A Level - Chemistry, George Facer

7Strurtu,r,o,bo@
al4d,
wgroryMtry
t
Atomic
structure
f&
Inffoduction
Much of chemistry depends upon Coulomb's Law which states that the
electrostatic force of attraction, F, is given by:
F*(q..Q)*r,
where q- and q- are the charges on the objects (e.g. the nucleus, an
electron, ions etc.) and r" 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.
<ta
W
Thingsto learn
iJ Atomic numbet (4 of an element is the number of protons in the

nucleusof its atom.
[l wtass number of an isotope is the number of protons plus the
number of neutrons in the nucleus.
E Isotopes are atoms of the sameelement which have the samenumber
of protons but different numbers of neutrons. They have the same
atomic number but different massnumbers.
E nehtive atomic mass (A) of an element is the average mass
(taking into account the abundanceof each isotope)of the atoms of
that element relative to llIzth the massof a carbon-LZatom.
f
Therelative
molecular
mass
isalso
called
therelative
formula
mass
especially
forionicsubstances.
nehtive isotopic mass is the massof one atom of an isotope relative

to lll2th the massof a carbon-L2atom.
f] Rehtive molecular mass (MJ of a substanceis the sum of all the

relative atomic massesof its constituent atoms.
E Molar mass is the massof one mole of the substance.Its units are
gramsper mole (g mol-'), and it is numerically equal to the relative
molecularmass.
lonisation
energies
arealways
endothermic
andrelate
tothe
formation
ofa positive
ion.
E fst lonisation energy is the amount of energyrequired per mole

to remove one electron from each gaseousatom to form a singly
positive ion
E(g)*E.(g)+e-
Zna ionisation energy is the energychangeper mole for the

removal of an electron from a singly positive gaseousion to form a
doubly positive ion
E.(g)-E'.(g)+e-
fl
=t*ucruRE,
BoNDtNG AND MAtN GRoup cHEMtsrRy
*i lst electron affinity is the energychangeper mole for the addition

of one electronto a gaseousatom to form a singly negativeion
E(g)+e---E(g)
J Znd, electron affinity is the energychangeper mole for the addition
of an electron to a singly negativegaseousion to form a doubly
negativeion
rG) + e--- E'-(g)
iJ s block elementsare thosein which the highestoccupiedenergylevel
is an s orbital. They are in Groups I and 2.
Similar definitions apply to p block (Groups3 to 7 and 0) and d
block (Scto Zn) elements.
^_______-
t::It/a
ixj
Thingsto understand
Mass spectra
and then bombardedby high-energy
t An elementis first vapourised
electrons that remove an electron from the element and form a positive
ion. This ion is then acceleratedthrough an electric potential, deflected
according to its mass and finally detected.
O Metals and the noble gasesform singly positively charged ions in the
ratio of the abundance of their isotopes.
t Non-metals also give molecular ions. For example Br, which has two
'nBr
will give three lines at m/e values of
and "Br 150o/o),
isotopes
15oo/o)
158, 160 and L62 in the ratio I:Z:L These are caused by ('nBr-'nBr;+,
ltnBr-ttBr;+ and (ttBr-ttB1;+'
A common
erroris to missoutthe
of a species
+ charge
ontheformula
fora linein a mass
responsible
spectrum.
I The relative atomic mass of an element can be calculated from mass

spectra data as follows:
A, = the sum of (mass of each isotope x percentage of that isotope)/l0O
Work"ei,oxaloLpb
in a massspectrometer.
Boronwasanalysed
below.
therelative
atomicmassof boronusingtheresults
Calculate
Peaks
at mleot
(%)
Abundance
10.0
18.7
11.0
81.3
A,=( 10.0x 18.7+ 11.0x 81.3)/ 100 = 10.8

Answer'.
Electron strrrcture
O The first shell only has an s orbital.
o The second shell has one s and three p orbitals.
o The third and subsequent shells have one s, three p and five d orbitals.
o Each orbital can hold a maximum of two electrons.
o The order of filling orbitals is shown in Figure 1.1 below.
Youshould
beableto sketch
the
variation
of 1stionisation
energies
withatomicnumber
forthefirst20
elements.
Thefirs!sixionisation
energies/
kJmol ofanelement
are:
1st
786
2nd
1580
3rd
3230
4th
4360
sth
16000
20000
6th
Thereis a bigjumpafterthefourth,
is inGroup
sotheelement
4.
st*ucruRE,
B'NDTNG AND MArN cRoup .HEMrsTRy
after Group 2 (this is because,for Group 3, it

O There are slight decreases
is easierto remove an electron from the higher energyp orbital), and
after Group 5 (this is because,for Group 6, the repulsion of the two
electronsin the p, orbital makesit easierto remove one of them).
There
is a decreasegoing down a Group. This is causedby the outer
O
electron being further from the nucleus.(The extra nuclear chargeis
balancedby the sameextra number of inner shielding electrons.)
Successive
ionisation
energies
o The 2nd ionisation energy of an element is alwaysbigger than the first,

becausethe secondelectron is removed from a positive ion.
ionisation
O When there is a very big jump in the value of successive
energies,an electron is being removed from a lower shell, e.g.if this
iump happensfrom the 4th to the 5th ionisation energy,four electrons
have been removed from the outer shell during the first four
ionisations, and so the element is in Group 4.
Electron
affinity
o The 1st electron affinity valuesare alwaysnegative(exothermic),as a

negativeelectron is being brought towards the positive nucleusin a
neutral atom. They are the most exothermic for the halogens.
o The 2nd electron affinity valuesare alwayspositive (endothermic),
becausea negativeelectron is being addedto a negativeion.
Checklist
Beforeattempting the questionson this topic, check that you can:
iJ pefin e A, , M, , and relative isotopic mass.
,J Calculatethe number of neutrons in an isotope,given the atomic and
massnumbers.
iJ Calculatethe relative atomic massof an element from massspectra
data.
[l Oefine first and subsequentionisation energies.
[l mplain the changesin first ionisation energiesfor elementsacrossa
Periodand down a Group.
f
Deducean element'sGroup from successive

ionisation energies.
E Work out the electronic structureof the first 36 elements.

E Oefine the Lst and 2nd electron affinities.
Youshould
beableto sketch
the
variation
of 1stionisation
energies
withatomicnumber
forthefirst20
elements.
Thefirs!sixionisation
energies/
kJmol ofanelement
are:
1st
786
2nd
1580
3rd
3230
4th
4360
sth
16000
20000
6th
Thereis a bigjumpafterthefourth,
is inGroup
sotheelement
4.
st*ucruRE,
B'NDTNG AND MArN cRoup .HEMrsTRy
after Group 2 (this is because,for Group 3, it

O There are slight decreases
is easierto remove an electron from the higher energyp orbital), and
after Group 5 (this is because,for Group 6, the repulsion of the two
electronsin the p, orbital makesit easierto remove one of them).
There
is a decreasegoing down a Group. This is causedby the outer
O
electron being further from the nucleus.(The extra nuclear chargeis
balancedby the sameextra number of inner shielding electrons.)
Successive
ionisation
energies
o The 2nd ionisation energy of an element is alwaysbigger than the first,

becausethe secondelectron is removed from a positive ion.
ionisation
O When there is a very big jump in the value of successive
energies,an electron is being removed from a lower shell, e.g.if this
iump happensfrom the 4th to the 5th ionisation energy,four electrons
have been removed from the outer shell during the first four
ionisations, and so the element is in Group 4.
Electron
affinity
o The 1st electron affinity valuesare alwaysnegative(exothermic),as a

negativeelectron is being brought towards the positive nucleusin a
neutral atom. They are the most exothermic for the halogens.
o The 2nd electron affinity valuesare alwayspositive (endothermic),
becausea negativeelectron is being addedto a negativeion.
Checklist
Beforeattempting the questionson this topic, check that you can:
iJ pefin e A, , M, , and relative isotopic mass.
,J Calculatethe number of neutrons in an isotope,given the atomic and
massnumbers.
iJ Calculatethe relative atomic massof an element from massspectra
data.
[l Oefine first and subsequentionisation energies.
[l mplain the changesin first ionisation energiesfor elementsacrossa
Periodand down a Group.
f
Deducean element'sGroup from successive

ionisation energies.
E Work out the electronic structureof the first 36 elements.

