A Level Chemistry Guide (Book)

Stuu /s
r:qcty
The relative mol ecular mass is al so
cal l ed the relative formula mass
especial l y for i oni c substances.
I oni sati on energi es are always
endothermi c and relate to the
formati on of a posi ti ve i on.
Atomi c st ructure
.
Much of chemistry depends upon Coulomb's Law which states that the
electrostatic force of attraction, 1, is given by:
1 * (q+.q_) l
where q+ and q_ are the charges on the obj ects (e. g. the nucleus, an
electron, ions etc. ) and r
2
is the square of the distance between their
centres. This means that the bigger the charge, the bigger the force, and
the further the centres are apart, the weaker the force.
t-
I
Atomic number (Z of an element is the number of protons in the
nucleus of its atom.
Mass number of an isotope is the number of protons plus the
number of neutrons i n the nucleus.
Isotopes are atoms of the same element which have the same number
of protons but different numbers of neutrons. They have the same
atomic number but different mass numbers.
Relative atomic mass (Ar) of an element is the average mass
(taking i nto account the abundance of each isotope) of the atoms of
that element relative to l/ 1 2th the mass of a carbon- 1 2 atom.
Relative isotopic mass is the mass of one atom of an isotope relative
to l / 1 2th
.
the mass of a carbon- 1 2 atom.
Relative molecular mass (Mr) of a substance is the sum of al l the
relative atomi c masses of i ts constituent atoms.
Molar mass is the mass of one mole of the substance. Its uni ts are
grams per mole (g mor1 ) , and it is numerically equal to the relative
molecular mass.
1st ionisation energ is the amount of energy requi red per mole
to remove one electron from each gaseous atom to form a si ngly
positive i on
2nd ionisation energy is the energy change per mole for the
removal of an electron from a singly positive gaseous i on to form a
doubly positive i on
A common error is to mi ss out the

+ charge on the formula of a speci es
responsi bl e for a l i ne in a mass
spectrum.
STRUCT UR E , BON D I NG AN D MAI N G ROU P CH E M I STRY
1st electron afinity i s the energy change per mol e for the addition
of one electron to a gaseous atom to form a singly negative i on
E(g) + e- r(g)
2nd electron afinity is the energy change per mole for the addition
of an electron to a singly negative gaseous ion to form a doubly
negative ion
E-(g) + e- E
2
-(g)
s block elements are those i n which the highest occupied energy level
is an s orbital . They are in Groups 1 and 2.
Si mi l ar defi nitions apply to p block (Groups 3 to 7 and 0) and d
block (Sc to Zn) el ements.
_ t- .
Mass spectra
An element i s first vapourised and then bombarded by high-energy
electrons that remove an electron from the element and form a positive
ion. This ion is then accelerated through an electric potential, deflected
accordi ng to i ts mass and fi nal ly detected.
Metal s and the noble gases form si ngly positively charged ions i n the
ratio of the abundance of thei r isotopes.
Non-metals also give molecular ions. For example Br21 which has two
isotopes
7
9
Br (SO%) and
8 1
Br (50%), wi l l give three l ines at m/e values of
1 58, 1 60 and 1 62 in the ratio 1 : 2: 1 . These are caused by (
9
Br-
7
9
Br)
+
,
(
9
Br-
8 1
Br)
+
and (
8
1
Br-
8
1
Br)
+
.
The relative atomi c mass of an element can be calculated from mass
spectra data as fol lows:
A, = the sum of (mass of each isotope ? percentage of that isotope)/ 1 00
+r/:
Boron was anal ysed i n a mass spect rometer.
Cal culate t he rel ati ve atomi c mass of boro n usi ng t he resul ts bel ow.
Peaks at m/ e of Abundance ( %)
10.0 18.7
11.0 81.3
Answer: A,= ( 10.0 x 18.7 + 11.0 x 81.3 ) I 100 10.8
Electron structure
The first shel l only has an s orbital .
The second shell has one s and three p orbitals.
The thi rd and subsequent shells have one s, three p and five d orbitals.
Each orbital can hold a maxi mum of two electrons.
The order of fi l l i ng orbitals is shown i n Figure 1 . 1 below.
gATOM I C STR UCTU R E
Fig 1. 1 The order of filling of atomic
orbitals
I n an atom, the outer el ectrons are
shi el ded from the pul l of the nucl eus
by the el ectrons i n shel l s nearer to
the nucl eus ( the i nner el ectrons) .
Fig 1.2 The first ionisation energies
(kj mor1) of the elements up to krton
Electron structures can be shown in two ways:
The s, p, d notation. For vanadium (atomic number 23) this i s:
1 s
2
, 2s
2
2p
6
, 3s
2
3p
6
3d
3
, 4s
2

J
The electrons in a box notati on. For phosphorus (Z * 1 5) thi s would be:
' '
1s 2s 2p
Sizes of atoms and ions

3s 3p
The atoms become smaller going across a period from left to right,
because the nuclear charge i ncreases, pul li ng the electrons in closer,
though the number of shel l s is the same.
The atoms get bigger goi ng down a group, because there are more
shel l s of electrons.
A positive i on i s smal l er than the neutral atom from whi ch it was made,
because the ion has one shell fewer than the atom.
A negative i on i s bigger than the neutral atom, because the extra
repul sion between the electrons causes them to spread out.
1st ionisation energ
There is a general increase going from left to right across a period (see
Figure 1 . 2) . This is caused mai nly by the i ncreased nuclear charge
(ato1ni c number) without an i ncrease in the number of i nner shi el di ng
electrons.
2400
~
2200
l
0
2000
s

1800
1 600
.
1400
C
1200
1 000
.9
800 .
C
600 ..
C
400

0 5 10
Ar
15 20
Atomic number
25 30 35
4
You shoul d be abl e to sketch the
variati on of 1 st i oni sati on energi es
wi th atomi c number for the fi rst 20
el ements.
The fi rst si x i oni sati on energi es/
-J
kJ mol of an el ement are:
1 st 786
2nd 1 580
3rd
3230
4th 4360
5th 1 6000
6th 20000
There i s a bi g jump after the fou rth,
so the el ement i s i n Group 4.
STRUCT UR E , BON D I NG AN D MAI N G ROUP CH E M I STRY
There are slight decreases after Group 2 (this i s because, for Group 3, i t
i s easier t o remove an electron from the higher energy p orbital ), and
after Group 5 (thi s i s because, for Group 6, the repul si on of the two
electrons in the Px orbital makes it easier to remove one of them) .
There i s a decrease going down a Group. This i s caused by t he outer
electron being further from the nucleus. (The extra nuclear charge i s
balanced by t he same extra number of i nner shiel ding electrons. )
Successive ionisation energies
The 2nd i oni sation energy of an element is always bigger than the first,
because the second electron is removed from a positive i on.
When there is a very big j ump in the value of successive i oni sation
energies, an electron i s being removed from a lower shell, e. g. i f thi s
j ump happens from the 4th to the 5th i oni sation energy, four el ectrons
have been removed from the outer shel l during the first four
i oni sations, and so the element i s in Group 4.
Electron affinity
The 1 st electron affini ty values are always negative (exothermi c) , as a
negative electron is being brought towards the positive nucleus i n a
neutral atom. They are the most exothermic for the halogens.
The 2nd electron affini ty val ues are always positive (endothermic),
because a negative electron i s being added to a negative i on.
_-.
Before attempting the questions on thi s topic, check that you can:
Defi ne A,, M,, and relative i sotopic mass.
Calculate the number of neutrons i n an i sotope, given the atomi c and
mass numbers.
Calculate the relative atomi c mass of an element from mass spectra
data.
Define first and subsequent i oni sation energi es.
Expl ai n the changes i n first i oni sation energies for el ements across a
Period and down a Group.
Deduce an element's Group from successive i onisation energi es.
Work out the electroni c structure of the first 36 elements.
Define the 1 st and 2nd electron affi ni ti es.
ATOM I C STR UCTU R E
Anr
, Mass 1 , charge + 1
Mass 1 , charge 0
Mass 1 /1 860 , charge -1
23 ( p+n) - 1 1 p " 1 2n
99 ( p+n) - 56n " 43.
Na( g) - Na ( g) + e-
Cl ( g) -Cl . ( g) + e-
Mg( g) - Mg
2
( g) + e-
1 S
2
, 2S
2
, 2p
2
1 S
2
, 2s
2
, 2p
6
, 3s
2

1 S
2
, 2s
2
, 2p
6
, 3s
2
, 3p
6
, 3d
6
, 4s
2
The answers to the numbered
questi ons are on page 1 21 .
t ,... .--
For the following set of questions, cover the margin, write down your
answer, then check to see i f you are correct. (You may refer to the Periodi
Table on the inside back cover)
State the masses and charges ( relative to a proton) of:
a proton (p)
a neutron (n)
an electron (e) .
How many neutrons are there in an atom of UNa ?
What is the atomi c number of an el ement which has an atom of mass
number 99 and contains 56 neutrons ?
Write equations with state symbol s for:
a the 1 st i oni sation energy of sodium
b the 1 st ionisation energy of chlorine
c the 2nd i onisation energy of magnesi um.
Using the l s, 2s 2p . . notation, give the electronic structures of the
el ements:
a
6
c
b
1 2Mg
c 2
6
Fe.
1 Explain the difference between relative i sotopic mass and relative
atomic mass. I l l ustrate your answer with reference to a specific element.
2 Lithium has naturally occurring i sotopes of mass numbers 6 and 7.
Explain why its relative atomi c mass i s 6. 9 not 6. 5.
3 Magnesi um was analysed in a mass spectrometer.
Peaks were found at three different m/e rati os.
m/e Abundance (%)
24. 0 78. 6
25. 0 1 0. 1
26. 0 1 1 . 3
Calculate the relative atomi c mass of magnesi um.
4 Gallium has a relative atomi c mass of 69. 8. I ts mass spectrum shows two
peaks at m/e of 69. 0 and 7 1 . 0.
Calculate
.
the percentage of each i sotope in gal l i um.
5 The successive i onisation energies of an element X are given below:
I onisation energy 1 st 2nd 3rd 4th 5th 6th 7th 8th
Val ue/kJ mor
1
1 060 1 900 2920 4960 6280 21 200 25 900 30 500
State, giving your reasons, which group the el ement X i s in.
6 a Sketch the variation of 1 st i onisation energy against atomi c number
for the fi rst 1 1 elements.
b Explain why the ioni sation energy is less for:
i the element of atomi c number (Z) of 5 than that for element of
Z = 4
ii the element of Z * 8 than that for element of Z *
c
1 mol of NaOH has a mass of 40 g
1 mol of 0
2
has a mass of 32 g.
STR UCTU R E, BON D I NG AN D MAI N G ROUP C H E M I STRY
iii the element of Z * 1 1 than that for element of Z * 3.
Usi ng t he electron i n a box notation, give t he electronic structure of
chl orine (Z * 1 7) .
8 Explain, i n terms of electronic structure, why t he chemical properties of
l ithi um, sodium and potassium are si mi lar but not identical .
9 a Give the equation, with state symbols, that represents the 1 st
electron affi ni ty of i l i thi um, ii chlorine, oxygen.
b Give the equati on that represents the 2nd electron affini ty of
oxygen.
c Why is the 2nd el ectron affi ni ty of oxygen endothermic whereas
the 1 st el ectron affini ties of l i thi um, chlorine and oxygen are al l
exothermic?
Formulae, equat i ons and moles
_ .
The keys to thi s topic are:
To be able to calculate the number of moles from data.
To set out calculations clearly.
_r-
. The Avogadro Constant is the number of carbon atoms in exactly 1 2 g
of the carbon- 1 2 isotope. I ts value is 6. 02 ? 1 0
2
3
mor
1

One mole of a substance is the amount of that substance that contai ns
6. 02 ? 1 0
23
particles of that substance. Thi s means that one mol e of a
substance is i ts relative atomic or molecul ar mass expressed in grams.
The mol ar mass of a substance i s the mass ( i n grams) of one mol e.
Amount of substance i s the number of moles of that substance.
The empirical formul a i s the simpl est whole number ratio of the
elements i n the compound.
r-..
Calculation of empirical formulae fom percentage data
It is best calcul ated usi ng a tabl e.
Element Percentage of element Percentage divided by A. of element Divide each by lowest
Carbon 48. 7 48. 7 12 * 4. 1 4. 1 2. 7 * 1 . 5
Hydrogen 8. 1 8. 1 7 1 8. 1 8. 1 72. 7 = 3
Oxygen 43. 2 43. 2 7 16 * 2. 7 2. 7 7 2. 7 * 1
FOR M U LAE, EQUAT I ONS AN D MOL E S
1
I oni c equati ons must al so bal ance
for charge.
Avoi d writi ng mol = 0. 1 1 . I nstead
state the name or formul a of the
substance
e. g. amount of Na = 0. 1 1 mol .
As vol ume in dm
3
=vol ume i n
em
3
/1 000, t he fol l owi ng formul a can
be used:
mol es = M x W1 000
or concentrati on = mol es x 1 000/V
where M is the concentrati on and
Vi s the vol ume i n cm
3

The last col umn gives the empi ri cal formula, but if any value in thi s
column comes to a number ending in . 5 or . 25, you must mul ti pl y al l the
val ues by 2 or 4 to get i ntegers. So here the empi rical formula i s C
3
H
6
02
Equations
These must balance. The number of atoms of an element on one side of
the equation must be the same as the number of atoms of that el ement on
the other side.
Ionic equations
There are three rul es:
Write the i ons separately for sol uti ons of i oni c compounds (salts, strong
acids and bases) .
Write ful l ' molecular' formul ae for solids and al l covalent substances.
Spectator i ons must be cancel l ed and so do not appear in the fi nal
equation.
Moles
There are three ways of calculating the amount of substance (in moles) :
For a pure substance X
The amount of A (in moles) " mass of A (in grams)/its molar
mass
Cal culate the amount of H
2
0 in 1 . 1 g of water
Answer: 1 . 1 g/1 8 g mol
-1
= 0.061 mol of H
2
0
For solutions:
The amount of solute " concentration (in mol dm-
3
) x volume
(in dm
3
)
Therefore concentration = moles I vol ume in dm
3
Cal culate the amount of NaOH in 22. 2 cm
3
of 0. 1 00 mol dm
-
3
sol uti on
Answer: 0. 1 00 x 0. 0222 = 2. 22 x 1 0
-
3
mol of NaOH
For gases:
Amount of gas (in moles) volume (in dm3)/molar
volume.
The molar volume of a gas is 24 dm
3
mol-
1
, measured at room
temperature and pressure ( RTP) .
b
I n Step 2, the stoi chi ometri c ratio i s
2/1 as there are 2NaOH mol ecul es
for each 1 Si 0
2
mol ecul e i n the
equati on.
STR UCT U R E , BON D I NG AN D MAI N G ROU P CH E M I STRY
+r/cX
Cal culate the amou nt of H2( g) i n 3.2 dm
3
at RTP.
Answer: 3. 2/24 " 0. 1 3 mol of H2( g)
Calculation of number of particles
The number of particles can be calculated from the number of moles.
The number of mol ecules = moles ? Avogadro's constant.
The number of i ons = mol es ? Avogadro's constant ? the number of
those i ons i n the formul a.
+r/cX
Cal culate the number of carbon di oxi de mol ecul es in 3. 3 g of C02.
Answer: Amount of C02 " 3. 3/44 " 0. 075 mol
Number of mol ecul es " 0. 075 x 6.02 x 1 0
23
" 4. 5 x 1 0
22
Cal culate the number of sodi um i ons i n 5.5 g of Na2C0
3
Answer: Amount of Na2C0
3
" 5. 5/1 06 " 0. 051 9 mol
Number of Na i ons " 0. 051 9 x 6. 02 x 1 0
23
x 2 ^ 6. 2 x 1 0
22
Calculations based on reactions
These can only be done if a correctly balanced equation is used.
Reacting mass questions
First write a balanced equation for the reacti on.
Then fol low the route:
Step 1 Step 2 Step 3
Mass A Moles A Moles B --Mass B
For Steps 1 and 3 use the relationshi p:
amount of A or B ( i n mol es) = mass/molar mass
For Step 2 use the stoichiometric ratio from the equation:
mol es of B = mol es of A ? ratio B/ A
+r/cX
Cal culate the mass of sodi um hydroxi de requi red to react wi th 1 . 23 g of si l i con
di oxi de.
Answer Equati on: Si 0
2
+ 2NaOH NazSi 0
3
+ H
2
0
Step 1 amount of Si 0
2
" 1 . 23/60 mol " 0.0205 mol
Step 2 amount of NaOH " 0. 0205 mol x 2/1 " 0.041 0 mol
Step 3 mass of NaOH " 0.041 0 x 40 " 1 . 64 g
FOR M U LAE, EQUAT I ONS AN D MOLE S
I n Step 2 the stoi chi ometric ratio i s
1 /2 as there i s 1 H
2
S04 mol ecul e
for every 2NaOH mol ecul es i n
the equati on.
Titrations (this will only be examined at AS in Unit test 38)
The route is much the same:
Step 1
Concentrati on and
Step 2 Step 3
answer
vol ume of A Moles A Moles B about B
For Steps 1 and 3 use the relati onshi p:
amount (i n moles) M ? V/ 1 000
For Step 2 use the stoichiometric rati o from the equation:
moles of B * moles of A ? ratio B/ A
25. 0 cm
3
of a sol uti on of sodi um hydroxi de of concentrati on 0. 21 2 mol dm-
3
was neutral i sed by 23. 4 cm
3
of a sol uti on of sul phuri c aci d. Cal culate the
concentrati on of the sul phuri c aci d sol uti on.
Answer Equati on: 2NaOH + H
2
S04 - Na
2
S04 + 2H
2
0
Step 1 amount of NaOH " 0. 21 2 x 25. 0/1 000 " 5.3 x 1 o-
3
mol
Step 2 amount of H
2
S04 " 5. 3 x 1 o-
3
x 1 /2 2. 65 x 1 o-
3
mol
Step 3 concentrati on of H
2
S04 " 2. 65 x 1 o-
3
mol /0. 0234 dm
3
" 0. 1 1 3 mol dm-
3
Concentration of solutions
Thi s is either: amount of solute (in mol es)
vol ume of solution in dm
3
or: mass of solute (in grams)
vol ume of solution in dm
3
Gas volume calculations
uni ts: mol dm-
3
uni ts: g dm-
3
1 For reacti ons where a gas is produced from solids or solutions,
fol low:
Step 1 Step 2 Step 3
Mass of A-.Moles of A Moles of gas B Vol ume of gas B
Step 1 use the relationshi p:
mol es mass/mol ar mass
Step 2 use the stoichiometric rati o from the equation:
moles of A moles of B ? ratio of B/ A
Step 3 use the relationshi p:
volume of gas B mol es of B ? mol ar vol ume
U
l0
I n Step 2 the stoi chi ometri c ratio i s
1 /2 as there i s 1 C0
2
mol ecul e for
every 2NaHC0
3
mol ecul es in the
equati on.
You must show al l the steps i n
you r cal cul ati ons
Don't c ut d own to two or t hree
si gn i fi cant fi gu res i n t he mi ddl e
of a cal c ul ati o n
Check every cal cul ati on to ensure
that you have entered the data
correctl y
STR UCTU R E, BON D I NG AN D MAI N G ROUP CH E M I STRY
Cal culate the vol ume of carbon di oxi de gas evol ved, measured at room
temperature and pressu re, when 7. 8 g of sodium hydrogen carbonate i s heated.
The mol ar vol ume of a gas i s 24 d m
3
mol-
1
at t he temperatu re and pressu re of
the experi ment.
Answer Equati on:
Step 1
Step 2
Step 3
2NaHC0
3
Na2C0
3
+ H20 + C02,g,
amount of NaHC0
3
" 7. 8/84 mol " 0. 0929 mol
amount of C02 ^ 0. 09286 mol x 1 /2 " 0. 0464 mol
vol ume of C02 ^ 0. 0464 mol x 24 d m
3
mol-
1
^ 1 . 1 dm
3
2 For calculati ons i nvolving gases only, a short cut can be used. The
vol umes of the two gases are i n the same ratio as their
stoichiometry in the equation.
+r/
What vol ume of oxygen is needed to burn compl etel y 15. 6 cm
3
of ethane?
Answer Equati on: 2C
2
H
6
,g, + 70
2
,g, 4C0
2
,g, + 6H
2
0, 1 ,
Cal culati on: vol ume of oxygen gas " ]_ " 3. 5
vol ume of ethane gas 2
vol ume of oxygen gas " 3. 5 ? 1 5. 6 " 54. 6 cm
3
Significant figures
You should always express your answer to the same number of significant
figures as stated in the question or as there are i n the data.
If you cannot work this out in an exam, give your answer to 3
signi ficant figures (or 2 decimal places for pH calculations), and you are
unl i kely to be penalised. Do not round up numbers i n the middl e of a
calcul ation. Any i ntermediate answers should be given to at least 1 more
signi ficant figure than your final answer.
-.
Before attempting questions on thi s topic, check that you can:
Calculate the empi rical formul a of a substance from the
% composition.
Write balanced i onic equati ons.
Calculate the number of mol es of a pure substance from its mass, of a
solute from the volume and concentration of its solution, and of a gas
from its vol ume.
. Calculate reacti ng masses and reacti ng gas vol umes.
. Use titration data to calculate the vol ume or the concentration of one
solution.
FOR M U LAE, EQUATI ONS AN D MOL ES
l l
a Pb
2
( aq) + 2cnaq) PbCI 2(S)

b Mg
2
(aq) + 20
W(aq)
Mg( OH)2(S)
c Cl-(aq) + Ag(aq) AgCI ( s)
d W(aq) + OW(aq) H20(1)
a 1 . 23/23 " 0. 0535 mol
b 4. 56/58. 5 " 0. 0779 mol
c 0. 789/24 " 0. 0329 mol
d 0. 1 1 1 x 0. 0321 " 3. 56 x 1 o-
3
mol
0. 0456/0. 222 " 0. 205 dm
3
" 205 cm
3
( 1 . 00/1 8) X 6. 02 X 1 0
23
3. 34 X 1 0
22
(1 .00/106) X6.02 X 1

? 2 " 1 . 1 4 X1 i
a 4. 44 g/0. 250 dm
3
" 1 7. 8 g dm-
3
b 4. 44/40 " 0. 1 1 1 mol
Therefore 0. 1 1 1 mol /0. 250 d m
3
" 0. 444 mol dm-
3
questi ons are on pages 1 21 -1 22.
_r ,... .--
For the first set of questions, cover the margi n, write down your an \er,
then check to see if you are correct.
The table below contai ns data which will help you.
Substance Solubility
Nitrates All soluble
Chlorides All soluble except for AgCl and PbCl2
Sodi um compounds Al l soluble
Hydroxides All i nsoluble except for Group 1 and
barium hydroxides
Write i onic equations for the reactions of solutions of:
a lead nitrate and potassium chl oride
b magnesi um chloride and sodium hydroxide
c sodium chl oride and si lver nitrate
d sodi um hydroxide and hydrochloric acid.
Calculate the amount ( i n moles) of:
a Na in 1 . 23 g of sodium metal
b NaCl in 4. 56 g of solid sodium chloride
c Cl2 in 789 cm
3
of chlorine gas at room temperature and pressure
d NaCl in 32. 1 cm
3
of a 0. 1 1 1 mol dm-
3
solution of sodi um chloride.
Calculate the vol ume of a 0. 222 mol dm-
3
solution of sodi um
hydroxide, which contains 0. 0456 mol of NaOH.
Calcul ate the number of water molecules i n 1 . 00 g of H20.
Calculate the number of sodium i ons in 1 . 00 g of Na2C0
3

4. 44 g of solid sodium hydroxide was dissolved i n water and the
solution made up to 250 cm
3
Calcul ate the concentration i n
a g dm-
3
b mol dm-
3

1 a An organic compound contains 82. 76% carbon and 1 7. 24%
hydrogen by mass. Calcul ate its empirical formul a.
b It was found to have a relative molecular mass of 58. Calculate its
molecul ar formul a.
2 Balance the equations:
a NH3 + 02 NO + H20
b Fe
3
+(aq) + Sn
2
+(aq) Fe
2
+(aq) + Sn
4
+(aq)
3 What mass of sodium hydroxide i s needed to react with 2. 34 g of
phosphoric(V) acid, H
3
P04, to form the salt Na
3
P04 and water?
4 What vol ume of 0. 1 07 mol dm
-3
potassi um hydroxide, KOH, solution is
needed to neutral ise 1 2. 5 cm
3
of a 0. 0747 mol dm-
3
solution of
sul phuric acid?
5 What vol ume, measured at room temperature and pressure, of hydrogen
sulphide gas, H2S, i s requi red to react with 25 cm
3
of a 0.55 mol dm-
3
J
c-bond
n-bond
Fig 1. 3 L and H bonds.
STRUCT U R E, BON D I NG AN D MAI N G ROUP CH E M I STRY
solution of bi smuth nitrate, Bi (N0
3
)
3
? The mol ar vol ume of a gas i s 24
dm
3
mor1 under these conditions. They react accordi ng to the equati on:
3H
2
S(g) + 2Bi (N0
3
)
3
(aq) - Bi
2
S
3
(s) + 6HN0
3
(aq) .
6 What volume of hydrogen gas i s produced by the reacti on of 33 dm
3
of
methane gas when it i s reacted wi th steam according to the equati on:
CH4(g) + H
2
0(g) - CO(g) + 3H
2
(g) ?
Structure and bondi ng
. .
You should be able to di stinguish between:
Chemi cal bonds
Ioni c
Covalent
Metal l i c
1
2
between separate i ons
which are divided into two types:
polar coval ent where the bondi ng pair of electrons
i s nearer to one atom
pure covalent where the bonding pair of electrons
i s shared equally
bondi ng caused by electrons delocal i sed
throughout the solid.
I ntermolecul ar forces (between coval ent mol ecules)
Hydrogen bonds - between 8+ H i n one molecule and 8- F, 0 or
N i n another molecule
Di spersion forces - between all mol ecules. Thei r strength
depends upon the number of electrons i n the
mol ecule.
Di pole/dipole forces - between o atoms in one molecul e and(
atoms in another molecul e.
_t-
An ionic bond is the electrostatic attraction that occurs between an
atom that has lost one or several electrons - the cation - and one that
has gained one or several electrons - the anion.
A covalent bond occurs when two atoms share a pair of electrons. It
results from the overlap of an orbital contai ni ng one electron belonging
to one atom with an orbital that contai ns one electron that belongs to
the other atom. The overlap can be head on, which results i n a c bond
or, side by side, which results i n an bond (see Figure 1 . 3) . A double
bond i s a c and a bond, with two pairs of electrons being shared.
A dative covalent bond i s a covalent bond formed when one of the
overlapping orbitals contained two electrons and the other none.
A metallic bond i s the force of attraction between the sea of
delocal i sed el ectrons and the positive ions which are arranged in a
regul ar l attice.
The electronegativity of an el ement i s a measure of the attracti on its
atom has for a pair of electrons in a covalent bond.
STRUCTU R E AND BON D I NG
I n hydrated cati ons, such as
[ Mg( H20)6(, the water mol ecul es
are bonded to the magnesi um i on by
dative coval ent bonds. Each oxygen
atom bonds wi th i ts l one pai r i nto
empty s and p orbital s in the Mg
2
+
lJ
A hydrogen bond is an i ntermolecular force that exists between a 8+
hydrogen atom in one molecule and a 8- fluorine, oxygen or
nitrogen atom i n another molecul e.
van der Waals forces are between covalent molecules and are caused
by dipole/dipole and induced dipole/i nduced dipole (dispersion) forces.
L-
i
on
_
.

_
t- .
I oni c substances wi l l be water
sol ubl e i f the energy requi red to
separate the i ons in the l atti ce
( l atti ce energy) i s compensated for
by the exothermi c nature of
hydrati on. Thi s i s the energy
rel eased when the very pol ar water
mol ecul es are attracted to the + and
- i ons.
I n HCI there are no hyd rogen bonds,
the di spersi on forces count for
about 80% of the total
i ntermol ecul ar forces, wi th
di pol e/di pol e accounti ng for the
remai ni ng 20%.
Ionic bonding
An i onic bond i s l i kel y if there is a l arge di fference (greater than about
1 . 5) in the el ectronegativities of the two atoms.
Cations wi th a small radi us and/or hi gh charge have a l arge charge
density, and so are very polarising. Ani ons with a large radi us and/or
high charge are very polarisabl e. I f either the cation is very polarising or
the anion i s very polarisable, the outer electrons in the ani on will be
pul led towards the cation and the bond wi l l have some coval ent
character.
Ioni c bondi ng gives rise to an ioni c l attice, which is a regular three
di mensional arrangement of i ons.
An ionic bond i s, on average, the same strength as a covalent bond.
Covalent bonding
Covalent substances are either:
i giant atomi c, such as diamond, graphite and quartz (Si02)
ii si mple mol ecular, such as I 2 and many organi c substances
iii hydrogen-bonded molecular, such as i ce, and ethanol
iv non-crystal l i ne, such as polymers l i ke poly(ethene) .
Polar covalent bonds may result in polar mol ecules, but for l i near
molecules of formul a AB2, planar molecul es of formul a AB3, tetrahedral
molecules of formul a AB
4
and octahedral molecules of formula AB6, the
polarities of the bonds cancel out, and the molecule i s not polar.
Intermolecular forces
The strongest i ntermolecular force is hydrogen bondi ng. In molecules
with many el ectrons, such as I21 the next strongest are induced
dipole/induced di pole forces (sometimes cal l ed dispersion forces) and, i n
most cases, the weakest are permanent dipole/permanent dipole (or
dipole/dipole) forces.
The strength of dispersion forces depends mai nly upon the number of
el ectrons i n the molecul e. Thi s i s why I 2 , wi th 1 06 electrons i s a solid,
whereas Cl
2
with 34 electrons is a gas.
Thi s explains the trend i n boi l i ng temperatures of the noble gases, as
the di spersion forces are l ess i n helium than i n neon than i n argon etc.
Li kewise the boi l i ng temperatures of the Group 4 hydrides i ncrease i n
t he Group from CH4 t o PbH4
The boil i ng temperatures of the hydrides of Groups S, 6 and 7 (see
Figure 1 . 4) can al so be explained. Because there i s hydrogen bonding
between HF molecules but not between the other hydrides i n the group,
HF has the highest boiling temperature. After the drop to HCl, there is a
steady upward trend in boiling temperatures from HCl to HI (i n spite of
a decrease i n the dipole/dipole forces) because the di spersion forces
i ncrease.
l4
400
350
300
250
K 200
1 50
100
50
0
NH3 PH3 AsH3
Group 5
Fig 1.4 Boiling temperatures of
Groups 3, and / hydrides
Do not say that the parti cles start to
vi brate, as they are vi brati ng even at
very l ow temperatures.
The stronger the force between
parti cl es, the more energy needed to
separate them and hence the hi gher
the mel ti ng temperatu re.
I t i s the bonds not the atoms that
repel .
Don't forget t o count t he n u mber
of l one pai rs.
K
SbH3
400 400
350 350
300 300
250 250
200 K 200
1 50 1 50
100 100
50 50
0 0
H20 H2S H2Se H2Te HF HCI HBr HI
Group 6 Group 7
If the number of electrons i n two different substances is about equal
and neither has hydrogen bonds, then di pole/dipole forces cause a
di fference in boi l i ng temperature. This is the case between butane
(34 electrons, non-polar, boil ing temperature - 0. 5 C) and propanone
(32 el ectrons, but polar, so boi l i ng temperature + 56. 2 C).
Effect of heat (melting)
When a solid is heated from room temperature unti l i t melts:
The particles (ions, molecules or atoms) vibrate more.
As the temperature ri ses the vibrations i ncrease unti l they become so
great that the forces between the particles are overcome, and the regul ar
arrangement i n the l attice breaks up. The substance i s then a l iqui d.
I n an ionic solid, such as NaCl , the vibrating particles are i ons whi ch
are held by strong forces of attraction, and so the i oni c solid has a high
melting temperature.
In a si mpl e molecular solid, such as iodine ( I2) or ice, the vibrating
particles are mol ecules which are held by weak van der Waal s or
hydrogen bonding forces of attraction, and so the solid has a l ow
mel ti ng temperature.
In a giant atomi c solid, such as di amond, the vibrating particles are
atoms which are held by strong covalent bonds, and so the solid has a
very high melti ng temperature.
Shapes of molecules
These are explained by the el ectron pai r repul sion theory which states:
i The electron pai rs arrange themselves as far apart from each other as
possible i n order to mi ni mi se repulsion.
ii The repulsion between l one pai rs is greater than that between a l one
pai r and a bond pair, which i s greater than that between two bond
pairs.
The number of O bond pairs of el ectrons and lone pairs i n the molecule
should be counted.
Any bond pairs should be ignored when working out the shape of a
molecul e.
STRUCTU R E AN D BON D I NG
2 bond pairs
linear
3 bond pairs
triangular
planar
4 bond pairs
tetrahedral
3 bond pairs -
.lone pair
pyramidal
2 bond pairs -
2 lone pairs
V-shaped
5 bond pairs
Trigonal
hi pyramid
6 bond pairs
octahedral
.
l
The total number of pairs of electrons i ndicates the arrangement of
the electrons.
2 = l i near
3 = triangular planar
4 = tetrahedral
S = trigonal bipyrami d
6 = octahedral
But the shape will differ i f any of the pai rs are lone pairs (see
Figure 1 . 5) .
4 pairs: 3 bond + 1 l one:
mol ecular shape i s pyramidal, e. g. NH
3
, or PCl
3
2 bond + 2 l one:
mol ecul ar shape i s bent or V-shaped, e. g. H20
6 pairs: 5 bond + 1 l one:
mol ecul ar shape i s a square-based pyrami d.
4 bond + 2 l one:
molecular shape i s square pl anar.
Shapes of ions
Negative ions have gained 1 electron for each negative charge.
?-
Thus S04 has 4 bonds (and 2 bonds) and no lone pairs around the
sulphur, and so the ion i s tetrahedral .
CO
/
- has 3 bonds ( and 1 bond) and no l one pai rs around the carbon,
and so it is triangul ar planar.
N0
3
- has one si ngle covalent, one dative covalent and one double covalent
bond (i. e. 3 and 1 :r) and no lone pairs around the ni trogen and so is
al so triangular planar.
Positive i ons have lost 1 electron for each positive charge.
Thus NH4+ has 4 bonds and no lone pairs around the nitrogen, and so is
tetrahedral
_-.
Fig 1.5 Shapes of molecules and ions Before attempting the questions on thi s topic, check that you understand:
the nature of i oni c, covalent and dative coval ent bonds
|
the effect of difference in electronegativity on type of bonding
that polar bonds may not give rise to polar molecul es
the effect of size and charge of i ons on the type of bonding
i ntermolecular forces such as hydrogen bonding and van der Waal s
the di fferent structures of solids and their properties
the trends i n boi l i ng temperatures caused by i ntermolecular forces
the nature of hydration of i ons
the changes i n moti on and arrangement of particles on change of state
a metal l i c bond
the shapes of molecules and i ons.
lb
.. .. .. === =
Anr
O and n
Al
3
, Mg
2
, Na, F,
N
3
-, 0
2
-
a Al
3

b Al
3

c Al
3

N
3
-
K
a u
b u
a F
b Cl
a Ca
b Na
a hydrogen fl uori de
b hydrogen fl uori de
c water
d al umi ni um chl ori de
HCI , H20, NH
3
, I CI , H2S
Xe ` Kr ` Ar ` Ne ` He
HCI
H2 0, NH
3
, HF, CH
3
0H, CH
3
NH2
=
questi ons are on pages 1 22-1 23.
STRUCT U R E, BON D I NG AND MAI N G ROUP C H E M I STRY
t ,...
For the first set of questions, cover the margin, write your answers, then
check to see i f you are correct.
State which types of bond are present in a double bond as in O=C=O.
State the value of the charge on the i ons of the fol l owing elements:
AI, Mg, Na, F, N, 0.
State which of the cations above:
a has the smal l est radius
b has the l argest charge density
c is the most polarising.
State which of the ani ons above i s the most polarisable.
Whi ch ion has the largest radi us: Lt or Na or K?
Whi ch of these three ions, Lt, Na+ or K, has:
a the largest surface charge density
b the largest polarising power?
Which i s the most electronegative element i n each l i st:
a C, 0, N, F
b Cl , Br, I ?
Which i s the l east electronegative element of:
a Be, Mg, Ca
b Na, Mg, Al ?
Which i s the mol ecul e i n each group with the most polar bond:
a HF, HCl, HBr
b HF, H20, NH
3
c H20, H2S, H2Se
d AlC1
3
, SiC14, PC15?
List all of the fol l owing molecules that are polar:
H
z
HCl H20 NH
3
CH4
C02 ICl H2S BH
3
CF4
Rearrange the noble gases in order of decreasing boi l i ng temperature:
Ar, He, Kr, Ne and Xe
State which of the fol lowing has the lowest boiling temperature:
HF, HCl, HBr, or HI
Which of the fol l owing form hydrogen bonds between their mol ecules?
H20 NH
3
HF HCl C02 CH4
CH
3
0H CH
3
NH
z
CH
3
F CHC1
3
CH2=CH2 poly( ethene)
1 Draw a diagram of two p orbital s overlapping which produce:
a
b
a O bond
a n bond
2 For each pair, state which i s the more covalent substance and give a
reason:
a AIF
3
or AlC1
3
b BeC12 or MgC12
@.-.--.AN D BON D I NG
3 I ntermolecular forces can be divided i nto three types:
a hydrogen bond
b dispersion (i nduced dipole/induced di pole)
c permanent di pole/permanent di pol e.
For al l the fol lowing substances state all the types of intermolecular
forces a, b and/or c that are present:
i HF ii I
2
iii HBr iv PH
3
v Ar
4 Solid structures can be divided into ix type :
a metallic, b giant atomi c (network co alent), c i onic,
d hydrogen bonded molecul ar, e si mpl e molecul ar, f polymeric.
l1
For each of the solids l i sted below, state the tructural type i n the sol i d.
i odi ne i ce, H
2
0(s) copper
si lica (sand), Si 0
2
dry ice, C0
2
(s) calcium oxide, Ca
poly( ethene) graphite sulphur
copper sulphate, CuS04 sucrose l ithi um fl uoride, Li F
5 Expl ai n the processes of mel ti ng and boi l i ng in terms of the
arrangement and motion of the particles.
6 State, for each of the fol l owing pairs, which has the stronger forces
between particles and hence has the higher boiling temperature, and
explain why i n terms of the types of force present:
a NH
3
or PH
3
b HCl or HBr
c CH
3
COCH
3
( propanone) or C4H
1 0
(butane)
d P- or S8
e NaCl or CC14
7 In order to work out the shape of a molecule or i on, you should first
eval uate the number of O bond pairs of el ectrons and the number of
lone (unbonded) pairs of el ectrons around the central atom.
Construct a table si mi l ar t o that shown below, and use i t t o deduce the
shapes of the fol l owing species.
SiH4, BF
3
, BeC1
2
, PC1
3
, SF6, XeF4, NH/, PC16-
Molecule/ Number of Number of Total number Shape
i on O bond pairs lone pairs of el ectron pairs
NH
3
3 1 4 pyrami dal
8 Expl ai n why sol id sodi um metal conducts electricity whereas solid
sodium chloride does not.
lb
There are two excepti ons with the
fi rst 40 el ements. Because of the
extra stabi l ity of a hal f fi l l ed or f ul l
set of d orbi tal s, chromi um i s [Ar]
4s\ 3d
5
, and copper i s [Ar] 4s
1
, 3d
1
0
.
The more el ectrons i n the mol ecul e,
the stronger the di spersi on force
and the hi gher the mel ti ng or boi l i ng
temperatu re.
STRUCTU R E, BON D I NG AN D MAI N G ROU P CH E M I STRY
The mel ti ng and boi li ng temperatures of the elements depend on the
type and strength of the bond or intermolecular force between particles.
There are trends in physical and chemical properties across a Period and
down a Group. For i nstance
1 Elements show decreasing metal l i c character across a Period.
2 Elements show increasing metall i c character down a Group.
t- .
Electronic structure
The el ements in the Periodic Table are arranged in order of atomi c
number, so each el ement has one more proton and hence one more
electron than the previous element.
Elements i n the same group have the same number of electrons i n their
outer shell s. These are called the valence electrons.
El ements i n the same Period have the same number of shel l s contai ni ng
electrons so their outer or valence electrons are in the same shell .
The order i n which el ectrons fil l the orbital types i s:
ls; 2s, 2p; 3s, 3p; 4s, 3d, 4p; Ss, 4d, Sp; 6s (see Figure 1 . 1 on page 3)
Melting (and boiling) temperatures of the Period 3
elements (Na to Ar)
The melting temperature depends upon the strength of the forces
between particles that separate during melting (or boil i ng) .
These particles may be:
i metal i ons in a sea of el ectrons in metals
ii covalently bonded atoms i n a giant atomi c structure
iii molecules with i ntermol ecular forces between them in si mpl e
molecul ar sol i ds.
To understand the trends i n mel ti ng temperatures, you shoul d first
decide what type of bonding or force i s between the particles.
I f the solid i s metallic: the greater the charge density of the i on in the
lattice, the stronger the force hol ding the lattice together and so the
higher the melting temperature.
If the solid i s a giant atomic l attice: the covalent bonds throughout
the lattice are strong and so the solid has a very high melting
ter perature.
I f the solid i s a simple molecular substance: the mel ti ng (or boi l i ng)
temperature depends upon the strength of dispersion ( induced
dipole/i nduced di pol e) force between the molecul es.
I n Peri od 3, sodi um, magnesi um and al umi ni um are metallic, si licon
forms a giant atomi c lattice, and phosphorus, P4, sul phur, 58, chlorine,
Cl2 and argon, Ar, al l form si mpl e molecular solids.
TH E PE RI ODI C TAB L E I
questi ons are on page 1 23.
l5
Electrical conductivity
Sol i ds conduct electricity by the flow of delocal i sed electrons.
Thus metals conduct electricity. Graphite al so conducts, but only i n the
plane of the layers. This i s due to the n-electrons that are delocali sed above
and below the layers.
_-.
Write the electroni c structure for elements numbers 1 to 36.
Expl ai n the variation of melting and boil ing temperatures for the
elements i n Period 3.
Expl ai n the change i n electrical conductivity of the elements in
Period 3.
Expl ai n the variation i n i oni sation energies of the elements i n Period 3.
_t ,...
1 What, in terms of electroni c structure, are the features that the
fol lowing have i n common:
a members of the same group , e. g. Group 2,
b members of the same period, e. g. Period potassium to krypton?
2 State the type of solid structure of the elements l i sted. Give your
answer as one of:
metall ic, giant atomic, i oni c, hydrogen bonded molecular, si mpl e
molecular, polymeric:
a hydrogen b sodium c si l i con d sulphur
e chlorine f argon.
3 Expl ain the difference i n melting temperatures of the fol lowing
elements:
Element Na Mg Si l
S
s
Cl
2
Melting temperature/C 98 650 1 41 0 44 1 1 3 -1 01
4 The i oni sation energies of sodi um and magnesi um are l i sted below:
Element 1 st i oni sation energy/kJ mor
1
2nd i oni sation energy/kJ mor1
Sodi um 494 4560
Magnesi um 736 1 450
a Explain the meaning of: i nuclear charge, ii screeni ng (or shielding)
by inner electrons.
b Use the concepts expl ained in (a) to explain why: i The 2nd
i oni sation energy of sodium is very much more than i ts 1 st
i oni sation energy. ii The 1 st ionisation energy of sodi um is less than
the 1 st i oni sation energy of magnesi um.
OIL RIG
I n an overal l equati on, the total
i ncrease in oxi dati on number of one
el ement (i ncrease x nu mber of
atoms of that el ement) must equal
the total decrease i n oxi dati on
n umber of another el ement.
STRUCT UR E , BON D I NG AN D MAI N G ROU P C H E M I STRY
I ntroduct i on to oxi dat i on and
reduct i on
.
Redox reacti ons are those which i nvolve a transfer of electrons
Remember OIL RIG (Oxidation Is Loss, Reduction Is Gain of electrons)
_t-
Oxidation occurs when a substance loses one or more electrons.
There i s an i ncrease i n t he oxidation number of t he element i nvolved.
An oxidising agent i s a substance that oxi di ses another substance
and so i s itself reduced. The half equation i nvolving an oxidising agent
has electrons on the left-hand side, i . e. i t takes electrons from the
substance being oxidised.
Reduction occurs when a substance gai ns one or more electrons.
There i s a decrease i n the oxidation number of the element i nvolved.
A reducing agent i s a substance that reduces another substance and
so i s itself oxidised. The hal f equation i nvolving a reducing agent has
electrons on the right-hand si de, i . e. it gives electrons to the substance
being reduced.
_t- .
Oxidation number
The oxidation number i s the charge on an atom of the el ement in a
compound calculated assumi ng that al l the atoms in the compound are
si mple monatomi c ions. The more electronegative element i s given an
oxidation number of -1 per bond.
There are some rules used for calculati ng oxidation numbers. They
should be applied i n the fol lowing order:
1 The oxidation number of an uncombi ned element is zero.
2 A si mpie monatomic i on has an oxidation number equal to its
charge.
3 The oxidation number of Group 1 metals is always + 1 , and of
Group 2 metals i s +2.
4 Fl uorine always has an oxidation number of -1 , hydrogen (except
in metal l i c hydrides) of +1 , and oxygen (except in F20 and
peroxides) of -2.
5 The sum of the oxidation numbers in a molecule adds up to 0, and
those i n a polyatomic i on (such as SO,)add up to the charge on
the ion.
When an element is oxidised, its oxidation number i ncreases.
I NTRODUCTI ON TO OX I DATI ON AN D R E DUCT I ON
Remember that an oxi di si ng agent
becomes reduced (l oses el ectrons) ,
and a red uci ng agent becomes
oxi di sed.
Hal f equati ons must bal ance for
atoms and for charge.
For exampl e, both si des of the 0|
equati on add up to -5.
If the questi on asks for the overal l
equati on for t he reacti on of A wi th B,
make sure that both A and B appear
on the left-hand si de of the fi nal
overal l equati on.
Cal cul ate the oxi dati on number of chl ori ne i n Cl2, Cl-, MgCI 2 and Cl 0
3
-.
Answers: i n Cl 2 " 0 (uncombi ned el ement: rul e 1 )
i n Cl- ^ -1 (monatomi c i on: rul e 2)
in MgCI 2 " -1 (Mg is 2+; ( +2) +2CI ^ 0; therefore each Cl is -1 :
rul es 3 and 5)
in Cl 0
3
- " +5 (CI + 3 x (-2) " -1 : rul es 4 and 5)
Half equations
These are written:
ei ther as reducti on wi th electrons on the l eft si de of the half equation,
e. g. Cl
2
(g) + ze- - zcr (aq)
here chlorine is being reduced and so i s acting as an oxidising agent.
or as oxidation with el ectrons on the ri ght side of the equati on,
e. g. Fe
2
(aq) - Fe
3
(aq) + e-
here iron( I I ) i ons are being oxidised, and thus are acting as a reducing
agent.
Many oxidi si ng agents only work i n aci d solution. Thei r half equations
have H
+
i ons on the left hand side and H
2
0 on the right. This i s l i kely
with oxdising agents contai ni ng oxygen (such as Mn04-),
+
2
+
e. g. Mn04-(aq) + 8H (aq) + Se- - Mn (aq) + 4H
2
0(l )
I f a redox system i s i n al kal i ne sol uti on, OH- may need to be on one
side and H
2
0 on the other,
e. g. ce
+
(aq) + 80H-(aq) - CrOt + 4H
2
0( l ) + 3e-
Overall redox equations
Overall redox equations are obtained by adding hal f equati ons together.
One half equation must be written as a reduction (electrons on the l eft)
and the other as an oxidation (electrons on the right) .
When they are added the electrons must cancel . To achieve thi s it may
be necessary to multiply one or both hal f equati ons by integers,
e.g. for the overal l equation for the oxidation of Fe
2
ions by Mn04-
i ons
add Mn04-(aq) + 8H.(aq) + Se- - Mn
2
(aq) + 4H
2
0(l )
to 5 ? Fe
2
(aq) - Fe
3
(aq) + e-
STR UCTU R E, B ONDI NG AN D MAI N GROUP CH E M I STRY

