14.

01 The different classes of to be kinetically stable: there are large activation barriers
associated with their reactions, so these reactions tend
organic compounds to be slow, or require strong heat, or need strong
reagents to get them going.
Many organic compounds can be considered as being
made up of two parts: a hydrocarbon chain (R) and a
functional group (Fg):
R- Fg
Most of the reactions of an organic compound are
reactions of the functional group it contains - the
hydrocarbon chain stays the same during the reactions.
For example, in the hydrolysis of bromoethane:
CH 3CH 2 Br + OH - CH 3CH 20H + Br-
Figure 14.0 I The substances that fo rm the basis of all the CH 3CH 2- chain (called the ethyl group) stays the
living things al"e organic compounds same. Furthermore, the conditions required for the
reaction (heating under reflux with aqueous sodium
Organic compounds are covalent compounds hydroxide) are the same no matter how long the chain
containing carbon atoms. There are over 10 million is, for example:
different organic compounds known today: they
outnumber inorganic ones by 80: I. Why are there so CH 3CH2CH 2CH2 Br + OH -
many? CH 3CH 2 CH 2CH 20H + Br-

One reason is that carbon forms strong bonds to other If two compounds contain the same functional group,
carbon atoms, so they can join together in chains and and differ only in the length of their carbon chain, they
rings. Another reason is that organic compounds tend are said to belong to the same homologous series.
 Table 14.0 I lists the functional groups you need to know about, and t he names of the classes of compounds that
contain them.

Name of functional I Formula I Class of compound I formula and name of an

group .-
bromo -Br bromoalkanes bromomethane
chloro -Cl chloroalkanes CH)CH 2Cl, chloroethane
hydroxy -OH alcohols CH)CHpH, ethanol
• --
carbonyl: aldehyde -CH=O aldehydes CH)CH 2CHO, propanal

carbonyl: ketone >C=O ketones C H)COCH), propanone

carboxylic acid -C0 2H carboxylic acids CH)C0 2H, ethanoic acid

ester -COl, esters CH)C0 2CH 2C H), ethyl ethanoate
acyl chl oride -COCl acyl chlorides CH)COCl, ethanoyl chlmide
amide - CONH 2 amides CH)CH 2CONH 2, propanamide
amino -NH2 am ines CH)NH2' methylamine
nitrile -C=N nitriles CH)CH 2CN, propanonitrile

Table 14.0 I The fu nctional groups you need to know about

14.02 The different formulae These six formulae al"e illustrated in Figure 14.02 for the
com pound methyl propanoic acid.
used to describe organic
C2H40
compounds empirical
CH3CH(CH¥02H or (CH 3hCHC0 2H
structural

Organic compounds can be represented by six different

types of formulae .Which one you use depends on the CH 3 0 0
level of detail about the structure of the molecule you \ II >--------<OH
want to co nvey. The simplest formula is the empirical CH 3 O- H
formul [Link] tells us th e simplest ratio of elements the
displayed stereochemical skeletal
compound co ntains.
Figul"e 14.02 The different types of formu lae for
The molecular formu la tells us the number of atoms of
each element that are in one molecule of the compound. methyl propanoic acid
The molecular formula of a com pound is always a
multiple of its empirical formula (e.g. X I, X 2, X 3).
Wh enevel" yo u w r ite the stl"UCtU I"aI
The structural formula indicates w hich atoms are 0 1" displayed fOI"mula of an ol"ganic
joined to wh ich in the molecule of the compound. co mpound, I"emeillbel" t o include all th e
The displ ayed fo rmula shows all the bonds and atoms hydmgen atoms. A lso check that t he
within a molecule of the compound. valency of each element is COITect.

The stereochemical formula is a displayed formula that • Hydmgen, bm illine and chlol"inc always
shows the three-dimen sional shape of the molecule. have a valency o f I.

Th e skeletal formula is a simplified version of the • Oxygen always has a va lency of 2.

disp layed formula: it shows all the bonds in a molecule,
• N itmgen always has a valency of 3,
except those to hydrogen atoms, but omits all carbon
except in t he l1 itlO (- N O ,) gmup.
atoms and th eir attached hydrogen atoms.
• Cal"bon always has a valency of 4.
 14.03 How to name organic
Remernbel" that the only hyc!mgen atorm
shown in a skele tal [Link] al'e those
compounds
jOillCd to oxygcrl 01" nitmgen: C 11 atoms The names of organic compounds tel l us what carbon
<l IT' not shown. chain and which functional group(s) they contain.
All names contain a stem and a stem-end. Most also
contain either a suffix or a prefix, or both. Tables

Although and Yy OH 're w""t

14.02-14.05 list some of these.
The stem specifies how many carbon atoms are in the
longest chain.

° The longest chain may not be the most

H
V obvious o ne from the way t he fonnula

H
N O H is wrong.
is dl'aw n out. Yo u should co unt each
of t he possible chains contained in t he
compound befol"e you make up you mind
° w hich is t he longest.

... - - " .
Progress check 14.01 .
meth- I
Draw the displayed formulae of three
eth- 2
compounds that have the molecular formula
C3 H6o. prop- 3
but- 4
2 Write down i the molecular; and ii the
pent- S
empirical formulae of the following
compounds: hex- 6
Table 14.02 T he fll"st six st em names

The stem-end shows the type of carbon- carbon bonds

that occur in the compound (Table 14.03).
r ,-,--

a b 'of bond" "

-an all C- C single bonds

-en one C=C double bond
-dien two C=C double bonds
(HO
-tl'ien three C=C double bonds
-yn one C=C triple bond

Table 14.03 Some of t he stem-en ds used

The suffix describes any oxygen-containing group that Structural formula 'I
might be present (Table 14.04). 3 carbon propane
CH)CH 2CH)
atoms, no
Suffix 1 Group functional
-al 0
group
II 4 carbon but-2-ene
CH)CH=CHCH)
atoms, C=C
an aldehyde group: starts at
-one second atom
0
II CH)CH(OH)CH) 3 carbon propan-2-01
/C"'" atoms, with
a ketone group: OH on second
-01 atom

-C-OH
I CHFH 2COCH 2CH) 5 carbon pentan-3-one
atoms, with
an alcohol group: I C=O on third
atom
-oic acid
-C:;/ CH)CH 2CH(CH))C0 2H 4 carbon 2-methyl butanoic
atoms in acid
\ OH chain, CH) on
a carboxylic acid group:
second atom,
Table 14.04 Four suffixes, all involving oxyge n carboxylic
acid group
The prefix indicates non-oxygen-containing groups, (assumed to
be carbon I)
which may be other carbon (alkyl) groups, or halogen
atoms which are substituted for H along the carbon ClCH 2CH 2CHO 3 carbon 3-chloropropanal
atoms in
chain (Table 14.05). chain, Cl on
.. - l -,
'..-'-'-
third carbon
Prefix . '
" .1 atom from
methyl- CH 1- the aldehyde
group
ethyl- CH 1CH,- (assumed to
propyl- CH 1CH 2 CH o- be carbon I)
butyl- CH 1 CH,CH,CH,- Table 14.06 Illustrating how the systematic names al-e
bromo- Br- bu ilt up
chloro- Cl-
Table 14.05 Some of t he p,-efl xes used
Progress check 14.02
Prefixes can be combined with each other; and they
Draw the structural formulae of the
might in turn be prefixed by 'di' or 'tri' to show multiple
following compounds (their molecular
substitution.
formulae have been given to help you):
Numbers can be added before the stem-end or the
a 2-methylbutanal (CsH,oO)
suffix or the prefix to show which carbon atom the
functional group is attached to. The carbon atoms are b 3-ethylpent-2-en-l-ol (C 7 H140)
numbered from the end nearest the functional group. c 3,3-dimethylpentan-2,4-dione (C7 H,20 2)
Table 14.06 contains some examples to show how 2 Name the following compounds:
naming works. Check that you can see how the names
are constructed for each compound. a b

o Br
:reo>"
14.04 Isomerism b Stereoisomers
There are two types of stereo isomerism.
Isomers are compounds that have the same molecular Geometrical isomerism , or cis- trans isomerism,
formulae, but have different arrangements of atoms. occurs with alkenes that do not have two identical
There are two main types of isomerism: structural and groups on either end of the C= C doub le bond.
stereoisomerism. Structural isomers have different Unlike the case of a C- C single bond, it is not
structural formulae from each other; but stereoisomers possible to rotate one end of a C=C double bond
have the same structural formulae. with respect to the other. For example , there are
two different structures of but-2-ene:
a Structural isomers
There are three types of structural isomerism.
Chain isomers have the same number of carbon
atoms as each other; but their carbon backbones are
different.
For example, pentane and 2-methylbutane are cis-but-2-ene trans-but-2-ene
isomers with the molecu lar formu la CsH 12:
The isomer with both methyl groups on the same
side of the double bond is called the cis isomer; and
that with the methyl groups on opposite sides is
called the trans isomer.
Note that CH3 - CH 2 - CH2 - CH 2 is not another isomer: The carbon atoms on both ends of the double bond
I must each contain two non-identical [Link]
CH3
fo llowing compounds do not exhibit geometrical
th is is just another way of writing the formu la of isomerism because one end, or both ends, of the
pentane. double bond have two identical atoms or groups
CH 3 attached:
I
Note also that CH 3- CH 2 - CH is not another CH
3" C=C
/ CH 3

I CH/ " H
CH3 3
isomer. This is another way of writing the formu la of
2-methylbutane. O ptical isomerism arises because of the tetrahedral
geometry of the Sp3 carbon atom. If a carbon atom
Positional isomers have the same carbon backbone,
is bonded to four different groups, it is cal led a chiral
but the positions oftheir functional group(s) differ. atom, or chiral centre.
Their systematic names reflect this. For examp le, There are two different ways of arranging four non-
I-bromobutane and 2-bromobutane are positional identical groups around a chiral carbon atom, which
isomers: result in two structures that are non-superimposable
CH)CH 2CH 2CH 2Br and CH)CH 2CHBrCH) mirror images of each other. For example, the amino
acid alanine can exist in these two fmms:
Fu nctional gro up isomers contain different
functional groups, and so they often have very
different reactions.
Examples wou ld be the carboxylic acid
CH 3CH 2C0 2 H (propanoic acid) , the ester
CH 3C0 2CH) (methyl ethanoate) and the ketone- ;f'"
r
C
H.....-:::::·
C0 2H
alcohol CH) COCH 2OH (hydroxypropanone).These H2N
are all isomers with the molecu lar formula C)H 60 2 . isomer I isomer II
mirror
 Optical isomers have identical chem ical reactions chain to the next carbon atom in the ring, one of
(un less they are reacted with other chiral them is CH 2CH 2-ring and the other is CH2CHC!-
compounds), and all their physical properties ring. Likewise with carbon atom a: this has - H, - C!,
are also identical - except for one. If a beam of - CH 2-I-ing and - CH2-ring attached to it, but the two
polarised light is passed through them , one isomer ring CH2 groups are not identical - extend ing to the
·• wi ll twist the plane of polarisation in one direction,
and the other isomer will twist the plane to exactly
next carbon produces CH2CH 2-ring for one and
CH2CH(side chain)-ring for the other.
•
the same extent in the opposite direction. Hence
Sometimes stel-eochemical formulae can be
the name optical isomerism. Some molecules contain
confusing. How many chiral centres can you see in
more than one chiral centre. Identifying the ch iral
the following molecu les?

O
J
centres in a complex molecule can be quite difficult,
especially if on ly the skeletal formul a is given .
For example, there are three chiral centres in the III
'H
N il H
fo llowing molecule: o
C/ A B C

OH
Molecule A contains just one ch iral centre (b):
carbon atom a has two (identical) methyl groups
The easiest ch iral centre to recognise is carbon attached to it. Molecule B also contains one chiral
atom C, attached to the -O H group. This has the centre, but molecule C contains none: if you follow
four non-identical groups: -H , -OH, -CH2CH 3 and the carbon atoms in the ring around until they meet,
- CH 2-ring. Carbon atom b has -H, -CH2-chain, you wil l find that the two routes to the ketone
- CH 2-ring, CH 2-ring. Note, however, that the two C=O group are identical.
ring CH 2 groups are not identical - if yo u extend the

Worked example 14.0 I

Draw the structures of all the structural isomers with Step 2: Each of these contains two different positions
the formula C4 H9 0H and name them. where an H can be rep laced by an OH, so
there are four structural isomers, named as
How to get the answer:
below.
Step I: There are two isomeric alkanes with four
carbon atoms: butane and 2-methylpropane. / CH 2 ........ / CH 3
CH 3 CH
CH 3 I
OH
I bulan-I-ol bulan-2-ol
/AH'-..,
CH 3 CH 3
CH 3
bUlane 2-melhylpropane
! ...- OH
CH 3 CH 3
2-melhylpropan-I-ol 2-melhylpropan-2-ol
 Progress check 14.03
There are five isomers with the molecular 3 Draw and name the structures of all the non-
formula C3 H6Cl2. Draw their structures (using cycl ic isomers (i.e. not containing a ring of carbon
stereochemical formulae where necessary), and atoms) with the molecular formula CsH 10' How
describe the types of isomerism shown. many are geometrical isomers of each other?
? Draw the structures of all the isomers with the
molecular formula C3H6BrCl. How many are
optical isomers of each other?

14.05 Types of organic reactions

The following units look in detail at the reactions reference (and revision) to collect together a list of all

' ' -' .

of some functional groups, but it will be useful for the reaction types you need to know (Table 14.07).

( group(s)'tttat - . .
undergoes -the
. _ ' . c _.' ". _ • - " " . . . ". 'c>" • 'c' _ •. ' ;

electrophilic addition alkene CH 2=CHCH 3 + HBr CH 3CHBrCH 3

0 ----..
electrophilic substitution arene N0
+ HN03 O 2 + H2O

nucleophilic addition carbonyl (ketone or

aldehyde)
CH3

/
H
'\=0 + HCN .. CH3
'\/
H/ "C=N
OH

bromoalkane CH 3Br + OH - CHpH + Br-

alcohol CH 3CHPH + HBr CH 3CH 2Br + Hp
nucleophilic substitution
carboxylic acid CH 3C0 2H + SOCl2 CH 3COCI + 502 + HCI
acyl chloride CH 3COCI + NH3 CHFONH 2 + HCI
radical substitution alkane CH 3CH 3 + Cl2 CH 3CH 2C1 + HCI
alcohol CH 3CH 2CHPH CH 3CH=CH 2 + Hp
elimination
bromoalkane CH 3CH 2Br + OH - CH 2=CH 2 + Hp + Br-
ester CH 3C0 2CH 2CH 3 + Hp CH 3C0 2H + CHFHpH
acyl chloride CH 3COCI + Hp CH 3C0 2H + HCI
amide CH 3CONH 2 + Hp CH 3C0 2H + NH3
hydrolysis
nitrile CH 3CH 2C= N + 2Hp CHFH 2C0 2H + NH3
nitroarene
ON02 + 6[H] ----.. ONH2 + 2H 2O

condensation carbonyl (ketone or CH 3 R

aldehyde)
CH 3
"C=O
/
+ H2N·R --.. "
/
C=N / + H2O

C2HS C2HS
-
 "Type of . I _. I
undergoes the

condensation carboxyli c acid +

alcohol
alkene CH
•
•
reduction
o
carboxylic acid + Hp
nitrile

alcohol
oxidation
aldehyde

Table 14,07 T he react ion types you need t o know,

The meanings of some of the terms used in Table 14,07 A condensation reaction is one between two
are given below, molecules to form a larger molecule, with the removal
of a molecule of water:
[H] represents hydrogen atoms that have come from a
chemical reducing agent (such as LiAlH4 or Sn + HCl) Reductio n is a reaction in which hydrogen is added to,
or oxygen is removed from, an organic compound,
[0] represents oxygen atoms that have come from a
chemical oxidising agent (such as + H 2S04) Oxidation is a reaction in which oxygen is added to, or
hydrogen is removed from, an organic compound.
An electrophile is an atom or group of atoms that
reacts with electron-rich centres in other molecules,
Electrophiles usually have an empty orbital in their
valence [Link] are either positively charged or have
Sample answer
a 8+ atom, Q uestio n:
A nucleophile is an atom or group of atoms that reacts Identify the reaction type of each of the following
with electron-deficient centres in molecules (such as reactions.
the C8+ in C8+ -Br'- compounds), All nucleophiles have
a lone pair of electrons and many are anions, ______

A rad ical is an atom or group of atoms that has an

unpaired electron, Radicals (sometimes called free + HBr
radicals) are highly reactive,

An add it ion reaction is one in which an organic

molecule (usually containing a double bond) reacts with
C30
another molecule to give only one product. d '("CHO
A substitution reaction is one in which one atom or
group replaces another atom or group in a molecule, Answer:

An elimin ation reaction is one t hat form s an alkene by a is an electro philic additio n. [I mark]
the removal of a molecule of H 20 from an alcohol, or a b is a free radical substit utio n. [I mark]
molecule of HBr from a bro moalkan e,
c is a hydrolysis. [I mark]
A hydrolysis reaction is one where water reacts with a
molecule and splits it into two smaller molecules, d is a reduction. [I mark]
Exam-style questions
For each of the following reactions: For each reaction:
state the type of reaction undergone write a balanced equation, including the
structures of the starting material and the
ii give the structure of the organic product
product (you may use [H] to represent a
iii give the systematic name of the product. reducing agent adding a hydrogen atom)
a C3H8 + Cl2 -7 C3H7 Cl [3] ii name the starting material and the product.
b C3 H70H -7 C3 H60 2 [3] a nucleophilic substitution [3]
C (CH)FOH -7 C4Ha [3] b nucleophilic addition [3]
Total: 9 c electrophilic addition (3]
2 Illustrate the following reaction types with a d reduction. [3]
suitable reaction of a straight-chain 4-carbon
Total: 12
compound of your choice (e.g. butane,
butan-2-ol).
There are four homologous series of hydrocarbons you need to know [Link] are listed in Table 15.0 I.
.' - --- - . -- - - ...,,
Name of class
__ , " -- - .. - '.

alkanes
CnH2n +2 propane C3HS /CH 2 or
CH 3 -""""CH
3

cycloalkanes CnH2n cyclohexane C 6 HI2 /CH 2

'--- CH

0
CH 2 2

I
CH 2 /
I
CH 2
or

'---CH 2

alkenes CnH2n but- I-ene C4 HS CH or

CH 3 ,--- /
CH 2 2

OC"'
arenes CnH2n - 6 m ethyl benzene C7HS H
H, / CH 3
C C
II I or
H"/ C"
C
-:r C' H
I
H

Table 15.0 I The four classes of hydrocarbon

This unit is concerned with the alkanes, cycloalkanes
and the alkenes. Arenes are covered in Unit 25. The H P
"c
/
= c\
reactions of cycloalkanes are very simi lar to those of H CH 3
alkanes; note, however, their general formul a is the same
D E
as that of alkenes.

Alkenes are named by using the longest carbon chain

15.0 I Physical properties that includes the C=C as the stem, with the position
of the double bond indicated by a number before the
All alkanes and alkenes are flammable. Those with fewer [Link] examples are:
than five carbon atoms are gases at room temperature;
the rest are mostly liquids.
3

15.02 Isomerism and trans-2-methylhex-3-ene dS-3-ethylhex-2-ene

nomenclature
Alkanes show two types of isomerism. Those with Progress check 15.01
four or more carbon atoms per molecule show chain
isomerism, whilst those with seven or more carbon Draw the structural and skeletal formulae
atoms can also exist as optical isomers. of all the isomers with formula CsH 12 and
name them.
The stem of their name is worked out from the longest
carbon chain, and the positions of side-chains are 2 The smallest alkane to show optical
indicated by numbers, as described in Unit 14. isomerism has the molecular formula C7H16•
Draw its structural formula and give its
name.
3 Name, and draw the skeletal formula of, the
A
alkane with the molecular formula CeH Ie
that contains two chiral carbon atoms.
For example, in the compound A, the longest carbon
chain has six carbon atoms, with a 2-carbon (= ethyl)
side-chain on the third atom of the chain, so its name is
3-ethylhexane. 15.03 Crude oil, and how
Alkenes show the same isomerism (chain and optical) alkanes and alkenes are
as alkanes, but in addition they can show geometrical prepared
(cis-trans) isomerism (see Unit 14).This is because
there is no rotation around the C=c, due to its'Tl' Crude oil is a complex mixture of alkanes, cycloalkanes
bond. and arenes, whose molecules contain from I to 30 or
40 carbon atoms. Fractional distillation separates this
The structural requirements for geometrical isomerism
mixture into a few fractions, which are still mixtures of
to occur are that there have to be non-identical
many different molecules.
atoms or groups at both ends of the double bond. So
structures Band C have geometrical isomers, whereas
structures D and E do not.

H l
H
"c = c
C// \,

B c

J ,-
The five most common initial fractions are listed
in Table 15.02.

Name of
fraction
• '-.

rumber
of carbon I in crude oil
IS;;';'e - " -

atoms per
molecule
refinery gas 1-4 <20 2 fuel, petrochemical feedstock

gasoline 5-12 20-180 20 fuel for petrol engi nes, petrochem ical feedstock
kerosene 10- 16 180- 260 13 aeroplane fuel, paraffin, cracked to give more gasoline
gas oil 12- 25 260- 380 20 fu el for diesel engines, cracked to give more gasoline
residu e >25 >380 45 lubricating oil, power station fuel, bitumen for roads,
cracked to give more gasoline

Table 15.02 The main fractions sepa,'ated fmm crude o il

As can be seen from the table, the kerosene and Unlike alkenes, alkanes are rarely made in the
gas oil fraction s (the most common in crude oil) are laboratory. Alkenes are often made by elimination
subsequently cracked to pmduce more gasoline (the reactions, from halogenoalkanes (see Unit 16) or
fraction most in demand) . alcohols (see Unit 17).

By-products of these cracking reactions include the CH3 CH 2CH 2Br + ow

lower alkenes, which are useful starting materials for
polymers.

Here is an exam ple:

tI heat with KOH
in ethanol

CH 3(CH 2)IO CH 3
dodecane
, - -_ _-'A '-_ _
(
CH 3CH = CH 2
,
+

tI heat with steam

at 800°C (CH 3hCHCH 20H

(
,--____A____-...

CH 3(CH 2)4 CH 3 +
,
3CH 2 = CH 2
tI pass vapour
over AI20 3 at 350°C

hexane ethene ,--____A'-_ _

( ,
(CH 3hC =CH 2 +

O OH _heat _
with cone._
H2S04 at _
180°C ....
•
o + Hp

Progress check 15.02

Suggest starting materials and co nditions for the
Figure 15.0 I A catalytic c"acker in an o il ,"efinery
synthesis of the following alkenes:

C H 3C H =CH CH 3
rhe balanced equation for' a c,'acking
,'eaction always includes one 0" mOt'e 2 2-methylpent-3-ene
alkenes, and either one alkane or H 2, but
3
flot both all alkane and H)'Take care to
check the c"acking equations you write.
15.04 Reactions of alkanes and rhod ium, deposited on a honeycomb-shaped
grid. The reactions catalysed can be represented by
Alkanes contain no specific fun ctional gro up. They are the fol lowing eq uations:
very unreactive . Apart fro m the cracking of long-chain cO(g) + NO(g) - - . cO 2 (g) + Yl N 2 (g)
alkanes, the only two reactions you need to kn ow are
combustion and halogenation (reaction with halogens). cO (g) + Yl0 2(g) ---... CO2(g)
unburnt hydrocarbons + 0 2(g) ---... CO2(g) + HP (g)
a T he combusti on of alkanes
These reactions re move the main poll utants, but the
In a plentiful supply of air or oxygen, alkanes burn
greenhouse gas CO 2 remai [Link]"e is no method
to give steam and carbon dioxide:
yet available to remove it from vehicle exhausts.
natural gas
CH 4 (g) + 20/g) ---... CO 2(g) + 2H 20(g)
Although you cannot wl"ite a balanced
b.H&= -890kJmol- equation for-the catalytic I"emoval of
c '
petrol/gasoline unbumt hydl'Ocalbons, you shou ld always
CsH, s(l) + 12);202(g) ---... 8C0 2(g) + 9H20(g) make sure that the other equations are
balanced in youl- answel-s.
b.H&= c
- 5470kJmol- '
The b.H&values
c
tell us that each of these is
Air pollution caused by the combustio n of fuels
a very exothermic reaction: both methane
can be monitored by infrared spectroscopy (see
and octane are important fue ls. Most alkanes
Un it 29).The common pollutant gases (C0 2, S02'
obtained from the fractional distillation of crude
N0 2, NO and CO) all have characteristic absorption
oi l are used as fuels.
bands in their infrared spectra. The intensities of
ii In a limited supp ly of air; 100% of the hydrogen these bands when a samp le of air is analysed in
part of the alkane still gets oxidised to water; but a spectrometer can give an indication of their
the carbon part does not burn completely. For concentrations in ppm (parts per million) in the
example: sample.
CHig) + I);202(g) ---... CO(g) + 2H20(g)
b The reaction of alkanes with halogens
carbon monoxide
In the presence of ultraviolet rad iation, or even
CsH,/I) + 6);2°2(g) ---... visible light, alkanes react with chlorine or bromine.
carbon monoxide 4CO(g) + 4C(s) + 9H 20(g) During the reaction, one or more of the alkane's
carbon (soot) hydrogen atoms is substituted by a halogen atom.
Apart from the poisonous carbon monoxide, and CH 4 +ct2 ---... CH)ct + Hct
the soot, which can cause lung diseases, other
pollutants are formed when hydrocarbon fuels CH )CH) + Br2---... CH )CH2Br + HBr
are burned in a car engine. The temperature of The mechanism of the reaction is free radical
combustion can rise high enough to allow the substitutio n. This is a chain reaction, in which a
reaction between oxygen and nitrogen (both are halogen radical is form ed in the first (init iation) step:
gases in the air) to occur: it reacts with the alkane in the second step: and is
N2(g) + 0 2(g) ---... 2NO(g) re-formed in the third step, to allow the 'chain' to
continue.
2NO(g) + 0 2(g) ---... 2N0 2(g)
In this reaction, the radicals are formed by the
Both NO (nitric oxide) and N0 2 (nitroge n dioxide) homolytic breaking of the X- X bond (X = ct or
cause smog and acid [Link] are co llectively Br). During homolytic fission, each atom takes one of
known as NOx ' the two electrons in the X- X bond:
The removal of poll utants fro m vehicle exhausts
is achieved by passing the exhaust gases through a homolytic
•• •• fission •• ••
catalytic converter: This contains the metals platinum :ct -:- ct. _-=c.:.:...::.._ _ :ct + ·ct.
•• •• •• ••

•
Only the 'odd' unpaired electron in a radical is molecules present. Eventually, two radicals co llide
normally shown, as a dot. with each other, producing a stable molecule:
There are three stages to the overall mechanism: termination: Cl' + Cl' Cl2
initiation, propagation and [Link]
or CH3' + Cl' CH 3Cl
propagation stage involves two reactions: the first
uses up the initiating chlorine radical, and the second or CH3' + CH3' CH3-CH3 (ethane)
regenerates it. Anyone of these three possible termination
light steps will stop the chain reaction, and a fu,-ther
photon will be needed to start it again. Note that
initiation:
the last termination step produces a 2-carbon
propagation I: CH4 + Cl' CH3' + HCl alkane, ethane. This could itself undergo free radical
chlorination, so an expected byproduct would be
propagation II: CH3' + Cl 2 CH3Cl + Cl'
CH 3CH [Link] is in fact found, which provides
evidence for a mechanism involving CH3' as an
Note t hat f,-ee hydrogen ato ms, H' , intermediate.
a,-e never foi-med dLwi ng f,-ee ,-ad ical
The main product, CH 3Cl, can also undergo
substit ution ,-eactions. Check t hat you
free radical chlorination, so other byproducts
do not write equations that include th em .
include CH 2Cl2, CHCl3 and [Link] relative
amounts depend on what Cl2:CH 4 ratio we
These two propagation steps can go on and on, started with.
as long as there are still methane and chlorine

Worked example 15.0 I 2 Step I: There are only two dichloroethanes,

CH 3CHCl2 and ClCH 2CH2Cl, so the other
Write the propagation steps needed to produce two compounds that contain two chlorine
CH 2 Cl2 · atoms must be dichlorobutanes (butane is
2 Suggest four byproducts, each containing two produced by two ethyl radicals combining in
chlorine atoms per molecule, from the reaction a termination step: 2C2Hs' C4 H IO)'
between ethane and chlorine. Step 2: Any two of the following would fit:
3 Suggest starting materials for the preparation of ClCH 2 CH 2 CH 2 CH 2 Cl or
the following compounds by radical substitution
reactions: CH 3CHClCH 2CH 2Cl or
CH 3CHClCHClCH 3 or

c CH 3CH 2CH 2CHCl2 or

CH 3CH 2CCl2CH 3
3 Step I: The starting materials will contain the same
How to get the answer: carbon skeleton, but with the halogen atom
I Step I: In order to produce a dichloroalkane, we replaced by a hydrogen atom.
need to start with a monochloroalkane, in Step 2: So the starting materials are:
this case chloromethane.
a propane (CH 3CH 2CH) + Br2
Step 2: Cl' + CH3Cl CH2CI' + HCl
b cyclohexane (C6H12) + Cl2
CH2 CI' + Cl2 CH 2 Cl2 + Cl'
c methylbenzene (C6HS-CH3) and Br2
 gained the bonding pair of electrons (step I ),This
15.05 Reactions of alkenes
is followed, in step 2, by the bromide ion forming a
a Electrophili c addit ion reactions bond with the intermediate carbocation:

Unlike alkanes, alkenes do not need light in order to

react with bromine, Shaking an alkene with bromine H
H/III',C _ _ C" " \\\ step 1
water or bromine in an organic so lvent, even in the
dark, causes an almost immediate reaction, and the CH 3 " ' " 'H
electrons move out to

0
orange colour of the bromin e disappears:
form a C-Br bond
Ot Br
CH 3CH=CH 2 + Br2 CH 3CHBr-CH 2Br electrons:
in bond :
orange colourless repelled' 00)
This is a good test for the presence of a C=C 8- Br
double bond in a compound,
Other small molecules also undergo addition step 2
reactions with alkenes:
--.
CH CH =CH + Hct room temperature. CH CHctCH
3 2 3 3

steam + cone.
H2S04 or H,P0.
CH CH=CH 2 + H 20 at 300°C. CH CH(OH)CH
3 3 3 The mechanism is usually represented in a simplified
Note that when Hct (or HBr) or H 20 is added way as follows:
to an unsymmetrical alkene such as propene, the
hydrogen atom joins onto the carbon with the
H
larger number of hydrogens already. and the ct, Br H" + /
C- - C- H
or OH join's onto the more substituted carbon, We
CH/r \
shall explain why thi s is later; when we look at the
\. Br
mechanism ofthese reactions,This is an example of 00
Markovnikov's rule, Br

b Markovnikov's rul e Br
When HX adds to a double bond: \ / H
H- C- - C- H
o the hydrogen atom attaches to the carbon that
CH 3
/ \Br
already has the most hydrogens, or
o the electrophi le adds in the orientation that
produces the most stable intermediate cation
When dl"awing mechanisms, make sure
c The mechan ism of electrophilic add it ion yOLI!" curly alTOWS al"e d,-awn accul"ately,
star-ting and fin ishing in the I"ight places,
As we saw in Unit 14 (section 14,05), an electrophile
/\Iso make SUI"e you include all chal"ges
is an atom or group of atoms that reacts with
and 0 1- partial chal"ges on t he con-ect
electron-rich centres in other molecules, When
atoms, and include olll"elevant lone pail"s
a bromine molecule approaches an alkene, the
of electmns,
electrons in the Br-Br bond wi ll be repelled by
the electron-rich clouds of the 1l' bond, causing an
induced dipole to form, Eventually. the electron Note that when the first bromine atom joins onto
shift becomes so great as to break the Br-Br bond, the double bond, the secondary carbocation, rather
forming a bond between the carbon at one end than the primary carbocation, is produced:
of the C=C bond and the nearest bromine atom,
leaving the further one as a bromine anion, having
 With H20 and acid:
secondary carbocat

H H
'0'
r
+
Br /
CH - CH2
\
CH 3 H

primary carbo cation

,
CH\ \ +
/C - CH 2
H I
Br

Although reacting alkenes with bromine in an organ ic

This is because the secondary carbocation has solvent (like hexane) produces the dibromide, as
/:'No alkyl groups pushing electrons into it via their outlined above, a significant second product in the
positive inductive effect, whereas the primary reaction between an alkene and bromine water
carbocation has only one electron-donating alkyl is the bromohydrin, due to the attack of a water

,+
group on its electron-deficient carbon. molecule on the intermediate carbocation:

3
CH

/ C-""-- CH Br 2
Progress check 15.03
H
Draw out the mechanism of the reaction
secondary - two primary - only one electron-donating
alkyl groups: more stable alkyl group: less stable. between bromine water and propene, giving
the bromohydrin, and predict which of the
two possible bromohydrins, CH 3CHBrCH 20H
A similar mechanism operates with other
or CH 3CH(OH)CH2Br; wili be formed.
electrophiles. Most other electroph iles are
unsymmetrical, and already possess a dipole, so one 2 Draw the structures of the products of
does not have to be induced by the 'IT bond, as in the fol lowing reactions. Do not forget
the case of bromine. Because of the inductive effect, Markovnikov's I-ule!
Markovnikov addition is usually observed. a CH 2=CHCH 2CH 3 + HCl-----..
With HBr:
b CH 2=C(CH)2 + H20 + H+-----..

'u'''' .
d Catalytic hydrogenation
Alkenes can be reduced to alkanes by reaction with
hydrogen over finely divided platin um or nickel.
Pt + heat
(CH 3)2C =CHCH 3+ H2 • (CH 3)2CHCH2CH3

o
cyclohexa- l ,4-diene
Ni + heat
• o
cyclohexane
C6HS C6 H12
e The oxidation of alkenes
Note that neither aldehydes such as
A lkenes burn well in oxygen or air:
R U 10. nor meLhanal (CH)O), nor
CH 2= CH 2 + 302 2C0 2 + 2H 20 methanoic acid (HCO,H) al'e fOI·med .
ii When shaken with alkenes at room temperature , These always get oxidised funhel: Check
purp le dilute KMn0 4(aq) is deco lorised. Like the that you do not illcl ude any of t hese in the
reaction with bromine water; described above, pmcluc ls of KM"O" oxidations of alkenes.
this is an excellent test for the presence of a
double bond. The product is the diol:
This I'eaction is very useful in wOl'king out the
CH)CH = CH 2 + H 20 + [OJ structure of a compo und from its cleavage products.
I (oxygen atom
, from KMn0 4) For examp le, if it is known that the oxidation
of com pound X, C 6 H 12, with hot KMn04 gives
CH)CH(OH)-CH 2 0H 3-methylbutanone and ethanoic acid, we can work
propan-I,2-diol out that X is 3.4-d imethylpent-2-ene:
iii Ifthe potassium manganate(VII) is hot,
concentrated and acidified, cleavage of the
double bond occurs. The types of compound ethanoic acid HO y Hy

formed depend on the extent of substitution

00 c) (
there is at each end of the double bond:
CH)CH=CH 2 + 5[OJ 3'methylbutanone 3,[Link]
CH)C0 2H + CO 2 + H 20 (X)

(CH))2C=CHCH2CH) + 3[OJ
(CH))2C=0 + CH)CH 2C0 2H If the double bond is part of a ring, no loss of carbon
atoms occurs, although the C=C is still cleaved:
Table 15.03 lists the possible products.

hot KMn0 4

R
o

H
"'/ c =
(carboxylic acid)

(ketone)

Table 15.03 T he compound s produced from t he

comp lete oxidation of C = C bon ds
 Progress check 15.04
Oraw the structures of the products
of reaction between hot KMn04 trace of peroxide (R-O-O-R) + heat and pressure
and each of the following isomers of
3,4-dimethylpent-2-ene (X):
a 2,3-dimethylpent-2-ene,

f t- tl
(CH})2C=C(CH)CH 2CH}
b 2,3-dimethylpent-l-ene,
CH}CH 2CH(CH})C(CH})=CH 2 H HJ n (5000 < n < 10 000)
c 2-methylhex-3-ene, poly(ethene)
(CH})2CHCH=CHCH2CH3
LOPE
2 Work out the structures of Y and Z:
a Compound Y, C6H10 ' reacts with hot However, if triethylaluminium is the catalyst, the average
KMn04 to give 3-methylpentan-1 ,5-dioic chain length increases, and high density poly(ethene),
acid (H0 2C-CH 2-CH(CH})-CH 2-C0 2H). HOPE, is formed:

b Compound Z, C 10 HI8 , reacts with hot

n CH 2=CH 2 AI(C2 HS)3 C- C
KMn04 to give 4-methylcyclohexanone
(C7 H I2 0) and propanone (C}H60). in hexane at SooC H H n (100000 < n < 200000)
ethene
poly(ethene)
HDPE

The van derWaals' forces between the chains in LOPE

15.06 The polymerisation are less than those in [Link] is reflected in their
of alkenes different properties and uses (Table 15.04).