E Oefine the Lst and 2nd electron affinities.
tt*ucruRE,
II
B.NDING
AND MAIN GRoup
cHEMIsrRy
Workêi,oxiloL\-lx'
theamountof H,(g)in 3.2dm"at RTP.
Calculate
= 0.13molof H,(g)
Answer'.
3.2124
Calculation
of number
of particles
The number of particlescan be calculatedfrom the number of moles.

r The number of molecules= molesx Avogadro'sconstant.
o The number of ions = molesx Avogadro'sconstantx the number of
those ions in the formula.
Workpi,oxilo7-h,
molecules
in3.3g ofC0,.
thenumber
ofcarbon
dioxide
Calculate
= 0.075
mol
Amount
Answer:
ofC0,= 3.3144
= 0.075
x 6.02x 10"= 4.5x 10"
Number
ofmolecules
ionsin5.5g of Na,CO,
thenumber
ofsodium
Calculate
= 0.0519
=5.51106
mol
Answer:
Amount
of NarCO,
x 6.02
x 10"x2 =6.2x10"
Number
ofNa-ions= 0.0519
Calculations
based on reactions
Thesecan only be done if a correctlybalancedequation is used.

Reocting moss questions
Firstwrite a balancedequation for the reaction.
Then follow the route:
Step1
Ma s sA -
Step2
Mol es A -Mol es
Step3
B + Mass
For Steps1 and 3 usethe relationship:

amount of A or B (in moles) = mass/molarmass
For Step2 use the stoichiometric ratio from the equation:
moles of B = moles of A x ratio B/A
oxilo7-h'
Workêi,,
to react
with1.23g ofsilicon
hydroxide
required
themass
Calculate
ofsodium
In Step2, thestoichiometric
ratiois
211asthereare2Na0Hmolecules
foreach1Si0,molecule
in the
equation.
dioxide.
Answer.
+ H,0
Equation:
SiO,+ 2Na0H---lNa,Si0,
= 0.0205
mol
mol
ofSiO,= 1.23160
Step1 amount
= 0.0205
molx 211= 0.0410
mol
of NaOH
Step2 amount
= 1.64g
x 40
of NaOH= 0.0410
Step3 mass
II
tt*ucruRE,
B.NDTNG AND MAIN GRoup
.HEMrsrRy
iii the element of Z = 11 than that for element of Z = 3.

7 Using the electron in a box notation, give the electronic structure of
chlorine (Z = I7).
8 Explain, in terms of electronic structure, why the chemical properties of
lithium, sodium and potassium are similar but not identical.
9 a
Give the equation, with state symbols, that representsthe 1st

iii oxygen.
ii chlorine,
electron affinity of i lithium,
Give the equation that representsthe 2nd electron affinity of

oxygen.
Why is the 2nd electron affinity of oxygen endothermic whereas

the 1st electron affinities of lithium, chlorine and oxygen are all
exothermic?
andmoles
equations
@ Formulae,
,-ld
tri
(H H
Introduction
The keysto this topic are:

I To be able to calculatethe number of moles from data.
t To set out calculationsclearlv.
Things to learn
iJ The Avogadro Constant is the number of carbon atoms in exactly 12 g
of the carbon-I} isotope. Its value is 6.O2 x 10" mol-'.
1 molof NaOH
hasa massof 40g
1 molof 0, hasa massof 32 g.
iJ O.re mole of a substance is the amount of that substance that contains

6.O2 x 1023particles of that substance.This means that one mole of a
substance is its relative atomic or molecular mass expressedin grams.
t] fne molar mass of a substance is the mass (in grams) of one mole.
[J Amount
of substance is the number of moles of that substance.
[] fne empirical formula is the simplest whole number ratio of the

elements in the compound.
Things to understand
Calculation
of empirical
formulae
from percentage
data
It is best calculated using a table.
Element Percentage of element

Carbon
48.7
Hydrogen
8.1
Oxygen
43.2
Percentage divided by A,of element

48.7+12-4.1
8 . 1+ 1 = 8 . 1
43.2+16-2.7
Divide each by lowest
4 . I + 2 . 7= 1 . 5
8 . 1+ 2 . 7= 3
2 . 7+ 2 . 7= 7
II

"t*ucruRE,
solution of bismuth nitrate, Bi(NO3)r?The molar volume of a gas is 24

dmt mol-' under these conditions. They react according to the equation:
3HrS(g) + 2Bi(NO3).(aq)'BirSr(s) + 6HNO,(aq).
6 What volume of hydrogen gas is produced by the reaction of 33 dm'of
methane gas when it is reacted with steam according to the equation:
CHn(g) + H,O(g)--' CO(g) + 3H,(g) ?
reandbonding
Structu
ffil
try
Introduction
You should be able to distinguish between:

o Chemical bonds
Ionic
Covalent
Metallic
between separateions
which are divided into two tyPes:
polar covalent where the bonding pair of electrons
is nearerto one atom
pure covalent where the bonding pair of electrons
is sharedequally
bonding causedby electronsdelocalised
throughout the solid.
O Intermolecular forces(between covalent molecules)

between 6- H in one molecule and 6 F, O or
Hydrogen bonds
N in another molecule
Dispersionforces
between all molecules. Their strength

depends upon the number of electrons in the
molecule.
Dipole/dipole forces -
between 6- atoms in one molecule and 6

atoms in another molecule.
Things to learn
o-bond
n-bond
Fig l . 3 o a n d n b o n d s .
E en 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.
c-I e covalent bond occurs when two atoms share a pair of electrons. It
results from the overlap of an orbital containing one electron belonging
to one atom with an orbital that contains one electron that belongs to
the other atom. The overlap can be head on, which results in a o bond
or, side by side, which results in a n bond (see Figure 1.3). A double
bond is a o and a n bond, with two pairs of electrons being shared.
tr n dative covalent bond is a covalent bond formed when one of the
_ overlapping orbitals contained two electrons and the other none.
U n metallic bond is the force of attraction between the sea of
delocalised electrons and the positive ions which are arranged in a
_ regular lattice.
of an element is a measure of the attraction its
iJ the electronegativity
atom has for a pair of electrons in a covalent bond.
tt*ucruRE,
II
B.NDING
AND MAIN GRoup
cHEMIsrRy
Workêi,oxiloL\-lx'
theamountof H,(g)in 3.2dm"at RTP.
Calculate
= 0.13molof H,(g)
Answer'.
3.2124
Calculation
of number
of particles
The number of particlescan be calculatedfrom the number of moles.

r The number of molecules= molesx Avogadro'sconstant.
o The number of ions = molesx Avogadro'sconstantx the number of
those ions in the formula.
Workpi,oxilo7-h,
molecules
in3.3g ofC0,.
thenumber
ofcarbon
dioxide
Calculate
= 0.075
mol
Amount
Answer:
ofC0,= 3.3144
= 0.075
x 6.02x 10"= 4.5x 10"
Number
ofmolecules
ionsin5.5g of Na,CO,
thenumber
ofsodium
Calculate
= 0.0519
=5.51106
mol
Answer:
Amount
of NarCO,
x 6.02
x 10"x2 =6.2x10"
Number
ofNa-ions= 0.0519
Calculations
based on reactions
Thesecan only be done if a correctlybalancedequation is used.