-.
Before attempting the questions on this topic, check that you can:
Define oxidation and reducti on.
Define oxidising agent and reducing agent.
Calculate oxi dation numbers i n neutral mol ecul es and i n i ons.
Write i oni c hal f equations.
Combine half equations and so deduce an overal l redox equation.
_t ,,..,. ,
a i odi de i ons
b none
c zi nc
d i ron(l l ) i ons
+4 -2
+6 +6
-1 +6 2(1 at +2 and 2 at +3;
average 2)
For the fi rst set of questions, cover the margin, write your answer, then
In the fol lowing equations, state which substance, i f any, has been
oxidised:
a 2Ce-+ (aq) + zr (aq) 2Ce
3
+ (aq) + 12 (aq)
b H+ (aq) + OH
-
(aq) H20 ()
c Zn (s) + 2H+ (aq) Zd+ (aq) + H2 (g)
d 2Fe
2
+ (aq) + 2Hg
2
+ (aq) 2Fe
3
+ (aq) + Hg2
2
+ (aq)
Calculate the oxidation number of the elements i n bold i n the
fol lowi ng:
S02, H2S,
Cr0-
2
-,
H
zOz
,
1 Construct i oni c half equations for:
a Sn
2
+ i ons being oxidi sed to Sn
4
+ ions in aqueous solution
b Fe
3
+ i ons being reduced to Fe
2
+ ions in aqueous solution.
c Now write the balanced equation for the reaction between Fe
3
+ and
Sn
2
+ i ons i n aqueous solution.
2 Construct i onic hal f equations for:
a hydrogen peroxide being reduced to water i n acid solution
b sulphur being reduced to hydrogen sulphide in acid solution
c Now write the balanced equation for the reacti on between
hydrogen peroxide and hydrogen sulphide in acid sol ution.
3 Construct i oni c hal f equations for:
a Pb02(s) being reduced to PbSOis) in the presence of H2S04(aq)
b PbS04 (s) being reduced to Pb(s) in the presence of water
c Now write the balanced equation for the reaction between Pb02
and lead in the presence of dilute sulphuric acid.
GROUP 1 AN D G ROUP 2
_th
heat i n
l ight out
3
rd --
Fig 1.6 Emission of a spectr/ line
J
Group and Gro p
Introduction
The properties of elements and their compounds change steadily down
a Group.
Thi s means that the answer to a question about whi ch i s the most/least
reactive, easiest/hardest to decompose, most/least soluble, etc. will be
an element, or a compound of that element, either at the top or at the
bottom of the Group.
Down a Group the elements become i ncreasi ngly metalli c in character.
Thus:
thei r oxides become stronger bases
they form positive ions more readi ly
they form covalent bonds less readi ly.
t- .
Physical properties of the elements
Group 1 : All are solid metals; their melti ng temperatures and hardness
decrease down the group; all conduct electricity.
Group 2: All are solid metals; their melting temperatures and hardness
decrease down the group (except magnesium which has a lower
melti ng temperature than calcium); all conduct electricity; thei r melting
temperatures are higher than the Group 1 element in the same period.
Flame colours of their compounds
Group 1 : l ithi um
sodium
potassium
Group 2: calcium
carmi ne red
yellow
lilac
brick red
stronti um cri mson red
barium green.
These colours are caused because:
1 Heat causes the compound to vaporise and produce some atoms of
the metal with electr<ns i n a higher orbital than the ground state
(e.g. in the 4th shell rather than the normal 3rd shell for sodi um).
2 The electron fal l s back to its normal shel l and as i t does so, energy i n
t he form of visible light i s emitted. The light that is emitted i s of a
characteristic frequency, and hence colour, dependent on the energy
level difference between the two shells ( see Figure 1 . 6) .
Ionisation energies
The value of the 1 st ionisation energy for Group 1 and of the 1 st and
2nd i oni sation energies for Group 2 decreases down the group. This i s
4
The vi gour of the reacti on i ncreases
down the group.
The rate of reacti on i ncreases down
the g roup.
because as the atoms get larger, the outer electrons are further from the
nucleus and so are held on less firmly. The i ncrease i n nuclear charge is
compensated for by an i ncrease i n the shielding by the i nner electrons.
Reactions of the elements with oxygen
Group 1 : All burn.
Li thi um forms an oxide: 4Li + 02 - 2Li20
Sodi um forms a peroxide: 2Na + 02 - Na202
Potassi um and the others form a superoxi de: K + 02 - K02
Group 2: All burn to form i oni c oxides of formula MO, except that i n
excess oxygen barium forms a peroxide ( Ba02) .
2Ca + 02 - 2Ca0
Reaction of the elements with chlorine
Group 1 : All react vigorously to form i oni c chlorides of formul a MCI .
These dissolve i n water to produce hydrated i ons, e. g.
NaCl (s) - Na (aq) + Cr
aq)
Group 2: All react vigorously to produce i oni c chlorides of formula
MC12, except that BeCl2 is covalent when anhydrous. All Group 2
chlorides are soluble in water producing hydrated i ons of formula
[M( H20)6t. Beryll i um chloride gives an acidic solution because of
deprotonati on:
[Be(H20)6]
2
+ H20 [ Be(H20)s(OH)r + H
3
o
Reaction of the elements with water
Group 1 : Al l react vigorously with cold water to give an alkali ne
solution of metal hydroxide and hydrogen gas, e. g.
2Na(s) + 2H20(l) - 2NaOH(aq) + H2(g)
Group 2: Beryl l i um does not react but magnesium burns in steam to
produce an oxide and hydrogen:
Mg + H20 - MgO + H2
the others react rapidly with cold water to form an alkal i ne suspension
of metal hydroxide and hydrogen gas:
Ca + 2H20 - Ca(OH)2 + H
2
Reactions of Group 2 oxides with water
BeO is amphoteric and does not react with water.
MgO is basic and reacts slowly with water to form a hydroxide.
All the others react rapidly and exothermically to form al kal i ne
suspensions of the hydroxide, which have a pH of about 1 3.
CaO + H20 - Ca(OH)2
Solubilities of Group 2 sulphates and hydroxides
Sulphates: their solubi l ities decrease down the group. BeS04 and MgS04
are soluble; CaS04 is sl ightly soluble, SrS04 and BaS04 are i nsoluble.
Hydroxides: their solubilities increase down the group. Be(OH)2 and
Mg(OH)2 are i nsoluble, Ca(OH)2 and Sr(OH)2 are sl ightly soluble, and
Ba(OH)2 i s fairly soluble.
Addition of aqueous sodium hydroxide to solutions of Group 2 salts
produces a white precipitate of metal hydroxide. (Barium produces a
fai nt precipitate) :
GROUP \ AN D GROUP 2
The compound is more l i kel y to be
decomposed on heati ng i f the cati on
pol ari ses the ani on. Thus
Group 2 compounds (cati on 2+)
decompose more readi l y than Group
1 compounds (cati on onl y 1 +) .
Compounds of metal s hi gher i n a
group (smal l er i oni c radi us)
decompose more easi l y than
compounds of metal s l ower i n the
Group.
Li thi um
K i s + 1 , Ca i s +2
I t i s extremel y i nsol ubl e.
Addition of aqueous sulphate i ons to a solution of Sr
2
+ or Ba
2
+ i ons
produces a white preci pi tate of metal sulphate:
Ba
2
+(aq) + SO/-(aq) BaS04(s)
Thermal stability of nitrates and carbonates
Thermal stability increases down both groups:
Group 2 nitrates all decompose to give a metal oxide, brown fumes of

nitrogen dioxide, and oxygen:
2Ca(N0
3
)
2
2Ca0 + 4N0
2
+ 0
2
Group 1 ni trates, except li thi um ni trate, decompose to give a metal
ni trite and oxygen:
2NaN03 - 2NaN0
2
+ 0
2
but 4LiN0
3
2Li
2
0 + 4N0
2
+ 0
2
Group 2 carbonates all decompose (except barium carbonate which i s
stable to heat) to give a metal oxide and carbon dioxide:
CaC03 - CaO + CO:
Group 1 carbonates are stable to heat except for lithium carbonate:
Li
2
CO - Li
2
0 + C

.
Before attempting the questions on thi s topic, check that you know:
the physi cal properties of the Group 1 and Group 2 elements
the flame colours caused by their compounds
the trends i n i oni sation energies withi n a group
the reacti ons of the elements with oxygen, chlorine and water
the reactions of their oxides with water
the oxidation states of the elements in Group 1 and in Group 2
the trends in solubilities of Group 2 sulphates and hydroxides
the reason for the trend in thermal stabi l i ty of Group 1 and Group 2
ni trates and carbonates.
_r ,...
For the first set of questions, cover the margin, write your answer, then
check to see if you are correct.
Which Group 1 metal has the highest melting temperature?
What is the oxidation number of:
i potassi um in K
2
Cr
2
0
7
and
ii calcium in CaC03?
Barium compounds normally are poisonous, but barium sulphate i s
given t o people i n order to outline thei r gut i n radiography (X-ray
i maging) . Why i s bari um sulphate not poisonous?
b
1 You are given solid samples of three chlorides. One i s li thi um chloride,
one i s potassi um chloride and the other i s barium chloride. Describe the
tests that you would do to find out whi ch was which.
2 Explain why sodium compounds give a yellow colour in a fl ame.
3 Explai n why the 1 st i oni sation energy of sodi um i s larger than the 1 st
i oni sation energy of potassi um.
4 Write balanced equati ons for the reacti ons of:
a calci um with oxygen
b calcium with water
c potassi um with water
d magnesi um with steam.
5 Explain why the addition of di lute sodium hydroxide to a solution of
magnesi um chloride produces a white precipitate, but little or no
precipitate when dilute sodium hydroxi de is added to a solution of
barium chloride.
6 State and expl ai n which Group 2 element forms the least thermally
stable carbonate.
7 Write balanced equati ons for the thermal decomposition of the
fol lowing, but i f there i s no reacti on at laboratory temperatures, say so:
a l i thi um ni trate, sodium nitrate and magnesi um nitrate
b sodi um carbonate, magnesium carbonate and bari um carbonate.
GROUP ( CH LOR I N E TO I OD
.
I N E )
1
Group ( ch l ori ne to i od i ne)
_ .
Group 7 characteristics are that:
The hal ogens are oxidi si ng agents with their strength decreasi ng down
the group.
1 Chlorine i s t he strongest oxidising agent and iodine i s the weakest.
2 Chloride ions are the weakest reducing agents, and so are the hardest
to oxidi se, whereas iodide ions are the strongest reducing agents, and
so are the easiest to oxidise.
They form hali de ions, such as cr, and oxoani ons, such as Cl 03-.
Solutions of the hydrogen hali des are strong acids.
t- .
Disproportionation
This occurs when an element is si multaneously oxidised and reduced. It
fol lows that there must be at least two atoms of that element, with the
same oxidation number, on the left of the equation, and that the element
must be able to exist i n at least three different oxidation states.
Chlorine disproportionates i n alkal i :
Cl2 + zoH- - cr
+ ocr
+ H20
(0) (-1 ) (+1 )
Physical properties (at room temperature)
Chlorine is a greeni sh gas.
Bromi ne a brown li qui d.
Iodi ne is a dark grey lustrous soli d which gives a violet vapour on
heating.
A solution of iodine i n aqueous potassi um i odide i s red/brown, and in
non-oxygen-contai ni ng organi c solvents i t i s violet.
Tests for the elements (only examined at AS in Unit
Test 3B)
First observe the colour of the halogen or its soluti on.
Chlorine rapidly bleaches damp l i tmus paper. I t will di splace bromi ne
from a solution of potassi um bromide (then test for bromi ne by adding
a suitable organi c solvent such as hexane, which wi l l show the brown
bromi ne colour) .
Bromine is brown and will (slowly) bleach li tmus. It will displace iodine
from a solution of potassi um iodide (then test for iodine with starch or
hexane as below) .
Iodi ne turns a solution of starch blue-black, and it forms a violet
solution when di ssolved in suitable organi c solvents such as hexane.
b
Chl ori ne is a stronger oxi di si ng
agent than bromi ne, whi ch i s
stronger than i odi ne.
STR UCTU R E , BON D I NG AN D MAI N G ROUP C H E M I STRY
Halides
All hydrogen halides are covalent gases, but are soluble in water because
they react with water to form i ons. Thei r solutions are strongly acidic:
HCl + H20 H
3
0 (aq) + Cr(aq)
Hydrogen fluoride i s a weak acid and is only partially i oni sed.
All metal halides are soluble i n water, except for si lver and lead halides.
Test for halides (only examined at AS in Unit Test 3B)
To a solution of the halide add dilute nitric acid to prevent carbonates
from i nterfering with the test. Then add silver nitrate solution followed by
ammoni a soluti on.
Chloride Bromide Iodide
Addition of Ag(aq) white precipitate cream preci pita te yellow precipitate
Addition of
dilute NH
3
precipitate di ssolves no change no change
Addition of
concentrated NH
3
precipitate dissolves precipitate dissolves no change
Addition of concentrated sulphuric acid to the solid
halide
Chlorides produce steamy acid fumes of HCl.
Bromi des produce steamy aci d fumes of HBr with some brown bromi ne
and some so2 gas.
Iodides give clouds of violet i odi ne vapour.
Thi s is due to the fact that HBr is j ust powerful enough as a reducing agent
to reduce some of the concentrated sulphuric acid to sulphur dioxide and
itself be oxidised to bromi ne.
The HI i nitially produced i s a very powerful reducing agent. I t reduces the
concentrated sul phuri c aci d and i s i tsel f oxidised to i odi ne.
Oxidation numbers
Chlorine is 0 in Cl2.
Chlorine i s -1 i n chlorides.
Chlorine i s + 1 i n Clo- ions.
Chlorine i s +5 i n Cl O ions.
Redox
Chlorine is a powerful oxidising agent and is reduced to the -1 state.
The half equation i s:
Cl2(aq) + 2e- 2Cr(aq)
and i s si mi lar for the other halogens.
Chlori ne di sproportionates i n alkali at room temperature:
Cl2(aq) + 20H-(aq) Craq) + OCr(aq) + H20(1)
(0) (-1 ) (+1 )
Chlorate(!) compounds disproportionate when heated:
3ocr zcr + Clo
3
-
3x(+1 ) 2x(-1 ) (+5)
Bromi ne i s extracted from seawater by bubbling i n chlori ne gas whi ch
oxidises the Br- i ons.
G ROUP ( CH LOR I N E TO I OD I N E )
5
Ad:
Bromi ne
Add starch. The sol uti on goes bl ue-
bl ack.
Chl ori ne
Hydrogen i odi de
-.
Before attempting questions on thi s topic, check that you can recal l :
the physical properties of the elements
the tests for the elements and for the halides
the reactions of concentrated sulphuric acid with the halides
examples of -1 , 0, + 1 and +5 oxidation states of chlorine and the
disproportionation of chlorine and chlorate(!) ions
the relative strengths of the halogens as oxidising agents.
t ,...
check to see if you are correct .
are the halogen that is a liquid at room temperature.
Describe the test for i odi ne.
Which of Cl2, Br2 and 12 i s the strongest oxi di si ng agent?
Which of HCl, HBr and HI is the strongest reducing agent?
1 Why is hydrogen chloride gas very soluble in water?
2 I t i s thought that a sample of solid sodium carbonate has been
contaminated by some sodium chloride. How would you test for the
presence of chloride ions in this sample?
3 Explai n why hydrogen chloride gas i s produced but chlorine i s not
when concentrated sulphuric acid i s added to solid sodium chloride,
whereas iodine and almost no hydrogen iodide i s produced when
concentrated sulphuric acid i s added to solid sodi um iodide.
4 Define disproporti onation and give an example of a di sproportionation
reacti on of chlorine or a chlorine compound.
JU
STR UCT U R E, BON D I NG AN D MAI N G ROUP C H E M I STRY
PrucrIce Tesr: tuIrI
Time allowed 1hr
All questions are taken from parts of previous Edexcel Advanced GCE questi ons.
The answers are on pages 1 25-1 26.
1 a Complete and balance the fol lowing equations.
i Ca + O
z
ii Na20 + H20
iii Na20 + HCl
[1]
[1]
[2]
b State and explain the trend in thermal stabi li ty of of the carbonates of the Group 2 elements as the
group i s descended. [3]
(Total marks)
[May 2002 Unit Test 1 question 2]
2 a State the structure of, and the type of bonding i n, the fol lowing substances. Draw labelled
diagrams to i l lustrate your answers.
i Graphite
ii Sodi um chloride
b Expl ai n why both graphite and sodium chloride have high melti ng temperatures.
c i Expl ai n why graphi te is able to conduct electricity in the solid state.
ii Explai n why sodi um chloride conducts electricity in the li qui d state.
[4]
[3]
[3]
[2]
[1]
(Total 13 marks)
3 a i Define the terms atomic number and mass number [2]
ii Identify the particle that contains 35 protons, 44 neutrons and 34 electrons.
[1]
Bromine consists of two i sotopes of mass numbers 79 and 8 1 . A sample of bromi ne gas, Br21 was
exami ned in a mass spectrometer. The mass spectrum showi ng the molecular i ons i s given below.
Pc|ativc
intcnsity
! 00
50
! 58 ! 60 ! 62
b i Explai n how the molecules in the sample are i oni sed.
ii State how the resulting i ons are accelerated.
iii Identify the speci es responsible for the peak at m/e 1 60.
[2]
[1]
[1]
(Total marks)
[Januar 2001 CH1 question 1 & June 2001 Unit Test 1 question 3]
4 Hydrogen forms compounds with most non-metallic elements and with some metal s.
a Calculate the empi rical formula of the compound used in the manufacture of artifi ci al rubber, which
has the following composition by mass:
hydrogen 1 1 . 1 % carbon 88. 9% [3]
b The boiling temperatures of hydrogen chloride and hydrogen iodide are:
hydrogen chloride -85 oc Hydrogen iodide -35 oc
Explain why hydrogen iodide has a higher boi l i ng temperature than hydrogen chloride
[2]
c Draw and expl ai n the shapes of:
i the PH
3
molecule
[2]
ii the Al H4- i on.
[2]
PRACTI CE TEST: U N I T \
d Calculate the number of molecules in 8. 0 cm
3
of gaseous phosphine, PH3 at room temperature
and pressure.
(The molar volume of a gas at room temperature and pressure should be taken as 2. 4 ? 1 0

cm
3
mor1
The Avogadro constant i s 6. 0 ? 1 0
23
mor1 . ) [2]
Jl
(Total 11 marks)
ranuar 200I CHI question 2]
5 a Hydrogen sul phide is produced when concentrated sulphuric acid is added to solid sodi um iodide, but
sul phur dioxide i s produced when concentrated sul phuric acid is added to solid sodium bromi de.
i Complete the fol lowing tabl e:
Compound Formul a
Sulphuric aci d
Hydrogen sul phide
Sulphur dioxide
Oxidation state of sulphur i n the compound
[3]
ii Use your answers to a part i to suggest which of the ions, iodide or bromide, ha the greater reducing
poweL
[
b i Write an ionic half-equation to show the oxidation of chloride ions, cr, to chlorine, Cl
2

[ 1]
ii Write an ionic half-equation to show the reducti on of chlorate(!) ions, OCr, to chloride ions, i n
acidic solution. [2]
iii Bleach is a solution of chlorate(!) i ons and chloride i ons. Combine the two ionic hal f-equati ons
above to produce an equation which shows the effect of addi ng aci d to bl each.
[ 1]
6 a Complete the fol l owing for the element sulphur
Number of electrons i n the 1 st shell *
Number of electrons in the 2nd shel l =
Number of electrons in the 3rd shell
(Total 9 marks)
[May 2002 Unit Test I question 7
[1]
b Write one equation i n each case to represent the change occurring when the fol l owing quantities are
measured.
i The first electron affini ty of sulphur [2]
ii The fi rst i onisation of sul phur. [1]
c The graph below shows the l ogarithm of the successive i oni sation energies of sul phur plotted agai nst the
number of the electron removed. Account for the form of the graph i n terms of the electronic structure
of sulphur.
6. 00
5. 50~
5. 00~
4. 50
._ 4. 00~
.2
^
50
`
g
^
.00~
_ 2. 50~
2. 00
0 : + - s !
0 !
2 !
4 !
6 ! 8
Numbcrof clcctron rcmovcd
d One of the chlorides of sul phur is sul phur dichloride, SC12 It is a l iquid at room temperature; the
electronegativity of S i s 2. 5 and that of chlorine i s 3. 0
[3]
i Draw a dot and cross diagram to show the bonding in SC12 [2]
ii The shape of the molecule is bent (V-shaped) . Explain why the molecul e has thi s shape.
[2]
iii State, with reasons, whether SC12 is a polar molecule overal l . [2]
(Total 13 marks)
ranuar 2002 CHI question 2 & May 2002 Unit Test I question 4]
Z :_+oa_o
/eur
Energeti cs I
_ .
I t fol l ows from thi s defi niti on that
the enthal py of formati on of an
el ement, i n i ts standard state, i s
zero.
You shoul d al ways give an equati on
as an exampl e for thi s and other
enthal py defi ni ti ons.
State symbols shoul d always be used i n equati ons i n thi s topic.
I n defi nitions i n thi s topic, there are three points to note:
1 the chemical change that is taking place
2 the condi ti ons
3 the amount of substance (reactant or product) .
It always helps to add an equation with state symbols as an example,
because this may gain marks lost by omi ssion i n the word defi ni tion.
It is assumed for si mpl icity that the value of Hi s an i ndi cator of the
di rection of a chemical reacti on. The more exothermic the reaction, the
more l i kely it i s to take place, but other factors, such as activation
energy (see page 44), also determi ne whether the reaction happens.
t-
r Standard conditions are:
gases at a pressure of 1 atmosphere
a stated temperature (usually 298 K)
solutions, i f any, at a concentration of 1 . 00 mol dm-
3
substances in their most stable states, e. g. carbon as graphite not
diamond.
Standard enthalpy of formation, Mf1 i s the enthalpy change, under
standard conditions, when one mole of a compound i s formed from
its elements i n their standard states, e.g. M1 -e for ethanol is the
enthalpy change for the reacti on:
2C(graphite) + 3H2 (g) +
'
120
2
(g) C2H50H(l )
Standard enthalpy of combustion, Mc-e i s the enthalpy change, under
standard conditions, when one mole of a substance i s completely
burned in oxygen, e. g. Mic-e for ethanol is the enthalpy change for the
reacti on:
C2H50H(l) + 302 (g) 2C02(g) + 3H20(l )
Standard enthalpy of neutralisation _ of an acid i s the enthalpy
change, under standard conditions, when the acid is neutralised by
base and one mole of water is produced, e. g. _ of sulphuric acid,
by sodium hydroxide solution, i s the enthalpy change for the reacti on:
'12H2S04(aq) + NaOH(aq)
'
12Na2S04(aq) + H20(l)
E N E RG ETI CS I
Route 1
A'
<
B
,

L l
Route 2
Fig 2. 3 A reaction cycle
for hydrochloric acid the enthalpy change is for the reaction:
HCl (aq) + NaOH(aq) NaCl(aq) + H20(1)
for any strong acid being neutral i sed by any strong base, the
enthalpy change i s for the reacti on:
H
(aq) + OH-(aq) H20(1) L = -5 7 kJ mor
1
JJ
Average bond enthalpy. This is the average quantity of energy
requi red to break one mole of covalent bonds in a gaseous species
(at one atmosphere pressure). It is always endothermic, e. g. the
C-H bond enthalpy i n a gaseous compound i s the enthalpy change for
the reacti on:
C-H(i n compound)(g) C(g) + H(g)
An exothermic reaction gets hot, o that heat is then given out to the
surroundings. For all exothermic reactions is negative (see
Figure 2. 1 ) . Thi s means that chemi al n r ' i being converted i nto
thermal ( heat) energy.
An endothermic reaction gets cold, o that heat i then taken in from
the surroundings. For all endothermi c reactions is positive
(see Figure 2. 2) .
1 Reactants
Enthalp
Products
- ----
Fig 2. 1 Enthalpy diagram for an
exothermic reaction
Products
Enthalpy
Reactants
Fig 2.2 Enthalpy diagram for an
endothermic reaction
Hess's Law. The enthalpy change for a given reaction is independent
of the route by which the reaction i s achieved (see Figure 2. 3) .
Thus the enthalpy change proceeding directly from reactants to
products is the same as the sum of the enthalpy changes of al l the
reactions when the change is carried out i n two or more steps.
! = !
I
+ tz + !
3
r- .
Calculation of !l reaction from ^ data
You can use the expressi on:
/eaction
= the sum of
torrati
on of products - the sum of H
o
rmati
on
of reactants
Remember that if you have two moles of a substance, you must double
the value of its !H.
The enthalpy of formation of an element (in its standard state) i s zero.
J4
A/,- A/because A/, represents
the reverse of combusti on.
I f an equati on i s reversed, t he si gn
of i t s A/must be changed.
The mass i n thi s expressi on i s the
total mass of the system ( usual ly
water) not the mass of the reactants.
ORGAN I C C H E M I STRY, E N E RG ET I CS, KI N ET I CS AN D EQU I L I B R I U M
+r/cX
Cal culate the standard enthal py change for the reacti on:
4NH
3
(g) + 50
2
(g) - 4NO(g) + 6H
2
0( g)
gi ven the fol l owi ng A|/\1 mol -
1
:
NH
3
(g) " -46. 2, NO(g) ^ t90. 4, H
2
0( g) " -242.
Answer A/_,,, sum 1! of products - sum A| of reactants
^ 4 ? ( +90. 4) t 6 ? (-242) -4 ? (-46. 2) -5 ? ( 0) --906 \1 mol -1
Calculation of i g from i _ data
To do thi s you use the alternative route:
Elements
A
1 mol of substance
combustion products of the elements

where f = the sum of the enthalpies of combustion of the elements
taking into account the number of moles of each element,
and f/ = the enthal py of combustion of 1 mol of the substance.
Therefore: fJormauon
A
+ f/
+r/cX
Cal cul ate the standard enthal py of formati on of propan-1 - ol , C
2
H
5
CH
2
0H, gi ven
the fol l owi ng A0",,,,,, /\1 mor
1 :
propan-1 -ol ( l ) " -201 0, C( graphi te) " -394, H
2
(g) --286
Answer 3C( s) + 4H
2
(g) + 0
2
( g) - C
2
H
5
CH
2
0H( I )
3 ? A/( graphi te) 4 ? A/( H
2
)

-
fHc( C
2
HsCH
2
0H)
3C0
2
(g) + 4H
2
0( 1 )
A
-Aof el ements - Aof compound

-3 ? (-394) + 4 ? (-286) - (-201 - - 31 6 \1mor1
Calculation of t values fom laboratory data (only
examined at AS in unit test 3B)
Calculation of heat change from temperature change:
heat produced = mass ? specifi c heat capacity ? rise i n temperature
Then heat produced per mole = heat produced i n experi ment
the number of moles reacted
Then enthalpy change, fH i s mi nus the heat produced per mole (for an
exothermic reacti on Aui s a negative number) .
For an endothermic reaction, calculate the heat lost per mol e. This
equals fH a positive number.
E N E RG ET I CS I
+r/
A 0. 1 20 g sampl e of ethanol was burnt and the heat produced warmed 250 g
of water from 1 7. 30 oc to 20. 72 C. The speci fi c heat capacity of water is 4. 1 8
J
Q
-1
Cal cul ate

^
/
.,,,,
of ethanol .
Answer Heat produced = 250 g ? 4. 1 8 J g-1
'? 3. 42
0= 357 4 J .
Amount of ethanol = 0. 1 20 g/46 g mol-1 = 2. 61 ? 1 o-
3
mol
Heat produced per mol e = 357 4 J/2. 61 ? 1 o-
3
mol = 1 370 ? 1 0
3
J mol-1 .
^/l.,,,.
,= -1 370 kJ mor1
J
Calculation of ! values from average bond enthalpies
Draw the structural formulae for all the reactants and all the products.
Decide what bonds are broken i n the reaction and calculate the energy
required to break the bonds (endothermic) .
Decide what bonds are made in the reacti on and calculate the energy
released by making the bonds (exothermi c) .
Add the posi tive bond breaking enthal py t o the negative bond making
enthalpy.
+r/
Cal cul ate the enthal py of the reacti on:
H H
H H
` /
C =C + H-H - H-C-C-H
/ `

H H
H H
Given the fol l owi ng average bond enthal pi es/kJ mol-1 :
0-0 is +348, C=C is +61 2, H-H is +436, and C-H is +41 2.
Answer break (endo) make (exo)
C=C +61 2 C-C -348
H-H +436 2 ? C-H -824
+1 048
-1 1 72
^h....
= + 1 048 - 1 1 72 = -1 24 kJ mor1
_-.
Before attempting questions on thi s topic, check that you:
Know t he standard conditions for enthalpy changes.
.Know the si gns of 6H for exothermic and endothermic reacti ons.
Can defi ne the standard enthal pies of formation, combustion and
neutralisati on.
Understand an energy l evel diagram.
Can define and use Hess's Law.
Know how to calculate values of 6H from laboratory data.
Can use bond enthalpies to calculate enthalpies of reacti on.
Jb
ORGAN I C CH E M I STRY, E N E RG ETI CS, KI N ETI CS AN D EQU I L I B R I U M
t ,....
1 State the conditions used when measuring standard enthalpy changes.
2 Give equations, with state symbols, which represent the following
enthal py changes :
i the enthalpy of formation of ethanoic acid, CH
3
COOH(l )
ii the enthalpy of combustion of ethanoi c acid
iii the enthalpy of neutralisation of an aqueous solution of ethanoic
acid with aqueous sodium hydroxide.
3 Draw an enthalpy l evel diagram for the fol l owing sequence of reacti ons:
1
12N2(g) + Oz(g) NO(g) + 1/202
1H = +90. 3 kJ mor1
NO(g) +
1
/202(g) N02(g)
1H = -57 . 1 kJ mor1
and hence calculate the enthalpy change for the reacti on:
1
/2N2(g) + 02(g) NOz(g)
4 Given that the standard enthalpies of formation of N02(g) and N20
4
(g)
are +33. 9 kJ mol -1 and +9. 7 kJ mor1 respectively, calcul ate the enthalpy
change for the reaction:
2N02(g) Nz0
4
(g)
5 The standard enthal py of combustion of lauric acid,
CH
3
(CH2)
10COOH(s), which is found i n some ani mal fats, i s -7377 kJ
mor1 The standard enthalpies of combustion of C(s) and Hz(g) are -394
kJ mor1 and -286 kJ mor1
Calculate the standard enthalpy of formation of lauric aci d.
6 1 00 cm
3
of 1 . 00 mol dm-
3
HCl was added to 1 00 cm
3
of 1 . 00 mol dm-
3
NaOH i n a polystyrene cup, both solutions being i niti al l y at 2 1 . 1 0 C.
On mi xi ng the temperature rose to 27. 90 C. Determi ne the enthal py of
neutrali sation and state whether the reacti on i s exothermic or
endothermic. You may assume that the polystyrene cup has a negligible
heat capacity, the solution has a density of 1 . 00 g cm-
3
and that the final
solution has a specifi c heat capacity of 4. 1 8 J g-l oc-
1

Calculate the enthal py change for the reacti on:
C2H
4
(g) + H20(g) CH
3
CH20H(g)
given the fol l owing average bond enthalpies i n kJ mot
1
:
C-C +348; C=C +61 2; C-H +41 2; H-0 +463; C-0 +360.
ORGAN I C C H E M I STRY I
Substance Alcohol Aldehyde
'
C=O
Group
- C-OH
|
R
/
J1
Organ i c che mi stry I
.
.
Organi c compounds consist of a chain of one or more carbon atoms
and contain functional group ee Table 2. 1 ) . The functional group
gives the compound certain chemical properties. For i nstance the C=C
group (except i n benzene ring react in a i mi l ar way i n al l
compounds. Thu kno" l edge of th chemi tr of ethene, H2C=CH21
enables you to predi ct the reaction of al l compound contai ni ng the
C=C group.

Ketone Acid Ester
Acid
Amide Nitrile Amine
chloride
R
L L L L
'
"C=O -C R-C -C
l -l N -C-NHz
R'
/
"oH "O-R' "Cl
"
NHz '
Table 2. 1 Functional groups. *These will only be met at A2. R is a carbon-containing group.
When you wri te structu ral formu l ae,
check that:
every carbon atom has four bonds
every oxygen has two bonds and
every hydrogen and every hal ogen
have onl y one bond.
You must l earn the equations and conditions for the reacti ons i n the
specifi cation.
t-
Homologous series: a series of compounds with the same functional

group, the same general formul a, and where one member differs from
the next by CH2
Empirical formula: shows the si mpl est whole number rati o of the
atoms present i n one mol ecul e.
Molecular formula: shows the actual number of atoms present i n
one molecule, e. g. propane is C
3
H8
Structural formula: shows each atom in the molecule separately and
how it i s bonded. A more condensed way is to show the groupings
around each carbon atom, e.g. propane can be written as CH
3
CH2CH
3
and propan-2-ol as CH
3
CH(OH)CH
3

Isomers: two or more compounds with the same molecular formul a.
Homolytic fission: when a bond breaks with one electron goi ng to
each atom ( formi ng radical s) .
Heterolytic fission: when a bond breaks with the two electrons going
to one atom.
Substitution: a reaction i n which an atom or group of atoms i n one
molecule i s replaced by another atom or group of atoms.
Addition: a reaction i n which two molecules react together t o form a
single product.
Jb
There are three structu ral i somers of
formul a C
3
Hs0:
propan-1 -ol CH
3
CH
2
CH
2
0H
propan-2-ol CH
3
CH( OH) CH
3
methoxyethane CH
3
0CH
2
CH
3
cis
trans
CH3 CH3
` /
C =C
/ `
H H
CH3 H
` /
C =C
/ `
H CH3
Fig 2.4 Geometric isomers of
but-2-ene
The decol ouri sati on of a brown
sol uti on of bromi ne i s a test for a
C=C g roup in a mol ecul e.
Wi th unsymmetri cal al kenes, the
hydrogen goes to the carbon that
al ready has more hydrogen atoms
di rectl y bonded to i t. Thi s i s
Markovni kov's rul e.
ORGAN I C CH E M I STRY, E N E RG ETI CS , KI N ETI CS AN D EQU I L I B R I U M
Elimination: a reacti on i n which the elements of a si mpl e molecule
such as HBr, H
2
0 etc. are removed from the organi c molecule and not
replaced by any other atom or group of atoms.
Hydrolysis: a reacti on i n whi ch water (often catalysed by aqueous acid
or aqueous al kali) splits an organic molecule into two compounds.
Free radical: a species which has a single unpai red el ectron, e. g. Cl
Nucleophile: a species which seeks out positive centres, and must
have a lone pair of electrons which i t donates to form a new covalent
bond.
Electrophile: a species whi ch seeks out negative centres, and accepts a
l one pair of electrons to form a new covalent bond.
t- .
Isomerism
Structural isomers may have:
i different carbon chai ns (straight or branched)
ii the functi onal group in di fferent places in the carbon chain
iii di fferent functional groups.
Geometric isomerism
i Geometric i somerism occurs when there is a C=C i n the mol ecule,
and both carbon atoms have two different atoms or groups attached.
ii Geometric i somers are not easi l y i nterconverted because of the
difficulty of rotating about the bond.
Alkanes (e.g. methane, CH4)
Alkanes burn in excess oxygen to form carbon dioxide and water:
CH
4
+ 20
2
C0
2
+ 2H
2
0
Alkanes react with chlorine (or bromi ne) in the presence of UV light i n
a stepwise substitution reacti on:
CH
4
+ Cl
2
CH
3
Cl + HCl
CH
3
Cl + Cl
2
CH
2
Cl
2
+ HCl
Alkenes (e. g. propene, CH3CH=CH2)
Alkenes add hydrogen:
CH
3
CH=CH
2
+ H
2
CH
3
CH
2
CH
3
conditions: pass gases over a heated ni ckel catalyst
Alkenes add bromine (or chlorine):
CH
3
CH=CH
2
+ Br
2
CH
3
CHBrCH
2
Br
conditions: at room temperature wi th the hal ogen di ssolved i n hexane.
Alkenes add hydrogen halides, e. g. HI
CH
3
CH=CH
2
+ HI CH
3
CHI CH
3
conditi ons: mi x gases at room temperature.
t
H H
t t
H H
t

L L L L
n , n
Fig 2.5
Poly( ethene)
Fig 2. 6
Poly( propene)
The rate of al l these reacti ons
i ncreases C-CI to C-Br to C-1 ,
because the bond enthal py and
hence the bond strength decreases
C-CI to C-Br to C-1 . The weaker the
bond the l ower the acti vati on energy
and hence the faster the reacti on.
H
-C-OH
H
t=
-C -C-OH

H
=t=

Z
-C -C-OH

t =
J5
Al kenes are oxidised by potassi um manganate(VI I ) solution:
CH3CH=CH2 + [0] + H20 CH3CH(OH)CH20H
condi ti ons: at room temperature, when mixed with sodium hydroxide
solution i t produces a brown precipi tate.
Alkenes can be polymerised. Ethene forms poly(ethene) (Figure 2. 5)
and propene forms poly(propene) (Figure 2. 6) :
n-
CH2=CH2 -(CH2-CH2)-"
conditions either: a very high pressure (about 2000 atm)
and a temperature of about 250 oc
or: a catalyst of titani um( IV) chloride and triethyl al umi ni um
at SO oc and pressure of about 1 0 atm.
Halogenoalkanes (e.g. 2-iodopropane, CH3CHICH3)
They substitute with aqueous sodium (or potassium) hydroxide
to give an al cohol :
CH3CHICH3 + NaOH CH3CH(OH)CH3 + Nal
conditions: boi l under reflux with aqueous sodium hydroxi de.
They eliminate with ethanolic potassium hydroxide to give an
alkene:
CH3CHICH3 + KOH CH3CH=CH2 + KI + H20
conditions: boi l under reflux with a concentrated solution of potassi um
hydroxide i n ethanol, and collect the gaseous propene over water.
They substitute with potassium cyanide:
CH3CHICH3 + KCN CH3CH(CN)CH3 + KI
condi ti ons: boil under reflux with a solution of potassi um cyani de in a
mixture of water and ethanol .
With ammonia they form ami nes:
CH3CHICH3 + 2NH3 CH3CH(NH2)CH3 + NH
4
I
conditions: heat excess of a concentrated solution of ammoni a
i n ethanol with the halogenoalkane i n a seal ed tube.
The test for halogeno compounds:
1 Warm the substance with aqueous sodium hydroxi de.
2 Add di l ute nitric acid unti l the solution is j ust acidic.
3 Add sil ver nitrate soluti on.
Result:
white precipi tate, soluble i n dilute ammonia i ndicates chl oro
compound
cream precipitate, soluble in concentrated ammoni a i ndicates bromo
compound
yell ow precipitate, i nsoluble in concentrated ammoni a i ndicates iodo
compound.
Alcohols
Primary ( 1 ) alcohols contain the CH20H group.
Secondary (2) alcohols have two C atoms attached to the CHOH group.
Tertiary (3) alcohols have three C atoms attached to the COH group (see
Figure 2. 7) .
40
I n equati ons i n organi c chemi stry,
an oxi di si ng agent can be written as
[0] and a reduci ng agent as [ H] , but
the equati on must sti l l bal ance.
Note that thi s reacti on works for al l
al cohol s, and i somers of the al kene
may be produced.
Thi s i s a test for an OH group.
Steamy aci di c f umes are gi ven off
when phosphorus pentachl ori de i s
added to the dry organi c su bstance.
ORGAN I C CH E M I STRY, E N E RG ETI CS, KI N ET I CS AN D EQU I L I B R I U M
Oxidation reaction with aqueous orange potassium
dichromate(VI), K2Cr2071 acidified with di l ute sulphuric acid.
a 1 o alcohols are oxidised via an aldehyde to a carboxylic acid. The
solution turns green ( [Cr(H20)6J
3
+ ions formed) .
CH
3
CH20H + [OJ CH
3
CHO + H20
then CH
3
CHO + [OJ CH
3
COOH
conditi ons: to stop at the aldehyde: add potassium dichromate(VI)
i n di lute sulphuric acid to the hot alcohol and al low the aldehyde to
di sti l off.
to prepare the acid: boi l the alcohol with excess acidifi ed oxidising
agent under refl ux.
b z
o
alcohols are oxidised to a ketone. The solution turns green.
CH
3
CH( OH)CH
3
+ [ OJ - CH
3
COCH
3
+ H20
condi ti ons: boil the alcohol and the acidified oxidising agent under
refl ux.
c 3 alcohols are not oxidised and so do not turn the solution green.
Dehydration of an alcohol to an alkene:
C2H50H H2C=CH2 + H20
conditi ons: add excess concentrated sulphuric acid (or concentrated
phosphoric acid) to the alcohol and heat to 1 70 C.
Halogenation 1 , z
o
and 3 alcohols react with:
1 Phosphorus pentachloride, PCl5, to form a chl oroalkane:
C2H50H + PCl5 C2H5Cl + HCl + POC1
3
conditi ons: at room temperature and the alcohol must be dry.
2 Solid sodi um bromide and SO% sulphuric acid to give a
bromoalkane:
NaBr + H2S04 HBr + NaHS04
then HBr + C2H50H C2H5Br + H20
conditi ons: add the sulphuric acid mixed with the alcohol to solid
sodi um bromide at room temperature.
3 Phosphorus and iodine to give the iodoalkane:
2P + 312 2PI
3
then 3C2H50H + PI
3
3C2H5l + H
3
P0
3
conditions: add the alcohol to a mixture of moi st red phosphorus
and iodine at room temperature.
A summary of reactions i s shown i n Figure 2. 8.
ORGAN I C C H E M I STRY
02
Spark
cone H2S04
4J
Boil under reflux
K2Cr207/ H2S04(aq)
at 1 UU L at 1 U L
Fig 2. 8 Summary of
organic reactions
The percent yi el d i s l ess than 1 00%
because of competi ng reacti ons and
handl i ng l osses.
Bonding and reactivity
Bond strength is the dominant factor that determines reactivity.
a A n-bond between two carbon atoms is weaker than a O bond
between two carbon atoms. Thus al kenes are more reactive than
al kanes and react by addi ti on, whereas al kanes react by substituti on.
b A C-I bond is weaker than a C-Cl bond, and so iodoalkanes are
rapidly hydrolysed by aqueous sodium hydroxide, unl i ke
chloroalkanes which react very slowly.
Quantitative organic chemistry
This i nvolves calculation of empi rical formulae from percent data (see
page 6) .
Thi s involves calculation of percentage yield.
Fi rst calcul ate the theoretical yield from the equation (see page 8),
then the % yield * actual yield i n grams ? 1 00%
theoretical yield in grams
Applied oganic chemistry
Liquid versus gaseous fels. You should consider the fol l owing
points:
1 the ease with whi ch gaseous fuel s can be pi ped into the home
2 the easier handl i ng of l i qui d fuel s at a fil l i ng station for cars
3 the extent and type of pollution produced:
a the quantity of carbon dioxide and any other greenhouse gases
produced per ki l oj oule of energy
b the emi ssi on of oxides of ni trogen and sul phur, and the way i n
which these can be l imi ted
c the emi ssion of particulates
4 the energy produced per uni t mass of fuel for aeropl anes
5 the extent to which the world's supply of fossi l fuel s is l i mited.
4
DDT i s a chl ori ne-contai ni ng
pesti ci de and i t has eradi cated
mal ari a from some countri es, but its
overuse has led to the destructi on of
wi l dl i fe. It i s a very i nert chemi cal
(owi ng to the strength of the C-CI
bond) and so persi sts i n an
organi sm, bei ng stored i n fatty
ti ssue.
ethene and but- 1 -ene
2-chl oro-3-methyl pentan-1 -ol
ORGAN I C CH E M I STRY, E N E RGETI CS, KI N ETI CS AN D EQU I L I B R I U M
Polymers. You shoul d real i se that si mpl e polyalkenes are resistant to
breaking down under environmental conditions. Thi s i s because of the
strength of the C-C and the C-H bonds.
Organic halogen compounds. There are three mai n uses of these:
1 As polymers. PVC is used as a waterproofing material, as an
electrical i nsulator and as a stabl e and maintenance free material for
wi ndow frames. When burnt it produces harmful fumes of
hydrogen chloride. PTFE i s used as a non-stick coating for saucepans
etc. These polymers are very stabl e owing to the strength of
carbon-hal ogen and C-C bonds.
2 As herbicides. Compl icated chlorine compounds, such as 2, 4-D and
2, 4, 5-T are used as selective weedki l lers. They are stable and so
persist in the environment.
3 Chlorofluorocarbons (CFCs) make excel l ent refrigerants, but they
are so stable in ai r and water that they diffuse to the stratosphere
Y here they are broken down by l ight energy and form chl orine
radical s. The e catalyse the destructi on of ozone. New substances
ha e been de eloped which contain hydrogen as well as chl ori ne,
fl uorine and carbon, and these are less stable and are broken down
by atmospheric oxidati on.
-.
Before attempting the questi ons on thi s topic, check that you:
Can name si mpl e organi c mol ecules.
Can write structural formulae of structural and geometric i somers.
Know the reacti ons of al kanes with ai r and halogens.
Know the reacti ons of al kenes wi th hydrogen, hal ogens, hydrogen
hal ides, potassi um manganate(VI I ) and in polymeri sation.
. Know the reacti ons of hal ogenoalkanes with potassium hydroxide (both
aqueous and ethanolic), potassium cyanide and ammoni a.
Know the oxidation, dehydration and halogenation reactions of
alcohols.
Can relate reactivity to bond strength and polari ty and to the stabi l i ty
of i ntermediates.
Can calcul ate the empirical formula of a compound.
Understand the advantages and disadvantages of the use of organi c
compounds.
t ,...
Whi ch of the fol lowing compounds are members of the same
homologous series:
ethene C2H
4
, cyclopropane C
3
H6, but- 1 -ene CH
3
CH2CH=CH21
but- 1 , 3-diene CH2=CHCH=CH2, cyclohexene C6H10?
Name CH
3
CH2CH(CH
3
)CHCICH20H
tetrachl oromethane, CCI 4
What product i s obtai ned i f a l arge excess of chlorine i s mixed with
methane and exposed to di ffused l ight?
A compound X contained 54. 5% carbon, 36. 4% oxygen and 9. 1 %
hydrogen by mass. Calculate its empirical formul a.
1 Write the structural formulae of:
a 1 , 1 -dibromo- 1 , 2-dichl oro-2, 3-difl uoropropane
b 1 -chlorobutan-2-ol .
2 Write out the structural formulae of the isomers of:
a C3H80 (alcohol s only)
b C5H
1
2
c C,H8 (no cycl i c compounds) .
3 Defi ne:
a free radical
b homolytic fi ssion.
4 Defi ne:
a an electrophi l e
b heterolytic fi ssi on.
5 Write equations and give conditions for the reaction of:
a ethane + chlorine
b ethane + oxygen.
4J
6 Write equations and give conditions for the reacti on of propene wi th:
a hydrogen
b bromi ne *
c hydrogen iodide
d potassi um manganate(VI I) solution *
For reacti ons marked *, state what you woul d see.
Write equati ons and name the products obtained when 2-iodopropane
i s:
a shaken wi th aqueous di lute sodi um hydroxide
b heated under reflux with a concentrated solution of potassi um
hydroxi de i n ethanol
c heated in a sealed tube with a concentrated solution of ammoni a i n
ethanol .
8 Write the equation and give the conditions for the reacti on of
propan-2-ol with sulphuric acid.
9 Write the structural formul a of the organi c product formed, i f any, give
its name and say what you would see when:
a propan- 1 -ol is heated under reflux with di lute sul phuric acid and
excess aqueous potassium dichromate(VI)
b 2-methylpropan-2-ol i s heated under reflux with di lute sulphuric
acid and aqueous potassium dichromate(VI)
c phosphorus pentachloride is added to propan-2-ol .
10 Why does bromi ne react rapidly wi th ethene at room temperature but
only slowly with ethane?
44
An i ncrease in temperature al so
causes an i ncrease i n the rate of
col l i si on, but thi s is uni mportant
compared wi th the i ncrease i n the
fracti on of mol ecul es wi th the
necessary activati on energy.
ORGAN I C C H E M I STRY, E N E RG ETI CS, K I N ETI CS AN D EQU I L I B R I U M
1 1 Why does 1 -bromopropane react more slowly than 1 -iodopropane with
water?
12 When 5 . 67 g of cyclohexene, C6H10, reacted with excess bromi ne, 1 5. 4 g
of C
6
H
1
0Br2 was obtained. Calculate the theoretical yield of C6H
1
0Br2 and
hence the percentage yield of the reacti on.
13 Expl ai n why compounds such as CC12F2 are harmful to the
envi ronment.
Ki net i cs I
The rate of a reacti on is determi ned by:
1 the rate at whi ch the molecules coll ide
2 the fraction of the col l iding molecules that possess enough kinetic
ener / ' to get over the activation energy barrier'
3 the orientation of the molecul es on col l i si on.
t-
Activation energy is the mi ni mum energy that the reactant
molecules must have when they coll ide i n order for them to form
product molecul es.
Factors which control the rate of a reaction are:
1 the concentrati on of a reactant in a solution
2 the pressure, i f the reactants are gases
3 the temperature
4 the presence of a catalyst
5 the surface area of any solids
6 l ight for photochemical reacti ons.
_t- .
Collision theory
The effect of an i ncrease in concentration of a solution, or the
i ncrease i n pressure of a gas, i s to increase the frequency of collision
of the molecules, and hence the rate of reacti on.
The effect of heating a gas or a solution is to make the molecules or
i ons:
1 move faster and so have a greater average ki neti c energy
2 which i ncreases the fraction of col l i di ng molecules with a combined
energy greater than or equal to the activation energy
3 which results i n a greater proportion of successful col l i sions.
The effect of heating can be shown by the Maxwel l-Boltzmann
distribution (see Figure 2. 9) of molecul ar energies at two temperatures T
1
and T2 where T2 is > T
1