Industrially, one of the most useful reactions of alkenes

is their addition polymerisation.
Polyalkenes are called addition polymers because they density low high
are made by adding monomer units to a growing alkyl m. pt. approx. I 30°C approx. I 60°C
chain, and the molecular formula of an addition polymer
tensile strength low higher
is a multiple of the molecular formula of the monomer
flexibility very flexible much more rigid
- both have the same empirical formula.
uses polythene bottles, buckets,
Addition polymerisation is a chain reaction in which bags, electrical crates
the alkene monomer units are added one-by-one to insulation,
the growing polymer chain. The reaction is initiated dustbin liners
by a catalyst - either an organic peroxide or an Table 15.04 Some properties and uses of po ly(ethene) .
organo-aluminium compound. If a peroxide is used
to initiate the polymerisation of ethene, low density A variety of important polymers can be obtained
poly(ethene), LOPE, is formed: by polymerising substituted ethenes. Representative
polymers are listed in Table 15.05.
 • • of (two I
repeat units shown) and
name
packaging, ropes, thermal clothing, carpets, car
components, containers

poly(propene)

chloroethene, CH 2 =CH-Cl water pipes, gutters, upholstery, rubber substitute

poly(chloroethene) or PVC

phenylethene, solid: disposable cutlery, plastic models, CD and

DVD cases
expanded: packing materials, insu lation, foam
drin ks cups

poly(phenylethene), polystyrene

tetrafl uoroethene, CF2 = CF2 non-stick surfaces for cooki ng ware; bridge
bearings, non-corrosive tubing

l F F F F

poly(tetrafluoroethene), PTFE

Table 15.05 Some ot her addition polymers and the ir uses

Worked example 15.02 a CH 2

/ CH2 /
' \H
Draw a section of the polymer chain, showing two I I
CN CN
repeat un its, of th e polymer formed from each of t he

..
fo llowing monomers. ,
+ CH 2 = CHCN " CH 2 / CH 2 ,,
,, ' CH ' CH
a CH 2 =CH- CN I I
CN CN
b
How to get the answer: b CH3 CH 3

Step I: Break t he double bond, and create two 'free'

I
CH ... /
I
CH /
'1:H ' CH
bonds. I
I C0 2H
C0 2H
Step 2: Jo in t hese free bonds to adjacent monomers.
In general, the po lymer wi ll have it s side-chains
alternating along the chain. + CH3CH =CHC0 2H
...
15.07 The disposal of polymers b Depolymerisation
Heating polymers to high temperatures in the
Polyalkenes are chemically inert and biodegrade only absence of air or oxygen (a process known as
very slowly, so many addition polymers can cause pyrolysis) can cause their chains to break up into
environmental problems when their usefu l lives are over: alkene [Link] process is sim ilar to the cracking
of long-chain hydrocarbons into [Link]
Four methods are avai lable for their safe disposal.
monomers produced can be separated by fracti onal
a Incineration distillation and re-used.
Under the right conditions, incineration can provide c Recycl ing
useful energy for space heating or power generation.
Many polymers can be melted and remoulded.
A high temperature of combustion is needed if
poisonous combustion products, such as dioxins, d Bacterial fermentation
are to be [Link] fumes from the incineration
chamber need washing with water to absorb Under the right conditions some polymers can be
noxious com bustion products such as HCl from the degraded quite quickly by certain strains of bacteria.
burning of PVc.

Sample answer
Question:
Hydrocarbon X, C4 H 10' undergoes the following series
of reactions.
heat with KOH
Cl2 + light in ethanol

t
Suggest structures for the compounds X, Y, Z
and P. [4]
CH
Answer: I
CH
3' CH
Z: CH 3-CH=CH-CH 3 [I mark] {
P: poly(but-2-ene), n [I mark]
Y: CH 3CH 2 CHClCH 3 [I mark]
[Link]- tyle questions
Crude oi l is a mixture of hydrocarbons with Dodecane, C 12H26 , is an alkane that occurs
molecules contain ing between I and about 40 in crude oil. It can be 'cracked' into smaller
carbon atoms. The first stage of converting it into alkanes and alkenes.
useful substances is fractional distillation. c State the general formulae of alkanes and
a Explain the meaning of the terms hydrocarbon alkenes. [2]
and fractional distillation. [2] d State the conditions under which cracking
b State the uses of two f,"actions from the reactions take place.
fractional distillation of CI"ude oi l. For each ii Write a balanced equation for the cracking
fraction state the approximate chain length of of dodecane into hexane and ethene. [2]
the hydrocarbons it contains. [2]
 to There are several structural isomers of ii Suggest the ratio of the amounts of the
hexane, C6 H14' two compounds produced. Explain your
answer. [31
Explain the meaning of the term
structural isomers. Total: 10
•
ii How many structural isomers are there 3 a State Markovn ikov's rule. [I]
·• with the formul a C6 H1) b Suggest the products of the following
iii Draw the skeletal formulae of three of reactions of three isomers with the formula
these isomers. [4] CsH lo '
Total: 12 (CH)2CHCH=CH2 warmed with di lute
sulfuric acid
2 Alkanes undergo free-radical substitution reactions
with chlorine. ii (CH))2C=CHCH) treated with HBr(g)
a Explain the meaning of the term free radical. [ I] iii CH 2=C(CH))CH 2CH) treated with
b State the conditions required for free-radical Br/aq). [3]
substitution reactions to occur. [ I] c Some alkenes can show geometrical
isomerism. State which, if any. of the above
c Write an equation for the reaction between
three alkenes show geometrical isomerism.
ethane and chlorine. [I]
Explain your answer, and draw the structures
d Describe the mechanism of this reaction, of any cis-trans isomers. [2]
labelling all the steps involved. [4]
d The above three isomers can be
e When 2-methylpropane reacts with chlorine, distinguished by the use of hot acidified
two different compounds with the formula KMn0 4• State the products that each isomer
C)H7 Cl are formed. would give on oxidation by this reagent. [5]
Draw structures for the two compounds. Total: I I
 R
16.01 Properties, isomerism I
R-C - Cl
and nomenclature I
R
a primary bromoalkane a secondary iodoalkane a tertiary chloroalkane
The halogenoalkanes are compounds in which one or
more halogen atoms are bonded to an alkyl chain,
The main intermolecular force in halogenoalkanes is the 16.02 Methods of preparation
van derWaals' induced dipole force ,Their boiling points
therefore increase with chain length, just like those of There are three ways of preparing halogenoalkanes,
the alkanes,
a Halogenation of alkanes by free-radical
Halogenoalkanes show chain, positional and optical
s ubstitution
iso merism,They are named as derivatives of the parent
alkanes, by appending the prefix 'chloro', 'bromo', etc. t o (see Unit 15)
the alkane name, We can illustrate th is by looking at the
light
..
ot
five isomers with the formula C4 H 9 Br; shown below, C2H6 + Br 2 CH 3CH 2Br + HBr

CH /CH2
3'CH 2
/ Br
' CH 2
CH 3
I
/ CH"
CH 3
./ Br
CH 2
CH 3

CH -
3
/Br
'c
\
CH 3
+ Cl2 .. 0'",<1
light or heat
+ HCl

l-bromobutane l-bromo-2-methylpropane 2-bromo-2-melhylpropane

/ CH 2 / CH 3 b Electrophilic addition to alkenes

CH ' c/ The addition of chlorine or bromine to alkenes gives
3

Br H
dihaloalkanes (see Unit 15),
I CH)CH 2CH=CH 2 + Br2------. CH)CH 2CH BrCH 2Br
optical isomers of 2-bromobutane
The add ition of hydrogen halides to alkenes gives
We can classify halogenoalkanes as primary, secondary monohaloalkanes, The orientation of the halogen
or tertiary, depending on how many alkyl groups are follows Markovnikov's ru le,
attached to the carbon atom joined to the halogen
CH)CH 2CH=CH 2 + HBr - - - . CH)CH 2CHBrCH)
atom,
 c Nucleophilic substitution of alcohols Whether the nucleo phile attacks before 01- after
A variety of reagents can be used to make the bromide ion has left depends on whether the
halogenoalkanes from alcohols. halogenoalkane is primary, secondal"y or tertiary. We
warm can explain this as follows.
CHF Hp H + PCls CH 3CH2Cl + HCl + POCl3
,.•, warm
Steps I and 2 together describe the SNI [Link]
•
CH 3CHP H + 50Cl2 CHF H2Cl + HCl + 50 2 's' stands for substitution; the 'N' stands for nucleophilic;
CH CH 0 H + HBr cone. H2S04 + NaBI" + heat. and the ' I' means that only one molecule is involved
3 2
in the slow step of the reaction. Step I is li kely to be
CH 3CH 2Br + Hp
much slower than step 2, since it involves the breaking
of a fairly strong bond and the separation of opposite
16.03 Nucleophilic substitution charges - both of which are endothermic processes.

reactions Its rate therefore depends only on how much

bromoalkane there is, and not how much OH - .lf
Halogens are more electronegative than carbon, and so [OH - ] is increased, the rate of step 2 would increase,
the C-Br bond in a bromoalkane is strongly polarised but the rate of the overall reaction would not increase,
CO+ -BrS- . During the reactions of bromoalkanes, this as step I would still be the slower step.
bond breaks heterolytically to give the bromide ion: Reaction 3, on the other hand, involves a single step
that includes both RBr and OH- , so the rate of reaction
18+ (;8- depends on how much there is of each [Link] is
-C----.-Br called the SN2 mechanism .The 's' and the 'N' mean the
I Step I same as they did for the SNI reaction, but the '2' now
means that two species are involved in the slow (and
only) step of the reaction.
The C+ formed is then liable to attack by nucleophiles
(anions or neutral molecules that possess a lone There are two factors that determine whether a
pair of electrons). We shall use hydroxide ion as the bromoalkane reacts via the SN I or the SN2 mechanism,
nucleophile to describe the mechanism. and both work in the same direction, encouraging
primary bromoalkanes to react via the SN2 mechanism,
and tertiary bromoalkanes to react via the SN I
-
HO:I' .... r mechanism. (Secondary bromoalkanes usually react via
a mixture of the two mechanisms.)
Step 2 As we saw in Unit 15, when we looked at the
Markovnikov addition of HBr to alkenes, alkyl groups
Sometimes, however, OH - will attack the C8+ carbon are electron-donating, and so their presence stabilises
before the bromide ion has left: carbocations by spreading out the positive charge.
Since the slow step in an SN I reaction is the formation
of a carbocation, this mechanism is favoured in the case
of tertiary bromides.

Step 3 CH 3
slow ,..
, +: Br
CH 3
Do not fOI"get to include all I"elevant
electron pail"s and dipoles (0+ and 0-)
" CH 3 :OH
when drawing reaction [Link] 3 electron-donating
'cudy armws' should always be dl-awn alkyl groups stabilise
the carbo cation
accLwately. showing exactly whel-e the
electron pairs al-e coming fi-om and going to. CH 3

__
I
CH - C- OH
+OW
.. 3 I
CH 3

L
On the other hand, the 'half-way-house' (called the less favoured w ith tertiary bromoalkanes, wh ich have
transition state) in an SN2 reaction invo lves squeezing three alkyl groups on the central carbo n, compared to
five groups around the central carbon atom. This is pl-imary bromoalkanes, wh ich have on ly one alkyl group.

I I (-)
----.. H-O- ----
'\,
R.., y- -----
R

CH 3
Br
(-)
+ :Sr

If R= alkyl, this transition

state is more hindered, so is
less stable, than if R= H.

These conclusions can be summarised in Table 16.0 I .

Reasons

primary SN 2 Less steric hindrance in 5-coordinated transition state. Little stabilisation of

carbocation by just one alkyl group.
secondary mix of SN I and SN2 A fair amount of steric hindrance in 5-coordinated transition state. Only poor
stabilisation of carbocation by two alkyl groups.
tertiary SN I Large amount of steric hindrance in 5-coordinated transition state. Good
stabilisation of carbocation by three electron-donating alkyl groups.

Table 16.0 I T he re lationship between mechan ism and structu re of halogenoalkanes

Progress check 16.0 I I 2-chloropentane

Predict whether each of the following compounds

2 3-bromopentane

will react with OH- by an SN I or SN2 mechanism, or 3 I-bromobutane

a mixture of the two.
4 3-ch loro-3-methylpentane.

A number of different nucleophiles undergo

nucleophilic substitution with bromoalkanes.
Some of them are listed in Table I 6.02.

when reacted with

...
water H 2O : heat in water CH 1 CH,oH + HBr
hydroxide ion HO:- heat with NaOH(aq) CH 1 CH,OH + Br-
ammonia :NH 3 heat under pressure in a sealed tube CH 3CH 2NH 2 + HBr
with NHl in ethanol
cyanide ion -:C=N heat in ethanol w ith NaCN CH 1 CH,CN + Br-
Table 16.02 Th e val-ious nucleoph il ic substitution reactions of halogenoalkanes
 The product from the reactio n of a halogenoalkane and
Be especially cal-eful to I-emember the cyanide ion is called a nitril e.
exact I-eagents and conditions for- these
Nitriles are impol-tant in organic synthesis, as they
reactions. Under dirfelcnt conditions,
provide either carboxylic acids on hydrolysis or primary
hydmxide ions can cause eli mination
,•. amines on reduction:
. I-eactions to OCCUI- with bmmoalkanes
• (see latel' in this unit); and cyanide ions "j0
al-e also used as a homogeneous catalyst R-C-Y
in nucleo philic addition I-eactions with ""OH
cal-bonyl compounds (see unit 18).
R- C=N

Worked example 16.0 I The relative rates of hydrolysis of chloro-, bromo- and
For each of the following compounds. suggest iodoalkanes can be compared by their reaction with
a suitable starting bromoalkane. and give the silver nitrate in an ethanol- water mixed [Link]
reagents and conditions needed to make the halogenoalkane slowly hydrolyses, releasing the halide
compound. ion, which reacts with Ag+ ions to form a silver halide
precipitate:
a (CH)2CHCH2NH2
b CH 3CH 2CH(OH)CH 3 R- X + H20 + Ag+ • R- OH + W + AgX(s)
The results are shown in Table 16.03.
How to get the answer:
a Step I: To make a primary amine, R-NH2'
we need a bmmoalkane with the
same carbon skeleton, so the starting
material will be (CH3)2CHCH2Br.
(CH)2CH - Cl slight cloudiness after white
Step 2: The reagent and conditions we need I hour
are: heat with NH3 under pressure in (CH3)2CH-Br cloudiness appears pale cream
ethanol (pressure is needed because after 10- 20 minutes
NH3 is a gas at atmospheric pressure, (CH)2CH- 1 thick precipitate pale yellow
so would escape fmm the heated appears within a
solution before it had time to react). minute
b Step I: The starting material will have the Table 16.03 How silver nitrate is used to differentiate
same carbon skeleton as the alcohol between halogenoalkanes
product: CH 3CH 2CHBrCH 3.
This trend in reactivity corresponds to the strengths of
Step 2: We need to treat this
the C-X bond (Table 16.04).The weaker the bond (i.e.
2-bromobutane with hot NaOH(aq).
the smaller the bond enthalpy), the easier it is to break,
so the faster the reaction.

Progress check 16.02 Bond Bond enthalpy

Write balanced equations, including the structures C- F 485
of the pmducts, for the reactions between: C- Cl 338
I-bmmopmpane and sodium hydmxide C- Br 285
C- I 2 13
2 2-bmmobutane and sodium cyanide
Table 16.04 C-halogen bond enthalpies
3 2-chlompmpane and ammonia.
16.04 Elimination reactions
Sample answer
In section 16.03 above, we saw hydroxide ions acting as
Question:
a nucleophile towal"ds a 8+ carbon atom . Hydroxide
ions can also act as bases, taking protons away from Suggest structures fOI" compounds A- D in the
other compounds, for example: following scheme, and state the reagents and
HO- + HCl H20 + Cl- conditions for reactions 2 and 3. [6]

Under the right conditions, hydroxide ions can take a

proton off a bromoalkane, which causes an elimination
reaction to occur; forming an alkene.
OH - + H20 + CH 2=CH 2 + Br-
The mechanism is as follows:
Answer:
A is CH 3CH(OH)CH 3 [I mark]
B is CH 3CH = CH 2 [I mark]
In general: C is (CH)2CH-NH2 [I mark]
• elimination reactions have higher activation energies, D is (CH3)2CH-CN [I mark]
so are favoured by higher temperatures
Reagent and conditions for reaction 2: heat with
• they are less prone to steric hindrance, so are KOH in ethanol [I mark]
favoured with tertiary bromoalkanes
Reagent and conditions for reaction 3: heat with
• they involve a greater spreading-out of charge in the NH3 in ethanol undel" pressure [I mark]
transition state than either the SN I or SN2 reactions,
so are favoured by less polar solvents such as ethanol
The usual conditions for an elimination reaction are to 16.05 Useful halogeno
heat RBr under reflux with KOH in ethanol (KOH is more
soluble in ethanol than is NaOH). compounds and their
environmental impact
Progress check 16.03 Halothane (CF3CHBrC0, isoflurane (CF3CHCl-O-CHF)
and sevoflurane ((CF3)2CH-O- CH/) are important
Suggest suitable bromoalkanes, reagents and
anaesthetics, used in surgery the world over.
reaction conditions for the synthesis of the
following compounds. The halons, such as CBrClF2, are useful fire
extinguishers. All of these contain many fluorine atoms:
CH 3CH 2C(CH)CH 2CN
the C-F bond is very strong, and so is quite unreactive.
2 CH 3C(CH)CHCH 2NH 2
Many polychloroalkanes such as I, I, I-trichloroethane
3 CH 3CH=CHCH 3 (CH 3CCl) are used as solvents.
4 CH 2=CHCH 2CH 3· Polychloroethene (PVC) is a very useful plastic, with
a variety of uses (see Unit 15). Once finished with, it
has to be disposed of with care: incineration under the
wrong conditions can produce irritant HCl(g), or the
highly poisonous tetrachlorodioxins.
 CFCs (chlorofluorocarbons) are inert, volatile liquids diffuses back into the lower atmosphere,Thel-e it can
that at one time found favour as refrigerator fluids and react with water vapoul' to produce hydrogen ch loride,
aerosol propellants, However; it was found that, once which can be flushed out by rain as dilute hydrochloric
I-eleased into the atmosphere, they diffused into the ac id,
stratosphere, where ultraviolet radiation from the Sun
•
",
Other stratospheric pollutants such as nitric oxide from
decomposed them into chlorine atoms,These fl'ee
high-flying ail'craft also destroy ozone,
• radicals catalysed the destl'uction of the ozone layer;
which is important in filtering out the harmfu l UV
radiation from the Sun,

ultraviolet light
CF)C/------='---..... CF)' + Cl'
Ozone is formed from oxygen molecules by the action
of UV light:
0 2----+ 20
°+ 0 2----+ 0 )
The chlorine atoms produced from CFCs act as
homogeneous catalysts (see Unit 9), decomposing
ozone, 0 ), into oxygen, 02' by a free radical chain
reaction:
C/' + 0 ) ----+ C/O' + 02
C/O' + ° ----+ C/' +02
Figul'e I6,0 I The dep leted ozone layer ovel' the
It has been estimated that one chlorine atom can
destroy over 105 ozone molecules before it eventually AntalTtic
F m- tyl qu tion
Study the following scheme showing some ii Describe how AgNO)(aq) can be
reactions of 2-bromobutane and answer the used to investigate this difference in
questions below. I-eactivity. You should describe the
observations you wou ld make with each
halogenoalkane. [3]
\ KCN in ethanol b Chlorofluorocarbons (CFCs) , such as
\ heat under reflux
dichlorodifluoromethane, CCll2, were once
A heat with HJO;' B used as aerosol propellants.
CSH 100 2
State two reasons why CFCs were used
a Name the type of reaction undergone in as aerosol propellants. [2]
reactions I and 2. [2] ii Explain what happens to CFCs in the
b State the reagents and the conditions for upper atmosphere in the presence of
reactions 1, 2 and 3. [6] ultraviolet light, and explain why they are
harmful to the ozone layer. Use CCll2
c Suggest the structures of compounds as an example of a CFC in any equations
A and B. [2] yo u write. [3]
Total: 10 Total: 10
2 a Chloroethane, bromoethane and iodoethane
differ in their reactivities in nucleophilic
substitution reactions.
State the trend in reactivity, and explain
the difference. [2]
 Two carboxylic acid molecules readily form dimers:
17.01 Formulae and properties
The alcohols form a homologous series with the #0 :
general formula Cn H 2n+ , OH. Carboxylic acids have the 2 CH
3 \
general formula Cn H 2n+ I C0 2 H.
O- H
Alcohols with small Mr values are totally miscible w ith s- &t
water; due to hydrogen bonding between the alcohol O;-----H- O
molecules and water molecules: ----="",,-- \ - - CH
\ &t 3
O- H-----: O

Carboxylic acids contain three sites for hydrogen

bonding to water molecules:

O- H

O.!'- - ---H
/
Th e boiling points of the alcohols are all much higher CH 3- C H
than alkanes w ith similar Mr values, due to strong \ O- ./
H--- O
intermo lecu lar hydrogen bonding: H /. 0 "-

"O - H" H

As a result of the electron-donating properties of

alkyl chains, alcohols are slight ly less acidic than water;
because the resulting alkoxide ion is less stable than is
the hydroxide ion.
As the ir name suggests, carboxylic acids are acidic,
though they are generally weak acids, incompletely
ion ised in aqueous solution:
 CH3C02H(aq) CH 3C0 2- (aq) + H+(aq) c Optical isomerism

In a 1.0moldm - 3 so lution of ethanoic acid, on ly about I

molecule in 1000 (0.1 %) is ionised. .
r
,.,
Nevertheless, carboxylic acids are about 1011 times
more acidic than alcohols. This is due to the ability
of the carbonyl group to delocalise the negative charge
in the anion, thus making the anion much more stable CH 3CH 2
/ c.:::::---oH
'%H
r CH 2CH 3
than the alkoxide ion from alcohols.

alcohol:
H - R- O:
anion not stabilised
by delocalisation
+ W
R-butan-2-ol

The two non-superimposable mirror images

mirror
S-butan-2-ol

carboxylic acid: ;l
C;0 ?- of butan-2-01.
R- ( ----
R- ( ------- W+ d Primary alcohols
\ H
'\:0.1
'-_ __=--__ .__----
o V These contain the - - CH 20H group.
or (Vd Examples are:
R--<O
butan-I-ol CH 3CH 2CH 2CH 20H
\(Vr)
anion stabilised by delocalisation
2-methylpropan-l-ol (CH3)2CHCH20H iOH
e Secondary alcohols
17.02 Isomerism and
These contain the jCHOH group.
nomenclature
An example is:
Alcohols are named by adding the suffix -01 to the name-
stem of the alkane that has the same number of carbon butan-2-01 CH 3CH 2CH(OH)CH 3
atoms. A number is added before the '-01' to show where
on the chain the -OH group is situated. If there are side- f Tertiary alcohols
chains in the molecule, their position is indicated by a These contain the group.
number added before the side-chain prefix.
An example is: /
Alcohols show three types of isomerism. The isomers of
C4 H90H can be used to illustrate these, and also their 2-methylpropan-2-01 (CH3)3COH
nomenclature.
g Functional grou p isomeri sm
Alcohols with the formula C4 H90H also illustrate the Both carboxylic acids and esters contain the carboxyl
three types of alcohol. group, - C0 2-, and those with the same molecular
formula are fun ctional group isomers of each other.
a Chain isomeri sm
The following three compounds are isomers with the
CH 3CH2CH 2CH 2OH butan-I-ol molecularformula C3H60 [Link] first is a carboxylic
(CH 3)2CHCH20H 2-methylpropan-l-ol acid, and the other two are esters.

b Positional isomerism
CH -
l
C
CH 3CH 2CH 2CH 2OH butan- I-ol 3 \
0 - CH 3
CH 3CH 2CH(OH)CH 3 butan-2-01
propanoic acid methyl ethanoate ethyl methanoate
(CH3)2CHCH20 H 2-methylpropan- l-o l
(CH)3 COH 2-methylpropan-2-01

1- .,:. , I
 c Reduction
Progress check 17.01 Aldehydes and ketones can be reduced to alcohols
by a variety of reducing agents:
a Draw the skeletal formulae, and write
down the names, of all the alcohols with • hydrogen gas over a nickel catalyst
the molecular formula CsH II OH. • sodium borohydride, NaBH4' in water
b Identify which of these are pl"imary, • lithium aluminium hydride (LiAIH 4) in dry ether
secondary and tertiary alcohols.
Aldehydes give primary alcohols:
c How many of these alcohols contain
chiral carbon atoms? NaBH 4
(CH])2CHCHO (CH3)2CHCH20H
2 Draw the skeletal formulae, and write down
the names, of all the compounds with the Ketones give secondary alcohols:
molecular formula C4Hs02 that contain the H2 + Ni
carboxyl group, -C0 2- . CH 3CH 2COCH] CH 3CH 2CH(OH)CH 3
Carboxylic acids can be reduced to primary alcohols.
The stronger reducing agent, LiAIH4' is required:
17.03 How are alcohols made? CH 3CH 2C0 2H
LiAlH4
CH]CH 2CH 20H

a Nucleophilic substitution
Heating a halogenoalkane with aqueous sodium Progress check 17.02
hydroxide produces an alcohol. Give the structural formulae and the names of the
CH]CH 2CH 2Br + NaOH(aq) --.. alcohols produced in the following reactions.
CH]CH 2CH 20H + NaBr(aq) CH) + KOH(aq) --..
b Electroph il ic add it ion
Ethene undergoes a hydration reaction when it is
passed with steam over a phosphoric acid catalyst
at an elevated temperature and pressure. This is the
main industrial method of making ethanol:
Hl04 at 300°C and 70atm 17.04 How are carboxylic acids
CH 2=CH2 + H20 CH 3CH20H
made?
The hydration can also be carried out in the
laboratory by absorbing the alkene in concentrated a Oxidation of primary alcohols or aldehydes
sulfuric acid, and then diluting with water :
CH 2=CH 2 + H2S04 --.. CH 3CH2-OS0 3H
CH 3CH 2-OS0 3H + Hp CH 3CHPH + H2S0 4
If the alkene is not symmetrical, the addition follows
Markovnikov's rule (see Unit 15), and the OH joins to b Hydrolysis of nitri les
the more substituted end of the double bond. heat w ith H2S0 4(aq)
CH] - C == N .. CH 3C0 2H
H+
CH3CH=CH2 + H20 --.. CH]CH(OH) CH3
propene propan-2-01

,-
 The most commonly used oxidising agent is acidified
You may be dsked kll' the othel' pmcluct potassium dichromate, which turns from orange to
of this l-e,lC llon, It is the ammon ium ion, green (Cr3+(aq)) as it is I-educed, Another oxidising
NII ,' ,Thl' flill bal,ulCeci eq uatioll is: agent that can be used is hot KMn04 + H+(aq) ,
R- CN + II + 211)0--,. Secondary alcohols:
R COI H + NH'11 heat under reflux
w ith +
WI-ite ionic I-a ther than moleculal'
(CH)2CH (O H) + [0] dil H 2S0 4
equations wllenevel- yo u can (but do
propan-2-01
not fOI-ge t the charges) ,l he mo leculal-
eq uation fO l' Lhis I-eac lion is a little mOI-e (CH3)2C=0 + H20
propanone (a ketone)
complicated!
2R-CN -I H)SO" + 4H)0 ii Primary alcohols, with an excess of oxidising agent:
2R CO 2H + (NH )ISO , heat under reflux
w ith +
CH CH CH 0H
3 2 2
+ 2[0] _d_
il H
_ 2_S_O_
4 _ _••

c Hydrolysis of acid derivatives such as esters or propan-I -01

acyl ch lorides CH 3CH2C0 2H + H20
This is not a generally useful method, as acid propanoic acid
derivatives are usually made from the carboxylic
iii Primary alcohols, adding the oxidising agent to
ac ids in the first place,
the alcohol, and distilling off the aldehyde as soon
as it is formed (see Unit 18):
Progress check 17.03 heat with +
dil H 2S0 4 , distil product
Suggest t he structures of the carboxylic acids CH CH CH OH + [0] as it is formed •
formed by the following reactions, identifying the 322
propan-I-ol (b, pt. 97°C)
intermediate compounds X and y, CH 3CH 2CH=0 + H20
(CH 3)2CHCH20H + Na2Cr20 7 and propanal (b. pt. 49°C)

iv Tertiary alcohols are resistant to oxidation.

2 (CH)2CHCH20H + HBr X
+ H 2S04 (aq)
3 X + KCN ---.. Y (CH 3)3C-OH >' • no reaction
4 Y + H30 +(aq), and heat ---.. Z 2-methylpropan- 2-01

b Nucleophilic substitution
There are several ways of converting alcohols into
17.05 The reactions of alcohols halogenoalkanes.

a Oxidation With an inorganic chloride:

Al l alcohols burn well in air or oxygen, producing gentle warming

carbon dioxide and water vapour:

CH3CH20 H + SOCl2 •
CH 3CH 2Cl + S02 + HCl
CH 3CH 20H + 302 2C02 + 3H 20 gentle warming

Ethanol is an im portant fuel in its own right (e,g, in (CH) 2CHCH20 H + PCls •
camping stoves) and in some countries it is also a (CH3)2CHCH2Cl + POCl3 + HCl
component of petrol (gasol ine) for motor transport. ii With concentrated HBr(aq) or a mixture of
Under more controlled conditions in the laboratory, KBI" + H2S04 (aq)
heat under reflux
primary alcohols can be oxidised to aldehydes or
carboxylic acids, depend ing on the cond itions used;
(CH)2CH(OH) + HBr •
(CH) 2CH- Br + H20
and secondary alcohols are oxidised to ketones,
 iii Tertiary alcohols are so reactive they can e The triiodomethane reaction
be converted into chlorides by shaking with This is a specific reaction undergone by alcohols
concentrated HCl at room temperature. containing the - CH(OH)CH) [Link]
(CH)))C- OH + HCl • (CH)))C- Cl + H20 warmed with alkali ne aqueous iodine, these alcohols
produce a pale yellow precipitate of triiodomethane.
c Elimination This is a good test for the presence of a methyl
Alcohols can be dehydrated to alkenes by heating secondary alcohol group in a [Link] reaction is
with concentrated sulfuric acid or phosphoric acid, also undergone by methyl ketones (see Unit 18).
or passing the ir vapour over heated alu mini um oxide:
CH)CH(O H)CH) + 60H - (aq) + 412(aq) ----..
CH)C0 2- + CH1 )(s) + 51 - + 5H20

All alcohols that give a positive

pass vapour over AI20 3 at 350°C tl'iiodomethane test al'e secondary alcohols
CH)CH 20H - - - - - - - - - - -...
except fOI- one: the pl'illlal-y alcohol ethanol
(CH3CH,O H) also gives a positive I-esult.
ceramic wool
soaked in ethanol

/ /": ethene gas collected

over water
17.06 Reactions of carboxylic
acids
a Reaction with reactive metals
Since they contain an - OH group, carboxylic acids
heat
react with sodium metal, giving off hyd rogen. With
ethanoic acid, the salt, sod ium ethanoate, is formed:
CH)C0 2H + Na ----.. CH 3C0 2- Na+ + J0. H2(g)
Carboxylic acids also evolve hydrogen with other
reactive metals, such as lithium, magnesium and calci um.

b Reaction w ith sodium hydroxide

Figure 17.0 I Dehydration of ethano l to ethene Carboxylic acids undergo typical ac id- base reactions,
and their solutions can be titrated with an alkali:
d Reactions of the - O-H bond CH)C0 2H + NaOH ----.. CH)C0 2Na + H20
Reaction with sodium
c Reaction with carbonates
When a small piece of sodium metal is added to a pure
alcohol, fizzing takes place as hydrogen gas is evolved: Carboxylic acids are acidic enough to liberate CO2
from carbonates.
CHFH 20H + Na -+ CH)CH20 - Na+ + J0. H2(g)
2CH)C0 2H + Na 2CO)----..
ii Esterification 2CH)C0 2Na + H20 + CO2(g)
When an alcoho l is heated under reflux with
a carboxylic acid and a catalytic quantity of d Reaction with alcohols: formation of esters
concentrated sulfuric ac id, an ester is formed: Esters al-e produced when a carboxylic acid and an
alcohol are heated under reflux with a small amount
of concentrated su lfu ric ac [Link] su lfuric acid is a
homogeneous catalyst for the reaction, and can drive
the eq uilibrium over to the ester side by removing
the water produced:
CH 3C0 2H + CH 3CH 20H CH 3CO 2CH 2CH 3 + H2
ethyl ethanoate
° LiAlI II is a vel-y stmng I-educing agent
that will I-educe cal boxylic ac ids, ester-s,
H20 + H2S04 • H 30 + + HSO 4- ,md keto nes to alcohols. I he
weakcl- ,-educing agent NaBI II will only
e Reduction to alcohols
,-educe aldehydes and ketones, and so can
When carboxylic ac ids are treated with lithium be used to selectively I euult' these gm ups
alumi nium hydride in dry ether; they are reduced to in a "lulU fun ctional compound:
primary alcohols (see section 17.3).