Reocting moss questions
Firstwrite a balancedequation for the reaction.
Then follow the route:
Step1
Ma s sA -
Step2
Mol es A -Mol es
Step3
B + Mass
For Steps1 and 3 usethe relationship:

amount of A or B (in moles) = mass/molarmass
For Step2 use the stoichiometric ratio from the equation:
moles of B = moles of A x ratio B/A
oxilo7-h'
Workêi,,
to react
with1.23g ofsilicon
hydroxide
required
themass
Calculate
ofsodium
In Step2, thestoichiometric
ratiois
211asthereare2Na0Hmolecules
foreach1Si0,molecule
in the
equation.
dioxide.
Answer.
+ H,0
Equation:
SiO,+ 2Na0H---lNa,Si0,
= 0.0205
mol
mol
ofSiO,= 1.23160
Step1 amount
= 0.0205
molx 211= 0.0410
mol
of NaOH
Step2 amount
= 1.64g
x 40
of NaOH= 0.0410
Step3 mass
tt*ucruRE,
B.NDTNG AND MArN GRoup
qHEMIsrRy
TableI
ThePeriodic
ffi
try Introduction
r The melting and boiling temperaturesof the elementsdepend on the
type and strength of the bond or intermolecular force betweenparticles.
a There are trends in physical and chemical propertiesacrossa Period and
down a Group. For instance
1
Elementsshow decreasing metallic characteracrossa Period.
2
Elementsshow increasing metallic characterdown a Group.
Things to learn and understand

Electronic structure
Therearetwoexceptions
withthe
first40 elements.
Because
of the
extrastability
of a halffilledor full
setof d orbitals,
is [Ar]
chromium
4s',3du,andcopper
is [Ar]4s',3d'o
O The elementsin the PeriodicTableare arrangedin order of atomic

number, so each element has one more proton and hence one more
electron than the previous element.
o Elementsin the samegroup have the samenumber of electronsin their
outer shells.Theseare called the valenceelectrons.
o Elementsin the samePeriod have the samenumber of shellscontaining
electronsso their outer or valenceelectronsare in the sameshell.
o The order in which electronsfill the orbital types is:
1s; 2s,2p; 3s, 3p; 4s,3d,4p; 5s,4d, 5p; 6s (seeFigure1.1 on page3)
(and boiling)
Melting
(Na to Ar)
elements
temperatures
of the Period
O The melting temperaturedependsupon the strength of the forces

betweenparticlesthat separateduring melting (or boiling).
Theseparticlesmay be:
i
metal ions in a seaof electronsin metals
ii
covalently bonded atoms in a giant atomic structure
iii
moleculeswith intermolecular forcesbetweenthem in simple
molecular solids.
o To understandthe trends in melting temperatures,you should first
decidewhat type of bonding or force is betweenthe particles.
Themoreelectrons
inthemolecule,
thestronger
thedispersion
force
andthehigherthemeltingor boiling
temperature.
o If the solid is metallic: the greaterthe chargedensity of the ion in the

lattice, the strongerthe force holding the lattice together and so the
higher the melting temperature.
o If the solid is a giant atomic lattice: the covalent bonds throughout
the lattice are strong and so the solid has a very high melting
temperature.
o If the solid is a simple molecular substance:the melting (or boiling)
temperaturedependsupon the strength of dispersion (induced
dipole/induced dipole) force betweenthe molecules.
o In Period3, sodium, magnesiumand aluminium are metallic, silicon
forms a giant atomic lattice, and phosphorus,Pn,sulphur, S' chlorine,
Cl, and argon, Ar, all form simple molecular solids.
t"E
PERroDrcTaeLE I
Electrical
conductivity
Solids conduct electricity by the flow of delocalised electrons.

Thus metals conduct electricity. Graphite also conducts, but only in the
plane of the layers. This is due to the n-electrons that are delocalised above
and below the lavers.
^.H
'
flK
l/H
Checklist
Beforeattemptingthe questionson this topic, checkthat you can:

i-i Write the electronic structure for elementsnumbers 1 to 36.
lJ Explain the variation of melting and boiling temperaturesfor the
elementsin Period3.
iJ Explain the change in electricalconductivity of the elementsin
Period3.
lJ Explain the variation in ionisation energiesof the elementsin Period3.
)H
j-lJ)/l
Testingyour knowledgeand understanding
T)()
H
to thenumbered
Theanswers
questions
areonpage123.
L What, in terms of electronic structure,are the featuresthat the

following have in common:
a membersof the samegroup , .8. Group 2,
membersof the sameperiod,e.g.Periodpotassiumto krypton?
2 Statethe type of solid structureof the elementslisted. Give your

answeras one of:
metallic, giant atomic, ionic, hydrogen bonded molecular,simple
molecular,polymeric:
a hydrogen
e chlorine
b sodium
f argon.
d sulphur
c silicon
3 Explain the differencein melting temperaturesof the following

elements:
Element
Na
Mg
Melting temperature/O6
98
650
Si
Pn
1 4 1 0 44
s8
CI,
1 1 3 -101
4 The ionisation energies of sodium and magnesium are listed below:
Element
lst ionisation energy/kJmol-' 2nd ionisation energy/kJmol-'
Sodium
494
4560
Magnesium
736
1450
Explain the meaning of: i nuclearcharge,ii screening(or shielding)

by inner electrons.
Usethe conceptsexplainedin (a) to explain why: i The 2nd
ionisation energyof sodium is very much more than its 1st
ionisation energy.ii The lst ionisation energyof sodium is lessthan
the 1st ionisation energyof magnesium.
a"RMULAE,
EeuATroNs
11
AND MoLEs
and understanding
Testingyour knowledge
For the first set of questions, cover the margin, write down your ans\\-er,
then check to see if you are correct.
r The table below contains data which will help you.
Substance
Solubility
Nitrates
All soluble
Chlorides
All solubleexceptfor AgCl and PbCI,
Sodiumcompounds
All soluble
Hydroxides
All insolubleexceptfor Group 1 and

barium hydroxides
Write ionic equations for the reactions of solutions of:
+ 2Cl-(aq)-- PbCl,(s)
a Pb"(aq)
+ 20H-(aq)-'Mg(0H),(s)
b Mg'-(aq)
+ Ag'(aq) -- AgCl(s)
c Cl-(aq)
+ 0H-(aq) --' H,0(l)
d H-(aq)
t
mol
a 1.23123= 0.0535
= 0.0779
mol
b 4.56/58.5
= 0.0329
mol
G 0.789124
mol
d 0.111x 0.0321= 3.56x 10-3
= 0.205d
m' = 205cm'
0.045610.222
(1.00n8)x 6.02x 10"= 3.34x 10"
(1.00/106)
x 6.02x 1d'x 2 =1.14x1ff
a 4.44g10.250
dm'= 17.8g dm-'
=
mol
E 4 . 4 4 1 4 00 . 1 1 1
Therefore
0.111mol/0.250
dmg
= 0.444moldm-'
Theanswers
tothenumbered
questions
areonpages
121-122.
a
b
c
d
lead nitrate and potassium chloride

magnesium chloride and sodium hydroxide
sodium chloride and silver nitrate
sodium hydroxide and hydrochloric acid.
Calculate the amount (in moles) of:

a
b
c
d
Na in I.23 g of sodium metal

NaCl in 4.56 g of solid sodium chloride
Cl, in 789 cm'' of chlorine gas at room temperature and pressure
NaCl in 32.1 cm'' of a 0.111 mol dm-' solution of sodium chloride.
I Calculate the volume of a 0.222 mol dm-'' solution of sodium

hydroxide, which contains 0.0456 mol of NaOH.
t Calculate the number of water molecules in 1.00 g of HrO.
o Calculate the number of sodium ions in 1.00 g of NarCO,,.
) 4.44 g of solid sodium hydroxide was dissolved in water and the
solution made up to 250 cmS.Calculate the concentration in
a
g dm-'
mol dm-'.
1.a
b
carbon and 17.24o/o

