FREE RADICAL SUBSTITUTION

Substitution reactions

These are reactions in which one atom in a molecule is replaced

by another atom or group of atoms. Free radical substitution for
A' level purposes involves breaking a carbon-hydrogen bond in
alkanes such as

methane CH4
ethane CH3CH3
propane CH3CH2CH3

A new bond is then formed to something else.

It also happens in alkyl groups like methyl, ethyl (and so on)

wherever these appear in more complicated molecules.

methyl CH3
ethyl CH3CH2

For example, ethanoic acid is CH3COOH and contains a methyl

group. The carbon-hydrogen bonds in the methyl group behave
just like those in methane, and can be broken and replaced by
something else in the same way.

A simple example of substitution is the reaction between

methane and chlorine in the presence of UV light (or sunlight).

CH4 + Cl2 CH3Cl + HCl

Notice that one of the hydrogen atoms in the methane has been
replaced by a chlorine atom. That's substitution.

Free radical reactions

Free radicals are atoms or groups of atoms which have a single

unpaired electron. A free radical substitution reaction is one
involving these radicals.

Free radicals are formed if a bond splits evenly - each atom

getting one of the two electrons. The name given to this
ishomolytic fission.

Note: If a bond were to split unevenly (one atom getting both electrons,
and the other none), ions would be formed. The atom that got both
electrons would become negatively charged, while the other one would
become positive. This is called heterolytic fission.

Warning! It is important that you get these terms the right way round.
"Fission" is obvious - it just means "splitting". "Homo" and "hetero" are
used in the sense of "same" (homo) or "different" (hetero). This is just like
their use in "homosexual" or "heterosexual".

So, homolytic fission is splitting a bond to produce two particles which are
the same in the sense that they both have a single unpaired electron
(both are free radicals). Heterolytic fission produces two particles which
are different because one is a positive ion and the other a negative ion.

To show that a species (either an atom or a group of atoms) is a

free radical, the symbol is written with a dot attached to show
the unpaired electron. For example:

a chlorine radical Cl
a methyl radical CH3

Note: If you wanted to be fussy, the dot showing the electron really ought
to be written next to the carbon atom in the methyl radical, because that's
the atom with the unpaired electron - in other words as CH3. This isn't
normally done unless the radical gets more complicated. Examples of this
will crop up when you look at the mechanisms.

Where would you like to go now?

To menu of free radical reactions. . .

To menu of other types of mechanism. . .

To Main Menu . . .
 Jim Clark 2000
THE REACTION BETWEEN METHANE AND CHLORINE

A Free Radical Substitution Reaction

This page gives you the facts and a simple, uncluttered
mechanism for the free radical substitution reaction
between methane and chlorine. If you want the mechanism
explained to you in detail, there is a link at the bottom
of the page.
The facts
If a mixture of methane and chlorine is exposed to a
flame, it explodes - producing carbon and hydrogen
chloride. This isn't a very useful reaction!
The reaction we are going to explore is a more gentle one
between methane and chlorine in the presence of
ultraviolet light - typically sunlight. This is a good
example of a photochemical reaction - a reaction brought
about by light.

Note: These reactions are sometimes described as examples

of photocatalysis - reactions catalysed by light. It is better to use the
term "photochemical" and keep the word "catalysis" for reactions
speeded up by actual substances rather than light.

CH4 + Cl2 CH3Cl + HCl

The organic product is chloromethane.

One of the hydrogen atoms in the methane has been replaced

by a chlorine atom, so this is a substitution reaction. However,
the reaction doesn't stop there, and all the hydrogens in the
methane can in turn be replaced by chlorine atoms. Multiple
substitution is dealt with on a separate page, and you will find a
link to that at the bottom of this page.

The mechanism

The mechanism involves a chain reaction. During a chain

reaction, for every reactive species you start off with, a new one
is generated at the end - and this keeps the process going.

Species: a useful word which is used in chemistry to mean any sort of

 particle you want it to mean. It covers molecules, ions, atoms, or (in this
case) free radicals.

