Halogenoalkanes and Alcohols

Halogenoalkanes
Halogenoalkanes contain a halogen as the functional group R-Hal.
The first part of the name of an halogenoalkane gives the position and name of the
halogen concerned.
The second part of the name is based on the rest on the hydrocarbon structure.
H C C C C
H
H
H
H
H
H
Cl
H
H
H C C C C
H
H
H
H
H
H
C
H
Br
H
H
H
1-chlorobutane 2-Bromopentane
H C C C C
H
H
I
C
H
H
H
H
H
H
H
H
2-odo-2-methylbutane
2!"-#ichloroheptane "-Bromo-"-methylhe$ane
Types of Halogenoalkanes
There are three types of halogenoalkane% primary! secondary and tertiary.
They are classified according to the number of carbon groups attached to the carbon &ith
the halogen! '! group.
(rimary )econdary Tertiary
-1-
H
H
H
C X R
H
H
C X
R
H
R
C X
R
R
R
C X
*o or one carbon +R, group
attached to the carbon &ith
the ' group is a primary
halogenoalkane.
T&o carbon +R, groups
attached to the carbon
&ith the ' group is a
seconary halogenoalkane.
Three carbon +R, groups
attached to the carbon
&ith the ' group is a
tertiary halogenoalkane
Cl
Cl
Br
Chemical properties of Halogenoalkanes
-luoroalkanes are different from the other halogen derivatives! since the C.- bond is so
strong that they are very unreactive. /ost of the discussion here &ill refer to RCl! RBr
and R.
Chloromethane! bromomethane! and chloroethane are gases! &hile the rest are li0uids
&hich do not mi$ &ith &ater as they do not have the ability to hydrogen bond.
Preparation of Halogenoalkanes
Halogenoalkanes are generally made by reacting the appropriate alcohol it &ith a
halogenating reagents.
Halogenating agents include phosphorus pentachloride! sodium chloride &ith
concentrated sulphuric acid! sodium bromide &ith concentrated phosphoric acid and
phosphorus &ith iodine.
(hosphorus pentachloride reacts vigorously &ith alcohols at room temperature.
C2H12H 3 (Cl1 C2H1Cl 3 HCl 3 (2Cl"
Choro- compounds can also be formed by heating the alcohol under reflu$ &ith sodium
chloride and concentrated sulphuric acid.
H2)24 3 *aCl HCl 3 *aH)24
HCl 3 C"H52H C"H5Cl 3 H22
To form a bromo- compound! the alcohol is heated under reflu$ &ith sodium bromide and
concentrated phosphoric acid. The concentrated phosphoric acid reacts &ith the sodium
bromide to form hydrogen bromide! and the hydrogen bromide carries out the
substitution.
H"(24 3 *aBr HBr 3 *aH2(24
HBr 3 C"H52H C"H5Br 3 H22
To produce iodo- compounds! the alcohol is mi$ed &ith red phoshorus and iodine is
added gradually. The mi$ture is then heated under reflu$.
( 3 162 ("
(" 3 "CH"CH+2H,CH" "CH"CHCH" 3 H"(2"
Concentrated sulphuric acid cannot be used to make bromoalkanes or iodoalkanes as
the halide ion is o$idi7ed to the halogen.
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Reactions of Halogenoalkanes
Halogenoalkanes commonly undergo nucleophilic substitution and elimination reactions.
Nucleophilic substitution reactions
8 nucleophile is a species +molecule or negative ion, &hich can donate an electron pair
in a chemical reaction.
Halogenoalkanes undergo substitution reactions &ith nucleophiles such as 2H
.
and *H".
with potassium hydroxide.
Conditions9 Heat under reflu$ in aueous solution. Both *a2H or :2H are suitable.
C!H"#r $ Na%H &a' C!H"%H $ Na#r
with potassium cyanide
Conditions9 Reflu$ solution of halogenoalkane and potassium cyanide in ethanol.
C!H"#r $ (CN C!H"CN $ (#r
propanenitrile
This adds a carbon atom to the chain and forms a nitrile.
with ammonia
Conditions9 Heat &ith concentrated ammonia in a sealed tube.
or heat &ith alcoholic ammonia.
C!H") $ NH* C!H" NH! $ H)
;thylamine +an amine,
2ther products include9 +C2H1,2*H and +C2H1,"*
8mines are molecules containing a * functional group.
+limination reactions
f a halogenoalkane is boiled &ith potassium hydro$ide solution in ethanol rather than
&ater an elimination reaction takes place in &hich an alkene is formed and hydrogen
halide is given off +eliminated,.
Conditions9 Heat under reflu$ &ith alkali and ethanol as solvent. <se :2H here.