An organic compound contains 82.760/o
hydrogenby mass.Calculateits empiricalformula.
It was found to have a relativemolecularmassof 58. Calculateits
molecular formula.
Balance the equations:

HrO
-Sn'.(aq) Fe'.(aq) +
NH.+O,-NO
Fe'.(aq) +
Snn.(aq)
What mass of sodium hydroxide is needed to react with 2.34 g of

phosphoric(V) acid, H3PO*,to form the salt Na,POnand water?
What volume of 0.107 mol dm' potassium hydroxide, KOH, solution is
needed to neutralise 12.5 cmt of aO.O747mol dm-' solution of
sulphuric acid?
What volume, measured at room temperature and pressure,of hydrogen
sulphide gas, HrS, is required to react with 25 cm" of a 0.55 mol dm-'
II

"t*ucruRE,
solution of bismuth nitrate, Bi(NO3)r?The molar volume of a gas is 24

dmt mol-' under these conditions. They react according to the equation:
3HrS(g) + 2Bi(NO3).(aq)'BirSr(s) + 6HNO,(aq).
6 What volume of hydrogen gas is produced by the reaction of 33 dm'of
methane gas when it is reacted with steam according to the equation:
CHn(g) + H,O(g)--' CO(g) + 3H,(g) ?
reandbonding
Structu
ffil
try
Introduction
You should be able to distinguish between:

o Chemical bonds
Ionic
Covalent
Metallic
between separateions
which are divided into two tyPes:
polar covalent where the bonding pair of electrons
is nearerto one atom
pure covalent where the bonding pair of electrons
is sharedequally
bonding causedby electronsdelocalised
throughout the solid.
O Intermolecular forces(between covalent molecules)

between 6- H in one molecule and 6 F, O or
Hydrogen bonds
N in another molecule
Dispersionforces
between all molecules. Their strength

depends upon the number of electrons in the
molecule.
Dipole/dipole forces -
between 6- atoms in one molecule and 6

atoms in another molecule.
Things to learn
o-bond
n-bond
Fig l . 3 o a n d n b o n d s .
E en 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.
c-I e covalent bond occurs when two atoms share a pair of electrons. It
results from the overlap of an orbital containing one electron belonging
to one atom with an orbital that contains one electron that belongs to
the other atom. The overlap can be head on, which results in a o bond
or, side by side, which results in a n bond (see Figure 1.3). A double
bond is a o and a n bond, with two pairs of electrons being shared.
tr n dative covalent bond is a covalent bond formed when one of the
_ overlapping orbitals contained two electrons and the other none.
U n metallic bond is the force of attraction between the sea of
delocalised electrons and the positive ions which are arranged in a
_ regular lattice.
of an element is a measure of the attraction its
iJ the electronegativity
atom has for a pair of electrons in a covalent bond.
eRouP I ANo Gnoup 2

O Addition of aqueous sulphate ions to a solution of Sr'* or Ba'* ions
produces a white precipitate of metal sulphate:
Ba'.(aq) + SOn'-(aq)- BaSOn(s)
Thermal
â/
H
of nitrates
and carbonates
o Thermal stability increases down both groups:

o Group 2 nitrates all decomposeto give a metal oxide, brown fumes of
nitrogen dioxide, and oxygen:
2Ca(NOr)r- 2CaO+ 4NO, + O,
O Group 1 nitrates, except lithium nitrate, decomposeto give a metal
nitrite and oxygen:
2NaNO,-- 2NaNO,r O,
but
4LiNO,,-- ZLirO+ 4NO, + O,
o Group 2 carbonatesall decompose(exceptbarium carbonatewhich is
stableto heat) to give a metal oxide and carbondioxide:
CaCO',-CaO+CO,
t Group 1 carbonatesare stableto heat exceptfor lithium carbonate:
Li?CO,-Li'O+CO.
Thecompound
is morelikely
to be
decomposed
onheating
if thecation
polarises
theanion.
Thus
(cation
Group
2 compounds
2+)
decompose
morereadily
thanGroup
(cation
1 compounds
only1+).
Compounds
ofmetals
higher
ina
group
(smaller
ionic
radius)
decompose
moreeasily
than
compounds
of metals
lower
inthe
Group.
'
stability
H
9
f__- Checklist
-
^-'-
Beforeattempting the questionson this topic, check that you know:

tJ ttre physical propertiesof the Group 1 and Group 2 elements
r-l ttre flame colours causedby their compounds
iJ the trends in ionisation energieswithin a group
iJ ttre reactionsof the elementswith oxygen, chlorine and water
J the reactionsof their oxides with water
,J the oxidation statesof the elementsin Group 1 and in Group 2
,J the trends in solubilities of Group 2 sulphatesand hydroxides
.J tfre reasonfor the trend in thermat stability of Group 1 and Group 2
nitrates and carbonates.

For the first set of questions,cover the margin, write your answer,then
check to seeif you are correct.
Lithium
o Which Group 1 metal has the highest melting temperature?
K is +1,Cais +2
o What is the oxidation number of:

i potassiumin KrCrrO,and
ii calcium in CaCOr?
It is extremely
insoluble.
o Barium compounds normally are poisonous,but barium sulphateis

given to people in order to outline their gut in radiography (X-ray
imaging).Why is barium sulphatenot poisonous?
II
400
350
300
250
K ZOO
150
100
50
0
NHs
=t*ucruRE,
400
350
300
400
3s0
300
250
K 200
150
100
50
0
2so
PH:
AsH3
Group 5
K 200
150
100
50
0
sbH3
Hzo
Fig 1.4 Boilingtemperatures

of
Groups5, 6 and 7 hydrides
B.NDTNGAND MA'N GRoup cHEMrsrRy
HzS
HrSe
Group 6
H2Te
HF
HCI
HBT
Group 7
HI
f If the number of electronsin two different substancesis about equal

and neither has hydrogen bonds, then dipole/dipole forcescausea
differencein boiling temperature.This is the casebetweenbutane
(34 electrons,non-polar,boiling temperature- 0.5 'C) and propanone
(32 electrons,but polar, so boiling temperature+ 56.2'C).
Effect
of heat
(melting)
When a solid is heated from room temperatureuntil it melts:

O The particles(ions, moleculesor atoms) vibrate more.
Donotsaythattheparticles
startto
vibrate,
astheyarevibrating
evenat
verylowtemperatures.
Thestronger
theforcebetween
particles,
themoreenergy
needed
to
separate
themandhence
thehigher
themelting
temperature.
o As the temperaturerisesthe vibrations increaseuntil they becomeso

great that the forcesbetweenthe particlesare overcome,and the regular
arrangementin the lattice breaksup. The substanceis then a liquid.
O In an ionic solid, such as NaCl, the vibrating particlesare ions which
are held by strong forcesof attraction, and so the ionic solid has a high
melting temperature.
o In a simple molecular solid, such as iodine (Ir) or ice, the vibrating
particlesare moleculeswhich are held by weak van der Waalsor
hydrogen bonding forcesof attraction, and so the solid has a low
o In a giant atomic solid, such as diamond, the vibrating particlesare
atoms which are held by strong covalent bonds, and so the solid has a
very high melting temperature.
Shapes of molecules
o lt isthebonds
nottheatoms
that
repel,
o Don't
forget
to count
thenumber
of lonepairs.
O Theseare explained by the electron pair repulsion theory which states:

i The electron pairs arrangethemselvesas far apart from each other as
possiblein order to minimise repulsion.
ii The repulsion betweenlone pairs is greaterthan that betweena lone
pair and a bond pair, which is greaterthan that between two bond
pairs.
o The number of o bond pairsof electronsand lone pairsin the molecule
should be counted.
o Any r bond pairs should be ignored when working out the shapeof a
molecule.
tt*,rcruRE,
B o N D T N GA N D M A r N G R o u p c H E M r s r R y
Practlce Test: Unit L