The over-all process is known as free radical substitution, or

as a free radical chain reaction.

Note: If you aren't sure about the words free radical orsubstitution, read
the page What is free radical substitution?Use the BACK button on your
browser to return quickly to this page.

Chain initiation
The chain is initiated (started) by UV light breaking a chlorine
molecule into free radicals.

Cl2 2Cl

Chain propagation reactions

These are the reactions which keep the chain going.

CH4 + Cl CH3 + HCl

CH3 + Cl2 CH3Cl + Cl

Chain termination reactions

These are reactions which remove free radicals from the system
without replacing them by new ones.

2Cl Cl2
CH3 + Cl CH3Cl
CH3 + CH3 CH3CH3

Where would you like to go now?

Help! Talk me through this mechanism . . .

Look at multiple substitution in this reaction . . .

Look at why side reactions happen in this reaction . .

.
 To menu of free radical reactions. . .

To menu of other types of mechanism. . .

To Main Menu . . .

Jim Clark 2000

III. REAKSI RADIKAL BEBAS
Seperti halnya ion, radikal dapat membentuk reaksi adisi, eliminasi, substitusi,
danpenyusunanulang. Langkah-langkah reaksi radikal:
(1)Inisiasi Inisiasi merupakan langkah pembentukan radikal melalui pemecahan rantai homolitik
(biasanya memerlukan panas atau cahaya).

(2)Propagasi Propagasi merupakan reaksi suatu radikal membentuk satu produk radikal baru.
Langkah ini meliputi adisi, eliminasi, substitusi, atau penyusunanulang

(3)Terminasi
Terminasimerupakanreaksicoupling/penggabunganduaradikalmembentukproduknon-radikal.
HYDROGEN BROMIDE AND ALKENES:
THE PEROXIDE EFFECT

This page gives you the facts and simple uncluttered

mechanisms for the free radical addition of hydrogen bromide to
alkenes - often known as the "peroxide effect". If you want the
mechanisms explained to you in more detail, there is a link at
the bottom of the page.

Addition to symmetrical alkenes

A symmetrical alkene is one like ethene where the groups at

both ends of the carbon-carbon double bond are the same.

The facts

The reaction happens at room temperature in the presence of

organic peroxides or some oxygen from the air. Alkenes react
very slowly with oxygen to produce traces of organic peroxides -
so the two possible conditions are equivalent to each other.

The reaction is a simple addition of the hydrogen bromide. For

example, with ethene:

With a symmetrical alkene you get exactly the same product in

the absence of the organic peroxides or oxygen - but the
mechanism is different.

The mechanism

Hydrogen halides (hydrogen chloride, hydrogen bromide and the

rest) usually react with alkenes using an electrophilic addition
mechanism. However, in the presence of organic peroxides,
hydrogen bromide adds by a different mechanism.

Note: If you are interested, you will find the electrophilic

 addition mechanism for the addition of hydrogen bromide and
other hydrogen halides to alkenes if you follow this link. You
may need to explore several pages in this section.

Use the BACK button (or the HISTORY file or GO menu) on

your browser to return to this page.

With the organic peroxides present you get a free radical chain
reaction.

Chain initiation

The chain is initiated by free radicals produced by an oxygen-

oxygen bond in the organic peroxide breaking.

These free radicals extract a hydrogen atom from a hydrogen

bromide molecule to produce bromine radicals.

Chain propagation

A bromine radical joins to the ethene using one of the electrons

in the pi bond. That creates a new radical with the single
electron on the other carbon atom.

That radical reacts with another HBr molecule to produce

bromoethane and another bromine radical to continue the
process.

etc

Chain termination

Eventually two free radicals hit each other and produce a

molecule of some sort. The process stops here because no new
free radicals are formed.

Addition to unsymmetrical alkenes

An unsymmetrical alkene is one like propene where the groups

at either end of the carbon-carbon double bond are different.