LiAlH4
• (CH 3hCHCH 20H

2-methylbutan-l-ol

(0)-< OH
phenylmethanol

The results of the tests show that A contains a

Sample answer - C0 2H group, a C=C and a ketone group. [I mark]
Compound A, C6 Hs0 3, decolorises Br/aq),
LiA1H4 will reduce both the - C0 2H and the >C=O
effervesces with Na2C0 3(aq), gives an orange
groups, but leave the C= C grou p. [I mark]
precipitate with 2,4-DNPH but does not produce a
silver mirror when warmed with Tollens' reagent. H2 + Ni will reduce the C=C and the >C =O
groups, but not the -C02H group. [I mark]
Compound A undergoes the following series of
reactions. NaBH4 will reduce the >C=O to a >CH(OH)
group, but not the other two groups. [I mark]
LiA/H, / The reaction from D to E looks like an 'internal'
esterification between the -CO 2 H and the
H2 + Ni C
>CH(OH) group in D.
A •
(C6Hs0 3) (C 6H120 3) Possible structures are:
OH

! NaBH4
°
2

heat with

OH
Question:
Suggest structures for compounds A- E and explain C (C 6H120 3)
the reactions involved. [9]
Answer:
Note that the question asks for exp lanations, in
addition to the structures of A- E.

[5]
17.07 The hydrolysis of esters 17.08Tests for alcohols and
If an ester is heated under reflux with dilute aqueous
carboxylic acids
sulfuric acid, it is hydrolysed to a carboxylic acid and Alcohols and carboxylic acids fizz with sodium metal
an alcohol. This is the reverse of the equilibrium (giving off H2 (g)) and with PCls (giving off steamy fumes
reaction described above, which makes an ester from a of HCl(g)). Unlike carboxylic acids, alcohols are neutral,
carboxylic acid and an alcohol. The equilibrium is shifted so universal indicator stays green when added to an
in the hydrolysis direction by the large amount of water alcohol, whereas with acids it turns red.
that is present.
Primary, secondary and tertiary alcohols can be
Hp+/heat distinguished by treating them with acidified dichromate,

-, -,
CH 3C02CH 2CH 3 + H20 < ' with results as in Table 17.0 I.
CH 3C02H + CH 3CH 20H
The reaction proceeds more quickly, and with a better Alcohol type 0!1' Effect of the .-
warming with ·' distillate on
yield, if hydroxide is used as the catalyst instead of an
acid. The formation of the salt of the acid drives the
:. universal
_ • . '._ ;s:. -'i... indicator_ ,.;
equilibrium wel l over to the hydrolysis side:
R)C-OH, tertiary stays orange neutral (stays
NaOH(aq) + heat green): water only
CH 3C0 2CH 2CH 3 + NaOH < '
produced
CH 3C02- Na+ + CH 3CH 20H f\CH-OH, turns green neutral (stays
secondary green): ketone
produced
Worked example 17.0 I RCH 2-OH,
primary
turns green acidic (goes red):
carboxylic acid
Suggest the products of the following reactions. produced
a CH 3CH 2C02CH 3 + H30 + + +B Table 17.0 I How primary, secondary and tertiary
b HC0 2CH 2CH 3 + NaOH(aq) + heat alcoho ls can be distinguished
C+D
How to get t he answer:
Progress check 17.04
a Step I: Splitting the molecule at the C-O
bond in the carboxyl group produces • Three compounds A. Band C are isomers with
the two fragments CH 3CH 2CO and the molecularformula CSHI2 o.
OCH)' • All three react with sodium metal.
Step 2: As these pick up water, the products • Only compounds Band C t'eact with acidified
will be A: CH 3CH 2C0 2 H (propanoic potassium dichromate when heated under
acid) and B: CH 30H (methanol). reflux: compound B gives an acidic product
whereas compound C gives a neutral product.
b Step I: Splitting the molecule at the C-O
bond in the carboxyl group produces • On heating with concentrated su lfu ric acid,
the two fragments HCO and compounds A and C give 2-methylbut-2-ene,
OCH 2CH 3· whereas compound B gives pent-I-ene.
Step 2: Hence C is HC0 2 H (methanoic acid) Exp lain the reactions described above, suggest
and D is CH 3 CH 20H (ethanol). structures for compounds A. Band C, and state
which, if any, contain a chiral carbon atom.
17.09 Uses of alcohols, acids
and esters
Both methanol and ethanol are used as additives for
2-methylpropyl methanoate (raspberry) pentyl ethanoate (pear)
automobile fuels ('gasohol' is petrol (gasoline) containing
10-20% ethanol). Ethanol is also used as a solvent, and CH 3 ....... ...CH 2 ...... 0, CH 3 ......... ....CH 2 /O......... .... CH 3
a skin disinfectant in hospitals. CH 2 £ CH 3 CH 2 II CH 2

Esters with low Mr find many uses as solvents for paints. °

methyl butanoate (apple)
°
ethyl butanoate (pineapple)
Natural food flavours are often esters, and many of
these are made artificially, to flavour fruit drinks, sweets Ethanoic acid is an important solvent for various plastics
and desserts. Some of the naturally occurring esters and glues. It is also found in vinegar. Salts of carboxylic
now made synthetically and used as artificial flavours in acids, such as sodium benzoate, are used as food
foodstuffs are as follows (their flavours are in brackets preservatives, and acid+ salt mixtures, such as citric acid
after their names): and sodium citrate, are used as buffering agents to keep
the pH of foodstuffs constant.

Exam-style questions
Malic acid (H0 2CCH 2CH(OH)C0 2 H) occurs in b Explain whether or not malic acid exhibits
apples and is used as a food additive. optical isomerism. [ I]
a The following is an outline of a 4-step c When malic acid is heated with concentrated
synthesis of malic acid starting from Hl0 4, a mixture of two isomeric
hydroxyethanal. compounds D and E with the molecular
formula C4 H40 4 is formed. Suggest the
step I step 2 step 3
structures of D and E and explain the
HOCH 2CHO ---. A ---. B---.
isomerism they demonstrate. [3]
step 4
Total: II
C ------. H0 2CCH 2CH(OH)C0 2 H
2 The ester F is used for flavouring fruit drinks.
Suggest possible structures for the
intermediate compounds A, Band C. [3] CH 3CH 2C0 2CH(CH 3) 2
ii Suggest suitable reagents and conditions F
for steps 1- 4. [4J

J -
When F is treated with hot aqueous acid, two Isomer J can be made from a tertiary
compounds (G and H) al"e formed. alcohol.
,1 What type of reaction is occurring hel"e? [I] ii Isomer K can be made from a primary
alcohol that has a chiral carbon atom.
ii W rite a balanced eq uation for the
reaction, showing the structures of the iii Isomer L can be made from an acid whose
two pro du cts G and H. [3] molecules contain a chi ral centre. [3]
b Describe a test (reagents and observations) d Describe how the alcohols that make up
by which samples of G and H could be esters F, J and L could be distinguished from
distinguished. [2] each other. [3]
c Draw the structures of the following isomers Total: 12
of F, all of which are esters.
18.01 Properties, isomerism
and nomenclature Worked example 18.01
There are eight carbonyl compound isomers with
The carbonyl group, >C =O, is a subunit of many other the molecular formula CsH 100. What are their
functional groups, such as carboxylic acids, amides and structures and their systematic names?
esters, but the term carbonyl compound is reserved for
How to get t he answer:
those compounds in which it appears on its own.
Step I: Let us start with a straight chain of five
There are two types of carbonyl compounds: aldehydes
and ketones. carbon atoms (pentane).The carbonyl
group can be on C-I, C-2 or C-3.
The properties of aldehydes and ketones are very
Step 2: If we consider the 2-methylbutane
similar to each other - almost all the reactions of
skeleton, the carbonyl group can be on
ketones are also shown by aldehydes. But aldehydes
C-I, C-3 or C-4, the first of which can
show additional reactions associated with their lone
exist as optical isomers.
hydrogen atom.
Step 3: Lastly. there is one carbonyl compound
R- /l'\ R- (
l based on the 2,2-dimethylpropane skeleton.
'\ The structures are as follows. Notice how they
H R'

general formula general formula are named.

of aldehydes of ketones

Aldehydes are named by adding the suffix -al to

o
Jy o
the stem, whereas ketones have the suffix -one
pentanal H pentan-2-one pentan-3-one 3-methyl butanone
(pronounced 'own'). Aldehydes and ketones are
positional isomers of each other. They can also show
structural and optical isomerism.
\
"",",0
..... H)/fH,-"
H
Y H
3-methyl butanal the two optical isomers of 2-methyl butanal 2,2-dimethyl propanal
 Because of the electro negativity of oxygen, the carbonyl
group is highly polar: If YO Li are asked to write a balanced
equation fO I- t hese oxidat io n I-eact ions,
do not panic! You can Li se the sym bol [OJ
for oxygen atoms co il ling from oxidising
agents, so the last equatio n can be wl-itte n:

ClI 3C1 j(O H) CH l + [OJ

CH FOCH j + H 20
The dipole moment of the carbonyl group is sometimes
represented by the following mesomeric pair of
A special procedure needs to be carried out to ensure
formulae .
that the oxidation of primary alcohols stops at the
aldehyde stage, since aldehydes are easily oxidised further
to carboxylic [Link] conditions used are as follows:

• set Lip a flask for simp le distillation, and add the

This polarisation dominates the reactivity of carbonyl alcoho l to the flask
compounds, but also has an effect on their physical • slowly drip the solution of acidified dichromate(Vl)
properties. Their molecules attract each other by into the flask containing the alcohol, so that the
dipole-dipole forces, so they have higher boiling points alcoho l is always the reagent in excess
than alkanes of similar M r . In addition, the lone pairs on
• keep the temperature of the flask just below the
oxygen can hydrogen bond with water molecules, so
boiling point of the alcohol
carbonyl compounds with low Mr are soluble in water.
If this procedure is followed, the aldehyde that is
formed will immediately distil off. and can be collected
18.02 Methods of preparation after it has been liquefied in the condenser. This
technique relies on the fact that aldehydes are always
Carbonyl compounds are usually made in the more volati le than the corresponding alcohols, because
laboratory by oxidising alcohols. Either potassium the alcoho l molecules hydrogen bond to each other;
manganate(VII) or potassium dichromate (VI) can be whereas the aldehyde molecules do [Link] 18.0 I
used, although the latter reagent is the more usual. Both shows two examples.
reagents need to be in acidified so lution, and heated.

CH 3
OH
I
...... CH
'CH 3
heat with KMn0 4

+ H2S0 4(aq)
.. 0
II
...... C ..........
CH 3 CH 3

CH 3
...... CH 2 ...... OH
'CH 2
heat with Na 2Cr20 7

+ H2S04(aq)
.. CH
3
...... CH 2
'c
H
I

CH 3CHPH 78 CH3CHO 20 58
CH 3CH2CHPH 97 CHFH2 CHO 49 48

Tab le 18.0 I Compal-ing the boiling points of aldehydes and alcoho ls

,-
18.03 Reactions common to R,C/
0-

aldehydes and ketones R/ '\.

A mentioned above, the carbon atom in the carbonyl N

group is slightly positively charged. Carbonyl compounds
The intermediate anion is a strong base. It can take
are therefore attacked by [Link] initial
a proton off an un-ionised molecule of hydrogen
reaction is an addition to the C=O double bond, but
cyanide:
this can be followed by an elimination.

a Nucleophilic add ition of He N

In the presence of a small amount of sodium cyanide
(or sodium hydroxide, which reacts with HCN to
form sodium cyanide), hydrogen cyanide adds on to
carbonyl compounds:

NaCN(aq) or NaOH(aq) /H
CH 3 - CHO + HCN • CH 3 - c..
H +
2-hydroxypropanenitrile

The reaction is catalysed by cyanide ions from the

sodium cyanide. Like the reaction between sodium
cyanide and a halogenoalkane, the reaction is an The cyanide ion that was used up in the first step
effective method of adding a carbon atom to a chain. is re-formed in the second step. It is acting as a
Cyanohydrins are useful compounds: they can be homogeneou s catalyst, so only a small amount of
hydrolysed to 2-hydroxycarboxylic acids by heating NaCN is required.
with dilute sulfuric acid, and can also be reduced to
c Red uction of t he carbonyl group
2-hydroxyamines:
Carbonyl compounds can be reduced to alcohols
using either complex metal hydrides, or using
hydrogen gas in the presence of nickel or platinum.
Aldehydes give primary alcohols, whilst ketones give
secondary alcohols:
nickel catalyst
• CH3- CHO
NaBH 4 in alkaline aqueous methanol
or LiAIH4 in dry ether
LiAIH 4 in dry ether HO"", /H
C .. C
CH3/ 'CH or NaBH 4 in alkaline aqueous methanol CH 3 / 'CH 3
Progress check 18.01 3

Suggest two-stage routes to the following two

compounds, starting in each case with a carbonyl
CH 3CH 2
'c =0
/
+ H2 ..
Pt at 1 atm or Ni at 5 atm

compound. CH 3

I CH3CH 2C(OH)(CH 3)CH2NH 2

Although ,-educing agents foI- o'-ganic
2 (CH 3)2C(OH)C0 2H.
,-eactions a,-e usually denoted by t he
single atom sym bol [H] in equations, you
should stil l make sUI-e that any eql,alion
b The mechanism of t he reaction
you w rite is atom balanced.
The first step is the attack on the 8+ carbon atom
by the nucleophilic cyanide ion, - CN:
d Condensation reactions 18.04 Oxidation reactions of
Carbonyl co mpounds react w ith primary amines
aldehydes
(RNH 2), hydrazines (RNHNH 2) and hydroxylamine
(HONH) to give compounds containing a C = N a With acidified dichromate (VI)
double bond. The reaction involves an initial
Unlike ketones, aldehydes can be oxidised to
nucleophilic addition to the C = O group (like
carboxylic acids. The reaction t akes place on gentle
the reaction with HCN discussed above) and
warming, and the co lour of the reagent changes
subsequent loss of water:
from orange to green.

The most important class of compounds formed in

this way are the 2,4-dinitrophenylhydrazones. These b With Fehling's solution
are crystalline orange solids whose formation as
The bright blue Fehling's solution is a solution of
precipitates is a definitive test for the presence of a
Cu H ions, complexed with salts of tartaric acid, in
carbonyl compound:
an aqueous alkaline solution. When warmed with
an aldehyde, the Cu H ions are reduced to Cu+
ions, which in the alkaline solution form a dull red
• H,N im..., ; "
precipitate of copper(l) [Link] aldehyde is oxidised
to the salt of the corresponding carboxylic acid:
N02
CH 3CHO(aq) + 2Cu H (aq) + 50H - (aq) ----.
2,4-dinitrophenylhydrazine (2,4-DNPH) blue solution

CH 3C0 2 - (aq) + Cu 20(s) + 3H 20(I)

red precipitate

c W ith Tollens' reagent

To ll ens' reagent contains silver ions, complexed with
ammonia, in an aqueous alkaline solution.
a 2,4-dinitrophenylhydrazone
(orange precipitate) These silver ions are readily reduced to silver metal
on gentle warming with an aldehyde. The metal will
The 2,4-dinitrophenylhydrazones of many aldehydes often silver-plate the inside of the test tube. Once
and ketones have distinctive melting points. Taking again, the aldehyde is oxidised to the salt of the
the melting point of the recrystallised orange corresponding carboxylic acid:
precipitate enables us to identify which carbonyl CH)CH 2CHO + 2Ag+ + 30H - •
compound is present. CH 3CH 2C0 2- + 2Ag(s) + 2H 20
si lver mirror
Either the formation of a red precipitate on warm ing
with Fehling's solutio n, or the formation of a silver
mirror on warming with Tollens' reagent, is a good
way to distinguish an aldehyde from a ketone.

Figure 18.0 I The ol-ange precipitate formed by the

I-eaction between 2,4-D NPH and a carbonyl compou nd
 Sample answer
Q uestion:
Thl"ee ketones, D, E and F, have the molecular
formula CsHloo. D and E undergo the
triiodomethane reaction, but F does not. On
treatment with hydrogen and nickel, followed by
heating with concentrated H 2S04, compounds E
and F produce the same alkene, G, with molecular
formula CsH 1o ' whereas compound D produces
Figure 18.02 The silvel" min"or formed when To llens' an isomeric alkene H.
reagent is war med with an aldehyde.
Suggest the structures of D, E and F, and the
structures of the alkenes G and H. Explain your
You should be awal"e that thel"e is answers. [7]
one othel' compound that I"eacts with
Answer:
Fehling's solution 01' To llens' l'[Link] is
methano ic acid (HCO}H), which contains Note that explanations need to be given, not just
a - CHO gl'Oup. the structures for D-H.
If compounds D and E undergo the iodoform
reaction, they must contain the -COCH) group.
[I mark]
Progress check 18.02 Taking this away from the molecular formula leaves
Three isomers, A, Band C, have the molecular so they must be CH) CH 2CH 2COCH) and
(CH)\CHCOCH) (we do not know which is which yet).
formula C 4 H so.
If F does not undergo the iodoform reaction,
A and B form orange precipitates with
2,4-DNPH whereas e
does not. it must be the ket one CH)CH 2COCH 2CH).
[I mark]
e decolorises bromine water, but A and B
do not. Compounds E and F contain the same carbon
chain, because on reduction and dehydration they
A gives a silver mirror when warmed with
Tollens' reagent, but Band e
do not.
produce the same alkene. [I mark]

On treatment w ith hydrogen and nickel, Compound E is CH )CH 2CH 2COCH), [I mark]
both Band egive the same compound, This leaves compound D to be (CH)2CHCOCH).
butan-2-01, whereas A gives butan-I-o l. [I mark]
Suggest structures for A, Band e, and explain all A lkene G can only be CH)CH 2CH=CHCH),
the reactions described. [I mark] but alkene H cou ld be either
(CH ))2CHCH=CH 2 or (CH ))2C=CHCH).
[I mark]
18.05 The triiodomethane
The following scheme shows the reactions involved.
reaction
Ketones that contain the group -COCH) (methyl
keto nes) form a ye llow precipitate of triiodomethane
D
(iodoform) when added to an aqueous alkaline solut ion
of iodine. The reaction is also shown by methyl alcohols,
containing the group -CH(OH)CH).
R R,
'c= o + 40W+ 312 ----.. / = 0 + CHI 3 + 3H 20 +31-
I
CH 3
-0
iodoform: pale yellow
precipitate
Exam-style questions
The compound 4-hydroxynonenal is produced 2 Compound A is a component of some suntan
by the oxidation of lipids in the body. creams. A has an Mr of 90 and its empirical
formula is CH 2o. Compound A gives an orange
H
precipitate with 2.4-DNPH but does not react
with Fehling's solution. A also effervesces with
sodium metal, but does not effervesce with
OH Na 2C0 3(aq).
4-hydroxynonenal
a Suggest a structure for A. Explain your
a Name the three functional groups reasoning. [3]
in the molecule of nonenal. [3]
b Suggest structures for organic products B, C,
ii Describe how you could test for the D and E, of the following reactions.
presence of each of these functional
groups. For each test you should state
the reagent used, and the observation
you would make. [6]
A (
b Calculate the empirical formula of
4-hydroxynonenal. [I]
heat with W(aq) E
c 4-hydroxynonenal shows two types of
stereoisomerism. Explain this statement. [2]
D
• [4]

c State the molecular formula of compound E,

d Suggest the structures of the products of the and calculate the volume of H2(g) that would
following reactions. be evolved (measured at 25°C and I atm)
if I.00 g of E were treated with an excess of
sodium metal. [4]
d Show the mechanism of the reaction
A D. In your answer you should use
curly arrows to show the movement of
electrons, and include relevant lone pairs
and charges. [3]
[6] Total: 14
Total: 18
19.0 1 Lattice energy • Mg2+ and Li+ ions are of similar size and S2- and Cl-
ions are of similar size but the lattice energy of MgS is
In ionic substances, the ions are held together by non- much more negative than the lattice energy of LiCl.
directional electrostatic attractions and the energy
changes occur when making or breaking an ionic lattice.
The lattice energy is the energy released when gaseous
Worked example 19.01
ions are brought to their places in an ionic lattice to Suggest the relative sizes of lattice energy for
make I mole of ionic solid: CaCl2, CaS and Na 2S.
Na+(g) + Cl- (g) -----+ NaCl(s) How to get t he answer:
il.H ,att [NaCl] = - 780 kJ mol-I Step I: State the charges on the ions: Ca2+, Cl- ,
S2-, Na+.
Mg2+ (g) + 0 2-(g) -----+ MgO(s)
il.H,att [MgO] = - 3791 kJ mol- I Step 2: State the relative sizes of the ions: Cl-
and S2-are about the same size; Ca2+ and
Ca2+ (g) + 2Br- (g) -----+ CaBr/s) Na+ are about the same size.
il.H,att [CaBr2] = - mol - I Step 3: Lattices with the highest ionic charges
Lattice energies are always negative as energy is have the most negative lattice energy: CaS.
released when an ionic lattice is formed. Step 4: With similar sizes and similar charges,
Ions with higher charges have a greater electrostatic Na 2S and CaCl2 have similar lattice
attraction and correspondingly more negative lattice energies.
energies; larger ions cannot get so close to each other
and so less energy is released on forming the lattice:
• The lattice energy gets less negative for a larger
Group I ion with the same anion or a larger halide
19.02 Born-Haber cycles
ion with the same cation. It is possible to calcu late a lattice energy from the
• Ca2+ and Na+ ions are approximately the same charges on the ions and their positions in the lattice but
size but the lattice energy of CaCl2 is much more we usually calculate them from experimental data using
negative than the lattice energy of NaCl. a Hess cycle - see Figure 19.0 I.
 I Na+(g) + C/(g) I
tJ,H reaction
Na+(g) + C/(g) NaC/(g) + 121 kJ mol- 1
I Na+(g) + jC/ig) I - 349kJ mol-
tJ, Hf(reactants) tJ, Hf(product)
route 2

I Na+(g) +Ct(g) I
Figure 19,0 I Forming the NaCl lattice +496kJ mol- 1

In Figure 19,0 I:
ilH rea ct'Ion = the lattice energy of NaCl Na(g) + jC/ig)
I I
ilHf[product] = the enthalpy of formation of + 107kJ mol- 1 route 1
NaCl(s) = -4 1 I kj mol-I
I Na(s) + lC!2(g) I
It is less clear how to evaluate ilHf[reactants] as it is
made up of a number of components (see Unit 6 for
enthalpy changes), 411 kJ mol-1
Solid sodium needs to be vaporised and ionised:
Na(s) Na(g)
NaC/(s)
The enthalpy change of atomisation, ilHat = + I mol- I I I
Na(g) Na+(g) Figure 19,02 The Born- Haber cycle for NaCl
The first ionisation energy, ilH,Ion = +496 kj mol - I
In Figure 19,02, most values are known and so the
The chlorine molecules need to be atomised and then
lattice energy can be calculated,
made into negative ions:
ilH,att = -ilHat[Na(s)] - ilH;on[Na(g)] - ilHat[Cl(g)]
IhCl2(g) Cl(g)
- ilHeJCl(g)] +
The enthalpy change of atomisation, ilHat = + 121 kj mol-I
= -[(+107)+(+496)+(+121)+(-349)]+
Cl(g) Cl- (g) (-411) = -786kjmol- 1
The electron affinity" ilHea = - 349 kj mol-I
The electron affinity is the energy change when each
If the route di l-ection opposes the
atom in I mole of gaseous atoms gains one electron to
enthalpy change a/TOW, mu ltiply the
become a negative ion,
enthalpy change by - I.
These energy changes are put into a Hess cycle known
as a Born-Haber cycle (Figure 19,02),

Worked example 19.02 ilH f [CaCl 2] = -796kjmol- 1

Calculate the lattice energy of CaCl2 from the ilHea [Cl(g)] = - 349 kj mol-I
enthalpy values given. How to get the answer:
ilHat[Ca(s)] = +178kjmol - 1

Step I: The equation for the lattice energy:

ilH;oJCa(g)] = +S90kjmol- 1 Ca2+(g) + 2Cl- (g) CaCl2(s)
ilH;on[Ca+(g)] = + 1145kjmol- 1 Step 2: The equation for the formation:
Ca(s) + Cl2 (g) CaCl2(s)
 Step 3: W hat energy changes are needed for Step 6: How many elect ro n affiniti es are needed?
Ca(s) Ca2+ (g)? Atomisation and Two for 2Cl(g).
io nisation: Ca(s) Ca(g) Ca2+ (g)
Step 7: Write t he equ ation usi ng the Born- Haber
Step 4: How many ionisation energies are requi red? cycle: i!lH'att = - i!lHat [Ca(s)] - i!lH;oJ Ca(g)]
First and second. - i!lH;on[Ca+(g)] - 2i!lHat [Cl(g)] -
2i!lHeJCl(g)] + i!lHr[CaCl2]
Step 5: What energy changes are needed for
Cl2(g) 2Cl- (g)? Atomisatio n and Step 8: Insert the values: i!lH'a tt = - [( + 178)
electron affinity: Cl2 (g) 2Cl(g) + (+ 590) + (+ I 145) + 2( + 12 1) +
2Cl- (g) 2( - 349)]+(- 796) = -2253kJmol- '

To calculate the lattice energy of calcium oxide, you MCO/s) MO(s) + CO/g)
need to form an oxide ion as well as including the first
two ionisation energies for calcium. The first electron The temperature of decomposition is lowest for
°
added to the gaseous atom releases energy but
energy is needed to add a second electron to an
MgC0 3 at 623 Kand highest for BaC0 3 at I 123 [Link]
reason lies in the different ion sizes. The cationic radius
already negative ion: increases down the group and so its polarising power
[Link] anion is relatively large (Figure 19.03).
i!lHat [0 (g)] = + 249 kJ mol - I
i!lHr[CaO(s)] = -635 kJ mol -I
i!lHeJO(g)] = - 141 kJ mol - I
i!lHeJO- (g)] = + 798 kJ mol-I Figure 19.03 Ion po larisation: a small highly chal"ged
cation can distort the shape of the anion but a largel"
cation cannot
Progress check 19.01
Identify each of the energy changes in Figure As shown in Figure 19.03, as the cationic radius
19.02 with the values in the equation to increases its polarising power decreases and so the
calculate the lattice energy. polarisation of the large carbonate ion
down the group.
2 For each of the following pairs of ionic
solids, explain which would have the most The carbonate ion is large; the electrons are easily
negative lattice enthalpy and why: pulled towards a small positive charge, distorting
the electron cloud. Mg2+ can polarise the carbonate
a potassium bromide and potassium iodide electron cloud the most but the distortion gets
b potassium bromide and sodium oxide less as the positive ion gets larger. The carbonate
in MgC0 3 is most distorted, breaking a carbon-
c magnesium oxide and calcium sulfide.
oxygen bond and releasing cO 2 (g). As the
3 Using values from the text above, show distortion decreases down the group, a higher and
that the lattice enthalpy for CaO = higher temperature is needed to decompose the
- 3454 kJ mol - I. carbonate.

b Group 2 nitrates
19.03Thermal stability of All the Group 2 nitrates decompose:

Group 2 nitrates and carbonates M(N0 3)2(S) MO(s) + 2N0 2(g) + YlO/g)
For similar reaso ns to the carbonates, the
a Group 2 carbonates deco mpositio n temperature is higher go ing down
We saw in Unit I I that Group 2 carbonates are the group.
decomposed by heat but that they become more
thermally stable down the group:
c Lattice energy and decomposition These forces keep t he ions in solution and the ions are
The decomposition of both the carbonates and the hydrated, Ions getting hydrated re lease energy - the
nitrates produces t he oxide ,The 0 2- ion is smaller enthalpy change of hydration,
than the N0 3- or CO/- ions and so the lattice When ionic so lids disso lve in water, energy is needed
energies of the oxides are much more negative than to pull t he ions from their positions in the lattice and
the lattice energies of the cal'bonates or nitrates, The energy is then released when the ions are hydrated,
difference in lattice energy is a driving force for the The overall enthalpy change is the enthalpy change of
decomposition, solution,

Progress check 19.02 19.05 The solubility of Group 2

A white solid is a mixture of barium carbonate sulfates and hydroxides
and barium nitrate, State the observations
when the following four tests are carried out on Group 2 sulfates become less soluble going down the
separate portions of the mixture and explain group,
what has happened. The energy change when an ionic solid dissolves in
Shake a portion with water. water is represented in Figure 19,05,
2 Heat a portion of the mixture and apply a
glowing splint to any gas produced,
3 Heat a portion of the mixture with a
Bunsen burner and then shake the residue
with dilute hydrochloric acid, M2+(g) + sot(g) + aq

4 Heat a portion of the mixture and then Figure 19,05 Solids disso lving can be t hought of as the
shake the residue with water and add sum of two processes
universal indicator.
• (I) is the enthalpy change of solution
• (2) is the reverse of the lattice energy
19.04 Formation of ionic solids • (3) is the enthalpy of hydration,
and solutions (2) depends on the size of the ion and becomes less
positive as the M2+ ion gets larger going down the
Above we discussed gaseous ions forming an ionic solid
group,
and giving out the lattice energy.
(3) depends on the charge density of the ions, which
When gaseous ions dissolve in water, they produce
does not change for the sulfate ion , As the Group 2
hydrated ions, The positive and negative ions are
ions get larger, their charge density gets smaller and
surrounded by water molecules and kept in solution by
the ion-dipole attraction between ion and water
ion-dipole attractive forces (Figure 19,04),
molecules gets weaker. The hydration enthalpy gets less
0+ 0+ negative,
H H
" o'-u;; - From the Hess cycle:
the enthalpy change of solution = - lattice energy +
hydration enthalpy
Figure 19,04 Ions surrounded by water molecu les (- lattice energy is energy absorbed; hydration enthalpy
experience ion- dipo le attractive fOITes is energy released)
The 8- ° atoms of H2 0 molecules form ion-d ipole
attractive forces with the positive ions; the 8+ H atoms
The sulfate ion is so large , it masks changes in the
small positive Group 2 ion when we consider the
form ion- dipole attractive forces with the negative ions, lattice energy so lattice energy changes are fairly
small. However; when going into solutio n, th e ions are Thus the enthalpy change of so lution becomes more
being hydrated separately; the radius of the positive positive going down the group and so the su lfates get
ion changes greatly and so the changes in hydration less so luble.
enthalpy are much larger.
The hydroxide ion is much smal ler than the sulfate
ion and for Group 2 hydmxides, the lattice energy
Both t he lattice energy and the hyd l-ation decreases more than the hydration enthalpies as the
enth alpy ge t sl m llel going down Gmup 2, gmup is descended. The enthalpy change of solution
_ ............_ _b_Ul dliul) erlthalpy becomes less positive and the hydmxides become
more soluble.

Sample answer Cu H is much smaller than BaH [I mark] , so

[CuS0 4J is greater than [BaS0 4J [I mark].
Question:
[CuH J is greater than [BaH J [I mark].
Explain why CuS0 4 is soluble but BaS0 4 is insoluble
in water. SO / - is lal'ge and masks changes in [I mark].
Answer: changes more than [I mark] , is less
+ve for CuS0 4 [I mark].
The solubil ity depends on [I mark] which is
equal to - lattice energy + hydration enthalpy
[I mark].

