two atoms
increases, the bond length decreases.
Unit : I
Average Bond Enthalpies

This table lists the
average bond enthalpies
for many different types
of bonds.
Average bond enthalpies
are positive, because
bond breaking is an
endothermic process.
Unit : I
Average Bond Enthalpies

NOTE: These are average
bond enthalpies, not
absolute bond
enthalpies; the CH
bonds in methane, CH4,
will be a bit different
than the
CH bond in
chloroform, CHCl3.
Unit : I
Enthalpies of Reaction
Yet another way to
estimate H for a reaction
is to compare the bond
enthalpies of bonds
broken to the bond
enthalpies of the new
bonds formed.
In other words,
Hrxn = (bond enthalpies of bonds broken)
(bond enthalpies
of
bonds
formed)
Unit : I
CH4(g) + Cl2(g)
CH3Cl(g) + HCl(g)
In this example, one
CH bond and one
ClCl bond are broken;
one CCl and one HCl
bond are formed.
Unit : I
So,
Hrxn = [D(CH) + D(ClCl) [D(CCl) + D(HCl)
= [(413 kJ) + (242 kJ)] [(328 kJ) + (431 kJ)]
= (655 kJ) (759 kJ)
= 104 kJ
Unit : I
Radical Reactions
Halogenation of Alkanes
In the presence of heat or light, alkanes react with halogens to
form alkyl halides.
Halogenation of alkanes is a radical substitution reaction.
Halogenation of alkanes is only useful with Cl2 or Br2. Reaction
with F2 is too violent, and reaction with I2 is too slow to be
useful.
With an alkane that has more than one type of hydrogen atom, a
mixture of alkyl halides may result.
Unit : I
Radical Reactions
When a single hydrogen atom on a carbon has been replaced
by a halogen atom, monohalogenation has taken place.
When excess halogen is used, it is possible to replace more
than one hydrogen atom on a single carbon with halogen
atoms.
Monohalogenation can be achieved experimentally by adding
halogen X2 to an excess of alkene.
When asked to draw the products of halogenation of an
alkane, draw the products of monohalogenation only, unless
specifically directed to do otherwise.
Unit : I
Radical Reactions
Three facts about halogenation suggest that the mechanism
involves radical, not ionic, intermediates:
Unit : I
Radical Reactions
Radical halogenation has three distinct parts.
A mechanism such as radical halogenation that involves two

or more repeating steps is called a chain mechanism.
The most important steps of radical halogenation are those
that lead to product formationthe propagation steps.
Unit : I
Radical Reactions
Halogenation of AlkanesEnergetics
Unit : I
Radical Reactions
Halogenation of AlkanesEnergetics
Unit : I
Radical ReactionsMechanism
Unit : I
Radical Reactions
Recall that chlorination of CH3CH2CH3 affords a 1:1 mixture of
CH3CH2CH2Cl and (CH3)2CHCl.
Note that CH3CH2CH3 has six 10 hydrogens and only two 20
hydrogens, so the expected product ratio of CH3CH2CH2Cl to
(CH3)2CHCl (assuming all hydrogens are equally reactive) is
3:1.
Unit : I
Radical Reactions
Since the observed ratio between CH3CH2CH2Cl and
(CH3)2CHCl is 1:1, the 20 CH bonds must be more reactive
than the 10 CH bonds.
Thus, when alkanes react with Cl2, a mixture of products

results, with more product formed by cleavage of the weaker
CH bond than you would expect on statistical grounds.
Unit : I
Radical Reactions
Chlorination versus Bromination
Although alkanes undergo radical substitutions with both

Cl2 and Br2, chlorination and bromination exhibit two
important differences.
1. Chlorination is faster than bromination.
2. Chlorination is unselective, yielding a mixture of
products, but bromination is often selective, yielding
one major product.
Unit : I
Radical Reactions
The differences in chlorination and bromination can be
explained by considering the energetics of each type of
reaction.
Calculating the H0 using bond dissociation energies reveals
that abstraction of a 10 or 20 hydrogen by Br is endothermic,
but it takes less energy to form the more stable 20 radical.
Unit : I
Radical Reactions
Conclusion: Because the rate-determining step is endothermic,

the more stable radical is formed faster, and often a single radical
halogenation product predominates.
Unit : I
Radical Reactions
Calculating the H0 using bond dissociation energies for
chlorination reveals that abstraction of a 10 or 20 hydrogen by
Cl is exothermic.
Since chlorination has an exothermic rate-determining step,

the transition state to form both radicals resembles the same
starting material, CH3CH2CH3. Thus, the relative stability of the
two radicals is much less important, and both radicals are
formed.
Unit : I
Radical Reactions
Conclusion: Because the rate-determining step in chlorination is

exothermic, the transition state resembles the starting material,
both radicals are formed, and a mixture of products results.
Unit : I
Chlorination
Chlorine gas rapidly hydrolyzes to hypochlorous acid according
to: Cl2 + H2O HOCl + H+ + ClAqueous solutions of sodium or calcium hypochlorite hydrolyze
too: Ca(OCl)2 + 2H2O Ca2+ + 2HOCl + 2OHNaOCl + H2O Na+ + HOCl + OHHypochlorous acid is a weak acid and will disassociate according
to: HOCl H+ + OCl -
The two chemical species formed by chlorine in water, hypochlorous

acid (HOCl) and hypochlorite ion (OCl - ), are commonly referred to as
free or available chlorine.
In waters with pH between 6.5-8.5, the reaction is incomplete and
both species (HOCl and OCl - ) will be present.
Hypochlorous acid is the more germicidal of the two.
Unit : I
Free Chlorine Distribution with pH

100
90
80
70
60
50
40
30
20
10
0
Best
disinfection
pH 6 - 7
...BUT...
50:50
equilibrium at
pH 7.5
HOCl
OCl-
Corrosivity
concerns
below pH 7.5

Chlorination

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Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

As a side note, Chlorine can also have valences of 3, 5

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

The atoms with full electron shells (Helium, Neon,

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Sodium Chloride (NaCl, common salt) involve the transfer

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Two electrons can also be transferred as in the compounds

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Ionic bonds are produced when the outermost electrons are

Cation (electron donar)

Subject : Heavy Metal Toxin

Covalent bonds form where a pair of electrons of equivalent

Subject : Heavy Metal Toxin

Covalent Bond Strength

Most simply, the strength of a bond is measured

Subject : Heavy Metal Toxin

Thus, atoms are pulled toward each other

Subject : Heavy Metal Toxin

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Subject : Heavy Metal Toxin

Bond Enthalpy and Bond Length

We can also measure an average bond length for

Subject : Heavy Metal Toxin

Average Bond Enthalpies

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Average Bond Enthalpies

Subject : Heavy Metal Toxin

Subject : Heavy Metal Toxin

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

A mechanism such as radical halogenation that involves two

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Thus, when alkanes react with Cl2, a mixture of products

Subject : Heavy Metal Toxin

Although alkanes undergo radical substitutions with both

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin

Lecturer N.Muthukrishnan, CARISM, SASTRA University

Subject : Heavy Metal Toxin