Time allowed Lhr
All questionsare taken from parts of previous EdexcelAdvancedGCE questions.
The answersare on pagesIZ5-t26.
Complete and balancethe following equations.
i Ca+O,
t1I
ii NarO + HrO +
tlI
iii NarO + HCI +
l2l
b Stateand explain the trend in thermal stability of of the carbonatesof the Group 2 elementsas the
group is descended.
t3l
(Totat 7 marks)
[May 2002 Unit Test1 question2]
La
2 a Statethe structure of, and the type of bonding in, the following substances.Draw labelled
diagrams to illustrate your answers.
i
Graphite
t4I
ii Sodium chloride
t3I
b Explain why both graphite and sodium chloride have high melting temperatures.
t3l
c i Explain why graphite is able to conduct electricity in the solid state.
r2l
ii Explain why sodium chloride conducts electricity in the liquid state.
tlI
(Totat 13 marks)
lMay 2002 Unit TestL question6l
3a i
ii
Define the terms atomic number and mass number

t2l
Identify the particle that contains 35 protons, 44 neutrons and 34 electrons.
tlI
Bromine consistsof two isotopesof massnumbers 79 and 81. A sampleof bromine gas,Br, was
examined in a massspectrometer.The massspectrumshowing the molecular ions is given below.
100
Relative
intensity
158
160
162
b i Explain how the moleculesin the sampleare ionised.

ii Statehow the resulting ions are accelerated.
iii Identify the speciesresponsiblefor the peak at mle = 160.
t2l
tll
tl]
(Total 7 marks)
llanuary 2001 CH1 questionL & lune 2001 Unit TestL question3l
Hydrogen forms compounds with most non-metallic elementsand with some metals.
Calculatethe empirical formula of the compound used in the manufactureof artificial rubber,which
has the following composition by mass:
hydrogen
tI.Lo/o
carbon
88.9o/o
t3l
b The boiling temperaturesof hydrogen chloride and hydrogen iodide are:
-85'C
-35 "C
hydrogen chloride
Hydrogen iodide
Explain why hydrogen iodide has a higher boiling temperaturethan hydrogen chloride
l2l
c Draw and explain the shapesof:
i
ii
the PH. molecule

the AIH; ion.
I2l
I2l
y, e*Ufrzo*irr
2 OfAA"niL,
l,/Va-/ a.tA VL'771

/
J,VVI
Mkr
Jvvl.v))
u
ar4d,e4uilib r i/,u,t
I
[nergetics
Introduction
o Statesymbolsshould alwaysbe used in equationsin this topic.
O In definitions in this topic, there are three points to note:
1 the chemical changethat is taking place
2 the conditions
3 the amount of substance(reactantor product).
o It alwayshelps to add an equation with statesymbolsas an example,
becausethis may gain marks lost by omission in the word definition.
O It is assumedfor simplicity that the value of LH is an indicator of the
direction of a chemical reaction. The more exothermic the reaction, the
more likely it is to take place,but other factors,such as activation
energy (seepage 44), alsodetermine whether the reaction happens.
Things to learn
It followsfromthisdefinition
that
theenthalpy
offormation
ofan
initsstandard
state,
is
element,
zero.
giveanequation
Youshouldalways
forthisandother
asanexample
enthalpy
definitions.
J Standardconditions are:
O gasesat a pressureof L atmosphere
o a statedtemperature(usually 298 K)
o solutions, if any,at a concentration of 1.00 mol dm-'
o substancesin their most stablestates,e.g. carbon as graphite not
diamond.
[-l Standardenthalpy of formation, AI{'is the enthalpy change,under
standardconditions, when one mole of a compound is formed from
its elements in their standardstates,e.g. AFII'for ethanol is the
enthalpy changefor the reaction:
2C(graphite)+ 3H,(g)+'/,Or(g) - C,H.OH(l)
[f Standardenthalpy of combustion, AF/,'is the enthalpy change,under
standardconditions, when one mole of a substanceis completely
burned in oxyger, .g.AI1.'for ethanol is the enthalpy changefor the
reaction:
C,H'OH(I) + 3O,(g)- ZCO,(g)+ 3H,O0)
AI/:.,, of an acid is the enthalpy
E Standard enthalpy of neutralisation
change,under standardconditions, when the acid is neutralisedby
of sulphuric acid,
baseand one mole of water is produced,e.g.A.Fif;",,
by sodium hydroxide solution, is the enthalpy changefor the reaction:
'/,HrSOn(aq)
+ NaOH(aq)-'l,Na,SO,(aq)+ H'O(l)
eNERGErrcs I
Workêi,exiloLf.b
A 0.120g sample
wasburntandtheheatproduced
of ethanol
warmed
250g
'Cto 20.72
'C.The
from17.30
ofwater
specific
heatcapacity
ofwateris4.18
J gto0-t.Calculate
A{omustion
of ethanol.
= 250g x 4.18J gj o6-tx3.42'C = 3574J.
Answer.Heatproduced
g mol-'= 2.61x 10-'mol
Amount
of ethanol = 0.120g146
=
produced
per
Heat
x 10-3
ffi010 3574J12.61
mol= 1370x 10'J mol-'.
= -1370 kJ mol-t
A4omuustion
Calculation
Calculation
of A^tI values from average bond enthalpies
O Draw the structural formulae for all the reactants and all the products.
il Decide what bonds are broken in the reaction and calculate the energy
requiredto breakthe bonds (endothermic).

Decidewhat bonds are made in the reactionand calculate the energy
releasedby making the bonds (exothermic).
Add the positivebond breakingenthalpy to the negative bond making
enthalpy.
Workpi,oxiloLplr,
Calculate
theenthalpy
of thereaction:
H
H
+ H_
t l
--__________+
H_ C - C - H
Given
thefollowing
average
bondenthalpies/kJ
mol-':
C-Cis +348,C=Cis +612,H-His +436,andC-His +412.
(endo)
Answer. break
C=C +612
H-H +436
(exo)
make
-348
c-c
2 x C-H -824
-1172
+1048
-124
=
=
A4,,,rion+1048 1172
kJ mol-'
Checklist
Before attempting questions on this topic, check that you:
i
Kno* the standard conditions for enthalpy changes.
J Kno* the signs of A,Hfor exothermic and endothermic reactions.

J Can define the standard enthalpies of formation, combustion and
neutralisation.
l-l Understand an energy level diagram.
J Can define and use Hess'sLaw.
li Know how to calculate values of A/{from laboratory data.
iJ Can use bond enthalpies to calculate enthalpies of reaction.
tt*ucruRE,
B.NDTNG AND MArN GRoup
qHEMIsrRy
TableI
ThePeriodic
ffi
try Introduction
r The melting and boiling temperaturesof the elementsdepend on the
type and strength of the bond or intermolecular force betweenparticles.
a There are trends in physical and chemical propertiesacrossa Period and
down a Group. For instance
1
Elementsshow decreasing metallic characteracrossa Period.
2
Elementsshow increasing metallic characterdown a Group.