Progress check 19.03

The ion ic rad ii of some positive ions in crystal lattices I Is CoS0 4 soluble in water? Explain your answer.
are given below:
2 Is Co(OH)2 soluble in water? Exp lain your
BaH O. I 35 nm answer.
COH 0.065 nm
MgH 0.072 nm

J -
 q ns
a Define lattice energy. [2] c How would you expect LlH,att [BeO] to
b A student was asked to calculate compare with i1H,att [MgS]? [ I]
i1H,att [BeO]. He looked up the following Total: 9
values:
2 Explain why:
i1Hf[BeO(s)]; i1Hat [Be(s)]; first ionisation
a MgS04 is soluble but BaS04 is insoluble. [6]
energy of Be(g); electron affinity of O(g)
b Mg(OH)2 is insoluble but Ba(OH)2 is soluble. [4]
What other enthalpy values does he
need? [3] Total: 10
ii Consider your answers in part i and,
for each of the enthalpy values in your
answer in turn, state whether the lattice
energy calculated without including
that enthalpy value will be more or less
negative than the proper value. [3]
 With CuS0 4 (aq) electrolyte, atthe cathode:
20.01 F = Le Cu2+ + 2e- Cu(s)
Electrolysis is the decomposition of an ionic substance I mole of copper is deposited by 2 moles of electrons.
(an electrolyte) by the passage of an electric current.
The charge on 2 moles of electrons = no. of electrons
The ions need to be free to move, so electrolysis can
X charge on I electron = 2 Le
occur in molten or aqueous salts, bases and aqueous
acids. Electrodes immersed in the electrolyte allow (L = Avogadro's number; e = charge on I electron)
electric current to pass. Positive ions attracted to the
The quantity of charge on a mole of electrons, Le, is the
negatively charged cathode are discharged by gaining
Faraday. F.
electrons; electrons flow from the anode to the
cathode (Figure 20.0 I). F = Le = 6.0nx 1023x 1.602X 10- 19
= 96500Cmol- 1

+ __ JI-=-=-- - directcurrent
I power supply
e- e- 20.02 Substance liberated
positive ------¥/. /j--- negative during electrolysis
electrode electrode
(anode) (cathode) a Molten lead bromide
In molten lead bromide, PbBr2, the ions present are
PbH and Br- .
j-----!97t-f--:::::==_ electrodes
At the cathode: Pb H + 2e- Pb(l)
electrolyte
At the anode: 2Br- Br/g) + 2e-
Figu l-e 20.0 I Electrons flow from the anode to the Lead and bromine are produced if the app lied
cathode voltage overcomes the ionic attractions.
b Ions discharged from a mixture
The ion discharged from a salt mixture is the one Worked example 20.0 I
which takes least energy. A molten mixture of lead
If a current of O.5A is passed for 2 hours, what
bromide and lead chloride produces bromine at the
anode as BI-- is more easily oxidised than Cl- , mass of copper is deposited on the cathode?
How to get the answer:
Step I: Work out the quantity of electricity
Species al-e oxidised at the anode and
= 0.5 X 2 X 60 X 60 C
reduced at the cathode,
Step 2: Quantity of electricity = nF; n = no, of
moles of electrons, F = Faraday
c In aq ueous solut ion Step 3: Work out n: nF = 0.5 X 2 X 60 X 60
In aqueous solution, small amounts of H+ and OH - n = (0.5 x 2 x 60 x 60) = 0,0373 mol
from the ionisation of water may be discharged, 96500
Step 4: Write the equation:
d Other condit ions Cu2+ (aq) + 2e- ------+ Cu(s)
Material of the electrodes Step 5: The number of moles of Cu
= );2 X 0,0373 = 0,0187 mol
CuS04(aq) electro lysed with inert electrodes of
platinum or carbon produces copper at the cathode Step 6: Mass of Cu deposited
and oxygen gas at the anode: = 0,0187 X 63.5 g = I, 18 g
2H 20(I) 02(g) + 4H +(aq) + 4e-
Using copper electrodes, Cu is oxidised at the anode
and goes into solution as Cu2+; the anode dissolves, Sample an swer
Similarly,AgN0 3 (aq) using platinum electrodes Question:
produces O/g) at the anode but using silver
0.65A is passed through H2S04 (aq) for l.5hours.
electrodes, Ag goes into solution as Ag+,
What volumes of hydrogen and oxygen,
ii Concentration effects measured at 25°C and I atm, are produced? [5]
The high activation energy for the discharge of Answer:
hydrogen or oxygen may prevent their discharge, In
Cathode: 2H +(aq) + 2e- ------+ H2(g)
the electrolysis of sodium chloride solutions, H+ is
discharged to form hydrogen gas at the cathode but Anode: 2H 20(I) 02(g) + 4H +(aq) + 4e-
Cl- is preferentially discharged at the anode, Only at [ I mark]
very low Cl- concentrations is OH - discharged. quantity of electricity = 0,65 X 1.5 X 60 X 60 C
= 35 10C [I mark] = nF
20.03 Electrolysis calculations n = 35 I 0 moles = 0.0364 mol [ I mark]
96500
no, of moles of hydrogen = );2 X 0,0364
An ammeter included in the circu it of Figure 20.0 I can
= 0,0182mol
measure the current flowing through the cell; a variable
voltage prevents the current changing as the solutions volume of hydrogen = 0,0182 X 24 dm 3 = 436 cm 3
warm up, The amount of charge flowing is given by: volume of oxygen = X X 0,0364 X 24dm 3
Q= IX t = 2 I 8 cm 3 [I mark]

I = current in amps; t = time in seconds; Q = quantity In practice, as oxygen is slightly so luble in water;
of charge in cou lombs, a smallel- volume of oxygen than this is collected
[I mark].
20.04 Determination of the 20.05 Electrode potentials and
Avogadro constant cell potentials
An apparatus simi lar to Figure 20,0 I with copper A copper rod immersed in water sets up an equi li brium
electrodes dipping in CuS0 4(aq) and including an (Figure 20,02): some copper ions enter the water,
ammeter and a variable voltage supply can be used to leaving their electrons on the rod:
determine the Avogadro constant. CuH(aq) + 2e- Cu(s)
The clean, dry cathode is weighed before being used, A potential difference between the rod and the water
A current of 0.5 A is kept constant for 30 minutes, The is set up,
cathode is then removed, dried and reweighed,
mass of cathode at start = mig
;- - - - negatively charged copper
mass of cathode at end = m2 g
mass of copper produced = (m2 - m l ) g
quantity of electricity passed = 0.5 X 30 X 60 C = nF
= nLe
m2 - ml
Ar[Cu] = 63.5, no, of moles Cu = 63.5
CuH(aq) + 2e- ----+ Cu(s)
2 (m 2 - ml )
Figure 20,02 A piece of co pper imm ersed in water
no, of moles electrons = 63.5
charge on the electron = 1,602 X 10- '9C If copper is immersed in CuS04(aq), fewer Cu H can go
2 (m - m) into solution so the potential difference between rod
0.5 X 30 X 60 = 2 I X 1,602 X 10- 19 X L and solution will be smaller. Silver immersed in silver
63.5
nitrate solution becomes less negative than copper as
silver ions are less good at leaving,
Progress check 20.0 I
What volume of hydrogen is produced
Redox reactions are an electron competition, Copper
immersed in silver nitrate solution disappears:
.
,.
I

at the cathode when a current ofO,75A

is passed through concentrated sodium Cu(s) + 2Ag+(aq) ---+ CuH(aq) + 2Ag(s)
chloride solution for 25 minutes? Writing the oxidation and reduction reactions
3 separately: •
2 123 cm of another gas is produced at the
anode of the cell in question I,What is the Cu(s) ----+ CuH(aq) + 2e-
gas? Suggest why the volume produced is
Ag+(aq) + e- ---+ Ag(s)
I23cm 3,
We cannot measure the potential difference between
3 In the electrolytic production of aluminium,
a piece of metal and a solution of its ions but we can
the current passed through molten alumina
compare redox equilibria by carrying out the oxidation
is high, What mass of aluminium is produced
and reduction reactions separately (Figure 20,03),
by passing a current of 100 OOOA through
molten alumina for I hour?
4 When a current of 0,80A is passed through
molten lead bromide for 45 minutes, the
mass of the cathode increases by 4.33 g, Find
a value for the Avogadro constant (charge
on an electron = 1,602 X 10- 19 C; Ar for
lead = 207),
._ - - - - - -
 Hydrogen gas is bubbled into HCl(aq) over an
inert platinum electrode - see Figure 20,04 for the
conditions, The equ ilib rium is achieved slowly and so a
copper ------{ f--- - silver powdered platinum catalyst (called platinum black) is
salt brid e used, The electrode potential of th is half-cell is given the
value 0,0 V; all other electrode potentials are measured
against the standal-d hydrogen electrode,
copper silver nitrate
sulfate solution
solution
20.07 Measuring standard
Figure 20,03 A silver half-cell combined with a copper
half-ce ll
electrode potentials
The standard electrode potential, fB, is the voltage
Both oxidised and reduced form of each redox reaction
produced when a half-cell is connected to a standard
are needed so that they can move in either direction; in
hydrogen electrode under standard conditions,
Figure 20,03, each beaker has a metal rod dipping into a
solution of its [Link] high-resistance voltmeter allows little The standard conditions are:
current to flow (otherwise, the potential difference falls),
• pressure of gases = 1,0 atm
The solutions are in electrical contact using a salt bridge -
a piece of filter paper soaked in potassium nitrate solution • concentration of solutions = 1,0 mol dm - 3
or a glass tube filled with potassium nitrate solution held • T = a defined temperature, usually 298 K
in place with porous plugs,The salt bridge allows ion
movement but keeps the solutions separate, a A metal dipping into a solut ion of one of its
The potential of the cell is the voltage read from the ions
voltmeter when no current flows in the circuit. It is See Figure 20,05 for the apparatus used to measure
the difference between the two electrode potentials, the standard electrode potential between CuH(aq)
Electrode potentials are measured against a standard and Cu(s),
hydrogen electrode; which is assigned an electrode
potential of 0,0 V T - 29BK

20.06 The standard hydrogen (opper

electrode salt bridge

[WI =1.0 mol dm-l

The electrode equilibrium:
platinum covered --+--+. 1.0 mol dm-l Cu" (aQ)
with platinum black
H+(aq) + e- Y2H 2(g)
Figure 20,05 Measu l-ing the standard electrode potential
to voltmeter
of the CuH ,Cu(s) electrode
hydrogen gas __
at 1.0 atm temperature =298 K Both the voltage and polarity of the electrodes are
noted, Here, the voltage is 0.34 V and copper is
sahbridge positive; electrons flow towards the copper:
fB= +0.34V
- 0 - - bubbles of hydrogen escaping
The reactions that actually occur:
'9-t-+- platinum covered with platinum black
[W(aq)] = 1.0 mol dm-3 reduction: CuH(aq) + 2e- Cu(s)
Figul-e 20,04 The standard hydrogen electrode oxidation: H2(g) ----. 2H+(aq) + 2e-
The overall reaction is: CuH(aq) + H2(g)
----. Cu(s) + 2H+(aq)
b Two different oxidation states in solution 20.08 Calculating sta!1dard cell
Examples of redox equilibria are: potentials
Cl2 (aq) + 2e- 2Cl- (aq)
The standard cel l potential, EBcell' is the voltage across
Mn04 - (aq) + 8H+(aq) + Se- Mn2+ (aq) + 4H 2 0(I) two connected electrodes under standard conditions
An inert electrode, usually bright platinum, is needed when no current is taken from the cell. It is also called
to allow electrons to flow (Figure 20,06) , the electromotive force, e,mJ

T - 298K V)--, EBcell = EB(right-hand electrode) - EB(left-hand

electrode)

Worked example 20.02

bright platinum
What is the EBcell for Ag+(aq), Ag(s) connected to
[WI = 1.0moldm-]
Zn2+ (aq), Zn(s) and what is the cell reaction?
platinum covered - +--t-. 1.0 mol dm-] Fe"
and 1.0 mol dm-] Fe"
with platinum black How to get the answer:
Figure 20,06 Measuring t he standal'd electrode potential Step I: Assume the silver electrode is at the left:
of two aq ueous oxidat ion states, EBcell = -0,76 - +0,8 = - 1.56 V

Both the oxidised and reduced forms (Fe H and Step 2: The right-hand electrode has the sign of
Fe2+) have to be in the beaker so the reaction is EBcell : zinc is negative,
reversible, Step 3: Oxidation occurs at the negative
The right-hand electrode is positive and P"[FeH(aq) electrode: Zn(s) Zn2+ (aq) + 2e-
+ e- , Fe2+(aq)] = +O,77V: Step 4: The si lver electrode is positive:
The '+' sign shows that FeH(aq) is reduced more Ag+(aq) + e- Ag(s)
readily than H+(aq),A more positive electrode Step 5: The cell reaction is the sum of the
potential shows the oxidised form of an electrode is oxidation and the reduction reactions
a stronger oxidising agent. in the right proportions to cancel the
P"[Mn04- (aq) + 8H +(aq) + Se- , Mn2+ (aq) + electrons:
4H 20(I)] = + 1.51 V shows that acidified Mn04 - (aq) Zn(s) + 2Ag+(aq) Zn2+ (aq) + 2Ag(s)
is a much better oxidising agent than Fe3+(aq),
Standard electrode potentials are quoted for
reduction electrode equilibria, 20.09 Electron flow and
Ag+ (aq) + e Ag(s) EB = +0,80V feasibility of a reaction
Zn2+ (aq) + 2e EB = -0.76V
The sign of EBcell is the sign of the right-hand electrode,
See a Data Booklet for other values of electrode
potentials, The positive electrode lacks electrons because they
have been used in a reduction reaction,The negative
electrode has excess electrons which have been left
When measLwing a standal'd electrode thel'e after an oxidation reaction,
potential, a half cell must contain both the
oxidised and [he I-educed forln in standal-d Electrons from the negative electrode move through
the vo ltmeter to the positive electrode,
concentrations,
Using these ideas, you can decide whether a reaction is
feasible,
 Worked example 20.03
Does ch lorine oxidise cobalt to CoCl2 or CoCl} Step 5: Put the half-reactions together:
How to get the answer: Cl2 (aq) + Co(s) -----. 2Cl-(aq) + Co2+(aq)
Step I: Find the electrode potentials: Step 6: Repeat the process for CoCl2 to CoCl3:
Cl2 (aq), 2Cl- (aq) E B-= + 1.36V EB-cell = + 1.36 - 1.82 = -0.46 V

Co2+ (aq), Co(s) E B-= -0.28V Step 7: The chlorine electrode is negative, where
oxidation occurs.
Co3+(aq), Co2+(aq) EB-= + 1.82V
Step 8: Write the equations:
Step 2: Assuming cobalt is at the left, E B-cell + 1.36
- (-0.28) = +1.64V 2Cl-(aq) -----. Cl/aq) + 2e-
Co3+(aq) + e- -----. Co2+(aq)
Step 3: From the polarity. the right-hand electrode is
positive and where reduction occurs. Step 9: Put the half-reactions together and sum up:
Step 4: Write the half-reaction equations: 2Cl- (aq) + 2Co3+(aq) -----. Cl2 (aq) + 2Co2+(aq)
Cl2 (aq) + 2e- --.2Cl- (aq) Ch lorine cannot oxidise CoCl2 to CoCl3 but instead
Co(s) -----. Co2+(aq) + 2e- CoCl3 oxidises chloride to chlorine.

Progress check 20.02

Using standard electrode potentials from the 2 Can AlCl3 oxidise chromium to CrCl2 or CrCl}
text what is the E B-cell ' which is the positive
AP+(aq), Al(s) E B-= - 1.66 V
electrode and where does oxidation take
place for: Cr+(aq), Cr(s) E B-= -0.91 V
a a silver electrode connected to a copper Cr3+(aq), Cr(s) EB-= -0.74V
electrode? 3 Can FeCl3 (aq) oxidise Fe(s) to FeCl/aq)?
•
b a hydrogen electrode connected to a Fe2+(aq), Fe(s) E B-= -0.44 V
chlorine electrode?
EB-= +O.77V

20.10 Balancing redox Write the first equation as an oxidation X6 and the
second as a reduction and then add them:
equations
6Fe2+(aq) + Cr20/- (aq) + 14H+(aq)
In Unit 7, you balanced redox equations using oxidation 6Fe3+(aq) + 2Cr3+(aq) + 7H20(I)
numbers. Here we balance redox equations from
Check the balance in numbers of the different types of
[Link] oxidation and reduction equations
atoms and in charge.
are combined in the right proportions to balance the
electrons.
For the oxidation of Fe2+ (aq) by acidified chromate(VI), 20.1 1 Electrode potentials and
the two half-reactions are: the reactivity of the halogens
Fe3+ (aq) + e- Fe2+(aq)
The standard electrode potentials for X2 (aq) + 2e-
Cr20/- (aq) + 14H+(aq) + 6e- 2Cr3+ (aq) + 7H 20(I) 2X- (aq) become less positive down Group 17 and so
t he halogens become weaker oxidising age nts.
20.12 Variation of electrode c For complex electrodes

potential with concentration VO/ (aq) + 2H +(aq) + e- V02+ (aq) + H20(I):

E = E e- + 0.059 10 [VO/ (aq)] [H +(aq)]2
Ion concentrations affect redox equilibria, z glo [V02+ (aq)]
Cu2+ (aq) + 2e- Cu(s) moves to the left if [H +] is included although [H20 ] changes can be
[Cu2+ (aq)] is lowered and more copper goes into ignored.
solution as Cu2+ ions, leaving more electrons on the
copper: The (reduction) electrode potential becomes d Combining Nernst equations
less positive, which affects Ecell ' Cell potentials for two complex electrodes are
found by combining the Nernst equations for the
two electrodes.
20.13 The Nernst equation
The quantitative effect of concentration changes on Progress check 20.03
electrode potentials is given by the Nernst equation,
What is the cel l potential between copper
a For a metal dipping into a solution of its ions dipping into 0.5 moldm- 3 CuS0 4 and zinc
electrode potential = E = E 6+ 2,!:T loglo [ion] dipping into 0.5 moldm- 3 ZnSO/

z = number of electrons involved in the electrode 2 What is the cel l potential between copper
reaction dipping into 1.0 X 10- 3 mol dm - 3 CuS04 and
zinc dipping into [Link]- 3 ZnS04?
2J is a conversion factor
3 What is the electrode potential of
R = molar gas constant Mn04-(aq) + 8H +(aq) + 5e- Mn2+(aq)
T = temperature (in K) + 4H 20 (I) if the acid is only 0.5 mol dm - 3
although all the other species are
F = Faraday constant 1,0 mol dm - 3?
At a constant temperature of 298 K, the factor
(2JRT/F) = 0.059 V and the equation becomes:
E = E e+ 0.059 Ioglo [.]Ion Do not fOI"get to include the numbel"
z
For copper dipping into: of tlansfen"ed electrons in the Nemst
equation.
[Cu2+] = [Link] - 3, 10glo( I.0) = 0
E = E e- = OJ4V
[Cu2+] = 0.5 mol dm - 3, 10glo(0.5) = -OJO 20.14 The fuel cell and batteries
E = Ee - X OJO = OJ3V
a Fuel cells
[Cu2+] = (1.0 X 10- 5) mol dm - 3,
10glQ( 1.0 X 10- 5) = - 5.0 Burning fuels to get power is inefficient. A fue l cell
converts fu el directly into electrical energy, is much
E = E e- - X 5.0 = O. 19 V more efficient and only water is produced.
The effect is small but significant at very low Typically H2 (g) (the fue l) loses electrons at the
concentrations. negative electrode and H+ moves through the
electrolyte to react with 02(g) at the positive
b If the electrode system is two ions
electrode. The cells are stacked to produce higher
Fe3+ (aq) + e- Fe2+ (aq) voltages but they are light. Hydrogen, however; is
The Nernst equation becomes: exp losive and difficult to store.
E = E e+ 0.059 10 [oxidised form]
z glo [reduced form]
z = number of electrons transferred (here z = I)
b Batteries It Lithium ion batteries rely on Li losing electrons.
Nickel/metal hydride batteries rely on the They are light, rechargeable and need low
metal hydride producing hydrogen wh ich then maintenance but provide a high voltage.
loses electrons, as in the fue l [Link] electrolyte
is usually [Link] cell can be r-echarged and
keeps a constant voltage for a long time.

Exam-style questions
a Draw a labelled diagram of the apparatus c What is the electrode potential for the
needed to measure t he standard electrode Fe3+, FeH electrode if both [Fe3+ (aq)] and
potential of Fe3+ (aq) + e- FeH(aq). [5] [Fe2+ (aq)] are 0.50moldm - 3? [ I]
b The following two electrodes are combined Total: 9
in an electrochem ical cell:
2 A coin is an alloy of 84% by mo les of copper
12(aq) + 2e- 2I - (aq) E &= +0.54 V and the rest is nickel. It is the anode of a cell
Fe3+ (aq) + e- FeH(aq) E &= +O.77V
with CuSO 4 (aq) electrolyte. A current of 0.5 A is
passed for I hour: What are the changes in mass
What is the E&cell? of the cathode and anode? [6]
ii Write the equation for the reaction Total: 6
which occurs. [3]
21.0 I pH, Ka, pKa, Kw Water is not only the solvent but is central to the
ionisation of acids and bases as it is slightly ionised:
The lower the pH, the more acidic is the solution; H20(I) + H20(I) H30 +(aq) + OH - (aq)
[H+(aq)J ranges from about I,Omol dm - 3to
1,0 X 10- 14 mol dm - 3,The pH scale is an easier way The equilibrium constant for this ionisation:
to represent acidity. Kc = [H30 +(aq)J [OH - (aq)J / [H 20(I)]2
pH = -log1o[H +(aq)J but as the concentration of water changes little, a new
Strong acids are fully ionised: constant, Kw ' the ionic product of water, is defined,

HCl(aq) H+(aq) + Cl-(aq) Kw = [H30 +(aq)J [OH - (aq)J

[H +(aq)J equals the concentration of the acid put into This important equilibrium constant links [H O +J and
the solution, [OH - J; if one increases, then the other
At room temperature,Kw = I,OX 10- '4 moI2dm - 6,
Weak acids are only partially ionised and [H +(aq)J is
far lower than the concentration of the acid put into
solution, An equi librium is set up:
Remember the val ue of K fO I- use in
CH3COOH(aq) + H20(I) calcu lations. .v
CH 3COO-(aq) + H30 +(aq)
[CH 3COO- (aq)J [H30 +(aq)J
Kc In pure water, [H30 +(aq)J = [OH - (aq)J and so 1,0 X
[CH3COOH(aq)J [H 20(I)J
10- 14 = [H30 +(aq)]2
'f' 1000
Th e concentration 0 water In pure water = -18- =
55,6 mol dm - 3 and in a dilute solution changes very little
Thus [H30 +(aq)J = 1,0 X 10- 7 mol dm - 3 and pH = 7
from this value, so it can be taken as constant. A new
constant, K,a is defined: 21.02 Calculating H +
[CH 3COO-(aq)J [H30 +(aq)J concentration and pH
K
a [CH3COOH(aq)J
a Strong monobasic acids
Ka is the acid dissociation constant and indicates how
[H30+(aq)J is the same as the acid concentration in
much ionisation of the acid takes place, Values of Ka
the solution,
range over many powers of 10 so pKa is often used:
pH of0.50moldm- 3 HCl = 0.30
pKa = - logl oKa
b Weak acids
Ka describes the amount of ionisation, Progress cherk 21.01
Calculate the [H 30 +(aq)] and pH of
Worked example 21.01 a 0,00 I mol dm-) HCl
Calculate the pH of a 0.50 mol dm - 3 CH 3COOH b 0,05 mol dm - 3 HN0 3,
solution,
2 Using the Kavalues given, calculate the
How to get the answer: [H 30 +(aq)] and pH of
Step I: Write the equilibrium: a 0,01 moldm - 3 HCOOH,
K = 1,6x 10-4 mo ldm- 3
CH )COOH(aq) + H 20(I) a

CH 3COO - (aq) + H30 +(aq) b 0,005 mol dm - 3 C6 HsOH,

K = 1,28 X I O- Iomol dm- 3,
Step 2: Write the Ka expression: a

3 Using the value of Kw given previously,

Ka = [CH 3COO - (aq)] [H30 +(aq)] /
calculate the [H 30 +(aq)] and pH of
[CH 3COOH(aq)]
a 0,005 mol dm - 3 KOH
Step 3: Find the Ka value (from a data book):
b 0,001 moldm - 3 NaOH,
Ka = 1,7X 10-S moldm- 3
Step 4: From the equilibrium equation: [H )O+(aq)]
= [CH)COO - (aq)]

Step 5: Consider [CH )COOH]: the amount of

21.03 Changes of pH during
ionisation is very small so the un-ionised titrations
acid concentration is little changed from the
original concentration added to the solution When an acid is added to a base, the pH of the
= 0.50 mol dm - 3, mixture, as measured with a pH meter; decreases,The
curve of pH against the volume of acid added depends
Step 6: Put the values in the Ka expression: on whether the acid and base are strong or weak.
1,7 X 10- s = [H3 0 +(aq)]2 Although the reaction is called neutralisation, it is rare
0.50 that the final mixture is neutral with a pH of 7, as we
shall see,
Step 7: Work out [H30 +(aq)] = 2,92 X 10-3 moldm- 3
An acid- base indicator changes colour at the end
Step 8: Work out pH = -log lo 2,92 X 10- 3
= 2.54
point, providing a visual method of knowing when the
right amount of acid has been added,
Generally, [H 30 +] = .Jc
x Ka where
The equivalence point is when the correct amount of
c = concentration of the acid.
acid has been added according to the equation,
The pH of the equivalence point and the end point
c Strong bases should be the same; for this to happen, we need to
These are completely ionised in solution, choose the right indicator for the titration,

[OH - (aq)] in 0.5 mol dm -) NaOH = 0.5 mol dm - 3 a Titrating a strong acid against a strong base
To calculate the [H 30 +(aq)], use Kw = 1,0 X 10- 14 See Figure 21 ,0 I ,
= [H 30 +(aq)] X 0.5 • 20cm 3 of 0, I moldm - 3 NaOH is placed in the
1,0 X 10- 14 titration flask, pH = 13,0,
[H 30 +(aq)] = 0.5 = 2,Ox 10- 14moldm - 3
o 0, I moldm - 3 HCl is added from the burette,The
pH = - Iog lo (2,0 X 10- 14) = 13.70
pH falls gradually.
 14
• Adding 19.5 cm 3 of HCl, pH = I 1.1; adding
20.1cm3 of HCl, pH = [Link] pH drops 12
abruptly around the equivalence point.
.)!l 10
The equivalence point is at the centre of the abrupt §
pH drop at pH = 7. An indicator needs to change 8 8
... 7-1- - - -
colour at a pH lying on the abrupt pH drop. 6
'0
J:
Q. 4
14
2
12

bromothymol o 4 8 12 16 20 24 28 32
.)!l 10 blue is blue
c: Volume of strong acid added to weak basej em J

...8
VI
8
7 +
________----11---
___
1 7.0
7_.6--}range for Figure 2 1.02 Titration of a strong acid against a weak
'"
q::
6 r---6.0-- bromothymol base.
'0 blue
J:
Q.
4
bromothymol c Titrating a weak acid against a strong base
blue is yellow
2 See Figure 21.03.
0 " o 25 cm 3 of 0.1mol dm - 3 NaOH, with a
0 4 8 12 16 20 24 28 32 pH = 13, is placed in the flask and 0.1 moldm - 3
Volume of 0.1 mol dm-J Hc/ addedj em J
CHFOOH is added from a burette.
Figure 2 1.0 I Titrat ion of a strong base against a
strong acid o The main pH drop is from approximately
pH = 12 to 7.0.
o The equivalence point is around pH = 9.5.
b T itrating a strong ac id against a weak base
o The pH does not fall as far as for a strong acid.
See Figure 21.02.
o Any indicator needs to change colour within the
o 20cm 3 of 0.1 moldm - 3 ammonia solution
range 7.0 to I 1.9.
is placed in the titration [Link] time, the
pH, approximately I 1.1, is lower than for the 14
NaOH(aq).
12
o As 0.1 mol dm- 3 HCl is added, the pH falls rapidly
and then the rate of fall slows as a mixture ofthe .l!l 10
c:
buffer solution (see section 21 .05), ammonia and .l!l
c:
8 8
ammonium chloride, is formed . ..:.:
Vl 7
ro
I;:: 6
• The pH drops at the equivalence point from '0
approximately 7.5 to 3.5 with the equivalence ::t:
Q.
4
point at approximately pH = 5.
2
o As a weak base is only partially ionised, the onset
of the pH drop is at a much lower value than for
a strong base. o 4 8 12 16 20 24 28 32
Volume of weak acid added to strong basel cm 3
o Any indicator needs to change colour in the pH
range 7.5 to 3.5. Figul-e 2 1.03 Titration of a weak acid against a strong base.
o The equivalence point when a strong acid is
titrated with a weak base is below 7. d Titration of a weak acid with a weak base
There is no clear pH drop and therefore no suitable
indicator can be chosen.

•
21.04 Choice of indicators 21.05 Buffer solutions
Indicators show one colour at low pH and another at
high pH .They are weak acids: a Definit ion
A buffer solution is one which minimises any change
Hln(aq) + H20(l) H30+(aq) + In - (aq) [Eqn IJ in pH when small amounts of ac id or base are
. . . [H30 +(aq)J [In- (aq)J added . It is a solut ion of a weak ac id with one of its
The Ionisation constant: K,n = [HlnJ salts or a weak base with one of its salts.

PKIn = pH + log IO [Hln(aq)J [Eqn 2J For a so lution of ethanoic acid and sod ium
[ln - (aq)J ethanoate, the acid is partially ion ised:
In acid solution, eqn I is pushed to the left; the indicator
is mostly Hln.
K = 1.7 X 10-5 = [H 30 +(aq)J [CH3COO- (aq)J
a [CH 3COOH(aq)J mol dm - 3
In alkaline solution, H30+(aq) is removed and eqn I Sodium ethanoate is completely ionised:
moves to the right; the indicator is mostly In - .
CH3COO-Na+(s) + aq
Hln gives the colour in acid and In- the colour in alkali. CH 3COO-(aq) + Na+(aq)
At the end point, [Hln(aq)J = [In-(aq)J so PK,n = pH . In this mixture, there are appreciable concentrations
Different indicators have different pKln values and of both un-ionised acid (CH 3COOH) and its
change colour at different pH values - see Table 21.0 I. conjugate base (CH 3COO -) and for this buffer;
*
[H30+(aq)J [CH3COO-(aq)].

b Finding the pH of a buffer solut ion

The un-ionised acid concentration is the
concentration of the acid at the start less a small
amount which has ionised. For weak acids, this
amount is very small and can be ignored.
The concentration of the conjugate base is the
concentration of the salt plus a small amount from
the ionisation of the acid. Again, this very small
Table 2 1.0 I pKln values fO I' some ind icatol's
amount can be ignored.
A suitable indicator for a titration has a pKln value lying The expression for Ka becomes:
within the sudden pH drop.
K = [H30 +(aq)J [saltJ
a [acidJ
Progress check 21.02 As Ka and the two starting concentrations are
Suggest indicators from Table 21.0 I which would known, the [H30 +(aq)J and pH can be calculated.
show the end point for the following titrations.
c How does a buffer solution world
0.1 mol dm - 3 HBr against 0.5 moldm - 3 KOH
A buffer solution needs high concentrations of both
2 0.1 mol dm- 3 HCl against 0.1 mol dm- 3 the acid and its conjugate base in the solution.
CH3NH2 CH3COOH(aq) + H20(I)
3 0.1 mol dm- 3 CCl3COO H against CH 3COO-(aq) + H30 +(aq)
0.1 mol dm - 3 NaOH
If acid is added, the equilibrium moves to the left to
4 0.5 mol dm- 3 CH3COOH against remove it.
0.1 moldm - 3 NaOH.
If base is added, it reacts with H30+(aq) to form
H20 and the equilibrium moves to the right.

J -
Worked example 21.02 The best buffenng action is when the acid
and its salt have equal concell tl'a tions.
What is the pH of a buffer solution made by
adding 50cm 3 of 0.1 moldm - 3 CH 3COOH
to 50cm 3 0.1 mol dm - 3 CH 3COONa?
K.[CH3COOH] = 1.7 X 10- 5 mol dm - 3. d Controlli ng the pH in blood
How to get the answer: For proteins to remain active , a pH in the range 6.8
to 7.8 has to be maintained. This is ach ieved by a
Step I: Look for the initial concentrations:
hydrogencarbonate buffering system coupled with
[CH 3COOH] = [CH 3COONa] = 0.05 moldm - 3 breathing out carbon dioxide:
Step 2: Write down the Ka expression for a cO2(g) + H20(I) H2C03(aq) HC03- (aq) + H+(aq)
buffer solution:
After exercise, acid enters the blood and reacts with
K = [H30 +(aq)] [salt] HC0 3- - pushing the equilibria to the left and finally
a [acid] expelling CO [Link] the pH is maintained.
Step 3: Use the value of Ka:
e Other uses of buffer solut ions
1.7 X 10- 5 = [H30 +(aq)] (0.05)
(0.05) • Cosmetics are buffered to prevent ingredients
Step 4: Calculate [H30 +(aq)] = such as sodium hydroxide irritating the skin.
1.7 X 10- 5 mol dm - 3 • Baby shampoo is buffered at a pH of 6.0.
Step 5: Find pH = -log lo [H 30 +(aq)] = 4.77. • Paints are buffered to prevent any caustic action
from their use.

Progress check 21 .03

Fill in the blanks in the following table.

:: 1K,' moldm-'
r
"
:Acld Concentration '
of acid in ' . "',' ' I:[H,o« aq)i ;
1- "0'"1 'moldm- 1
solution I .'
,
moldm-;l
... ...... l
'II'
., .....

CH 3COOH 1.7 X 10- 5 0.1 0.5moldm- 3

HCOOH 1.6 X 10- 4 1.0 3.5

C6HPH 0. 1 0.2moldm- 3 6.4 X 10- 11

-
CH 3COOH 1.7X 10- 5 0.5 2.5 g in I 00 em 3
._'--- -- --
2 What is the pH of the buffer solution made 3 Using an acid from the table, suggest how you
by dissolving 0.34g sodium methanoate, could make a buffer solution of pH = 4.8.
HCOONa, in 100cm 3 of 0.1 moldm - 3
methanoic acid?The Ka(HCOOH) =
1.6 X 10- 4 mol dm - 3.

J - , •
2 1.06 So lu bility product and c C alculating a solubility product from the
solubil ity
common-ion effect For ZnCO J, Ksp = [Zn2+ (aq)] [CO/- (aq)] and
[Zn2+ (aq)] = [CO/- (aq)].
a Solubility product
Many insoluble salts have a small solubility; producing The solubility of ZnCO J is 3.74 X 10- 6moldm- 3
= co ncentl-ation of Zn2+ (aq).
a few ions in solution and setting up an equilibrium
which lies well over to the left: Ksp = [Zn2+ (aq)]2 = (3.74 X 10- 6),
AgCl(s) Ag+(aq) + Cl- (aq) = lA x 10- 11mol 2 dm - 6

K [Ag+(aq)] [Cl- (aq)]

= d The common-ion effect
c [AgCl(s)] AgCl(s) in pure water: AgCl(s) Ag+(aq) + Cl- (aq)
[AgCl(s)] depends on density; which is constant, so
If Cl- ions are added, the equilibrium is driven to the
the so lubility prod uct, Ksp ' is defined as:
left and less AgCl dissolves. Any common ion added
Kc X [AgCl(s)] = Ksp = [Ag+(aq)] [Cl- (aq)] will lower the solubility.
For Fe(OH)2' Fe(OH)/s) Fe2+ (aq) + 20H - (aq) Ksp forAgCl = 2.0x 10- lo mo I2dm - 6.,
Ksp = [Fe2+ (aq)] [OH - (aq)]2 [Ag+(aq)] in pure water = lAx 10- smoldm- 3

b Calculating a concent ration from a solu bility For AgCl in 1.0mol dm- 3 NaCl(aq),
prod uct 2.0x 10- 10 = [Ag+(aq)]X 1.0
For AgI: Ksp = [Ag+(aq)] [I - (aq)] so now [Ag+(aq)] = 2.0 X I0- lo mo ldm - 3, which is
= 8.0 X 10- 17mo I2dm - 6
very much less than in pure water!
But [Ag+(aq)] = [1 - (aq)],
so [Ag+(aq)]2 = 8.0 X 10- 17
21.07 The partition coefficient
[Ag+(aq)] = 8.9 X 10-9mo ldm- 3
A solute shaken with two immiscible solvents divides
To find the units of the solubility product, insert the
between the two solvents. At equilibrium, the solute
concentration units into the expression.
is divided in a definite ratio called the partition
As the [AgI] in the solution is the same as [Ag+], the coeffici ent, which is the ratio of the solubilities of the
solubility of AgI is 8.9 X 10- 9mol dm - 3. solute in the two solvents.

Worked example 21.03 Step 3: Work out the relative concentrations:

What is the solubility of Co(OH)} [OH - (aq)] = 2[Co2+ (aq)]

Ksp [CO(OH)2] = 6.3 X 10- 16mol J dm - 9 Step 4: Insert into Ksp:

4 [Co2+ (aq)]3 = 6.3 X 10- 16mo I3dm - 9
How to get the answer:
Step 5: Evaluate the concentration.
Step I: Write the equilibrium:
16
CO(OH)2(S) Co2+ (aq) + 20H - (aq) [Co2+ (aq)] = 3 0- = S.4x 10- 6mo ldm- 3
Step 2: Write the Ksp expression:
Step 6: Decide which ion concentration gives t he
Ksp = [Co2+ (aq)] [OH - (aq)J2 = solubility. [CO(OH)2] = [Co2+] so solubility
6.3 X 10-1 6mo IJdm - 9 of Co(OH)2 =
SAx 10- 6mo ldm- 3
 [equilibrium concentration until equi librium is reached, the so lute might divide so
in mol dm- 3 in first solvent] that just I g of solute is left in A. Solvent B therefore
Partition coefficient = -----------''--
[equilibrium concentration dissolves 4 g of so lute ,
in mol dm- 3 in second solvent] [solute]A = ( 11M) I 0,1; [solute]B = (4/M) I 0,1
For example, if 5 g of solute dissolved in 100 cm 3 of " , (11M,.) 10,1
solvent A were shaken with I 00cm 3 of so lvent B partition coefficient = (4/M,.) I 0, I = 0,25

Sample answer partition coefficient = 1.35

= (xIM r) I 0, I I ((5 -x)IMr) I 0,05 [I mark]
Question:
x = 3.65g [I mark]
5,0 g of solute is dissolved in 100 cm 3 of solution,
100 cm 3 of an imm iscible solvent is available t o For second extraction, 1.35 g remains in solution
extract the solute,The partition coefficient = 1.35, [I mark].
How much solute can be extracted if the immiscible y = mass of solute remaining in solution and so
solvent is added in two 50cm 3 portions? [6] (1.35 - y) = mass extracted
Answer: 1.35 = ylO, I I (1.35 - y)/0,05 [I mark], y = 0,99 g
For first extraction, let x = mass of solute remaining [I mark]
in so lution and so (5 -x) = mass extracted total extracted = 4,64 g [I mark]

An aqueous mixture, including the desired product, may

More solute is extl"acted if the solvent result after a reaction, An immiscible solvent, chosen
is added in small pOI"tions I"athel" than to dissolve just the desired product, is shaken with
one amount but it takes mOI"e effort in the aqueous mixture and then allowed to settle in a
sepal'ating small pOI"t ions. separating funnel. The aqueous layer is discarded. The
solvent containing the desired product is dried and
fractionally distilled to give the pure product.