The facts

The reaction happens under the same conditions as with a

symmetrical alkene, but there is a complication because the
hydrogen and the bromine can add in two different ways. Which
way they add depends on whether there are organic peroxides
(or oxygen) present or not.

Normally, when a molecule HX adds to a carbon-carbon double

bond, the hydrogen becomes attached to the carbon with the
more hydrogens on already. This is known as Markovnikov's
Rule.

Because the HBr adds on the "wrong way around " in the
presence of organic peroxides, this is often known as
theperoxide effect or anti-Markovnikov addition.

In the absence of peroxides, hydrogen bromide adds to propene

via an electrophilic addition mechanism. That gives the product
predicted by Markovnikov's Rule.
The free radical mechanism

Chain initiation

This is exactly the same as in the ethene case above.

Chain propagation

When the bromine radical joins to the propene, it attaches so

that a secondary radical is formed. This is more stable (and so
easier to form) than the primary radical which would be formed if
it attached to the other carbon atom.

That radical reacts with another HBr molecule to produce 1-

bromopropane and another bromine radical to continue the
process.

etc

Chain termination

Eventually two free radicals hit each other and produce a

molecule of some sort. The process stops here because no new
free radicals are formed.

Why don't the other hydrogen halides behave in the same

way?

The reason that hydrogen bromide adds in an anti-Markovnikov

fashion in the presence of organic peroxides is simply a
question of reaction rates. The free radical mechanism is much
faster than the alternative electrophilic addition mechanism.

Both mechanisms happen, but most of the product is the one

from the free radical mechanism because that is working faster.

With the other hydrogen halides, the opposite is true.

Hydrogen fluoride

The hydrogen-fluorine bond is so strong that fluorine radicals

aren't formed in the initiation step.

Hydrogen chloride

With hydrogen chloride, the second half of the propagation

stage is very slow. If you do a bond enthalpy sum, you will find
that the following reaction is endothermic.

This is due to the relatively high hydrogen-chlorine bond

strength.

Hydrogen iodide

In this case, the first step of the propagation stage turns out to
be endothermic and this slows the reaction down. Not enough
energy is released when the weak carbon-iodine bond is
formed.

In the case of hydrogen bromide, both steps of the propagation

stage are exothermic.
THE POLYMERISATION OF ETHENE

A Free Radical Addition Reaction

This page gives you the facts and a simple, uncluttered

mechanism for the polymerisation of ethene by a free radical
addition reaction. If you want the mechanism explained to you in
detail, there is a link at the bottom of the page.

The facts

An addition reaction is one in which two or more molecules join

together to give a single product. During the polymerisation of
ethene, thousands of ethene molecules join together to make
poly(ethene) - commonly called polythene.

The number of molecules joining up is very variable, but is in the

region of 2000 to 20000.

Conditions

Temperature: about 200C

Pressure: about 2000 atmospheres
a small amount of oxygen as
Initiator:
an impurity

Note: The oxygen is sometimes described as a catalyst for

the reaction. That's not strictly true. A catalyst can be
recovered unchanged at the end of a reaction, but in this
case the oxygen is used up. It gets incorporated into the
polymer molecules - as you will see shortly.

The mechanism

The over-all process is known as free radical addition.

Chain initiation
The chain is initiated by free radicals, Ra , produced by reaction
between some of the ethene and the oxygen initiator.

Chain propagation

Each time a free radical hits an ethene molecule a new longer

free radical is formed.

etc

Chain termination

Eventually two free radicals hit each other producing a final

molecule. The process stops here because no new free radicals
are formed.

Because chain termination is a random process, poly(ethene)

will be made up of chains of all sorts of different lengths.
THE REACTION BETWEEN
METHYLBENZENE AND CHLORINE

A Free Radical Substitution Reaction

This page gives you the facts and a simple,

uncluttered mechanism for the free radical
substitution reaction between methylbenzene
(previously known as toluene) and chlorine. If you want the
mechanism explained to you in detail, there is a link at the
bottom of the page.

Methylbenzene has a methyl group attached to a benzene ring.