Electronic structure
Therearetwoexceptions
withthe
first40 elements.
Because
of the
extrastability
of a halffilledor full
setof d orbitals,
is [Ar]
chromium
4s',3du,andcopper
is [Ar]4s',3d'o
O The elementsin the PeriodicTableare arrangedin order of atomic

number, so each element has one more proton and hence one more
electron than the previous element.
o Elementsin the samegroup have the samenumber of electronsin their
outer shells.Theseare called the valenceelectrons.
o Elementsin the samePeriod have the samenumber of shellscontaining
electronsso their outer or valenceelectronsare in the sameshell.
o The order in which electronsfill the orbital types is:
1s; 2s,2p; 3s, 3p; 4s,3d,4p; 5s,4d, 5p; 6s (seeFigure1.1 on page3)
(and boiling)
Melting
(Na to Ar)
elements
temperatures
of the Period
O The melting temperaturedependsupon the strength of the forces

betweenparticlesthat separateduring melting (or boiling).
Theseparticlesmay be:
i
metal ions in a seaof electronsin metals
ii
covalently bonded atoms in a giant atomic structure
iii
moleculeswith intermolecular forcesbetweenthem in simple
molecular solids.
o To understandthe trends in melting temperatures,you should first
decidewhat type of bonding or force is betweenthe particles.
Themoreelectrons
inthemolecule,
thestronger
thedispersion
force
andthehigherthemeltingor boiling
temperature.
o If the solid is metallic: the greaterthe chargedensity of the ion in the

lattice, the strongerthe force holding the lattice together and so the
higher the melting temperature.
o If the solid is a giant atomic lattice: the covalent bonds throughout
the lattice are strong and so the solid has a very high melting
temperature.
o If the solid is a simple molecular substance:the melting (or boiling)
temperaturedependsupon the strength of dispersion (induced
dipole/induced dipole) force betweenthe molecules.
o In Period3, sodium, magnesiumand aluminium are metallic, silicon
forms a giant atomic lattice, and phosphorus,Pn,sulphur, S' chlorine,
Cl, and argon, Ar, all form simple molecular solids.
t"E
PERroDrcTaeLE I
Electrical
conductivity
Solids conduct electricity by the flow of delocalised electrons.

Thus metals conduct electricity. Graphite also conducts, but only in the
plane of the layers. This is due to the n-electrons that are delocalised above
and below the lavers.
^.H
'
flK
l/H
Checklist
Beforeattemptingthe questionson this topic, checkthat you can:

i-i Write the electronic structure for elementsnumbers 1 to 36.
lJ Explain the variation of melting and boiling temperaturesfor the
elementsin Period3.
iJ Explain the change in electricalconductivity of the elementsin
Period3.
lJ Explain the variation in ionisation energiesof the elementsin Period3.
)H
j-lJ)/l
T)()
H
to thenumbered
Theanswers
questions
areonpage123.
L What, in terms of electronic structure,are the featuresthat the

following have in common:
a membersof the samegroup , .8. Group 2,
membersof the sameperiod,e.g.Periodpotassiumto krypton?
2 Statethe type of solid structureof the elementslisted. Give your

answeras one of:
metallic, giant atomic, ionic, hydrogen bonded molecular,simple
molecular,polymeric:
a hydrogen
e chlorine
b sodium
f argon.
d sulphur
c silicon
3 Explain the differencein melting temperaturesof the following

elements:
Element
Na
Mg
Melting temperature/O6
98
650
Si
Pn
1 4 1 0 44
s8
CI,
1 1 3 -101
4 The ionisation energies of sodium and magnesium are listed below:
Element
lst ionisation energy/kJmol-' 2nd ionisation energy/kJmol-'
Sodium
494
4560
Magnesium
736
1450
Explain the meaning of: i nuclearcharge,ii screening(or shielding)

by inner electrons.
Usethe conceptsexplainedin (a) to explain why: i The 2nd
ionisation energyof sodium is very much more than its 1st
ionisation energy.ii The lst ionisation energyof sodium is lessthan
the 1st ionisation energyof magnesium.
II
tt*ucruRE,
B.NDTNGAND MArN GRoup cHEMrsrRy
Introduction
to oxidation
and
reduction
Introduction
o Redoxreactionsare those which involve a transfer of electrons
o RememberOIL RIG (Oxidation Is Loss,Reduction fs Gain of electrons)
4A
'W
Thingsto learn
E Oxiaation occurswhen a substancelosesone or more electrons.

There is an increasein the oxidation number of the element involved.
[l nn oxidising agent is a substancethat oxidisesanother substance
and so is itself reduced.The half equation involving an oxidising agent
has electronson the left-hand side,i.e. it takes electronsfrom the
substancebeing oxidised.
l] neduction occurswhen a substancegains one or more electrons.
There is a decreasein the oxidation number of the element involved.
|J A reducing agent is a substancethat reducesanother substanceand
so is itself oxidised.The half equation involving a reducing agent has
electronson the right-hand side,i.e. it gives electronsto the substance
being reduced.
orl Rtc
- ^ f"/ ,- |
J,,+
Things to understand
!---.-.-l'
Oxidation
Inanoverall
equation,
thetotal
increase
inoxidation
number
ofone
(increase
element
x number
of
atoms
ofthatelement)
mustequal
thetotaldecrease
inoxidation
number
ofanother
element.
number
I The oxidation number is the chargeon an atom of the element in a

compound calculatedassumingthat all the atoms in the compound are
simple monatomic ions. The more electronegativeelement is given an
oxidation number of -1 per bond.
O There are some rules used for calculatingoxidation numbers.They
should be applied in the following order:
1
The oxidation number of an uncombined element is zero.
2
3
4
A simple monatomic ion has an oxidation number equal to its

charge.
The oxidation number of Group 1 metals is always+1, and of
Group 2 metals is +2.
Fluorine alwayshas an oxidation number of -1, hydrogen (except
in metallic hydrides) of +1, and oxygen (exceptin FrO and
peroxides)of -2.
The sum of the oxidation numbers in a molecule addsup to 0, and

those in a polyatomic ion (such as SOr*)add up to the chargeon
the ion.
O When an element is oxidised, its oxidation number increases.
41,
oRcnrurc cHEMrsrRY I
zCOz+3HrO
cH2oHCH2OH
CH2BTCHTBT
o2
Spark
Brz
KMnOn
NaOH(aq)
cH3cooH
Boil under reflux
KtCtrOrlHrSOn(aq)
conc H2SO4
at 100'C
at l7O"C
Crz
W
NaOH
cH3cH2cl
NH, in ethanol
cH3cH2cN
Fig 2.8 Summory of
orgonic reoctions
cH3cH2NHz
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 alkenes are more reactive than
alkanes and react by addition, whereas alkanes react by substitution.
A C-I bond is weaker than a C-Cl bond, and so iodoalkanes are
rapidly hydrolysed by aqueous sodium hydroxide, unlike
chloroalkanes which react very slowly.
Quantitative
yieldis lessthan100%
Thepercent
because
of competing
reactions
and
handling
losses.
organic
chemistry
unThis involves calculation of empirical formulae from percent data (see

page 6).
w This involves calculation of percentage yield.
First calculate the theoretical yield from the equation (seepage B),
x 10oo/o
then the o/oyield = actual yield in grams
theoretical yield in grams
Applied
organic
chemistry
* Liquid versus gaseous fuels. You should consider the following

points:
L
2
3
4
5
the
the
the
a
easewith which gaseousfuels can be piped into the home

easier handling of liquid fuels at a filling station for cars
extent and type of pollution produced:
the quantity of carbon dioxide and any other greenhouse gases
produced per kilojoule of energy
the emission of oxides of nitrogen and sulphur, and the way in

which these can be limited
the emission of particulates
the energy produced per unit mass of fuel for aeroplanes

the extent to which the world's supply of fossil fuels is limited.
cHEMrsrRy,
ENERGETT.', KrNETrcs AND EeurLrBRruM
"RGANrc
a Polymers. You should realisethat simple polyalkenesare resistantto