Progress check 21.04

Write Ksp expressions for the following b Th e solubility in water of I J-dinitrobenzene
substances: is 500 mg dm - 3, 100 cm 3 of a saturated
aqueous solution of 1,3-dinitrobenzene
NiC0 3 Cr(OH) 3 PbI 2 PbCr0 4 Mg(OH)2 AgBr
is shaken with 100 cm 3 of octan-I-ol until
2 What is the so lubility of PbBr2 if K sp = an equilibrium is established, How much
3,9 X 10- 5 mo l3dm- 9 ? I ,3-dinitrobenzene is left in the water?
3 Wh at is the solubility of PbBr2 in 0, I mol dm - 3 c How much more I ,3-d initrobenzene can
NaBr solution? be extracted from 100 cm 3 of a saturated
4 a I ,3-dinitrobenzene is 31 t imes more soluble aqueous solution if t he octan-I-ol is added
in octan-I-ol than in water. What is the in two amounts of 50 cm 3 instead of one
partition coefficient of 1,3-dinitrobenzene amount of 100 cm 3?
between octan- I-ol and water?
Exam-style questions
a Explain what a buffer solution is. [3] 2 a i Define partition coefficient. [2]
b What is the pH of a 0.10 mol dm - 3 solution ii Describe how you can extract a solute
of ethanoic acid (CH 3C0 2H)? from an aqueous solution using a
solvent. [5]
Ka = 1.7 X I O-s mol dm - 3 [2]
b 100 cm 3 of an aqueous solution contains
c What are the pH values of the following
4.0g of solute. I 00cm 3 of solvent with a
mixtures?
partition coefficient of 3.8, is available to
100 cm 3 of 0.1 0 mol dm - 3 ethanoic extract the solute.
acid mixed with I 00cm 3 of 0.1 mol dm - 3
Calculate the mass of solute extracted by the
HCl.
following amounts of solvent:
ii i 00 cm 3 of O. 10 mol dm - 3 ethanoic acid
All I 00cm 3 of solvent is shaken with the
mixed with 150 cm 3 of 0.10 mol dm - 3
aqueous solution. [2]
NaOH.
ii The solvent is added as two separate
iii 100cm 3 [Link] - 3 ethanoic acid
50 cm 3 volumes and these two are then
mixed with 50cm 3 [Link] - 3
combined. [3]
NaOH. [7]
iii Suggest how you could get the most
Total: 12
solute from an aqueous solution. [2]
Total: 14
22.0 I Rate equations • k is the constant of proportionality in the
experimentally determined rate equation and is
We saw before that reaction rates depend on called the rate constant.
temperature, reactant concentrations and catalysts. The order of a reactant is the power to which the
For this discussion, we assume a constant temperature concentration is raised in the experimentally determined
and look at the steps that the reactants take to make rate equation. It is found experimentally by altering one
the products. Some steps may be slow and some fast; concentration whilst the others are kept constant.
slow steps determine how fast the reaction proceeds
and so we cannot decide how each reactant affects the If the above general reaction is investigated by altering
reaction rate by looking at the overall equation. [A], the other constant concentrations can become part
of the rate constant:
Here is an example: iodine reacts with propanone in
acid solution: rate = k[AY
12(aq) + CH 3COCH/aq) -------. If x = 0 this is called a zero-order reaction, if x = I it is
CH)COCH/aq) + HI(aq) a first- order reaction and if x = 2 it is a second-order
The reaction rate depends on [CH3COCH3(aq)] and reaction, with respect to A.
[acid] but not on [I2(aq)]. The rate of (CH3)3CCl hydrolysis can be investigated
In general, the reaction rate depends on reactant and using a large water concentration and a small measured
catalyst concentrations raised to a power which is amount of the halogenoalkane in ethanol as solvent. The
found experimentally: [H 20(I)] hardly changes as it is large.

catalyst C (CH3)3CCl + H20(I) -------. (CH3)3COH + HCl(aq)

Overall equation: A + B • products
The rate is found to be first order with respect to the
Rate equation: rate = k [AY[BJY[C]z
halogenoalkane:
• x, y and z are the orders of t he reaction with
respect to A, Band C respectively.
• (x + Y + z) = the overall order of the reaction. Concentration units are usually mol dm- 3 and rate units
are usually mol dm- 3S- I (although concentration and
• Square brackets mean concentration in mol dm- 3.
time units given in a particular question do need to be
followed).The rate constant has dimensions depending The zero-order reaction produces a straight line, but
on the order of the reaction. the other two produce curves which look similar. The
grad ient at any point is a measure of the reaction rate
For a first-order reaction:
at that [Link] gradient is found by drawing a tangent
(mol dm- 3 S- I) = (units of k) (mol dm- 3) to the curve (Figure 22.02).
units of k = S- I

22.02 Concentration/time
graphs
c
o
If the reactant concentration is found at measured time .""
intervals and the values plotted graphically. the curve c
produced depends on the order of reaction (Figure 22.0 I). o gradient = =rate of reaction at this point
u

zero order: constant rate of decline

first order: declines in a shallow curve y
second order: a deeper curve

'? zero order

E
x Time
"0
E
Figure 22.02 To find a grad ient, draw a tangent to the
---g first order
curve
.....
c
'"
t:l second order
'" A zero-order reaction has a constant gradient:
'0
c
0
rate = k
.""
'"c
J=
The gradient of a first-order reaction depends on the
Q)
'-'
c
0
concentration:
U

rate = k [reactant]
The gradient also depends on concentration for a
Time/s second-order reaction:
Figure 22.0 I The shapes of the graphs for zero-, flrst- rate = k [reactantJ2
and second-order reactions Plotting rates against concentrations shows the
difference between the three orders (Figure 22.03).

Concentration Concentration Concentration

rate = k rate = k [concentration) rate =k [concentrationF

Figure 22.03 Rate/concentration graphs

 Progress r.h ck 22.0 I
Find the units of k for zero- and second-order by monitoring the reduction in pressure.
reactions. The [H2(g)] is constant at 0.02 moldm- 3 and
the [NO(g)] is much [Link] data in
2 For the following reaction and data in Table
Table 22.02 show the rates of reaction with
22.0 I, plot a concentration/time graph. By taking
NO(g) concentration. By plotting a rate/
gradients at five suitable points, plot a rate/
concentration graph, decide whether the value
concentration graph . Deduce the order of the
of m in the rate equation is 0, I or 2.
reaction with respect to N20 S '
2H2(g) + 2NO(g) ----+ N/g) + 2H20(g)
2N 20 S(g) ----+ 2NO/g) + 02(g)
ItIs . ,
rate = k[NO(g)]m

0.2 0
0.142 50 0.0040 4.0 X 10-7
0.112 100 0.0035 3.06 x 10-7
0.088 150 0.0030 2.25 x 10-7
0.065 200
0.0025
--- -
1.56 x 10-7
0.050 250 -
0.037 300 0.0020 1.0 x 10-7
-
0.029 350 0.0015 5.63 x 10-8
0.023 400 0.0010 2.50 x 10-8
----
Table 22.0 I Data fO I the decomposition of N20)(g) 0.0005 6.25 x 10-9

3 The rate of the gaseous reaction between Table 22.02 NO(g) concentratio n and I'ate of I'eaction
hydrogen and nitrogen monoxide is followed

Plotting a concentration/time graph and finding two

When plotting gl"aphs, label the axes half-lives enables you to distinguish between fi rst- and
cleal'ly with the un its and enSUI"e you have second-order reactions (Figure 22.04).
lineal' scales.W hen dl'awing the line of
best fit, use a shal"p pencil and dl'aw on ly
one line and not several sketches. [M]
c::
o
.""
22.03 Using half-life to find the c::
8
order of reaction
HM] ,
I
I
The half-life, t y,' is t he time taken for half a reactant I
I
I
concentration to be used up. {- [M] --- -:,-
I
- - - --
I
It is useful to distinguish between first- and second- I
I
I
order reactions: I
I

• for a fi rst-order reaction, the half-life is constant Time

4

• for a second-order reaction the half-life gets larger as Figure 22.04 A concentration/time graph showing half-lives
the reaction proceeds.
For a first-order reaction, ty, = (tv. - ty,)' For a second-
order reaction, ty, < (tv. - ty,)'
The half-life can also be used to evaluate the rate
constant for a first-ol-der reaction:

k = 2.3log ,o2 / t y, = 0,693 / ty,

Progress check 22.02

For Progress check 22,0 I, question 2, find
two consecutive half-lives and state whether
they show the reaction is first or second
order:
2 The reaction between hydrogen and nitrogen Time
monoxide is first order with respect to
Figure 22,05 Vo lume of CO 2 against t ime
hydrogen, Use the value of m you calculated
in Progress check 22,0 I, question 3. The initial rate of reaction is the gradient of the tangent
If [NO(g)] = 0,0030moldm-3; drawn at t = 0,
[H 2] = 0,02 mol dm- 3; the rate For some reactions, we can use a 'clock' method which
= 2,25 X 10-7 mo ldm- 3 s- , depends on letting each reaction mixture get to the
'
same point when there is a very obvious visual change,
Find a value for the rate constant. Include the units
For this to work, the reaction must use only small
in your answer:
amounts of reactants before the visual change happens
so that we can assume the reactant concentrations
are unchanged from the initial concentrations, Each
experiment is timed to the visual change, The reciprocal
22.04 The initial rate method of this time is a measure of the rate of reaction,
for finding an order of reaction This method is suitable for reactions in which iodine is
The initial rate is the reaction rate at the start of the produced, Iodine in low concentrations is pale yellow
reaction, This method depends on finding the initial but with a small amount of starch produces an intense
rate for a range of experiments, each of which differs blue colour:
in the concentration of just one reactant. All other A range of experiments with known reactant
concentrations (and the temperature) are kept the same, concentrations including a measured amount of starch
There are two ways of proceeding: is set up,To each mixture, the same small measured
amount of sodium thiosulfate solution is added; this
Draw concentration/time graphs for each experiment reacts with any iodine produced, When the thiosulfate
and draw the tangent at t = 0, However; drawing has been used up, the iodine and starch gives the strong
accurate tangents at this point can prove difficult. This blue coloration, The time taken to produce the colour is
is suitable for an experiment such as calcium carbonate a measure of the initial rate of reaction - the longer the
reacting with aqueous hydrochloric acid, Carbon time, the slower the rate,
dioxide is given off and the volume of gas collected can
be measured at known time intervals (Figure 22,05),
 When dealing with data, take cal'e Step 2: Repeat for the other reactants. From
to identify the question as eitllel experiments I and 3, [0] stays the same
colKentratiollitime 01 concelltl'ation/initial but [E] is halved:
late. Concentl ation/til11c data fol low one
concentration of all exper'iment with time; 1.80 X 10- 4 /8 .92 X 10- 5 = k (0.30)" I k (0.15)"
initial I'ate data show the times fO I' a I'ange 2.02 = 2e so e = I
of expel-iments to get to the same point The order with respect to E = I.
<1nri the I-CIte of 1'f'Clction ic; pmrol-tional to
I/time. Step 3: Use the orders to write the rate
equation:
rate = k[E]
22.05 Calculating initial rates Step 4: Use the rate equation and data from one
and rate constants experiment in the table:
I.80 X I0-4 = k X 0.30
As we have seen, the initial rate from a concentrationl
time graph is the gradient of the tangent drawn at t = Step 5: Evaluate k = 6.0 X 10-4
O. Using the clock method, if t = time for the colour to Step 6: Put the units in the rate equation to find
appear; IIt is proportional to the rate of reaction. the units of k:
The rate constant can be found once the orders have (mol dm- 3 S- I) = (units of k) (mol dm- 3)
been established. The initial concentrations, orders and
initial rate are inserted in the rate equation and the only units of k = S-I

unknown, k, can be evaluated.

Worked example 22.0 I Progress check 22.03

For the reaction, 0 + E -----+- products, the For the reaction between nitrogen
initial rates for three experiments are shown in monoxide and hydrogen at a higher
Table 22.03. temperature than we used before,

I
Experiment [0] I
mol dm- 3
I[E] I
mol dm- 3
I
Initial rate I
mol dm- 3 5-'
2NO(g) + 2H 2(g) -----+- N/g) + 2H 20(I)
use the initial concentration data in Table
0.050 0.30 1.80 X 10-4 22.04 and show that the rate equation is
2 0.Q25 0.30 1.81 X 10-4 rate = k[NO(g)]2[H2(g)]
3 0.050 0.15 8.92 X 10-5 Evaluate the rate constant.
Table 22.03 Data of initial rates 1[NO(g)] (I [H2(g)] I lin'itial rate"
" " mol dm- 3 mol dm- 3 '1191 5- '..
Find the orders of reaction, write the rate I 0.53 0.195 0.483
equation and evaluate k. 2 0.53 0.0488 0.121
How to get the answer: 3 0.27 0.390 0.249
- - -
Step I: Choose two experiments using the Table 72.04 Initia l concentl-ations and I-ate fO I the
same concentration for one reactant and I-eaction between NO and H2
find how the rate varies with the other
reactant. From experiments I and 2, [0]
is halved, the rate does not change and
so the rate does not depend on [[Link]
order with respect to 0 = O.
 2 Bmmine and nitrogen monoxide react N0 2(g) + N0 2(g) X slow
together to form nitrosyl brom ide.
X + CO(g) N0 2(g) + CO 2(g) fast
2NO(g) + Br2(g) 2NOBr(g)
suggest X = N0 3(g) [I mark]
Use the initial concentration data in Table
22.05 to find the orders of the reaction and suggested mechanism: N0 2(g) + N0 2 (g)
write the rate equation . N0 3(g) + NO(g) slow
N0 3(g) + CO(g) N0 2 (g) +
moldm- 1 rate I CO 2(g) fast [I mark]
lor '.' [Link]-1s- 1 Adding the two steps together:
I 0.0150 0.0050 1.35 x 10-4
N0 2(g) + NO/g) + N0 3(g) + CO(g)
2 0.0150 0.0100 2.70 x 10-4 N0 3(g) + NO(g) + N0 2(g) + CO/g)
3 0.0300 0.0100 1.09 x 10- 3 which simplifies to
Table 22.05 Initial concentrations and ,oates foI-the N0 2(g) + CO(g) NO(g) + CO 2(g)
f'eaction of NO(g) and B'-/g) [I mark] (for working)

An important principle of a mechanism is that the steps

22.06 Reaction mechanisms added together must give the balanced stoichiometric
equation.
The reaction mechanism is the series of steps that the
reactants take to form the pmducts. Much mechanistic
information is found fmm the rate equation as one step
is often much slower than the others and determines
Progress check 22.04
the reaction rate .The slow step is called the The following mechanism is proposed for the
rate-determining step. reaction of nitrogen dioxide with ozone.
0 3 + N0 2 N0 3 + 0 2 slow
Sample answer fast
Question: I Write the stoichiometric equation.
Suggest a mechanism for the reaction between 2 Write the rate equation.
nitrogen dioxide and carbon monoxide, explaining
your working:
CO(g) + NO/g) CO/g) + NO(g) 22.07 Techniques for studying
rate = k[NO/g)J2 [8J rates of reaction
Answer: As we have seen, the two main ways of studying
The slow step determines the rate of reaction reaction rate are plotting a concentration/time graph
[I mark]. and finding initial rates.

The order with respect to N0 2 is 2 and so there a To follow the progress of a reaction, at known
must be a slow step involving two molecules time intervals
of N0 2 [I mark] and the other steps in the This can be done by:
mechanism must be fast [I mark].
• measuring the volume of a gas pmduct
The overall equation on ly has one N0 2 so a
slow step invo lving two N0 2 molecules must • mixing a large volume of reactant mixture and
be followed by a fast step producing one N0 2 removing small portions to titrate
[I mark]. The fast step must include CO(g) and
produce CO 2(g) [I mark].
 • keeping the pressure of a gas reaction constant oxidised by peroxodisu lfate. FeCl/aq) acts as a
and measuring the volume change catalyst.
• following a colour change with a colorimeter Nitrogen dioxide catalyses the oxidation of sulfur
dioxide to su lfu r trioxide:
• measuring the conductivity if an ion ic substance is
produced or used up N0 2(g) + S02(g) - . . . NO(g) + S03(g)
b To find the initial rate 2NO(g) + O)(g) - . . . 2N0 2(g)
This can be done by:
This fast production of S03 and its subsequent
• using all the above ways to draw a range of solution in water form acid rain.
concentration/time graphs
The layer of high-level ozone is broken down by
• using the clock reaction. chlorine atoms:

Cl + 03-'" Oel + 02
22.08 The effect of temperature
on the rate constant OCl + 0 - . . . 02 + Cl
Enzymes are water-soluble proteins in which
In Unit 9, we saw that the reaction rate increases with the protein chain is folded and held in an almost
temperature; the main reason is that more molecules spherical shape. They have a cleft, called the active
have energy greater than the activation energy and so site, into which the reactant molecule (called the
can react on collision. substrate) fits exactly and where it reacts and
The rate equation shows the concentration releases the [Link] is called the lock-and-key
dependency of reaction rate; as the concentrations mechanism (Figure 22.06).
do not change with temperature, it must be the rate
constant that has the temperature effect.

Make sure yo u can dl'aw suitable

Boltzmann distl-ibutions and, by using
them, explain the effect of tempel'atlwe
and catalysts on a reaction.
enzyme may
enzyme-substrate P be used again
complex
22.09 Homogeneous and e>s:E\
heterogeneous catalysis P[Link]. CJ
Reaction coordinate
a Homogeneous catalysis Figul-e 22.06 The lock-and-key model of enzyme
A homogeneous catalyst is one which is in the same catalysis
physical state as the reactants.
Only one substrate fits the active site, making
The peroxod isulfate electrode potential is more
enzymes high ly specifi c catalysts, unlike transition
positive than that of iodine but the reaction of
metal catalysts.
iodide with peroxodisulfate is slow as two negative
ions have to co llide: b Heterogeneous catalysis
21- (aq) + S20/- (aq) - . . . 2S0/- (aq) + 12(aq) A heterogeneous catalyst is in a different phase,
usually a solid, to that of the [Link] reaction
The electrode potential for Fe H lies in between takes place on the catalyst surface so heterogeneous
those for iod ine and peroxodisulfate so Fe H can catalysts are used as a powder or fine mesh.
oxidise iodide and the Fe2+ produced can be
 • The reactant molecules diffuse to the catalyst • Neighbouring atoms and molecules on the catalyst
surface where they are adsorbed, making weak surface form new bonds to produce the product,
bonds. which is desorbed.
• The reactant bonds are weakened so the Iron in the Haber process and catalytic converters are
activation energy is lowered. heterogeneous catalysts.

Exam-style questions
a How could the rate of the acid hydrolysis of b The reaction A + B - - - . [Link]
ethyl ethanoate be followed? [6] temperature and [A] are kept constant. Plot a
graph of the following data and use it to find
CH )COOCH 2CH)(I) + H2°(l) ---.
the order of the reaction with respect to B.
CH)COOH(I) + CH )CH 2 0H(I)
Any construction lin es should be clear: [7]
b Use the data in the table to find
the orders with respect to HCl and
CH)COOCH 2 CH ). [2] 1.0 o
ii Write the rate eq uation. [2]
0.715 9.5

5.3 x 10- 3 0.500 19.8

0.2 0.2
0.424 25.0
0.1 0.2 2.6 x 10-3
0.1 0.1 1.2 X 10- 3
Total: 10
2 a The decomposition of ammon ia using an iron 0.155 53.0
---11---
catalyst is a zero-order reaction. 0.120 60.0
Exp lain what zero-order reaction means. Total: II
ii Suggest why this decomposition is a
zero-order reaction. [4]
23.0 I Entropy from water to the less orderly vapour and the
entropy change is positive,
a What is entropy? Every substance has a positive entropy value, Solids
have the lowest entropy values and gases the
As we have already seen, substances have a
highest. A change of state from solid to liquid or
particular energy associated with them, their
from liquid to gas has a positive entropy change,
enthalpy. Energy can neither be created nor
because the particles become more disordered,
destroyed although it can change in form; thus
potential energy may be changed into kinetic energy
which in turn may be changed into electrical energy. Entt-opy values ar-e quoted in tenlls of
Hess's law depends on energy conservation, joules per mole per degr-ee, and not
kilojoules per- mole as foI- f1H values,
Another quantity associated with substances indicates
how their constituent particles and their associated
energy are distributed,This is their entropy,The more
At - 273 0c, the absolute zero temperature,
disordered the particles and the greater the distribution
elements and compounds are in their most ordered
of energy, the higher is the entropy. Particles in gases
state and the entropy of all ofthem = OJ mol-I K- ',As
are more disordered than particles in liquids or solids
the temperature is increased, the entropy increases,
and so gases have higher entropy [Link] energy
from burning fuel spreads out and warms a whole b Some entropy changes
room and the entropy of the room increases,
If separate gas jars of nitrogen and oxygen are
During any spontaneous change, the entropy increases, put into contact, the two gases spontaneously
A spontaneous change is one which proceeds by mix and spread through the whole of the
itself without needing an outside source of energy available volume, The distribution of the
to drive it. The entropy is the amount of disorder in molecules becomes more random and so the
a system, entropy has increased,

During a chemical reaction, the entropy changes II When a solid dissolves in a liquid, the particles
undergone by the reactants might increase or spread out and the entropy increases,
decrease, but if the entropy of the surroundings is III Photosynthesis, in which carbohydrates are
also taken into account, it is found that the total produced from CO 2 and H20, has a negative
entropy always increases, entropy change as there are far fewer product
For example, a pool of water evaporates even when molecules than reactant molecules:
it is well below the boiling point of water as long as 6H 20(I) + 6C0 2(g) ----. C6 H I20 6 (S) + 60 2(g)
more molecules can enter the air than will condense
from the air - the two processes are random,The Energy from sunlight is needed to drive the reaction,
evaporation is driven by the movement of molecules
c Calculatio n of entropy changes 23.02 Gibbs Free Energy
Many entropy values are listed in data tables.
entropy change in a reaction = 2:(entropyof a Total e ntropy change
products) - 2:( entropy of reactants) For a spontaneo us change, the total entropy change
must be positive as entropy always increases:
Worked example 23.0 I .15> 0
What is the entropy change when calcium If energy is lost from a reaction, the temperature
carbonate decomposes? of the surroundings increases and this means the
How to get the answer: entropy of the surroundings increases. Both the
entropy change of the substances in the reaction
Step I: Write the balanced equation:
and the entropy change in the surroundings need to
CaCO/s) CaO(s) + cO 2(g) be considered.
Step 2: Look up all the entropy values, 5-9:
b Entropy change of the surroundings. d SslIl'1'
CaCO/s) = 92.9; CaO(s) = 39.7; The entropy change of the surroundings depends on
CO 2(g) = 2 13.6
both the energy given out from the reaction and the
Step 3: Note the units: J mol- IK- '. temperature of the surroundings; the same amount
Step 4: Insert the values into the relationship: of energy has a far larger effect at a low temperature
than at a high temperature .
.15-9= 39.7 + 213.6 - 92.9
This can be illustrated by the following: if you
Step 5: Calculate the answer:
possess no money and then someone gives you a
= + 160.4J mol- I K- ' small amount, your wealth increases by an infinite
Step 6: Check that the sign is correct. A solid percentage; if you already have a lot of money and
produces a solid and a gas so the entropy then someone gives you a small amount, you would
change is expected to be positive. hardly notice! Giving you money has a far larger
effect when you start off with none.

c Re lating entropy and enthalpy changes

Progress check 23.0 I .15total =.15surr +.15 reaction
.
Which of the following would have a As we saw above, .15surr depends on both the
positive entropy change? amount of energy given to the surroundings (.1H)
a solid sodium chloride dissolving in water and the temperature (7).
.15surr - - .1H-
b gaseous sulfur dioxide and oxygen T
reacting to produce liquid sulfur trioxide
There is a negative sign as .1H for an exothermic
c ethene molecules reacting to produce reaction is negative but the entropy change in the
polyethene surroundings is positive.
d magnesium burning in oxygen Multiplying through the equation by - T gives
e water dissolving in ethanol - T.15 tota l = - T.15SUI, - T.15reaction
.
f crystallisation of copper su lfate from a
so lution. = .1H - T.15 reaction
.

2 Some standard entropy values in J mol- IK- ': d G ibbs free e nergy
N2 = 19 1.6 NH3 = 192.3 'T.15' is a quantity of energy. The American physicist,
What is the entropy change of reaction for Willard Gibbs, realised that account needed to be
taken for both the entropy change in the reaction
N/g) + 3H2(g) 2NHig)?
and the entropy change in the surroundings. A
new quantity, the Gibbs free energy change is Progres check 23.02
defined to cover this:
H20 (g) + ccs) ---. H2(g) + CO(g)
= d'
rea Ion
= + 135kJmol- '
As the total entropy change for a spontaneous change Under what conditions wou ld the reaction be
is positive and = - the free energy change spontaneous?
must be negative for a spontaneous change: Explain your
0

rhe encl-gy ( hange fOI' evel'y I-eaction is in Sample answer

two parts olle due to enthalpy changes
Question:
and the othel' due to entro py changes, I he
two toge Lhel determine whethel' 0 1- not a Using the given values, work out B at 300 K
r-eaction is sr olltalleous. and decide whether the following reaction is
spontaneous: [4]
CH 3CH 2CH 20H ---. CH 3CH(OH)CH 3
SB [CH 3CH 2CH20H] = 196.6Jmol- K- ' 1

Worked example 23.02

SB [CH 3CH(OH)CH 3] = 180.5 Jmol-I K- I
Under what conditions is the Haber
process for the production of ammonia a = - 302.7 kJmol-I
spontaneous reaction? = - 3 17.9 kJ mol-I
How to get the answer: Answer:
Step I: Write the equation: , = 180.5- 196.6 = - [Link]- ' K-'
reaction

N2(g) + 3H 2(g) ---.2NH /g) [I mark]

Step 2: Write down what yo u know about d' = 302.7 - 3 17.9 = - 15.2 kJ mol-I
rea Ion

enthalpy changes. is negative as this is [I mark]

an exothermic reaction. ,
reaction

Step 3: Work out the sign of the entropy change = - I5.2 - 300 X - I6. I / 1000
of reaction. is negative as 4 moles = - IOAkJmol- ' [I mark]
of gas produce only 2 moles of gas.
As B is negative, the reaction is spontaneous
Step 4: Use the relationship = - [I mark].
d'
rea Ion
for low temperatures.
< the negative is dominant,
so is negative and the reaction is
spontaneous.
Step 5: Use the re lationship = -
for high temperatures. >
the negative is dominant, making
the - term large and positive, so
is positive and the reaction is not
spontaneous.
Exam-style questions
a Which of these reactions has a positive b Work out LlG B at 298 Kfor the fo llowing two
entropy change? reactions:
PCls(s) PCl3 (1) + Cl/g) PCls(s) PCl3(1) + Cl/ g) [3 ]
ii 2Na(s) + 2H 20(I)
2NaOH(aq) + H2(g) 2Mg(s) + 0 2(g) 2MgO(s) [3]

ii i Ba2+(aq) + SO/ -(aq) BaS04 (s)

iv 2Ca(s) + 0 2(g) 2CaO(s) [2]

I"PCls(s) I PC1ii) I Clz(g) I Mg(s) IOz(g) I MgO(s)

SBf Jmol -I K- ' 166.5 217.1 223.0 32.7 205.0 26.9
LlH&r f kJ mol-I -443.5 -319.7 -601.7
Total: 8
2 a Under what temperature condition is the ii At what temperature does it change from
following reaction spontaneous? being spontaneous? [2]
N20/g) 2NO/g) is an endothermic reaction. [4]
I CH z .CHz(g) I L£tI;CH 3(g)
b i Under what temperature condition is the SBf Jmol-I K-' 219.5 130.6 229.5
following reaction spontaneous? LlH&J./ kJ mol-I +52.2 -84.7

Total: 9
24.0 I Electron configurations Atom
. .,. - 'r. -
-'"' "c:onf!guration
" .. ". - --
of the transition elements potassium [Ar]4s '
calcium [Ar] 452
In this series of elements, electrons fill the 3d orbitals scandium [Ar] 3d ' 45 2
which are higher in energy than the 3p and 4s orbitals.
titanium [Ar] 3d 24s 2
The five 3d orbitals (Figure 24.0 I) can accommodate
vanadium [Ar] 3d 3 4s2
ten electrons, giving ten transition elements.
chromium [Ar]3d 5 4s l
z z manganese [Ar] 3d5 4s2

--- y
1-
x - ( ---
y
---. y
Iv .-.-. y
Iron
cobalt
[Ar] 3d 6 4s2
[Ar] 3d?45 2

I x I nickel [Ar] 3d B45 2

dX1 dxy copper [Ar] 3d '04s '
zinc [Ar] 3d lO4s 2
gallium [Ar] 3d lO4s24pl
Table 24.0 I T he electron configurations of some of t he
elements of Pel-iod 4

Fig. 24.0 I The shapes of the five 3d orbitals. ---

A lthough you can look at the Pel-iodic
Along the series there is little change in atomic radius Table, yo u w il l fi nd it helpful to kilOW
and the ionisation energy rises gradually; the ions, lhe t l ansit ion elements in t he COITect
formed by loss of the 4s electrons, are small. The ordcl' and be able to w l-ite the il' electmn
electron configurations are shown in Table 24.0 I .There conflgLwations.
are two discrepancies, at Cr and Cu, in the regular filling
of the 3d orbitals.
The 3d electrons enter 'inner orbitals' and it is the
Cr has one electron in each of the 3d and 4s orbitals 4s electrons that are lost on ionisation. Once the
and Cu has one electron in the 4s but full 3d orbitals. 4s electrons have been lost, varying numbers of 3d
This gives a symmetrical charge distribution, conferring electrons may be lost (Table 24.02).
stability, in each case.
 [Link]. ISc ITi Iv ICr IMn --I Fe ICo I ICu IZn
+7 Mn04 -

+6 CrO/ -
+5 VO J +
+4 Ti0 2 VOH Mn02

+3 Sc3+ V3+ Cr.3+ Fe3+

+2 VH MnH Fe 2+ COH NiH Cu H ZnH

+1 Cu+

Tab le 24.02 The ox. no. of the main ions of t he t l"ansit ion elements

To be included as a transition element, an element

needs at least one stable ion with a partially filled set of Yo u need to remembel" th e five
d orbitals. We can see in Table 24.02 that Sc produces propel"ties of tl"ansition elements and give
Sc 3+; this has lost all its 3d electrons and thus scandium suitable examples.
is not included. At the other end of the series, Zn
produces Zn 2+ with the electron configuration [Ar] 3d 10.
With no partially filled d orbital, zinc is not included.
24.02 Catalysis
The particular properties of transition elements shown
by the eight remaining elements are: See Unit 22 for more information about catalysis.

• similar physical properties Here are some important transition metal catalysts you
have met:
• variable oxidation state and redox reactions
• Fe in the Haber process
• coloured compounds
• V20 S in the Contact process
• catalytic activity
• Ni in the hydrogenation of alkenes to produce
• complex formation
margarine
•
• Fe H in the reaction between 1- and S20/-
Progress check 24.0 I
Work out the oxidation numbers and give the
24.03 The physical properties
corresponding electron configurations of the
transition elements in the following compounds: of the elements
Cu 212 The melting points of the elements are higher than
2 Fe 2 (S04)3 calcium, indicating they have giant structures. The
electrical conductivity is good, indicating metallic
3 K2Cr20 7 bonding, so they are malleable and ductile, strong and
4 VOCl2 [Link] all have much higher densities than that of
calcium.
5 VCl 3
6 CU(NO)2'
24.04 The oxidation states b C hromate (VI) ions

and redox reactions of the In acidic solution these exist as orange Cr20 / - ; in
alkaline solution they exist as yellow CrO /-,When
elements acting as an oxidising agent, Cr (VI) ions are reduced
to green Cr3+,Acidified potassium dichromate(Vl) is
When forming ions, these elements lose the 4s often used in organic chemistry to oxidise primary
electrons and varying numbers of 3d electrons, Highly and secondary alcohols,
charged and small, these ions are stabilised by species
such as oxygen forming covalent or dative covalent
bonds with them, Transition elements show a variety
of oxidation states (see Table 24,02), From titanium to
Worked example 24.0 I
manganese, the highest oxidation state is the sum of A sample of FeS04 had partially oxidised to
the 4s and 3d electrons, After manganese, the + 2 state FeiS04)3' 0.56g ofthe sample was dissolved in
becomes more important. aqueous sulfuric acid to form I00,Ocm 3 of solution,
A 25,0 cm 3 portion of this solution required
With variable oxidation states, redox reactions are 21.35 cm 3 of 0,005 mol dm- 3 KMn04 to reach the
important. Electrode potentials indicate the oxidising end-point. What is the mole percentage of Fe2+ in
power in aqueous solution (see Unit 20): the amount of iron present in the sample?
FeH(aq) + e- Fe2+(aq) E 6-= +O,77V
How to get the answer:
Cr20/-(aq) + 14H+(aq) +6e-
Step I: Work out the number of moles of
2CrH(aq) + 7H 20(I) E 6-= + 1.33V
KMn04 used:
Mn04 - (aq) + 8H+(aq) + 5e-
Mn2+(aq) + 4H 20(I) E 6-= + 1,52V 0,005 x 21.35 = 1,0675 X 10-4
1000
A more positive E 6- value indicates a stronger Step 2: Work out the number of moles of FeS04
oxidising agent and you can see that both acidified in 25,0 cm 3 of solution:
manganate(Vll) and acidified chromate(Vl) can oxidise
Fe2+(aq) to Fe 3+(aq), 5 X 1,0675 X 10- 4
Step 3: Work out the number of moles of FeS0 4
a Oxidation w it h manganate(VII)
in 0.56g ofthe sample:
Reduction: Mn04-(aq) + 8H+(aq) + 5e- - - .
Mn2+(aq) + 4H 20(I) 4 X 5 X 1,0675 X 10-4

Oxidation: Fe2+(aq) - - . FeH(aq) + e- Step 4: Work out the mass of FeS0 4 in 0.56g of
the sample:
The oxidation equation needs to be multiplied by 5
to balance the electrons: 2,135X 10- 3x 151,9 = 0.324g

Mn04-(aq) + 8H +(aq) + 5Fe2+(aq) - - . Step 5: Work out the mass of Fe2(SO 4)3 in 0.56 g
Mn2+(aq) + 4H 20(I) + 5Fe 3+(aq) ofthe sample:

As manganate(VII) is deep purple, Mn2+(aq) is very 0.56 - 0.324 = 0,236 g

pale pink and FeH(aq) is yellow, this self-indicating Step 6: Work out the number of moles of Fe H
reaction can be used to find Fe2+ concentrations by in 0.56g ofthe sample:
titration, The manganate(VII) solution is placed in the 0,236
burette and run into a known volume of the Fe2+ 2 X 399,9 = 1,180 X 10- 3
solution, The mixture remains almost colourless until
the end-point when the first permanent pink tinge Step 7: Work out the total moles of iron
appears, (Fell and Felli) in 0.56 g of the sample:
3.315X 10- 3
Step 8: Mole percentage of Fe2+:
3
2,135 X 10- = 64.4%
3.315 X 10- 3
 bonds. Ligands are simi lar to bases and nucleo philes,
Progress check 24.02 which also have a lone pair of elect ro ns used to form a
covalent bond.
a W rite the equ ation for the reaction
betwee n zinc and vanadium( II I). A complex is formed when a number of ligands fOI-m
dative covalent bonds with a cent ral metal ion.
V3+ (aq) + e- V2+ (aq)
E B= - 0.26V Complex form ation spreads out the ionic charge and
stabilises t he metal ion.
Zn2+ (aq) + 2e- Zn (s)
E B= -0.76V a Charge and oxidation number
b Is the reaction represented by The sum of the oxidation numbers of metal ion and
your equation able to proceed ligands = charge on the comp lex.
thermodynamically?
2 If acid is added to CrO/-, the orange
Cr20/ - is formed .Write the balanced
Worked example 24.02
reversible equation for this conversion. What is the oxidation number of Co in
[Co(NH3)sBr]2+?
How to get the answer:
Learn the main oxidation states of Step I: State the known ox. nos. and charges:
chrom ium, manganese, iron and coppel- charge on NH 3 = 0; Br- = -I.
and the coloul-s expected of t he ions in
solution. Step 2: Equate the sum of charges and [Link]. to
the overall charge: [Link].[Co] + 0 -
= +2.
Step 3: The answer : [Link].[Co] = + 3.
24.05 Complex formation
b Shapes of compl exes
Small, highly charged, transition metal ions strongly
attract any species with a lone pair; the lone pair is used The coord ination number is the number of
to form a dative covalent bond. attached ligands.
A ligand is a species with a lone pair of electrons which The coordination number is often six, but complexes
it donates to an ion and forms a dative covalent bond. with four or two ligands are also known. There are
four common shapes (Figure 24.02).
Ligands are species such as Cl- , OH - , H20 and NH 3. Of
these, NH 3 forms the strongest and H20 the weakest

[Cu(HP)J2+ L octahedral
[Fe(CN)J 3-
l'",. 1. .-,/ l
M

l/ 'j'''l
L

1 -
 > ,-

Examples Diagram
-
Shape I Bond
CUCl42- L tetrahedral 109Y
NiC142-
j
M
L/
L

[Pt(NH)4J2+
--
L L square planar 90°
[PtC14J2-
M
/
L/
[Ag(NH 3)2J + L • M 0( L linear 180°
[CuCl2J-

Fig. 24.02 The most common complex shapes

The dative covalent bond is shown as an arrow +

drawn from the lone pair on the ligand pointing
towards the transition metal ion.
The blue copper sulfate solution is due to the
octahedral complex [Cu(H 20)6]2+ (Figure 24.03).
2+

+
.
,.,

Fig. 24.04 The cis (Iowel") and trans (upper) isomers of a

cobalt(lIl) comp lex
There is no rule as to which shape is taken up by a
comp lex but most are octahedral. Even tetrahedral d Polydentate ligands
complexes usually change to the octahedral aquo
Some molecules act as ligands at two or more
complex when in water as more bonds are formed.
places in a chain.
c Isomerism I,2-Diaminoethane (H 2 NCH 2CH 2 NH 2) contains
If the surrounding ligands are different, the complex two nitrogen atoms, each with a lone pair of
may show isomerism. The octahedral comp lex electrons; it is a bidentate ligand. Isomerism is
[CoCl2(NH 3)4]+ shows cis and trans isomerism again possible (Figure 24.05).
(Figure 24.04) .
 When eaten , cisp latin slowly hydrolyses and the
product forms bonds to the base guanine in
separate DNA strands. Cross linking between
DNA molecules destroys cancer cells.
Transplatin has no such effect and is toxic, so the
anticancer medication is required to only contain
the cis isomer.