KI N ETI CS I
Note that the peak has moved to the
ri ght for 7, and that the total areas
under the curves are the same, but
the area under the curve to the ri ght
of fa equal s the fracti on of the
mol ecul es wi th energy fa, whi ch i s
greater for 7 than for G
Fig 2.9 Maxwell-Boltzmann distribution
v
0
'
L
0
0
8
LH6i_
Fig 2. 10 Efect of a catalyst
Fig 2. 1 1 Energy profile diagrams
v
0
'
L
0
0
8
+
Ener '
Catalysts work by pro iding an al ternati e route with a lower
activation energy. Thus, at a gi en temperature, a greater proportion of
the col l i di ng molecul es wi l l possess this l ower activation energy by
fol lowing the route with the catalyst, and so the reacti on will be faster.
This is shown on a Maxwell-Bol tzmann diagram (see Figure 2. 1 0) .
The enthalpy profil e diagrams for an uncatalysed and a catalysed
reaction are shown in Figure 2. 1 1 .
Do not say that a catalyst l owers the activation energy.
Note that the tH values are the same for both paths.
- - - - - - - -
Transition
state
Intermediate
Uncatalysed Catalysed
Thermodynamic stability
Thi s is when the enthalpy l evel of the products is much higher than the
enthalpy l evel of the reactants.
Thus the substances on the l eft-hand si de of a very endothermic
reaction are said to be thermodynamical ly stable relative to those on the
right.
The substances on the l eft-hand si de of a very exothermic reacti on are
said to be thermodynamical ly unstable relative to those on the right.
Whether a reacti on wil l then take place depends upon its kinetic
stabi l ity.
Kinetic stability
If a reaction has such a high val ue of activation energy that no molecules
possess sufficient energy on collision to react, the system i s said to be
kinetically stabl e. An example i s a mixture of petrol and ai r, which i s
4b
An:
Pressu re, temperatu re, and catalyst
Concentrati on, temperature and
catalyst
The surface area of the sol i d
Fe (Haber) , or V
2
0
5
(Contact) , or Ni
or Pt (addi ti on of hydrogen to C=C)
ORGAN I C C H E M I STRY, E N E RG ET I CS, KI N ET I CS AN D EQU I L I B R I U M
thermodynami cal ly unstabl e but kinetically stable. No reacti on occurs
unless the mixture is ignited.
_-.
Before attempting the questi ons on thi s topic, check that you:
.Can recal l the factors which effect the rate of reacti on.
Can explain these rate changes i n terms of collision theory.
Can draw the Maxwel l-Boltzmann distribution of molecular energies at
two different temperatures.
Can use thi s to explain the effect of a change of temperature and the
addition of catalyst.
.Understand the concepts of thermodynamic and kinetic stabi l i ty.
_t ,...
For the fol l owing questions, cover the margin, write your answer, then
For a reaction i nvolving gases, state three factors that control the rate of
the reacti on.
For a reaction carried out i n solution, state three factors that control the
rate of the reaction.
For the reacti on of a solid wi th a gas or wi th a solution, state one other
factor that controls the rate of reacti on.
Gi ve an example of a solid catalyst used i n a gas phase reaction.
1 Define
i activation energy
ii catalyst.
2 Expl ai n, in terms of col l i sion theory, why changes in temperature and
in pressure and the addition of a catalyst alter the rate of a gas phase
reacti on.
3 Draw the Maxwel l-Boltzmann di stribution of energy curve for a gas:
i at room temperature (mark this T
1
) and
ii at 50 oc (mark thi s T2) .
Now mark i n a typical value for the activation energy of a reaction that
proceeds steadily at room temperature.
4 Expl ai n, i n terms of activati on energy, why ani mal products such as
meat and milk stay fresher when refrigerated.
5 Draw energy profi l e diagrams of:
i an exothermic reacti on occurring in a si ngle step
ii the same reacti on in the presence of a sui table catalyst
iii a reacti on where the reactants are thermodynami cal ly stable
iv a reacti on where the reactants are both thermodynamically and
kinetically unstabl e.
CH E M I CAL EQU I L I B R I A I
41
Che mi cal equi l i b ri a I

Le Chatel i er's pri nci pl e states that
when one of the factors governi ng
the posi ti on of equi l i bri um i s
changed, t he posi ti on wi l l al ter i n
such a way as i f t o restore the
ori gi nal condi ti ons.
Do not say ' the si de wi th a smal l er
vol ume' , as a gas wi l l always f i l l i ts
contai ner.
.
Many reactions do not go to completion because the reacti on is reversible.
As the rate of a reaction i s dependent on the concentrati on of the
reactants, the reaction wi l l proceed up to the point at which the rate of the
forward reaction equals the rate of the reYer e reaction, when there i s no
further change i n concentrati ons. The y tern i then said to be at
equilibri um.
_t- -- .-
Dynamic equilibrium
At equil ibrium, the rate of the forward reaction equals the rate of the
reverse reacti on.
Both products and reactants are constantly bei ng made and used up,
but their concentrations do not change.
Thi s can be demonstrated by using isotopes. For the reaction:
CH
3
COOH(l ) + C2H50H(l ) CH
3
COOC2H5(l ) + H20( l)
Mix the four substances in their equilibrium concentrations, but
have the water made from the i sotope
1
8
0. After some time the
1
8
0
isotope wi l l be found (by means of a mass spectrometer) in both the
ethanoic acid and the water, but the concentrations of the four
substances will not have changed.
Effect of changes in conditions on position of
equilibrium
Le Chatelier's principle may hel p you to predict the di rection of the
change i n the position of equi librium, but it does not explain i t.
Temperature. An increase i n temperature wi l l move the position of
equi l ibrium i n the endothermic directi on. Li kewise a decrease i n
temperature wi l l move the equilibrium i n the exothermi c di rection:
N2(g) + 3H2(g) 2NH
3
(g) !H = -92. 4 k] mol-
1
As thi s reaction is exothermic left to right, an i ncrease in temperature
will cause less ammoni a to be made, thus l owering the yield.
Pressure. This appl i es only to reacti ons i nvolving gases. An i ncrease in
pressure will drive the equilibrium to the side with fewer gas molecul es.
Thus, for the reacti on above, an i ncrease i n pressure wi l l result in more
ammonia in the equilibrium mixture, i . e. an i ncreased yield. Thi s is
because there are only two gas molecules on the right of the equation
and four on the left.
Concentration. This applies to equilibrium reacti ons in solution. I f a
substance is physically or chemically removed from an equilibrium
system, the equi l ibrium wi l l shi ft to make more of that substance:
4b
Al l i ndustri al processes that i nvol ve
passi ng gases through a bed of
catalyst must work above
1 atmosphere pressure in order to
force the gases through the system.
ORGAN I C C H E M I STRY, E N E RG ETI CS, K I N ET I CS AN D EQU I LI B R I U M
2Cr0/-(aq) + 2H+(aq) Cr20,(aq) + H20(1)
Addition of alkali wi l l remove the H. ions, causing the equilibrium to
move to the l eft.
Catalyst. Thi s has no effect on the posi ti on of equilibri um. What i t
does i s to increase the rate of reachi ng equilibrium, thus a catalyst
all ows a reacti on to be carried out at a reasonable rate at a lower
temperature.
Optimum industrial conditions
Temperature
Many i ndustrial reacti ons, such as the Haber process for manufacturing
ammonia, are reversible and exothermi c. For such reacti ons:
I f a high temperature i s used, the yi el d at equilibrium i s small, but the
rate of reaction i s fast.
I f a l ow temperature i s used, the theoretical yield i s higher, but the rate
of reacti on i s slow.
I n systems such as thi s, a catalyst is used to allow the reaction to
proceed rapidly at a temperature at which the yield is reasonably good.
Thi s i s often called a compromi se temperature, bal ancing yield with
rate. Any unreacted gases are then separated from the products and
recycled back through the catalyst chamber.
Pressure
High pressures are extremely expensive, and are only used i f the yield at
lower pressures i s too small to be economic.
Two exampl es of manufacturing processes that use very high pressures
are the Haber process and the polymerisation of ethene.
-.
Before attempting the questions on thi s topic, check that you:
Understand that equi l ibria are dynami c.
Can deduce the effect of changes i n temperature, pressure and
concentration on the posi ti on of equi l ibri um.
Can predict the economic conditions for an i ndustrial process.
_t ,...
1 Consider the reversible reacti on at equi libri um:
A(g) B(g)
Whi ch statements are/is true about thi s system?
i There is no further change i n the amounts of A or B.
ii No reactions occur, now that it has reached equi l ibri um.
iii The rate of formation of B i s equal to the rate of formation of A.
2 Consider t he equi librium reacti on:
N204(g) 2N02(g) ^ * +58. 1 k] mot
1
State and explain the effect on the position of equilibrium of:
I N DUSTRI AL I NORGAN I C CH E M I STRY
i
ii
iii
decreasing the temperature
halvi ng the vol ume of the contai ner
addi ng a catalyst.
3 Ethanoic acid and ethanol react reversibly:
CH
3
COOH + C2H50H T CH
3
COOC2H5 + H20 t * 0 k) mot
1
i Expl ai n the effect of adding an alkali .
ii What wi l l happen to the position of equil ibri um if the
temperature i s increased from 25 oc to 35 oc?
45
4 White i nsoluble l ead( I I) chloride reacts reversibly with aqueous chloride
i ons to form a colourless solution:
PbC12(s) + 2Craq) + PbCl,(aq)
State and explai n what you would ee when concentrated hydrochloric
acid i s added to the equi l ibrium mi xture.
5 I n the manufacture of ul phuri c acid, the critical reaction is:
2S02(g) + 02 g) + 2 (g) = -1 96 k] mot
1
The reaction is very sl ow at room temperature. Wh are conditions of
725 K and a catalyst of vanadi um( ) oxide u ed?
I ndustri al i norgan i c chemi stry
_. .
I ndustrial chemi sts always need to keep manufacturing costs down. They
do this by:
1 making the reaction as fast as possible
2 ensuring a high yield
3 keeping the temperature and pressure as l ow as possible.
t- .
The Haber process for the manufacture of ammonia
Nz (g) + 3H2(g) + 2NH
3
(g) t -92. 4 k) mot
1
Because thi s reaction, l eft to right, is exothermic and the number of gas
mol ecules decreases, the yield and kinetics are affected accordi ng to the
table below:
Reaction conditions Effect on yield Efect on rate
Increase in temperature Decrease I ncrease
I ncrease in pressure I ncrease Very sl ight i ncrease
Addition of catalyst None Very l arge i ncrease
Thus the fol l owing conditions are found to be the most economic:
Temperatre: 400 C. A higher temperature woul d reduce the yield,
and a lower one would make the reaction
uneconomi cally sl ow.
a0
Uses of ammoni a:
manufacture of nitri c aci d
manufact ure of ferti l i sers such as
ammoni um nitrate and u rea
manufact ure of pol yami des such
as nyl on.
Uses of sul phuri c aci d:
the manufacture of ferti l i sers
such as ammoni um sul phate
the manufacture of phosphate
ferti l i ser
the manufacture of pai nts and
detergents.
ORGAN I C C H E M I STRY, E N E RG ET I CS, KI N ETI CS A N D EQU I LI B R I U M
Pressure: 200 atm. The yield at 1 atm is too low, and so a high
pressure i s necessary even though i t i s very expensive.
Catalyst: Iron. This allows the reacti on to proceed at a fast, and
hence economic, rate at a moderate temperature.
Yield per cycle: 1 5%. The gases from the catalyst chamber are cooled i n
order t o l iquefy t he ammonia, and then t he unreacted
nitrogen and hydrogen are recycled, giving a final
conversion of nearly 1 00%.
The oxidation of ammonia to nitric acid
Thi s happens in three stages:
1 The ammonia and ai r are passed over a platinum/rhodi um catalyst at
900 C:
4NH3(g) + 502(g) 4NO(g) + 6H20(g)
2 On cool ing, the nitrogen( I I ) oxide reacts with more ai r:
4NO(g) + 202(g) 4N02(g)
3 The nitrogen(IV) oxide and air are then absorbed into water:
4NOz(g) + 02(g) + 2H20(l ) 4HN03(aq)
The contact process for the manufacture of sulphuric
acid
Thi s takes pl ace in three stages:
1 The combustion of sulphur:
S(l ) + 02(g) S02(g)
2 The reversible oxidation of the sulphur dioxide:
S02(g) +
1
/zOz(g)
SOlg)
3 Absorption by the water i n 98% sul phuri c acid.
The conditions for stage two, which i s exothermic and has fewer gas
molecules on the right, are:
Temperature: 425 C. A higher temperature would reduce the yield,
Pressure:
Catalyst:
Yield:
and a l ower one would make the reaction
uneconomically slow.
2 atm. Thi s is enough to force the gases through the
pl ant. A higher pressure i s not necessary because the
yield i s high under these condi ti ons.
Vanadium(v) oxide.
96% per ccle. The gases from the catalyst chamber are
passed i nto the absorber contai ni ng the 98% sulphuric
acid, and al l the S03 i s removed. The gases then go
back through another bed of catalyst, giving a final
conversion of 99 . 8%.
Manufacture of aluminium
Al umi ni um i s too reactive for its oxide to be reduced by carbon
monoxide or other cheap reducing agents, so the expensive method of
electrolysis of a molten ionic compound has to be used.
The ore contains aluminium oxide (amphoteric) with l arge i mpurities of
iron oxide (basi c) and si l icon dioxide (weakly acidic) . The ore is treated
with a hot 10% solution of sodium hydroxide, which reacts with the
amphoteric alumi ni um oxide to form a solution of sodium al uminate.
Iron oxide does not react as i t i s a base, and si l icon dioxide does not
I N D USTR I AL I NORGAN I C C H E M I STRY
l
Al umi ni um i s protected from
corrodi ng by its l ayer of oxi de whi ch
reforms when i t i s scratched. I t i s
al so l ess dense than i ron. These
properti es make i t i deal as a materi al
for aeropl ane wi ngs and fusel age
and for dri nk cans (even though i t i s
more expensi ve than i ron). I t i s al so
an excel l ent conductor of el ectri ci ty,
and so i s used in overhead power
cabl es because of these three
properti es.
As the el ectrol yti c method of
manufacture i s very expensi ve, it i s
economi cal l y sensi bl e to recycl e
al umi ni um objects.
Chl or i ne is used for:
water steri l i sati on
i i the manufactu re of organi c
chl ori ne compounds, such as the
pl asti c PVC and the herbi ci de
2, 4-0
i i i the manufacture of HCI .
Sodi um chl orate(! ) i s used:
i as a domesti c bl each
i i as a di si nfectant.
react because of its giant atomi c structure. These solids are filtered off,
and carbon dioxide is blown through the solution precipitati ng
al umi ni um hydroxide. Thi s i s obtained by filtration and heated to
produce pure al umi ni um oxide.
The purified al umi ni um oxide i s di ssolved in molten cryolite, Na
3
AlF6,
at 900 C.
The solution is electrolysed using carbon anodes dipping i nto a steel
cell l i ned with carbon, which i s the cathode.
At the cathode, al umi ni um i ons are reduced:
Al
3
+ + 3e- -Al (l)
The molten al umi ni um si nks to the bottom of the cell and i s si phoned
off.
At the carbon anode, oxygen ions are oxidised and react with the
anode:
2
2
- C s C02(g) - 4e
-
Because of the expen e of thi method of manufacture, it is economi c to
recycle al umi ni um drink cans.
The production of chlorine
Thi s i s done by the electrolysis of an aqueous solution of odium
chloride (brine) .
At the titani um anode (+) : NaCl contai ns cr i ons and these are
oxidised to Cl
2
:
2Cr(aq) -Cl
2
(g) ze
chlorine gas is produced.
At the steel cathode (-) : water i s i oni sed i n an equilibrium reacti on:
H
2
0(l ) T H+(aq) + OH- (aq)
Na+ i ons are very hard to reduce, and so H+ i ons are preferenti al ly
reduced:
2H+(aq) + ze- - H2(g) .
The removal of the H+ i ons drives the water equi l i bri um to the right,
producing OH- i ons. The overall equati on for the reaction at the
cathode i s:
2H20 + ze- --20H-(aq) H2(g)
Thus sodium hydroxide and hydrogen are produced.
The anode and cathode compartments are separated by an i on-exchange
membrane which all ows Na+ ions to pass through but keeps the
chlorine separated from the hydroxide i ons that are produced at
the cathode.
Manufacture of sodium chlorate(l)
I f the electrolysi s of sodium chloride solution i s carried out with the
solution being stirred, sodi um chlorate(!) and hydrogen are obtained. The
chlorine produced at the anode di sproportionates when in contact with
the alkali from the cathode:
Cl2(aq) 20H-(aq) -- OCr(aq) + Cr(aq) + H20( l)
Ad:
A temperature of 350 to 450 C, a
pressu re of 200 to 250 atm and an
i ron catalyst
To make ferti l i sers, and to make
nyl on (or ni tri c aci d)
A temperature of 900
0and a
pl at i num/rhodi um catalyst
A temperatu re of 400 to 450C, a
vanadi um(V) oxi de catalyst and a
pressure of 2 atm
To make ferti l i sers, and pai nts (or
detergents)
I t i s amphoteri c.
Molten el ectrolyte
Cathode Al
3
+ 3e- - AI
Anode: 20
2
- + C C0
2
+ 4e-
ORGAN I C CH E M I STRY, E N E RG ET I CS, KI N ET I CS AN D EQU I LI B R I U M
_-.
Know the conditions for the manufacture of ammoni a.
Know the conditions for the manufacture of ni tric acid.
Know the conditions for the manufacture of sulphuric acid.
Can j ustify the conditions i n terms of the economics and the chemistry
of these processes.
Know some of the uses of ammonia, ni tric acid and sul phuric acid.
Know the conditions and electrode reactions used i n the manufacture
of al umi ni um.
Can recal l the detai l s of the production of chl ori ne and sodi um
chl orate(I ) and thei r uses.
t - , ..
For the fol l owing que tions, cover the margin, write your answer, then
State the condition used in the manufacture of ammoni a.
State two uses of ammoni a.
State the conditions used for the oxidation of ammoni a i n the
manufacture of ni tric aci d.
State the conditions used for the oxidation of sul phur dioxide i n the
Contact process.
State two uses of sulphuric acid.
What property of al umi ni um oxide is the basis of its purifi cation from
bauxite?
What i s the essential condition used i n the manufacture of al umi ni um?
Write the equations for the reactions at the cathode and at the anode i n
the manufacture of al umi ni um.
1 Expl ai n the economic reasons for the choice of the conditions used i n
the Haber process.
2 I n the Haber process why i s the gas mixture cooled after it has left the
catalyst chamber?
3 Write the equati ons for the reactions at the anode and at the cathode in
the manufacture of chlorine.
PRACT I CE : TEST U N I T 2
J
PrucrIce Tesr: tuIrZ
Time allowed 1hr
All questions are taken from parts of previous Edexcel Advanced GCE questions.
1 a Propene, C
3
H6, and but-2-ene, CH
3
CH=CHCH
3
, are i n the same homologou
homologous series.
b Draw a representative l ength of the polymer chai n of poly(propene)
c i Draw the geometric isomers of but-2-ene.
ii Expl ai n how geometric isomerism arises.
eries. Expl ai n the term
[3]
[2]
[2]
[1]
(Total S marks)
[une 2001 Unit Test 2 question 2 & May 20 2 [nit Te t 2 question 5]
2 The rate of any chemical reaction is increased i f the temperature i s i ncreased.
a Draw a diagram to represent the Maxwel l-Boltzmann di stribution of molecular ener ie at a
temperature T1 and at a higher temperature T2
[3
b Use your di agram and the i dea of activation energy to explain why the rate of a chemical reaction
i ncreases with i ncreasing temperature. [
4
3 Consider the fol lowi ng reaction scheme:

step 1
" C
3
H
7
Br (maj or product)
KMn04
i n alkali
s
aqueous NaOH
C
3
H
8
0
p
step 3 (oxidation)
CH
3
COCH
3
a i Give the reagent and the conditions needed for step 1 .
ii Give the structural formul a of S.
b i Give the structural formul a of P.
ii State the type of reaction i n:
step 1
the conversion of S to P.
c i Give the reagent and the conditions needed for step 2.
ii Give the reagent and the conditions needed for step 3.
d Give the structural formul a of compound Q.
4a State Hess's Law.
b Define the term standard enthalpy change of combustion.
c The equation for the combustion of ethanol in ai r i s
C2H50H(l ) 302(g) 2C02(g) 3H20( 1)
Total marks)
[une 2001 Unit 1 t 2 que tion 3]
[2]
[1]
[1]
[2]
[2]
[2]
[3]
[1]
(Total 14 marks)
[2]
[3]
4
ORGAN I C C H E M I STRY, E N E RG ETI CS, K I N ETI CS AN D EQU I LI B R I U M
And the structural representation of thi s i s:
H H

u -c c o - H - so-ozo-c-o- su-o -u

H H
i Calcul ate the enthalpy change for thi s reaction using the average bond enthal py val ues given below.
[3]
Bond Average bond energy/kJ mor
1
Bond Average bond energy/kJ mol-1
C-H + 41 2 CC + 348
CO + 360 O-H -463
0=0 496 C=O -743
ii Draw and l abel an enthalpy level diagram to represent this reaction.
[2]
(Total tO marks)
fune 2001 Unit Test 2 question 5]
5a The reaction i n the Haber Process that i s used t o produce ammonia i s:
N2(g) + 3H2(g) 2NH3(g) D * 9zk] mor'
i What temperature is used in the Haber Process? [1]
ii Justify the use of thi s temperature. [3]
iii Name the catalyst used in the Haber process. [1]
iv How does a catalyst enable a reacti on to occur more quickly?
[2]
b Another industrial process is the one which recovers chlorine from HCl, which often is a by-product i n
organic preparations
4HCl (g) 02(g)
2Cl2(g) + 2H20(g)
This is a homogeneous dynamic equil ibrium reacti on.
State the meani ng of the terms
i homogeneous
ii dynamic equilibrium
D * -1 1 5 kJ mor
1
[1]
[2]
c State and explain the effect on the position of equi l i brium of the reaction in b of:
i decreasing the temperature.
ii decreasi ng the vol ume of the reacti on vessel
[2]
[2]
(Total 14 marks)
[May 2002 question 3 Unit Test 2 & Januar 2001 question 4 Module Test 2]
6 Al umi ni um metal is manufactured by a process in which purifi ed bauxite, dissolved in molten cryol i te,
i s electrolysed at 800 C. Graphite el ectrodes and a current of about 1 20 000 amperes are used.
a Give the i oni c equation for the reaction taking place at the anode.
[1]
b Give the i oni c equation for the reaction taking place at the cathode.
[1]
c State which of these reacti ons is an oxidation process. [1]
d Expl ai n why the anodes need to be replaced frequently. [2]
e Expl ai n why an electrolyte of pure molten bauxite is not used. [2]
(Total marks)
fune 2001 Unit Test 2 question 7]
[
Paper total 60 marks]
O rJLorao
r
cty
I on Fl ame colour
Lt cami ne red
Na+ yel l ow
K+ l i lac
Ca
2
+ brick red
Sr
2
+ crimson red
Ba
2
+ pale green
Laboratory chemi stry I
The specifi cation for these tests i ncludes al l of Uni ts 1 and 2.
Uni t Test 3B wi l l contain many of t he calculations for AS level , and so
Topic 1 . 2 (pages 6 to 1 2) must be thoroughly revised.
t.. -, . .

Thi s is either i nternal ly assessed or a practical exam.
Notes and textbooks are al lowed i n the tests.
The practical exam wi l l contai n ore quantitati e work, probably a
titration or an enthal py change experi ment.
You should know the fol l owing gas tests:
H2 burns with a squeaky pop
02 rel ights a glowing spi l l
C02 turns l i me water mi l ky
NH
3
turns red l i tmus blue
Cl2 bleaches damp l i tmus; turns KBr solution brown
N02 brown gas which turns starch/iodide paper blue-black
S02 turns acidifi ed potassium dichromate(VI) solution green.
You should know the tests for the fol lowing i ons:
Add acid. Test for C02
Add to al most boiling water. Test for C02
Gives white precipi tate when di l HCl and BaC12(aq) are
added to the solution.
HS04- Solution is acidic to l itmus, then test as for sot above.
S0
3
z
- Add di l acid to solid and warm. Test for S02
Hal ide i on: To solution add di l HN0
3
then AgN0
3
(aq). White
precipitate soluble i n di l ammoni a i ndi cates chloride;
cream precipitate i nsoluble i n di l but soluble i n cone
ammoni a i ndicates bromide; pale yellow precipitate
i nsol ubl e in cone ammonia i ndicates iodide.
N0
3
- Heat sol i d. Al l ni trates give off 02 Al l but sodi um and
potassi um ni trates al so give off N02 Alternatively add
al umi ni um powder and sodium hydroxide solution.
Nitrates give off ammonia gas.
NH4 Add di l NaOH and warm. Test for ammoni a.
Mg
2
+ Gives white precipitate when di l ammoni a is added
to a solution.
You must know how to carry out a flame test and the colours obtained.
b
C=C group
C-OH group
Organi c halides
LABORATORY CH E M I STRY
_tc - ,-- ,
Decolourises
brown bromi ne
in hexane
Steamy fumes
with PC15
Warm with
sodium
hydroxide
solution. Acidify
with di lute nitric
acid and then
test as for ionic
hal i des as on
page 55
This i s a written paper, taken by all candidates.
It is designed to assess a candidate's abil ity (related to the topics i n
Units 1 and 2) to:
i eval uate i nformation generated from experiments
ii describe and plan techniques used i n the laboratory.
Tests
You should know the tests l i sted in Uni t 3A above.
You should al so know the tests for al kenes, the OH group and the
halogen i n halogenoalkanes.
You should be able to deduce the identity of a compound from the
re ul t of a erie of tests.
Techniques
You should be able to describe techniques used i n:
titration and enthal py change measurements
simple organi c procedures such as distillation and heating under
refl ux.
Planning
You should be able to:
Plan a seri es of tests to determi ne the identity of an i norgani c or
organi c compound.
Describe how to make up a solution of known concentration for
titrati ons.
Plan an experi ment to determine the enthalpy of a reaction such as
the combustion of a liquid, or the neutral isation of an acid.
Pl an an experiment to fol l ow the progress of a reacti on in whi ch
there is a change in physical state, such as the production of a gas.
Calculations
You should be able to calculate:
empi ri cal formul ae
reacting masses
results from titration data
enthalpy changes from experimental data.
Evaluation
You should be able to criticise:
an experimental pl an or apparatus
the results of an experiment i n terms of significant figures, accuracy
or experimental error etc.
Safety
You should be able to suggest specific safety precautions when a substance
is flammable, toxic or irritating.
U N I T TEST L
1
PrucrIce Tesr: tuIr3B
Time allowed 1 hr
All questions, except 5, are taken from parts of previous Edexcel Advanced GCE questions.
1 Complete the table below.
Gas Reagents or test
Hydrogen Burni ng splint
Oxygen Glowing spl i nt
Carbon dioxide
Sulphur dioxide Potassi um dichromate I)
solution acidified with di l ute
sulphuric aci d.
Moist blue l itmus paper
Observation expected for a positive result
Solution turn from orange to . . . . .
Turn red and i then bleached white
[6]
(Total 6 marks)
[une 2002 Unit Test 3B question 2]
2 In a series of experiments to i nvestigate the factors that control the rate of a reaction, aqueous
hydrochloric acid was added to calcium carbonate in a conical flask placed on an el ectroni c balance.
The loss i n mass of the flask and its contents was recorded for 15 mi nutes.
CaC0
3
(s) 2HCl (aq) CaC12(aq) H20(1 ) C02(g)
Four experiments were carried out.
Experiments 1, 3 and 4 were carried out at room temperature (20C) .
The same mass of calcium carbonate (a l arge excess) was used i n each experiment.
The pi eces of cal ci um carbonate were the same si ze i n experi ments 1, 2 and 4.
Experi ment Calcium carbonate Hydrochl oric acid
1 Smal l pieces 50. 0 cm
3
1 . 00 mol dm-
3
2 Small pieces 50.0 cm
3
1 . 00 mol dm-
3
heated to 80 oc
3 One large piece 50. 0 cm
3
1 . 00 mol dm-
3
4 Smal l pieces 50.0 cm
3
2. 00 mol dm-
3
a The results of experiment 1 give the curve shown on the graph below.
Mass loss/g
2. 00-
1 . 50 -
5 10 1 5 Time/mi n
b
LABORATORY C H E M I STRY 1
i Expl ai n why there is a loss in mass as the reacti on proceeds.
ii Expl ai n the shape of the curve drawn for experiment 1 .
b Draw curves on the graph above to represent the results you woul d expect for experiments 2, 3
and 4.
c i Calculate the mass of cal ci um carbonate that exactly reacts with 50. 0 cm
3
of 1 . 00 mol dm-
3
aqueous hydrochloric acid. (Molar mass of CaC03 = 1 00 g mor
1
)
[2]
[2]
l
3
!
[3]
ii Based on your answer to c part (i), suggest a suitable mass of calcium carbonate to use in the
experiments. Expl ai n your answer.
[2]
(Total 12 marks)
fanuar 2002 Unit Test 3B question 2]
3 A student was requi red to determi ne the enthalpy change for the reacti on between i ron and copper
sulphate solution. The student produced the fol lowing account of their experi ment.
A pi ece of i ron, mass about 3 g, was pl aced i n a gl ass beaker. Then 50 cm3 of 0. 5 mol dm-3 aqueous
copper sul phate sol uti on was measured usi ng a measuri ng cyl i nder and added to the beaker. The
temperature of the mi xture was measured i mmedi atel y before the addi ti on and every mi nute afterwards
unti l no further change took pl ace
Fe + CuS04 FeS04 + Cu
Ti mi ng Before 1 mi n 2 mi ns 3 mi ns 4 mi ns 5 mi ns
addi ti on
Temperatu re/C 1 6 27 29 26 24 22
a Suggest two i mprovements you would make to thi s experiment. Give a reason for each of the
i mprovements suggested. [4]
b In an i mproved versi on of the same experiment a maxi mum temperature rise of 1 5 . 2 oc occurred
when reacting excess iron with 50. 0 cm
3
of 0. 500 mol dm-
3
aqueous copper sulphate solution.
i Using thi s data and taking the specifi c heat capacity of al l aqueous solutions as 4. 1 8 J g_, deg-1 ,
calculate the heat change.
ii Calcul ate the number of moles of copper sul phate used.
iii Calculate the enthalpy change for this reacti on i n kJ mor1
[I]
[2]
(Total S marks)
fune 2002 Unit Test 3B question 4]
4 A student carried out an experiment to fi nd the percentage of calcium carbonate, CaC03, in a sample
of l i mestone fol lowi ng hi s own pl an. The student's account of the experiment, resul ts and calculations
of the mean titre are given below.
Account
I M
ass of pi ece of l i mestone = 5. 24 g
II A pi pette was used to transfer 50 cm3 of 2. 00 mol dm-3 aqeous hydrochl ori c aci d (an excess) to a
1 00 cm3 beaker. The pi ece of l i mestone was pl aced in the beaker and left unti l there was no more
effervescence.
Equati on
I l l The aci di c sol uti on i n the beaker was fi ltered i nto a 250 cm3 vol umetri c fl ask. A smal l amount of the
sol i d i mpurity remai ned i n the fi l ter paper. The sol uti on i n the vol umetri c fl ask was careful ly made up
to 250 cm3 wi th di sti l l ed water.
IV A pi pette was used to tranfer 25.0 cm3 porti ons of the aci di c sol uti on to coni cal fl asks. The sol uti on
was then titrated wi th 0. 1 00 mol dm-3 aqueous sodi um hydroxi de.
HCI(aq) + NaOH(aq) NaCI(aq) + H20(1 )
U N I T TEST L
5
Results
2 3
Burette readi ng (fi nal ) 1 4. 90 1 5.40 30. 25
Burette readi ng (at start) 0. 00 0. 05 1 5. 40
Titre/cm
3
1 4. 90 1 5. 35 1 4.
8
5
M
ean ti tre
1 4
90 + 1 5
5 + 1 4
8
5
1 5. 033 cm3
a The accuracy of the student's method was j udged to be poor by hi s teacher. The teacher suggested that
the procedure i n II could be i mproved, and that the titres used to calcul ate the mean were i ncorrectly
chosen.
i Suggest, with a reason, one i mprovement to the student's procedure in I I . [2]
ii Recalculate a value of the mean making clear which titres you choose. [2]
b i Usi ng your answer to a part (ii), calculate the amount in moles of sodium hydroxide in the mean
titre. [1]
ii Hence state the amount i n moles of hydrochl oric acid i n a 25. 0 cm
3
portion of the acidic solution
transferred i n IV. [1]
iii Hence calculate the amount in moles of hydrochloric acid remai ni ng after the reaction in I I .
[1]
iv Calculate the amount i n moles of hydrochloric acid transferred to the beaker in I I .
[1]
v Hence calculate the amount in moles of hydrochl oric acid used in the reacti on.
[1]
vi Hence calculate the amount i n moles of calcium carbonate and the mass of calcium carbonate i n
the sample of l i mestone {M, (CaC0
3
)
1 00} [2]
vii Hence calculate the percentage of cal ci um carbonate by mass in the sample of l i mestone.
[1]
c The burette used i n the titrations had an uncertai nty for each reading of 0. 05 cm
3

i Which of the fol l owi ng should be regarded as the actual value of the titre in titration 3?
A between 1 4. 80 and 1 4. 90 cm
3
:
B between 1 4. 825 and 1 4. 875 cm
3
:
C between 1 4. 75 and 1 4. 95 cm
3

[1]
ii Suggest one reason why a student may obtai n vol umes outside the uncertainty of the burette when
carrying out a titrati on.
l
1
!
(Total 14 marks)
[une 2001 Unit Test 3B question 4]
5 Propan-2-ol (molar mass 60 g mol - l and boi l i ng temperature 82 C) can be prepared by the reacti on
between 6. 1 5 g of 2-bromopropane (mol ar mass 1 23 g mor
1
and boiling temperature 59 C) and excess
aqueous 2.0 mol dm-
3
sodium hydroxide. This reacti on is sl ow at room temperature.
a Describe the procedure, identifying the apparatus that you would use, to prepare a pure sample of
propan-2-ol from 6. 1 5 g of 2-bromopropane. [5]
b Calculate the mi ni mum vol ume of sodium hydroxide solution that must be taken to ensure compl ete
reaction of the 2-brompropane. [2]
c Your teacher suggested that an 80% yield would be an excellent resul t. Calculate the mass of pure
propan-2-ol that you woul d need to prepare to obtain thi s yield. [2]
d Suggest one reason why your yield wi l l be below 1 00%.
[1]
(Total 10 marks)
4
1 Fm
!
eur : u+
_rou oty
tHa for chl ori ne i s the enthal py
change for:
1/
2
CI
2
(g) Cl (g)
tHhyd for the Na i on i s the enthal py
change for:
Na(g) + aq Na(aq)
1at for sodi um chl ori de i s the
enthal py change for:
Na (g) + Cr(g) NaCI (s)
e e i cs I I
-
This topic extend the use of Hess's Law to reacti ons i nvolvi ng ions.
You must be able to construct a Born Haber cycl e.
Lattice energy i s cruci al to the understanding of i oni c bondi ng, because
it i s this release of energy that makes the formation of an i oni c
substance thermodynamically favourabl e.
Definitions of enthalpy changes must i nclude:
i the chemical change taking pl ace
ii the conditions
iii the amount of substance (reactant or product)
iv an exampl e of an equation with state symbols, as this may gai n
marks l ost through omi ssi on i n your word defi ni tion .
t-
The sign of the value of tH tells you the di recti on of the movement of
heat energy:
positive (endothermic) for heat flowi ng into the system
negative (exothermic) for heat flowing out of the system.
Enthalpy of atomisation, ^_ i s the enthalpy change for the
production of one mole of atoms in the gas phase from the
element i n its standard state. I t i s always endothermi c.
Enthalpy of hydration, ^___y is the enthalpy change when one
mole of gaseous ions is added to excess water. It is always exothermic.
Lattice energy, ^,au' i s the energy change when one mole of
ionic solid i s made from its separate gaseous ions. I t i s always
exothermic.
Born-Haber cycle
Thi s relates the enthal py of formation of an i oni c solid to the
enthalpies of atomi sation of the elements concerned, the i onisation
E N E RG ET I CS I I
Mg
z
+
(g)
zcr(g)
Mg
+
(g) 2Cl (g)
Mg(g)
t
Mg(s) Cl2(g)
Fig 4. 1 Bor-Haber cycle
energies for the formation of the cation, the electron affi nity for the
formation of the ani on and the l attice energy of the i oni c substance.
cl
This can either be drawn as a Hess' Law cycle, or as an enthalpy l evel
diagram (see Figures 4. 1 and 4. 2) .
M,
+
(g) 2Cl (g)

Mg
2
+
(g) Cl2( a)
S
Mg
+
(g) Cl2( )
M
z
. |g zcr (g)
6
Mg(g) Cl2(g)
Mg(s) Cl2(g)
|
MgC12(s)
V
Fig 4.2 Enthalpy level diagram
^ of MgC12 * m. of Mg (tl
1
) 1 st i oni sation energy of Mg (tlf2) 2nd ionisation ener _ O V 2 7
m. of Cl (tl 4) 2 ? electron affinity of Cl (tl s) tl latt of MgClz (tl 6) * m
l
m: 2 D 2 M6
If a bond is parti al l y coval ent, the
experi mental l atti ce energy (from
Born Haber) wi l l be bi gger (more
exothermi c) than the val ue
cal cul ated from a purel y i oni c
model .
The greater the di fference between
the experi mental and theoreti cal
val ues, the greater the extent of
coval ency. Thi s wi l l happen i f the
cati on i s very pol ari si ng (smal l or
hi ghl y charged) or the ani on i s very
pol ari sabl e (l arge) . See page 1 3.
Any one value can be calcul ated when al l the other ar n \VO.
Lattice energ
Lattice energy is always exothermic.
Its value depends upon the strength of the fore of attraction
(sometimes cal led the ionic bond) between the ion .
The strength of thi s force depends upon the Yal ue of the charges and
the sum of the radi i of the ions:
i the l arger the charge on either or both of the ions, the larger ( more
exothermic) the lattice energy
ii the l arger the sum of the ionic radi i , the smal l er (less exothermic)
the lattice energy.
Theoretical val ues of l attice energy can be calculated assuming that the
substance i s 1 00% i oni c.
Variation of lattice energies in a Group
Group 2 sulphates. As the radius of the cation i ncreases down the
Group, the l attice energy decreases. But because the radi us of the
sul phate i on is much l arger than the radi i of any of the Group 2
cations, the sum of the radi i of the cation and the anion alters only
slightly, and so the l attice energy only decreases slightly.
Group 2 hydroxides. As the radius of the cati on i ncreases down the
Group, the lattice energy decreases. But because the ani on i s smal l , and
matches the size of the cation (the i oni c radi i of Ba
2
+ and OH- are about
the same), the sum of the radi i al ters signifcantly, and so the l attice
energy decreases by a large amount.
b
PE R I ODI CI TY, QUANTI TAT I VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP C H E M I STRY
You must not use !Hhyd when
referri ng to a compound. I t refers to
separate i ons. The enthal py change
for NaCI ( s) + aq Na+(aq) + Cl-(aq)
is cal l ed the enthal py of sol uti on.
Note that both latti ce and hydrati on
enthal pi es are negati ve numbers, so
-1Kan i s posi ti ve
Enthalpy of hydration
Enthalpy of hydration is always exothermic.
For a cation it i s the resul t of the force of attraction between the i on
and the r oxygen i n the water.
For an anion i t i s the result of the force attraction between the ion and
the 8 hydrogen i n the water.
The value of enthal py of hydration wi l l depend upon the val ue of the
charge on the i on and its radi us:
i the l arger the charge, the l arger (more exothermic) the enthalpy of
hydration,
ii the l arger the i oni c radi us, the smal ler (less exothermic) the
enthalpy of hydration.
Variation of enthalpies of hydration in a Group
The value wi l l become less exothermic as the radi us of the cation increases
down the Group.
Solubility
The di rection of a chemical reaction i s parti al ly determi ned by the value of
the enthal py change. When discussing solubil ities, i t is assumed that the
more exothermic the enthalpy of solution, the more soluble the substance
is l ikely to be. The enthalpy of solution can be estimated from a
consideration of l attice energies and enthalpies of hydration of the two
i ons as can be seen from a Hess's l aw diagram.
M+(g) + x-(g)
- .
_
-
MX(s) + aq M+(aq) x-(aq)
Hs
o
ln
= (lattice energy) + (hydration enthal py of each cation + hydration enthalpy of each ani on)
Solubility of Group 2 sulphates
i The enthalpy of hydration becomes much less as the cati ons
become bigger.
ii Because the radius of the sul phate ion is much bigger than the
radius of any of the cations, the lattice energy onl y decreases
slightly - see above.
iii (i ) and (i i ) together mean that the enthalpy of solution becomes
considerably less exothermic and causes the solubility of the
sul phates to decrease down the Group.
Solubility of Group 2 hydroxides
i The enthalpy of hydration becomes less as the cati ons become
bigger.
ii Because the radi us of the hydroxide ion is a si mi l ar size to that of
the cations, the l attice energy decreases considerably.
iii (i) and (i i ) together mean that the enthalpy of solution becomes
considerably more exothermic and causes the solubi l i ty of the
hydroxides to increase down the Group.
E N E RGETI CS I I
a MgC0
3
b MgC0
3
c NaF
Ba( OH)
2

W
_-.
Can defi ne enthal py of atomisation.
Can defi ne enthalpy of hydration.
Can define l attice energy.
Can construct a Born-Haber cycl e.
Can use a Born-Haber cycle to cal culate lattice energy or electron
affi ni ty.
Understand why the value of M
1
au from Born-Haber might be more
exothermic than the theoretical val ue.
Can state and expl ai n the change i n solubilities of the Group 2
sul phates and hydroxides.
bJ
t ,....
For the fol lowing questions, cover the margi n, write your answer, then
In each of the fol lowing state which compound has the l arger (more
exothermic) lattice energy:
a MgC0
3
or BaC0
3
b Na2C0
3
or MgC0
3
c NaF or NaCl .
Arrange the fol l owing i ons i n order of decreasing ( l ess exothermic)
enthalpy of hydrati on: Na+, Mg
2
+, Ba
2
+ and A
e
+
State the formula of the most soluble Group 2 hydroxide.
1 The fol l owing data, i n kJ mor
1
, should be used i n thi s question.
Enthalpies of atomi sation: calcium +1 93; chlorine +1 21 .
I oni sation energies for calci um: 1 st +590; 2nd + 1 1 50
Electron affi ni ty for Cl (g): -364
Latti ce energi es: for CaC12(s) -2237; for CaCl (s) -650 (estimated) .
a Construct a Born-Haber cycle for:
i the formation of CaCl (s)
ii the formation of CaC12(s) .
b Calculate the standard enthalpy of formation of:
i CaClz(s)
ii CaCl (s)
iii hence calculate the enthalpy of the reacti on:
2CaCl (s) Ca(s) + CaC12(s)
and comment on the fact that CaCl (s) does not exist.
2 Comment on the values of the lattice energies, i n k] mor
1
, given
below:
Experimental Theoretical
NaF -91 8 -91 2
Mgl
2
-2327 -1 944
b4
:
PE R I OD I C I TY, QUANTI TATI VE EQU I L I B R I A A N D FU NCTI ONAL G ROU P C H E M I STRY
The Peri odi c Table I I