The hexagon with the circle inside is the standard symbol for
this ring. There is a carbon atom at each corner of the hexagon,
and a hydrogen atom on each carbon apart from the one with
the methyl group attached.

Note: There is no need to worry about the bonding in the

benzene ring at this point. If you are interested, you can
follow the link - but it isn't important for now.

The facts

The reaction we are going to explore happens between

methylbenzene and chlorine in the presence of ultraviolet light -
typically sunlight. This is a good example of a photochemical
reaction - a reaction brought about by light.

Note: These reactions are sometimes described as

examples of photocatalysis - reactions catalysed by light.
It is better to use the term "photochemical" and keep the
word "catalysis" for reactions speeded up by actual
substances rather than light.
The organic product is (chloromethyl)benzene. The brackets in
the name emphasise that the chlorine is part of the attached
methyl group, and isn't on the ring.

One of the hydrogen atoms in the methyl group has been

replaced by a chlorine atom, so this is a substitution reaction.
However, the reaction doesn't stop there, and all three
hydrogens in the methyl group can in turn be replaced by
chlorine atoms. Multiple substitution is dealt with on a separate
page, and you will find a link to that at the bottom of this page.

Important! There is another reaction which happens

between methylbenzene and chlorine in the absence of light
and in the presence of a number of possible catalysts. In
that one, substitution happens in the benzene ring instead
of in the methyl group. You will find this reaction discussed
underelectrophilic substitution reactions.

The mechanism

The mechanism involves a chain reaction. During a chain

reaction, for every reactive species you start off with, a new one
is generated at the end - and this keeps the process going.

Species: a useful word which is used in chemistry to mean

any sort of particle you want it to mean. It covers molecules,
ions, atoms, or (in this case) free radicals.

The over-all process is known as free radical substitution, or

as a free radical chain reaction.

Note: If you aren't sure about the words free

radical orsubstitution, read the page What is free radical
substitution?Use the BACK button on your browser to return
quickly to this page.
Chain initiation
The chain is initiated (started) by UV light breaking a chlorine
molecule into free radicals.

Cl2 2Cl

Chain propagation reactions

These are the reactions which keep the chain going.

Chain termination reactions

These are reactions which remove free radicals from the system
without replacing them by new ones. If any two free radicals
collide, they will join together without producing any new
radicals.

The simplest example of this is a collision between two chlorine

radicals.

2Cl Cl2
THE REACTION BETWEEN METHANE
AND BROMINE

A Free Radical Substitution Reaction

This page gives you the facts and a simple, uncluttered

mechanism for the free radical substitution reaction between
methane and bromine. If you want the mechanism explained to
you in detail, there is a link at the bottom of the page.

The facts

This reaction between methane and bromine happens in the

presence of ultraviolet light - typically sunlight. This is a good
example of a photochemical reaction - a reaction brought
about by light.

Note: These reactions are sometimes

described as examples of photocatalysis -
reactions catalysed by light. It is better to use
the term "photochemical" and keep the word
"catalysis" for reactions speeded up by actual
substances rather than light.

CH4 + Br2 CH3Br + HBr

The organic product is bromomethane.

One of the hydrogen atoms in the methane has been replaced

by a bromine atom, so this is a substitution reaction. However,
the reaction doesn't stop there, and all the hydrogens in the
methane can in turn be replaced by bromine atoms. Multiple
substitution is dealt with on a separate page, and you will find a
link to that at the bottom of this page.

Warning! Check your syllabus at this point. If

your syllabus wants you to know about the free
radical substitution reaction between methane
and chlorine as well as this one, don't waste
time trying to learn both mechanisms.
 The two mechanisms are identical. You just
need to learn one of them. If you are asked for
the other one, all you need to do is to
write bromine, say, instead of chlorine.

In writing the bromine mechanisms on these

pages, that's exactly what I've done! If you read
both chlorine and bromine versions, you'll find
them boringly repetitive!