Cl + IV The linear complex, [Ag(NH 3)2] +' is formed when

silver chloride or silver bromide dissolves in
1 , (f
o"
./ H2N , aqueous ammonia.
H2C ',.... )../

HJ / c e Ligand exchange reactions

"H2N INH2 A stronger ligand, forming a stronger dative
covalent bond, can replace a weaker one.
CH 2
When concentrated HCl is added to the blue
1
NH 2 . /
I
./CH 2 [Cu(H 20)6]2+(aq), it changes to yellow as the Cl-
ligands replace the H20 ligands:
Fig. 24.05 The isomers of a cobalt( lll) ion with a
[Cu(H 20)J2+ + 4Cl- [CuCl4]2- + 6H 20(I)
bidentate ligand
Diluting with water moves the equilibrium to the
The second of these complexes, cis-[Co(en)2Cl2]+ left, returning the solution to the original blue
and also [Co(en)3]3+ are both [Link] do not colour. A stability constant, Kstab , can be written,
have a plane of symmetry. with [H 20 ] assumed constant:
K = [CuCl}-]
II The ligand usually known as EDTA (Figure 24.06)
stab [CU(HP)6/] [Cl-]4
is a hexadentate ligand as it can donate six pairs
of electrons. The larger the value of Kstab , the further to the
right is the equilibrium and the more stable is the
o complex.
NH3 is a weak [Link] it is added to blue
[Cu(H 20)6F+(aq) a pale blue precipitate of
• [Cu(H 20\(O H)2] is produced. Excess ammonia
HOy 0 OH dissolves the precipitate to form a deep blue
o solution as NH3 ligands replace H20 ligands to
form a charged complex:
Fig. 24.06 EDTA
[Cu(H 20)6]2+(aq) + 4NH3(aq)
EDTA is usually used as the salt with a 4- charge. [Cu(NH 3)4(H20)2F+(aq) + 4H 20(I)
It wraps around a metal ion forming an octahedl-al The stability constant for the deep blue complex
complex as it has two N atoms and four is much larger than the value for [CUCl42-].
carboxylate groups, all of which can act as ligands.
III Colourless ammonium thiocyanate solution and
III Some of the square planar complexes of orange FeCl3(aq) form a blood red complex
platinum form anti-cancer drugs (Figure 24.07). which can be used as a sensitive test for iron (III).
(f NH3 H3 N C/ [Fe(H 20)6]3+(aq) + SCN-(aq)
[Fe(H 20\SCN]2+(aq) + H20(I)
(f/ (f/
cis-platin trans-platin
Fig. 24.07
 IV Ligands are exchanged one by one with a
different stability constant for each equilibrium:
[Cu(H 20)J2+ (aq) + NH3(aq)
[Cu(H 20\NHl+(aq) + H20(I)
<1)
c
w

K, = 1.8x 104 mol- 'dm 3 .1H

3d - - - - - - - - - - -
[Cu(H 20)s NH3]2+ (aq) + NH3(aq)
[Cu(H 20MNH)2J2+(aq) + H20(I)
= 4. I X 103mol- Idm 3 five degenerate 3d in an octahedral
orbitals in a symmetrical complex
charge distribution

Progress check 24.03 Fig. 24.08 The splitting of the 3d orb itals in an
octahedral complex
I What shape is [Fe(H 20)sSCN]2+?
2 What is the oxidation state of the transition For the ligand H2o' the energy splitting, LlE, is small
metal ions in the following complexes: and electrons are distributed between all the orbitals
until they have to pair. For CN -, the splitting is large
[Fe(CN)J4- Cu(NH 3)/ [V(CN)6]4-
and the lower energy orbitals are filled first. Felli has
[CrCI 6]3- [ MnF6F- [Co(H 20)4 Ci2] the electron configuration [Ar] 3ds; in [Fe(H 20\]3+,
there is one electron in each of the 3d orbitals but
3 Draw three-dimensional representations
in [Fe(CN)6]3-, all five d electrons are in the lower
ofthe two isomers of[Co(en)3]3+
orbitals and there is just one unpaired electron.
(en = 1,2-diaminoethane).
The frequency of radiation corresponding to
LlE = hflies in the visible region.
(h = the Planck constant; f = frequency of light)
24.06 d orbitals and colour
An electron in a lower energy 3d orbital can absorb
a Octahedral complexes light of just the right frequency and jump into a
space in one of the higher energy orbitals. That
The six ligands of octahedral complexes define absorbed frequency cannot be seen but all the
three orthogonal axes. Three of the 3d orbitals other frequencies in white light can be seen; the
have lobes pointing between the axes and two have complex is the complementary colour to the colour
lobes pointing along the axes (Figure 24.0 I). As the absorbed.
ligands donate electron pairs along the axes, they
experience repulsion from electrons in the d orbitals The electron loses its absorbed energy by molecular
with lobes pointing along the axes but there is less vibration, dropping down into the lower orbital
repulsion between the lone pairs and electrons in d without emitting any light so the whole process can
orbitals with lobes pointing between the axes. The happen again.
five degenerate 3d orbitals are split into two sets [Cu(H 20)6]2+ absorbs in the red-orange region,
with different energies (Figure 24.08). (Degenerate the complementary colour being blue. In
orbitals are orbitals with the same energy.) [Cu(NH 3)4(H 20)2]2+ the LlE is larger and the
frequency absorbed is larger. The absorption moves
into the orange region and the complementary
colour becomes dark blue (Figure 24.09).
 Progress check 24.04
Explain why Ti0 2 is white.
2 In solution, potassium iodide red uces
copper(lI) su lfate to insoluble copper(l)
iodide and some of the iodide is oxidised to
iodine.
a Write a balanced equation for the
reaction.
b What would be observed during the
reaction?
3 EDTN- is a strong ligand producing a large
d- d splitting.
Fig. 24.09 The complemental"y coloul"s are opposite to
a What is the oxidation number of cobalt
the ones absorbed
in [CoEDTAr?
b Write down the electron configuration of
b Tetrahedral complexes
cobalt in [CoEDTAr.
In a tetrahedral complex such as [CuCl J2 - , the 3d
splitting is reversed and the three orbit:ls with lobes c How many unpaired electrons does Co
between the axes are at a higher energy than the have in the complex [CoEDTAr?
two with lobes along the axes.
Exam- tyl tion
a Write down the electro n configurations of: b Fe3+(aq) + e- Fe2+(aq)
EB"= +O.77V
Fe
Fe2+ (aq) + 2e- Fe(s)
ii Ni 2+. [2]
Write the equation for the
b What shape is Ni(H 20)/+?[I]
disproportionation (the same species is
ii Explain why Ni(H 20)/+ is green but both oxidised and reduced in the same
Ni(NH 3\ 2+ is blue. [5] reaction) of Fe(aq)2+ . [2]
c Suggest why [Fe(H 20)6J3+ has more ii Explain whether the disproportionation
unpaired electrons in the d orbitals than reaction is feasible . [2]
[Fe(CN\J 3- . [5] Total: 9
Total: 13
2 a What would you see if separate portions
of copper sulfate solution are reacted with
NaOH(aq) and NH3(aq).Write equations for
any reactions which occur. [5]
25.0 I The structure of benzene
Are nes are one of the homologous series of
hydrocarbons that were mentioned in Unit [Link]
are hydrocarbons that contain at least one benzene
each carbon atom forms
[Link] general term aromatic is used to describe the six p-orbitals overlap to form a 1t bond whose
three C5 bonds, leaving an electrons are delocalised over all six carbon atoms
non-hydrocarbon compounds (e.g. ketones, carboxylic electron in a p orbital
acids) that contain a benzene ring (some of the earliest
discovered aromatic compounds had pleasant odours - H

o
I
hence the name).This is to contrast them from ali phatic H C H
...... C/
compounds, for example ethanoic acid, that do not or
contain a benzene ring. H C H
I
The structure of benzene is a ring of six carbon atoms, H
each with a hydrogen atom attached. Each carbon atom Kekule's original formula for benzene
uses three of its valence electrons to form (J' bonds
with adjacent atoms, leaving one electron in a p orbital.
The delocalised 'IT bond makes benzene more stable
Rather than overlap in pairs to form normal C=C
than expected.
double bonds, these six p orbitals overlap to form one
6-centred 'delocalised' 'IT orbital, which is represented
in the skeletal formula by a circle inside the hexagon.
25.02 Nomenclature and
The alternative formula, showing three double bonds, isomerism
was originally proposed by Kekule in the 19th century,
You may still find benzene structures drawn like this Substituted benzenes show positional isomerism. There
(especially on some Internet sites): are three dichlorobenzenes, named as follows:
 CCI
CI C/ C/ b Halogenation

CA" ¢
When warmed in the presence of anhydrous A/Cl3
or FeCl3, chlorine or bromine undergo substitution
reactions with arenes. Two examples aloe:
C/
1,2-dichlorobenzene 1,3-dichlorobenzene

If the substituent groups are different. the 'major'

1A-dichlorobenzene

0 + C!2(g)
A/C!3 + heat.
OC!

chlorobenzene
+ HC/(g)

group is the last-named of the p,-eflxes, and the ring CH3

M
3
numbering starts from that group, as the following OCH + Br2O) FeC/3 + heat.
+ HBr(g)
examples illustrate (in each case the 'major' group is at Br
the top of the ring): methyl benzene 4-bromomethylbenzene

c Nitration
Arenes react with concentrated nitric acid in the
presence of concentrated sulfuric acid to form nitm-
2,4-dibromomethylbenzene 3·methyl·4·nitrobenzoic acid 3·chloro·5·ethylphenylamine
arenes. Strict temperature control is necessary to avoid
more than one nitro group substituting in the ring:
25.03 T he reactions of the
benzene r ing
(one. HN03+ cone.
T sO'C-ss'C
a
JVl
CH3
+ H20
02 N
4·nitromethylben2ene
a Hydrogenation
Benzene and other arenes can be hydrogenated by d A lkylation and acylation
reaction with hydrogen at 200°C and 60 atm pressure.
Arenes react with chloroalkanes or acyl chloride
These conditions are much more extreme than those
when warmed with anhydrous A/Cl3, giving alkyl or
sufficient for the hydrogenation of alkenes (H2(g) at
acyl benzenes (these are known as Friedel- Crafts
room temperature and pressure - see Unit 15):
reactions):

Ni at 2WC
and 60 atm
.. 0 cyclohexane
+ Hc/

Think carefully wheneve,- you draw a A/C/3 •

hexago nal ,-ing: do you want to rep,-esent heat

benzene 0'" cyclohexane ? In the ,"ush
of sitti ng (In examination paper" it is
very easy to fo"get to d,-aw the circle
in the benzene '"ing. An examine,- might 25.04 The mechanism of
th ink you a,"e talking about the wmng
compound. electroph il ic substitution
Study the names given to the compounds
reactions
me'ltioned ill this chaplet' the Ilumbe" ing of
The halogenation and the nitration of arenes are
the G ltbO '1 atorns rmmel the ring sla, ts with the examples of electrophilic substitutions. The benzene ring
major" substituent clS C I. is electron-rich, with its 'IT electron ring on its surface,
so is attacked by electron-deficient [Link]
electro philes (electron-loving ions) are made when the
relevant reage nt reacts with the homogeneo us catalyst.

a Brom ination
H,SO, + HN O,

H,SO, + H,O
-- HSO.- +

HSO,- + H,O'
H, +
H - H20 + N02+

the electrophile

overall equation: 2H,SO, + HNO, _ 2HSO, + H,O' + NO,'

• In the first ste p, Br2 reacts with the catalyst AlCl3
(AlBr3' FeCl3 or FeBr3 can also be used) to give t he
electrophile Br+.The initial interaction is a dative
bond from a lone pair of electro ns on bromine to a
V NO,' ______
H

-
O
Ne,
+ H'

intermediate Y
vacant orbital on the aluminium atom.
• This then reacts with benzene in a two-stage
reaction, in which the intermediate X is a carbocation c General mechan ism
that has the four remaining 'IT electrons delocalised There are many other electrophilic substitution
over five carbon atoms of the ring. Intermediate X reactions. In each one an electrophile E+ is attacked
loses a proton to form the product, bromobenzene. by the 'IT electrons to form an intermediate cation
• In the last step, this proton reacts with the complex similar to X or Y above, and this cation then loses a
anion formed in the first step, to produce HBr(g) and proton to form the product:

o
to re-form the AlCl3 catalyst, which can react with
another Br2 molecule.
-
+ /(1
Br-Br''"'' [Link]
, t>' - Br
the electrophile
[
Br-A(,-CI
CI
] The electrophile in the Friedel- Crafts reaction
is generated by the reaction between AlCl3 and
the alkyl or acyl chloride:
CH 3Cl + AlCl3 » CH/ + A1Cl4-
intermediate X

H' +
HBr(g) + Aiel, Progress check 25.0 I
(catalyst regenerated)
Suggest the mechanism for the formation of the
electrophile and its subsequent reaction with
b Nitration benzene to form the product, for each of the
• In the first step, the nitric acid molecule is following reactions.
protonated by the concentrated sulfuric acid, and
The production of ethylbenzene from
then loses water to form the nitronium cation. (The
benzene, bromoethane and iron(lll)
water is further protonated by another sulfuric acid
bromide.
molecule.)
2 The production of ethanoylbenzene from
• The NO/ ion then reacts with benzene to form
benzene, ethanoyl chloride (CH3COCl) and
an intermediate cation Y, which, like intermediate X
aluminium chloride.
above, has the four remaining 'IT electrons delocalised
over five carbon atoms of the ring. Intermediate
Y then loses a proton to form the product,
nitrobenzene.
• The proton th at is released can then protonate ethyl benzene ethanoylbenzene
another nitric acid molecule and so on:

}-
25.05 Orientation in [Link]
"". "-n-,-- -
Electron-donating
.-- - '--

electroph il ic substitution -•
Name
•
Formula
I
group-s
Name Formula
In benzene all six positions are equivalent: there is only aldehyde - CHO methyl - CH
one bromobenzene. In methylbenzene, however; there ketone -COR alkyl -R
are three different positions round the ring that could carboxylic acid -C0 2H hydroxy - OH
be substituted by bromines, so there are three possible (phenolic)
bromomethylbenzenes: nitro -NO amino -NH

o
ammonium -NH +

Table 25.0 I Some electron-w ithdrawing and elect ron-

donating groups
Br
2-bromomethylbenzene 3-bromomethylbenzene 4-bromomethylbenzene

Which one of these isomers is formed when Progress check 25.02

methyl benzene is brominated is determined by the
methyl group already attached to the ring, rather than Suggest the structures of the products of the
the nature ofthe incoming substituent. In general, following reactions.
groups that are electron-withdrawing cause the
incoming substituent to be attached to the 3-position,
whereas electron-donating groups produce a mixture
of the 2- and 4-substituted compounds. Because

H0'Q
methyl (like all alkyl groups) is electron-donating, the
bromination of methylbenzene produces a mixture of 2
2-bromomethylbenzene and 4-bromomethyl benzene.
The same is true when methyl benzene is nitrated:

+
o Br
3

25.06 Two reactions of the

side-chain s in arenes
a Oxidation of t he side-chain
On the other hand, the electron-withdrawing CHO
group causes the incoming substituent to be attached The benzene ring is much more resistant to oxidation
to the 3-position: than alkyl side-chains. Heating an arene with a strong
oxidant, such as alkaline potassium manganate(VII), causes

o
all the side-chains to be completely oxidised to carboxylic
acid groups, but leaves the benzene ring unchanged:
(HO
.-------Be, • AfCl,
heat with KMn04 + OW(aq)
then acidify

b H alogenation of t he side-chain

Table 25.0 I summarises the effect of some substituents.

 Worked example 25.0 I Progress check 25.03
Suggest ro utes for synthesising the fo llowing two Suggest structures for compounds A- C in the
compounds from methyl benzene. following scheme:
3-bromobenzoic acid A

2 4-nitrobenzoic acid
How to get the answer:
Ci2 + light
Step I: We need to use three different reactions B
here:
to form a bromobenzene we need
to heat with Br2 + AlCl)
• to form a nitrobenzene we need
cone. HNO) + H2S04 at 55 DC
to form - C0 2H from -CH) we need
hot alkaline KMn04' followed by 25.07 The properties and
acidification.
reactions of phenol
Step 2: Consulting Table 25.02 (there is a similar
one in the Data Booklet) we see that the Aromatic compounds that contain a hydroxy group
- CH) group is 4-directing, whereas the attached to the ring are called [Link] presence of
- C0 2H group is 3-directing. So the order the benzene ring means that the reactions of the -OH
in which the I-eactions are carried out is group are different to the usual reactions of alcohols, and
important: for 3-benzoic acid we need to the presence of the -OH group on the ring has quite a
oxidise before bromination; for reaction 2 dramatic effect on the ring's reactivity towards electrophiles.
we need to oxidise after nitration.
a Acidit y
,., Phenols are more acidic than alcohols, but less so
than carboxylic acids:

R-O-H R-O- + H+ Ka = 1.0xlO- 16 moldm-J

KMn04
_h_ea_t --I." ¢ co H o-0-H 0-0-

(H - (
J
IP
\_
+ H+

+ H+
Ka= 1.3 x 10-10 mol dm-J

N0 2 o

The phenoxide anion is more stable than either a

Under the influence of light or heat. and without hydroxide or an alkoxide anion because its negative
any catalyst such as AlCl), chlorine or bromine will charge can be delocalised over the benzene ring:
undergo a free-radical substitution in the side-chain
o
of an arene. The hydrogen atoms on the carbon
adj acent to the ring are replaced:
-:-0
+ Hc/

l-phenyl,l -chloroethane or
 c Electrop hilic substit ut ion on t he ring
You may be asked to pl 'edict the effect of Because of the delocalisation of the lone pair of
electl'Oll witi1( h'Clwillg 01 electl'Oll-donatillg electrons on oxygen, the ring of phenol is more
gmups (sc:c fable 2).02) Oil the acidity electron-rich than that of the ring in benzene.
of YOLI might expect, electmll- Reaction cond itions for electroph ilic substitution can
w itildl awillg gmupe; Oil the I-ing enhance the be much mi lder; and more substitution occurs:
acidity of phenol. FOI ' example, 4-ni tmphenol
is mOI-c l ilan SOO times as acidic as phenol. dilute HNO,

(not cone. and no H2S04 needed)

As a consequence of its acidity, phenol not only 4'nitrophenol

reacts like alcohols with sodium metal, giving off OH
hydmgen gas: _ _ _ _B_r2(_aq_l B r n Br
V

6
(not Br2(1), and no NO, needed)
Br
2,4,6-tribromophenol
+ Na (white precipitate)

The decolorisation of orange bromine water; with

sodium phenoxide the formation of a white precipitate, is a good
(a white solid)
test for the presence of phenol (Figure 25.0 I ) (or
but, unlike alcohols, it also dissolves in aqueous phenylamin e - see Unit 27).
sodium hydroxide:

6 + NaOH

Phenol is visibly acidic: the pH of a 0.1 mol dm- 3

solution in water is 5.4, so it will turn universal
indicator solution yellow. An old name for phenol
is carbolic acid.

b Esterification
Because of the delocalisation over the ring of
the lone pair on the oxygen atom, phenol is not
Fig. 25 .0 I A wh ite prec ipitate is formed when orange
nucleophilic enough to undergo esterification in the
brom ine water is added to aqueous phenol
usual way, that is, by heating with a carboxylic acid
and a trace of concentrated sulfuric acid:
Remembel- t hat phenylamine (see Unit 27)

o + CH,C0 2H
cone H2S04
,\L fOO_C(H
/\ -
' H0
V
+

ester not formed

2
1 also decolori ses BI-/aq) and gives a white
precipitate. Alkenes also decolorise bmmine
watel- (but do not give a wh ite precipitate).
A unique test shown by alkcnes but by 110
othel- functional gl'Oup is the dccolol-isatlon
Phenol can, however; be esterified by add ing an
acyl chloride, usually in the presence of a base: of cold acidified KMnO,(aq).

(NaOH) . 0 .. o
&
/ CH 3
+ HCl The bromine atoms only substitute at the 2,4 and 6
positions, not the 3 or 5 position. If one of the three
phenyl ethanoate

I r
 possible positions is blocked by another substituent, A reaction of phenol that is not undergo ne by
only two bromines are substituted: benzene is coup ling with a diazo nium salt:
OH OH
to + 2Br2(aq)
__.. CH'* " Br
+ 2HBr
in NaOH(aq)
+ NaC/

phenyldiazonium chloride

This reaction is covered in more detail in Unit 27.

Sample answer Answer:

Q uestio n: Two compounds, X and Y, have the

molecu lar formu la C7 Hso. Both react with sodium
metal, but on ly Y reacts with NaO H(aq). When [1] + [1]
treated with ethanoyl chloride, compound X gives x v
compound V, and Y gives compound W . V and W
are isomers with the formula C9H I00 2• One ofthe
isomers X or Y deco lorises brom ine water, and
O( - ocy [1] + [1]

produces compound Z (C 7 H6 Br2 0) . Y w

Suggest the structures of al l lettered compounds
V-Z. [5] [1]

z
Y(auld also be 4-methylphenol:
Br

M
w
0 N Y
OH

BrYaQ) AA
A r 0H

z
Br
Exam-style q J . Ion
For each of the fo llowing reactions, draw 2 Describe and explain how t he acid ities of
the structure of the product and give its phenol and phenyl methanol differ. [3J
systematic name. [ ,]

HN03 + H2S0 4 at 55°C

• 6
phenol phenylmethanol
OH
Describe a test (reagent + observations)

Q
Ii
you could use to distinguish between
phenol and phenylmethanol. [2]
b How might the acidities of compounds F

o
and G compare to that of phenol? Explain
yo ur answer. [2]
C
(C 9H12)

b Compounds D and E can be obtained from

methyl benzene by reacting it with chlorine
under two different conditions.

6"
F G

c Phenyl ethanoate , H, cannot be prepared by

the fol lowing reaction.

6 D

heat with
6
o
II
/c ""'-

¢
C!
6 +
00"'.H,SO, .

H
CH,

E
Explain why th is reaction does not occur. [2]
Suggest the reagents and conditions
ii Suggest an alternative route to make H
needed for reaction I and reaction 2. [2]
from phenol. [ I]
ii Suggest a reaction you could use to
Total: 10
distinguish between samp les of D and E.
You should describe the observations you
would make with each compound. [2]
Total: 10
26.0 I The acid ities of chlorine-
substituted carboxylic acids Progress check 26.0 I
Making use of the trends shown in Table 26.0 I,
We explained in Unit 17 why carboxylic acids are more choose an appropriate pKa for each of the
acidic than alcohols, because the negative charge on following acids from the pKa values given below. In
the anion can be delocalised over two electronegative each case explain your choice.
oxygen atoms.
iodoethanoic acid
If the R group in R-C0 2 - contains an electronegative
2 fluoroethanoic acid
atom, this will help to spread out even more the
negative charge of the anion, and so cause the acid to 3 trifluoroethanoic acid.
be more [Link] 26.0 I shows some examples. pKa values: 0.59, 2.57, 2.87, 3.16,4.87
i Name ofr'acid <"'. 'Formula of..... acid
-'0 " . K __ , rpK'
cf} .--';; i..:.,,,,_ .. • a "

ethanoic acid 4.76

1;0 26.02 The oxidation of
CH 3 --- C
\H
methanoic and ethanedioic acids
chloroethanoic acid 2.87 Although most carboxylic acids do not undergo further
1;0
oxidation, there are two that do.

a Methanoic acid
dichloroethanoic acid Ci 0 1.26 Methanoic acid contains a -CHO group, and has
\ some of the reactions of aldehydes. When Fehling's
H- CI;
solution orTollens' reagent are warmed with
Ci l \H
methanoic acid, they are reduced:
trichloroethanoic CI 0.66 Fehling's: HC0 2H + 2Cu 2+ + 60H- ----.
acid
CO/- + Cu 20(s) + 4H 20
Ci--.;"/- \l red ppt.
Ci OH
Tollens': HC0 2 H + 2Ag+ + 40H- ----.

Table 26.0 I The pKa values some cal'boxylic acids

cot + 2Ag(s) + 3H 20
silver mirror
b Ethanedoic acid
Learn to I-ecognise I-eaction types: these
Ethanedoic acid is readily oxidised by warm acid ified
al-e al l nucleophi lic substitution I-eactions,
manganate(VII), turning the purple so lution co lourless:
the nucleorh ilc attacking the 0--1 cal'bon
SH0 2C-C0 2H + 2Mn04 - + 6H+ - - + atom of the C - 0 group, and displ acing
IOC0 2 + 2Mn 2+ + 8H 20 t he ch lol'ide ion, CI .

Although alkyl esters can be made by the usual method

26.03 Formation of acyl chlorides (i.e. heating the carboxylic acid and the alcohol with
concentrated H 2S0 4), this method does not work for
Heating carboxylic acids with either phosphorus
phenyl esters, because phenol is not a strong enough
pentachloride or thionyl chloride produces acyl chlorides:
nucleophile. Phenyl esters can be made in good yield by
reacting acyl chlorides with phenols.
I/O
+ PCls CH 3 - C + POCl3 + HCI
\1
ethanoyl chloride Progress check 26.02
0< o

OH
+ 50Cl2
o-
benzoyl chloride
l
C
\{
+ 50 2 + HCI
Suggest reagents for two-step synthetic routes to
the following compounds, starting with suitable
carboxylic acids.

(CH3)2CHCONHCH(CH3) 2

26.04 The reactions of acyl 2

chlorides with water, alcohols,

phenols and amines
Acyl chlorides are readily hydrolysed by water - or
even moist air - to give fumes of HCl(g) and the
carboxylic acid: See Un it 30 on ol-gan ic synthesis
fO I- fUI-thel- t ips on how to devise
synt hetic routes.
As the following scheme shows, they are useful
intermediates in organic synthesis, being used to make
esters (especially phenyl esters) and amides.

26.05 The relative reactivities

Q R
-!
_
50Cl2
R-
I/o
C
Y CH CH OH
3 2 )0 R- C
l
of various organochlorine
compounds
As we saw in Unit 16, the reactivity of R-X increases
'" from X = Cl to X = I. But even organochlorine
compounds differ quite markedly in their reactivities.
NH3
o "-NHCH For examp le, if we look at their reactions with water or
3
R an N-methylamide NaOH(aq) (a stronger nucleophile), we find the results
"- NH2 in Table 26.02.
an amide
 Compound "';i-th' 'IReaction with effect is sign ificant enough to make the C-Cl bond
stronger; and less easy to break.
•
water
I '-. _
_ •
NaOH(aq)
, ,

acyl chlorides, readily, at mom vel-y vigorous,

RCOCt temperature at room
temperature
tertiary slowly, at room speedily on
chloroalkanes, temperature, warming
R,C-Ct quicker on heating
primary hardly at all at steadily on 2 Because the ring hinders the attack of a nucleophile
chloroalkanes, room temperature; warming
from the back of the C-Cl bond, the SN2 route (see
R-CHjCt slowly on heating
Unit 16) is unavailable for a nucleophilic substitution
ch loroarenes, no reaction still no reaction
reaction. Since there is no means of stabilising the
Q-C/ intermediate carbocation, the SN I route is also not
favoured .
Table 26,02 The I-elative reactivities of organochlorine
compounds

The reactivities are in the order RCOCl > R-Cl >

Ar-Cl.
Why are acyl chlorides so much more reactive that Worked example 26.0 I
chloroalkanes?
Arrange the following halogeno compounds in
There are two reasons. order of reactivity. with the most reactive first.
In acyl chlorides, the chlorine is bonded to a carbon
atom that already has an electronegative oxygen A (CH3hCHCI
atom [Link] makes the carbon very 0+, so it B CH 3CH 2COCI
is more prone to being attacked by the lone pair on
the nucleophile (e.g. H2o' NHJ C (CH 3hCBr

2 Acyl chlorides have a double [Link] allows the

nucleophile to bond with the carbon atom before the D o-CI

chloride ion has left. This extra bonding lowers the

activation energy. and hence speeds up the reaction.

GO 0- -cr 00
R- C
t "--C/
• R- f1S How to get the answer:
NU:.../ Nu "" Nu
Step I: We can see from Table 26.02 that acyl
ch lorides are the most reactive, and aryl
This is known as the addition-elimination mechanism. chlorides are the least. So B will be first,
Why are chloroarenes so much less reactive than and D last.
chloroalkanes?
Step 2: From Unit 16, we know that tertiary
Here, again, there are two reasons. halides are more reactive than primary
halides, and primary halides are more
One of the lone pairs on the chlorine atom can
overlap with the 'IT bond in the benzene ring. The reactive than secondary halides. We also
overlap is less complete than, say. the overlap of know that bromides are more reactive
than chlorides. So C is more reactive than
the oxygen's lone pair in phenol (see Unit 25),
because chlorine's lone pair is in a 3p orbital, which, E, and E more reactive than A
being larger; overlaps with the 2'IT ring orbitals less Step 3: The order is therefore B > C >
effectively than the 2p lone pair on oxygen. But the E > A > D.
 Sample answer Answer:

Question: COC/

Predict the products A- D of the following series of

reactions. [4]
A
"JOB C D

0 ..
C/JA/C/3
A
(C7HsC/02)
SOC/2
.. B
(C7HP20)

+CICH CH OH
2 2
[ I mark for each structure]
In D the Cl could be at the asterisked position instead
of the one shown.

D
(C gHP00
.. A/C/3
C
(C gHsCl2 0 0

Exam-style questions
a i Describe and explain the relative acidities CHlC02H CH 2BrC0 2H CHCl2C0 2H
of ethanoic acid and chloroethanoic ClCH 2CH 2C0 2H
acid. [3]
b Suggest the structures of compounds A-C
ii How would the acidities of the following in the following scheme, explaining your
acids compare to that of chloroethanoic reasoning.
acid? Explain your answers. [4]

soc". '--- ON", .

'I 'c/
B

C/

[4]
Total: I I

,-
 2 a When one mole of compound D , C 4H 60 4, b The hydrolysis of compound J, C6Ha0 2'
is hydrolysed, on e mole of compound E, produces compound K, C6H ,oO )' When
C 2H 60 2, and two moles of compound F K is treated with hot acidified KMn04'
are produced. When E is warmed with the only product is compound L, C 3H 40 3.
acidified K2Cr20 7 (aq), compound G, C 20 4H 2, Compounds K and L produce a yellow
is formed. Compound F produces a red precipitate with alkaline aqueous iodine.
precipitate when warmed with Fehling's Compounds J and K decolorise Br2(aq).
When one mole of compound G is Suggest structures for compounds J- L. [3]
heated with acidified KMn04' two moles of
Total: I I
compound H are formed.
Suggest reagents and conditions for the
conversion of D into E and F. [ I]
ii Suggest the structures of compounds
D-H, explaining all the reactions
involved. [7]

.
,
27.0 I The synthesis of amines
How to get the answer:

a A liphatic am ines Step I: The first am ine contains a chain of four

carbon atoms, whereas propan-I -ol only
There are three ways of making primary aliphatic
contains three. So we need to use NaCN
[Link] following scheme also shows how the
to add a carbon atom, and then reduce
starting materials can be made from more readily
the - CN to -CH 2NH 2.
available compounds:
R-C0 2 H R-Br R-CHPH
Step 2: NaCN only reacts with halogenoalkanes,
so we need first to make
SOCl
2t I-bromo propane from propan-I-ol.
R-COCI
heat with heat with Step 3: The second amine contains the same
NaCN in HBr
NH,! ethanol
number of carbon atoms as propanoic
acid, so we can first make the amide, and
then reduce it.
R-CONH2 R-CN
Step 4: The complete routes are as follows:

LiAlH4
in dry ether
heat in a
sealed tube
with NH3
CH)CH 2CHpH
HBr+ heat
• CH)CH 2CH 2Br
---
KCN. heat

in ethanol
CH)CH 2CH 2CN

t H2+Ni

----
in ethanol
2 SOC/2
CH)CH 2CH 2CH 2NH 2
CH)CH 2C0 2H CH)CH 2COCI

t NH)
LiA/H.
CH)CH 2CONH2 CH)CH 2CH 2NH 2
Worked example 27.0 I in dry etrer

Suggest synthetic routes to the following amines.