_ .
You wi l l need to look agai n at Topic 1 . 4.
The elements become more metallic down a Group. Thi s means that
their compounds, such as their chlorides, become more i oni c and thei r
oxi des become more basic.
The elements become less metallic from left to right across a Period.
Thi s means that thei r chlorides become more covalent and their oxides
become more acidic.
There are many formulae and equations that must be learnt in
this Topi c.
The properties of elements and their compounds change steadi ly from
the top to the bottom of a Group and from left to right across a Period.
_t- .
Variation of properties across Period 3
A table is given below showing the formulae of the products of the
reactions of the elements with oxygen, chlorine and water:
Oxygen
Chl orine
Water
Na
Na20 or
Na202
l !
NaCl
NaOH +
H
z
Mg
MgO
MgC12
MgO +
H 2
Al
Al20
3
A1Cl
3
<
2
1
No
reaction
Si
Si02
SiC14
No
reaction
l s Cl Ar
P40
1
0 so
z
No No
reaction reacti on
PC1
3
S2Cl2 No
PC15 reacti on
No No HCl + No
reaction reaction HOCl reaction
O!6S. W !H6XC6SS OXj_6H SOGUH Q6iOXG6 S!OiH6G, d UH H UHCH Oi G6 SCOVd6H!, W!H 6XC6SS
CHOiH6, W!H S!6dH.
The hydroxi des become l ess basi c and
more aci di c as the su rface charge
density of the cati on i ncreases.
Si l i con di oxi de i s such a weak aci d that
molten sodi um hydroxi de is requi red.
The oxi des of t he non-metal s form
i ncreasi ngl y strong aci ds as the
number of oxygen atoms i n the aci d
i ncreases.
Metal hydroxides and oxides
NaOH alkali ne: NaOH(s) + aq -Na+(aq) + OH-(aq)
Mg(OH)2 basic: Mg(OH)2(s) + 2H+(aq) -Mg
2
+(aq) + 2H20(l )
MgO basi c: MgO(s) + 2H+ (aq) -Mg
2
+(aq) + H20(1 )
Al (OH)
3
amphoteric: Al (OH)
3
(s) + 3H+(aq) - A
e
+(aq) + 3H20(l )
Al (OH)
3
(s) + 30H-(aq) Al (OH),
(aq)
Al20
3
amphoteric: Al20
3
(s) + 6H+(aq) - zA
e
+(aq) + 3H20(1 )
Al20
3
(s) + 60H-(aq) + 3H20(1) 2Al (OH)
,(aq)
Non-metal oxides
Si 02 weakly acidic: Si 0
2
(s) + 2NaOH(l ) - Na2Si 0
3
(l ) + H20(g)
P406 weakly acidic: P406 + 6H20 - 4H
3
P03 4H+(aq) + 4H2P0
3
-
P401 strongly acidic: P40
1
0 + 6H20 - 4H
3
P04 - 4H.(aq) + 4H2P04-
TH E PE R I ODI C TABLE I I
I oni c chl ori des di ssol ve i n water to
form hydrated i ons.
These hydrated i ons may
deprotonate, if the su rface charge
densi ty of the metal i on i s hi gh.
Coval ent chl ori des ( of Peri od 3)
react wi th water to form HCI and
ei ther the oxi de or the oxoaci d.
The trend i n metal l i c character i s
caused by the decrease i n i oni sat i on
energy as t he radi us of the atom
i ncreases, maki ng i t energeti cal l y
favourabl e for the formati on of i oni c
bonds.
Chlorides
weakly acidic: S02 + H20 - H2S03 H(aq) + HS03-
strongly acidic: S03 + H20 - H2S0
4
- H (aq) + HS04-
NaCl i oni c sol i d, dissolves in water:
NaCl (s) + aq - Na (aq) + Cr(aq)
MgC12 ionic solid, di ssolves in water:
MgC12(s) + aq - Mg
2
(aq) -2C
r(
aq)
Hydrated A1Cl3 ionic sol id, deprotonated by water:
[Al (H20)b]
3
.( aq) + H20 - [Al ( H20)5(0H)]
2
(aq) + H30.(aq)
Anhydrous A1 Cl3 co alent solid, reacts with water:
A1 Cl3(s) + 3H20(l) - Al (OH)ls) + 3HCl (aq)
Si Cl

covalent l i quid, reacts with water:
SiClJl) + 2H20(l ) - Si 02(s) + 4HCl (aq)
PCll covalent l i quid, react 'ith water:
PCl l ) + 3H: () - H P03
(aq) + 3HCl (aq)
PCl5 co alent olid, reacts with water:
PCls( ) + -H20( 1 ) - H PO-aq) + SHCl (aq)
Variation of properties down Group 4
The metallic character i ncreases down the Group:
carbon and si l icon are non-metallic ( not malleable; only graphi te
conducts electricity)
germani um i s semi-metal l i c (semi-conductor) .
ti n and l ead are metall i c (mall eable and electrical conductors) .
b
The +2 oxidation state becomes more stable relative to the +4
state. Lead( IV) is oxidising and is itself reduced to lead( I I) , whereas
ti n( I I) i s reducing and i s itself oxidised to ti n(IV) . This is i l l ustrated by:
lead( IV) oxide oxidises concentrated hydrochloric acid to chlorine:
Pb02 + 4HCl - PbC12 + Cl2 + H20
ti n( I I) ions are oxidised to ti n( IV) i ons by chlorine:
Sn
2
+ Cl2 - Sn-l + zcr
Tetrachlorides. Both CC14 and Si Cl
4
are covalent and are tetrahedral
molecules owing to the repul si on of the four bond pairs of electrons.
Si Cl4 i s rapidly hydrolysed by water. A lone pair of electrons from the
oxygen i n the water forms a dative bond i nto an empty 3d orbital i n
the si licon atom. The energy released is enough to overcome the
activation energy barrier i nvolved i n the breaking of the Si-Cl bond.
Carbon's bonding electrons are i n the 2nd shel l and there are no 2d
orbital s. The empty orbitals in the 3rd shell are of too hi gh an energy to
be used in bonding, and equal ly i mportant i s that carbon i s such a
smal l atom that water molecules are prevented from reaching it by the
four much l arger chlorine atoms arranged tetrahedrally around it.
Acidity of the oxides. Thi s decreases down the Group:
Carbon dioxide i s weakly acidic, and reacts with metal oxides and
al kal i s:
C02(g) + 20H-(aq) - C03
2
-(aq) + H20(1)
Si licon di oxi de i s very weakly acidic, and reacts with molten sodi um
hydroxi de:
Si 02(s) + 2Na0H(l ) - Na2Si 03(1) + H20(g)
Lead oxides (and hydroxide) are amphoteric, and react with aqueous
acids and al kalis, but lead( I I ) oxide is the strongest base of the Group
4 oxides:
PbO(s) + 2H.(aq) - Pb
2
\aq) + H20(1)
PbO(s) + 20H-(aq) + H20 - Pb(OH)t(aq)
bb
PE R I OD I C I TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP CH E M I STRY
Pb O an d Pb0
2
PbO
q uesti ons are on pages
1 32-1 33.
_-.
Before attempting the questions on thi s topic, check that, for the Period 3
elements, you:
Can write equations for the reactions of the elements with oxygen and
with chlorine.
Can write equati ons for the reaction of the elements with water.
Can state and explain the acid/base nature of the metal hydroxides.
Can state and explain the acid/base nature of the non-metal oxides.
Know the formul a of their chl orides and their reacti ons with water, and
can relate the reacti ons to thei r bonding.
Before attempting the questions on thi s topic, check that, for the Group 4
elements, you:
. Know why t he elements become more metallic down t he Group.
Know that the +2 oxidation state becomes more stable down the
Group.
Know why Si C14 i s rapidly hydrolysed by water, whereas CCl4 i s
unreactive wi th water.
Can write equations to show the acid/base character of the oxides of
carbon, si li con and lead.
_t ,...
For the following questions, cover the margi n, write your answer, then
State the formulae of lead( I I) oxide and lead(IV) oxide.
State the formula of the most basic Group 4 oxide.
1 a Write equations for the changes caused by the addition of water to:
i sodi um chloride
ii si l i con tetrachloride
phosphorus pentachloride.
b Relate these reactions to the bonding in the chlorides.
c Explain why si licon tetrachl oride, Si Cl4, reacts rapidly with water,
but tetrachloromethane, CCl4, does not react even when heated with
water to 1 00
C.
2 Write two i oni c equati ons to show that al umi ni um hydroxide i s
amphoteric.
3 Write i oni c equations for the reacti ons, if any, of:
a aqueous acid wi th:
i magnesi um hydroxi de
ii l ead monoxide
sulphur dioxide
b aqueous al kal i with:
i magnesium hydroxide
ii lead monoxide
sul phur dioxide.
4 a Write an equation to show lead(IV) oxide acting as oxidising agent.
b Write an equation to show aqueous ti n( I I ) i ons acting as a reducing
agent.
C H E M I CAL EQU I LI B R I U M I I
The val ue of I i s speci fi c to a
reacti on - and to the equati on used
to represent that reacti on - and can
onl y be al tered by changi ng the
temperature.
Chemi cal equi li bri a I I
Concentration, i n the context of equilibrium, i s always measured i n
mol dm-
3
, and the concentrati on of a substance A i s written as [A] .
b1
The common errors i n thi s topic are to use moles not concentrations
and i nitial values not equilibrium values when substituted i n
expressi ons for Kc.
Calculations of K must be set out clearly, showing each step.
A homogeneous equilibrium is one in which al l the substances are i n
t he same phase, vherea in a heterogeneou equilibri um there are two
or more pha e .
t- .
The equilibrium constant Kc
The equilibrium constant, measured i n terms of concentrations, is found
from the chemical equation.
For a reacti on:
rA + nB T xC + yD
where m, n, x and y are the stoichiometric numbers i n the equati on:
Kc = [cre
q
[ DY e
q
[A]"'e
q
[BJe
q
Al l the concentrations are equi librium val ues.
I n a heterogeneous equi l ibrium a solid substance does not appear i n the
expression for Kc
Kc i s only equal to the quotient [CY [ DY
[A] ,
[ B]
"
when the system is at equi l ibrium.
If the quotient does not equal Kc , the system is not in equilibrium and
wi l l react until i t reaches equilibrium when there wi l l be no further
change i n any of the concentrations.
Kc has uni ts. For the reacti on:
the units of Kc are
N2 + 3H2 T 2NH3
Kc = [NH3]
2
e
q
[Nz] e
q
[ Hz]
3
eq
(mol dm-
3
)
2
1
--- = mor
2
dm
6
(mol dm-
3
) (mol dm-
3
)
3
=
(mol dm-
3
)
2
bb
.
PE R I ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP CH E M I STRY
C(s) does not appear i n the K
c
expressi on because it is a sol i d.
The amount of CO made i s twi ce
the amount of C0
2
reacted.
Calculation of 1
Thi s must be done using equi librium concentration values, not i niti al
concentrati on val ues. The calculation i s done i n 5 steps:
i Draw up a table and fi l l in the i nitial number of moles, the change
for each substance and the equi l ibrium number of moles of each
substance.
ii Convert equilibrium moles to concentration in mol dm-
3

iii State the expression for Kc.
iv Substitute equi l i bri um concentrati ons i nto the expression for Kc.
v Work out the uni ts for Kc and add them to your answer.
+r/
An i mportant reacti on in the bl ast furnace i s the formati on of carbon monoxi de
from carbon and carbon di oxi de. Thi s reacti on i s an exampl e of a
heterogeneous equi l i bri um.
When 1 . 0 mol of carbon di oxi de was heated wi th excess carbon t o a
temperatu re of 700 oc in a vessel of vol ume 20 dm
3
, 95% of the carbon
di oxi de reacted fo form carbon monoxi de. Cal culate Kc for
C( s) + C0
2
(g) 2CO( g)
Answer
C0
2
( g) CO( g)
I ni ti al amount 1 . 0 0
Change -0. 95 +0. 95 ? 2
Equi l i bri um amount 1 . 0 - 0. 95 " 0. 05 1 . 9
Uni ts
mol
mol
mol
Equi l i bri um concentrati on 0. 05/20 " 0. 0025 1 . 9/20 " 0. 095 mol dm-
3
K
c
[ C0]
2
eq " ( 0. 095)
2
( mol dm-
3
)
2
" 3. 6 mol dm-
3
[ C0
2
J eq 0. 0025 mol dm
Partial pressure
The partial pressure of a gas A, pA, in a mixture is the pressure that the
gas would exert i f it al one fil led the contai ner. I t i s calculated from the
expressi on:
parti al pressure of a gas = mole fracti on of that gas ? total pressure
where the mole fracti on the number of moles of that gas
the total number of moles of gas
The total pressure, P, i s equal to the sum of the partial pressures of each
gas in the mi xture.
The equilibrium constant Kv
The equilibrium constant, measured i n terms of partial pressure, only
applies to reacti ons i nvolving gases. Solids or liquids do not appear i n
the expression for K
P
.
For a reacti on:
mA(g) xB(g) + yC(g)
where m, x and y are the stoi chiometric numbers in the equati on:
K
p
=
(sYeg
?
( Yeq
C H E M I CAL EQU I LI B R I U M I I
As carbon i s a sol i d i t i s i gnored i n
t he expressi on.
Al l partial pressures are equi l ibrium values.
So for the reaction:
C02(g) + C( s) 2CO(g)
K
P
p(CO/e
q
and its uni ts are atm
2
= atm
p(C02)e
q
atm
Calculations involving KP
b5
The calculation of K
P
from equil ibrium data i s done i n a si mi lar way to
those i nvolving Kc:
i Draw up a table and fi l l in the i ni tial number of moles, the change
for each substance, the equilibrium number of moles of each
substance and the total number of moles at equilibrium.
ii Convert equi l ibri um moles to mole fraction.
iii Multi ply the mol e fracti on of each by the total pressure.
iv State the expression for K
P
.
v Substitute equilibrium concentration i nto the expression for K
P
.
vi Work out the units for K
P
and add th m to your an wer.
0. 080 mol of PCI5 was pl aced in a vessel and heated to 1 75 C. When
equi l i br i um had been reached, it was found that the total pressu re was 2. 0 atm
and that 40% of the PCI 5 had di ssoctated. Cal culate Kp for the reacti on:
PCI 5 ( g) PCI3(g) + Cl
2
gj
Answer As 40% had di ssociated, 60% was l eft. Thus at equi l i br i um:
0. 60 ? 0. 080 ^ 0. 048 mol of PCI 5 was present and therefore
0. 080 - 0. 048 0. 032 mol of PCI 5 had reacted.
PCI5 PCI
3
Cl
2
I ni ti al amount/mol 0. 080 0 0
Change/mol -0. 032 +0. 032 +0. 032
Equi l i bri um amount 0. 60 ? 0. 080
/mol ^ 0. 048 0. 032 0. 032
Mol fracti on 0. 048/0. 1 1 2 0. 032/0. 1 1 2 0. 032/0. 1 1 2
0. 429 " 0. 286 " 0. 286
Parti al pressure 0. 429 ? 2 0. 286 ? 2 0. 286 ? 2
/atm " 0. 857 0. 571 0. 571
Kc " p( PC1
3
)eq p(CI2)eq ^ 0. 571 atm ? 0. 571 atm " 0. 38 atm
p( PCi s)eq 0. 857 atm
Total
0. 1 1 2
Variation of K with conditions
K only equal s the quoti ent when the
system i s at equi l i bri um. I f the
quoti ent i s greater than K, the
reacti on wi l l move to the left unti l _
the two are equal . I f the quoti ent i s
l ess than K, the reacti on wi l l move
to the ri ght unti l the two are equal .
Temperature changes al ter the val ue
of K , unl ess !H " 0, . Concentrati on
and pressure changes alter the val ue
of the q uoti ent.
Temperature. Thi s i s the only factor that alters the value of K.
i If a reacti on is exothermic left to right, an i ncrease in temperature
will l ower the value of K. This means that the position of
equilibrium will shi ft to the left (the endothermic di recti on) .
ii I f a reaction i s endothermic left to right, an i ncrease in temperature
will increase the value of K. This means that the position of
equi l i bri um will shift to the right.
Catalyst. Thi s neither alters the value of K nor the position of
equi l ibrium. I t speeds up the forward and the reverse reacti ons equal ly.
Thus it causes equil ibrium to be reached more quickly.
10
:
PE R I ODI C I TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROU P CH E M I STRY
p(N
2
) " 0. 781 x 1 04 " 81 . 2 k N m-
2
p(0
2
) " 0. 21 0 X 1 04 " 21 . 8 kN m-
2
p(Ar) " 0. 009 ? 1 04 " 0. 9 kN m-
2
a l " [ S0
3
]
2
" mol-1 dm
3
[ S0
2
]
2
[ 0
2
]
b
*
" [ H
2
0] [ CI
2
] ^ mor
1 1
2
dm
31
2
[ HC!f [ 0
2
f
1
2
a Kp " p(CH
3
0H) atm-
2
p(CO) ? p(H
2
))
2
b " p(C0
2
) no units
. >
p(CO)
Concentration. A change i n the concentrati on of one of the
substances i n the equilibrium mixture will not alter the value of K, but
i t wi l l alter the value of the quotient. Therefore the reaction wi l l no
longer be at equi l ibrium. It wi l l react unti l the value of the quotient
once agai n equals K. I f the concentrati on of a reactant on the left hand
side of the equation i s i ncreased, the position of equi li bri um will move
to the right.
Pressure. A change i n pressure does not alter K. I f there are more gas
molecules on one side than the other, the value of the quotient will be
altered by a change i n pressure. Therefore the reacti on wi l l no longer be
at equilibrium, and wi l l react unti l the val ue of the quotient once agai n
equals K. If there are more gas molecules on the right of the equation
and the pressure i s i ncreased, the posi ti on of equilibrium will move to
the left. For example, i f the pressure i s i ncreased on the equilibrium
N20
4
(g) 2N02(g), the position of equi l i brium will shi ft to the left as
there are fewer gas molecules on the left si de of the equation.
_-.
Can defi ne t he partial pressure of a gas.
Can deduce the expressi on for Kc and its units given the equation.
Can deduce the expression for K
P
and its units given the equati on.
Can calculate the value of Kc given suitable data.
Can calculate the value of K
P
given suitable data.
Know not to i nclude values for solids and liquids in the expression
for K
P
.
Know that only temperature can alter the value of K, and how it will
affect the position of equi l i brium.
_t ,...
For the fol lowing questions, cover the margi n, write your answer, then
Dry ai r at a pressure of 1 04 kN m-
2
contains 78. 1 % nitrogen 21 . 0%
oxygen and 0. 9% argon by moles. Calculate the partial pressures of
each gas.
Write the expressi on for K
CI
stating its units, for the fol lowing reacti ons:
a 2S02(g) + 02(g) 2S0
3
(g)
b 2HCl (g) +
1
/202(g)
H20(g) + Cl2(g)
Write the expression for K
P
, stating its units, for the fol lowi ng reacti ons:
a CO(g) + 2H2(g) CH
3
0H(g)
b Fe20
3
(s) + CO(g) 2Fe0(s) + C02(g)
1 When a 0. 0200 mol sample of sulphur trioxide was i ntroduced i nto a
vessel of volume 1 . 52 dm
3
at 1 000 C, 0. 01 42 mol of sulphur trioxide
was found to be present after equilibrium had been reached.
ACI D-BASE EQU I LI B R I A
1l
Calculate the value of Kc for the reacti on:
2S0
3
(g) 2S02(g) + 02(g)
2 1 . 0 mol of ni trogen( I I) oxide, 0, and 1 . 0 mol of oxygen were mi xed in
a container and heated to 450 C. At equilibrium the number of moles
of oxygen was found to be 0. 70 mol. The total pressure i n the vessel was
4. 0 atm. Calculate the alue of K
P
for the reaction:
2 0 g + 02(g) 2N02(g)
3 This question concern the equilibrium reaction:
2S02(g) + _ ) 2 M = -196 kJ mor
1
K = 3 ? 1 0
4
mor
1
dm
3
at 450 C
a 2 mol of sulphur di oxi d g 1 mol of oxy en and 2 mol of sulphur
trioxide were mi xed in a \ e I of volume 1 0 dm
3
at 450 oc i n the
presence of a cataly t. tat ' h th th e ub tances are i ni ti al ly i n
equil ibri um. I f not, explain ' hi h ' a! th ter ' auld react.
b State and explain the ff t on th \ alu of K n on the po ition of
equilibri um of:
i decreasing the temperature
ii decreasing the pressure
iii addi ng more catalyst.
Aci d-base equi li bri a
_ .
It is essential that you can write the expression for Ka of a weak acid.
Make sure that you know how to use your calculator to evaluate
logarithms, and how to turn pH and pKa values i nto [ H+] and Ka values.
This means using the lg key for log
1
0 and l Ox key for i nverse log
1
0
Give pH values to 2 deci mal places.
Buffer solutions do not have a constant pH. They resist changes in pH.
You may use H+, H+(aq) or H
3
0+ as the formula of the hydrogen i on.
_t-
A Bronsted-Lowry acid is a substance that donates an H+ ion (a
proton) to another species.
A monobasic ( monoprotic) acid contai ns, per molecule, one hydrogen
atom which can be donated as an H+ i on. A dibasic acid contains two.
A Bronsted-Lowry base is a substance that accepts an H+ ion from
another species.
Kw = [ H+(aq)] [ OH-(aq)] = 1 . 0 ? 1 0-
1
4
moe dm-
6
at 25 C.
'
A neutral solution is one where [H+(aq)] = [OH-(aq) ] .
pH = -log
1
0 [H+(aq)] , or more accurately = -log
1
0( [ H
3
0+(aq)] /mol dm-
3
) .
1
;
PE R I ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D FU NCT I ONAL G ROUP C H E M I STRY
I f the aci dity of a sol uti on i ncreases,
[W] i ncreases but the pH decreases.
The 2nd i oni sati on of a di basi c aci d
such as H
2
S04 i s weak. So [ W] for
0. 321 mol dm-
3
H
2
S04 i s not 0. 642
mol dm-
3
, but i s only 0. 356 mol dm-
3

For an al kal i wi th 2 OH per formul a,
the [ OW] i s 2 x the [ al kal i ] .
The pH of a 0. 1 09 mol dm-
3
sol uti on
of Ba( OH)
2
i s
pOH " -l ogg(2 x 0. 1 09) " 0. 66
Therefore pH " 1 4 - 0. 66 " 1 3. 34
Remember that aci ds have a pH 7
and al kal i s a pH ` 7.
,pOH = -log
1
0 [0H-(aq) ] .
pH + pOH = 1 4 at 25 C.
A strong acid is total ly ioni sed in aqueous solution, and a weak acid
i s only partially i oni sed i n aqueous solution.
Ka for a weak acid, HA, * [ H+] [A-] I [ HA] .
pKa = -log
1
0 K o
A buffer solution i s a solution of known pH which has the abil ity to
resi st changing pH when small amounts of aci d or base are added.
_r- .
Conjugate acid/base pairs
These are l i nked by an H+ i on:
Acid - H+ its conj ugate base:
CH
3
COOH (acid) - H+ CH
3
COo- (conj ugate base)
Base + H+ its conj ugate acid:
NH
3
(base) + H+ NH/ (conj ugate acid)
When sulphuric acid i s added to water, it acts as an acid and the water
acts as a base:
H2S04 + H20
acid base
H
3
0+
conj ugate acid of H20
+ HS04-
conj ugate base of H2S04
Hydrogen chlori de gas acts as an acid when added to ammonia gas:
HCl + NH
3
NH4+ + cr
aci d base conj ugate acid of NH
3
conj ugate base of HCl
pH scale
Water partially i oni ses
H20 H+(aq) + OH-(aq)
As the [ H
2
0] i s very large and so is effectively constant, its value can be
i ncorporated i nto the K for the reaction:
Kw = [ H+] [OH-] = 1 . 0 ? 1 0-
l
+
1nol
2
dm- at 25 C
or pH + pOH * 14 at 25
o
c
So at 25 t.
A neutral solution i s one where [ H+] = (OH-] , and the pH = 7.
An acidic solution i s one where [H+] > [ OH-] , and t he pH < 7.
An alkaline solution i s where [ H+] < [ OH-] , and the pH > 7.
pH of strong acids and bases
For a strong monobasic acid:
pH = -log1 0 [ acid]
Therefore the pH of a 0. 321 mol dm-
3
solution of
HCl = -log
1
0 (0. 321 ) = 0. 49
For a strong al kal i wi th one OH- ion i n the formul a:
pOH = -log1 0[alkali] and
pH = 1 4 - pOH
ACI D-BAS E EQU I LI BR I A
At half way to the end poi nt ( 1 2. 5
cm
3
i f t he end poi nt i s at 25 cm
3
) ,
the curve for a weak aci d and a
strong base wi l l be al most hori zontal
at a pH of about 5. Thi s i s when the
sol uti on i s buffered and [ HA] [AT
Thus at the hal f way pH, pJ pH
f or the weak aci d.
Fig 4. 3 Ttrtion curves
1J
Therefore the pH of a 0. 1 09 mol dm-
3
solution of NaOH is calculated:
pOH = -log
1
0(0. 1 09) = 0. 96
Therefore pH = 1 4 - 0. 96 = 1 3. 04
pH of weak acids
Weak acids are parti al l i oni ed. A general equation for thi s i s:
HA(aq H(aq) + A-(aq)
The acid produces equal amount of H. and A-, so that:
[ H. (aq) ] = [A-(aq)]
Thi s enables either the pH of a Y ak acid olution or the value of Ka of a
weak acid to be calculated.
Cal culate the pH of a 0. 23 mol dm sol u i on o an aci d
K " 4. 56 x 1 o-s mol dm-:
HA(aq) H (aq) A-{ aq)
Answer: K3 " [ W(aq) ] [A-(aq) ] [ W(aq) r
[ HA(aq) ] [ HA(aq)]
[ W(aq) ] ( J . [ HA(aq) ] )
( 4. 56 x 1 0-
5
x 0. 1 23) 2. 37 x 1 0-
3
mol dm-
3
pH " - l og
1 0
( 2. 37 x 1 o-
3
) " 2. 63
Titration curves
hie has
These are drawn either for the addition of base to 25 cm
3
of a 0. 1 mol
dm-
3
solution of aci d unti l the base i s i n excess, or for additi on of acid
to a base (see Figure 4. 3) .
I f the acid and base are of the same concentration, the end poi nt i s at
25 cm
3

There are several pH values to remember.
Starting End point Vertical pH Fi nal
pH pH range pH
Strong acid/strong base 1 7 3. 5 to 10. 5 1 3
Weak acid/strong base 3 9 7 to 1 0. 5 1 3
Strong acid/weak base 1 5 3. 5 to 7 1 1
1
1
1
1 1
1 1
1 1
9
9
9
pH
7
7
7
5
5
5
0 25 0 25 0 25
Volume of alkali / cm
3
Volume of alkal i / cm
3
Volume of alkal i / cm
3
14
"
PE R I ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP C H E M I STRY
Indicators
For use in a titration, an indi cator must change colour within the pH of
the vertical part of the titration curve.
Vertical range of pH Suitable indicator
Strong acid and base 3. 5 to 1 0. 5 Methyl orange or phenolphthalein
Weak acid/strong base 7 to 1 0. 5 Phenolphthalein
Strong acid/weak base 3. 5 to 7 Methyl orange
Buffer solutions
These consist of an acid/base conj ugate pair, e.g. a weak acid and its salt
such as CH
3
COOH/CH
3
C00Na, or a weak base and its salt, e. g.
NH
3
/NH4Cl .
To be abl e to resist pH changes, the concentration of both the acid and
i ts conj ugate base must be similar.
Consider a buffer of ethanoic acid and sodi um ethanoate. The salt i s
flly i oni sed:
CH
3
C00Na(aq) - CH
3
COO-(aq) + Na(aq)
The weak acid i s partially ioni sed:
CH
3
COOH(aq) H+(aq) + CH
3
COO-(aq)
The CH
3
COo- ions from the salt suppress most of the i onisation of the
acid, and so both [CH
3
COOH(aq)] and [ CH
3
COO-(aq)] are l arge.
If H+ i ons are added to the solution, almost al l of them are removed by
reaction with the large reservoir of CH
3
COO- ions from the salt:
H+(aq) + CH
3
COO-(aq) - CH
3
COOH(aq)
If OH- ions are added, al most all of them are removed by reaction with
the large reservoir of CH
3
COOH molecules of the weak acid:
oH-(aq) + CH
3
COOH - CH
3
Coo-(aq) + H20(1)
Calculation of the pH of a bufer solution
Consider a buffer made from a weak acid, HA, and its salt NaA.
The acid i s partial l y i oni sed:
HA(aq) H+(aq) + A-(aq)
Thus Ka * [H+(aq)] [A-(aq)]
[HA(aq)]
The salt i s totally i onised, and suppresses the i oni sation of the acid,
Therefore [A
-
(aq)] = [salt]
and [ HA(aq)] * [weak acid]
I f the concentrati ons of the weak
aci d and its sal t are the same, then:
[ W (aq) ] ^ J g and
Thus Ka = [ H+ (aq)] [salt]
[weak acid]
or [ H+ (aq)] * Ka [weak acid]
pH " pJ.
[salt]
pH = -log[H+(aq)]
ACI D-BAS E EQU I LI B R I A
+r/
Cal culate the pH of 500 cm
3
of a sol uti on contai ni ng 0. 1 21 mol of ethanoi c aci d
and 0. 1 00 mol of sodi um ethanoate.
pJ for ethanoi c aci d = 4. 76
Answer pJ = 4. 76,
Therefore J = i nverse l og(-pK) = 1 . 74 x 1 0-
5
mol dm-
3
[weak aci d] = 0. 1 21 0. 500 = 0. 242 mol dm-
3
[sal t] = 0. 1 00 0. 500 = 0. 200 mol dm-
3

[ W(aq) ] = J . [weak aci d] = 1 . 74 x 1 0-5 x 0. 242 = 2. 1 0 x 1 0-
5
mol dm-
3
sal t] 0. 200
pH = -l og
,
0[ W(aq) ) = 4. 68
Enthalpy of neutralisation
When a strong acid is neutralised by a solution of a tron ba e,
Lneut
=
-57 k] mor1 , because the reaction for stron a id WI h tron ba es i s:
H(aq) + OH-(aq) = H_ I
1
The value for the neutral i sation of a weak acid i l b au n r : ha to
be used to ionise the mol ecul e to form H. i ons.
_-.
Before attempting the questions on thi s topic, che k that u:
Can identify acid/base conj ugate pai r .
Can defi ne pH and Kw.
Can define Ka and pKa for weak acids.
Understand what i s meant by the term tr nc and weak as applied to
acids and bases.
Can calculate the pH of solutions of tron acids, strong bases and weak
acids.
Can recal l the titration curves for the neutral i sation of strong and weak
acids.
Can use the curve to calculate the al ue of Ka for a weak acid.
Understand the reasons for the choice of indicator i n an acid/base
titrati ons.
Can defi ne a buffer solution, explain i ts mode of action and calculate its pH.
_t ,...
Aci d H2S04: its conj ugate base HS04-
Base CH
3
COOH: its conj ugate aci d
CH
3
COOH2
a 0. 96
b 1 3. 04
c 1 3. 34
For the fol lowi ng questions, cover the margin, write your answer, then check
to see i f you are correct.
Identify the acid/base conj ugate pairs in the reaction:
H2S0
4
+ CH
3
COOH - CH
3
COOH/ + HS0
4
-
Calculate the pH of:
a 0. 1 1 mol dm-
3
HCl
b 0. 1 1 mol dm-
3
Li OH
c 0. 1 1 mol dm-
3
Ba(OH)2
1b
PE R I OD I C I TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP CH E M I STRY

The two i somers are not
i nterconverti bl e at ordi nary
temperatures because there is no
rotati on about a doubl e bond.
1 Calculate the pH of 0. 22 mol dm-
3
C2H5COOH which has pKa = 4. 87.
2 25 cm
3
of a weak acid HX of concentration 0. 1 0 mol dm-
3
was titrated
with 0. 1 0 mol dm-
3
sodi um hydroxide solution, and the pH measured at
i nterval s. The results are set out below:
Volume Na0H/cm
3
5 1 0 1 2 20 23 24 25 26 30
pH 4. 5 4. 8 4. 9 5. 5 6. 5 7. 0 9. 0 1 2. 0 1 2. 5
a Draw the titration curve and use it to calculate pKa for the acid HX.
b Suggest a sui table indi cator for the titrati on.
3 a Define a buffer solution and give the name of two substances that
act as a buffer when i n soluti on.
b Explain how thi s buffer would resist changes in pH, if small
amounts of H+ or OH- i ons were added.
4 Calculate the pH of a solution made by adding 4. 4 g of sodium
ethanoate, CH
3
C00Na, to 1 00 cm
3
of a 0. 44 mol dm-
3
solution of
ethanoic acid. Ka for ethanoic acid = 1 . 74 ? 1 0-s mol dm-
3

Organ i c chemi stry I I
t- .
Isomerism
Structural There are three types:
a Carbon chai n. Here the i somers have different arrangements of
carbon atoms in a molecule,
e. g. butane, CH
3
CH2CH2CH
3
, and methyl propane, CH
3
CH( CH
3
) CH
3

b Positional . Here a functional group is on one of two or more
different places in a given carbon chain,
e. g. propan-1 -ol, CH
3
CH2CH20H, and propan-2-ol, CH
3
CH( OH)CH
3

c Functional group. Here the i somers have different functional groups,
e. g. ethanoic acid, CH
3
COOH and methyl methanoate, HCOOCH
3

Stereoisomerism. There are two types:
a Geometric. Thi s is caused by having two different groups on each
carbon atom of a >C=C< group ( see Figure 4. 4) .
H H
cis-but-2-ene trans-but-2-ene
Fig 4. 4 ci s and I|R3 isomers of but-2-ene
ORGANI C C H E MI STRY I I
Havi ng four di fferent groups
attached to one carbon atom wi l l
cause thi s. Thi s carbon atom i s
cal l ed a chiral centre.
A 50/50 mi xture of the two i somers
wi l l have no effect on pl ane
pol ari sed l i ght. Thi s type of mi xtu re
is cal l ed a racemi c mi xtu re and i s
often the resul t when chi ral
substances are produced by a
chemi cal reacti on.
Methanal produces a pri mary
al cohol .
11
b Optical. Optical isomers are defined as isomers of which one is the
non-superimposable mirror i mage of the other.
Thus l actic acid (2-hydroxypropanoic acid), CH
3
CH(OH)COOH,
exists as two optical i somers. These must be drawn three
dimensionall y so as to show that one i s the mi rror i mage of the
other (see Figure 4. 5) .
COOH
_
L
.
HO CH
3
H
Fig 4.5 Optical isomers of lactic acid
One i somer wi l l rotate th pl n of p lari ation of plane polarised
monochromatic li ht clo , l n h ther ,,. i l l rotate it anti
clockwi e.
Further reaction
Grignard reagents
These ha e the formula R-Mg-halogen uch a 2H5f I . Th ) ar u d to
i ncrease the carbon chai n l ength, because the are nucleophi l e an
contain a 8- carbon atom whi ch wi l l attack a 8+ carbon atom in other
compounds.
Preparation
Hal ogenoalkane + magnesium
Conditions: dry ether solvent ( flammable, therefore no flames), under
reflux with a trace of iodine as catalyst: e. g.
C2H51 + Mg - C2H5Mgl
Reactions
+ aldehydes to produce (after hydrolysis with di l ute hydrochloric acid) a
secondary alcohol:
C2H5Mgl + CH
3
CHO -- CH3CH( OH)C2H5
butan-2-ol
+ ketones to produce (after hydrolysi s) a tertiary alcohol:
C2H5Mgl + CH3COCH3 - CH3C(CH3) (0H)C2H5
2-methyl butan-2-ol
+ solid carbon dioxide (dry ice) to form (after hydrolysis) a carboxylic
acid:
C2H5Mgl + C02(s) - C2H5COOH
propanoic acid
Grignard reagents react with water to form alkanes:
C2H5Mgl + H20 - C2H
6
which is why they must be prepared and used in dry conditions.
Carboxylic acids
These have the functional group:
0
/
L
`
0-H
1b
PE RI ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D FU NCT I ONAL G ROUP C H E M I STRY

Test for a carboxyl i c aci d. When
added to aqueous sodi um
hyd rogencarbonate ( or sodi um
carbonate) , i t gi ves a gas, C0
2
,
whi ch turns l i me water mi l ky.
The aci d i s a catalyst. Thi s reacti on
has a l ow yi el d because i t i s a
reversi bl e react i on.
Thi s reacti on has a hi gh yi el d
because it i s not reversi bl e.
Preparation
They can be made by the oxidation of a primary alcohol . The alcohol i s
heated under reflux with di lute sulphuri c acid and excess potassi um
dichromate(VI) .
Reactions
+ alcohols to produce esters:
CH
3
COOH + C
2
H50H CH
3
COOC
2
H5 + H
2
0
ethyl ethanoate
conditions: heat under reflux with a few drops of concentrated
sulphuric acid.
+ lithium tetrahydridoal umi nate( I I I ) to produce a pri mary alcohol:
CH
3
COOH + 4[H] -- CH
3
CH
2
0H + H
2
0
ethanol
conditions: dissolve i n dry ether, followed by hydrolysi s with H(aq) .
+ phosphorus pentachloride to produce an acid chloride:
CH
3
COOH + PC15 CH
3
COC1 + HCl + POC1
3
ethanoyl chloride
condi ti ons: dry; observation: steamy fumes given off.
Esters
These have the general formula RCOOR' where R and R1 are alkyl or aryl
groups, and which may or may not be different.
0
/
R -C
`
0-R'
Reactions of ethyl ethanoate
Hydrolysis with aqueous acid to produce the organic acid and the
alcohol :
CH
3
COOC
2
H5 + H
2
0 CH
3
COOH + C
2
H50H
ethanoic acid
conditions: heat under reflux with dil ute sulphuri c acid.
Hydrolysi s with aqueous alkali to produce the salt of the acid and the
alcohol :
CH
3
COOC
2
H5 + NaOH -- CH
3C00Na + C
2
H50H
sodi um ethanoate
conditions: heat under reflux with aqueous sodium hydroxide.
Carbonyl compounds (aldehydes and ketones)
These contain the C=O functional group. Aldehydes have the general
formula RCHO, and ketones the general formula RCOR' where R and R' are
alkyl or aryl groups, and may or may not be different.
0 0
/ /
R -C R -C
` `
H R'
Aldehyde Ketone
ORGANI C C H E MI STRY I I
The formati on of an orange or red
preci pitate wi th 2, 4-DNP is a test for
carbonyl compounds, i . e. for both
al dehydes and ketones.
,
Reactions in common
Addition of hydrocyani c acid, HCN, to produce a hydroxynitrile:
CH
3
CHO + HCN CH
3
CH(OH)CN
2-hydroxypropanenitrile
conditions: there must be both HCN and CN- present,
e. g. HCN + a trace of KOH, or KCN(s) + some dilute sulphuric aci d.
Reduction with l ithium tetrahydridoal umi nate( I I I) to produce an
alcohol :
CH
3
CHO 2[ H] CH
3
CH20H
CH
3
COCH
3
+ 2[H] CH
3
CH(OH)CH
3
conditions: dissolve in dry ether, followed by hydrolysis with H+(aq) .
Or reduction with sodium tetrahydridoborate(I I I) , al so to produce an
alcohol :
CH
3
CHO 2[ H] CH
3
CH20H
CH
3
COCH
3
2[ H] CH
3
CH( OH)CH
3
conditions: aqueous solution, fol lowed by hydrol ysi s with H+(aq).
Reaction with 2, 4-dinitrophenylhydrazine (2, 4-DNP) to give an
orange/red preci pitate:
15

,
_
The formati on of the si l ver mi rror

wi th ammoni acal si l ver nitrate is the
test whi ch di sti ngui shes al dehydes,
whi ch gi ve a posi ti ve resul t, from
ketones, whi ch have no reacti on.
Al dehydes are al so oxi di sed by
potassi um manganate( VI I ) or
aci di fi ed potassi um di chromate(VI ) .
The onl y al dehyde t o do thi s i s
ethanal , CH
3
CHO.
Thi s reacti on i s often used i n
organi c ' probl em' q uesti ons. The
pal e yel l ow preci pitate produced on
addi ti on of sodi um hydroxi de and
i odi ne i s the cl ue. The organi c
compound that produces thi s
preci pitate wi l l ei ther be a carbonyl
wi th a CH
3
C
=
O group or an al cohol
wi th a CH
3
CH( OH) group. I t i s not a
general test for ketones.
2, 4-DNP
Specific reaction of aldehydes
Aldehydes are oxidised to carboxylic acids by a solution of si lver nitrate i n
di lute ammoni a. On warming the si lver i ons are reduced to a mi rror of
metalli c silver.
Aldehydes are also oxidised by warmi ng with Fehl ing's solution, which i s
reduced from a bl ue solution to a red precipitate of copper(!) oxide:
CH
3
CHO + [0] CH
3
COOH
Iodoform reaction
This is a reaction which produces a pale yel low precipitate of iodoform,
CHI
3
, when an organi c compound i s added to a mixture of iodine and
di lute sodi um hydroxide (or a mixture of KI and NaOCl ).
The group responsible for thi s reaction i s the CH
3
C=0 group, and the
reaction involves breaking the C-C bond between the CH
3
group and
the C=O group.
CH
3
COC2H5 produces C2H5C00Na + CH1
3
(s)
All ketones contai ni ng the CH
3
C=0 group will give thi s precipitate.
This reaction is also undergone by alcohols contai ni ng the CH
3
CH( OH)
group. They are oxidised under the reacti on conditions to the CH
3
C=0
group, which then reacts to give iodoform.
Acid chlorides
These have the general formul a RCOCl, and the functional group i s:
o
/
L
`
e. g. ethanoyl chloride, CH
3
C0Cl, and propanoyl
chloride, C2H5COCl.
b0
PE RI ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D FU NCTI ONAL G ROUP C H E M I STRY
Th e ami ne can be regenerated from
the sal t by addi ng a strong al kal i .
Nitri l es can be prepared by t he
reacti on of a hal ogenoal kane wi th
KCN i n aqueous ethanol .
Hyd roxynitri l es can be prepared by
t he addi ti on of HCN t o carbonyl
compounds i n the presence of base.
Reactions of ethanoyl chloride
+ water to produce the carboxylic acid, ethanoic aci d:
CH
3
C0Cl + H2 0 CH
3
COOH + HCl (g)
observati on: steamy fumes of HCl .
+ alcohols to produce an ester:
CH
3
C0Cl + C2H50H CH
3
COOC2H5 + HCl
observation: characteristic smel l of the ester, ethyl ethanoate.
+ ammonia to produce the amide, ethanamide:
CH
3
COC1 + 2NH
3
CH
3
CONH2 + NH4Cl
+ primary ami nes to produce a substituted amide:
CH
3
COC1 + C2H5NH2 CH
3
CONH( C2H5) + HCl
Nitrogen compounds
Primary amines
They contain the -NH2 group, e. g. ethyl ami ne C2H5NH2
They are soluble i n water (i f the carbon chai n i s fairly short) because
they form hydrogen bonds with water molecules.
They are weak bases.
Reactions of ethylamine
+ acids, to form an i oni c salt that is soluble in water:
C2H5NH2 + H+(aq) - C2H5NH/(aq)
+ acid chl orides, to form a substituted ami de:
C2H5NH2 + CH
3
C0Cl CH
3
CONHC2H5 + HCl
Nitri/es
They contai n the C=N group, e. g. propanenitrile C2H5CN.
Reations of prpanenitrile
Hydrolysi s either with acid:
C2H5CN + H+ + 2H20 C2H5COOH + NH/
conditions: heat under reflux with dilute sulphuric acid
or with al kali .
C2H5CN + OH- + H20 C2H5COO- + NH
3
conditi ons: heat under reflux with dilute sodium hydroxide
Reduction by l i thi um tetrahydridoal uminate( I I I ) :
C2H5CN + 4[H] C2H5CH2NH2
conditions: dry ether, followed by addition of dilute acid
Amides
They contain the CONH
2
group, e. g. ethanamide CH
3
CONH2
o
/
CH -C
`
NHz
Reactions of ethanamide
Dehydration with phosphorus(V) oxide:
CH
3
CONH2 - H20 CH
3
CN
conditi ons: warm and di sti l off the ethanenitril e.
ORGANI C C H EM I STRY I I
bl
Hofmann degradation reaction:
CH
3
CONH2 + Br2 + 2NaOH CH
3
NH2 + C02 + 2NaBr + 2H20
Ami des can be prepared from aci d
chl ori des + ammoni a.
Ami des can be converted i nto an
ami ne ei ther wi th the same number
of carbon atoms ( reducti on) or wi th
one l ess ( Hofmann degradati on) .
conditions: add li qui d bromi ne to the ami de at room temperature, and
then add concentrated aqueous sodium hydroxide soluti on and warm.
The ami ne distil s off.
Amino acids
These contain an NH
2
and a COOH group (usually bonded to the same
carbon atom). They react both a acids and bases.
They are water-soluble ionic solid because they form a zwitterion.
NH
z
CHzC H H
3
+ CH2COO
-
Reactons
With acids:
NH2CH2CO H H ( aq) . 'H -cH2COOH(aq)
Ami no aci ds can be prepared from
chl oroaci ds by heati ng them i n a
seal ed tube wi th an ethanol i c
sol uti on of ammoni a.
With bases:
H2CH2
Figure 4. 6 ummari e the reaction of or ani ub tan e .
Grignard
C2H5MgBr
Esters
CH3COOC2H5
C02 C2H5COOH
HCHO C2H5CH20H
CH3CHO C2H5CH( OH)CH3
CH3COCH3 -C2H5C(CH3)z0H
E
C2H50H
LiAlH4 -- CH3CH20H
PC15 -- CH3COC1
H'
CH3COOH + C2H50H
OH- -- CH3Coo- -C2H50H
_HCN -->C(OH)CN
Aldehydes and
ketones
2 4-DNP
>C=O
, __ red precipitate
[H] -- >CH(OH)
Aldehydes only
Ag
+
/NH3
-
__
CH3COO- + silver mirror
CH3CHO
Fehl i ng's __ CH3Coo- + red precipitate
Fig 4. 6 Summary of organic reactions
Acid
chlorides
CH3COC1
H20 CH3COOH
C2H50H -CH3COOC2H5
NH3 CH3CONH2
CH3NH2 -CH3CONHCH3
H+
_ CH3COOH
ow CH3coo-
LiAIH4 CH3CH2NH2
b
a
b
c
a
b
a
b
c
a
b
PE R I OD I C I TY, QUANTI TATI VE EQU I LI B R I A AN D F U NCTI ONAL G ROUP C H E M I STRY
Anr
CH3CH
2
CH( OH) CH3
CH3CH
2
C(OH) ( CH3 ) CH3
CH3CH
2
0H
Heat u nder refl ux wi th di l ute
sodi um hydroxi de, then add
di l ute sul phuri c aci d.
Add l i thi um
tetrahydri doal umi nate, l l l ) i n d ry
ether, fol l owed by di l ute
sul phuri c aci d.
water
methanol
ammoni a
CH3CHzNH3 Cr
CH3CONHCH
2
CH3
-.
|
Can recogni se stereoisomerism (geometric and optical) in organic
compounds.
Know the effect of an opti cal isomer on pl ane polari sed light.
Understand the nature of a racemi c mixture.
Can recal l the preparation and reacti ons of Grignard reagents.
Can recal l the reactions of carboxylic acids.
Can recal l the reacti ons of esters.
Can recal l the reacti ons of carbonyl compounds (aldehydes and
ketones) .
Can recal l the reacti ons of ethanoyl chl oride.
Can recal l the reacti ons of ami nes with acids and with aci d chlorides.
Can recal l the hydrolysi s and the reduction of ni tri l es.
Can recal l the reactions of amides with P40
1
0 and with Br2/Na0H.
Know that ami no acids are both acids and bases.
t ,...
For the fol lowing questions, cover the margin, write your answer, then
Write the formulae of the products of the reaction of CH
3
Mgl with:
a propanal
b butan-2-one
c methanal.
State the names of the reagents and give the conditions for the
fol l owing conversions:
a C
2
H5COOCH
3
to C
2
H5COOH + CH
3
0H in a high yield
b C
2
H5COOH to CH
3
CH
2
CH
2
0H.
State the names of the reagents needed to convert ethanoyl chloride to:
a ethanoic acid
b methyl ethanoate
c ethanamide.
State the structural formul ae of the product obtai ned by reacti ng:
a ethyl ami ne with di lute hydrochloric acid
b ethylamine with ethanoyl chloride.
ORGANI C C H EM I STRY I I
a Heat under refl ux wi th NaOHaqj
then aci dify.
b Add Li AI H4 in d ry ether, fol l owed
by di l ute al kal i .
c Warm wi th l i qui d bromi ne and
concentrated aqueous sodi um
hydroxi de.
Because i t forms t he zwitteri on
+ NHaCH2coo-
State the conditions for the conversion of:
a ethanenitrile, CH
3
CN, to ethanoic acid, CH
3
COOH
b ethanenitri le, CH
3
CN, to ethylami ne, C2H5NH2
c propanamide, C2H5CONH21 to ethylamine, C2H5NH2
Expl ai n why ami noethanoic aci d i a ol i d that is sol ubl e i n water.
1 Draw the stereoisomers of:
a CH
3
CH=C(Cl )CH
3
b CH
3
CH( OH) F.
2 Outline how you would prepare 2-methylpropanoic acid from
2-i odopropane.
3 Describe the tests that you could do to di sti n i h between:
a ethanoic acid and ethanoyl chloride
b propanal and propanone.
bJ
b+
* ' PE R I ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D FU NCT I ONAL G ROUP CH E M I STRY
PrucrIce Tesr: tuIr+
Time allowed 1 hr 30 min
All questions are taken from parts of previous Edexcel Advanced GCE papers
1 a Draw a Born-Haber cycle for t he formation of magnesi um chloride, MgC121 and use t he values below to
calculate the l attice energy of magnesi um chloride. [5]
Mr/k] mor
1
1 st electron affini ty of chlorine -364
1 st i oni sation energy of magnesium +736
2nd i oni sation energy of magnesium +1 450
Enthalpy of atomi sation of chlorine +1 21
Enthal py of atomi sation of magnesium +1 50
Enthalpy of formation of MgC12(s) -642
b Use the fol l owing to answer the questions i n thi s secti on.
fl /k] mor1
Enthalpy of hydration of Sr
2
+ -1 480
Enthalpy of hydration of Ba
2
+ -1 360
Enthalpy of hydration of OH- -460
Lattice energy of Sr(OH)2(s) -1 894
Lattice energy of Ba(OH)2(s) -1 768
i Expl ai n why the lattice energy of strontium hydroxide is different from that of bari um hydroxide. [2]
ii Expl ai n why the hydration enthalpy of a cation is exothermic. [2]
iii Use the lattice energy and hydration enthalpy values to explain why barium hydroxide is more
soluble i n water than strontium hydroxide. [4]
(Total 13 marks)
[anuar 2001 CH 3 question 4]
2 a i Give the structural formul a of a nitrile, CH
7
N, that has an unbranched chai n
[1]
ii Primary ami nes can be made by reducing nitriles. Suggest a reagent that could be used for thi s
purpose.
[1]
iii Draw the structural formula of the ami ne produced by reduci ng the nitrile given in a part i. [1]
b i What feature of an ami ne molecul e makes it both a base and a nucleophi le?
[1]
ii Give, by wri ti ng an equation, an example of an ami ne acti ng as a base [1]
c Ethanoyl chl oride, CH
3
COC1, reacts with both ami nes and alcohols
i Give the ful l structural formula of the compound produced when ethanoyl chloride reacts with
ethylamine, C2H5NH2 [1]
ii Name the type of the compound produced i n c part i. [1]
iii State one of the advantages of reacti ng ethanoyl chloride with ethanol to make an ester rather than
reacti ng ethanoi c aci d with ethanol . [1]
iv Write the ful l structural formul a of the ester made i n c part iii [1]
(Total 9 marks)
[anuar 2002 Unit Test 4 question 5 - modifed]
PRACTI CE TEST: U N I T
b
3 Compound A is a secondary alcohol which has a molecular formula of C4H
1
00.
A exhi bi ts optical i someri sm.
a Draw the structural formulae of the two optical i somers of A.
[2]
b Suggest reagents and conditions which would enable its preparation via a reaction i nvolving a
Grignard reagent. (You are not expected to describe how you would prepare a Grignard reagent)
[3]
c Compound 3 is obtai ned by oxidi si ng the secondary alcohol A with potassi um dichromate(VI)
aci difi ed with dilute sulphuric acid.
i Draw the structural formula of 3. [1]
ii To which class of compounds does 3 belong? [1]
iii Describe the tests you would do on 3, and the results ou \Ould expect, to show that your
classifi cation i s correct. [4]
iv Both A and 3 give a yel l ow precipitate when treated with iodin in the presence of sodium
hydroxide soluti on. Write the structural formulae of the or ani product of thi s reacti on.
[2]
(Total 13 marks)
[June 20 I H - que tion 1 - modified]
4 At about 1 000 oc, when al umi ni um chloride vapour i heated with ol i d al umi ni um, the fol lowing
equilibrium is set up:
A1 Cl
3
(g) 2Al(s) 3A1Cl (g)
a Give the expression for the equi l ibrium constant, K
P
, for thi s reaction.
[ 1]
b At a particular temperature, a mixture of the above system at equilibrium was found to contain 0. 67 g
of Al Cl
3
and 0. 63 g of AlCl vapours at an equilibri um pressure of 2. 0 atm. Calculate the value of the
equilibrium constant, K
P
, at thi s temperature, stati ng its uni ts.
[4]
c The position of equi librium moves to the right as the temperature is rai sed. State what thi s suggests
about the enthalpy change for the forward reaction.
[1]
d State, with reasoning, the effect of an increase in the pressure on the system on the value of the
equilibrium constant and on the position of the equi l ibri um.
[3]
e Suggest how thi s reversible reacti on could be used in a process to recycle al umi ni um by extracti ng i t
from i mpure alumi ni um. [2]
a i
ii
b i
ii
c
d
(Total 11 marks)
[June 2001 CH3 question 3]
Write an equation for the reaction between magnesium oxide and dilute sul phuric acid, i ncl udi ng
the state symbol s.
[2]
Describe what you woul d see during this reacti on. [2]
Write an equation for the reaction between phosphorus(V) oxide and aqueous sodium hydroxide
solution.
[2]
With the aid of two equations, show how al umi ni um hydroxide exhibits amphoteric behaviour.
[3]
With reference to the reacti ons in a and b, describe the variation in the metal l i c character of the
elements across Period 3 of the Periodic Tabl e (sodium to argon) [2]
Suggest, with reasoni ng, the acid-base character of Indi um( I I I ) oxide, I n20
3
I ndi um is the fourth
el ement down Group 3 of the Periodic Tabl e.
l
2
!
(Total 13 marks)
[June 2002 Unit Test 4 question 4]
bb
6a
b i
ii
c
d
i
ii
PE RI ODI CI TY, QUANTI TATI VE EQU I L I B R I A AND FU NCTI ONAL G ROU P C H E M I STRY
I n the context of Bronsted-Lowry acid-base behaviour, explain the terms:
acid weak acid dilute acid. [3]
Define pH
[1]
Calculate the concentration, in mol dm-
3
, of a solution of chloric(I) acid, HOCl, which has a pH of
4. 23. Chloric acid i s a weak acid with Ka = 3. 72 ? 1 0- mol dm-
3
. [4]
Sketch, on a grid of pH (y-axis) versus volume of al kal i added I cm
3
(x-axis), the ti tration curve for
the titration of 25 cm
3
of the chloric(I) acid solution in b part ii with SO cm
3
of a solution of
sodi um hydroxide of equal concentrati on. [5]
The concentration of hydrogen i ons in a 0. 1 00 mol dm-
3
solution of sulphuri c acid is 0. 1 05 mol
dm-
3