breaking down under environmental conditions. This is becauseof the
strength of the C-C and the C-H bonds.
* Organic halogen compounds. There are three main usesof these:
1
DDTis a chlorine-containing
pesticide
andit haseradicated
malaria
fromsomecountries,
butits
hasledto thedestruction
overuse
of
lt is a veryinertchemical
wildlife.
(owing
to thestrength
of theC-Cl
in an
bond)andso persists
organism,
beingstoredin fatty
tissue.
As polymers. PVC is used as a waterproofing material, as an

electricalinsulator and as a stableand maintenancefree material for
window frames.When burnt it producesharmful fumes of
hydrogenchloride.PTFEis usedas a non-stickcoatingfor saucepans
etc. Thesepolymers are very stableowing to the strength of
carbon-halogenand C-C bonds.
As herbicides.Complicatedchlorine compounds,such as 2,4-D and
2,4,5-Tare usedas selectiveweedkillers.They are stableand so
persistin the environment.
Chlorofluorocarbons(CFCs)make excellent refrigerants,but they
are so stablein air and water that they diffuseto the stratosphere
where they are broken down by light energyand form chlorine
radicals.Thesecatalysethe destructionof ozone.New substances
have been developedwhich contain hydrogenaswell as chlorine,
fluorine and carbon,and theseare lessstableand are broken down
by atmosphericoxidation.
Checklist
Before attempting the questions on this topic, check that you:
tJ Can name simple organic molecules.
tf Can write structural formulae of structural and geometric isomers.
lJ Know the reactions of alkanes with air and halogens.
Ll Know the reactions of alkenes with hydrogen, halogens, hydrogen
halides, potassium manganate(Vll) and in polymerisation.
[J Kno* the reactions of halogenoalkanes with potassium hydroxide (both
aqueous and ethanolic), potassium cyanide and ammonia.
[f Kno* the oxidation, dehydration and halogenation reactions of
alcohols.
'J
Can relate reactivity to bond strength and polarity and to the stability
of intermediates.
if Can calculate the empirical formula of a compound.
iJ Understand the advantages and disadvantages of the use of organic
compounds.

-ene
ethene
andbut-1
-ol
2-chlo
ro-3-methylpentan-1
o Which of the following compounds are membersof the same

homologousseries:
ethene CrHn,cyclopropaneCrHu,but-l-ene CHTCHTCH=CH,
but-1,3-dieneCH'=CHCH=CH',cyclohexeneCuH,o?
Name CH3CHTCH(CH3)CHCICHTOH
eRouP I AND GRoup 2
@ G r o u1pa n dG r o u2p
fntroduction
J fne propertiesof elementsand their compoundschangesteadilydown
a Group.
J fnis meansthat the answerto a questionabout which is the most/least
reactive,easiest/hardest
to decompose,most/leastsoluble,etc. will be
an element,or a compound of that element,either at the top or at the
bottom of the Group.
J Down a Group the elementsbecomeincreasinglymetallic in character.
Thus:
o their oxidesbecomestrongerbases
O they form positive ions more readily
O they form covalentbonds lessreadily.
-H
Gt'\ tlz'l
t/''Ea'
Physical properties
of the elements
I Group1: All aresolidmetals;their meltingtemperatures

and hardness
decrease down the group; all conduct electricity.
o Group 2: AII are solid metals; their melting temperatures and hardness
decrease down the group (except magnesium which has a lower
melting temperature than calcium); all conduct electricity; their melting
temperatures are higher than the Group 1 element in the same period.
Flame colours of their compounds

O Group 1:
O Group 2:
,A l*
light out
3rd
Fig 1,6 Emissionof a spectrolline
lithium
sodium
potassium
calcium
strontium
barium
carmine red
yellow
lilac
brick red
crimson red
green.
o These colours are caused because:

I Heat causesthe compound to vaporise and produce some atoms of
the metal with electrons in a higher orbital than the ground state
(e.g. in the 4th shell rather than the normal 3rd shell for sodium).
2 The electron falls back to its normal shell and as it does so, energy in
the form of visible light is emitted. The light that is emitted is of a
characteristic frequency, and hence colour, dependent on the energy
level difference between the two shells (seeFigure 1.6).
Ionisation
energies
o The value of the lst ionisation energy for Group 1 and of the lst and
2nd ionisation energies for Group 2 decreases down the group. This is
'RGANrc cHEMrsrRy, ENERGETT.',KrNETrcs AND EeurLrBRruM
2CrOn'z-(aq)
+ 2H.(aq) + Cr,O,'-(aq) + HrO(l)
Addition of alkali will remove the H'ions, causingthe equilibrium to
move to the left.
O Catalyst. This has no effect on the position of equilibrium. What it
doesis to increase the rate of reaching equilibrium, thus a catalyst
allows a reaction to be carried out at a reasonablerate at a lower
temperature.
Optimum industrial
conditions
Temperoture
Many industrial reactions,such as the Haber processfor manufacturing
ammonia, are reversibleand exothermic. For such reactions:
o If a high temperatureis used,the yield at equilibrium is small, but the
rate of reaction is fast.
r If a low temperatureis used,the theoretical yield is higher, but the rate
of reactionis slow.
O In systemssuch as this, a catalystis used to allow the reaction to
proceedrapidly at a temperatureat which the yield is reasonablygood.
This is often called a compromisetemperature,balancing yield with
rate. Any unreactedgasesare then separatedfrom the products and
recycledback through the catalystchamber.
Pressure
processes
Allindustrial
thatinvolve
passing
gases
through
a bedof
catalyst
mustworkabove
pressure
1 atmosphere
inorder
to
force
thegases
through
thesystem.
O High pressuresare extremely expensive,and are only used if the yield at

lower pressuresis too small to be economic.
o Two examplesof manufacturing processesthat usevery high pressures
are the Haber processand the polymerisation of ethene.
Checklist
Beforeattempting the questionson this topic, check that you:
J Understandthat equilibria are dynamic.
J Can deducethe effect of changesin temperature,pressureand
concentration on the position of equilibrium.
lJ Can predict the economic conditions for an industrial process.
yourknowledge
Testing
andunderstanding
ffi
Theanswers
to thenumbered
questions
areonpage
129.
Considerthe reversiblereaction at equilibrium:

A(g) + B(g)
Which statementsare/is true about this system?
i
ii
There is no further changein the amounts of A or B.
No reactionsoccur, now that it has reachedequilibrium.

iii
The rate of formation of B is equal to the rate of formation of A.
Considerthe equilibrium reaction:
NrOn(B)+ 2NO,(g) NI = +58.1 kJ mol-'
Stateand explain the effect on the position of equilibrium of:
eRouP I ANo Gnoup 2

O Addition of aqueous sulphate ions to a solution of Sr'* or Ba'* ions
produces a white precipitate of metal sulphate:
Ba'.(aq) + SOn'-(aq)- BaSOn(s)
Thermal
â/
H
of nitrates
and carbonates
o Thermal stability increases down both groups:

o Group 2 nitrates all decomposeto give a metal oxide, brown fumes of
nitrogen dioxide, and oxygen:
2Ca(NOr)r- 2CaO+ 4NO, + O,
O Group 1 nitrates, except lithium nitrate, decomposeto give a metal
nitrite and oxygen:
2NaNO,-- 2NaNO,r O,
but
4LiNO,,-- ZLirO+ 4NO, + O,
o Group 2 carbonatesall decompose(exceptbarium carbonatewhich is
stableto heat) to give a metal oxide and carbondioxide:
CaCO',-CaO+CO,
t Group 1 carbonatesare stableto heat exceptfor lithium carbonate:
Li?CO,-Li'O+CO.
Thecompound
is morelikely
to be
decomposed
onheating
if thecation
polarises
theanion.
Thus
(cation
Group
2 compounds
2+)
decompose
morereadily
thanGroup
(cation
1 compounds
only1+).
Compounds
ofmetals
higher
ina
group
(smaller
ionic
radius)
decompose
moreeasily
than
compounds
of metals
lower
inthe
Group.
'
stability
H
9
f__- Checklist
-
^-'-
Beforeattempting the questionson this topic, check that you know:

tJ ttre physical propertiesof the Group 1 and Group 2 elements
r-l ttre flame colours causedby their compounds
iJ the trends in ionisation energieswithin a group
iJ ttre reactionsof the elementswith oxygen, chlorine and water
J the reactionsof their oxides with water
,J the oxidation statesof the elementsin Group 1 and in Group 2
,J the trends in solubilities of Group 2 sulphatesand hydroxides
.J tfre reasonfor the trend in thermat stability of Group 1 and Group 2
nitrates and carbonates.