I CH3CH2CH2CH2NH2 from propan- I-ol
2 CH 3CH 2CH 2NH 2 from propanoic acid
b Aromatic amines Basicity depends on the availab ility of the lone pair
Aromatic amines are usually made by reduc ing of electrons on nitrogen to form a dative bond with
nitroarenes with t in and concentrated hydrochloric a proton. Electron donation from an alkyl group will
acid: enco urage dative bond form ation:
R R

Sn + HCI is the only ,-educing agent that ""

R ",,/
, H+
...
R
"'
",#, '
+
gives a goorl yielrl of rhenyli'lrn ine. Note
that t he tin is not a catalyst, but a reagent
- it is used up dLwing t he reaction . In phenylamine the lone pair of electrons on the
nitrogen atom is delocalised over the benzene ring.
The bonds around the nitrogen atom can take up

O cone HNO, + H2S0 4

at 55'C
• Ao
NO,

V
(Q heat with sn + cone Hc/ .
(ii) then add NaOH (aq)
AO'
V
NH a planar arrangement, with the nitrogen's lone pair
in a p orbital, so that extra stability can be gained
by overlapping this p orbital with the delocalised 'TT
bond of the benzene ring:
The NaOH(aq) is added after the reduction is

,, ----- -'.. N
. .. ",
complete, to liberate the free amine from its salt:
RNH 3+Cl- + NaOH RNH 2 + NaCl + H20 .....
<:
------- - ....

Note that it is not possible to

make aromatic ami nes by ,-eacting
or c.VNH2 ...... -O NH2 ---- etc

halogenobenzenes with amrnonia, as the This overlap, which is similar to that described for
a,-yl- halogen bond is too strong to be phenol in Unit 25, has two effects on the reactivity
broken by nucleophiles. of phenylamine:
• It causes the lone pair to be much less basic (see
above).
• It causes the ring to be more electron rich, and
so to undergo electrophilic substitution reactions
much more readily than benzene.
27.02 Reactions of amines
This increased reactivity is similar to that of
phenol, one example being the ease with which
a Reactions as bases
phenylamine decolorises bromine water.
Like ammonia, all amines are weak bases, being
protonated on the lone pair on their nitrogen atom.
They react with acids to form salts: o·
O
NH2

3B,,('q) -
srUNH2 Sr

Y
Sr
· JHB,

The decolorisation of orange bromine water; with

the production of a white precipitate of the tribromo
Those amines that are soluble in water form
compound, is a distinctive test for the presence of
weakly alkaline solutions, just as am monia does,
phenylamine (or phenol- see Chapter 25).
due to partial reaction with the solvent, prod ucing
OH - ions:
b Reactions as nucleophil es
CH 3CH2NH 2 + H20 CH 3CH2NH/ + OH - The lone pair on the nitrogen atom of amines makes
Aliphatic am ines are slightly more basic than them good nucleop [Link] react with alkyl halides
ammonia. However; phenylamine is considerably less and acyl halides.
basic than ammonia.

J - .:.
 0- OH + OH' 0- 0- + H0
2

o-NHCOCH J + HC;

c The formation and reactions of diazonium

+ 0-0- Q-N
=N
-Q-OH
an azo compound
salts (this one is bright orange)

When phenylamine is reacted with a mixture

A zo dyes are used to dye cloth es, and also for
of sodium nitrite and hydrochloric acid, at a
co louring foodstuffs and paints.
temperature lower than 5°C, a solution of a
diazonium chloride is produced.
The sodium nitrite and hydrochloric acid react to
give the unstable nitrous acid:
NaN0 2 + HCl NaCl + HN0 2
The nitrous acid then reacts with the phenylamine in
acidic solution:

0' +

"cr "H,O

Fig. 27.0 I Th e azo dye fO t"med from phenyldiazonium

phenyldiazonium chloride
and pheno l

If you dt-aw OLit the full bonding in the

diazonium ion, make su t-e YOLi put t he Progress check 27.0 I
-+ charge on the COtTect atom, wit h the Draw the structures of the amines that need to
t-ight numbet- of [Link]-e are two be diazotised to form the following dyes.
mesomeric forms: you can choose

(1"))
'anilineyetlol'l'
""'g-«J>
0 0
'faslredN

g-
Phenyldiazonium chloride is unstable at
HO "N-Q-NO,
temperatures above 10°C. If warmed in water it
0
produces phenol and nitrogen gas:
"N

o
a
NaOJS O SOJNa
N 'para red'
',unset yetlol"
OH
warm to >50'C
- ----I... + N2(g) + W

The most important reaction of diazonium salts is

to make azo dyes, by reacting them with phenoxide
ions or aromatic [Link] are known as
coupling reactions:
 Sample answer Answer:

Question: 4-Nitrophenol can be made fmm benzene a

N

6"
III
by the following steps.

-step 3
x
t step4 b
X is
[I mark]
Step I: HN0 3 + H2S0 4 [I mark] ,
concentrated, at 55°C [I mark]

¢- 6
NO,
stepS
Step 2: Sn + cone. HCl [I mark]
Step 3: HCl + NaN0 2(aq) [I mark] , at T <
5°C [I mark]
a Suggest the stl-ucture of compound X in the
above scheme. [I mark] Step 4: boil in water [I mark]

b Suggest reagents and conditions for the five Step 5: dilute HN0 3(aq) [I mark]
steps in the above scheme. [7]

27.03 Properties and reactions oII

heat with C
o
CH{C.'NH,CH 2CH ;CH 3 + ow
of amides NaOH (aqt CH/ 'O-Nt
sodium ethanoate
+ CH 3CH 2CH 2NH 2
propylamine
N-propylethanamide

Unlike amines, amides are neutral compounds, and do

not form salts with dilute acids. This is because the lone heat with
HCi (aq) • + NH4Ci
pair on the nitrogen atom in amides is in a p orbital, ammonium chloride
benzamide benzoic acid
and can overlap with the '1T orbital of the adjacent
carbonyl group - the electrons are attracted to the
electronegative oxygen atom: b Reduction
As mentioned above, amides can be reduced to
o
- amines with LiA1H4 in dry ether:
.......f - -_•_ R- C /
or
o
+NH,

O'LNH>
benzamide benzyl amine
As we have seen above, amides can be prepared by
reacting ammonia or an amine with an acyl chloride:
27.04 Amino acids
Amino acids are important building blocks for peptides
and [Link] have the general formula
N-ethylbenzamide
H2 N-CHR- C0 2H
There are two main reactions of am ides. where R can be H or an organic group.

a Hydrolysis There are about 20 different amino acids that make up

naturally occurring proteins. The following al-e six of the
Hydrolysis can be carried out by heating the amide more common amino acids:
with dilute aqueous acid or alkali, and produces an
am ine (or its salt) and a carboxylic acid (or its salt) .
 ,NH,
Like ordinary amides, peptides and polypeptides can be
.NH, .CH, -CH ,NH,
H-CH
'CO,H
H,C - CH
'CO,H HO 'cO,H
hydrolysed by heating them with HCI(aq).
glvcine (GIV) alanine (Ala) serine (Ser)

.NH,
}H, -CH, ... CH I ....... (H1
.... NH 1
...... CH CH, -CH
/NHl Progress check 27.02
/-CH, CO,H H,N 'CH, 'CH, 'CO,H HS' 'CO, H
HO glutamic acid (Glu) lysine (Lys) cysteine (Cvs) Draw the structure of the dipeptide
made from the amino acids cysteine and
Amino acids contain both the amino group and the glutamic ac id.
carboxylic acid group, and so can react with either acids 2 Identify the amino acids, and the number of
or bases: molecules of each, that will be formed by
H2NCH 2C0 2H + HCl Cl-H3N+CH2C0 2H hydrolysing the following peptide.
H2NCH 2C0 2H + NaOH H2NCH 2C0 2- Na+
The two groups are of opposite chemical characteristics:
the - NH2 group is basic , whilst the -C0 2H group is
acidic. An internal acid-base reaction can take place,
whereby a proton is transferred from the acidic - C0 2H
group to the basic -NH2 group, to form a bipolar ion
called a zwitterion .
27.05 Electrophoresis of amino
H, H\ +
/N - (H 2 H
.. H',.. N- (H 2 acids and peptides
H \
(-
I
0
\ (- -
0
Ii Ii Electrophoresis is the movement of the electrically
o a zwitterion 0
charged molecules (ions) of a compound in an electric
field. When dissolved in a buffer at a particular pH,
A zwitterion is a molecule that contains both a cationic
different amino acids are likely to be ionised to different
group and an anionic group.
extents. The overall charge on an amino acid depends
An amino group on one amino acid can also react with on the pH of the solution it is dissolved in. For example,
the carboxylic acid group on another amino acid, to if glycine is dissolved in an acidic solution, its molecule
form an amide: will be protonated and it will exist as a cation:
H2NCH 2C0 2H + H2NCHRC0 2H NH 2CH 2C0 2H +W NH 3+CH 2C0 2H
H2NCH 2CO- NHCHRC0 2H + H20
If, however; glycine is dissolved in an alkaline solution, it
An amide bond formed between two amino acids is loses a proton to become an anion:
called a peptide bond, and the 'dimer' is called a dipeptide.
NHFH 2C02H + OH - NH 2CH 2C0 2- + H20
In neutral solutions, it exists as its zwitterion, which
Note that a dipeptide contains two am ino although charged, has no overall charge:
acid I-esidues, but only one peptide bond. NH 2-CH 2-C0 2H NH/CH 2C0 2-
Amino acids that contain a basic group in their side-
Further amino acids can form amide (peptide) bonds chain, such as lysine, will exist as cations even in neutl-al
at each end of the dimer; and eventually a polypeptide solution:
chain can be formed. NH 2CH2CH2CH2CH2CH(NH2)C02H + H20
+NH 3CH2CH2CH2CH2CH(NH2)C02H + OH-
Amino acids that contain an acidic group in their side-
chain, such as glutamic acid, will exist as anions even in
neutral solution:
H02CCH2CH2CH(NH2)C02H + H20 electrode) and the glyc ine would not move at all
-0 2CCH2CH2CH(NH)C02H + H30+ (Figure 27.02).

If a so lution contain ing the above three amino acids Because each am ino acid side-chain will affect the
were app lied to the middle of a gel electrophoresis average charge on an am ino ac id mo lecu le / ion to a
plate soaked in a buffer so lution at pH 6 (where different extent, and because the speed at which ions
glyc ine has an overall charge of zero), and a potential move through the gel depends on their size and shape
difference is applied, we wou ld see that the mixture as well as their charge (the larger a molecule is, the
would separate into three spots: the lysine would slower it moves), it is possible to separate and identify
move towards the cathode (negative electrode); the not only all of the amino ac ids but also small peptides
glutamic acid would move towards t he anode (positive derived from them.

conducting gel in a spot of mixture applied here electrode joined to a power

buffer solution on 8 supply of 250 V dc
a solid support

appearance before electrophoresis

Glu Gly Lys

1 / 18

appearance after electrophoresis

Fig. 27.02 Electrophoresis
 m-«it, flu n
Study the following scheme and answer the questions below.

6"
+

o OH ' / r
¢
N(CH,),

II>N

OJ N"N

C OJ
a State the reagents and conditions for reactions I-V. [5]
b To what classes of compounds do compounds A. Band C belong? [3]
c The fol lowing two compounds are made by coupling reactions. For each compound draw the structures
of the two starting compounds required for their synthesis.

[4]
Total: 12
2 a 2-methylpropylamine, G, can be synthesised from 2-methylpropanoic acid by the following three-step
reaction scheme.

VI VII )-
F CONH 2

G
 Draw the structure of the intermediate F. [I]
il State the reagents and conditions for each ofthe reactions VI- VIII. [3]
iii Draw the structure of the compound formed when G reacts with F. What closs of compound is
formed in this reaction? Write its molecularformu la. [3]
b Below are the structures of two amino acids.

/ C02H / C0 2H
CH CH
I
CH 3
I
CH 2
alanine (Ala) " C0 2H
aspartic acid (Asp)

Draw the full displayed formula of the zwitterion of alanine. [2]

ii Draw the st ructure of the dipeptide Asp-Ala, showing the peptide bond in full . [2]
iii Draw the structu re of aspartic acid that exists in an aqueous solution at pH 7. [ I]
Total: 12

,.•,

•
·•
 formed, a molecule of H 20 (or sometimes HC!) is
28.0 I Condensation polymers
produced by a condensation reaction.
The polyalkenes mentioned in Unit 15 are called
a Polyesters
addit io n po lymers because they are made by adding
monomer units to a growing alkyl chain, and the If we react a diol (a compound having two -OH
molecular formula of an addition polymer is a multiple groups in each molecule) with a dicarboxylic
of the molecular formula of the monomer - both have acid (which has two -C0 2H groups in the same
the same empirical formula. molecule), we can form an ester bond at each end
of the diol, and similarly at each end of the diacid. A
Another class of polymer is the co ndensation polymers. polymer is therefore produced. A common polymer
These are usually polyesters or polyamides, and are of this type is the polyester known as Terylene TM :
so called because when each ester or amide bond is

J[0- CH,CH, _ 0) -0CI?1l

ethane-l,2-diol benzene-l ,4-dicarboxylic acid one repeat unit of
Terylene, a polyester
 The chemical structures of the diacid (or diacyl ch loride) Terylene can be drawn into fine fibres and spun
and the diol can be altered at will, to make polyesters into yarn. Jointly woven with cotton or wool, it is a
with different properties. A general formation equation component of many everyday textiles. Cloth made from
starting with acyl chlorides cou ld be written as follows:

nHO
O OH + n /
CI
C,
C/
- nHc/
..
Notice that there are usually two different monomers Terylene is hard wearing and strong, but under strongly
that make up a polyester: a diacid (or diacyl chloride) alkaline or acidic conditions the ester bonds can be
and a [Link] repeat unit of a polyester contains one hydrolysed, causing the fabric to break up.
molecule of each - as is shown in the diagram above.

Progress check 28.0 I b

r---ICOC!
Draw the repeat unit of the polymer formed and / \
COC!
when each of the following pairs of compounds
is polymerised. 2 Draw the structures of the monomers of the
a CH 3CH(OH)CH 2CH(OH)CH 3 and following polymer:
CH 2(C0 2H)2

b Polyam ides
Just as a diacid or diacyl chloride can react with a Nylons are [Link] most common one is
diol to produce a polyester; so they can react with a made by co-polymerising I ,6-diaminohexane and
diamine to produce a polyamide. hexan-I ,6-dioic acid:

+ H02C -f 74 CH 2 C0 2H

diaminohexane hexanedioic acid

•

t,-( N CH2 t-;'c -f 74 c1

6
o
N
'
H
'
CH 2 4

nylon-6,6

Nylon 6 is unusual because it is made from only one

monomer which contains both the amino and the
carboxylic acid groups, 6-aminohexanoic acid:

q1
n
nylon 6
 28.02 The relationship between
a polymer, its repeat unit and
its monomer(s)
We can recognise which type of polymer w ill be formed
from given monomers by looking at their structures.
• If each of the monomers contains a c=c group, they
are likely to produ ce an add ition polymer:
• If the monomers contain two functional
groups (carboxylic acid or acyl chloride,
amine or alcohol) at the end of a chain of
carbon atoms, they are likely to produce a
condensation polymer (even if they also contain
a C=C double bond).
If we are shown a section of a polymer chain, we can
recognise what type of polymeri sation has produced
the polymer:
• If the chain contains only carbon atoms, the polym er
is an addition polymer (side chains could contain
ester or amide groups, however).
FigLwe 28.0 I Climbers rely on nylon's elast icity and high • If the chain contains oxygen or nitrogen, the polymer
tensile stl-ength t o minimise t he effects of a fall is a condensation polymer:

Worked example 28.0 I Step 2: To join the monomers in a, we break the

two C=C bonds and join their ends:
Draw the structural formula of one repeat unit of the
polymer formed from each of the following monomers
or pair of monomers. State whether addition or
condensation polymerisation takes place.
a CH 2=CHCl and CH 2=CH-CH 3
Step 3: In b we form ester groups between the two
b HOCH 2CH 20 H and H0 2CCH=CHC0 2H monomers:

c H2NCH2CH2CH2NH2 and ClCOCH 2CH 2COCl.

How to get the answer:
Step I: To decide w hether addition or co ndensation
polymerisation has taken place, we look at
the functional groups in t he monomers. Step 4: In c we form amide groups between the
In a there are C=C double bonds, but no two monomers:
alcoho l or acid groups, so t hese w ill react by
addition polymerisation.

In b and c there is one C=C bond, but in

each case there is an acid or acyl ch loride
and an alcohol or an am ine, so these wi ll
react by condensation polymerisation.
 the 1t-bond of the carbonyl group next to it, the
Pro ress check 28.02 peptide group is rigid and planar: It exists in the trans
arrangement (Figure 28.02) .
The following are sections (not necessal"ily I"epeat
units) of addition or condensation polymers.
Draw the monomers from which they free 8-

are formed, and state whether addition or

\ rotation i?
c ""' c H
condensation polymerisation has taken place.
- CH 2-CH (CN)-CH 2-CH (CN)-CH 2- HR
If --c- '\
8+
""' 11'
N--c- '
R
II
R

2 - CH 2-O-COCH 2CH 2CO-O-CH 2CH 2-0-

' / free \ \
H rotation
3
Figure 28 .02 Th e peptide li nkage is quite rigid and planar

This inflexibility of the peptide group allows parts

of the polypeptide chain to take up an a-helical
28.03 Proteins arrangement (see Figure 28.03).This causes some
protein structures to be quite rigid. Strong hydrogen
Proteins are naturally occurring polymers of bonds can form between the N-H of one peptide
amino acids. They are polyamides. An amide bond group and the C=O of another one, four amino
between two amino acids is called a peptide bond, acids along the chain.

o
and the polymers are known as polypeptides. Some
proteins contain just one (very long) polypeptide
..,'" = the C-C -N backbone
chain, but most proteins are composed of several of the polypeptide chain
chains wrapped around each other.
\ N-\\""
/ ••• =the hydrogen bond between
In Unit 27 we looked at the structures of some amino .,,\ the c=o and N-H groups
acids, and saw how the polypeptide chains of proteins o
are made by joining together amino acid residues. Here
•
•H
we look in greater detail at the overall structure of
\ "
proteins, and at some of their properties.
/
There are several levels of protein structure. ,
o•
a Primary structure •H
The primary structure of proteins is the sequence \N ""
of amino acids, covalently joined by peptide bonds, /
making up the polypeptide chain.

b Secondary structure
The secondary structure describes how some
C
protein chains are held together by hydrogen Figure 28.03 T he a-helix
bonding between peptide groups.
Another type of secondary structure is the
Because of the overlap between the lone pair of p-p leated sheet. This is formed by the C=O group
electrons on the nitrogen atom (in a p-orbital) and of one chain hydrogen bonding to the N-H group in
 another chain. The chains are described as
anti-parallel because adjacent chains run in
opposite directions (Figure 28.04).
O=C
"I
/

/
H. .
o .---- -H
CH-CH2
\
0
0- \

(H
/
'
c=o

NH NH
\ /
Ser Tyr

0 =(
/ o : -----H-O c=o
\
"CH - CH (H CII "CH - cH'
- - -NH co- - - / 22\ 2,
NH O(H) NH
\ /
Glu Ser
- - -co NH- - -
• Ion ic attractions occur between side chains
containing functional groups that exist in their
an ionic form at pH 7 (e.g. aspartic acid and
glutam ic acid) and those that exist in their
Figure 28.04 The sheet cation ic form (e .g. lys ine and argini ne):

You shou ld be able to dl'aw from memory

part of a sheet, and also to
exp lain the /Jrinci/)/e of hydmgen bonding Glu Lys

fot'ming the a-helix, though an aCCLlI'ate

• Disulfide bridges can form between the side
dl'awing of this will nevel- be I-equired.
chains of two cysteine residues:

c Tertiary structure
The tertiary structure involves interactions between
the side-groups of amino acids.
There are four different interactions between side Cys Cys
chains, depending on their different structures.
/
• van der Waals' attractions occur between non- O=C \

polar side chains (e.g. glycine, alan ine, valine and

phenylalanine):
oxidation
-2H NH
"/

\
CH2
- CH - ,
S
! /
S-CH2-CH
NH
C=O

/
a disulfide bridge
\ c =o

Ala
1111111111

1111111111
0- Phe
/

/
The tertiary structure is important in determining
both the overall shape and the function of the
protein. Many enzymes are globular (i.e. fairly
spherical) proteins that are soluble in water. In these,
the non-polar side chains are often pointing towards
\ the central, hydrophobic, part of the molecu le,
/c= o
H- CH
1111111111
whereas the hydrogen bonding and ionic groups are
""""" NH
\
on the outside, where they can be solvated by water
/ molecules.
Val Gly

• Hydrogen bonding occurs between side chains

that contain -OH (e.g. serine and tyros ine),
-NH/-NH 3+ (e.g. lysine) and -C0 2H/-C0 2-
(e.g. aspartic acid and glutamic acid):
 The strongest of the tertiary interactions is the On ly four different bases occur in DNA: aden ine (A),
disulfide bridge. Once these are formed the various cytosine (C), guanine (G) and thymine (T). A single
parts of the chain are drawn together; and this DNA molecule may contain thousands of monomer
allows the other interactions to play their part in units. It is the order in which the bases are bonded
creating the overall three-dimensional structure. to the deoxyribose-phosphate chain that determines
Like all amides, proteins can be hydrolysed - the the genetic information needed to construct specific
proteins in the cell.
peptide bonds are broken and smaller fragments
(e.g. dipeptides, tripeptides) and single amino acids A DNA molecule contains two chains joined together
are formed. by hydrogen bonding between the bases. Which base
bonds to which is unique, and is determined by the
o i R' H 0
number and orientation of the possible hydrogen bonds
"NH )l ,/,' /CHI ' I )
"" between them (Figure 28.06). Adenine bonds only
"CH i' N Y " CH '
I " I II " I to thymine, whereas cytosine bonds only to guanine.
R 'H 0 R"
When DNA is duplicated during cell division, the chains
I H 0 + HCI
2 unwind and each chain is used as a template for making
• heat two new chains. The unique pairing of the bases allows
their order along the chains to be preserved.
H
1
O"' H-N N

The hydrolysis can be carried out under much N---( Q0

milder conditions if a proteolytic enzyme is used.
For example the gut enzyme trypsin can hydrolyse
® T
0
A
peptide bonds at body temperature of 37°C and at (thymine) (adenine)
nearly neutral pH.

H""
28.04 DNA riN-H"'\-fN'l

DNA (deoxyribonucleic acid) consists of a primary (

structure, which is the covalent bonding that joins the N---( FN Q0
monomers together; and a secondary structure, which is
formed by hydrogen bonding between the chains.
® O"'H- N

c
"'H
The backbone chain of DNA consists of molecules of G
deoxyribose joined by phosphate groups. Bonded to (cytosine) (guanine)
each deoxyribose unit is a nitrogen-containing base (see
x= the deoxyribose in each of the chains
Figure 28.05).
Figure 28.06 The pairing of the bases in DNA by
NH2
hydrogen bond ing

°1
o= p-o ---
base example shows
cytosine as the base) Thel-e is no need to lean, the stl-uctul-es
of the fOLII' bases of DNA, but yo u sho uld
b- 0 0 I-emembel- t hat they hydrogen bond in
H H
t he pairs A- T and C- G: the A- T pail- is
H H bonded by two hydmgen bonds, and the
o H
I C G pair by th l-ee hydmgen bonds.

Figul-e 28.05 The monomer unit of DNA

 Th e high electronegativity of f luo rine means
that its atoms keep a t ight contro l on their
bonding electrons, which are therefore much
less polarisable than normal. Van der Waals'
forces between fluorine atoms are small. If
all the hydrogen atoms in poly(ethene) are
replaced by fluorine atoms, th e resulting polymer,
polytetrafluoroethene (PTFE), makes an excell ent
non-stick surface for cooking pans and bridge
bearings. (The 'stickiness' of materials is usually
associated with the large van der Waals' forces
between their molecules.)

F F
3n "c = c/
/ \
F F
lFFFFFF n
tetrafluoroethene
3 monomer units of PTFE

b Kevlar
The synthetic polyamide Kevlar ™ contains strong
hydrogen bonding between its chains:

Figure 28.07 A por tion of D N A showing t he backbone

of deoxyriboses (th e pentago ns) and ph osph at es (the
circles), and the hydrogen bonding between the base
pairs of adjacent chains

The tensile strength of Kevlar is five times that of

28.05 Properties of some steel, but it is quite flexible. It is used in tyres for cars
and bicycles, bullet-proof body armour and the 'skins'
polymers on modern drumheads.

a Polyalkenes and PTFE

c N on-solvent based adh esives
The properties of polymers - density, melting
Two common glues are the cyanoacrylates and the
point. strength, flexibility, hydrophilicity, conductivity,
epoxyresins.
adhesiveness - all depend on their structures, the
bonding within the polymer chain, and the side • The liquid inside a tube of cyanoacrylate glue
groups that are attached to it. Csuperglue') is methyl 2-cyanopropenoate. In
the presence of nucleophiles (H 20 molecules
Simple examples are the two main forms of
in moist air are often sufficient), addition
poly(ethene), LOPE and HOPE, which we saw in
polymerisation takes place to produce a solid
Unit 15.
which can use van derWaals' forces to bind with
the articles that are being glued together:
 methyl 2-cyanopropenoate
3 monomer units of polycyanopropenoate

• Epoxyresins are glues made from two liquid

components. One component is a medium- You can I-ecognise a cond ucting polymer if
length polymer containing epoxide groups. The its chain cont ains nil spJ carbo n atoms, and
other is a 'hardener' that contains a diamine. no Sp l carbon atmllS.
When the two components are mixed, the
amino groups open up the epoxide rings and
allow polymerisation to take place:

hardener containing amine groups

28.06 Degradable polymers
polymer contain\oxide groups /'
In Unit 15 we looked at the problems of the disposal
of addition polymers. In general, condensation polymers
/
NH, R

\.( , NH, are more easily biodegraded because they can undergo
NH, 0 0
hydrolysis to re-form their monomers, which can often

! -2H'
be metabolised by bacteria.
One way of overcoming the problems of polymer
disposal is to make polymers that are easily
biodegraded. An example is poly(2-hydroxypropanoic
acid) (poly(lactic acid), PLA):

o
HO C
"CH' 'OH
I
CH l

etc. hydroxypropanoic acid

Hydroxypropanoic acid is a naturally occurring

d Conducting polymers
• compound which is made industrially by the
Conducting polymers are 'molecular wires', and fermentation of corn starch or sugar. PLA is easily
are finding uses in light-emitting diodes (LEDs) and hydrolysed, either chemically or by esterase enzymes,
photovoltaic (PV) solar panels. They conduct an to re-form hydroxypropanoic acid, which is readily
electric current through the delocalised 'It bond that metabolised by all living matter into CO 2 and water.
encompasses the whole molecule. Two examples are The uses of PLA include replacing conventional
polyacetylene (the simplest) and the polyphenylene plastics in the manufacture of bottles, disposable cups
vinylidenes: and textiles, but it is also used to make self-dissolving
stitches for surgery.

polyacetylene (polyethyne)

RO n
a disubstituted polyphenylene vinylene {PPV}
Progress check 28.03
The repeat un it of another biodegradable 2 Draw the monomers from which Kevlar can be
polymer is as follows: formed.
3 Draw the monomers from which the fo llowing
polymers are formed.

Draw the structu res of the products of the

hydrolysis of this monomer: b

Sample answer
Question: What functional group has been introd uced
during cross-linking?
The following structure shows part of the chain in a
water-absorbent polymer gel. ii Draw the structure of the molecule used to
cross-link the polymer:
iii Suggest one effect on the properties of the
polymer gel that the (I-oss-linking would
have . [3]
a Name the type of polymerisation that has Answer:
formed this polymer.
a addition [I mark]
ii Draw the structure of the monomer(s) . [2]
ii CH 2=CH-C0 2H [I mark]
b What type of bonding will attract water
b hydrogen bonding [I mark]
molecules to this polymer gel?
ii
ii Draw a diagram to show at least two water
molecules bonded to the gel. [2]
c Some polymers used in water-absorbent
gels have their polymer chains cross-linked
as indicated.
[I mark]

c ester [I mark]
ii
HOX OH
HO '" OH
[I mark]

iii increased rigid ity [I mark]

 Exam-style questions
a For each of the following polymers, state the 2 a Explain the following terms, illustrating your
type of polymerisation that forms it, and give answers by drawing part structures where
the structures of its monomer(s). appropriate.
primary protein structure [2]
ii the p-sheet [2]
A
iii disulfide bridge. [2]
b Explain in outline how the two strands of the
• DNA molecule are held together. [4]
NH n
c State one similarity and two differences in
structure between a typical protein and nylon
6,6. [3]
c d Name an example of a polyester: [I]
ii Describe the reagents and conditions that
convert a polyester into its monomers. [I]
[6]
Total: IS
b Draw the repeat unit of an example of each
of the following types of polymer:
a conducting polymer
ii a biodegradable polymer
iii a 'superglue'. [3]
Total: 9

,-
 The moving phase is usually an organic solvent such
29.0 I Chromatography
as ethanol or ether. The more polar a compoun5 is,
Chromatography relies on the distributing of the more strongly it will be adsorbed onto the polar
compounds between a mobile phase and a stationary stationary phase so it will spend more time on the
phase in order to separate the components of a stationary phase than in the moving solvent, and so
[Link] mobile phase is a liquid or a gas, and the it does not move very far (Figure 29.02).
stationary phase is either a solid onto which the solutes
are adsorbed, or a thin layer of liquid on the surface of lid
an inert solid.
The two types of chromatography we shall look at here thin layer of
Si0 2 or Al20 3
are thin-layer chromatography (TLC) and gas-liquid coated onto a
chromatography (GLC). glass or plastic

a Thin-layer chromatography (TLC) • surface

TLC relies on the principle of adsorption: the extent

to which a compound is adsorbed onto a solid •
surface differs from one compound to another
(Figure 29.0 I).The solid stationary phase is powdered
• mixture of
solutes
silica or alumina, spread onto a glass or plastic sheet.
solute molecules adsorbed on the
"
LJ .J
solvent

surface of the stationary phase

Figul-e 29.02 Th in-layer chromatography
. . . . . . · · · · · · · ( _0_0_0 _0 _0 _1_0_0--" Once the chromatogram has been run, the positions
of the spots and their retardation factors, R( values,
polar solid surface can be measured, and compared to the R( values of
Figure 29.0 I Sepal-ation by adsorption known reference compounds (Figure 29.03).
 The column, made of glass or metal, is from I m to 3 m
in length, and is packed with fine solid particles (brick
dust is often used), coated with a high-boiling oil.
The components of mixtures that are separated by

• GLC need to have a reasonable vapour pressure at

the temperature of the oven, which can be up to
start to solvent front
(b) t start to centre of spot
(a)
about 250°[Link] more volatile components travel
through the column faster; the less volatile ones
take longer to be carried through the column by the
flowing gas, so have longer retention t imes.
• ft f'I

The gas emerging from the column passes through a

detector, which records the presence and amount of
Figure 29 ,03 The retardation factor each component on a chart recorder or computer:
On a chart print-out of the results, the area
The retardation factor, Rr is defined by the equation: underneath each peak is often proportional to the
R= = distance moved by solute amount of that component responsible for that peak
f b distance moved by solvent Analytical GLC machines are routinely coupled to
an in-line mass spectrometer: This allows the mass
Each compound has a characteristic Rf value for a spectrum of each component in a sample to be
given solvent and a given solid phase. taken, which enables further verification of the
identity of the component.
If yo u al-e asked to calculate an Rr value
fmm a drawing of a TLC plate, make
SLwe you measUl-e the distance fmm the
29.02 Infrared spectroscopy
stal'ting line to the centre of the spot, to The frequency with which bonds in molecules vibrate
the nearest mm. is similar to the frequency of'light' in the infrared region
of the electromagnetic spectrum. If the frequency of
incident radiation matches that of a particular bond
b Gas-liquid chromatography (GLC) vibration, the light will be absorbed as the bond
The apparatus for GLC is shown in Figure 29.04. vibrates more strongly. Bonds to electronegative atoms

dried carrier

replaceable
silicone rubber
septum = •
recorder

injector detector
port
oven
oven

column, typically 3m
long and 2mm inside diameter
column oven
Figure 29.04 A diagram of GLC ap paratus
like oxygen (e.g. in alcohols (O-H) and carbonyl The absorption of infrared radiation is important in
compounds (C=O)) show very strong absorptions. another context: small molecules in the atmosphere
Although an infrared spectrum shows a series of (especially CO 2, CH 4, H20 and CFCs) are responsible
absorptions (see Figure 29.05), these are always for the greenhouse [Link] absorb the infrared
referred to as peaks rather than troughs. Note also that radiation being emitted from the surface of the Earth,
the x-axis of infrared spectra runs from low frequencies and so prevent it from being lost to space. As result, the
on the right to higher frequencies on the left. amount of heat lost is less than that gained from so lal"
radiation, and the Earth warms up.
The infrared spectrum of a compound often enables
us to identify the functional groups it contains, as
each functional group has a characteristic absorption
frequency. Some groups are listed in Table 29.0 I. Worked example 29.0 I
Bond I'(wavenumber)
of
I cri- I
Figure 29.06 shows the IR spectrum of
compound A, with the formula C3 H6 0 2 .
O-H 3200-3500 Determine which functional groups compound A
N-H 3400 contains and hence suggest its structure.
O-H in RCO,H 2500-3300
100
C-H 2800-3100
C=O 1700-1740
C=C 1600- 1650
C-O 1100- 1250
Table 29.0 I Some IR absmption freq uencies for ol"ganic
groups
3000 2000 1500 1000 500
Wavenumber / em-I
In molecules with more than half a dozen or so atoms
there can be many different modes of vibration of the Figul"e 29.06 Infrared spectrum of compound A
molecule as a whole. This leads to a complicated series
of peaks in the region from 500 to 1500 cm- I • Unless How to get t he answer:
they are very strong (such as the c-o absorption), Step I: We fi rst need to determine which peaks
the peaks cannot be assigned to individual bonds, but are significant: there are three to the left
their pattern is unique to the particular [Link] of the fingerprint region, and of those
is known as the 'fingerprint' region of the spectrum, and within the fingerprint region only the
is very useful in detecting the presence or absence of a strongest should be considered. The four
particular compound in a sample. most significant ones are at 3400cm- ' ,
2900cm- ' , I720cm- ' and II OOcm- l.
100
Step 2: Table 29.0 I shows that the groups
responsible for these peaks are as follows:
broad peak at 3400cm- ' = O-H
peak at 2900cm- ' = C- H
strong peak at I720cm- ' = C=O
strong peak at 1100 cm- ' = C-O

4000 3000 2000 1500 1000 500

Step 3: Since A contains an - OH group (but
Wavenumber / em-I not as part of a -C0 2 H group), its one
remaining oxygen must be in a ketone
Figure 29.05 The infl"al"ed spectl"um of propeno l,
or aldehyde group. This fits with A being
CH2 =CII CH)OH
CH 3COCH 2 0H , CH 3CH(OH)CHO or
HOCH 2CH 2CHo.
 Progress check 9.0 I
Figures 29.07 and 29.08 show the IR spectra of two other compounds Band C, with the formu la C 3 H6 0 2
.