Write equations to show the two successive i oni sations of sulphuri c acid, H2S04, in water. [2]
Suggest why the concentration of hydrogen ions is not 0. 20 mol dm-
3
i n 0. 1 00 mol dm-
3
sulphuri c
acid.
[1]
(Total 16 marks)
[anumy 2001 CH2 question 4 & Januar 2002 CH2 question 2]
o uu:
uuk
H+(aq)
1 mol dm-
3
Salt
bridge
oroty
Redox equi li bri a
_ .
You must revise Topic 1 . 5 ( I ntroduction to oxidation and reduction) .
The si gn of I"i ndi cates the di rection of spontaneous reacti on.
A useful mnemoni c i s OI L RI G. When a substance i s Oxidi sed It Loses
one or more el ectrons, and if Reduced It Gains one or more electrons.
A hal f equation always contai ns electrons.
Hal f equation data are usual ly given as reduction potentials, i . e. with
the electrons on the lef-hand side.
An oxidising agent becomes reduced when it reacts.
_t- .
The standard hydrogen electrode
Thi s consists of hydrogen gas at 1 atm pressure bubbl i ng over a platinum
electrode i mmersed i n a 1 mol dm-
3
solution of H+ ions, at a temperature
of 25 C. By defi niti on the potential of a standard hydrogen electrode is
zero (see Figure 5 . 1 ) .
Standard electrode potential, E-
This is the el ectric potential (EMF) of a cell composed of the standard
el ectrode connected to a standard hydrogen electrode, measured when
the concentrati ons of al l the i ons are 1 mol dm-
3
, the temperature is
25 C and any gases are at 1 atm pressure.
Fig S. 1 A standard hydrogen electrode for a metal the standard el ectrode potenti al is when the metal i s
i mmersed in a solution of i t s i ons at a concentrati on of 1 mol dm-
3

For the reaction:
Zn
2
+(aq) +2e- - Zn(s)
it is for a zinc electrode i mmersed in a 1 mol dm-
3
solution of Zn
2
+
i ons at 25 C.
for a non-metal the standard electrode potential i s when the non
metal at 1 atm pressure (or a solution of it at a concentration of
1 mol dm-
3
) i s in contact with a platinum electrode i mmersed in a
bb
TRANS I TI ON M ETALS, QUANTI TATI VE K I N ET I CS AND APPL I E D ORGAN I C CH E M I STRY
1
/
2
CI
2
+ e - cr I" " + 1 . 36 v
1
1
2
Br
2
+ e- 8( E^ + 1 . 07 V
As + 1 . 36 ` + 1 . 07, chl ori ne is a
stronger oxi di si ng agent than
bromi ne.
Sn
4
+ + 2e- Sn
2
+ I" " +0. 1 5 V
Fe
3
+ + e- Fe
2
+ I" " + 0. 77 V
As +0. 1 5 +0. 77, Sn
2
+ i ons are a
better reduci ng agent than Fe
2
+ i ons.
sol uti on of the non-metal's ions at a concentration of 1 mol dm-
3
at 25 C.
For the reaction:
1
/
2
Cl
2
(g) + e-
Cr(aq)
it i s for chlorine gas, at 1 atm pressure, being bubbled over a
pl atinum electrode di ppi ng i nto a 1 mol dm-
3
solution of cr i ons
at 25 C.
for a redox system of two ions of an element the standard
electrode potential is when a platinum el ectrode is i mmersed in a
solution contai ni ng all the i ons in the half equation at a
concentration of 1 mol dm-
3

For the reaction:
Fe
3
+(aq) + e- Fe
2
+(aq)
it i s for a plati num electrode i mmersed in a solution which is 1 mol
dm-
3
i n both Fe
3
+ and Fe
2
+ i ons at 25 C.
The equations are always given as reduction potentials, i . e. with the
electrons on the left.
Comparing substances on the left of two half equati ons, the one with
the larger positive value of Ii s the more powerful oxidising agent (i t
i s the most easi l y reduced) .
Comparing substances on the right of two hal f equations, the one with
the smaller positive (or more negative) val ue of Ii s the more
powerful reducing agent.
Calculation of
f........ |!..-|
The value can be deduced in one of three ways:
1 From a cell diagram:
Icell
=
right-hand elect rode
-
I
left-hand electrode
If I
..
works out to be a negative value, you have written the cell
diagram backwards, and so the reaction wi l l go right to left .
2 From an overal l equati on: write both hal f reactions as reduction
potentials, i . e. with el ectrons on the l eft.
Irea
ction
is calculated as:
I
,ea
ction
= ,Iof hal f equation of the reactant bei ng reduced) - ,Iof
half equation of reactant bei ng oxidised.
Thus for the reaction:
Zn(s) + Cu
2
+(aq) Zn
2
+(aq) + Cu(s)
The hal f equati ons are:
Cu
2
+(aq) + 2e- Cu(s)
Zn
2
+(aq) + 2e- Zn(s)
I= +0. 34 V
I
-
* -0. 76 V
In the reaction the Cu
2
+ ions are being reduced (electron gai n), and the
zinc atoms are being oxidi sed (el ectron loss) :
I
-
reaction = +0. 34 - (-0. 76) * + 1 . 1 0 V
3 From half equati ons:
To do thi s one of the half equati ons has to be reversed (see Worked
example below) . Thi s process al ters the sign of its I".
RE DOX EQU I L I B R I A

+
+ - I
When a redox hal f equati on i s
reversed, i ts si gn must be changed.
The number of el ectrons on the left
hand si de of one hal f equati on must
equal the number on the ri ght-hand
si de of the other hal f equati on.
When a redox hal f equati on i s
mul ti pl i ed, i ts E
f
val ue i s not
altered.
Always ensure that t he reactants
that are speci fi ed i n the questi on
( here they are i ron ( l l ) and
manganate(VI I ) i ons) are on the l eft
hand si de of the fi nal overal l
equati on.
I n the reacti on above, t he oxi dati on
number of the manganese decreases
by 5 from +7 to +2, and as the i ron
i ncreases by 1 , there must be 5
i ron( l l ) i ons to each Mn04- i on in the
overal l equati on.
+r/
Use the fol l owi ng data to deduce the overal l equati on and the val ue of E
f
reacuon
for the reacti on between aci di fi ed potassi um manganate(VI I ) and i ron ( I I ) i ons.
i Mn04-(aq) +
8W(aq) + 5e- Mn
2
(aq) + 4H
2
0(aq) E
f
" +1 . 52 V
i i Fe
3
(aq) + e- Fe
2
+(aq) r " +0. 77 V
Answer
Reverse equati on ( i i ) and mul ti pl y it by 5. Then add i t to equati on ( i ) :
5Fe
2
{aq) 5Fe
3
(aq) + 5e- r " -(+0. 77 V) " -0. 77 V
Mn04-(aq) +
8W(aq) + 5e- Mn' {aq) + 4H20( 1 ) E
f
" + 1 . 52 V
Mn
o
4-(aq) +
8W
(aq) + 5Fe
2
(aq) Mn
z
(aq) + 4H
2
0(
1
) + 5Fe
3+
(aq)
r -. 11 + 1 . 52 +0. 75 v
Stoichiometry of an overall equation
The total i ncrease in oxidation number of one element mu t equal the
total decrease in another.
Spontaneous change
b5
Electrode potential data can be used to predict the feasi bi lity of a
chemical reaction. A reaction is feasibl e (thermodynamically unstable) if
E
ce
u i s positive.
However the rate of the reaction may be so slow that the reaction is not
observed (kinetical ly stable) .
Non-standard cells
Non-standard conditions may result i n a reaction taking place even if
the standard el ectrode potential i s negative.
The reacti on:
2Cu
2
+ (aq) + 4r(aq) 2Cul (s) + I2(aq)
should not work because Ee (assuming all species are soluble) * -0. 39 V.
However copper(!) iodide i s preci pitated and thi s makes [Cu+(aq)] very
much less than 1 mol dm-3 The equi l ibrium is driven to the right by
the removal of cu+ (aq) ions, so that reaction becomes positive and the
reaction takes pl ace.
Potassium manganate(VII) titrations - estimation of
reducing agents
Acidifi ed potassi um manganate(VI I ) wi l l quantitatively oxidise many
reducing agents.
The procedure i s to pi pette a known vol ume of the reducing agent i nto
a conical flask and add an excess of di lute sulphuri c aci d.
The potassium manganate(VII) solution of known concentrati on i s put
i n the burette and run in until there is a faint pink colour.
Thi s shows that there i s a mi nute excess of the manganate(VII) i ons.
I f the stoichiometry of the reaction i s known, the concentrati on of the
reducing agent can be calculated. No i ndi cator i s needed as the
manganate(VII) i ons are very i ntensely coloured.
UU
TRANS I T I ON M ETALS, QUANT I TAT I VE KI N ETI CS AND APP L I E D ORGAN I C CH E M I STRY
Th e ratio of i ron( l l ) to
manganate(VI I ) i ons i n the equati on
i s 5: 1 and so the number of mol es
of Fe
2
+ i s 5 ti mes the number of
mol es of manganate(VI I ) .
The ratio of i odi ne t o thi osul phate
i ons is 1 : 2, so the mol es of i odi ne
are
1
/
2
the mol es of thi osul phate.
+r/
25. 0 cm
3
of a sol uti on of i ron( I I ) sul phate was aci di fi ed, and ti trated agai nst
0. 0222 mol dm-
3
potassi um manganate(VI I ) sol uti on. 23. 4 cm
3
were requi red
to gi ve a fai nt pi nk col our. Cal cul ate the concentrati on of the i ron( l l ) sul phate
sol uti on.
Answer: The equati on f or t he reacti on i s:
Mn
o
-(aq) +
8W
(aq) + 5Fe
2+
(aq) Mn
2+
(aq) + 4H20(
1
) + 5Fe
3+
(aq)
-4
Amount of manganate(VI I ) = 0. 0222 ? 23. 4/1 000 = 5. 1 95 ? 1 0 mol
Amount of i ron ( l l ) sul phate = 5. 1 95 ? 1 0-4 ? 5/1 = 2. 597 ? 1 0
3
mol

Concentrati on of i ron ( l l ) sul phate = 2. 597 ? 1 0 0. 0250 = 0. 1 04 mol dm
lodine/thiosulphate titrations - estimation of oxidising
agents
The procedure i s to add a 2S. 0cm
3
sampl e of an oxidising agent to
excess potassi um iodide solution (often i n the presence of di lute
sul phuric acid) .
The oxidising agent l iberates iodine, which can then be titrated agai nst
standard sodi um thi osul phate solution. When the iodine has faded to a
pale straw colour, starch i ndi cator is added, and the addition of sodi um
thi osul phate continued unti l the bl ue colour disappears.
Iodine reacts with thiosul phate ions accordi ng to the equati on:
_ 2S,O, 2l+ S,O
+r/
25. 0 cm
3
of a sol uti on of hydrogen peroxi de, H
2
0
2
, was added to an excess of
aci di fi ed potassi um i odi de sol uti on, and the l i berated i odi ne requi red 23. 8 cm
3
of 0. 1 06 mol dm-
3
sodi um thi osul phate sol uti on. Cal culate the concentrati on of
the hydrogen peroxi de sol uti on.
Answer The equati on f or t he oxi dati on of i odi de i ons by hyd rogen peroxi de i s:
H
2
0
2
+ 2W + 2r l
2
+ 2H
2
0
Amount of sodi um thi osul phate = 0. 1 06 ? 23. 8/1 000
Amount of i odi ne produced = 2. 523 ? 1 o-
3
? 1 /2
Amount of hydrogen peroxi de = 1 . 261 ? 1 o-
3
? 1 /1
Concentrati on of H
2
0
2
= 1 . 261 ? 1 o-
3
0. 0250
Disproportionation
= 2. 523 ? 1 o-
3
mol
= 1 . 261 ? 1 o-
3
mol
= 1 . 261 ? 1 0
3
mol
^ 0. 0505 mol dm-
3
A disproportionation reaction can be predicted by usi ng el ectrode
potenti al s. Use the data to work out Ecell
for the proposed
disproportionation reaction. If it is positive, the reaction wi l l occur.
RE DOX EQU I L I B R I A
Fig 5.2 Rusting
Stai nl ess steel is i ron contai ni ng a
hi gh proporti on of chromi um, whi ch
forms a protective layer of Cr
2
0
3
over the whol e surface of the metal .
I f the surface i s scratched, a new
protecti ve l ayer of Cr
2
0
3
i s formed.
The reacti ons for chargi ng the cel l
are the opposi te, and only take pl ace
if a potenti al >2. 05 V i s appl i ed, wi th
the anode bei ng connected to the
negati ve termi nal of the chargi ng
sou rce.
Wi l l copper( I ) i ons di sproporti onate i n aqueous sol uti on to copper and
copper( l l ) i ons?
cu(aq) + e- Cu( s)
Cu
2
(aq) + e- cu(aq)
r " +0. 52 v
r " +0. 1 5 v
Answer Reverse the second equati on and add i t to the fi rst. Thi s gi ves the
equati on:
2Cu(aq) Cu
2
(aq) + Cu(s) Eceu " +0. 52 - ( +0. 1 5) " +0. 37 V
Because fceu
is posi ti ve, the reacti on is feasi bl e. and so aqueous copper( ! ) i ons
wi l l di sproporti onate.
Corrosion (rusting)
UJ
Thi s i s an electrolyti c process. When i ron i s stre d or pitted, some areas
become anodic and some cathodic. In the presence of water and oxygen
the fol l owing reacti ons take place (see Figure 5. 2).
At the anodic areas i ron atoms become oxidi ed and l 1 e & electrons:
Fe(s) Fe
2
+(aq) + 2e
-
The electrons travel through the metal and reduce oxyaen :
1
/202(aq) + 2e- + H20 20H-(aq)
The Fe
2
+ and the OH- i ons meet and i ron( I l ) hydroxid i pr ipitated:
Fe
2
+(aq) + 20H-(aq) Fe(OH): )
Fi nal ly oxygen oxidises the iron( I I ) hydroxide to i ron I I I o i de (rust) :
2Fe(OH)2(s) +
1
/202(aq) Fe203(S + 2H ( l
Prevention of corrosion
This can be done by:
placing a physical barrier between the teel and the environment. Such
barriers are pai nt, tin or chromi um platin .
adding a sacrificial metal . This can be done by coating with zinc
(galvani si ng) , or by attachi ng bl ock of magnesi um at i nterval s.
Storage cells
These store electrical energy as chemical energy. The reactions must be
fully reversible and the chemicals produced i n the redox reactions must be
i nsoluble.
The lead acid battery
When electricity is drawn from the cel l (dischargi ng), the following
reactions take place.
At the anode (oxidation) which i s negative:
Pb(s) + SO/-(aq) PbSOis) + ze- E
-
= +0. 36 V
At the cathode (reduction) which is positive:
Pb02(s) + 2e- + SO.(aq) + 4H+(aq) PbS04(S) + 2H20(1)
E
-
= +1 . 69 V
The overal l discharging reaction i s:
Pb( s) + Pb02(s) + 2SO/-(aq) + 4H\aq) 2PbS04(s) + 2H20(1)
E
-
* +1 . 69 + (+0. 36) * +2. 05 V
5
TRANS I TI ON M ETALS, QUANTI TATI VE KI N ETI CS AN D APP L I E D ORGA N I C C H E M I STRY
1
/
2
H
2
( g) W( aq) + e
-
.
State symbol s are essenti al .
H
2
( g) at 1 atm pressure,
[ W( aq) ] " 1 mol dm-
3
+7 and +2
+4 and +6
5: 2 So that oxi dati on numbers of
both change by 1 0
Because the manganate( VI I ) i ons are
i ntensel y col oured.
_-.
Defi ne standard electrode potential .
Describe t he construction of a standard hydrogen el ectrode.
Write half equations and use them to deduce overal l equations.
Predict the feasi bi l i ty of redox and disproportionation reacti ons.
Deduce oxidation numbers and use them to balance redox equati ons.
Recal l the pri nci pl es of manganate(VI I ) and thiosul phate titrations.
Recal l the corrosi on of i ron and its prevention.
Understand the chemi stry of the l ead/acid battery.
_t ,...
For the fol lowing set of questions, cover the margin before you answer,
Write the equation representing the reaction that takes place in a
standard hydrogen electrode.
What are the conditions, other than temperature, for thi s electrode?
What are the oxi dati on numbers of manganese i n Mno- and in Mn
2
+?
What are the oxidation numbers of sulphur i n 50
3
2
- and in sot?
What is the ratio of 50
3
2
-
to Mno- in the reaction between them?
Why i s it not necessary to have an indicator present i n potassium
manganate(VI I ) titrations?
1 a Write i oni c half equati ons for the reduction of:
i Cr
2
07
2
- to Cr
3
+ in acidic solution E- * 1 . 33 V
ii Sn-
!
+ to Sn
2
+ E- * +0. 1 5 V
iii 1odate(V) ions, ( ! 0
3
-
) to 12 in acidic solution E- = +1 . 1 9 V
iv 12 to l E- = +0. 54 V
b Write overall i oni c equations, calculate Ereacuon values and hence
comment on the feasibi l i ty of the reacti ons between:
i potassium di chromate(V1) and tin( I I) chloride in acid solution
ii potassium iodate(V) and potassium i odide i n acid solution.
2 1 . 32 g of mi l d steel fil ings was reacted with excess di lute sul phuric acid,
and the resulting solution made up to a volume of 250 cm
3
25. 0 cm
3
samples of this were titrated agai nst 0. 0200 mol dm-
3
potassium
manganate(VI I ) solution. The mean titre was 23. 5 cm
3
Calculate the
percentage of i ron in the steel .
3 Write the hal f equations for the redox reacti ons i nvolved i n the
corrosion of i ron.
TRANS I T I ON M ETAL CH E M I STRY
5J
Nei ther scandi um nor zi nc is a
transi ti on metal al though they are i n
the d bl ock, because t hei r i ons have
the el ectroni c structure [Ar] 3d
0
, 4s
0
and [Ar] , 3d
1
0
, 4s
0
respecti vely.
Note that the number of d el ectrons
i ncreases left to ri ght, except that Cr
and Cu have 4s1 el ectron structures,
whereas the others have 4s
2
. Thi s i s
because stabi l ity i s gai ned when the
d shel l i s hal f ful l or ful l .
Fig S. 3 Electron arrangement in the
hexa-aquairon(1) ion
Transi t i on metal chemi stry
.
You should know the colour of the aqua complex i ons and of the
hydroxides of the d block element candi um to zi nc.
You must be able to l i nk the reaction i n thi topic to the theory of
redox equi l i bria, Topic 5 . 1 .
t- .-
d block elements are tho e in " hich the highe t occupied energy
l evel is a d orbital .
A transition element i s one that has at least one of i ts i ons with a
partly fi l led d shel l .
Electron structure of the atoms
Sc Ti N Cr Mn Fe Co Ni Cu Zn
3d 1 2 3 5 5 6 7 8 10 10
4s 2 2 2 1 2 2 2 2 1 2
Electron structure of the ions. The element first loses its 4s
el ectrons when forming an i on. Thus the el ectron structures of iron and
its i ons are:
Fe [Ar] , 3d
6
, 4s
2
Fe
2
+ [Ar] , 3d
6
, 4s0
Fe
3
+ [Ar] , 3d5, 4s0
t- .
Properties of transition metals
Complex ion formation
Bonding in complex ions. The simplest view is that the l igands form
dative coval ent bonds by donating a lone pair of electrons into empty
orbital s of the transition metal ion. These coul d be empty 3d, 4s, 4p or
4d orbital s in the ion (e. g. see the arrangement of electrons in boxes in
Figure 5. 3) .
3d 4s 4p 4d
, _ ,
Fe
2
+ electrons Ligand electrons: six pairs
54
TRANS I TI ON M ETALS, QUANTI TATI VE K I N ETI CS AN D APPL I E D ORGAN I C CH E M I STRY
[ Cu( Hz0)6f+ i s turquoi se bl ue,
[ Cu( NH3)4( H20)2]2+ i s deep bl ue, and
[ CuC1 4t i s yel l ow.
Hydrated cati ons of charge 4+ or
more do not exi st because the sum
of al l t he i oni sati on energ i es i s too
l arge to be compensated for by the
hydrati on energy.
Copper forms Cu+ and Cu2+, and
chromi um Cr2+ and Cr3+.
Typical l igands are:
neutral molecul es: H20 (aqua), NH
3
(ammi ne)
ani ons: F- ( fl uoro), Cl(chloro), (CNt (cyano) .
Shapes of compl ex i ons (see pages 1 4-1 5) . If the complex i on has 6 pairs
of electrons donated by l igands, the complex will be octahedral. This
i s so that the electron pairs i n the l igands wi l l be as far apart from each
other as possi bl e.
Coloured complex ions
If the ion has parti al ly fi l l ed d orbitals, it wi l l be coloured. Sc
3
+ and Ti
4
+
have d0 structures, and Cu+ and Zn
2
+ have d and so are not coloured.
d orbitals point in di fferent directions in space, and so i nteract to
different extents with the electrons in the ligands.
This causes a spl itting of the d orbitals into two of higher energy and
three of l ower energy.
When white l ight i s shone i nto the substance, a d electron is moved
from the lower energy to the higher energy l evel .
The frequency of the l ight that causes thi s j ump i s i n the vi sibl e range,
so that colour at thi s frequency i s removed from the white light.
The colour depends on the size of the energy gap which varies with the
metal ion and with the type of l igand.
Variable oxidation state
Successive i oni sation energies i ncrease steadi ly unti l al l the 4s and the
3d electrons have been removed, after which there i s a large j ump i n
the val ue.
Formati on of cations. The i ncrease between successive i oni sation
energies i s compensated for by a si mi l ar increase in hydration energi es.
Thus cati ons i n different oxidation states are energetically favourable for
al l transition metal s.
Formation of coval ent bonds. Transition metal s can make available a
vari able number of d electrons for covalent bonding. The energy
requi red for the promotion of an electron from a 3d to a higher energy
orbital is compensated for by the bond energy released.
Formation of oxoions. In i ons such as Mn04-, V0
3
-
, VO/ and V0
2
+, the
oxygen i s covalently bonded to the transition metal which uses a
varying number of d el ectrons.
Manganese exists:
i n the +2 state as Md+
in the +4 state as Mn02
i n the +6 state as MnOt
i n the +7 state as Mn0
4
-.
Catalytic activity
Transition metal s and their compounds are often good catalysts.
Vanadi um(V) oxi de i s used i n the oxidation of S02 to S0
3
i n the contact
process for the manufacture of sul phuric aci d.
I ron i s used i n the Haber process for the manufacture of ammoni a.
Ni ckel i s used i n the addition of hydrogen to al kenes (hardening of
vegetable oils) .
TRANS I TI ON M ETAL C H E M I STRY
5
I on
a
Colour
Cr
3
+ Green
Mn
2
+ Pale pi nk
Reactions of transition metal compounds
Reactions with sodium hydroxide and ammonia solutions
The table gives a summary of these reacti ons.
Addition of Excess NaOH(aq) Addition of Excess NHl aq)
NaOH(aq) NH
3
(aq)
Green ppt Green solution Green ppt Ppt remai ns
Sandy pptb Ppt remai ns Sandy pptb Ppt remai ns
Fe
2
+ Pale green Di rty green pp( Ppt remai ns Di rty green pp( Ppt remai ns
Fe
3
+ Brown/yel l ow Foxy red ppt Ppt remai ns Foxy red ppt Ppt remai ns
Ni
2
+ Green Green ppt Ppt remai ns Green ppt Bl ue sol n
Cu
2
+ Pale bl ue Blue pptc Ppt remai ns Pal e blue ppt Deep bl ue sol n
Zn
2
+ None Whi te ppt Colourless solution White ppt Colourless soln
a
The correct formula for the ions should be the hexa-aqua ion, except for zinc, which forms a tetraqua ion.
b The precipitate of Mn(OH)2 goes brown as it is oxidised b air.
c
The precipitate of Fe(OH)2 goes brown on the surface a it is o idi ed by the o.y en in the air.
The precipitate of Cu(OH) goes black as it lo e 'ater to form u .
Amphoteri c hydroxi des ' redi ssol ve'
i n excess strong al kal i , e. g.
Cr ( OH)J( s) + 30W( aq) [ Cr( OH)st
( aq)
and Zn( OH)2( s) + 20W(aq)
[Zn( OH)4t(aq) .
Thi s reacti on i s used as a test for:
a ni ckel ( l l ) : wi th aqueous ammoni a
ni ckel ( l l ) i ons fi rst gi ve a green
preci pitate whi ch then forms a
bl ue sol uti on wi th excess
ammoni a.
b copper( l l ) i ons gi ve a pal e bl ue
preci pitate whi ch forms a deep
bl ue sol uti on wi th excess
ammoni a and
c zi nc i ons g i ve a white preci pitate
whi ch forms a col ou rl ess sol uti on
wi th excess ammoni a.
Deprotonation
The aqua ions in solution are parti al ly deprotonated by water. he
greater the surface charge density of the ion the greater the e t nt of
thi s reaction, e. g. hexa-aqua iron( I I I ) ions:
[Fe(H20)6]
3
+(aq) + H20 .:
[ Fe( H20)5(0H)]
2
+(aq) + H
3
0
+
(aq)
Thi s means that solutions of iron( I I I) i ons are acidic (pH < 7) .
When an al kal i such as sodium hydroxide is added, the equi l i brium i s
driven to the right, the i on i s considerably deprotonated to form a
neutral molecule which l oses water to form a precipitate of the metal
hydroxide:
[ Fe(H20)6f+(aq) + 30H-(aq) Fe(OH)
3
(s) + 6H20
If aqueous ammonia is added, the same precipitate is formed:
[ Fe(H20)6f+(aq) +3NH
3
(aq) Fe(OH)
3
(s) + 3NH/(aq) + 3H20
Ligand exchange
When aqueous ammoni a is added to aqua compl exes of d block
elements such as those of ni ckel, copper and zinc, l igand exchange takes
place and a solution of the ammi ne compl ex i s formed.
Fi rst the hydroxide i s precipitated i n a deprotonation reacti on:
[Cu(H20)6]
2
+(aq) + 2NH3
(aq) Cu(OH)2(s) + 2NH/(aq) + 4H20
The hydroxide then ligand exchanges to form an ammi ne complex with
excess ammoni a:
Cu(OH)2(s) + 4NH3(aq) +2H20 [Cu(NH
3
)4(H20)z]
2
+ + 20H-(aq)
The final result is that the NH
3
l igand has taken the pl ace of four H20
ligands.
Addition of cyani de ions to iron( I I ) ions produces a solution of
hexacyanoferrate( I I ) :
[Fe( H20)6]
2
+(aq) + 6CN-(aq) [Fe(CN)t-(aq) + 6H20
A test for iron( I I I ) ions i s to add a solution of potassium
thi ocyanate, KCNS. Iron( I I I ) i ons give a blood red solution:
[Fe(H20)6]
3
+(aq) + SCN-(aq) [Fe(SCN)( H20)5]
2
+(aq) + H20
Ub
TRANS I T I ON M ETALS, QUANTI TATI VE KI N ETI CS AN D APPL I E D ORGAN I C CH E M I STRY
VO/
Fe3+
Vanadium chemistry
Vanadium compounds exist in four oxidation states:
+5: V0
3
-
(aq) which i s colourless, but i n acid solution reacts to form a
yellow solution of VO/(aq) i ons:
V0
3
- + 2H+ VO/ + H
z
O
+4: V0
2
+(aq), which is blue.
+3: V3+(aq) which is green and i s mi ldly reduci ng.
+2: V
2
+(aq) which is lavender and is strongly reduci ng.
Reduction by zinc. I f zinc and di lute hydrochloric acid are added to a
solution of sodium vanadate, NaV0
3
, the colour changes in distinct
sequence, as it is steadi ly reduced from the +5 to the +2 state:
start: yellow caused by V0
2
+(aq)i ons (+5 state)
then: green caused by a mixture of yellow VO/(aq) and blue
then:
then:
final ly:
V0
2
+(aq)
blue caused by V0
2
+(aq) i ons ( +4 state)
green caused by V3+ (aq) ions ( +3 state)
lavender caused by V
2
..(aq) ions ( +2 state)
Redox reactions
Vanadium compounds can be oxidi sed or reduced by suitable reagents. For
a redox reaction to work, the E-ceu value must be positive. A l i st of E-values
for the half reactions of vanadi um in its various oxidati on states and for
some oxidi si ng and reducing agents is gi en below. These values show, for
in tance, that anadi um( ) v\T ill be reduced only to vanadi um ( IV) by Fe
2
+
ion , \Yherea n
2
ion \\ill reduce it fi rst to vanadium ( IV) and then
to vanadium ( I I I ).
+5 VO/ +5
+ 2H+ + e
-
F V0
2
+ H20 E- +1 .
+ e
T Fe
2
+ E- = +0. 77 Fe
2
+
1
/2Cl2 e
-
cr E- * +1 . 36
y
Cl
2
+4 +4
Fe3+
No
z
+ 2H + e
-
V3+ + H20 E- e +0. 34 V
Sn
4
+ + 2e
-
Sn
2
+ E-e * +0. 1 5 V Sn
2
..
Fe3 .. + e
.
Fe
2
.. E- * +0. 77 V
y
+3
v3+ + e
.
N
z
.. E- = -0. 26 V
Zn
2
+ + 2e
Zn E- e -0. 76 V Zn/H+
H+ + e
-
. 1/zHz
E-e = U. UU N
y
+2 +2
E-ceu for the reduction of: E-cell for the oxidation of:
vo
z
+ by Fe
2
+ = +1 . 0 - (+0. 77) * +0. 23 N
V0
2
+ by Sn
2
.. = +0. 34 - (+0. 1 5) = +0. 1 9 N
V3+ by Zn = -0. 26 - (-0. 76) = +0. 50 N
_-.
v
z
+ by H+ = U. U ~ (-0. 26) * +0. 26 N
V3 .. by Fe3+ = +0. 77 - (+0. 34) = +0. 43 N
vo
z
.. by c12 * +1 . 36 - (+LO) * +0. 36 N
Before attempting the questions on this topic, check that you:
Can defi ne d bl ock and transition elements.
Can write the electronic structure of the d block elements and their ions.
TRANS I TI ON M ETAL CH E M I STRY
51
[ Cu( H
2
0)6t turquoi se-bl ue.
Dati ve coval ent ( l i gand t o i on) and
coval ent (wi thi n t he water mol ecul e)
Octahedral
Deprotonati on
Li gand exchange
t5, VO/, yel l ow. t4, V0
2
, bl ue.
+3, V
3
, green. +2, V
2
+, l avender.
I ron in the Haber process to
manufactu re ammoni a
Vanadi um(V) oxi de in the Contact
process to manufacture sul phuri c
aci d
Can recal l the characteristic properties of the transi tion elements.
Understand the nature of the bondi ng i n complex ions, the shape of
the i ons and thei r colour.
Can recal l the action of aqueou odium hydroxide and ammoni a on
solutions of their aqua i ons.
Understand deprotonation and l i and e change reacti ons.
Can recal l the oxidation state of vanadium, and the colours of its i ons.
Know reactions to interconvert th oxi d tion tate of vanadi um.
Can recall examples of anadi um, ir n nd ni kel and their compounds
as catalysts .
P
t-your k1 1 o1 \ | J JuJ uuJ r --
For the follm. i ng t of que tion g COVer th mar rin o th p Y for ) ou
answer, then check to see if you are orr t.
Write down the el ectronic structure of a anadium atom and ion.
State the formul a and colour of the aqua complex of copper( I I ) .
State the formula and colour of the ammi ne compl ex of copper( I I .
Name the types of bonding in the aqua complex of iron( I I ) .
What i s the shape of the iron( I I ) aqua complex i on?
State the type of reaction that occurs when aqueous sodium hydroxide
i s added to a solution of the aqua complex of copper(I I ) .
State t he type of reaction that occurs when excess aqueous ammoni a i s
added to a solution of the aqua complex of copper( I I ) .
What are the oxidation states of vanadium? Give the formula and the
colour of the cation for each oxidation state.
Give an example of the use of i ron as an industrial catalyst.
Give an industrial use of a vanadium compound as a catalyst.
1 Expl ai n why the [Cu( H20)6]
2
ion is coloured.
2 Give the equati ons for the reactions caused by smal l additions of
sodi um hydroxide solution, followed by excess to:
a a solution of the aqua complex of chromium( I I I)
b a solution of the aqua complex of i ron( I I )
c a solution of the aqua compl ex of zinc( I I ) .
3 Give the equati ons for the reactions caused by smal l additions of
ammonia solution, fol l owed by excess to:
a a solution of the aqua complex of iron( I I I )
b a solution of the aqua complex of copper( I I ) .
4 Write the hal f equations for the fol l owi ng changes in oxidation state:
a vanadi um(V) to vanadi um( I I )
b vanadi um(V) to vanadium ( IV)
c vanadium( I I I) to vanadi um( IV)
5b
TRANS I TI ON M ETALS, QUANTI TATI V E KI N ETI CS AN D APP L I E D ORGA N I C CH E M I STRY
Organ i c chemi stry I l l
_Thi ngs to learn and unders tand
The structure of benzene and reactions of aromatic
compounds
The benzene ri ng does not consi st of alternate double and si ngle bonds.
Al l t he bond l engths are t he same and t he molecule i s pl anar.
There is an overl ap of p orbitals above and below the pl ane of the
mol ecule, formi ng a continuous or delocalised system.
This gives stabil i ty to the benzene structure whi ch i s why i t undergoes
substitution rather than addition reactions.
Benzene can be represented either by:
Reactions of benzene
Benzene reacts mai nly by electrophilic substitution:
Nitration. Benzene reacts with a mixture of concentrated nitric and
sul phuric acids to form nitrobenzene:
C6H6 HN03
C6H5N02 H20
Bromination. Benzene reacts with l i qui d bromi ne in the presence of a
catalyst of anhydrous i ron( I I I) bromide (made in situ from i ron and
l iquid bromi ne) or of anhydrous aluminium bromi de:
C6H6 Br2(l ) C6H5Br -HBr
Friedel-Crafts reaction. Benzene wi l l react wi th hal ogenoalkanes or
with acid chlorides i n the presence of a catalyst of anhydrous
al umi ni um chloride:
C6H6 C2H5Cl C6H5C2H5 HCl
ethylbenzene
C6H6 CH
3
COC1 C6H5COCH
3
HCl
phenylethanone (a ketone)
Reactions of compounds with a carbon-containing side
chain
Compounds such as methyl benzene C6H5CH
3
and ethyl benzene
C6HSC2HS can be oxi di sed, and the product will contain a COO group
on the benzene ring, regardless of the number of carbon atoms in the
chai n. On acidification benzoic acid is produced:
C6HsCzHs 6[0] OH
-
C6HsCOO- COz 3Hz0
conditions: heat under refl ux with potassium manganate(VI I) and
aqueous sodium hydroxi de.
ORGAN I C CH E M I STRY I l l
Phenol i s a weaker aci d than
carboni c aci d, and so i t wi l l not
l i berate C0
2
from sodi um hydrogen
carbonate, unl i ke carboxyl i c aci ds
whi ch wi l l .
The sol uti on of d i azoni um i ons can
react wi th phenol . A yel l ow
preci pitate of di azo compound i s
obtai ned.
N N OH
Phenol
OH

55
Although it forms some hydrogen bonds with water, it is only parti al ly
soluble and forms two l ayers when added to water at room temperature.
+ alkali. Phenol i s a weak acid and i t forms a colourless solution with
aqueous sodi um hydroxi de:
C6H50H(l ) + OH-(aq) C6H50-(aq) + H20(l )
+ bromine water. The presence of the OH group makes substitution
i nto the benzene ring much easier. o catalyst is requi red:
OH OH

(aq) + 3Br2(aq)
BrBr
(s) + 3HBr(aq)
Br
observation: when brown bromi ne water is added, a white precipitate i s
rapidly formed.
+ acid chlorides. Phenol reacts as an alcohol, and an ester i s formed:
C6H50H + CH
3
C0Cl CH
3
COOC6H5 + HCl
Phenylamine
Phenyl ami ne has a NH2 group attached to the benzene ring.
Preparation
Nitrobenzene is reduced by ti n and concentrated hydrochloric acid when
heated under refl ux. Then sodium hydroxide is added to l iberate the
phenylami ne, which i s removed by steam distillati on.
Reactions
+ acid
+ nitrous acid
C6H5NH2 + 2H+ + N02- C6H5N/ + 2H20
conditions: add di lute hydrochloric acid to phenyl ami ne and cool the
solution to S C. Sodium ni trite solution i s then added, keepi ng the
temperature close to S C and above 0 C.
l00
TRANS I T I ON M ETALS, QUANTI TAT I VE K I N ETI CS AN D APP L I E D ORGAN I C C H E M I STRY
Ensure that the curl y arrow starts
from a bond or an atom with a l one
pai r of el ectrons.
Ensure that the arrow poi nts
towards an atom ei ther formi ng a
negati ve i on or a new coval ent bond.
Another way of pol ymeri si ng ethene
i s by usi ng ti tani um tetrachl ori de
and al umi ni um tri ethyl , but thi s i s
not a homol yti c mechani sm.
Wi th t he addi ti on of a hydrogen
hal i de to an unsymmetri cal al kene,
the hyd rogen atom adds to the
carbon whi ch al ready has more
hydrogen atoms di rectl y bonded to
i t.
Thi s i s because the secondary
carbocati on,
e. g. .-.-:

is more stabl e than a pri mary one.

e. g. CCC f

Mechanisms
A curly arrow ({) represents the movement of a pair of electron , either
from a bond or from a lone pair. A half-headed arrow ( 0) repre ent the
movement of a single electron.
Homolytic, free radical substitution
Reaction between an alkane and chlorine or bromine
An example is shown of reaction between methane and chlori ne.
There are three stages in thi s type of reacti on:
1 Initiation: l ight energy causes homolytic fissi on of chlorine:
Cl2 2Cl
2 Propagation: each propagation step involves a radical reacting
with a molecule to produce a new radi cal :
CH
4
+ Cl CH
3
+ HCl
then
3 Termination: i nvolves two radicals j oi ni ng with no radicals being
produced, e. g.
Homolytic, free radical addition
Polymerisation of ethene
The conditions are a very high pressure ( 1 000 atm) and a trace of oxygen.
The conditions produce radicals, R , which attack a n ethene molecul e:
R H2C=CH2 R-CH2- CH2
then R-CH2-CH2 + H2C=CH2 R-CH2-CH2-CH2-CH2 etc
Heterolytic, electrophilic addition
Reactions of alkenes with halogens or hydrogen halides
The reaction takes place in two steps:
1 The electrophi l e accepts the n electrons to form a new bond with
one of the carbon atoms and at the same ti me the Br-Br bond
breaks.
2 The i ntermediate carbocation then bonds with a Br- i on.
Br-Br
`
H2C =CH2
Heterolytic, electrophilic substitution
Nitration of benzene
Br Br
1 Sul phuric acid is a stronger acid than nitric and so protonates i t:
H2S04 HN0
3
H2NO/ + HS04-
then the cation loses water:
H2N0
3
+ H20 NO/
ORGAN I C C H E M I STRY I l l
Si mi l ar mechani sms occu r for
bromi nati on, where the catalyst
reacts with bromi ne to provi de the
el ectrophi l e Br+, and i n the Fri edel
Crans reacti on where the catalyst
reacts wi th the hal ogen compound
to provi de el ectrophi l es such as
CH
3
C+O or C
2
H_
I n the transi ti on state, the new 0-C
bond forms as the C-Br bond
breaks. The transiti on state has a
charge of -1 .
Any opti cal acti vity is mai ntai ned i n
a SN2 reacti on.
I f the mechani sm i s SN 1 , a reactant
whi ch i s an opti cal i somer wi l l
produce a racemi c mi xtu re, as the
carbocati on can be attacked from
ei ther si de.
The CW i on i s a catal yst, and the
condi ti ons must be such that there
is a si gnifi cant amount of both HCN
mol ecul es and CW i ons present, i . e.
a mi xtu re of HCN and KCN.
2 The N02+ ion is the electrophi l e and attacks the benzene ring.
3 The HS04- i on pul l s off a H+ and reforms H2S04 (the catalyst) .
l0l
The l oss of H+ results in the reforming of the benzene ring and the gain i n
stabi l i ty associated with t he ring.
Heterolytic, nucleophilic substitution
Reaction between halogenoa/kanes and hydroxide or cyanide ions
There are two mechani m dependi nc on the type of hal o enoalkane.
With primar 1 ) hal o enoal kane , an S-2 me hani m i dominant.
Reaction proceeds ia a transition state when the lone pair of electrons
on the nucleophile attacks the hal ogenoal kane.
CH3
t CH3 ] - CH3
- '
HO: ,C -Br HO
- -
H
-
_- c_
- -
H
- -
Br -HO -C : Br
H
-
-
-
l |
-
-
,
H
H H
transition state
With tertiary (3) hal ogenoalkanes the S
N
l mechanism is dominant.
Thi s happens i n two steps:
1 The hal ogenoal kane ionises in the relatively slow, and hence rate
determining step, to form an intermediate carbocation.
CH3 CH3

CH
3
-C -Br CH3 -C+ + : Br-

CH3 CH3
2 This then rapidly forms a bond with the nucleophi le, OH
-
.
Heterolytic, nucleophilic addition
Reaction between a carbonyl compound and hydrogen cyanide
Although the reaction is the addition of HCN, the fi rst step is the
nucleophi l i c attack by the CN- ion on the 8+ carbon atom i n the
carbonyl group.
l0
Benzene
c6

TRANS I T I ON M ETALS, QUANTI TATI VE K I N ET I CS AND APP L I E D ORGAN I C CH E M I STRY
The negatively charged oxygen i n the ani on then removes an H+ from
an HCN molecul e. Thi s produces another CN- i on, which reacts with
another carbonyl group and so on.
0-H
R-C -H R-C -H

CN CN
The conditions for thi s reaction are either HCN and a trace of base or
KCN and a smal l amount of dil ute sul phuric acid.
Reactions of aromatic substances ( Figure 5. 4) and mechani sms ( Figure 5. 5)
are summari sed schematically.
cone HN03 C6H5N02
cone H2S04
Br2 C6H5Br
Fe catalyst
C2H5 Cl C6H5C2H5
Al Cl3 catalyst
CH3COCl C6H5COCH3
AlCl3 catalyst
Fig 5.4 Summary of reactions of aromatic substances
Free radical :
Substitution
alkanes Cl2
Addition
Free radical : polymerisation of alkenes
Nucleophilic: halogenoalkanes OH-(aq) Nucleophil ic: carbonyl + HCN
Electrophil ic: benzene
Fig S.S Summary of mechanisms
compounds
HN Electrophilic: alkenes
Br2(1) + HCl HBr/ HI
+ RCl
RCOCl
_-.
Before attempting the questions on thi s topic, check that you:
Understand the structure of benzene and why it reacts by substitution
rather than by addition.
ORGAN I C C H E M I STRY I l l
a C6HsCoo
b C6H
5
0- Na+
c C
2
H
5
COOCsHs
The brown bromi ne water woul d go
col ourl ess and a white preci pitate
woul d form.
Heat under refl ux wi th ti n and
concentrated hydrochl ori c aci d, cool
and then add aqueous sodi um
hydroxi de.
questi ons are on page 1 3
8
.
Can recal l the reactions of benzene with ni tric acid, bromi ne and
hal ogen compounds.
Can recal l the product of oxidising si de chai ns.
Can recal l the reacti ons of phenol with al kal i , bromi ne and aci d
chlorides.
l0J
Can recall the preparati on of phenyl ami ne and its reacti on with ni trous
acid and the coupling of the product with phenol .
Understand the mechani sms of free radical substitution and additi on.
Understand the mechani sms of electrophi l i c substitution and additi on.
Understand the mechani sms of nucleophi l i c substitution and additi on.
Testing your knowledge and understanding
For the following set of questions, cover the margin before you answer,
State the structural formul ae of the organic product obtai ned by the
reacti on of:
a propylbenzene with al kal i ne potassium manganate(VI I )
b phenol with sodium hydroxide solution
c phenol with propanoyl chloride.
What would you observe i f bromi ne water were added to aqueous
phenol?
State the conditions for the conversi on of nitrobenzene to
phenylami ne.
1 a Describe the mechanism for the reacti on of bromi ne with benzene.
b Why does benzene undergo a substitution reaction with bromi ne
rather than an addition reaction?
2 I n the reaction between propanone and hydrogen cyanide no reaction
occurs unless a small amount of a base such as sodium hydroxide is
added. Expl ai n these observati ons.
3 When benzenediazoni um chloride i s prepared, the reacti on i s carried
out at about S C.
a Why are these conditions chosen?
b What is the formula of the product obtained by the reaction of the
benzene diazoni um chl oride solution with phenol i n alkali ne
solution?
l 04
TRANS I T I ON M ETALS, QUANTI TATI VE K I N ETI CS AN D APP L I E D ORGAN I C C H E M I STRY
The uni ts of k are:
for a zero-order reacti on:
mol dm-
3
s-1
for a fi rst-order reacti on: s_
,
for a second-order reacti on:
mol-1 dm
3
s-1
The hal f-l i fe of a fi rst-order reacti on
i s constant.
Chemi cal ki n et i cs I I
Introducti on
You must al so revise Topic 2. 3 i n Chapter 2, page 44 and especial l y how
the changes in the Maxwel l-Boltzmann distribution of energy with
i ncrease in temperature affect the rate of reacti on.
Thi ngs to learn