The mechanism

The mechanism involves a chain reaction. During a chain

reaction, for every reactive species you start off with, a new one
is generated at the end - and this keeps the process going.

Species: a useful word which is used in

chemistry to mean any sort of particle you want
it to mean. It covers molecules, ions, atoms, or
(in this case) free radicals.

The over-all process is known as free radical substitution, or

as a free radical chain reaction.

Note: If you aren't sure about the words free

radical orsubstitution, read the page What is free
radical substitution?Use the BACK button on
your browser to return quickly to this page.

Chain initiation
The chain is initiated (started) by UV light breaking a bromine
molecule into free radicals.

Br2 2Br

Chain propagation reactions

These are the reactions which keep the chain going.

CH4 + Br CH3 + HBr

 CH3 + Br2 CH3Br + Br

Chain termination reactions

These are reactions which remove free radicals from the system
without replacing them by new ones.

2Br Br2
CH3 + Br CH3Br
CH3 + CH3 CH3CH3

Reaksi Radikal
Reaksi radikal

Radikal bebas adalah molekul yang kehilangan elektron, sehingga molekul

tersebut menjadi tidak stabil dan selalu berusaha mengambil elektron dari molekul atau
sel lain. Dengan kata lain radikal bebas merupakan atom/gugus yang memiliki satu atau
lebih elektron yang tidak berpasangan. Radikal bebas ini merupakan spesies yang
sangat reaktif sehingga umurnya pendek. Radikal bebas dibentuk jika ikatan terbelah
menjadi dua yang sama-sehingga setiap atom mendapat satu dari dua elektron yang
dipakai untuk berikatan.

Reaksi ini tapi terbagi menjadi 3 tahap; yaitu inisiasi, progasi, dan terminasi.

Inisiasi
Tahap ini adalah tahap untuk pemaksapisahan (cleavage) homolitik molekul Cl2
dengan bantuan panas dan uv menjadi 2 radial bebas klor.
Cl2 Cl + Cl

Propagasi
Tahap ini adalah tahap untuk membuat suatu senyawa atau unsur menjadi radikal
dengan mereaksikannya dengan suatu radikal.

Terminasi
Tahap ini adalah tahap untuk menghilangan atau mengubah radikal bebas menjadi
radikal bebas stabil dan tidak reaktif.

Ada dua cara yang digunakan untuk menulis rumus radikal bebas, yaitu:

a. Dengan cara rumus lewis, yakni dengan menggambarkan semua elektron pada
atom, baik yang berpasangan maupun tidak dengan lambang berupa titik.

b. Dengan hanya menuliskan elektron yang tidak berpasangan dengan lambang titik.
lambang ini lazim di pakai pada penulisan reaksi radikal bebas
contoh: Cl , RO, RN
ARI LISTIYANI
Rabu, 01 Januari 2014

Radikal Bebas
Radikal bebas adalah atom atau molekul yang kehilangan elektron / memiliki elektron yang tidak
berpasangan, sehingga molekul tersebut menjadi tidak stabil dan selalu berusaha mengambil elektron
dari atom atau molekul lain.
Radikal bebas dapat dihasilkan dari hasil metabolisme tubuh dan faktor eksternal seperti asap
rokok, beberapa logam, hasil penyinaran ultra violet, radiasi, zat kimiawi dalam makanan dan polutan
lain.
Contoh Radikal Bebas
Contoh radikal bebas sederhana adalah radikal hidroksil (HO), yaitu senyawa yang mempunyai satu
atom hidrogen terikat pada satu atom oksigen. Contoh radikal bebas yang lain adalah karben (:CH2) yang
mempunyai dua elektron tak berpasangan, dan anion superoksida (O
2) yaitu molekul yang kelebihan elektron. Perhatikan radikal bebas oksigen berikut ini.

Perlu diketahui bahwa anion hidroksil (HO), kation karbenium (CH+

3) dan anion oksida (O2) bukan radikal karena ikatan yang terbentuk faktanya diakibatkan oleh adanya
penambahan atau pelepasan elektron.