CH*CH!#r CH!CH! $ H#r
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)dentification of halogenoalkanes , Reaction with -il.er nitrate solution.
n the presence of &ater! halogenoalkanes undergo hydrolysis.
The halogenoalkanes have a slightly polarised C-Hal bond. =ater acts as a nucleophile
to&ards the carbon atom in this bond. 8s a result ! the -2H group substitutes for the
halogen! giving an alcohol and a hydrogen halide.
The reaction is much slo&er than &ith an alkali.
R' 3 H22 R2H 3 H'
The hydrogen halide formed &ill dissolve in the &ater forming H
3
and '
-
ions. The ions
then react &ith the silver ions in the solution producing a precipitate.
The appearance of the precipitate depends upon the halide ion generated in the
hydrolysis reaction.
8g
3
+a0, 3 '
-
+a0, 8g'+s,
This reaction is used to test for halogenoalkanes.
Heat sample of halogenoalkane &ith a0ueous hydro$ide ions.
8cidify &ith dilute a0ueous nitric acid.
8dd a fe& drops of a0ueous silver nitrate.
8 &hite precipitate soluble in dilute a0ueous ammonia! indicates chloride.
8 buff precipitate insoluble in dilute a0ueous ammonia but soluble in concentrated
a0ueous ammonia! indicates bromide.
8 yello& precipitate insoluble in concentrated a0ueous ammonia indicates iodide.
Reacti.ity of halogenoalkanes
Results of investigations sho& that the rate of hydrolysis of the halogenoalkanes occurs
in the order9
/0iodobutane 1 /0bromobutane 1 /0chlorobutane
The ease of reaction depends on the ease of breaking the C-Hal bond9
Bond 9 C- C-Br C-Cl C--
Bond enthalpy terms +k> mol
-1
,9 32"? 325@ 3""? 34?4

Thus the ease of bond breaking is! C0) 1 C0#r 1 C0Cl 1 C02.
+This out&eighs the effects caused by greater polari7ation in the C-Hal bond,.
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3ses of halogenoalkanes
Halogenoalkenes are use as fire retardants and refrigerants as they are unreactive and
particularly for the fire retardants they are non-combustible.
-reon 12 C-2Cl2 is a refrigerant and an e$ample of a chlorofluorcarbon +C-C,. The C--
and C-Cl bonds are very strong. The result is that it does not decompose easily so lasts
for the lifetime of a refrigerator. t does not decompose 0uickly &hen discarded but does
so in the upper atmosphere. The radicals it forms react &ith o7one. The loss of o7one
leads to an increase in <A radiation reaching the ;arthBs surface and a corresponding
increase in skin cancers in humans.
/odern refrigerants are hydrofluorocarbons! H-Cs! such C-"CH2-. They do not lead to
o7one depletion.
(AC used as electrical insulator -C-CH2-CHCl-Dn-
The C-Cl bond is strong so (AC insulation lasts a long time but &hen discarded it does
not rot +it is not biodegradable,.
Teflon! or poly&tetrafluoroethene' is essentially poly+ethene, chains in &hich all the H
atoms have been replaced by fluorines9 .C-2.C-2.C-2.C-2.C-2.C-2.C-2.C-2.C-2.
etc. t is used to line non0stick frying pans and saucepans! and for lo&-friction
bearings. 8s the C-- is very strong it is non-biodegradable.
##T is a pesticide used to kill mos0uitos. CCl"
E
Cl-C@H1-C-C@H1-Cl
E
H
The strong C-Cl bonds give ##T a long life in the field killing pests. t is ho&ever so long
lived that it persists in the environment and builds up in the food chain threatening
creatures at the top of the chain.
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Alcohols
8lcohols contain the -2H functional group.
Feneral formula . CnH!n$/%H
The first part of the name of an alcohol is according to the longest carbon atom
se0uence. The second part of the name is .ol. 8 number &ill be included to indicate the
position of the alcohol group.
2
H
2
H
2
H
Pentanol or pentan-1-ol Pentan-2-ol 3-methylbutan-2-ol
Types of Alcohol
There are three types of alcohol% primary! secondary and tertiary.
They are classified according o the number of carbon groups attached to the carbon &ith
the 2H group.
(rimary )econdary Tertiary
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H H
H
H
C O R H
H
H
C O
R H
H
R
C O
R H
R
R
C O
*o or one carbon +R,
group attached to the
carbon &ith the 2H group
is a primary alcohol.
T&o carbon +R, groups
attached to the carbon &ith
the 2H group is a
secondary alcohol.
Three carbon +R, groups
attached to the carbon &ith
the 2H group is a tertiary
alcohol.