The rate equation for the reaction:
xM + yN products, i s:
Rate of reacti on k M] [N] b where O and b are i ntegers and are
experimentally determined.
The rate constant, k, i s the constant of proportional ity i n the rate
equation:
Its value depends on the activation energy of the reacti on and the
temperature.
Reactions with a large activation energy wi l l have smal l values of k.
The order with respect to one substance is the power to which
the concentration of that substance is raised i n the rate equati on. In the
exampl e above the partial order of the chemi cal M i s O.
The order of reaction i s the sum of the parti al orders. In the
exampl e above, the order of the reacti on i s O + b.
The activation energy, Ea, i s the total kinetic energy that the
molecules must have on col l i si on i n order for them to be able to react.
Half-life, f_, i s the tilne taken for the concentration to fal l from any
selected value to hal f that val ue.
Thi ngs to understand
Determination of rate equation from initial rates
Consider the reaction:
A + B+ C products
The i ni ti al rates of reacti on with di fferent concentrations of A, B and C are
found, and by taking the experiments two at a time, the order with respect
to each substance can be found.
Look for two experi ments where the concentration of only one substance
varies. I f doubl i ng that concentration causes the rate to double, the order
with respect to that substance i s 1 .
CH E M I CAL KI N ET I CS I I
Note that for the fi rst-order graph,
t he hal f-l ife remai ns constant
throughout the reacti on, whereas for
the second-order the hal f-l ife
i ncreases as the concentrati on fal l s.
.9
+
C
+
0
L
O
<
1 00
80
60
40
20
0
Zero order
* 1 st order
" 2nd order
20
Time
40
Experiment [A] [B] [C] Relative rate
1 1 1 1 1
2 2 1 1 2
3 1 2 1 4
4 1 2 2 4
From experiments 1 and 2: [A] doubles and rate doubles. Therefore
order with respect to A = 1
From experiments 1 and 3: [B] doubl es and rate ? 4. Therefore order
with respect to B = 2
l0
From experiments 3 and 4: [C] doubles and rate unal tered. Therefore
order with respect to C = 0
Rate of reaction = k [Af [Bf [C]
0
, and the reaction is 3rd order.
Experimental techniques for following a reaction
1 Ti tration method. Mix the chemical and start the clock. t intenal
withdraw a sample, add it to i ed water to low the reaction. Then
ti trate one of the ub tan e in the reacti on. Thi method can b u ed i f
an acid, an al kal i or iodine i a reactant or a product.
2 Colorimetric method. Thi s can be used when either a r actant or a
product is coloured (iodine or potassi um manganate VI I ) are exampl e ) .
The colorimeter must first be cal ibrated using solutions of the coloured
substance of known concentrati ons. Then the reactants are mixed and
the clock started. The i ntensity of the colour i s measured as a function
of time. The concentrati on of the coloured substance i s proportional to
the amount of l ight absorbed.
3 Gas vol ume method. If a gas is produced in the reaction, its vol ume can
be measured at i nterval s of time. The gas can be coll ected in a
horizontal gas syri nge or by bubbl i ng it i nto an i nverted measuring
cyl i nder fil l ed with water.
Graphs of results
If the concentration of a reactant is plotted against time, three shapes of
graph are l ikely depending on the order of the reaction.
Mechanisms
A suggested mechani sm must be consistent with the order of reacti on. The
partial order of any species which occurs i n the mechani sm afer the rate
determi ni ng step wi l l be zero. The rate-determi ni ng step i s the sl owest
step, e. g.
N02(g) CO(g) NO(g) C02(g) has the rate expression:
Rate = k [N02]
2
[ COJ
0
A suggested mechani sm i s:
Step 1 (slow) :
Step 2 (fast) :
N0
3
CO NOZ C02
As the CO enters the mechani sm afer the rate determi ni ng step, the
1nechani sm i s consistent with the fact that the reaction i s zero order with
respect to CO.
l0b
TRANS I TI ON M ETALS, QUANTI TAT I VE KI N ETI CS AND APPL I E D ORGAN I C CH E M I STRY
Energy profile diagrams
The first diagram is for a reaction that takes place in a singl e step, and the
second diagram is for thi s reacti on with a catalyst (see Figure 5. 6) .
- - - - - - - - - Transition
state
Intermediate
Uncatalysed
Fig 5. 6 Energy profile diagrams
Catalysed
An exampl e of a reaction with a transition state is the S 2 reaction of
bromoethane with hydroxide i ons.
An exampl e of a catalysed reaction formi ng an i ntermediate i s Fe
2
+ i ons as
a catalyst i n:
S20,(aq) + Zr(aq) - 2SO,-(aq) + 12(aq)
I n this mechanism the catalyst fi rst reduces the S208
2
- i ons:
2Fe
2
+(aq) S208
2
-(aq) - 2Fe
3
+(aq) + 2SO/-(aq)
then the Fe
3
+ ions are reduced back to Fe
2
+ i ons:
2Fe
3
+(aq) + Zr(aq) - 2Fe
2
+(aq) + 12(aq)
Checkl is t
Can define rate constant, order of reaction and hal f-l i fe.
Can deduce rate equations from i ni ti al rate data.
Understand the concept of activation energy and its relation to the rate
constant.
Understand that i nfonnation about mechani sms can be deduced from
the partial orders of the reactants.
Can recal l the energy profil es of reacti ons with and without catalysts.
Can suggest suitable methods for fol lowing reacti ons.
Can deduce the order of a reaction from concentration/time graphs.
CH E M I CAL K I N ETI CS I I
a From experi ments 1 and 2, order
wi t h respect to N0
2
" 2
b From experi ments 1 and 3, order
wi th respect t o CO " 0
c Order of reacti on is 2 + 0 " 2
d Rate " k [ N02]2
a Reacti on 8
b Reacti on 8
Step 2 as i t has the l argest fact val ue
1 00 to 6. 25 " 4 hal f-l i ves, therefore
ti me 4 x 25 " 1 00 mi nutes
l01
For the fol l owi ng set of questions, cover the margi n before you answer,
The fol l owing results were obtai ned from a study of the reacti on:
NOz(g) + CO(g) - NO(g) + C02(g)
Experi ment [N02] /mol dm-
3
[CO] /mol dm-
3
1 0. 02 0. 02
2 0. 04 0. 02
3 0. 02 0. 04
a What is the order with respect to N02?
b What is the order with respect to CO?
c What is the order of reaction?
d State the rate expre si on.
Relative rate
1
4
1
Reaction ha a high ,al ue of E , and rea ti n B ha a lower Ea ' al ue.
a Which reaction has the l arg r rate con tant?
b Which is the faster reacti on?
A reaction takes pl ace i n 3 steps. The EalkJ 1nor
1
for each tep are:
step 1: 32, step 2: 5 1 , step 3: 20
Which step determi nes the rate?
The decomposi ti on of N205 is fi rst order. At 200 C the reacti on has a
hal f-l i fe of 25 mi nutes. Calcul ate how long it wi l l take for the
concentrati on of N205 to fal l to 6. 25% of its origi nal value.
1 The rate of the second order reaction:
2HI (g) - H2(g) + I2(g)
is 2.0 ? 1 0-
4
mol dm-
3
s-
1
when [ HI] = 0. 050 mol dm-
3
at 785 K. Calculate
the value of the rate constant, givi ng i ts units.
2 Describe how you woul d fol low, at 60 C, the rate of the reacti on:
CH
3
COOH(aq) CH
3
0H(aq) - CH
3
COOCHll) H20(1 ).
3 The decomposi ti on of 3-oxobutanoic aci d, CH
3
COCH2COOH, was
studied:
CH
3
COCH2COOH - CH
3
COCH
3
+ C02
The results, at 40 C, are tabul ated below.
Ti me/mi n [ 3-oxobutanoi c acid] /mol dm-
3
0 1 . 6
26 0. 8
52 0. 4
78 0. 2
Deduce the order of the reacti on.
l0b
TRANS I TI ON M ETALS, QUANTI TAT I VE K I N ETI CS AND APPL I E D ORGAN I C C H E M I STRY
Organ i c che mi st ry V
Introducti on
Questions on thi s topic wi l l form part of t he synoptic assessment i n
Uni t Test 5.
Thi s Topic bri ngs together al l the organi c chemistry that has been
covered in earlier topics, so you wi l l need to revise Topi cs 2. 2, 4. 5
and 5. 3.
Thi ngs to learn and unders tand
Organic analysis
You should know the tests for:
Alkenes
Test: Add bromi ne i n hexane.
Observation: The brown bromi ne becomes colourless.
Halogenoalkanes
Test: Heat under reflux with sodium hydroxide solution, then
acidify with di l ute ni tric acid. Add si lver nitrate soluti on.
Observation: Chlorides give a whi te precipitate that i s soluble i n dilute
ammoni a.
Bromides give a cream precipi tate that i s i nsol ubl e i n
di lute ammoni a but dissolves i n concentrated ammoni a.
I odi des give a yel low precipitate that i s i nsoluble i n
concentrated ammoni a.
OH group ( i n al cohol s and acids)
Test: To the dry compound add phosphorus pentachl oride.
Observation: Steamy fumes of hydrogen chl oride produced.
Alcohols
Test: Warm with di l ute sul phuric acid and potassi um
dichromate(VI) solution.
Observation: Primary ( 1 ) and secondary (2)alcohols reduce the
orange dichromate(VI) i ons to green Cr
3
+ i ons.
Tertiary (3) al cohol s do not affect the colour as they are
not oxidised.
To distinguish between 1 o and 2 repeat the experiment,
but di sti l the product into ammoniacal silver nitrate
soluti on:
1 o al cohol s are oxidised to aldehydes, which give a si lver
mi rror.
2 al cohol s are oxidi sed to ketones, which do not react.
Carbonyl, C=O group (aldehyde or ketone)
Test: Add a sol ution of 2, 4-dini trophenyl hydrazi ne.
Observation: A red or orange preci pitate i s seen.
ORGAN I C C H E M I STRY I V
The sol i d must b e puri fi ed by
recrystal l i sati on in order to have a
sharp and accurate mel ti ng
temperatu re.
When i denti fyi ng speci es that cause
l i nes i n the spectru m, always gi ve a
structural formul a for the i on and its
+ charge.
Fig 5. 7 Mass spectrum of ethanol
The peaks gi ven by 0-H and N- H are
usual ly broad owi ng to hydrogen
bondi ng.
To di sti ngui sh between aldehydes and ketones:
Test: Warm with ammoniacal si lver nitrate solution.
l05
Observati on: Aldehydes give a si lver mi rror, ketones have no reaction.
Iodoform reaction
Test: Gently warm with a solution of sodi um hydroxide and
i odi ne.
Observati on: A pal e yel low preci pitate of CHI
3
This test works with carbonyl compounds contai ni ng the
CH3C=O and alcohols contai ning the CH3CH(OH) groups.
Carboxylic acids, COOH group
Test: Add to a solution of odimn hydrogen carbonate.
Observation: Bubbles of gas, which turn l i me water mi l ky.
Interpretation of data
You should be able to deduce structural formulae of organi c molecules
given data obtained from:
Chemical methods
Carry out tests as above to detern1i ne th functional roup in the
molecule. Measure the melting point of the ub tance. f ake a ol i d
derivative (such as the 2, 4-D deri ati e from carbonyl ompound ),
purify it, and measure its mel ti ng temperature. Check the m l ti n
temperature values wi th a data bank to identify the substance.
Mass spectra (see Figure 5 . 7)
Observe the fragments obtai ned and look for the value of the
molecular ion (M)
+
, i f any.
See if there is a peak at (M- 1 5)
+
. I f so the substance probably had a
CH3 group which is l ost forming the (M- 1 5)
+
peak.
I f there i s a peak at (M-28)
+
, the substance probably had a CO group.
Other fragments wi l l hel p to identify the structure.
1 00
80
v
C
60
.s
0
40 ~
T
20
0
1 0 1 5 20 25 30 35 40 45
m/z
Infrared spectra (see Figure 5 . 8)
These are used to identify functional groups i n the substance, and
al so to compare the spectrum of the unknown with a data bank of
spectra ('fi nger printing' ) .
Peaks to l ook for are at:
1 650 to 1 750 cm-
1
2500 to 3500 cm-
1
3300 to 3500 em -1
1 000 to 1 300 cm-1
given by C=O
given by 0-H
given by N-H
given by C-0
l l0
TRANS I TI ON M ETALS, QUANTI TATI VE KI N ETI CS AN D APP L I E D ORGAN I C C H E M I STRY
Fig 5. 8 Infrared spectrum of ethanol
The chemi cal shift i s the di fference
between the absorpti on frequenci es
of the hyd rogen nucl ei i n the
compound and those i n the
reference compound.
Fig 5. 9 High resolution NMR spectrum
of ethanol
o
4000 3000 2000 1 500 1 000 500
Wavenumber I cm-
1
NR spectra
|
1 1
The phenomenon of nuclear magnetic resonance occurs when nucl ei
such as
1
H are placed i n a strong magnetic fiel d and then absorb
appli ed radio frequency radiation.
The nuclei of hydrogen atoms in different chemical environments
within a molecul e wil l show up separately i n a NMR spectrum. The
values of their chemical shi ft, 8, are di fferent.
The hydrogen nucl ei i n a CH
3
group will have a di fferent chemical
shi ft from those i n a CH2 or i n an OH group. The value of o of the
peak due to the hydrogen i n OH (or in NH) depends upon the
solvent.
I n low resolution NMR, each group wi l l show as a si ngle peak, and
the area under the peak i s proporti onal to the number of hydrogen
atoms i n the same environment. Thus ethanol, CH
3
CH20H wil l have
three peaks of relative i ntensities 3: 2: 1 and methyl propane
CH
3
CH( CH
3
) CH
3
, wil l have two peaks with relative i ntensities of 9: 1 .
I n high resolution NMR spin coupl i ng i s observed. Thi s i s caused
by the i nterference of the magnetic fiel ds of neighbouring hydrogen
nucl ei . I f an adj acent carbon atom has hydrogen atoms bonded to
i t, they wi l l cause the peaks to spl i t as fol l ows:
1 neighbouring H atom peak spl its into 2 l ines (a doublet)
2 neighbouring H atoms peak splits into 3 l ines (a tripl et)
n neighbouring H atoms peak splits into (n + 1) l i nes.
Thus ethanol gives three peaks (see Figure 5 . 9) :
1 peak due to the OH hydrogen, which i s a si ngl e l i ne
( as it i s hydrogen bonded)
1 peak due to the CH2 hydrogens, which i s spl it into four l ines
by the three H atoms on the neighbouring CH
3
group.
1 peak due to the CH
3
hydrogens, which i s spl i t into three l i nes
by the two H atoms on the neighbouring CH2 group.
| | |
1 0 9 8
|
| |
6 5
ppm
l
| | | | |
4 3 2 1 0
ORGAN I C CH E M I STRY I V
1 A common error is to t hi nk that
KCN or HCN wi l l react wi th
al cohol s to form RCN. You must
fi rst convert ROH to R-hal ogen.
2 Many questi ons on organi c
synthesi s requi re, somewhere i n
the sequence, the conversi on of
the starti ng substance to a
carbonyl compound or a
hal ogenoal kane.
Recrystal l i sati on i s onl y sui tabl e for
puri fyi ng sol i ds.
When a speci fi c safety precauti on i s
asked for, do not gi ve the use of
safety gl asses, l ab coats etc. as
exampl es. The answer is probabl y
' no naked fl ames (ether sol vent) ' or
' carry out the experi ment i n a fume
cupboard' , i n whi ch case the speci fi c
hazard such as toxi ci ty must be
stated .
1 00% X
Y Z 1 00%
B
Fig 5. 1 0 Boiling
temperature/omposition diagram
Visible and UV spectra
H bonds wi l l absorb l ight energy as an electron is promoted from a
bonding to an anti-bonding n orbital.
The energy gap i s i n the near UV or visible range, and the group
causing this i s called a chromophore.
If the n bonded el ectrons are l i nked to a conj ugated system (alternate
double and si ngle carbon-carbon bonds), the absorption will shift to
a l ower frequency, and the sub tance may be coloured. The colour
observed wi l l be the complementar colour of that absorbed.
Organic synthesis
Reagents and conditions for the preparation of substance from A
If the number of carbon atoms in the chain i :
increased by one, consider:
a halogenoal kane with KCN
b carbonyl with HCN
c the Grignard reagent CH3MgBr
d a Grignard reagent added to C02 or methanal
increased by more than one, consider:
a a Grignard reagent with more than one carbon l m
b Friedel-Crafts reacti on for aromatic substan e
decreased by one, consider:
a the Hofmann degradation
b the i odoform reaction.
Practical techniques
Recrystallisation. Di ssolve the ol i d in a mni mum f hot olvent.
Fi l ter the hot solution through a preheated funnel u in futed fi lter
paper. Allow to cool. Fi lter under reduced pre ure (Buchner funnel ) ,
wash wi th a l ittle col d olvent and al low to dry. The ol id shoul d have
a sharp mel ti ng temperature.
Heating under reflux is nece ary when either the reactant has a low
boiling temperature or the reaction is slow at room temperature.
Safety precaution. You must use a fume cupboard when a reactant or
product i s toxic, i rritant or i s carcinogeni c.
Fractional distillation. This i s used to separate a mixture of two
l iquids. These mixtures can usual ly be separated into pure samples, but
if the boi l i ng points are too close, a good separation wi l l be difficul t.
I f a l i quid of composition X i s heated, it wi l l boil at T
1
o
c to give a vapour
of composition Y (see Figure 5. 1 0) . I f this i s condensed and reboi led, i t wi l l
boil at a temperature of T
2
o c giving a vapour of composition Z. Eventual ly
pure B will di sti l l off the top and pure A will be l eft in the flask.
Applied organic chemistry
Targeting pharmaceutical compounds. Those which are i oni c or
have several groups that can form hydrogen bonds with water, will tend
to be retained i n aqueous (non-fatty) ti ssue. Compounds with long
hydrocarbon chains and with few hydrogen bonding groups wi l l be
retained i n fatty ti ssue. The l atter will be stored i n the body, whereas
water-sol uble compounds wi l l be excreted.
Nitrogenous fertilisers are of three types:
1 quick release, such as those contai ni ng N03- and NH/ i ons
2 slow release, such as urea, NH2CONH2
3 natural, such as sl urry, compost and manure.
The first two are water-soluble and can be l eached out. The l ast is bul ky
and contai ns l i ttl e ni trogen.
l l
TRANS I T I ON M ETALS, QUANTI TATI VE K I N ETI CS AN D APPL I E D ORGAN I C C H E M I STRY
Pol ymers usual ly soften over a
range of temperatu res rather than
have a sharp melti ng temperature.
The mai n reason f or t hi s i s that the
pol ymer i s a mi xture of mol ecul es of
di fferent chai n l engths.
n
Esters, oils and fats. Si mpl e esters are used i n food flavouri ngs,
perfumes and as solvents for glues, varnishes and spray paints. Ani mal
fats are esters of propan- 1 , 2, 3-triol and saturated aci ds such as stearic
acid C
1
7 H35COOH. When hydrolysed by boi l i ng with aqueous sodium
hydroxide, they produce soap which is the sodi um salt of the organi c
aci d.
Vegetable oi l s are liquids which are esters of propan- 1 , 2, 3-triol and
unsaturated acids.
Margarine i s made from polyunsaturated vegetable oils by parti al
hydrogenation (addition of hydrogen) so that onl y a few doubl e bonds
remain.
Polymers are of two di stinct chemical types:
1 Addition. The monomers contain one or more C=C groups.
Polymerisation i s the addition caused by breaking the bonds, and
the pol ymer and the monomer have the same empirical formul a.
Examples are poly(ethene), poly(tetrafl uoroethene) (PTFE) and
poly(propene) .
2 Condensation. Both the monomers have two functional groups,
one at each end. Polymerisation i nvolves the loss of a simple
mol ecul e (usual ly H20 or HCl ) as each link forms. Examples are
nylon, a polyami de (see Figure 5 . 1 1 ), and terylene, a polyester.
a diacid chloride a diamine a polyamide
Fig 5. 1 1 A polyamide
Synthetic polymers are not easi ly biodegraded and can cause an
environmental problem of disposal . One answer i s for them to be recycled .

Checkl is t
Can recall the tests for C=C, C-Hal, COH, C=O, CHO and COOH groups.
Can deduce the functional groups present from results of chemical tests.
Can i nterpret mass, I R, NMR and UV spectra.
Can deduce pathways for the synthesis of organic molecules.
Appreciate how the structure of a pharmaceutical affects its sol ubility.
Can disti ngui sh between types of polymer and understand
polymerisati on.

1 How would you di stingui sh between:
a pentan-3-one and pentanal
ORGANI C C H E MI STRY I V
b 2-bromopropane and 2-chl oropropane
c methylpropan-2-ol, methyl propan- 1 -ol and butan-2-ol ?
l lJ
2 The mass spectrum of a substance X of molecul ar formul a C8 H
80 had
peaks at mass/charge values of 1 20, 1 05, and 77. Identify the peaks and
suggest a structural formula for X.
3 The IR spectrum of aspirin showed peaks at 3200, 1 720 and 1 1 50 cm-1
Use the data on page 1 09 to identify the groups which cause these
peaks.
4 Low-resolution NMR spectra of two aromatic isomers with molecul ar
formula C8H1 were obtai ned. I somer Y had three peaks of relative areas
5: 2: 3, and isomer Z had two peaks of relative areas 6: 4. Suggest
structural formulae for Y and Z.
l l4
TRANS I T I ON M ETALS, QUANTI TAT I VE K I N ET I CS AND APP L I E D ORGAN I C CH E M I STRY
PrucrIce Tesr: tuIr
Time allowed 1hr 30 min
All questions are taken from parts of previous Edexcel Advanced GCE papers
The answers are on pages 13 9-1 4 1 .
1 a The kinetics o f the hydrolysis of the hal ogenoalkane (where R i s an al kyl group) RCH
2
Cl with aqueous
sodium hydroxide was studied at S0C. The following results were obtained:
Experiment [ RCH2Cl] [ OH-] I ni ti al rate/mol dm-
3
s-
1
1 0. 0S0 0. I 0 4. 0 ? 1 0
2 0. I S 0. 1 0 I . 2 ? I 0
3 0. I 0 0. 20 1 . 6 ? 1 0-
3
i Deduce the order of reaction with respect to the halogenoalkane, RCH2Cl, and with respect to the
hydroxide ion, OH-, giving reasons for your answers. [4]
ii Hence write the rate equation for the reaction. [1]
iii Calculate the value of the rate constant with its units for thi s reacti on.
[2]
iv Using your answer to part ii, write the mechani sm for thi s reacti on.
[3]
(Total 10 marks)
fanuar 2001 CH6 question 1 ]
2 Benzene, C
6
H
6
, reacts with ethanoyl chlori de, CH
3
C0Cl, by an electrophi l i c substitution reaction in the
presence of al umi ni um chloride as catalyst.
a Identify the electrophi l e i nvol ved in thi s reaction and write the equation to show its formation.
[2]
b Draw the mechanism for the electrophi l i c substitution of benzene by ethanoyl chloride.
[3]
c Suggest a reaction scheme, stating reagents and conditions, to convert the product of the reaction i n
b i nto OH
C H -C-COOH
6 5
CH
3
[5]
d Ethanoyl chloride can be used to prepare esters such as 3-methylbutyl ethanoate,
( CH
3
)2CHCH2CH200CCH
3
, which is a bee alarm pheromone that signals danger to a honey bee. If thi s
compound i s warmed wi th aqueous sodium hydroxide, a slow reaction takes place to produce sodi um
ethanoate and 3-methylbutan- 1 -ol . The reaction i s fi rst order wi th respect to both 3-methylbutyl
ethanoate and the aqueous hydroxide ion. Explain the term first order and give experi mental detai l s
showing how thi s i nformation coul d be obtained. [
8]
(Total 18 marks)
fune 2001 CH6 questions 2 & 7
PRACTI CE TEST: U N I T 5
3 Study the reaction scheme below, and then answer the questions that follow.
step 1 +D
C2H5Br C2H5MgBr C
4
H
1 0
0
step 2
E
C2H40
D
F
l l
a Give the reagents and conditions necessary for step 1 [2]
b Compound D reacts with ammoniacal si lver nitrate solution to give a sil er mi rror.
i Give suitable reagents for the conversion of B to D.
[2]
ii What precautions should be taken to ensure that B was converted mai nly to D and did not react
further?
[1]
iii Give the name or the structural formula of the organic compound formed when D reacts with
ammoni acal si lver nitrate soluti on.
c Give the structural formula of compound E (CH
1 0
0) .
d Compound F reacts with 2, 4-dinitrophenylhydrazine solution but has no effect upon ammoniacal
si lver nitrate sol ution. F will also undergo the iodoform reaction.
i Expl ai n the significance of the results of the test with ammoniacal si lver ni trate and 2, --
di nitrophenyl hydrazine concerning the functional group i n F.
ii What structural feature in F i s identi fi ed by the iodoform reaction? Give the formula of the
products of the reacti on.
iii Give the structural formula of F.
[1]
[2]
[2]
[3]
[2]
e The 1nass spectrum of F showed maj or peaks at m/e values of 72, 43 and 29. Identify the p ie
responsible for these peaks.
[3]
(Total H marks)
[anuar 2002 CH- question 1 ]
4 a Describe how you would measure the standard electrode (reduction) potential of the Fel-(aq)/ Fe2+(aq)
system.
[
5
]
b A standard Fe
3
+(aq)/Fe
2
+(aq) electrode is connected to a standard gold electrode, Au.-(aq)/ Au(s), at 25 C.
The gol d electrode acts as the cathode and the electrons flow, i n the external circuit, from the
Fe
3
+(aq)/Fe
2
+(aq) electrode to the gol d electrode.
i Write the half equati ons for the reacti ons that take place at each el ectrode when an electric current
is drawn from the cel l . [2]
ii Hence write the overal l i oni c equation for the reaction that takes place.
[1]
iii The potential of thi s cel l is +0. 73 V and the standard el ectrode potential for a Fe
3
+(aq)/Fe
2
+(aq)
electrode i s +0. 77 V. Calculate the standard el ectrode potential of the gold electrode. [2]
(Total 10 marks)
[anuar 2001 CH3 question 3]
llb
TRANS I TI ON M ETALS, QUANTI TATI VE K I N ET I CS AN D APPL I E D ORGA N I C C H E M I STRY
5 I ron and chromi um are very i mportant i ndustrial metal s.
a Complete t he boxes below to show t he el ectroni c configurations of:
3d 4s
Fe: [Ar]

Cr: [Ar]

Cr
3
: [Ar]

[3]
b Chromite, FeCrOo or Fe0. Cr03, is a mi xed oxide of i ron and chromi um that is used i n the manufacture
of stainl ess steel . It can be reduced by heating with carbon to produce iron, chromi um and carbon
monoxide.
Write an equation to represent the reduction of chromite. [2]
c The mixture of metals that results from the reducti on in b was reacted with excess dilute sulphuri c
aci d to give a solution of i ron(II) sulphate and chromi um(III) sul phate. Sodi um hydroxide solution
was added to the mixture until i n excess. The mi xture was then filtered to give a precipitate Q
contai ni ng al l the iron, and a filtrate R, containi ng al l the chromi um.
i What is the formula of the i ron-contai ni ng i on i n the aqueous iron(II) sul phate solution?
[1]
ii Write an i oni c equation for the reaction between sodium hydroxide solution and thi s i on. State
what type of reacti on i s taking place.
[3]
iii State the colour of the preci pitate Q. [1]
iv Give the formul a of the chromi um-contai ni ng i on in R.
[2]
v State what you woul d see if solution R was slowly acidified with di l ute sulphuric acid unti l there
was no further change. [2]
Electrode reacti on Ee/V Electrode reaction Ee/V
1
/zFz + e- +2. 87
Cr
3
+ e- Cr
2
-0. 41
1
/2Cl2 + e- Cl + 1 . 36
1
/2Cr20,+ 7H+ + 3e- Cr
3
+ 3
1
/2H20 +1 . 33
1
/2Br2 + e- Br- + 1 . 07
lflz + e- l +0. 54
d Use the standard electrode (reduction) potentials of the chromi um i ons and the halogens shown below
to answer the questi ons that fol low.
i Define the term standard electrode potential. [2]
ii List those halogens which wi l l oxidise chromi um( I I ) to chromi um( I I I ) .
[1]
iii List those halogens which wi l l oxidise chromi um( I I) to chromi um(III) but not to chromi um(VI ).
[1]
iv Chromi um(II) in aqueous solution is sky blue whereas aqueous chromi um( I I I) solution is dark
green. Describe how you woul d show that your prediction in d part ii actual ly worked in practice.
[2]
(Total 19 marks)
ranuar 2002 CHl question 3 & June 2001 CH3 question 5]
r /scs
'
Laboratory che mi st ry I I
The specifi cation ( syllabus) for the tests on thi s module includes al l the
AS and A2 material .
The Uni t Test 6B i s a synoptic paper, taken by al l candidates, and wi l l
also assess the candidate's qual ity of written communi cati on.
Uni t Tes t 6A: Assessment of practical
ski l ls II
Thi s i s either i nternally assessed or a practical exam.
r
Notes and books may be used in the tests.
The practical exam wi l l be broadly qualitative i n its approach.
You should be able to:
i observe and i nterpret detai l s of the chemi stry of the elements and
compounds l isted i n Uni ts 4 and 5.
ii recognize the results of experi ments t o identify functional groups i n
organi c compounds.
iii carry out the techniques described i n Topic 5. 5 and those used in
volumetric analysis, kinetics and equi libria.
iv present and i nterpret quantitative and qualitative results.
v devise and pl an si mpl e experiments based on the chemistry and
techniques as above.
Uni t Tes t c
Al l candidates wi l l do thi s paper
The Unit Test question (exam) paper
Section A wi l l consist of a compulsory question and wil l assess a
candidate's abi l i ty to i nterpret data from laboratory situati ons.
Section B wi l l consi st of three questi ons and the candidate must
answer two of the three questions.
These questions will require candidates to make connections between
di fferent areas of chemi stry, for exampl e by applying knowledge and
understandi ng of principles to situations in contexts new to them.
l lb
ADVANCE D LABORATORY C H E M I STRY
Questions wi ll be set on any of t he topics i n t he AS and A2
specifi cati on.
The questions wi ll require much l ess factual recall than those i n earlier
uni t tests. Much more emphasis will be placed upon appli cation of
knowl edge.
Questions wi l l test a candidate's abi l i ty to analyse i nformation from
several di fferent areas of the specificati on.
The words ' suggest' and ' deduce' wi l l occur more often i n questions
t han ' state' or ' recall ' .
Tackling the paper
Spend some ti me looking through Secti on B and decide whi ch questions
you are goi ng to attempt. Read all of the question before rej ecti ng it.
You may be abl e to answer al l but the fi rst part and so sti l l score good
marks. If you are getting nowhere in a question, abandon it and try
another, but do not cross out what you have written, because you
might score more for i t than for the other question. The exami ner wi l l
count your better mark.
Do not be put off by unusual compounds or situations. I n these
questions you are not expected to know the answer, but to be able to
work i t out, usi ng your knowledge and understandi ng of si mi l ar
compounds or situations.
Synoptic questi ons wi l l contai n material from several topics. Thi s is
done by usi ng the l i nks that exist between di fferent branches of
chemi stry.
Each question should have a thread or l i nk connecti ng the di fferent
parts. Identification of thi s thread will help you to focus on the relevant
chemi stry. So do not treat each part of a question i n isolation from the
other parts of i t.
For exampl e in the questions i n the Uni t Test 6B on pages 1 1 9 and 1 20.
Question 2 i s based on organi c and i norgani c nitrogen compounds,
with questi ons on ferti l i sers, pKa, polymers, amine preparati on, and
K
P
for ammoni um ni trate l i nked to thermodynami c and ki neti c
stabi l i ty.
Question 3 i s a reacti on scheme where the carbon chai n i s i ncreased
leading to a carboxyl i c acid, then a pH and buffer question about that
acid.
Question 4 i s about the chemi stry of i ron, l i nki ng bonding, transi ti on
mental properties, Br0nsted-Lowry pairs, tests for Fe
3
+
and redox
titrations.
To do well in this paper you must revise the enti re specification
(syllabus) and especially Topi c 1 . 2. Do not become put off by this l oad
as many of the Topi cs in A2 are extensi ons of those in AS. For example:
Topi c 4. 1 wi th 2. 1 - Energeti cs
Topi c 4. 2 wi th 1 . 4, 1 . 6 and 1 . 7 - The Peri odi c Table
Topi c 4. 3 and 4. 4 with 2. 4 and 2. 5 - Equi l ibri um
Topi c 4. 5, 5. 3 and 5. 5 wi th 2. 2 - Organi c chemi stry
Topi c 5 . 1 with 1 . 5 - Redox
Topi c 5. 4 with 2. 3 - Ki netics
This leaves Topics 1 . 1 (Atomic structure), 1 . 2 (Formulae, equations and moles)
and 1 . 3 (Structure and bonding) all of which are fundamental to chemistry and
much of these topics will have been revised by your teacher during the A2 year.
PRACT I CE TEST: U N I T U L ( SY NOPTI C)
l l5
PrucrIce Tesr: tuIrB {SyuoprIc)
Time allowed 1 hour 30 min
Al l questi ons are taken from previous Edexcel Advanced GCE questions.
Secti on A
1 A ferti l i ser is known to contain ammoni um sulphate, (NH4)
2
S04, as the onl y ammoni um salt. Thi s
question concerns methods for the determination of the ammoni um and sul phate i ons.
a A sample weighing 3. 80 g was dissolved in water and the vol ume made up to 250 cm
3
To 25. 0 cm
3
portions of thi s solution about 5 cm
3
(an excess) of aqueous methanal was added. The fol l owing
reaction took place:
4NH/(aq) + 6HCHO(aq) C6H
1
2N4(aq) + 4H+(aq) 6H20 l
The l i berated acid was titrated di rectly with 0. 1 00 mol dm
-
3
aqueou odium hydroxi de. The average
vol ume requi red was 28. 0 cm
3
Calculate the percentage of ammoni um sul phate in the ferti l i ser.
[5]
b I n a second determi nation of the ammonium ion content, the same mass of fertiliser ( i . e. 3. 80 g) was
treated with excess sodium hydroxide and heated. The ammonia l iberated was passed i nto a known
excess of hydrochl oric aci d. The unreacted hydrochl oric acid was then titrated with standard aqueous
sodi um hydroxide.
The calculation of the percentage composition of the ferti l i ser gave a value that was 5% lower than the
value obtai ned by the method i n a. Suggest reasons for this error other than those arising from the
measurement of vol umes. [2]
c To determi ne the sulphate i on concentration of the ferti l i ser, aqueous barium chloride was added in
excess to the ferti l i ser solution. The precipitate produced was fi l tered off and dried by strong heating.
i Give the ionic equation, with state symbols, for the precipitation reacti on.
[2]
ii Suggest why the aqueous barium chl oride was added in excess.
[1]
d Many carbonates are al so insoluble, and can be precipitated, dried and weighed in experiments si mi lar
to c. However the strong heating needed to drive off al l the water can cause a probl em in determi ni ng
the mass of the carbonate precipitated. Suggest what thi s problem is, and, choosing a suitable exampl e,
write an equation for a reaction that might occur when the preci pi tate i s heated.
[4]
(Total 14 marks)
[une 2002 Unit Test 6B question 1 ]
Secti on c
Answer TWO questions only
2 a The coval ent compound urea, (NH2)
2
C = 0, i s commonl y used as a ferti l i ser i n most of the European
Uni on, whereas i n the UK the most popul ar ferti l i ser i s ionic ammoni um ni trate, NH4N0
3
Apart from
its nitrogen content suggest two advantages of using urea as a ferti l iser compared with usi ng
ammoni um nitrate. [2]
b The ammoni um ion in water has an acid di ssociation constant Ka 5. 62 ? 1 0-
1
0
mol dm-:. The
conj ugate acid of urea has Ka = 0. 66 mol dm-
3
. Use thi s data to explain which of ammoni a or urea is the
stronger base. [2]
c Some organi c ni trogen compounds are used to manufacture polyamides by condensation
polymerisation. With the aid of di agrams, define the terms condensation polymerisation and polyamide.
[4]
d Ethanamide, CH3CONH21 can be converted to methylamine, CH
3
NH
2

i State the reagents and conditions for carryi ng out thi s conversi on.
l
3
!
ii Suggest the formula of the l ikely product if urea were used instead of ethanamide in thi s
conversion.
e Ammoni um ni trate can explode when heated strongly.
NH4N0
3
(s) N20(g) + 2H
2
0(g) D = -23 k] mor
1
[1]
l0
ADVANCE D LABORATORY C H E M I STRY
With moderate heati ng the ammoni um nitrate volati l i ses reversibly
NH4N03
(s) NH
3
(g) + HN03
(g) t + I I kJ mor
1
i State why the expression for K
P
for the reversible change does not i nclude ammoni um nitrate.
[1]
ii Explain the concepts of thermodynamic and kinetic stabilit with reference to these two reacti ons.
[5]
(Total 18 marks)
[une 2001 CH6 question 4]
3 The pri ncipal source of the odour in sweat is the organic acid HA, C7H
1 2
0
2
It will decolourise bromi ne
water i mmedi ately, and i t shows geometric i someri sm.
a HA can be made by the fol l owing sequence of reactions:
CH
3
CH
2
CH
2
CH( CH
3
) CH
2
0H
2-methylpentan- 1-ol
.
CH
3
CH2CH2CH( CH
3
) CH( OH)CN
t
+ H0l
D
COHC. M:bL+
+ H0l
HA
i Give the reagents and conditions for the oxidation of 2-methylpentan- 1 -ol to . [3
]
ii State the conditions and write the mechani sm for the reaction of HCN with .to give C.
[4]
iii Give the equation for the hydrolysi s of C to D, and hence draw the structural formula of D.
[2]
iv Draw the structure of HA. [2]
b HA has a dissociation constant Ka * 4. S0? I 0
mol dm-
3
, and i s a monobasic (monoprotic) acid which
di ssociates according to the equati on:
HA(aq) + H20(l) H
3
0+(aq) + A-(aq)
i Write the expression for K
a
and calculate the pH of a solution of HA of concentration 0. 0I 00mol
dm.
ii The pH of ski n is almost constant. Explain how, in principle, thi s could be achieved by using HA
and one of its salts. (Given its smell, it is perhaps fortunate that ski n does not use this compound
as a pH regulator)
[4]
(Total 18 marks)
[anuar 2002 CH6 question 3]
4 Iron( I I I) chloride exists in two forms, the coval ent anhydrous chloride and the i oni c hydrated chloride.
a Explain why anhydrous i ron( I I I) chloride i s covalent whereas sodium chloride i s ionic.
[4]
b Hydrated i ron( I I I ) chloride is soluble in water and its solution is acidic.
i Write an i oni c equation to show why its solution is acidic and identify the acid-base conj ugate
pairs i n thi s reacti on. [3]
ii Describe what you would see when a solution of sodium hydroxide is added unti l in excess to a
solution of i ron( I I I ) chloride.
Write an i oni c equation for thi s reaction and identify the type of reacti on. (4]
iii A test for Fe
3
+ i ons is to add a solution of thiocyanate ions, SCN-(aq), which react to form a blood
red i on of formula [FeSCN( H
2
0)5]
2
+. What i s the bonding between the SCN- ion and the Fe
3+
ion,
and what i s the cause of the colour of the i on?
[3]
c I ron also forms the intensely red coloured anion, FeO.t. In acidic solution thi s is a powerful oxidi si ng
agent, and is itself reduced to Fe
3+
i ons.
Calculate the oxidation number of i ron i n Feot. Suggest, in outli ne, how you could determine the
concentration of a soluti on of Feo_t i ons. [4]
(Total 18 marks)
[anuary 2001 CH6 question 6]
U0 ' 1
Topi c 1 . 1 Atomi c s tructure
The rel ative isotopic mass is the mass of a si ngl e
i sotope of an el ement ( rel ative to l / 1 2th the mass
of a carbon 12 atom), whereas the rel ative atomic
mass is the average mass taki ng i nto account the
i sotopes of the el ement. The rel ative i sotopi c
masses of the two chl ori ne i sotopes are 35 and 3 7,
but the rel ati ve atomi c mass of chl ori ne is 35. 5
2 There are many more 7Li atoms t han
6
Li atoms i n
natural l i thi um, s o t he average i s cl oser t o 7 .
3 A, of magnesi um
= ( 24. 0 ? 78. 6 + 25 . 0 ? 1 0. 1 + 26. 0 ? 1 1 . 3 ) = 24. 3
1 00
4 Let the % of
6
9Ga be x,
and so the % of 7
1
Ga = ( 1 00 - x)
69. 8 [69. 0x + 7 1 . 0 1 00 - x)|
1 00
Therefore 6980 69x + 7 1 00 - 71 x
Therefore 2x = 1 20 and x = 60. 0
Gal l i um contai ns 60. 0% of the <Ga isotope.
5 Group 5 . There is a bi g j ump between the 5th and
6th i oni sati on energies. Therefore the 6th el ectron
i s being removed from a l ower shell ( nearer to the
nucl eus) than the first fi ve el ectrons.
b a
=
~
O
-
v
a
.9
<
v
~
2500
2000
1 500
1 000
500
1 2 3 4 5 6 7 8 9 1 0 1 1
Atomi c number
D A 2p el ectron, whi ch i s i n a hi gher energy
level , is bei ng removed. So l ess energy i s
requi red to remove i t compared to that
requi red to remove a 2s el ectron.
There are t wo el ectrons i n t he 2px orbi tal
whi ch repel one another, so l ess energy i s
requi red to remove one of t he pai r than i f
there had onl y been one el ectron i n that
orbital .
ANSWE RS
Although the element with Z 1 1 has 8 more
protons, it also has 8 more shielding electrons, but as
the 3s electron is further from the nucleus than a 2s
electron, so less energy is required to remove it.
The el ectron i n a box notati on for chl ori ne i s:
8 Al l have one el ectron i n thei r outer shel l s, but K i s
bi gger ( l arger atomi c radi us) than Na, whi ch i s
bi gger than Li . Therefore the outer el ectron i s hel d
on l ess fi rmly ( the extra nucl ear charge i s bal anced
by the same extra number of shi el di ng el ectrons)
and so i s the easi est to remove from potassi um and
the hardest to remove from Li . Thi s makes
potassi um the most reactive.
9 W Li (g) + e- Lr ( g)
Cl (g) + e- Ll (g)
0 (g) -e- 0- (g)
D
L
N0!O ! H8! ! HO SQOO| OS 0O !HO | O! H800 S| 0O |S 8 g8SO0J S
8l0m 8O0! HO0OO 0O! HO| | gH! | S8 088l| 8 | 0O.
. . 2
0 (g) + e 0 ( g)
For the 1 st el ectron affi ni ty, the ( negative)
el ectron i s brought cl oser to the posi tive
nucl eus i n a neutral atom, and so energy is
rel eased. For the 2nd electron affi ni ty, the
negative el ectron i s brought towards a
negative i on, and so repul si on has to be
overcome, whi ch requi res energy.
Topic 1 . 2 Formulae, equati ons
and moles
1 W
L
H
%
82. 76 1 2 = 6. 90
1 7. 24 1 1 7. 24
6. 90
1
2. 5
Therefore t he empi ri cal formul a i s C2H
5
D Mass of C2H5 is 29, but 58,
Therefore the mol ecul ar formul a i s CH
1 0
2 W 4NH3 + 502 4NO -6H20
D 2Fe
3
+(aq) + Sn
2
+(aq) 2Fe
2
+(aq) -Sn
+( aq)
l
ANSWE RS
I oni c equat i ons mu st al so bal ance i n charge. He re
both si des are 8+.
3 Equati on: H3PO
J
3NaOH Na3PO 3 H20
Amount of H
3
P04 = 2. 34/98 = 0. 02388 mol
Amount of NaOH = 0. 02388 ? 3/1 = 0. 07 1 63 mol
Mass of NaOH = 0. 07 1 63 ? 40 = 2. 87 g
4 Equati on: 2KOH H
2
S04 = K
2SO 2H20
Amount of H2SO = 0. 01 25 dm3 ? 0. 0747 mol dm-.
= 9. 338 ? 1 0-
4
mol
Amount of KOH = 9. 338 ? 1 0-4 ? 2/ 1
= 1 . 868 ? 1 0
-
3
mol
Vol ume of KOH sol uti on = mol /cone
= 1. 868 ? 10-3 mol
0. 1 07 mol dm-
3
= 0. 0 1 75 dm
3
= 1 7. 5 cm
3
5 Amount of Bi (N03) 3 = 0. 025 dm
3
? 0. 55 mol dm-
3
= 0. 0 1 38 mol
Amount of H
2S = 0. 01 38 ? 3/2
= 0. 0206 mol
Vol ume of H
2
S gas = mol ? mol ar vol ume
= 0. 0206 ? 24 = 0. 50 dm
3
6 Ratio mol of H2
(g) : mol of CH ( g) = 3 : 1
Vol ume o f H
2
(g) : vol ume o f CH4( g) = 3 : 1
Vol ume o f H2(g) = 3 ? 3 3 = 9 9 dm:
1
Topi c 1 . 3 Structure and bondi ng
1
n-bond
a-bond
2 W A1 Cl3 because either there is l ess di fference i n
electronegativity between AI and Cl than
between Al and F
3
or AP
+
is very pol ari si ng and the bi gger Cl- i on
i s more pol ari sabl e than the smal l er F
-
i on.
D BeC1
2 because either there i s l ess di fference i n
el ectronegativity between Be and Cl than
between Mg and Cl
or Be
2
+ i s smal l er than Mg
2
+ and so i s more
pol ari si ng.
a Hydrogen b Di spersi on c Di pol e
bond /dipol e
HF Yes Yes Yes
1 2
No Yes No
HBr No Yes Yes
PH
3
No Yes Yes
Ar No Yes No
4 i odi ne
i ce
e si mple mol ecul ar
d H bonded mol ecul ar
copper
Si 02
sol i d C02
CaO
poly( ethene)
graphite
sul phur
CuS04
sucrose
LiF
a metal l i c
b gi ant atomi c
e si mpl e mol ecul ar
c i oni c
f pol ymeri c
b gi ant atomi c
e si mpl e mol ecul ar
c i oni c
d H-bonded mol ecul ar
c i oni c
5 Mel ti ng: on heati ng, the molecul es or i ons vi brate
more unti l the i ntermol ecul ar forces ( i n mol ecul ar)
or i on/i on forces ( i n i oni c) substances are overcome
and the l attice breaks down.
Do not say that t he mol ecul es or i ons start to vi brate.
Boi l i ng: on heati ng the average ki neti c energy of
the molecul es i ncreases. Those wi th a l arge enough
ki neti c energy and hence speed escape, not only
from the surface but al so from the body of the
l i qui d, formi ng bubbl es.
b W NH
3
There are stronger intermol ecul ar forces
in NH3 as i t forms H bonds and PH
3
does not.
D HBr. It has more el ectrons i n i ts mol ecul e, and

so i t has stronger di spersi on forces ( whi ch
outwei gh the di fference i n di pol e/di pol e
forces) .
L Propanone. Both have about t he same strength
of dispersion forces because they have about
the same number of el ectrons, but propanone i s
pol ar and so has di pol e/di pol e forces as wel l .
U S8 I t has about twice as many el ectrons as P 4,
and so has stronger di spersi on forces.
V NaCl . I t has i on/i on forces that are very much
stronger than the weak i ntermol ecul ar
di spersi on forces between CCI ,. mol ecul es.
Number of Number Total Shape
L bond of l one number of
pai rs pai rs electron
pai rs
Si H
4
4 0 4 Tetrahedral
BF3 3 0 3 Tri angul ar
pl anar
BeC1 2 2 0 2 Li near
PCl3 3 1 4 Pyrami dal
SF6 6 0 6 Octahedral
XeF4 4 2 6 Square
pl anar
NH.j+ 4 0 4 Tetrahedral
PCl6- 6 0 6 Octahedral
8 I n Na ( s) there are l oosely hel d del ocal i sed
electrons that can move t hrough the l attice. I n
NaCl ( s) the electrons are l ocal i sed on the i ons, not
l oosely hel d and the i ons are fi xed i n thei r
posi ti ons i n the l attice and so are not free to move.
Topic 1 . 4 The Periodic Table I
1 W They al l have the same number of el ectrons i n
thei r outer shel l . For Group 2 thi s number i s 2.
D Thi s peri od is Period 4, and so al l the members
have el ectrons i n four shel l s.
2 W H2 is si mpl e mol ecul ar
D Na i s metal l i c
L Si is gi ant atomi c
U S8 i s si mpl e mol ecul ar
C Cl
2
i s si mpl e molecul ar
I Ar is si mple molecul ar ( argon is monatomi c) .
The answe r ' hydr ogen bonded' or ' i oni c' cannot appl y to
el ements.
3 Sodi um and magnesi um are metal s. Magnesi um i s
2+ and has a smal l er i oni c radi us, therefore i t wi l l
have stronger metal l i c bonds and a hi gher mel ti ng
temperature. Si l icon forms a gi ant atomi c structure
with each si l i con atom j oi ned coval entl y to four
other si li con atoms. These strong coval ent bonds
have to be broken. Thi s requi res a huge amount
of energy and so the mel ti ng temperature i s very
hi gh.
Carbon , in t he form of di amond, has a si mi l ar struct ure,
but as t he smal l er car bon atom f or ms stronger bonds
t han si l i con, di amond's mel t i ng te mperat u re i s even
hi gher.
White phosphorus, sul phur and chl ori ne al l form
si mpl e mol ecul ar sol i ds. The mel ti ng temperatures
depend upon the strengths of their i ntermol ecul ar
forces whi ch are dispersion ( i nduced di pol e/i nduced
di pol e) forces. The strength of this force depends
upon the number of electrons i n the molecule.
The si mpl est way i n whi ch to work thi s out i s to add
toget her t he atomi c n u mbe rs of al l t he atoms i n the
mol ecul e.
P4 has 4 ? 1 5 = 60, S
R
has 8 ? 1 6 1 28 and Cl2 has
2 ? = 34 el ectrons per mol ecul e. Thus sul phur
has the strongest i ntermol ecul ar forces and the
highest mel ti ng temperature and chl ori ne has the
weakest i ntermol ecul ar forces and the l owest
melting temperature.
ANSWE RS
l J
4 W Nucl ear charge is equal to the number of
protons i n the nucl eus.
Screeni ng or shi el di ng occurs when an outer
el ectron i s i nsul ated from the pul l of the
posi ti ve nucl eus by el ectrons i n i nner shel l s.
D The 1 st i oni sati on energy of sodi um i s for
the removal of the 3s el ectron. Sodium has a
nucl ear charge of +1 1 , but the 3s el ectron i s
shi el ded by t he 1 0 el ectrons i n t he 1 st and
2nd shel l s. The second el ectron t hat i s
removed comes from t he 2nd shel l ( i t i s a 2p
el ectron) . Thi s el ectron i s shi elded from the
nucl eus onl y by el ectrons whi ch are i n a
l ower shel l , whi ch in thi s case is by the two
1s el ectron and so i t i s held much more
strongly by the nucl eus. I t i s also nearer to
the nucleu , 'vhi ch makes i t even harder to
remove.
Sodium ha a nuclear charge of +1 1 and its
3s el ectron i hielded by the inner 1 st and
2nd shel l el ectron . . 1 a nesi um ha a
nucl ear charge of +1 2 one more than
sodi um) , but i ts 3s electron i s shi el ded by
the same i nner el ectrons . Thus its 3s
el ectrons are pul l ed more strongly to the
nucl eus and are harder to remove.
L: cr
It is because of t hi s ext ra pu l l that a magnesi u m
atom i s smal l er t han a sod i u m atom.
Topi c 1 . 5 Introducti on to
oxi dation and reducti on
El ect r ons are on r i ght because Sn
2
i s oxi di sed : 2e
i s needed because oxi dati on n u mber changes by 2.
D Fe( aq) + e- Fe
2
'(aq)
L Sn
2
- ( aq) + 2Fe
1
(aq) Sn
+
+( aq) + 2Fe
2
"( aq)
2 W
Eq uat i on b has to be doubl ed, so t hat t he el ect r ons
cancel when 2 t i mes b i s added to a.
L: cr
H20
2
is reduced , so el ectrons are on t he l eft.
l4
ANSWE RS
2e- are needed o n t he l eft because S i s reduced and i ts
oxi dati on n u mber goes from 0 to -2.
Bot h H2S and H202 must be on t he l eft because they are
t he reactants; equat i on b is reve rsed and added to a;
note t hat t he W i ons cancel out.
3 W Pb02(s) -2H2S04 (aq) -2e- PbS04(s) + 2H20( 1 )
+ so,(aq)
2e- are needed on t he l eft as Pb0
2
i s red uced and i ts
oxi dati on n u mbe r changes from +4 to +2.
D PbS04(s) -2e- Pb( s) -SO,(aq)
2e- are needed on t he l eft because PbS04 i s red uced and
t he oxi dat i on n u mbe r of l ead changes from +2 to 0.
L Pb02(s) + Pb( s) + 2H2S04(aq) 2PbSOls) +
2H20( l )
Because Pb i s a reactant, equat i on i i has t o be reversed
and then added to i . Thi s i s the react i on t hat takes pl ace
when cu rrent i s d rawn from a l ead-aci d battery.
Topic 1 . 6 Group 1 and Group 2
1 Di p a hot pl ati num ( or ni chrome) wi re in cl ean
concentrated HCl and then i nto the sol i d. Pl ace i n a
hot bunsen fl ame. The substance that turns the
fl ame carmi ne red i s Li Cl , the one whi ch turns the
fl ame l i l ac i s KCl and the one that turns the fl ame
appl e green i s BaCl 2
2 The heat of the fl ame vapori ses the sodi um
chl ori de, produci ng some Na and Cl atoms.
Electrons are promoted i nto the 4th shell in some
of the sodi um atoms . These electrons then fal l back
to the ground state, whi ch i s the 3s orbi tal , and
energy i s given out i n the form of light. The fl ame
i s yel l ow because the energy di fference between the
4th shel l and the 3s orbi tal i s equi val ent to the
yel low l i ne i n the spectrum.
3 The sodi um atom i s smal l er than the potassi um
atom, because sodi um has three shel l s of el ectrons
and potassi um has four. Thus sodi um's outer s
electron is hel d on more firmly, and more energy i s
requi red to remove i t.