Pembentukan Radikal Bebas

Pembentukan radikal bebas diakibatkan oleh adanya pemeahan ikatan kovalen secara homolitik.
Pemecahan homolitik membutuhkan energi yang sangat besar. Sebagai contoh, pemecahan H 2 menjadi
2H mempunyai H sebesar +435 kJ/mol dan Cl2 menjadi 2Clmembutuhkan +243 kJ/mol. Hal ini
dikenal dengan energi disosiasi homolitik yang disingkat dengan DH. Energi ikatan antara dua atom
berikatan kovalen dipengaruhi oleh struktur molekul. Pemecahan homolitik kebanyakan terjadi pada dua
atom yang mempunyai elektronegativitas yang hampir sama. Dalam kimia organik, sering terjadi pada
ikatan O-O pada peroksida.

REAKSI KIMIA RADIKAL BEBAS

Dalam reaksi kimia, radikal bebas sering dituliskan sebagai titik yang ditempatkan pada simbol atom atau
molekul. Contoh penulisan radikal bebas berikut sebagai hasil dari pemecahan homolitik:

Cl2 Cl + Cl

Mekanisme reaksi radikal menggunakan panah bermata tunggal untuk menjelaskan pergerakan elektron
tunggal :

Pemutusan homolitik pada pemecahan ikatan digambarkan dengan penarikan satu elektron. Hal ini
digunakan untuk membedakan dengan pemutusan heterolitik yang menggunakan anak panah bermata
ganda pada umumnya.

Radikal bebas juga memainkan peran terhadap adisi radikal dan substitusi radikal sebagai intermediet
yang sangat reaktif. Reaksi rantai melibatkan radikal bebas yang biasanya dibagi menjadi tiga tahap,
meliputi inisiasi, propagasi dan terminasi. Contoh dalam hal ini adalah reaksi klorinasi metana.
Inisiasi
Inisiasi adalah tahap pembentukan awal radikal-radikal bebas. Hal ini menyebabkan jumlah radikal bebas
meningkat pesat. Dalam klorinasi metana, tahap inisiasi adalah pemutusan secara homolitik ikatan Cl-Cl.

Cl2 Cl + Cl
Propagasi
Propagasi adalah reaksi yang melibatkan radikal bebas yang mana jumlah radikal bebas akan tetap
sama. Setelah terbentuk, radikal bebas klor akan menjalani sederetan reaksi. Tahap propagasi yang
pertama adalah radikal bebas klor yang merebut sebuah atom hidrogen dari dalam molekul metana,
menghasilkan radikal bebas metil dan HCl.

Cl + H:CH3 + 1 kkal/mol H:Cl + CH3

Radikal bebas metil juga sangat reaktif. Dalam tahap propagasi kedua, radikal bebas metil merebut
sebuah atom klor dari dalam molekul Cl2.
Terminasi
Terminasi adalah reaksi yang berujung pada turunnya jumlah radikal bebas. Umumnya, penurunan ini
diakibatkan oleh adanya penggabungan radikal bebas yang masih tersisa.

Cl + CH3 CH3Cl

Efek Radiasi Terhadap Manusia

Jika radiasi mengenai tubuh manusia, ada 2 kemungkinan yang dapat terjadi: berinteraksi
dengan tubuh manusia, atau hanya melewati saja. Jika berinteraksi, radiasi dapat mengionisasi atau
dapat pula mengeksitasi atom. Setiap terjadi proses ionisasi ataueksitasi, radiasi akan kehilangan
sebagian energinya. Energi radiasi yang hilang akan menyebabkan peningkatan temperatur (panas)
pada bahan (atom) yang berinteraksi dengan radiasi tersebut. Dengan kata lain, semua energi radiasi
yang terserap di jaringan biologis akan muncul sebagai panas melalui peningkatan vibrasi (getaran) atom
dan struktur molekul. Ini merupakan awal dari perubahan kimiawi yang kemudian dapat mengakibatkan
efek biologis yang merugikan.