Use the information in Table 29.0 I to suggest what functional groups the compounds contain and hence
suggest the structure of each compound.

100

.g.
---c::
11:1

50
V\
c::

4000 3000 2000 1500 1000 500

Wavenumber / em-I
FigLwe 29.07 Infral-ed spectrum of compound B

100

.g.
---c::
E 50
V\
c::

4000 3000 2000 1500 1000 500

Wavenumber / em-I
Figul"e 29 .08 Infl-ared spectrum of compound C

29.03 Mass spectrometry • Measuring the abundance ratio of its molecular

ion M+ peak and the [M + 1]+ peak allows us
When high-energy electrons bombard a molecule in to calculate the number of carbon atoms in a
t he gas phase, further electrons are knocked off to form molecule.
positive ions. These ions have often been given enough • Measuring the abundance ratios ofthe [M + 2t,
energy by the impact to undergo fragmentation through [M + 4]+ and [M + 6] + peaks allows us to find out
bond breaking. A mass spectrometer measures the whether a compound contains ch lorine or bromine
relative masses of molecules and their fragmented ions. atoms, and if so, how many of each.
There are four main ways we can use the information a • Looking at the fragments produced when an ion
mass spectrum provides: decomposes inside a mass spectrometer often allows
• The mle ratio ofthe molecular ion gives us the Mr of us to work out the structure of a molecule .
the compound.
a Analysing the molecular ion c The [M + 2] + and [M + 4] + peaks
If we vaporise an organic molecule and subject it to Chlorine and bromine each have two st able isotopes.
the ionising conditio ns inside a mass spectrometer, the Table 29.02 shows their relative abundances.
mass/charge ratio (m/e) for t he molecular io n (i.e. t he
ion with the highest m/e ratio) can be [Link] Element IIsotope Iabundance
Natural IApproximate
ratio
gives us a measure of the relative molecu lar mass.
ch lorine 35Cl 75.5 3: I
b The [M + Ir peak I--
37C1
I-
24.5
The relative abundances of the two stable isotopes of bromine 79Br 50.5 I: I
carbon, 12C and 13C are 98.9% 12C and 1.1 % '3C. This BIBr 49.5
means that out of every 100 methanol molecules
(CH 30H) about 99 molecules will be 12CH OH and Tabl e 29.02 The abundances of t he chlol-ine and
. 3
JUst one molecule will be 13CH 30H. For ethanol. bro mine isotopes.
C 2H sOH, the chances of a molecule containing one
13C atom will have increased to about 2 in 100, Any compound containing one chlorine atom,
because each C atom has a chance of I in 100 to therefore, will have two 'molecular ion' peaks, one
be 13C and there are two of them. By measuring th e due to molecules containing 3sCl and the other due
r
abundance ratio of the M + to [M + I peaks, we to molecules containing 37Cl. For example, the mass
spectrum of chloroethane, CH 3CH 2Cl, will have peaks at
can thus work out the number of carbon atoms the
molecule [Link] formula we use is: m/e 64 (24 + 5 + 35 = 64) and at m/e 66 (24 + 5 + 37
= 66), corresponding to the species CH 3CH/sCr
n= 100 AM +I and CH 3CH/ [Link] relative abundances of the two
1.1 AM
peaks will be in the ratio 3: I, which is the ratio ofthe
where n = number of carbon atoms abundances of the two Cl isotopes.

AM+ I = the abundance of the [M + I r peak and A similar situation occurs with bromine, although
in this case the two molecular ion peaks will be of
AM = the abundance of the molecular ion peak.
equal heights, since the isotopic abundance ratio of
79Br: BI Br = I: I .
You wi ll need to I"emember t his What happens when the molecule contains more
formu la. You might be given the relative than one halogen?
abundances of the M I and [M + I ] I peaks
The simplest situation is for a molecule
as numbel"s, 01" you might be expected to
containing two bromine atoms. Take the molecule
meaSUI"e t hem on a give n spect l"Um, using
bromoethanoyl bromide. BrCH 2COBr. Each carbon
a
can be attached to either a 79 Br or a 81 Br atom,
and there is a (rough ly) equal chance of either.

Worked example 29.02 Step 2: The contribution of carbon atoms to

M r =8x I2=96
The molecular ion peak of a compound has an m/e
This leaves 106 - 96 = 10.
value of I 06, with a relative abundance of 17%,
r
and an [M + I peak at m/e 107 whose relative Step 3: The most likely other elements are
abundance is 1.5%. hydrogen, oxygen and nitrogen, but since N
Calcu lat e the number of carbon atoms in the
= 14 and 0 = I 6, the other element must
molecule, and suggest its molecular formula. be hydrogen only.

How to get the answer: Step 4: Formula is therefore CoH ,o'

Step I: We apply the formula to find n:

100 1.5
1 X 17 = 8.02, so the co mpound
n = -1.-
has 8 carbon atoms.

,-
 We therefore arrive at the four possibilities shown
in Table 29.03 , each of which is eq ually likely. Progress check 29.02
Formula I mle value Compound D contains the elements C,
79BrCH2C079Br 200 H and 0. Its mass spectrum has a peak
79BrCH,C081 Br 202 at mle 132 with a relative abundance of
81 BrCH 2 C079 Br 202 43.9 and a peak at mle 133 with a relative
81 BrCH,C081 Br abundance of 2.9. Calcu late the number of
204
carbon atoms in D and suggest its molecular
Table 29.03l he mo lecular ions of bmmoethanoyl formula.
bmm ide
2 Compound E has molecular formula
C3H6 0 2, and major peaks at mle = 27,28,
There will therefore be three molecular ion peaks,
29,45,57,73 and 74. Suggest formulae for
with relative abundances of I :2: I.
these fragments, and a structure for E.
d Analysing molecular fragments
Given enough energy, the ionised molecules formed a
in a mass spectrometer can [Link] mle values 100
of these fragments give us a clue as to the structure
of the parent molecule. 80

For example, pmpanal (CH 3CH2 CHO) and

propanone (CH3COCH) are isomers with Mr. =
.i 60

58. Breaking the C- C bond next to the C=O group "' 40

would give the following fragments, all of which can
carry a positive charge by the loss of an electmn, 20
and hence show as peaks in the mass spectrum:
10 15 20 25 30 35 40 45 50 55 60 65
propanal propanone Mass number
,..I
CH,
/ C H2
I ,r'CHO CH,
/co,/
,7'CH,
b
100
( A,-_ _,"",\
( A,-_ _
80
CH,- CO CH,
CH,- CH 2 CHO

m/e29 m/e29 m/e43 m/e 15

.i 60

"' 40

CH 2 = CH 2
-H
CH 2 = CH
20
m/e28 m/e27

10 15 20 25 30 35 40 45 50 55 60 65
We therefore expect the mass spectrum of propanal to Mass number
contain a strong peak at mle 29, with others at mle 28
and mle 27, whereas we expect the mass spectrum of Figul'e 29.09 a Mass spectrum of pmpanone; b mass
pmpanone to contain peaks at mle = 15 and [Link] is spectl-um of propanal.
in fact what is observed (Figure 29.09).
29.04 Nuclear magnetic C 13C NMR spectra
resonance (N MR) The 13C NMR spectrum of a compound shows a
single-peak absorbance at a different chemical shift
spectroscopy value for every carbon atom in a different chemical
[Link] can be illustrated in the spectrum of
a The basis of NMR spectroscopy propyl methanoate, HC0 2CH 2CH 2CH3, in Figure 29, 10.
Nuclei w ith an odd number of nucleons (e,g, 'H We can see that the spectrum consists of four peaks,
and 13C) have an overall magnetic moment, which corresponding to the four different carbon atom
can take up two possible orientations in an external environments in the molecule, Consulting the CIE Data
magnetic field: aligned either w ith the fie ld, or against Booklet, we see that these can be assigned as follows:
it. If a nucleus is irradiated w ith rad iation of the
peak at 0 161: carbonyl carbon, HCO-
correct frequency, it can flip from one orientation to
the other; and energy is absorbed, peak at 0 66: CH 2 next to oxygen, -O-CH 2-
The frequency of absorption depends on both the peak at 0 22: CH 2 in middle of chain, -CH 2-
strength of the external field and the molecular
peak at 0 10: C H 3 at end of chain, - C H3
environment of the nucleus,
N,B, the heights of the peaks bear no re lationship to
b Analysing organic molecules the number of carbon atoms responsible for them,
Protons in organic molecules absorb at different unlike 'H NMR (see below),
frequencies, depending on the elect ronegativity of
groups nearby. This difference is measured by the
chemical shift, For convenience, the hydrogen or
carbon atoms in the compound tetramethylsilane,
(CH3)4Si (known as TMS), are used as a reference,
The chemical shift, symbol 0 (delta), is the extent of
the change in frequency of absorption, f Chemical
shift is defined as:

o= 106(( - frMS) / frMS

Values of 0 are quoted in parts per million (ppm),
200 180 160 140 120 100 80 60 40 20 0
Th e values of some chemical shifts for hydrogen and
8
carbon atoms within different organic groups are
given in the C IE Data Booklet. Figure 29, I 0 17C NMR spect rum of propyl methanoat e
 Hydrogen atoms on the adjacent carbon atom
Progress check 29.03 sp lit the peak into a multiple [Link] sp litting
pattern te lls us how many adjacent hydrogens

'I
Two isomers with the molecular formula there are (Table 29.04).
CsH100 are pentan-2-one and pentan-3- , '-.-
one. Predict the number of peaks in each of "Number of adjacent
hydrogens intensities
their 13C NMR spectra.
0
- singlet
-
I
2 The 13C NMR spectrum shown in Figure
I doublet I: I
29. 1 I is of another ketone isomer of
CsH,oo. Use the spectrum to suggest its 2 triplet I :2: I
structure. 3 quartet I :3:3: I

Table 29.04 Some simple splitting patterns for 'H NMR

The solvents used for I H NMR must not contain

any protons, or else the signals due to protons in the
sample would be swamped. Common solvents used
are CC/4' CDC/3 and D20, where'D' is deuterium r H).
Protons directly attached to oxygen or nitrogen

1 I atoms can be identified by deuterium exchange. If

the compound containing them is dissolved in D20
('heavy water', D = 2H), the protons are exchanged
200 180 160 140 120 100 80 60 40 20 0 with deuterium atoms in the water. The peaks due
o to the -OH or - NH2 protons disappear:
FigLwe 29. 1 I 13C spectrum of C,H,oO CH 3CH 2-OH + D20 CH 3CH 2-OD + HDO

d 'H NMR
The'tr-iplet + quartet' pattern seen in
In general, the I H NMR spectrum of a compound flg ur-e 29.12 is ver-y typical of the ethyl
is always more complicated that its 13C NMR group, CHFH [Link] tr-ip let due to the
spectrum, but it can often tell us more about the
CH 3 group is usually ver-y near- to 0 1.1,
structure of a [Link] is because oftwo
but t he 0 value fo r the CH} quar-tet
features of a 'H NMR spectrum not shown by a 13C
depends a lot on what the ethyl group
spectrum.
is joined to (see tab le 6 in the CIE Data
The area underneath each peak is proportional to Booklet).
the number of hydrogen atoms responsible for that
peak
Worked example 29.03
Interpret the 'H spectrum of ethyl ethanoate, C4 Hs0 2' shown in Figure 29, 12,

11 10 9 8 7 6 5 4 3 2 o
I)

Figure 29, 12 The 'H NMR spectrum of ethyl ethanoate

How to get the answer:
Step I: The spectrum shows peaks at three 0 (ppm) values, suggesting there are three different types of
proton, One type (at 0 2, I) has no H atoms adjacent to it; the other two do have adjacent H atoms,
Step 2: Using the CIE Data Booklet, we can assign the peaks as follows:
o4, I: 2H quartet, O-CH split by the three adjacent H atoms on the -CH3 group
2
-

o 2, I: 3H singlet, CH 3-CO, with no adjacent H atoms

o 1.3: 3H triplet, -CH3 split by the two adjacent H atoms on the -OCH group 2

Progress check 29.04

The spectrum shown in Figure 29, 13 is that of
compound D, C3H60 2, Suggest the structure of D
and identify the peak that would disappear if the
sample were shaken with 0 20.

1 1- ' - - - - -------""L.-I,l 1
12 10 8 6 4 2 o
I)

Figure 29, I] 'H NMR spectl-um of compound D

Sample answer b CH 3COCH 20H: 3 singlet peaks, at 82.2-3.0
(CH 3) [I mark]
Q uestion: The compounds CH 3COCH 20H and
HC0 2CH2CH3 are isomers. 8 3.2-4.0 (CH 2) [I mark]
a Describe one major difference and one 8 0.5-6.0 (OH) [I mark]
simi larity between their infrared spectra. [2] the OH peak would disappear in 0 20
b Describe the details of their 'H NMR [I mark]
spectra, including approximate 8 values, HC0 2CH 2CH3: one singlet peak at 8
splitting patterns and how the spectra would 9.3- 10.5 (CHO) [I mark]
change (if at all) when the samples were
shaken with 0 20. [8] quartet at 8 3.2-4.0 (CH 2, split by CH3)
[I mark]
Answer:
trip let at 8 0.9- 1.7 (CH 3, split by CH 2)
a Both will show C=O absorption at [I mark]
1700- 1740 cm- I [I mark]
no peaks would disappear in 0 20 [I mark]
CH 3COCH 20H wi ll also show an O-H
absorption at 3200-3500cm- ' [I mark]
F ::Im-c;tyl ,qu ti n
Data from the spectroscopy section of the Doto Booklet wil l be needed to answer these questions.
The following figures show the mass, infrared, 'H NMR and 13C NMR spectra of compound A.

100

80

·f
60
<IJ
',E;
'"
40

20

I I I I I I I I
10 W m m 00
mle
Figu l-c 29.1'1 Mass spectrum of A

100

4000 3000 2000 1500 1000 500

Wavenumber / em-)

figul-e 29. IS Infl-al-ed spectrum of A

 c Use the I3C NMR spectrum to determine
the number and type of the carbon atoms in
a molecule of compound A. [3]
6H
d Use the 'H NMR spectrum to suggest the
structure of A. [4]
e Suggest the stl-ucture of the ion at mle = 43
in the mass spectrum. [ I]
Total: 13
2 Two compounds, Band C, have the molecular
lH lH
formula C3H6 0 2. Compound B boils at 140°C
and readily dissolves in water to give a solution
12 10 8 6 4 2 o of pH 3. Compound C boils at 57°C and is
o much less soluble in water; giving a solution
Figul-e 29. 16 1H NMR spectl-um of A of pH 7.
The 13C spectra of both compounds show
three absorptions.
The infrared spectra of both compounds
show a peak in the region 1700- 1750 cm- I .
• The 1H N MR spectru m of C shows two
singlet peaks.
a Suggest structures for Band C. [2]
b Suggest the chemical shift (0) values for the
three absorptions in each of the 13C NMR
spectra. [6]
200 180 160 140 120 100 80 60 40 20 0 c Suggest the chemical shift (0) values in each
o of the 1H spectra, and the splitting patterns
Figure 29. 17 " C NMR spectrum of A for the peaks in the spectrum of C. [6]
Your answers to each of the following questions d Suggest a feature present in the infrared
should explain how you arrive at your conclusion. spectrum of one of B or C but absent in the
a Use the mass spectrum to determine the M,. spectrum of the other compound, that would
of compound A. [I] allow you to distinguish between them . [ I]
b Identify the peaks at 2500-3300cm- ' , e Which of the two compounds, B or C,
1700 cm- I and 1230 cm - I in the infrared would have the shorter retention time in
spectrum and use them to determine the a gas-liquid chromatograph? Explain your
functional group(s) in compound A. [4] answer. [I]
Total: 16
30.0 I Devising synthetic routes groups, so that we can decide which reactions are
appropriate for our particular scheme.
Most of the millions of organic compounds that It is useful to learn the reactions you have come across
chemists have made have used simple and readily in this course in two ways:
available materials as their starting [Link] could
• which products are formed during a particular
be naturally occurring compounds found in plants or
reaction of a functional group
the products from the refining of crude oil. In order
to piece together a route from a common starting • which reactions could be useful in making a particular
material to a target compound, we need to have an functional group
expert knowledge of the reactions of organic functional

Worked example 30.0 I

Suggest how ethanoic acid could be made from e reaction with cold KMn04 gives
ethene. HOCH 2CH 20H
CH 2=CH 2 CH 3C0 2H Step 2: Reactions that produce ethanoic acid:
How to get the answer: a ,"eaction of CH 3CN with H+ + H20
This cannot be carried out directly; we need at least b reaction of CH 3C0 2R with H+ + H20
two steps in the transformation. We start cataloguing c reaction of CH 3CHO with Cr20 /- + H+
possible reactions from both ends. d reaction of CH 3CH 20H with
Cr20 72 - + H+
Step I: Reactions of ethene:
Step 3: We can see that there is a reaction of ethene
a reaction with HBr gives CH 3CH 2Br which produces the starting material for one
b reaction with Br2 gives BrCH 2CH 2Br of the reactions that produces ethanoic acid,
c reaction with H+ and H20 gives so the synthetic route is as follows:
CH 3CH 20H
CH 2= CH 2----. CH 3CH 20H ----. CH 3C0 2H
d reaction with H2 + Ni gives CH 3CH 3
 Step 4: Monobromo compounds can be made by
Worked example 30.02 the following three methods:
Suggest a method for carrying out the following
conversion. • alkenes + HBr
• alcohols + HBr (or NaBr + H2S0 4)

cfNH'
• alkanes + Br2 in UV light

o
How to get the answer:
> So there are three possible starting materials
for the intel"mediate bromo compound:

Step I: Consider the reactions of the starting

compound, [Link] is only one way
to add a side chain to the benzene ring:
the Friedel-Crafts reaction. There are two
possible two-carbon reagents we could use:
CHFH 2Cl or CH 3COCl.

Step 5: We have now arrived at a common point

between the reactions of the starting
material (benzene) and those that form the
Step 2: Consider the reactions that produce the product amine: the common intermediate
final amine. Aliphatic amines can be made by compound is [Link] overall
the following route: synthesis can be carried out in the following
three steps.
RBr+ NH3 R- NH2
RCN + H/Ni RCH 2NH 2
The second is no good in this case, as we do
not have a -CH 2NH 2 group in the product.
Step 3: So an intermediate compound must be
o CH3CHP

+A/Cl3
heat
.-
d light .. (f"
NH3
0
or"
in ethan: NH2
(heat in sealed tube)

• I
 YOll can sec how iIT1poi !(lIlL it is to leal'll
the ttansfonnc1Llons of one organic
fu nc tional )c;IOLIP into anolhel: Always 1('(11'11
these as ,W,tlcrul reactions of fu nctional
gm ups (e .g. those of ull plimalY alcohols) salbutamol
rathel' th,1I 1 as leactior1s of a specific
compoun d (e.g. lhose of just ethanol).

adrenaline ephedrine
Progress check 30.0 I
Suggest routes to convert the following starting Since the enzymes and receptors with which the
materials into the stated products: drugs interact are built up from chiral amino acids,
I CH 3CH 20H => CH 3CH(OH)C0 2H their active sites are also chiral. Usually only one
(3 steps) optical isomer of a drug is physiologically active.
The other isomer is often either inactive, or worse,
2 CH 3CH=CH 2 => (CH3)2CHCH2NH2 responsible for harmful side-effects. It is therefore
(3 steps)
important for a pharmaceutical company to design a
synthesis that will produce just the desired isomer.
3 (3 steps)

Progress check 30.02

How many chiral centres are there in a
30.02 The design of drugs salbutamol; b ephedrine?

Various methods are used to decide which molecules 2 Draw the stereochemical formulae of the
may be useful as drugs: isomers of salbutamol, and decide which
isomer would be the physiologically active
• The natural substrate can be used to suggest one. Explain your reasoning.
compounds that could mimic its effect.
• If the molecular structure of a traditional remedy,
such as the active ingredient of a plant extract, is
known then that structure can be used as a basis for 30.03 Chemical tests for
further development. functional groups
The following formulae show the chemical similarities
Throughout the previous units we have listed the
between the synthetic drug salbutamol (used in the
reactions of, and the tests for; each functional group as
treatment of asthma), the body's own drug adrenaline,
we have come across them. In Table 30.0 I we collect
and the plant extract ephedrine (known as ma huang,
together all the tests the other way round, based on the
and which has been used for over 2000 years in China).
reagent used.
 · .
Reagent
·.T ,. Progress check 30.03
universal turns red R-C0 2H Suggest structures for the fo llowing
indicator solution compounds.
universal turns blue R- NH2 a Compound A, C 4 H 80 3, fi zzes when
indicator solution Na2C0 3 (aq) is added, form s a pale yellow
Na(s) Azzes/gas (H 2) ROH,ArOH ppt. with 12 + OH - (aq), and on w arming
evolved (phenol) or with acidified dichromate turns the colour
RC0 2H of the reagent from orange to green.
NaOH(aq) substance ArOH or RC0 2H b Compound B, C4 H 60, gives an orange
dissolves
ppt. with 2,4-DNPH but does not react
Na 2C03(aq) substance RC0 2H with Tollens' reagent It decolorises
dissolves and gas KMn0 4 (aq),
(C0 2) evolved
2 Suggest a reagent that could distinguish
PCls(s) fizzes/gas (HCZ) ROH or RC0 2H
between the following pairs of isomers.
evolved
State what you would observe with each
warm with turns from RCHPH, compound.
Cr20/- + H+ orange to green
RCHO 0

adding Hp fizzes/gas (HCZ) RCOCl and

0('
drops evolved

Mn0 4-
(cold)
+ H+ decolorises alkene, C=C b and
if'"'
decolorises CH 3
Br2(aq) alkene, C=C

ofC!
or"
0 0
Br2(aq) decolorises and ArOH or ArNH2
white ppt.
and
2,4-DNPH orange ppt. RCHO
C/
warm with red ppt. RCHO
Fehling's solution
warm with silver mirrol- RCHO
Tollens' reagent

12 + OH - (aq) pale yellow ppt. RCOCH 3 or 30.04 Recognising reaction

RCH(OH)CH 3
types
Tab le 30.0 I Testing fO I- functional groups
We can recognise what type of reaction is taking place
during a chemical transformation either by looking
If in a question you al-e given t he I-esults
at the reagent involved, or by looking at how the
of various tests, you shou ld always explain
functional group has changed.
what information they give you about
wh ich functional groups al-e pl-esent, even
if you have ali'cady worked out what
t he 'unknown' compound is fmm othel-
evidence,

, ,
Sample answer
Q uestion:
State the types of reaction occurring in each of the steps I- VI. [6]

III
CH COC!
3
M
• 0
NHCOCH3

IV C!2 + light

NH

P 0 ..
2 VI pNHCOCH3
.......
11----- V
heat with HC!(aq) CN heat with KCN
C0 2H in ethanol

Answer:
I is an electrophilic aromatic substitution reaction. V is a nucleophilic subst itution. [I mark]
[I mark]
VI is a hydrolysis (of two groups at once: an amide
II is a reduction. [I mark] and a nitrile). [I mark]

III is a nucleoph ilic substitution. [I mark]

IV is a free radical substitution. [I mark]

Sorne I'eactions can have mOI'e than

one descl'iption. FOI" example, most
hydl-o lysis I"eactions are also nucleoph ilic
substitutions; the I"eaction of an alkene
with hydrogen + nickel is both an addition
I'eaction and also a I-eduction.
Propress check 30.04
Identify the reaction types in t he following scheme.

.. ..
II III

) HBr >-Br
heat with
NaOH(aq) > - OH
heat with

H+ + Cr2ol-
)=0

IV
t CN
NaCN
'

XOCOCH3

CH 2NH 2
.. VI

H2 + Ni
XOCOCH3 .. V
heat with
CH 3C0 3H XO
H

CN + cone. H2SO4 CN

Fxam -style questions a Explain the functional group that each of the
above four reagents tests for. [4]
Compound A has the molecular formula C9 H I6 o. b Suggest the structures of these three
When A is heated with concentrated acidified
compounds. [ 3]
KMn0 4 (aq), two compounds are produced: B,
CsHloo' and C, C 4 H 60 [Link] results of five tests c When compound A is treated with HBr;
carried out on these three compounds are given two different positional isomers with the
in Table 30.02. molecular formula C9 HI7BrO are fOI-med.
Draw the structures of these two isomers,
indicating with an asterisk any chiral carbon
atoms they contain. [4]

cold dilute decolorises no reaction no reaction Total: II

KMn0 4 (aq)
2 The plant extract containing ephedl-ine has been
Tollens' silvel- mirror no reaction no reaction used in China as an anti-asthmatic and stimulant
reagent formed
since ancient t imes. Ephedrine can be synthesised
I/aq) + no reaction no reaction yellow in the laboratory by the following route.
OH - (aq) precipitate

2,4-DNPH orange orange orange

reagent precipitate precipitate precipitate

Table 30.02
 OH

o step 1
D ,lop 2

step 3

eIY'H" vY
ephedrine

a Suggest the structure of intermediate e State, giving a reason in each case, whether
compound D, [ I] or not ephed,"ine will be soluble in:
b Suggest reagents and conditions for steps NaOH(aq)
2- 5, [5]
ii HCl(aq) , [2]
c State the types of reaction that are occurring
l atal: 15
in steps 1- 5, [5]
d Deduce the number of optical isomers
that have the same structure as ephedrine,
Explain your answer. [2]
 This course will test your skill in manipulating apparatus, observation, and your ability to make logical conclusions
how well you present your data, your analysis and from those observations.
evaluation. It also tests your powers of accurate

I Plan an experiment
Progress check P.O I
You cou ld be given equipment and asked to use it to
Plan an experiment to compare the enthalpy
find the answer to a question.
changes when iron and zinc are separately
Here is an example. disso lved in aqueous hydrochloric acid.
Find the enthalpy of neutralisation of HCl(aq) with You have avai lable samples of iron and
NaOH(aq) given the following chemicals and apparatus: zinc; [Link] - 3 HCl; 100 cm 3 beaker;
[Link]- 3 HCl thermometer graduated to 1.0 DC; balance;
[Link] - 3 NaOH 50cm 3 graduated cylinder.
thermometer measuring to 1.0 DC
50 cm 3 graduated cylinder
100 cm 3 beaker
2 Observation and recording
Before you start any practical work, you need to be a Specified experiments
clear what you are going to do and what you need to You may be asked to carry out specified
measure. Put your thoughts down on paper. experiments to investigate an unknown substance or
You need to add the acid and alkali. How much of substances. It is important to follow the instructions
each? How wi ll you measure the volume? What and record each observation carefu lly.
vessel wil l you add them to? Here is an example.
II You need to measure a temperature change. The
You are provided with solutions A and B,AgNO/aq)
initial temperature needs to be taken. Are the two
and NH/aq).
solutions at the same temperature? What wi ll you do
if they are not? When do you take the temperatures? The observations need to be recorded at the time
III Write out what you are going to do and what you are they are made.
going to measure and how you are going to measure it.

ii iii iv
 discard that portion ofthe solut ion). Fill it so
that there are no bubbles in the so lution and
the bottom of the meniscus is level w ith the
gradation mark. Allow t he solution to empty
precipitate dissolves to form a naturally into the con ical fl ask (do not blow t he
colourless solution
solution out) and at the end touch the end of
the jet onto the top of the solution.

b Accuracy III The burette needs to be rinsed with the solution

t o be measured before filling it. Make sure the
Another aspect of this skil l is taking measurements
jet is filled below the tap and there are no air
to the right degree of accuracy:
bubbles round the tap or in the cylinder.
• With a thermometer graduated in 0c, the best
iv During the titration, swirl the con ical flask
you can do is to take a measurement to +/-
continuously to ensure the so lutions are mixed.
0.5 0c.
Take a 'rough' titre (to the nearest 0.5 cm 3) and
• A graduated cylinder with markings for every several 'accurate' titres, each recorded to the
I cm 3 can be read to +/ - 0.5 cm 3. nearest 0.05 cm [Link] average of the accurate
• A burette graduated in 0.1 cm 3 can be read to titres can be recorded to 2 d.p. (e.g. the average
+/- 0.05cm 3. of 20.1 Ocm 3 and 20.05 cm 3 is 20.08 cm 3) .

• The timing on a stopwatch is probably dependent v Read the burette with your eye horizontal to the
on your own reaction time, so the larger the time meniscus.
measured, the lower is the proportion which d Some titration tips
is uncertain due to your reaction time and the Acid-base titrations: remember to check
measured value is more accurate. the end-point co lour change of the indicator
• A beaker marked for I 00 cm 3 would have an provided.
uncertainty in this value of +/ - 5 cm 3. II KMnO 4: th is is usually put into the burette and
the vo lume is read from the top of the meniscus.
Wh en using any pat"ticulal- measul'ing III I/thiosulfate: the thiosulfate goes into the burette.
instl-ument. the smallel til e amount you When the 12 colour in the con ical fl ask has faded
meaSUI'e, the lal-gel will be the pel'centage to a light straw co lour, the starch indicator is
uncel-tainty in the value. added to give an intense blue co louration.
e Rates experiments
Record your measurements clearly as you Swirl the conical flask vigorously at the start of the
take them. experiments to ensure mixing.
c Titration procedure
One question that you may encounter is about Stit- a so lutio n well befoi-e t aking a
titrations, so it is important that you know how to t empel-atlwe. Keep t he th el-momeLel- in
carry these out accurately. the so lution w hilst I-eading it and I-ead
the scale wiLh YOlW eye hOI-i70nta l t o the
The conical flask needs to be clean and rinsed with
gl-ading mark.
deionised water but it does not need to be dry.
II The pipette needs to be rinsed out with th e
solution which is to be measured (and then
3 Reaching conclusions b Examination
During examination you wi ll be able to use the
When you have carried out all the experiments and wet test observations / inferences table provided,
collected al l the data, you can come to some conclusions, However; you do need to familiarise yourself with it
This depends on your chem ical knowledge,You need to so that you can use it constructively to help you ,
write your conclusions clearly and methodically.

a What you shou ld know

4 Evaluation
• The reactions of the following cations:
NH4+, Mg2+, Af3+, Ca2+, 0 -3+, Mn 2+, Fe2+, Fe 3+, Cu 2+, a A better way?
Zn 2+, Ba2+, Some experiments allow you to make choices,Your
evaluation allows you to put forward a better way of
• The reactions of the following anions:
carrying out an [Link] of each piece of
CO/- , N0 3- , N0 2- , SO/- , SO/- , CI- , Br- , 1- ,
apparatus or procedure in turn.
• Tests for the following gases: NH 3, CO 2, Cl 2' H 2,
For example, in the neutralisation experiment" ,
02' S02'
• Would different volumes of solutions have been
better? Could you have used larger volumes, and
Sample answer what effect would this have?

Question: • Would a more accurate thermometer have given

a more accurate result? (It may be reasonable
For the experiment in section 2, above, make
to decide that the thermometer was accurate
suitable observations and draw conclusions, [7]
enough but you do need to say why.)
Answer:
• Is there a significant heat loss when using a
I Experiment I Observation I Conclusion beaker? Would a lid or lagging have prevented
some heat loss?
i A colourless
solution Which of these effects gives the most inaccuracy to
[I mark] your value?
II add white a white
AgN0 3(aq) precipitate precipitate b When plotting a graph
[I mark] with
AgN0 3(aq) Choose a suitable scale to fill as much of the
is a test for a graph paper as possible but which can be read
chlol-ide: A is with ease,
a chloride
[I mark] Label the axes clearly with what is being plotted
and the units,
III add NH3(aq) precipitate AgCl
dissolves dissolves in III Use the origin as a 'point' if appropriate,
to form a NH3(aq); this
colourless confirms the IV Plot a smooth line/curve that best fits the points
solution ch loride and point out any anomalous points,
[I mark] [I mark]
IV add B yellow this is
pl-ecipitate the very
[I mark] insoluble Agl:
B is an iodide
[I mark]
This course tests the following ski lls:
2 Analysis and conclusions
• planning
You need to be able to:
• analysis, conclusions and evaluation
• recogn ise the significance of observations from
All that has been written above for AS level applies
qualitative tests
also to A level but at A level you are assumed to be
competent at carrying out practical work. At this level • complete tables of the data to enable conclusions to
you are therefore expected to be able to reach a be drawn
higher level of skill in planning experiments, analysing
results, reaching a suitable conclusion and evaluating For quantitative work, you also need to be able to:
the work. • identify and carry out any calcu lations which will
enable you to draw conclusions

Plann ing • analyse data from experimental work and from

spectra to draw conclusions
a You need to be able to: • draw graphs showing the independent variable on
• put forward a safe and efficient procedure which the x-axis and the dependent variable on the y-axis
wou ld lead to a reliable resu lt
• state how you would carry it out and point out 3 Evaluatio n
any risks involved
• explain what apparatus is required You need to be able to:

• identify both the independent variable and the • identify any unexpected, anomalous resu lts or values
dependent variable and suggest why they are anomalous

• predict what you expect to happen and explain • decide w hether the controlled variables really have
why your procedure w ill be effective been contro lled (e.g. was the temperature really
constant?)
• identify any variables which need to be controlled
• decide whether the results are reliable enough
b Now you need to think about the method in detail: to make any conclusion; has repetition of the
experimental work led to the same result?
• What volumes of solutions will you use?
• identify any weaknesses in the experimental method
• How wil l you put the reaction mixtures together?
and in the apparatus (e.g. 'the calorimeter shou ld
c Finally show how the data gathered might be have been lagged' or 'the reactant shou ld have been
displayed - perhaps in a table in this case . powdered so it reacted quickly') and explain what
effect these weaknesses would have on the final
resu lt
Progress check P.02
Four unlabelled colourless liquids are known to
be CH 3CH 2 0CH 2 CH 3, CH 3CH 2CH 2CH 2 0H,
CH 3CH 2CH(OH)CH 3 and (CH) 3COH .
Suggest a series of experiments wh ich wil l allow
you to identify them.
 am-style n
When magnesium nitrate(V) and calcium nitrate(V) b Draw and label the apparatus you would need
are heated, they decompose to form the metal oxide, to carry out the decomposition, absorb the
nitrogen(IV) oxide and oxygen. Nitrogen(IV) oxide is nitrogen(IV) oxide as it is produced and then
an acidic gas that reacts completely with alkalis. collect the oxygen. [1]
You are to plan an experiment to investigate the c Decide what maximum volume of oxygen you
relative rate of decomposition of the nitrates by will col lect and then calculate the masses of
collecting the oxygen prod uced. magnesium nitrate(V) and calcium nitrate(V)
which need to be heated to give this volume.
Nitrogen(IV) oxide can have severe effects on
(A,.[O] = I6.0; Ar[N] = 14.0;A r [Mg] = 24.3) [2]
breat hing, particularly if you suffer from asthma.
d Explain what measurements yo u would need
You are provided with the separate anhydro us
to make to ensure the comparison is as fair as
nitrates and usual labo ratory ap paratus and reagents.
possible. [4]
a Write the equation for the thermal
e Descri be how yo u wo uld use your
decomposition of magnesium nitrate(V). [ I]
measurements to show the relative rates of
ii Calculate the volumes of nitrogen(IV) oxide oxygen production. [3]
and of oxygen produced when O. I mol of
f How would you ensure the experiment was
magnesium nitrate(V) decomposes. [I ]
carried out safely? [ I]
(Assume 1.0 mol of any gas occupies 24.0 dm 3 at
Total: 16
roo m temperatu re and pressure.)