\ $ w
P

Thi s is t he case in spi te of t he fact t hat potassi u m has
ei ght more protons than sod i u m, because i t al so has
ei ght more el ectrons between t he n ucl eus and t he oute r
el ectron , so t he extra n ucl ear c harge is bal anced by t he
extra shi el di ng.
4 W 2Ca -02 2Ca0 ( or Ca 1 /202 CaO)
D Ca 2H20 Ca( OH)2 -H2
L 2K + 2H
2
0 2KOH H2
U Mg( s) + H20(g) MgO( s) + H2(g)
5 The whi te preci pi tate i s the i nsol ubl e magnesi um
hydroxi de. Bar i um hydroxide i s sol ubl e and so i s
not preci pi tated.
6 Beryl l i um, as BeC01 is the l east thermal ly stabl e of
the Group 2 carbonates. I t decomposes very easi l y
on heati ng because the Be
2
+ i on i s very pol ari si ng.
The other Group 2 i ons are l ess pol ari si ng because
they are l arger.
7 W 4Li N03 2Li20 + 4N02 -02
2NaNO] 2NaN02 + 02
2Mg(NOJ2 2Mg0 + 4N02 -02
D Na2C01 no reaction
MgCO_ MgO + C02
BaC0
3
no reaction
Topic 1 . Group
1 Coval ent HCl i oni ses when added to water, and the
hydrati on energy gi ven out by the i ons bondi ng
wi th the water mol ecul es i s greater than the energy
requi red to break the coval ent H-Cl bonds:
HCl (g) -H20( 1 ) H1
0
+
( aq) -Cl ( aq)
2 Fi rst a sol uti on has to be made. The sampl e can be
di ssol ved either i n water or i n di l ute ni tri c acid. ( I f
water i s chosen, di l ute ni tric aci d must then be
added to destroy t he carbonate) . To thi s sl ightl y
aci di c sol uti on, add si lver nitrate sol uti on. I f there
i s chl oride present, there wi l l be a whi te preci pi tate
that will di ssolve i n di lute aqueous ammoni a.
3 H2SO i s a stronger acid than HCl ( or HI ) , and so i t
wi l l protonate the Ll i ons i n the sodi um chl ori de
produci ng HCl gas . HCl i s not a strong enough
reducing agent to reduce sul phuric acid, and so
no further reaction will take place. With sodium
i odi de, HI is produced by the protonati on of the
i odi de i ons, but the HI i s a very strong reducing
agent, and so i t wil l reduce the sul phuric aci d and
itsel f become oxi di sed to i odi ne.
4 Di sproporti onati on i s a reacti on i n whi ch an
el ement i s si mul taneously oxi di sed and reduced.
Chl ori ne di sproporti onates when added to al kal i :
Cl 2 + 20H- - .+ Cl O- + H
2
0
(
0) (-1 ) (+1 )
Al so, chl orate( ! ) di sproporti onates when heated:
sc. c z.+ . c
(+1 ) (-1 ) ( +5)
Answers to Practi ce Tes t Uni t 1
The al l ocati on of marks fol lows Edexcel mark
schemes.
The marks that you wi l l need for each grade are
approxi matel y:
A
B
D
E
1 a i 2Ca + 02 2Ca0
ii Na20 + H20 2NaOH
70%
61 %
52%
44%
36%
iii Na20 + 2HC1 2NaCl + H20
[ 1]
[ 1]
Speci es [ 1] , bal anci ng [ 1] [2]
b The thermal stabi l i ty i ncreases down the group
[1] as the cation size i ncreases [1] and so the
carbonate ion is di storted ( or pol ari sed) l ess [ 1]
= [3]
b Do not attempt to answer thi s type of quest i on i n
terms of si ze match .
2 a i Graphite has a gi ant atomi c ( or gi ant
coval ent) structure [ 1] . The bondi ng between
atoms i s coval ent [ 1] .
Your di agram must show several i nterl i nked
hexagons [1] in layers [ 1] [ 4]
ii Sodi um chl ori de has a l atti ce structure [ 1] .
The bondi ng i s i oni c [ 1] .
Your di agram must show a 3-D arrangement
of i ons, Na+ al ternati ng with . [ 1] * [3]
ANSWE RS
l
ii
b Graphi te ha coYal ent bonds between atoms that
have to be broken [ 1] ; sodi um chl ori de has
el ectrostatic fore between the i ons [ 1] . I n both
these force ar trong and so a l ot of energy i s
needed to break them [ 1 ] = [3]
c i Graphi te ha del o ali ed el ectrons above and
bel ow the pl an of h xagons [1], whi ch can
fl ow ( whi ch ar mobi l e I [ 1] [2]
ii The l atti ce i brok n do\\n i n the l i qui d and
to mo\e = [ 1]
a Struct ure means g i an a omi c. i oni c l att i ce,
si mpl e or hydr ogen bonded mol ecul ar or a
l atti ce o me al i ons in a sea of el ectrons.
0 A subs ance I cond uct el ectri city i f i t has
del oca sed el ectrons t hr oughout t he struct ure
or ons hi ch are f ree to move.
3 a i Atomi c number is the number of protons i n
t he nu l eu [ 1 ] Mas s number i s t he total ( or
urn of the ) number of protons and neutrons
[ 1 ] [2]
ii
b i
1 - Br [ 1]
Hi h energy el ectrons bombard t he Br2
mol ecul es [1] and knock out an el ectron [1]
4 a
[2]
ii They are accel erated by charged pl ates ( or
across an el ectric fi el d) = [1]
iii Br-
1
Br = [1]
a i i As t he part i cl e has 1 fewe r el ectrons t han
protons, i t wi l l be a posi ti ve i on.
a i i i I n a mass spectromet er most el ements
prod uce i ons contai ni ng one atom, but
d i atomi c el ements such as N2, 02 and t he
hal ogens g i ve mol ecul ar i ons such as Br2
whi ch may contai n two d i fferent i sotopes.
Divi de each % by thei r Ar values [1] and then di vi de
by the smal l est [1]
H 1 1 . 1 - 1 = 1 1 . 1 then - 7. 4 = 1 . 5
C 88. 9 -; 1 2 = 7. 4 then - 7. 4 = 1
Mul ti pl y both by 2 to get whol e numbers
:. E. F. i s C2H] [1] [3]
lb
ANSWE RS
5
b HI has more el ectrons [I] .. i nduced di pol e
or di spersi on or London or v. d. Waal s
are stronger [I] [2]
c i 3 bond pai rs and 1 l one pai r repel to get
as far apart as possi bl e [I] see di agram
below [I]
ii 4 bond pairs around repel to get as
far apart as possi bl e [I] see diagram
bel ow [I]
(i) (ii)
* [2]
[2]
d Mol es of gas vol ume mol ar vol ume
a
8. 0 cm
3
/ 2. 4 * 1 0
4
cm
3
mor
1
* 3. 33 ? 1 0 mol
[1]
Number of mol ecul es 6. 0 * 1 0
2
\
* number of
mol es * 2. 0 * 1 0
2
[1] * [2]
i
ii
l:
L w 1 I* a +I ',
b Do not say because t he mol ar mass of H I is l arger.
0 Remember that it is t he el ectron pai rs not t he
atoms nor t he bonds that r epel to gi ve maxi mu m
separati on.
The oxi dati on number of sul phur: i n H2SO i s
+6 [ I] , i n H2S i s +2 [ I] , i n S02 i s +4 [ I] * [3]
The ! ion i s the stronger reduci ng agent
because i t reduces sul phur from +6 to +2 [I],
whereas Br- only reduces i t to +4 [I] [2]
b i 2Cr Cl 2 + 2e- or cr
1
/2Cl 2 + e- [I]
ii
iii
ocr + ZH+ + ze- cr + H20
speci es [I], bal ance [I]
ocr + zH+ + cr c.2 + H2o
* [2]
[I]
.
l: cJ
W*
b i & i i For an oxi dat i on reacti on, t he el ectrons are
on t he r i ght, and f or red ucti on they are on t he l eft.
i i i You wou l d n ot be penal i sed for fai l i ng to cancel
one of t he Cl - i ons, i . e . havi ng t he eq uati on .
OCI - + 2W + 2CI- Cl 2 + H
2
0 + Cl -
6 a 2, 8, 6 * [1]
b i S(g) + e- b (g) [1]
ii S(g) S+( g) + e- [I]
and [I] for state symbol s i n both equati ons
* [3]
c big j ump in i oni sati on energy means that an
electron has been removed from a new shel l [I]
The fi rst bi g j ump i s after 6 el ectrons and so
there are si x el ectrons i n the outer shel l [I]
The second bi g j ump i s after 8 electrons and so
there are 8 i n the 2nd shel l [I] [3
]
d i [I] for the el ectrons around S and [I] for the
electrons around both Cl atoms. * [2]
e e
e
b
ii The 2 bond pairs and the 2 lone pairs [I]
repel each other to get as far apart as
possi bl e [I] [2]
iii Cl is more el ectronegative than S, so the
bonds are pol ar [I], but as the mol ecul e i s
bent, t he pol ari ti es do not cancel [I] * [2]
U0 '
Topic 2. 1 Energetics I
I Gases at a pressure of 1 atmosphere, a stated
temperature (298 K) and all sol uti ons of
concentrati on 1 . 00 mol dm-
3
Substances i n thei r
most stabl e state.
2 i 2C( s) + 2H2(g) + 02(g) CH
3
COOH( l )
3
ii CH
3
COOH( l ) + 20z(g) 2C02(g) + 2H20( l)
iii CH
3
COOH( aq) + NaOH( aq) CH3C00Na( aq)
+ H20( l)
or CH3COOH( aq) + OH-(aq) CH3COO-( aq)
+ H20( l )
:
M
' (
,' *
+ ~
Note t hat ethanoi c aci d is a weak aci d, and so i ts
formul a must be wri tten i n f u l l and not as H .
Enthalpy
+ 90. 3 kJ
]- 57. 1 k]
N02(g)
MI, +90. 3 kJ (
-
5 7 . 1 ) kJ * +33. 2 kJ mor
1
Note that t he + si gn is gi ven in t he answer in order
to e mphasi se t hat t he react i on i s endot her mi c.
4
r
2N02(g) N204(g)

, = ^
1
+ =
-
2 ? (+33. 9) + (+9. 7) =
-
58. 1 kJ mor
'
5
a a

@ , m
tH
1
" mi nus 2 t i mes t he ent hal py of for mat i on of
N0
2
( g) , because t he react i on represents t he
formati on of N0
2
( g) reversed and tH
2
ent hal py of
f or mat i on of Nz04( g) .
|
1 2C(s) + 1 2H2(g) + 02(g) CH3(CH2h0COOH(s)
r,
1 2C02(g) + 1 2H20(1)
where M
1
= 1 2 ? enthal py of combusti on of carbon
(graphi te) + 12 ? enthal py of combusti on of hydrogen
and
Mi2 = minus the enthalpy of combustion of lauric acid.
^ = 1 2 ? (-394) + 1 2 ? (-286) - (-7377) = -783 kJ mor
'
.
6 HCl + NaOH NaCl + H20
Amount of HCl = conc( mol dm-
3
) ? vol ( dm
3
)
= 1 . 00 ? 1 00
1 000
= 0. 1 00 mol
Ri se i n temperature = +6. 80 oC
Heat produced when 0. 1 00 mol reacts
= total mass ? specific heat capacity ? rise i n
temperature
= 200 g ? 4. 1 8 J g-l C-
1 ? 6. 80 C = 5685 }
= 5 . 685 kJ
Heat produced when 1 mol reacts
= 5. 685/0. 1 00 = 56. 9 kJ mor'
therefore tHncut = -56. 9 kJ mor
1
(exothermi c) .
tsc
w ~= " ~ = =
= <= ~ >
Because t he mi xtu re became h otte r, t he reacti on i s
exother mi c. The mass used i s t he mass of t he whol e
sol ut i on, 1 00 cm
3
+ 1 00 cm
3
200 cm
3
200 g , not t he
mass of t he HCI .
ANSWE RS
H H H H
` /
l1
C=C + H-O-H H-C-C-0-H
/ `
H H
H H
Break ( endo)
1 ? C=C = +61 2 kJ
1 ? H-0 = +463 kJ
Make (exo)
1 ? C-C = -348 kJ
1 ? C-H = -41 2 kJ
1 ? C-0 = -3 60 kJ
Total = +1 075 kJ Total = -1 1 20 kJ
= net result of bonds broken and bonds made
= +1 075 - 1 1 20 = -45 kJ mor
1

Topi c 2. 2 Organic chemis try I
b 1 a
Br F F

Br -C-C-C-H

Cl Cl H
Cl OH H H

H-C-C-C-C-H

H H H H
Thi s type of u nambi guous formu l a is al l owed u n l ess a
fu l l structu ral for mul a is asked f or.
D CH
3
CH2CH
J
CH2CH1, CH
3
C( CH
1
) 2CH3
and
CH3CH2CH ( CH3
) CH.
L CH
3
CH=CHCH3 ( both the ci s and trans
i somers) , ( CHl )2C=CH2 and CH3CH2CH=CH2
3 W A free radi cal is a speci es wi th a si ngl e unpaired
electron, e. g. Cl .
D Homolyti c fi ssi on is when a bond breaks wi th
one el ectron goi ng to each atom.
4 W An el ectrophi l e is a speci es whi ch seeks out
negative centres and accepts a l one pai r of
el ectrons to form a new coval ent bond.
D Heterolytic fi ssi on i s when a bond breaks wi th
the two electrons goi ng to one atom.
5 a C
2
H6 + Cl 2 C2H5Cl + HCl
then: C2H5Cl + Cl 2 C2H4Cl2 + HCl etc
condi ti ons : ul travi ol et l i ght
D C2H6 + 3
'
/ 202 2C02 + 3 H20
condi ti ons: fl ame or a spark
b W CH3CH=CH2 + H2 CH3CH2CH3
condi ti ons: heat and Pt catal yst
D CH
3
CH=CH2 + Br2 CH3CHBrCH2Br
condi ti ons : sol uti on in hexane
observati on: goes from brown to col ourl ess
L CH
3
CH=CH2 + HI CH3CHI CH3
condi ti ons : mix gases at room temperature
U CH
3
CH=CH2 + [ 0] + H20 CH
3
CH( OH) CH20H
condi ti on: aqueous
observati on: goes from purpl e to brown
preci pi tate
lb
ANSWE RS
7 W CH
3
CHI CH
3 + NaOH CH
3
CH( OH) CH3 + Nal
propan-2-ol
D CH3CHI CH
3
+ KOH CH
3CH=CH2 + KI + H20
propene
L CH3CHI CH
1
+ 2NH
3
CH
3CH( NH2) CH
1
+ NH4 I
2-ami nopropane
8 CH3CH( OH) CH
1
- H20 CH
3
CH=CH2
condi ti ons: concentrated aci d at 1 70 oc
9 W
H H
0
/
H-C-C-C
,
\
0-H
Propanoic acid
observati on: sol uti on goes from orange to green
D No reacti on
observation: sol uti on stays orange
L CH
3
CHC1 CH3
2-chl oropropane
observati on: steamy fumes
10 The carbon-carbon bond i n ethene i s weaker
than the L carbon-carbon bond in ethane. Thi s
makes the activation energy l ess, and so the
reacti on i s faster.
1 1 The C-Br bond is stronger than the C-I bond. Thi s
makes the acti vati on energy more, and so the
reacti on i s sl ower.
12 C
6
H10 + Br2 C
6
H10Br2
5. 67 g of C6H10 = 5. 67/82 = 0. 069 1 mol
Because the reaction i s a 1 : 1 reacti on, the amount
of product i s al so 0. 069 1 mol .
Therefore t he theoreti cal yi el d of C6H10Br2
= 0. 0691 ? 242 = 1 6. 7 g
The % yi el d = ? 1 00 = 92%.
1 6. 7 g
13 They are stabl e i n ai r owi ng to the strong C-CI
and C-F bonds.
They then di ffuse i nto the stratosphere where
they form radi cal s and destroy the ozone l ayer.
Topic 2. 3 Ki netics I
1 i The activati on energy is the mi ni mum energy
that the reacti ng mol ecul es must have when
they col l i de i n order for them to react . I t i s
measured i n kJ mor1
ii A catalyst i s a substance that speeds up a
chemi cal react i on wi thout bei ng used up. I t
works by providi ng an alternative route with a
smal l er activation energy.
Neve r say t hat a catal yst l owers t he acti vat i on energy.
Li ght i s not a catal yst, because i t i s not a su bstance
and i t i s used up. I t i s j ust a speci f i c form of energy.
W
2 Pressure. As the pressure is i ncreased, the number
of mol ecul es i n a gi ven vol ume i ncreases, and the
frequency of col l i si on i ncreases and hence the rate
of reacti on, whi ch i s dependent upon thi s
frequency of col l i si on, i ncreases too.
3
Temperature. If the temperature is i ncreased, the
average ki neti c energy of the mol ecul es i s also
i ncreased. Thi s means that a greater proporti on of
the col l i di ng mol ecul es wi l l have, between them,
energy greater than or equal to the activati on
energy. There wi l l be a l arger number of successful
col l i si ons and a faster rate of reacti on.
Catalyst. Thi s i ncreases t he rate of reacti on by
provi di ng an al ternative path with a lower
activati on energy, thus a greater proportion of the
col l i di ng mol ecul es have energy greater than or
equal to the l ower catal ysed activati on energy.
w
0
'
L
0
0
s
Energy
4 Bacteri al and enzyme reacti ons are al so sl owed
down by a decrease i n temperature for exactly the
same reason as ordi nary chemi cal reacti ons, whi ch
i s that fewer col l i di ng mol ecul es wi l l have the
necessary acti vati on energy to react on col l i si on. So
the l ow temperature i n the refrigerator wi l l sl ow
down the bi ol ogi cal decay reacti ons.
5 i ii
iii
iv
l
K is the reactant and P is the product.
Topic 2. 4 Chemical equi li bria I
1 i true
ii fal se
iii true
2 i Posi ti on moves R--L, because that is the
exothermi c di recti on.
ii Pressure i ncreases, therefore posi ti on moves
R--L as fewer gas mol es on l eft
iii None, catal yst speeds up the forward and
reverse reacti ons equal ly, reduci ng the ti me
taken to reach equi l i bri um.
3 i Al kal i removes ethanoi c acid, therefore posi ti on
moves R--L.
ii No change because i s zero
4 Solid di ssolves because high [ Cl l drives equi l i bri um
L--R.
b Too hi gh a temperature produces too l ow a yi el d.
Too low a temperature produces too sl ow a rate
Catalyst al lows reaction to proceed at a fast rate at
a temperature where the yi el d i s hi gh.
Topic 2. 5 Indus trial i norganic
chemis try
I Reacti on i s sl ow at moderate temperatures.
Therefore a catalyst is used whi ch al lows a fast rate
and reasonabl e yi el d at 400 C, that i s, an economi c
rate and yi el d. A very hi gh pressure (200 atm) i s
used, even though thi s i s very expensive because
the yi el d at ordinary pressures i s very l ow. A very
high pressure drives the equi l i bri um L--+R to the
si de wi th fewer gas moles. After NH
3
is separated,
the unreacted gases are recycl ed.
2 The ammoni a l i quefies under the hi gh pressure and
i s removed from the unreacted nitrogen and
hydrogen, whi ch are then put back through the
reacti on chamber.
3 Anode: 2Cr( aq) -- + Cl2(g) + 2e-
Cathode: 2H20( 1 ) + 2e- -- 20H-(aq) + H2(g)
or 2H+(aq) + 2e- -- H2(g)
Answers to Practi ce Tes t Uni t 2
The al l ocati on of marks fol l ows Edexcel mark
schemes.
The marks that you wi l l need each grade are
approxi mately:
A 70%
B 61 %
c 52%
44%
L 36%
ANSWE RS
l5
I a I t is a series of compounds wi th the same general
formul a [1] whi ch di ffer by CH2 [I], and have
the same functi onal group [I] * [3]
b -( CH( CH3) CH2) "- : correct carbon chai n [1] wi th
extensi on bonds at both ends [1] [2]
c i See Fi g 2. 4 on page 38. [I] for each
i somer [2]
ii Rotati on around the J bond i s restri cted [I]
b Do not have t he 3 carbon atoms i n a strai ght
chai n.
0 Do not draw t he struct u re wi t h a bond angl es of
goo around t he C=C g roup.
2 a See Fi g 2. 9 on page 45: [ I] for havi ng t he axes
correct (y-axi s l abel l ed fracti on of mol ecul es,
x-axi s energy) , [I] for havi ng the curves wi th the
correct shape, and [I] for havi ng the T2 curve
flatter with the peak moved to the right * [3]
b Draw the acti vati on energy on the graph to the
ri ght of both peaks [I], expl anati on that the area
under the curve to the ri ght of the L_ l i ne
measures the number of mol ecul es wi th E Ea
[1], which i l arger at T2 than at T [ 11 so there
are a greater proportion of uccessful col l i si ons
[I] [4]
a The total a rea u nder t he two cu rves shoul d be t he
same.
b Ment i on must be made of col l i si ons.
3 a i The reagent i s HBr [I] and the condi ti ons are
i n the gas phase [ I] * [2]
ii h is CH3CHBrCH3 * [1]
b i P i s CH3CH( OH) CH3 * [1]
ii The type of reacti on i n step 1 i s electrophi l i c
[I] addi ti on [ I] [2]
in the conversi on of h to P the type i s
nucl eophi l i c [ I] substi tuti on [I] * [2]
c i For step 2, the reagent i s cone sul phuri c ( or
phosphori c) aci d or al umi ni um oxi de [1] and
the condi ti on i s heat [I] * [2]
ii For step 3, the reagents are potassi um
di chromate( VI ) [I] and sul phuri c aci d [I] and
the condi ti ons are heat under refl ux [I] [3]
d Q is CH3CH( OH) CH20H [I] [1]
l J
- ANSWE RS
lJ: c *
=~ ) -. , MP w
a I f t he f ul l stru ctu ral formu l a had been asked, you
must t hen show each atom separate l y, wi th al l
bonds shown .
b As t here are 2 marks f or each , you must make
2 poi nts.
0 i i Potassi u m manganate( VI I ) i s an al te rnati ve to
potass i u m d i c h romate( VI ) . Al ways g i ve ei t her t he
f ul l names or t he ful l formul ae, e. g. not
' aci di fi ed di chromate' nor ' Cr20t/W' . Al so ' refl ux'
by i tsel f does not i mpl y heat.
4 a Hess's l aw states that the enthal py change for a
reacti on [I] is i ndependent of the route [I] = [2]
b The defi ni ti on i s the enthal py (or heat but not
energy) change when 1 mole [ I] of a substance i s
compl etely burnt i n oxygen ( or burnt i n excess
oxygen) [I] under standard condi ti ons (at 1 atm
pressure) [I] = [3]
c i Bonds broken bonds made
1 * C-C = + 348 4 * C=O = -2972
5 * C-H = + 2060 6 * 0H = -27 78
1 ^ C-0 = + 360 Total = -5 750 kJ [I]
1 * 0-H = + 463
3 ^ 0=0 = + 1 488
Total = + 47 1 9 kJ [I]
tl = + 47 1 9 - 5 750 = -1 03 1 kJ mor
1
[I] = [3]
ii See Fig. 2. 1 on page 33.
Label l i ng of reactants and products [I],
wi th energy of reactants hi gher than
products and tl s hown [I] = [2]
0 i Remember that bond b reaki ng i s al ways
endot hemi c ( +) and bond maki ng exother mi c
(-) .
i i I f t h e react i on profi l e had been asked for,
t hen you must show an energy barri e r ( the
acti vat i on energy) i n you r enthal py l evel
di agram.
5 a i Your answer for the temperature shoul d be
between 350 and 500 ac (623 and 773K) = [I]
ii A high temperature favours a hi gh rate of
reacti on [I], but gi ves a low yield [I], so a
temperature is chosen whi ch gives a bal ance
between rate and yi el d [I] = [3]
iii The catal yst used i s i ron = [I]
iv A catalyst provides an al ternative pathway
[I], which has a l ower activation energy [I]
= [2]
b i Homogeneous means t hat al l the substances
are i n the same phase ( here al l are i n the
gaseous state) = [1]
ii Dynami c means that the reaction i s occurri ng
i n both di recti ons [1] and equi l i bri um means
that there i s no change i n concentrati ons
[I] = [2]
c i A lower temperature wi l l move the posi ti on
to the ri ght [I], because that i s the
exothermi c di recti on ( or thi s produces heat)
[1] = [2]
ii Decreasi ng the vol ume i ncreases the pressure
and so moves the equi l i bri um to the ri ght [I]
as the ri ght has fewer gas mol ecul es [1] = [2]
l !
w -
a i i I n i ndustri al processes, t he choi ce of
t emperatu re depends on rate ( h i gh
t emperat u re good) an d posi t i on of
equi l i bri u m ( hi gh t emperatu re bad for
exot her mi c react i ons) . A catal yst al l ows a
fast rate at a l ower temperatu re.
6 a 20
'
- 02 + 4e- ( or 0
2
- 1 /202 + 2e) * [I]
b Al
3
+ + 3e- Al = [I]
c The reaction at the anode. = [I]
d The oxygen produced at the anode reacts wi th
the carbon anode and eats i t away = [I]
e Al umi ni um oxi de ( pure bauxi te) has an
extremely high mel ti ng temperature [1], and so
the process woul d be too expensive [1] = [2]
l:cu !
l . =
a Remember that t he oxi de i on has a charge of 2-.
b I n both el ectrol ysi s and cel l s, oxi dat i on occurs at
the a node (o and a are both vowel s) .
Answers to Practice Tes t Uni t 3B
The marks t hat you wi l l need for each grade are
approxi mately:
A 70o
B 62o
c 54o
D 47o
E 40o
I Hydrogen: burns wi th a squeaky pop [1]
Oxygen: rel i ghts spl i nt [I]
Carbon di oxi de turns l i me-water [I] mi l ky [I]
Sul phur di oxi de: the sol uti on turns green [I]
The gas whi ch turns moi st l i tmus red then bl eaches
i t i s chl ori ne [I] = [6]
2 a i There is a l oss i n mass because C02 gas [I] i s
l ost from the fl ask [ I] = [2]
ii At first the slope of the graph i s steep, so the
reaction i s fast, then as the sl ope gets l ess i t
slows down [1] , when the l i ne i s hori zontal
( after 6 or 7 mi nutes) the reacti on has
stopped ( al l the aci d has been used up) [1]
= [2]
b For experi ment 2: your graph shoul d i ni ti al ly be
steeper than in 1 but i s hori zontal earl i er, but
wi th the same mass l oss ( 1 g) as i n 1 . [1]
For experi ment 3: your graph shoul d i ni ti al ly be
l ess steep. I t shoul d become hori zontal l ater, but
at the same mass l oss as i n 1 . [1]
For experi ment 4: your graph shoul d be steeper
than in 1 and become hori zontal at twice the
mass l oss ( 2 g) as i n 1 . [1] = [3]
c i Amount of HCl = 1 . 00 mol dm-
3
^ 50/ 1 000 dm
3
= 0. 0500 mol [1],
amount of CaC03 =
1
/2 ^ 0. 0500 mol
= 0. 0250 mol [1] : mass of CaC0
3
=
0. 0250 mol ^ 1 00 g mor
'
= 2. 50 g [1] = [3]
ii As t he amount of acid in experi ment 4
is twice that of the other experi ments
[1], the mass of CaC0
3
must be at l east
2 * 2. 50 = 5. 00 g [l] = [2]
a To answer thi s you have to work out i f the
reacti on i s fast er or sl ower t han i n 1 and whet her
t he mass of C02 l ost i s t he same, more or l ess
t han i n 1 .
0 i You have to hal ve t he mol es of HCI because
t here are hal f as many mol es of CaC03 as
mol es of HCI .
3 a Any two of:
use a pipette to measure out the CuS04 sol uti on
[1] as the vol ume i s measured more accurately;
[1] use smal l er pi eces of iron [1] as there will be
l ess heat l oss i n a faster reaction [1];
use a pol ystyrene ( or pl asti c) cup [1] as thi s
reduces heat l oss [ 1] ;
measure temperature for several mi nutes before
addition of i ron [1] as this al lows for a more
accurate determi nati on of the i ni ti al
temperature [1];
measure temperature more frequentl y [1] as thi s
makes the extrapol ati on more accurate [ 1] ;
use a thermometer whi ch reads to 0. 5 or 0. 1 L
[1] as thi s gives a more accurate temperature [ 1] ;
sti r the reacti on mixture gentl y [1] as thi s
ensures an even temperature i n the l i qui d [1] .
= [4]
b i Heat given out = 50. 0g ^ 4. 1 8Jg-
1
deg-
'
^ 1 5. 2 L
= 3 1 80 ] or 3 . 1 8 k] = [1]
ii Amount of CuS04 = 0. 500 mol dm-
3
^ 50/ 1 000
dm
3
= 0. 025 mol = [ 1]
iii -3. 1 8 kJ 0. 025 mol = -127 kJ mor
'
= [2]
( 1 mark for the negative s ign and 1 for the
number)
ANSWE RS
l Jl
,
g g ^
b The t emperatu re goes up, so heat is produced, and

t he reacti on i s exother mi c; .. !H i s negati ve.
4 a i Any one of:
use a l arger beaker [1] as this will prevent
aci d spray escaping [1];
powder the l i mestone [1] as this speeds up
the reacti on [1];
use more aci d [1] as thi s gi ves l arger and
hence more accurate ti tres [1] . = [2]
ii Choose ti tres 1 and 3 [1];
mean =
1
/2 ( 1 4. 90 + 1 4. 85) = 1 4. 875 cm
3
[1]
= [2]
b i Amount of NaOH i n ti tre = 0. 1 00 mol dm-
3
^
1 4. 875 / 1 000 dm
3
= 0. 001 4875 mol = [1]
ii Amount of HCl i n porti on = 0. 001 488mol
= [ 1]
iii Total amount of HCl remai ni ng =
1 0 ^ 0. 001 488 = 0. 01 488 mol = [ 1]
iv Ori gi nal amount of HCl = 2. 0 mol dm-
3
^
50/ 1 000 dm
3
= 0. 1 00 mol = [1]
v Amount of HCl used = 0. 1 00 - 0. 01 488
= 0. 085 1 2 mol = [1]
vi Amount of CaC0
3
=
1
/2 ^ 0. 085 1 2 = 0. 04256
mol [1] = 0. 04256 mol * 1 00 g mor
'
= 4. 256g
[1] = [2]
vii Purity = 1 00 ^ 4. 256 g/5 . 24 g = 8 1 . 2% = [1]
c i C whi ch i s between 1 4 . 75 and 1 4. 95 = [1]
ii One of:
not readi ng from bottom of meni scus, not
readi ng meni scus at eye l evel , burette not
verti cal , ai r bubbl e bel ow tap, funnel l eft i n
top of burette = [1]
a i If possi bl e ti trat i on exper i ments shoul d be
desi gned to g i ve ti tres of about 25 cm
3
.
i i You shoul d only ch oose ti trat i on val u es t hat
are l ess t han 0. 2 cm
3
apart .
b vi Don' t forget that t he rat i o of HCI to CaC0
3
i s
2 . 1 .
5 a Place the chemi cal s i n a round bottomed fl ask
[ 1] , fi tted wi th a refl ux condenser [1] . Heat for
several mi nutes [1] . Di sti l off the propan-2-ol
[1] . Col lect the fracti on that boi l s off around
82 L [1] = [5]
b Amount = 6. 1 5 g 1 23 g mor
'
= 0. 0500 mol [1]
vol of NaOH = 0. 0500 mol 2. 0 mol dm-
3
=
0. 025 dm
1
= 25 cm
3
[1] = [2]
c 1 00% yi el d would give 0. 0500 mol of propan-2-
ol = 0. 0500 mol ^ 60 g mor
'
= 3. 00 g [1] .
80% yield = 3. 00 ^ 80/ 1 00 = 2. 4 g [1] = [2]
d One of: the reaction did not go to compl eti on;
i t i s an equi l i bri um reacti on;
some propene was formed by el i minati on. = [1]
lJ
ANSWE RS
( a) The react i on i s sl ow, s o i t mu st b e heated.
1 - b romopropane i s vol at i l e, so a ref l ux condenser
must be used . Fi nal l y the product must be d i sti l l ed
off to separate i t f r om t he react i on mi xure.
U0 ' +
Topic 4. 1 Energetics II
1 W
ca+(g) + Cl (g)
+590
Ca(g) + Cl(g)
+1 21
Ca(g) + 1/2 Cl( g)
+193
Ca( s) + Y2Cl2(g)
t
Ca
2
+(g) + 2Cl (g)
+1 1 50
Ca+(g) + 2Cl (g)
+590
Ca(g) + 2Cl (g)
+1 21 x 2
Ca(g) + Cl2(g)
+1 93
Ca(s) + Cl2(g)
|
.
-364
ca+(g) + cr(g)
-650
CaCl (s)
-364 ? 2
-2237
CaC12(s)
Note t hat the ent hal py of atomi sat i on of chl or i ne i s
f or t he react i on 1/2CI 2 ( g) Cl ( g) .
D of CaCl 2(S)
* +1 93 +590 + 1 1 50 + 2 ? 1 2 1 + 2 ? (-364) +
(-2237)
-790 kJ mol
-
1
! of CaCl ( s)
* +1 93 +590 +1 2 1 + (-364) + (-650) -1 1 0 kJ
mor
1
of (2CaCl ( s) - CaC1 2(s) + Ca( s) )
* -790 -2 ? (-1 1 0) -5 70 kJ mor
1
Therefore products are more
thermodynami cal l y stable than reactants.
Thus CaCl wi l l di sproporti onate.
2 NaF: Experi mental l attice energy
theoretical l atti ce energy.
Therefore it is nearly 1 'Ai i oni c.
Mgl 2: Experi mental >> theoretical .
Therefore i t i s considerably coval ent, because the
doubl y charged Mg
2
+ i on i s much more pol ari si ng
than the si ngly charged Na+ i on.
Al so the much bi gger l i on i s more pol ari sabl e than
the smal l er F- i on.
Topic 4. 2 The Periodic Table II
1 W NaCI ( s) + aq Na+(aq) + Cr(aq)
SiCl4 + 2H20 - Si02 + 4HCI
PC15 + 4H20 - H
3
P04 + 5HCI .
Do not be t empted to g i ve t he total l y wrong equat i on:
NaCI + H20 - NaOH HCI .
D NaCl i s i oni c and so j ust di ssolves
Si Cl 4 and PCl5 are coval ent and so react to give
HCL
L A l one pai r of el ectrons on the oxygen atom of
H2 0 forms a dative bond i nto the empty 3d
orbi tal i n t he si l icon atom. Thi s releases
enough energy to break the Si-Cl bond.
I n CC14, the carbon atom has no 2d orbi tal and
so a dative bond cannot form before the C-Cl
bond breaks, and the four l arge chl ori ne atoms
around the smal l carbon atom sterical ly hi nder
the approach of a water mol ecul e.
2 As a base:
Al ( OH)3( s) + 3H+(aq) Al
3
+(aq) +3H20( 1 )
and as an aci d:
Al ( OH)3( s) + 30H-(aq)
[Al ( OH)
}
- ( aq)
For t he reacti ons of oxi des and hyd roxi des, i oni c
equat i ons are us ual l y easi er. Basi c oxi des/hyd roxi des
react wi th W i ons to gi ve si mpl e posi ti ve i ons, and aci di c
oxi des/hyd roxi des react wi t h OW i ons to gi ve negati ve
i ons.
3 W i Mg( OH)2( s) + 2H+(aq) Mg
2
+( aq) + 2H20( 1 )
ii PbO( s) + 2H+(aq) Pb
2
+(aq) + H20( l )
iii so2 + aci d: no reacti on.
b i Mg( OH) z + al kal i : no reaction
ii PbO( s) + 20H-( aq) + H20( 1 ) Pb( OH)t(aq)
iii S02(g) + 20H ( aq) SO
-( aq) + H20( l )
4 W Pb02 + 4HC. PbC1 2 + 2H
2
0 + Cl2
b Sn
2
+( aq) + 2Fe1+(aq) Sn
4
+( aq) + 2Fe
2
( aq)
Topic 4. 3 Chemical equi li bria II
1
2
Start ( mol es)
Change ( mol es)
2SO
0. 0200
-0. 0058
2S02 +
0
+0. 0058
02
0
+0. 0029
1 mol e of 80
3
g i ves 1 mol e of 802 and 1 /2 mol e of 02
Equlib. moles
[
]eq/mol C
0. 01 42
0. 0142/ 1 . 52
0. 0058 0. 0029
0. 0058/ 1 . 52 0. 0029/ 1 . 52
= 0. 00934 = 0. 00382 = 0. 001 91
Kc= [ SOzf ? [ OJ
[ SOt
= ( 0. 00382)
2
? 0. 001 9 1
( 0. 00934)
* 3 . 1 9 ? 1 0- mol dm-1
2NO( g)+ 02(g) 2Nz( g)
Start ( mol es) 1 . 0 1 . 0 0
Change ( mol es) -0. 60
Equi l ib. ( mol es) 0. 40
Equi l i b. mol e
fracti on
Parti al
0. 40/ 1 . 7
= 0. 235
pressure/atm 0. 235 ? 4
= 0. 94
Kl * ( p of N02)
2
(p of NO
/
? p of 02
= (1 . 41/
(0. 94? 1 . 65
= 1 . 4 atm
Total = 2 mol
-0. 30 +0. 60
0. 70 0. 60
Total = 1 . 7 mol
0. 70/ 1 . 7
= 0. 4 1 2
0. 60/ 1 . 7
= 0. 353
0. 41 2 ? 4 0. 353 ? 4
= 1 . 65 * 1 . 4 1
3 W
[SOJlnitiat
2
' '1..
? , 1..
( 0. 2? 0. 1
= 1 0 mor1 dm
1
whi ch i s not equal to Kc so it is not at equi l i bri um.
As the quoti ent <Ktl the reacti on moves l eft t o
right, unt i l equi l i bri um i s reached.
The [ ] term on l y equal s K when t he system i s i n
eq u i l i bri u m.
ANSWE RS
lJJ
b i Because reaction lK i s exothermi c, a
decrease in temperature causes Kc to
i ncrease, and so the posi ti on of equi l i bri um
moves to the ri ght.
ii As the reaction goi ng from right to left
causes an i ncrease in the number of mol es of
gas, a decrease in pressure wi l l cause the
posi ti on of equi l i bri um to shi ft from ri ght to
left. Kc i s unal tered.
iii There wi l l be no effect on ei ther. A catal yst
speeds up the rate of both forward and back
reacti ons equally, and so equi l i bri um is
reached sooner.
Topi c 4. 4 Acid-base equi l ibria
1 C2H
5
COOH H
+
+ C2H,COO
pK. = 4. 87
Therefore K " i nverse l og(-4. 8 7) = 1 . 35 ? 1 0 ' mol
dm
f H J = [ C_H
K = [H+] ? [
[ C2H
[H
I
= 1 . 35 1 0 mol dm
[ C,H, CO H]
[ Hl = (K, ? [ C2H5COOH] )
= |( 1 . 35 ? 1 0-
5
? 0. 22) = 1 . 72 ? 1 0 mol dm
pH = )-log[ H1 = 2. 76
2 a End poi nt is at 25 em NaOH.
pH
1 2
1 1
1 0
9
Hal f way
8
7
6
5
4
4 1 0 20
Volume NaOH/ cm
3
Hal f way to end poi nt is 1 2. 5 cm
1
,
whi ch is when [ HA] * [ A l .
p H a t thi s poi nt i s 4. 95.
Therefore pKa = 4. 95 .
b Phenol phthalei n.
25 30
3 W A buffer is a sol uti on of known pH, whi ch wi l l
Thi s i s a sui tabl e i ndi cator because i t s r ange of pH
for i t s ent i re col our change i s wi th i n t he verti cal part
of t he g raph.
lJ4
ANSWE RS
4
resi st change i n pH when contami nated wi th
smal l amounts of either aci d or base. I t consi sts
of any weak aci d and i ts conj ugate base, such as
ethanoi c aci d and sodi um ethanoate.
Do n ot say that t he pH i s constant. ' Nearl y constant'
i s acceptabl e.
D The sal t i s ful l y i onised:
CH
3
C00Na( aq) -- CH
3
COO-( aq) + Na+(aq)
The weak aci d i s parti al ly i oni sed:
CH3COOH( aq) " H+(aq) + CH3COO-(aq)
The CH
3
COO- i ons from the salt suppress most
of the i oni sati on of the aci d.
I f H+ i ons are added to t he sol uti on, al most al l
of t hem ar e removed by reacti on with t he large
reservoir of CH3COO- i ons from the sal t, thus
the pH hardly al ters.
H+(aq) + CH3COO-( aq) -- CH3COOH( aq)
I f OH
-
i ons are added, al most al l of them are
removed by reaction with the large reservoir
of CH
3
COOH mol ecules from the weak aci d,
thus the pH hardl y al ters.
OH-(aq) + CH
3
COOH
-
-- CH
3
COO-( aq) + H
2
0( 1 )
Fou r equat i ons are necessary f or a good answer,
wi th one of t hem as an equi l i br i um react i on.
[ H1 = Ka ? [weak aci d] / ( sal t]
[ weak aci d] = 0. 44 mol dm-
3
Amount of sal t = 4. 4/82 = 0. 053 7 mol .
Therefore [ sal t] = 0. 053 7/0. 1 = 0. 537 mol dm-
3
( H1 = 1 . 74 ? 1 0
-
5
_ ? 0. 44
0. 537
= 1 . 43 ? 1 0-
5
mol dm-
3
Therefore pH = -log ( 1 . 43 ? 1 0-
5
) = 4. 85.
The concent rat i on not t he n u mber of mol es shou l d be
u se d i n buffer cal cu l ati ons.
Topic 4. 5 Organi c chemis try II
1 a
(a) H Cl
` /
C =C
/ `
CH3 CH3
H CH3
` /
C =C
/ `
CH3
Cl
D
2
If t here is a doubl e bond, l ook f or geometri c i somer s.
Draw t hem wi t h t he cor rect bond angl es, not 90.
Look for fou r d i fferent g roups around a carbon atom
for opti cal i someri sm.
Mg I dry ether
CH3CHI CH3 CH3CH(Mgl)CH3
C02(s) then
HCl(aq)
CH3CH(Mgl)CH3 CH3CH( CH3)COOH
or KCN
CH3CHICH3 CH3CH(CH3)CN
heat under reflux
with HCl( aq)
An i ncrease i n t he n u mber of carbon atoms i n a chai n
i ndi cates t he use of a Gri gnard reage nt or a cyani de.
3 W Add water to each: ethanoyl chl oride gives off
steamy fumes of HCl ; ethanoi c aci d shows no
vi si bl e reaction.
Add PCl
5
to each: ethanoi c aci d gives off steamy
fumes of HCl ; ethanoyl chl ori de shows no
vi si bl e reacti on.
D Add to a sol uti on of i odi ne and sodi um
hydroxi de: propanone gi ves a pal e yel low
preci pitate; propanal gives no precipitate.
Add ammoni acal silver ni trate sol uti on and
warm: propanal gives a si lver mirror;
propanone gives no mi rror.
Answers to Practice Tes t Uni t 4
The al locati on of marks fol lows Edexcel mark
schemes.
approxi matel y:
A 70%
B 6 1 %
c 52%
D 44%
E 36%
1. a
MgZ+(g) 2cr (g)
' '
LE
Mg+(g) 2Cl ( g)
'
'
Mg( s) + Cl2(g) MgC12(S)
Correct cycle wi th all state symbols [2]
|,,,,
,
sum of all other changes
-642 +1 50 +736 + 1 450 + 2 ^ 1 2 1
+ 2 ^ (-364) + L E [2]
LE * -2492 kJ mor
1
[1] [5]
b i The i oni c radi us of Sr
2
+ i s < that of Ba2 [1],
and so there i s a stronger force of attraction
between cati on and ani on i n Sr( OH) 2 than in
Ba( OH)2 [1] * [2]
ii Energy i s released when the 6-oxygen atom in
water [1] i s attracted to the posi tive cation [1]
[2]
iii
j[j * -Lattice energy + opy

,__ of cation +
_
pyqtz;; of the ani ons [1]
Ba( OH) 2 * +2228 - 1 360 - 920 -52k]

[1]
^
j
,,
Sr( OH) 2 * +2354 - 1 480 - 920 -46kJ
[1]
so m,,,of Ba( OH) 2 i s 6 kJ more exothermi c
and so i t i s more sol ubl e [ 1] [4]
l: c
w
a Remember that l atti ce ene rgi es are negati ve .
b i i i If you f orgot to mu l t i pl y -460 by 2 ,t here
are 2 OW i ons,you woul d l ose 1 mar k.
Anot her way to score t he 3rd and 4th
marks i s: from Sr Ba, t he l atti ce energy
decreases by 1 26 kJ [1 ] , b ut c,,,,of the
cat i on on l y decreases by 1 20 kJ [1]
2 a i CH3CH2CH2C=N [1]
ii LiAlH4 or NaBH4 * [1]
iii CH3CH2CH2CH2NH2 [1]
b i The l one pai r of electrons on the N atom
make i t a base * [1]
ii RNH2 + H+ RNH3+ * [1]
c i
H
H
H H
\
N -C-C-H
H
--
_ H H
H
0
ii I t forms a substituted ami de [1]
3 a
ANSWE RS
lJ
iii One of: the reacti on is faster, or no catalyst i s
requi red, or wi th ethanol the reacti on i s an
iv
equi l ibri um * [1]
H H