Physical properties of alcohols
The 2H group can take part in hydrogen-bonding! both as a donor +H is sufficiently 3,
and as an acceptor +through the t&o lone pairs on the o$ygen atom,. 8s a result alcohols
have higher melting and boiling points than hydrocarbons of comparable molar mass.
They are also more soluble in &ater because of H-bonding9 ethanol is miscible &ith &ater
in all proportions. 8s the non-polar hydrocarbon chain becomes longer! it becomes
harder for &ater to dissolve the alcohol9 from C4 alcohols are less soluble! and donGt mi$
&ith &ater.
Reactions of Alcohols
Combustion
8ll alcohols undergo combustion to form carbon dio$ide and &ater. -or e$ample the
e0uation for the combustion of butanol is as follo&s%
C4HH2H 3 @22 4C22 3 1H22
Reaction with sodium
8ll alcohols react &ith sodium.
2R2H 3 2*a 2R2*a 3 H2
This e0uation is similar to the reaction of sodium &ith &ater! e$cept that an alkoxide is
formed rather a hydro$ide.
e.g. ;thanol and sodium 2C2H12H 3 2*a 2 C2H12*a 3 H2
)odium etho$ide
Reaction with phosphorus pentachloride
8ll alcohols react &ith phosphorus pentachloride.
This is used as a test for the 0%H group. The presence of the 2H group can be sho&n
by adding phosphorus pentachloride to the compound. 8 reaction takes place forming
hydrogen chloride &hich appears as steamy &hite fumes.
R2H 3 (Cl1 RCl 3 (2Cl" 3 HCl
n the reaction &ith phosphorus pentachloride a chloro group replaces the -2H group.
e.g. (ropanol and phosphorus pentachloride
CH"CH2CH22H 3 (Cl1 CH"CH2CH2Cl 3 (2Cl" 3 HCl
Reaction with other halogenating agents
8lkyl bromides can be made from the reaction of an alcohol &ith HBr.
HBr is made in situ from :Br and H2)24 forms bromoalkanes during heating under reflu$.
C2H12H 3 HBr C2H1Br 3 H22
8lkyl chlorides can be made by reflu$ing the alcohol &ith conc. HCl in the presence of InCl2
C2H12H +l, 3 HCl +g, C2H1Cl +l, 3 H22 +l,
odoalkanes can be made in a reaction phosporus triiodide from iodine and red phosporus.
"C2H12H 3 (" "C2H1 3 H"(2"
The relative reactivities of alcohols in halogenation are tertiary J secondary J primary alcohol.
-7-
%xidation of alcohols
(rimary and secondary alcohols can be o$idised by heating &ith a mi$ture of dilute
sulphuric acid &ith sodium or potassium dichromate+A, solution.
8cidified dichromate+A, solution is produces a colour change from orange to blue0green
&hen it has undergone o$idation reactions.
n &riting e0uations for these o$idation reactions C2D is used to represent the o$idising
agent.
(rimary alcohols form an aldehyde! and then on further o$idation! form carbo$ylic acids.
(rimary alcohol 8ldehyde Carbo$ylic acid
)econdary alcohols form ketones! but no further o$idation takes place.

)econdary alcohol :etone
e.g. CH*CH&%H'CH* $ 4%5 CH*C%CH* $ H!%
propan-2-ol propanone
Tertiary alcohols do not react &ith o$idi7ing agents.
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R H
H
H
C O C
H
O
R
C
O
R
H O
R H
H
R
C O
C
R
O
R
Partial %xidation to aldehydes
e.g. ethanol to ethanal.
CH"CH22H 3 C2D CH"CH2 3 H22
Total %xidation to Carboxylic acids
e.g. ethanol to ethanoic acid. The mi$ture of reagents is heated under reflux.
CH"CH22H 3 2C2D CH"C22H 3 H22
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To make the aldehyde! the one
reagent is added drop&ise to the
other and the product is distilled off as
it forms.
By distilling the aldehyde off as it
forms! it means it &ill not undergo
further o$idation to the acid.
Heating under reflux
The apparatus sho&n here is used a large
number of organic preparations.
The reaction mi$ture is placed in the pear
shaped flask. t has a reflu$ condenser6 fitted.
This means that as the reactants are heated
and the volatile li0uids boil off! they are
converted back to li0uid in the condenser and
return to the flask.
68 reflu$ condenser Kis not a special type of
condenser! it is an ordinary condenser fitted so
that reflu$ takes place.
Heat
Heat
2nce the carbo$ylic has been formed! it needs to be separated from the reaction mi$ture
and other products. This is done by distillation.
-1-
#istillation is used to separate a
volatile product from a mi$ture
of involatile substances! or
substances that have a boiling
point of at least 1L
o
C higher
than the component being
collected.
Heat
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