H
0 -C -C
-
H
H-
_ H H
H
0
a As a f ul l structu ral f ormu l a was not asked, you need
n ot show al l t he atoms.
b Any ami ne wou l d do.
0 Ful l structu ral formu l ae wer e asked, so al l atoms
and bonds must be shown.
b Reagents: C2H
5
CH0[1] and CH3 MgBr [1] or
CH3CHO [1] and C2H
5
MgBr [1]
Condi ti ons; dry ether sol vent [1] [3]
c i Y i s CH3CH2COCH3 [1]
ii Y i s a ketone * [1]
iii Add 2, 4-di ni trophenyl hydrazi ne [1] whi ch
gi ves an orange ppt. [1]
Add Fehl i ng's sol uti on ( or ammoni acal si l ver
ni trate) [1] whi ch stays bl ue ( does not gi ve a
silver mi rror) [1] [4]
iv CHI3 [1] and C2H5COONa [ 1] [2]
a You must make an attempt at a 3-D drawi ng and
t he two i somers must be mi rror i mages of each
other.
b i i i You mu st show that it is a carbonyl
compound and t hen t hat i t i s not an
al dehyde.
b i v C2H5COOH woul d be accepted as t he other
organi c product .
4 a
K
_ p( Al CI / [1]
'
-
p( Al C1 3)
b Amount of Al Cl 0. 63g/62. 5 g mor
1
* 0. 01 mol
Amount of Al C1 3 * 0. 67 g/ 1 33. 5 g mor
1
*
0. 005mol [1] total mol es 0. 0 1 5
mol e fracti ons: Al Cl 0. 667, A1 Cl3 0. 333 [1]
parti al pressures: p( Al Cl ) " 0. 667 ^ 2 * 1 . 33 atm
p( Al Cl3) 2 ^ 0. 333 0. 667 atm [1]
K" ( 1 . 33 atm)
3
/0. 667 atm 3. 56 atm
2
[1] [4]
lJb
ANSWE RS
c An i ncrease i n temperature shifts the equi l ibri um
i n the endothermi c di recti on. .. ^ i s
positi ve = [ 1]
d K" stays constant [1] The posi ti on of equi l i bri um
moves to the side wi th fewer gas mol ecul es [1],
whi ch i s to the l eft [1] = [3]
e Mix scrap al umi ni um metal wi th A1 Cl3 and heat
to form AlCI [1], remove from excess AI, then
cool ( or i ncrease pressure) and pure Al and A1 Cl
3
are formed. The latter is then used agai n [1] = [2]
a Sol i ds do n ot appear i n h_ expressi ons.
b Parti al press u re i s mol e f racti on ^ total press u re.
0 h i s onl y al tered by t emperaure .
5 a i MgO( s) H2S0o( aq) MgSO(aq) H20( 1 )
Correct equati on [1] state symbol s [1] = [2]
ii A whi te sol i d [1] reacts to form a col ourl ess
sol uti on [1] = [2]
b i P
010 1 2NaOH 4Na

3
PO 6H20
or P20, 6Na0H 2Na.
1
P04 3 H20
Al l species correct [1], bal anced [1] = [2]
ii For havi ng 2 equati ons, one wi th H+ ( or HCI )
and the other wi th OH- ( or NaOH) [1] and:
Al ( OH) 1 + 3H+ AC+ 3 H
2
0 or
Al ( OH)
1
3 HCI Al C13 + 3H2
0 [1] pl us
Al ( OH) 1 30H- Al ( OH)63- or
Al ( OH)3 3NaOH Na3Al ( OH) 6 [1] = [3]
c MgO is basic, Al ( OH):
1
i s amphoteri c and P40
1
0 is
aci di c [1] showi ng the metal l i c character of the
el ement decreasi ng across the peri od [1] = [2]
d As a Group i s descended the oxi des get more
basi c [1] . I ndi um i s i n the same Group as
amphoteri c al umi ni um, so i ndi um oxi de wi l l be
basic [1] = [2]
Many st udents are very bad at wri t i ng eq uat i ons.
You must make sure that you l earn t he eq uat i ons i n
Topi c 4. 2 of t he speci f i cati on.
a Whenever you are asked t o state what you woul d
see, you must descr i be t he appearance before and
after reacti on .
6 a An aci d i s a proton donor [1],
Weak means that i t i s i ncompl etely di ssoci ated
( i oni sed) [1], but di lute means that its
concentrati on i s small [1]
b i pH = -log
1
0 [ H1
ii K. = 3. 72 ^ 1 0-1 = [ H1 [ OCl l
[ HOCI )
( H1 = 1 0-pH = 5. 89 ^ 1 0-s mol dm-1
[H1 = [ OCl l [1]
:. [ HOCl ] = ( 5. 89 ^ 1 0-
5
)
2
3 . 72 ^ 1 0-
= 0. 0932 mol dm [1]
= [3]
= [1]
[1]
[1]
= [4]
c
1 4
1 2
1 0
pH
8
6
4
2
0--------------
25 50
Vol . NaOH/cm
3
Shape of curve correct [1], start at pH = 4 [1],
vertical at 25 cm
3
[1] and at a pH of between 7 and
1 1 [1], curve flatteni ng off at pH 13 [1] = [5]
d i H
2
SO H+ HS04- [1]
HSO- H+ 504
2
- [1] = [2]
ii The second i oni sati on i s i ncomplete and i s
suppressed by the H+ from the first i oni sati on,
and so produces very few H+ i ons = [1]
l8:6m !
* R
a Don' t confuse weak how i on i sed,wi th dilute
how many mol es, .
b To get f rom pH to [ W] , use t he 1 ox button on
your cal cul at or.
d Su l ph u ri c aci d is onl y strong i n its 1 st
i oni sat i on, so t hi s sol ut i on has a pH of 0. 98 n ot
0. 699.
U0 ' J
Topic 5. 1 Redox equi l ibria
1 W Cr20,- ( aq) + 1 4H+( aq) 6e- 2Cr
1
+(aq)
7H,O
Sn"aq) + 2e- Sn
2
+( aq)
1 0 ( aq) 6H+( aq) Se- 1 /2 1 2 + 3H20
V 12 2e- Z ( aq)
@ l1Gm
m ~
Al l are reduct i ons and so have el ect r ons on t he l eft .
The n u mbe r of el ectrons equal s t he total change i n
oxi dat i on n u mber.
b i Cr20,
2
-(aq) + 1 4H.(aq) + 3Sn
2
(aq) -. 2Cr
1
(aq) +
7H20 + 3Sn
4
(aq)
-|..
= + 1
.
33 - 0. 1 5 = + 1 . 1 8 V.
Feasibl e as
,,.,+.-
> 0
.
Eq uat i on a i i is mu l t i pl i ed by 3, reversed and
added to eq uati on a i .
ii I O ( aq) + 6H.( aq) + Sr( aq) 3 I2 + 3H20
c....-
= + 1 . 1 9 - 0. 54 = +0. 65 V.
Feasi bl e as
c.c+o
> 0
.
Equat i on a iv is mu l t i pl i ed by 5/2, reversed and
added to eq uati on a i i i .
2 Equati ons are:
Fe( s) + 2H.( aq) - Fe
2
(aq) + H2(g)
5Fe
2
( aq) + Mn04 ( aq) + 8H.( aq) - S Fe
.
(aq) +
Mn
2
(aq) + 4H20
Amount of Mn04- = 0
.
0235 ? 0. 0200
= 4. 70 ? 1 0-1 mol
A f F `

2
3 ~
mount o e 1n 5 em sampl e = 4. 70 ? 1 0 ? 5 / 1
= 0. 00235 mol
5/1 because t he re are 5Fe
2
to 1 Mn 04- i n t he equati on .
Amount of Fe
2
i n 250 cm
3
sampl e = 0. 0235 mol
Mass of Fe
2
= mass of Fe = 0. 0235 ? 56 = 1 . 3 1 6 g
Puri ty of i ron i n steel = 1 . 3 1 6 ? 1 00 = 99. 7%
1 . 32
3 Anode area: Fe( s) - Fe
2
(aq) + 2e-
Qxi dat i on at the Anode, so el ectrons on the ri g ht.
Reduct i on at t he Gat hode, so el ectrons on t he l eft.
Between anode and cathode:
2Fe( OH)z( s) + 20H-(aq) Fe20l( s) + 3H20( 1 ) + 2e-
1 /202( aq) + H20( 1 ) + 2e 20H-(aq)
ANSWE RS
Topic 5. 2 Transi ti on metal
chemistry
lJ1
1 The water l igands spl i t the d orbi tal s i nto two of
hi gher energy and three of l ower energy. When
whi te l ight shi nes on the sol uti on, an el ectron
absorbs vi si bl e light energy and moves ( j umps)
from the l ower to the higher energy level,
absorbing some of the red/green light and l eavi ng
bl ue l i ght.
2 W [ Cr( H20) J
1
(aq) + 30H-( aq) Cr( OHL( s) + 6H20
Thi s reacti on is deprotonat i on.
t hen Cr( OH) ( s) + 30H ( aq) Cr( OH) .l ( aq)
Thi s occurs because Cr ( l l l l 1 s ampho 8|| C.
D [ Fe( H20).
(( aq) + 20H ( aqJ - Fe
then no further reacti on.
c [ Zn( H20)i.( aq) + 20H ( aq) Zn( H)2 ) 4H
then Zn( OH)z(s) + 20H
-
( aq) - Zn( OH) _2 aq)
3 W [ Fe( H20Ul( aq) + 3NH
1
( aq) Fe( OHL( s) +
3NH; ( aq) + 3 H20
Thi s reacti on i s deprotonat i on.
then no further reacti on.
b [ Cu( H20)6t( aq) + 2NHl ( aq) Cu( OH)2( s) +
2NH; ( aq) + 4H20
Thi s reacti on i s al so deprotonat i on .
then Cu( OH)2( s) + 4NH1 ( aq) + 2H20( 1 )
[ Cu( NH
1
) 4 ( H20) 2t(aq) + 20H-(aq)
The overal l react i on i s l i gand exchange.
Vanad i u m(V) i s reduced , so el ectrons are on t he l eft. The
oxi dati on n u mber changes by 3 , so t here must be t hree
el ectrons.
l Jb
ANSWE RS
D \c,( aq) + 2H+( aq) + e- - V0
2
+( aq) + H20
L V
3
+( aq) + H20 -- V0
2
+(aq) + 2H+( aq) + e
U V0
2
+( aq) + H20 - \c,( aq) + 2H+(aq) + e-
Topi c 5. 3 Organic chemis try III
1 W The bromi ne reacts wi th the i ron catalyst to
form FeBr
3
:
2Fe + 3Br2 - 2FeBr3
The FeBr1 then reacts wi th more bromi ne to
form Br+ ( the el ectrophi l e) and FeBr:.
The i ntermedi ate cati on l oses H+ to the FeBr4-.
HEr ] -
_Br
Br i: -Br
Br
+ uBr + FeBr _
Check t hat :
t he arrow starts on t he del ocal i sed r i ng and goes
towards the B r+ ( and n ot to the of Br+)
the i nt ermedi ate has a b roken del ocal i sed r i ng
wi t h a i nsi de i t
t he arrow starts from t he O bond of t he r i ng/H
at om and goes i nsi de t he hexagon ( but n ot
d i rectl y to t he ) .
D I t i s energeti cal l y favourabl e for t he i ntermedi ate
cati on to lose an H
+
and gai n the stabi l i ty of the
benzene ri ng, rather than add Br as happens wi th
al kenes.
2 The fi rst step i s the addi ti on of a C i on. HCN i s
too weak an aci d to produce a si gni fi cant amount
of C i ons. NaOH wi l l deprotonate HCN
mol ecul es, produci ng the necessary CN- i ons.
3 W If the temperature is too low ( <5 C) , the rate i s
too sl ow.
If the temperature is too hi gh ( >5 C) , the
benzene di azoni um chl ori de wi l l decompose.
D C6H
5
N=NC6H40- but C6H
5
N=NC6H40H i s
acceptabl e.
Topic 5. 4 Chemical ki netics II
1 Rate = k[ HI ]
2
k = rate
u.]
= 2. 0 ? 1 0-
1
mol dm-
3
s-1
( 0. 050 mol dm-
= 0. 080 s-
1
mol
-1
dm3
2 Carry out the fol l owi ng procedure:
Place equal vol umes of solution, e. g. b cm
3
of 0. 1 0
mol dm ethanoic acid and methanol i n flasks i n a
thermostatical ly controlled tank at 60 L.
Mi x, start the clock and repl ace in the tank.
At i nterval s of ti me, pi pette out 1 0 cm
3
porti ons
and add to 25 cm
3
i ced water i n a coni cal flask.
Rapi dl y ti trate wi th standard sodi um hydroxi de
sol uti on usi ng phenol phthal ei n as the i ndi cator.
Repeat several ti mes.
Plot a graph of the ti tre ( whi ch i s proporti onal to
the amount of ethanoi c aci d l eft) agai nst ti me.
3 Ti me taken for the concentrati on to halve from 1 . 6
to 0. 8 mol dm-3 = 26 mi nutes.
Ti me taken to halve agai n to 0. 4 mol dm-
3
= 26
mi nutes.
Ti me taken to halve agai n to 0. 2 mol dm-
3
= 26
mi nutes.
t
1
12 i s a constant, t herefore reacti on i s 1 st order.
Topic 5. 5 Organic chemis try IV
1 W Add 2, 4-di ni trophenyl hydrazi ne. Both give an
orange preci pi tate.
Add ammoni acal si lver nitrate sol ution. Onl y
pentanal wi l l give a si lver mi rror on warmi ng.
_
"

X rCYY.u: L! . .. "
+ 7 W ~"
Feh l i ng's sol uti on, whi ch gi ves a red preci pi tate ,
cou l d be used i n pl ace of ammon i acal si l ver ni trate.
D Heat under refl ux wi th aqueous sodi um
hydroxi de.
.
t
J
.
Lrcm
. ~
a
Hal ogenoal kanes are coval ent and so must fi rst be
hyd rol ysed to produce hal i de i ons.
Cool and aci di fy wi t h di l ute ni tri c aci d, t hen
add si l ver ni trate sol uti on.
The 2-bromo compound gi ves a cream
preci pi tate i nsol ubl e in dilute ammoni a but
sol ubl e i n concentrated ammoni a.
The 2-chl oro compound gives a whi te
preci pitate whi ch di ssolves i n di l ute ammoni a.
L Warm wi th di l ute sul phuri c acid and potassi um
di chromate( VI ) soluti on and di sti l l off any
product i nto ammoni acal si lver ni trate
sol uti on.
Methyl propan-2-ol does not change the col our
of the potassi um di chromate( VI ) .
Methyl propan- 1 -ol turns it from orange to
green and the di sti l l ate gives a si l ver mirror.
Butan-2-ol turns it from orange to green and
the di sti l l ate has no effect on the silver ni trate
sol ution. To confi rm, add a few drops of the
butan-2-ol to i odi ne and aqueous sodi um
hydroxi de and warm gentl y. A yel l ow
preci pi tate of i odoform wi l l be produced.
The 1
al cohol is part i al l y oxi di sed to an al dehyde.

The 2 al cohol i s oxi di sed to a ketone.
The 3 al cohol i s not oxi d i sed .
Butan- 2- ol contai ns t he CH
3
CH( OH) g roup and so
gi ves a posi ti ve i odoform test.
2 The substance i s probably aromati c (:: 6 carbon
atoms and about the same number of hydrogen
atoms) .
1 20 is the mol ecul ar i on.
1 05 i s 15 l ess than 1 20 and i s probably caused by
l oss of CH
3

7 7 is probably caused by the ( C6H5f group ( 7 7 i s 43
l ess than 1 20 and i s probably caused by l oss of
COCH1) .
X is probably C0H5COCH3
The 1 20 peak is caused by (C
6
H
5
COCHJ+,
the 1 05 peak by (C6HsCOf,
and the 7 7 peak by (C6Hsf
3 3200 cm-1 i s due to 0-H, 1 720 cm-1 i s due to C=O,
and 1 1 50 cm
-
1 i s due to C-0.
4 Si x of the carbon atoms are i n a benzene ri ng. The
remai nder are either C2H
5
group or 2 ? CH
3
groups.
Y i s C6H
5
CH2CH .
[ 5 H's i n C6H,, 2 H's i n CH2 and 3 H's i n CH
1
. ]
Z i s C6Hi CH3)z.
[ 6 H's i n 2 ? CH1 groups, 4 H's i n C6H4. ]
Answers to Practice Tes t Uni t 5
The al l ocati on of marks fol lows Edexcel mark
schemes.
ANSWE RS
lJ5
approxi matel y:
A 68%
B 59%
L b'
41 '
E 32%
1 a Con i der experi ments 1 c 2: when [ RCH2Cl] i s
i ncrea ed 3 ti mes, rate al so i ncreases 3 ti mes
[ 1] , .. 1 t order wi th respect to [ RCH2Cl ] . [1]
Con 1 der experi ments 1 c 3: when
con entrati ons of both are doubl ed, the rate i s
i ncr a ed + ti mes [1], :. 1 st order wi th respect
to I H ] a wel l [1] = [4]
Rat = b R H2Cl ] ^ [ OH-] = [1]
b " ldl I I R H2Cl] * [ OH-] )
+. 1 0 mol dm-l b
-
mol dm * 0. 1 0 mol dm- l
[ I ] mol dm [1] = [2]
V l rd r i n both. it i a S 2 mechani sm
[ 1 ] .
K
H =
H
K
H
H
H
urh arrm from 0 of OH to C and from C-CI O
bond to l [ 1 ] . correct transi ti on state [1] = [3]
| You must make it cl ear what data you are
usi ng and how you arri ve at each order.
| Make s u re that al l you r cu rl y arows start
ei ther at a bond and go to an atom or at an
atom and go to a bond .
2 a The el ectrophi le i s CH3CO+ [1] . The equati on i s:
b
CH COCl + A1 Cl 1 CH3CO+ + A1 Cl 4- [1] = [2]

H
I I
C+ C
\ \
CH_ CH_
Curl y arrow from ring to C of CO+ [1], correct
i ntermedi ate [1], curl y arrow from C-H bond to
ring [1] = [3]
L React the phenylethanone, C6H
5
COCH3, wi th
HCN [1], with a trace of base (or i n a sol uti on
buffered anywhere between pH 5 to 9 or add a
mi xture of HCN and KCN) [1] . Thi s produces
l4
- ANSWE RS
Now add aqueous sul phuri c acid ( or any
named aci d) [I] and heat under refl ux [I]
[I]
= [5]
d Mix known amounts of ester and OH- [I]
remove sampl e [I]
at known ti me [I]
quench the reaction by addi ng i ce col d water [I]
ti trate unreacted OH- wi th aci d [I]
Calcul ate rate = change i n [ OHl ti me [I]
Repeat wi th doubl e [ ester] and the same [ OHl [I]
Repeat wi th doubl e [ OHl and the same[ ester] [I]
= [8]
b The c u rl y arrow must go towards t he C of t he CO not t he
C of t he CH3 g roup. The i nt er medi ate must have a b roken
ri ng goi ng across al l but t he C atom whi ch has for med
t he bond wi th t he CH3CO g roup.
d The p H woul d hardl y change, so a met hod i nvol vi ng
measuri ng t he p H change over t i me wou l d score a
maxi mu m of 6.
3 a The reagent f or step 1 i s magnesi um [ It and the
condi ti ons are dry ether [I] = [2]
b i Potassi um dichromate( VI ) [I] and sul phuri c
aci d [I] = [2]
ii Di sti l off as i t i s formed [I] = [I]
iii Ethanoi c aci d ( CH3COOH) or ethanoate i ons
( CH3COO) [1] = [I]
c E i s CH
3
CH2CH( OH) CH:1 [I] for any secondary
al cohol and [I] for the correct formul a = [2]
d i F is a carbonyl compound as it reacts wi th
2, 4-di ni trophenyl hydrazi ne [I], but i t must
be a ketone and not an al dehyde as it does
not react wi th ammoni acal si lver ni trate [1]
= [2]
ii In order to do the i odoform reaction must
have the CH3CO group [I] and the products
are CHI 3 [I] and CH3CH2COO- [I] = [3]
iii F i s CH3CH2COCH3 [2] = [2]
e The species are: ( CH3CH2COCH3f for m/e = 72 [1],
( COCH3f for 43 [I] and ( CH3CHz) for 29 [1]
b i i i The al dehyde D i s oxi di sed to an aci d by t he
si l ver/ammoni a compl ex i ons.
0 G ri g nard reage nts react wi th an al dehyde to gi ve a
secondary al cohol .
= [3]
d i i The onl y su bstances to do the i odoform react i on are
al cohol s wi th a CH3CH( OH) g roup, ketones wi th a
CH3CO g rou p and ethanal .
e Don't forget the charge on the speci es i n a mass spectru m.
4 a Di p a pl ati num el ectrode [I] i nto a sol uti on
whi ch i s 1 mol dm-
3
i n both Fe
2
and Fe l+ i ons [ I] .
Thi s i s connected vi a a sal t bri dge ( contai ni ng
potassi um chl ori de sol uti on) [I] to a standard
hydrogen electrode [1] . The potenti al i s measured
with a high resi stance voltmeter (or a
potenti ometer) [I] = [5]
b i Au
3
+ 3e- - Au [I]
5 a
Fe
2
-+ Fe
3
+ e- [I] = [2]
ii Au
3
+ 3Fe
2
-
+ Au + 3Fe
3
+ = [ I]
iii Au
3
+ 3e- - Au L ( gol d)
3Fe
2
- 3Fe
3
+ + 3e- L = -0. 7 7 V
addi ng the two hal f-equati ons gives L cel l
L (gold) + (-0. 7 7) =
` ( cel l ) = + 0v 73 [I]
L( gol d) = + 0. 73 + 0. 77 = + l . SOV [1] = [2]
b Reduct i on ( gai n of el ectrons) takes pl ace at t he
gol d el ectrode because i t acts as t he cat hode.
Thus Au3 i ons gai n el ectrons t hat fl owed i n t he
external ci rc u i t from Fe2 i ons whi ch l ost t hem.
i i i Mu l t i pl yi ng t he Fe2+ hal f-equat i on by 3 does not
al te r its val ue.
Another way of doi ng t he cal cu l ati on i s to use
t he standard red uct i on potenti al s t hus:
of oxi di si ng agent ( gol d) - of red uci ng
agent ( i ron) * of t he cel l .
3d 4s
Fe : [ Ar]
1iiii 1
Cr : [Ar]
iiii
Cr
. [Ar]
iii
b FeCr04 + 4C - Fe + Cr + 4CO
species [I], bal anci ng of equati on [I]
c i [ Fe( H20)i
ii [ Fe( H
2
0) 6]
2
+ + 20H-
-
+ Fe( OH) 2 + 6H20
= [2]
= [1]
or [ Fe( H20)6]
2
+ + 20H- - [ Fe( OH)2( H20L] + 2H20
correct i ron speci es in product [I] bal ance
[1] = [2]
iii The preci
E
i tate's col our i s pale green = [1]
iv [ Cr( OH)6] - = [I]
v The sol uti on of woul d fi rst gi ve a green
preci pi tate [I], which forms a green sol uti on
with excess acid [I] = [2]
d i The standard el ectrode potenti al i s the
potenti al di fference between a standard
hydrogen el ectrode and the hal f-cel l [I] where
al l concentrati ons are 1 mol dm-1 and the
pressure of al l gases i s 1 atm. [I] = [2]
ii Al l four hal ogens wi l l oxi di se Cr
2
= [I]
iii Both bromi ne and i odi ne wi l l not oxi di se Cr
3

further = [I]
iv Mi x the bl ue Cr
2
+ sol uti on separately with
bromine and iodine [1], the solution goes
green and stays green wi th excess halogen
[1] = [ 2]
_ ` l1c
M m .
a Remember t hat 3d5, 4s

1
is more stabl e t han 3d4 ,
4s
2
( and si mi l arl y f or Cu whi ch i s 3d
1
0 , 4s
1
) . Al so
t he 4s el ectrons are l ost fi rst when cat i ons are
f or med .
0 i Al l transi t i on metal i ons are hydrated i n
sol uti on, wi th 6 water mol ecul es coor di natel y
bonded on.
i v Chromi u m i s amphoteri c. [ Cr ( OH) X woul d be
an acceptabl e answer.
v Add i t i on of aci d wi l l fi rst preci pi tate t he
hyd roxi de whi ch, as i t i s basi c, wi l l t hen react
wi th excess aci d to form a sol ut i on of t he
hyd rated metal i ons.
Answers to Practice Tes t Uni t 6B
The al l ocati on of marks fol l ow Edexcel mark schemes.
approxi mately:
A 66%
B 5 7%
L 48%
40%
E 32%
1 a Amount of NaOH = 0. 1 00 mol dm-
1
^ 0. 0280 dm1
= 0. 00280 mol [1] = mol es of H+
Rati o H+ to NH/ = 1 : 1 .
Amount o f NH4 i n 2 5 em = 0. 00280 mol .
Amount i n 250 cm3 = 0. 0280 mol [ 1]
Amount of ( NH4) 2S04 =
1
/2 ^ 0. 0280 = 0. 01 40 mol
[1],
mass of ( NH4)2SO . . = 0. 01 40 mol ^ 1 32 g mar' =
1 . 848 g [1],
% ( NH4)2S04 i n ferti l i ser = 1 . 848 ^ 1 00/3. 80 =
48. 6% [1] = [5]
b Any two of: not all ammoni a driven off [1];
ammoni a i ncompl etel y absorbed by the HCl [1];
some ammoni a gas escapes [I] * [2]
c i Ba2+(aq) + b\_ (aq) BaSOJs)
Speci es [1], state symbol s [1] = [2]
ii To ensure that all the sul phate i ons were
preci pitated = [I]
d Many carbonates wi l l decompose on heating [I],
and the C02 gas evolved wi l l resul t i n a lower
mass bei ng recorded [ I] . An exampl e i s CaCO [1]
CaCO. CaO + C02 [I] = [4]
ANSWE RS
l4l
a Don't forget to mu l t i pl y by 1 0 to get t he total
amount of t he NH4+ i ons, and then hal ve i t as t here
is 1/
2
a mol e of ammoni um su l phate per 1 mol of
NH4+ i ons.
Forgett i ng to d i vi de by 2 g i ves t he answe r 97. 3%
( obtai ned by about
3
/4 of t he cand i dates) whi ch
scores 4 mar ks.
0 i I n a preci pi tati on reacti on t here are j ust two i ons
on t he l eft and t he f ul l formul a of t he sol i d on
the r i ght of t he equat i on.
d Don' t g i ve a g rou p 1 carbonat e, nor BaC0
3
, as i t
doesn t d ecompose on heat i ng i n t he l ab, nor
BeCO because t t decomposes bel ow room
temperatu re.
Answer any two of the section questions
2 a Any two of : it i s consi derably cheaper [I];
l ess ri sk of l eachi ng [1]
i t does not effect the pH of the soi l [I]
it rel eases the ni trogen sl owly [I] = [2]
b The smal l er the K. of the conj ugate aci d, the
stronger the base [1] . Therefore ammoni a i s the
stronger base [I] = [2]
c Pol ymeri sati on occurs when many mol ecul es j oi n
to form a l ong chai n [I]; condensati on i s wi th
the el i mi nati on of water or a smal l i norgani c
mol ecul e such as HCl [I].
A polyami de contai ns the -CONH- l i nk [1] as i n:
0 0 H H
,
CH2
,,
-
CH2
,,
-
,
[ 1 ]
d i The reagents are : l i quid bromi ne [1] and
concentrated sodi um hydroxide [I] . The
condi ti on i s that i t must be heated [I] = [3]
ii NH2NH2 = [I]
e i Sol i ds are not i ncl uded in Kr expressi ons and
ammoni um ni trate i s a sol i d. = [I]
ii As the react i on i s endothermi c, the energy
level of the products is hi gher than that of the
reactants [1], therefore the reacti on i s sai d to
a The d i sadvantages of usi ng u rea are that some u rea
evaporates especi al l y i f t here i s no rai n wi th i n 4 days of
appl i cat i on. I t cannot be bl ended wi th phosphate nor
potassi u m f ert i l i sers, and i t i s l ess su i tabl e on chal ky
soi l s. It can cause damage to seed l i ngs. It does not work
i f t he soi l i s too col d.
0 Th e stronger t h e base, t h e weaker i ts conj ugate aci d.
d Ther modynami c stabi l i ty i s t o do wi th ^Hand ki neti c
stabi l i ty i s to do wi th t he rate of t he reacti on.
l4
ANSWE RS
be thermodynami cal l y stabl e [1] and the
equi l i bri um l i es to the l eft [1] .
As the reaction proceeds on moderate heati ng,
the activati on energy i s fai rl y smal l [1] and so
the reacti on i s ki neti cal l y unstabl e [1]
3 a i The reagents are potassi um di chromate( VI ) [1]
and sul phuri c aci d [1] . The condi ti ons are
careful heati ng and di sti l off the al dehyde as i t
i s formed [1] . = [3]
ii The condi ti ons for the addi ti on of HCN to a
carbonyl compound are KCN in aqueous
ethanol at a pH of 8 ( or a mixture of KCN and
HCN) [1]
The mechani sm i s :
u
u
/
r -CCN r -C -CN
+ N
+
v
r -C -CN
Ou
[ 1] for a curl y arrow goi ng from the C i n C
[ 1] for a curly arrow goi ng from the C=O bond
to the oxygen atom
[1] for the i ntermedi ate with i ts - charge " [4]
iii CH
3
CH2CH2CH( CH
3
) CH(OH) CN + HCl + 2H20
iv
CH3CH2CH2CH( CH
3
) CH( OH) COOH
+ NH4Cl [1],
correct formul a of organi c product [1] = [2]
C+ +
\ /
CC O
/ \ /
Cu, C
\
O-u
MP
= [1]
b i !, [H01 * [Al or [ H1 i nstead of [ H
3
01 [1]
[ HA]
[ H
3
0
1
= [ Al = ,!,c) = ( 4. 5 ^ 1 0-
3
^ 0. 01 00)
" 6. 7 1 * 1 0-
t
mol dm-
3
[1]
pH = -log ( 6. 7 1 * 1 0-
1
) " 3. 1 7 [1] " [3]
ii The acid is parti al l y i oni sed: HA H+ + A
The sal t is total l y i oni sed: NaA Na + A- [I]
Thi s suppresses the i oni sati on of the aci d and
so both [ HA] and [ A l are l arge compared to
any H+ or OH- that may be added. [I]
When H+ i s added, i t i s removed by the
reacti on:
H+ + A- HA [I]
I f OH- i s added, i t i s removed by:
OH- + HA A- + H20 [I] " [4]
a i Care has to be taken i f you wi sh to stop the oxi dati on
of a pri mary al cohol at t he al dehyde.
i i As al ways make s u re that you r cu rl y arows start on
an at om and go to form a bond or start on a bond
and go to an atom.
i i i t h e reacti on i s si mpl y R-CN RCOOH.
i v t h e c on e s u l ph u ri c dehyd rates t h e al cohol t o a C=C.
You were tol d i n t he stem that HA decol ouri sed
b romi ne water and so i t i s unsatu rated .
b i i Thi s i s t h e standard answer t o t h e mode o f act i on of
a buffer and must be l earnt.
4 a The Fe i on i s 3+ whereas the Na i on i s onl y 1+ [1]
The Fe
3
+ i on i s much more pol ari si ng than the Na+
ion [I], and so i t draws the el ectrons [1] from the
l arge Ll i on towards i tsel f and the bond becomes
coval ent. [1] = [4]
b i [ Fe(H20)
6
] 1+ + H20 H
3
0+ + [ Fe( H20),0H]
2
+ [1]
aci d [ Fe( H20) i+: conj ugate base [ Fe( H20),0H]
2
+
[1]
base H20: conj ugate aci d H3 0+ [1] [3]
ii a red precipitate wi l l form [ 1]
whi ch stays wi th excess NaOH [I]
[Fe( H20) 6f+ 30H- Fe( OH) 3 + 6H20 [1] or
[ Fe( H20)i+ + 30H- [ Fe( H20)3( 0H) ,] + 3 H20
The reaction is deprotonati on. [ 1] = [4]
iii The bondi ng is dative coval ent (coordi nate) [!]
The l igands spl i t the d-orbi tal s i nto two l evel s
[1]
The l ight i s absorbed and a d el ectron
promoted from the l ower to the higher level .
[I] = [3]
c Each oxygen is ~Z, .. 4 oxygens = -8. The ion is
2-, and so the Fe is +6 (6+ and 8- make 2-) [1]
There are two ways. The first i s: add excess
aci di fi ed potassi um i odi de sol uti on to an al i quot
of the Fe04
2
- sol uti on [1], then ti trate the
l i berated i odi ne agai nst standard sodi um
thi osul phate sol uti on [1], addi ng starch when the
sol uti on becomes pal e yel low and stoppi ng when
i t i s col ourl esss [1]
The second method i s: add excess aci d to an
al i quot [1], then ti trate agai nst standard FeSOo
sol uti on [1] unti l the sol uti on becomes very pal e
pi nk [1] = [4]
l
= - . ` = +O =m ~ v=.J=_@
a A compari son wi th NaCI must be made.
b Make sure that you i denti fy both aci d-base pai rs and
l abel t hem cl earl y.
i i I ron i s not amphoteri c and so the ppt stays i n excess.
i i i Afte r t he el ect r ons have been exci ted they g radual l y
fal l back to t he l owe r l evel gi vi ng out heat , and are
t hen ready to absor b phot ons.
0 Feo,- is ve ry l i ke Mn 04- in col ou r and in oxi di si ng power.
So you can use ei t her t he standard met hod of est i mat i ng
oxi di si ng agents ( i odi ne ti trati on) or t he manganat e(VI I )
method whi ch i s d i rect ti trat i on wi th i ron ( l l ) i ons.
011 e1l 01:
1 . AS onJA2 (yn0||c)
Alkanes, e. g. ethane CH3CH3
Ethane carbon di oxi de and ,ater
Reactant: oxygen ( ai r)
Equati on: 2CH_CH3 + / + 01 - 6H_
Condi ti ons: burn I spark
Cl assi fi cati on: combusti on
Ethane chl oroet hane
React ant : chl ori ne
Equati on: CH3CH1 Cl U1 H H |
Condi ti ons: sunl i ght
Cl assi ficati on: free radi cal ub t i t ut ion
Al kenes, e. g. ethene, H2C=H2
Ethene et hane
Reactant: hydrogen
Equati on: H2C=H_ + H2
Condi ti ons: heated ni ckel or Ql ti nUm L tal ) t
Cl assi ficati on: addi ti on or r U ti n r hydro enation
Ethene 1 , 2- di bromoethane
Reactant: bromi ne
Equati on: H2C=H Br H1Br H Br
APPE N D I X
Condi ti ons: bubbl e ethen i nto bromi ne di ssol ved i n hexane
Cl assi fi cati on: el ectrophi l i ddi tt on
Ethene bromoethane
Reactant: hydro en bromi d
Equati on: H2C= H - HBr H CH2Br
Condi ti ons: mi x ga e at ro m t emperature
Cl assi ficati on: el ectrophi l i ddi ti on
Ethene ethan- 1 , 2-di ol
Reactant: pota i um manoanate( I I ) sol uti on
Equati on: H2C=H1 ( ] H2 CH2 ( 0H) CH20H
Condi ti ons: a sol uti on made al kal i ne wi th sodi um hydroxi de
Ethene -> pol y(ethene)
Reactant: ethene
Equati on: l I H_ =Hz CH2-CH2+,
Condi ti ons: 2000 atm pre ure, 250 "L
Cl assi ficati on: addition pol ymeri sati on
Halogenoalkanes, e. g. 1 - bromopropane
1 - bromopropane propan- 1 -ol
Reactant: sodi um ( or pota si um) hydroxi de
Equati on: CH1CH. HtBr . 1a0H CH3CH2CH20H
Condi ti ons: heat und r refl ux i n aqueous sol uti on
Cl assi fi cati on: nucl eophi l ic ub t i tuti on
1 - bromopropane propene
Reactant: pota i um hydroxi de
Equati on: CH1CH. H2Br KOH CH3CH-CH2 + KBr H20
Condi ti ons: heat under refl ux i n ethanolic sol uti on
Cl assi ficati on: el i mi nati on
1 -bromopropane butaneni t ri l e
Reactant: potas i um cyani de
Equati on: CH3CH2CH2 Br + KCN CH3CH2CH2CN KBr
Condi ti ons: heat under refl ux i n a sol uti on of ethanol and water
Cl assi ficati on: nucl eophi l i c substi tuti on
1 -bromopropane 1 -ami nopropane
Reactant: ammoni a
Equati on: CH3CH2CH2Br 2NH3 CH3CH2CH2NH2 NH4Br
Condi ti ons: heat a sol uti on of ammoni a i n ethanol i n a seal ed tube
Cl assi ficati on: nucl eophi l i c substi tuti on
l41
l4b
APPE N D I X
1 - bromopropane Gri gnard reagent (A2 onl y)
React ant : Magnesi um
Equati on: CH1CH2CH2Br + Mg CH3CH2CH2MgBr
Condi ti ons: warm ( i n water bath) under refl ux i n dry ether
Alcohols, e. g. ethanol
ethanol ethanal
Reactant: potassi um di chromate( VI ) + di l ute sul phuri c aci d
Equati on: C2H5 0H + ( OJ CH3CHO + H20
Condi ti ons: heat careful l y and di sti l out the al dehyde as i t i s formed
Cl assi fi cati on: oxi dati on
ethanol ethanoi c aci d
Reactant: potassi um dichromate(VI ) + di l ute sul phuri c aci d
Equati on: C2H50H + 2 [ 0J CH3COOH + H20
Condi ti ons: heat under refl ux
NOTE: Secondary al cohol s are oxi di sed to ketones and terti ary al cohol s are not
oxi di sed.
CH3CH( OH) CH3 + [ OJ CH3COCH3 + H20
(CH3LCOH + [ OJ no reacti on; potassi um di chromate sol uti on stays orange
ethanol ethene
Reactant: concent rated sul phuri c (or phosphoric) aci d or al umi ni um
oxi de
Equati on:
Condi ti ons:
C2H5 0H - H20 H2C=CH2
heat
Cl assi fi cati on: dehydrati on
ethanol chl oroethane
React ant : phosphorus pentachl ori de
Equati on: C2H50H + PC15 C2H5Cl + P0Cl 1 + HCl
Condi ti ons: dry
ethanol bromoethane
Reactant: hydrogen bromi de
Equati on: C2H5 0H + HBr C2H5Br + H20
Condi ti ons: HBr made /n 5//u from oUY sul phuri c aci d and sol i d potassi um
bromi de
ethanol iodoethane
Reactant: hydrogen i odi de
Equati on: C2HOH + HI C2H,I + H20
Condi ti ons: HI made /n / /ufrom iodi ne and moi st red phosphorus
2. A2 0n/y
Grignard reagents, e. g. ethyl magnesium bromide
Ethyl magnesi um bromi de ethane
Reactant: water
Equati on: C2H,MgBr + H20 C2H6 + Mg compounds
Ethyl magnesi um bromi de a secondary al cohol
Reactant: an al dehyde such as ethanal
Equati on: C2H5MgBr + CH3CHO CH1CH( OH) C2H5
Condi ti ons: dry ether sol uti on, then hydrol yse wi th di l ute aci d
Cl assi ficati on: nucl eophi l i c addi ti on to t he al dehyde
Ethyl magnesi um bromi de a tertiary al cohol
Reactant: a ketone such as propanone
Equati on: C2H5MgBr + CH3COCH 1 (CHJ2C( OH) C2H5
Cl assi fi cati on: nucl eophi l i c addi ti on to the ketone
Ethyl magnesi um bromi de a carboxyl i c aci d
Reactant: (sol i d) carbon di oxi de
Equat i on: C2H,MgBr + C02 C2H5COOH
Carboxylic acids, e. g. ethanoic acid
ethanoi c aci d an ester
Reactant: ethanol
Equati on: CH1COOH + C2H50HCH3COOC2H5 + H20
Condi ti ons: heat under reflux wi th a few drops of concentrated sul phuric acid
Cl assi fi cati on: esteri fi cati on
APPE N D I X
l45
ethanoi c aci d an al cohol
React ant : l i t hi um al umi ni um hydri de ( l i t hi um tetrahydri doal umi nate( I I I ) )
Equati on: CH3COOH 4[ H] CH1CH20H H20
Condi ti ons: dry ether sol uti on then hydrol yse wi th di lute aci d
Cl assi fi cati on: reducti on
ethanoi c aci d an aci d chl ori de
React ant : phosphorus pentachl ori de ( or PC1 3 or SOC12)
Equati on: CH3COOH + PCl s CH OCl POC1 1 HCl
Condi ti ons: dry
ethanoi c aci d a sal t
Reactant: sodi um carbonate
Equati on: 2CH3COOH Q
s
2CH COONa( aq) C02(g) H20( l )
Cl assi ficati on: neutral i ation
ethanoic aci d a sal t
Reactant: rb n te
Equati on: H J CH COO a( aq) C02(g) H20( 1 )
Cl assi fi cati on:
Esters, e. g. ethyl ethanoate
ethyl ethanoate aci d - al coh
Reactant:
Equati on:
Condi ti ons:
Cl assi ficati on:
Carbonyl compounds al dehyd
Bot h react wi t h:
Reactant:
Equati on:
Condi ti ons:
Both react wi th:
Reactant:
ul phuric aci d
H
HO, and ketones, e. g. CH3COCH3
Equati on: H)C
Condi ti ons: pota i um _ ni ore di l ute sul phuri c aci d
Cl assi fi cati on: nucl >phi l i J00 ion
Both react wi t h:
Reactant:
Equati on:
l i t hi um JI um n um hydri de ( or sodi um borohydri de)
CH =( H) CH CH20H (a pri mary al cohol )
CH H =[ H) CH1CH(OH) CH3 (a secondary al cohol )
Condi ti ons: dry ether th n h) drol y e wi th di l ute aci d
Cl assi ficati on: reducti on
Al dehydes onl y react wi th:
Reactant: Fehl i n P ol uti on or ammoni acal si l ver ni trate
Equati on: CH H - ( ] - H CH,Coo- H20
Condi ti ons: warm
Carbonyl compounds \\ i th a H group give a yel l ow preci pi tate of i odoform
wi t h:
Reactant: iodi ne and odi um hydroxi de sol uti on
Equati on: CH LL H 31 2 + -oH- CH3Coo- CHI 3r- 3H2o
Acid chlorides, e. g. ethanoyl chloride
ethanoyl chl ori de ethanoi c aci d
Reactant: water
Equati on: CH3C0Cl + H.O CH3COOH HCl
Cl assi ficati on: hydrol y i s
ethanoyl chl ori de an ester
Reactant: an al cohol
Equati on: CH3COCI C2H50H CH1COOC2H5 HCl
Condi ti ons: rapi d reacti on at room temperature
Cl assi fi cat i on: esteri fi cati on
l0
APPE N D I X
ethanoyl chl ori de ethanami de
Reactant: ammoni a
Equati on: CH3C0Cl 2NH3 CH3CONH2 NH4Cl
ethanoyl chl ori de a substi tuted

ami de
Reactant: an ami ne
Equati on: CHl COCl C2H5NH2 CHlCONHC2H5 + HCl
Ami nes, e. g. C2H5NH2
ethyl ami ne a sal t
Reactant : any aci d such as hydrochl ori c
Equati on: C2H, NH2 HCl C2H5NH/Cr
ethyl ami ne a substi t uted amide
Reactant: an aci d chl ori de
Equati on: C2H,NH2 CH3C0Cl CH1CONHC2H5 + HCl
Nitril es, e. g. CH3CN
et haneni tri l e ethanoi c aci d
Reactant: di l ute sul phuric aci d ( or sodi um hydroxi de fol l owed by
aci di fi cati on)
Equati on: CH1CN H+ + 2H20 CH3COOH NH4+
Cl assi fi cati on: hydrol ysi s
ethaneni tri l e ethyl ami ne
Reactant: l i thi um al umi ni um hydri de
Equati on: CH1CN 4 [ H] CH3CH2NH2
Condi ti ons: dry ether then hydrol yse wi th di l ute acid
Cl assi fi cation: reducti on
Amides, e. g. CH3CONH2
ethanami de methyl ami ne
Reactant: bromi ne and sodi um hydroxi de
Equati on: CH3CONH2 + Br2 + 2NaOH CH3NH2 2NaBr + H20 C02
Condi ti ons: l i qui d bromi ne and cone sodi um hydroxi de
Cl assi ficati on: Hofmann degradati on reacti on.
ethanami de ethaneni tri l e
Reactant: phosphorus(V)oxi de
Equati on: CH3CONH2 - H20 CH3CN
Condi ti ons: warm
Cl assi fi cati on: dehydrati on
Benzene
benzene ni trobenzene
Reactant: concent rated ni tri c aci d
Equati on: C6H. + HN03 C6H5N02 H20
Condi ti ons: mi x wi th concentrated sul phuri c aci d at bU "L
Cl assi ficati on: el ectrophi l i c substi tuti on
benzene bromobenzene
Reactant: bromi ne
Equati on: C6H6 Br2 C6H5 Br HBr
Condi ti ons: l i qui d bromi ne wi th an i ron catal yst
Cl assi fi cati on: el ectrophi l i c substi tuti on
benzene ethyl benzene
Reactant: chl oroethane
Equati on: C6H6 C2H5Cl C6H5C2H5 HCl
Condi ti ons: anhydrous al umi ni um chl ori de catal yst
Cl assi fi cati on: el ect rophi l i c substi tuti on
benzene phenyl et hanone
Reactant: ethanoyl chl ori de
Equati on: C6H6 CH3COC1 C6H5COCH3 HCl
Condi ti ons: anhydrous al umi ni um chl ori de as catal yst
Cl assi ficati on: el ectrophi l i c substi tuti on
Alkylbenzenes, e. g ethylbenzene
ethyl benzene ethanoate i ons
Reactant: potassi um manganate( VI I ) + sodi um hydroxi de
Equati on: C6H5C2H5 + 6[0] + OH- C6H5COO- 3H20 C02
Cl assi fi cation: oxi dati on
Phenol
phenol sodi um phenate
React ant : sodi um hydroxi de
Equati on: C6H5 0H + NaOH C6HO a + H20
Cl assi ficati on: neutral i sati on
phenol 2, 4, 6-tri bromophenol
Reactant: bromi ne
Equat i on: C6H50H + 3Br: H H2Br1 + 3HBr
APPE N D I X
Condi ti ons: aqueou ; oran e bromi ne water forms a whi te preci pi tate
Cl assi ficat i on: el ectrophi l i c ub ti tuti on
phenol phenyl ethanoate
Reactant: ethano | chl ori de
Equati on: C6H50H + CH,CO 1 H OOC
I
> Hs + HCl
Cl assi ficati on: esteri fi cati on
Nitrobenzene
Ni trobenzene phenyl ami ne
Reactant: t i n and concentr ted hydrochl ori c aci d
Equati on: C6H ` + 6[ H) L H H + 2H20
Condi ti ons: heat under retl ux, th n add odi um hydroxi de
Cl assi fi cati on: reducti on
Pheuylamine
Phenyl ami ne di azoni um ion
Reactant: step 1 : ni t rou , lCQ . phenol
Equati on: C,H . ' H _H. H 2 2H\
CbH 4 H

-
C
6
H
s -
H
z
O
ll
Condi tions : mi x phcny|Jm n V lh um ni t ri te and hydrochl ori c aci d at
o "L, th n UU QhCnOI n di um hydroxi de ol uti on.

A Level Chemistry Guide (Book)

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Stuu /s

A common error is to mi ss out the

Sizes of atoms and ions

( aq) + 2cnaq) PbCI 2(S)

STR UCTU R E, B ONDI NG AN D MAI N GROUP CH E M I STRY

Group 2 nitrates all decompose to give a metal oxide, brown fumes of

combustion products of the elements

-Aof el ements - Aof compound

Cal cul ate

Homologous series: a series of compounds with the same functional

Che mi cal equi l i b ri a I

3 Consider the fol lowi ng reaction scheme:

The Peri odi c Table I I

PE R I OD I C I TY, QUANTI TATI VE EQU I L I B R I A AN D F U NCTI ONAL G ROUP CH E M I STRY

PE RI ODI CI TY, QUANTI TATI VE EQU I L I B R I A AN D FU NCT I ONAL G ROUP C H E M I STRY

The formati on of the si l ver mi rror

Thi ngs to learn

Testing your knowledge and understanding

D HBr. It has more el ectrons i n i ts mol ecul e, and

b The t emperatu re goes up, so heat is produced, and

j[j * -Lattice energy + opy

Ba( OH) 2 * +2228 - 1 360 - 920 -52k]

010 1 2NaOH 4Na

al cohol is part i al l y oxi di sed to an al dehyde.

a Remember t hat 3d5, 4s

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