Lithium
o Which Group 1 metal has the highest melting temperature?
K is +1,Cais +2
o What is the oxidation number of:

i potassiumin KrCrrO,and
ii calcium in CaCOr?
It is extremely
insoluble.
o Barium compounds normally are poisonous,but barium sulphateis

given to people in order to outline their gut in radiography (X-ray
imaging).Why is barium sulphatenot poisonous?
cHEMrsrRy,
"RGANrc
Pressure:
Uses
ofammonia:
I manufacture
ofnitric
acid
t manufacture
offertilisers
suchas
ammonium
nitrate
andurea
o manufacture
ofpolyamides
such
asnylon.
200 atm. The yield at 1 atm is too low, and so a high

pressure is necessary even though it is very expensive.
Catalyst:
Iron.This allows the reaction to proceed at a fast, and
hence economic, rate at a moderate temperature.
Yieldper cycle: 15o/o.The gasesfrom the catalyst chamber are cooled in
order to liquefy the ammonia, and then the unreacted
nitrogen and hydrogen are recycled, giving a final
conversion of nearly lOoo/o.
The oxidation
of ammonia
to nitric
acid
This happensin three stages:

1 The ammonia and air are passedover a platinum/rhodium catalystat
900 "c:
4NH.(g) + 5O,(g)+ 4NO(g) + 6H,O(g)
2 On cooling, the nitrogen(Il) oxide reactswith more air:
aNO(g) + 2O,(g)-* 4NO,(g)
3 The nitrogen(IV) oxide and air are then absorbedinto water:
4NO,(g) + O,(g) + 2H,O(l) + 4HNO,(aq)
The contact
acid
process
for the manufacture
of sulphuric
O This takesplace in three stages:

1 The combustion of sulphur:
S(l)+O,(g)-SO,(8)
Uses
ofsulphuric
acid:
I themanufacture
offertilisers
suchasammonium
sulphate
r themanufacture
of phosphate
fertiliser
r themanufacture
ofpaints
and
detergents.
2 The reversibleoxidation of the sulphur dioxide:

SOr(g)+'lrOr(g)+ So,(g)
3 Absorption by the water in 98o/osulphuric acid.
I The conditions for stagetwo, which is exothermic and has fewer gas
moleculeson the right, are:
Temperature: 425 "C. A higher temperaturewould reducethe yield,
and a lower one would make the reaction
uneconomically slow.
Pressure:
2 atm. This is enough to force the gasesthrough the
plant. A higher pressureis not necessarybecausethe
yield is high under theseconditions.
Catalyst:
Vanadium(v)oxide.
YieId:
per cycle.The gasesfrom the catalystchamber are
960/o
passedinto the absorbercontaining the 980/osulphuric
acid, and all the SO,is removed.The gasesthen go
back through another bed of catalyst,giving a final
conversionof 99.8o/o.
Manufacture
of aluminium
O Aluminium is 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.
o The ore contains aluminium oxide (amphoteric) with large impurities of
iron oxide (basic) and silicon dioxide (weakly acidic). The ore is treated
with a hot 10olosolution of sodium hydroxide, which reacts with the
amphoteric aluminium oxide to form a solution of sodium aluminate.
Iron oxide does not react as it is a base, and silicon dioxide does not
El
o*.ANIc
cHEMrsrRy, ENERGETT.',KrNETrcsAND EeurLrBRruM
And the structural representationof this is:

H
t
H-C t
H
l
l
C-O-
H + 3O:O
2O-C:O
+ 3H-O
-H
Calculatethe enthalpy changefor this reaction using the averagebond enthalpy valuesgiven below.
t3I
Bond
C-H
c-o
Ot:O
Averagebond energy/kJmol-'
+ 4L2
+ 360
+ 496
Bond
C-C
+ 348
+ 463
+ 743
o-H
c:o
tt Draw and label an enthalpy level diagram to representthis reaction.
I2l
Gotaf 1O marks)
200L
Unit Test2 question5f
lJune
5 a The reaction in the Haber Processthat is used to produce ammonia is:

N,(g) + 3Hr(g) : 2NH,(B)
N:I=-92k1mol-'
i What temperatureis used in the Haber Process?
tl]
ii Justify the use of this temperature.
t3I
lii Name the catalystused in the Haber process.
tll
iv How does a catalyst enable a reaction to occur more quickly?
t2l
b Another industrial processis the one which recoverschlorine from HCl, which often is a by-product in
organic preparations
NI = -115 kJ mol-'
rhisisahomog.-X.:l13)oi'*!?.il,u1*11i1f,1;"3,?:1t'
Statethe meaning of the terms

i homogeneous
ii dynanic equillbrium
Stateand explain the effect on the position of equilibrium of the reaction in b of:
I decreasingthe temperature.
ti decreasingthe volume of the reaction vessel
tlI
l2l
l2l
r2l
(Total 14 marks)
lMay 2002 question3 Unit Test2 & lanuary 2001 question4 Module Test2l
a
b
c
d
e
Aluminium metal is manufactured by a processin which purified bauxite, dissolved in molten cryolite,
is electrolysedat 800'C. Graphite electrodesand a current of about 120 000 amperesare used.
Give the ionic equation for the reaction taking place at the anode.
tlI
Give the ionic equation for the reaction taking place at the cathode.
tlI
Statewhich of thesereactionsis an oxidation process.
tll
Explain why the anodesneed to be replaced frequently.
tzl
Explain why an electrolyte of pure molten bauxite is not used.
r2l
Gotaf 7 marks)
lJune2001 Unit Test2 question7f
[Paper total 6O marks]
B.NDTNG ^ND MAIN GRoup
II
cHEMIsrRy
"t*ucruRE,
Halides
o All hydrogen halides are covalent gases,but are soluble in water because
they reactwith water to form ions. Their solutions are strongly acidic:
HCI + HrO + H,O*(aq) + Cl-(aq)
Hydrogen fluoride is a weak acid and is only partially ionised.
All
metal halides are soluble in water, except for silver and lead halides.
o
Test for
halides
(only
examined
at AS in Unit
Test 38)
To a solution of the halide add dilute nitric acid to prevent carbonates

from interfering with the test. Then add silver nitrate solution followed by
ammonia solution.
Bromide
Chloride
cream precipitate
Addition of Ag-(aq) white precipitate
Addition of
precipitate dissolves no change
dilute NH,
Iodide
yellow precipitate
no change
Addition of
concentrated NH, precipitate dissolves precipitatedissolvesno change
Addition
halide
of concentrated
sulphuric
acid
to the solid
o Chloridesproduce steamyacid fumes of HCl.

O Bromidesproduce steamyacid fumes of HBr with some brown bromine
and someSO,gas.
a Iodides give clouds of violet iodine vapour.
This is due to the fact that HBr is just powerful enough as a reducing agent
to reducesome of the concentratedsulphuric acid to sulphur dioxide and
itself be oxidisedto bromine.
The HI initially produced is a very powerful reducing agent. It reducesthe
concentratedsulphuric acid and is itself oxidised to iodine.
Oxidation
numbers
o Chlorine is 0 in Clr.
o Chlorine is -1 in chlorides.
o Chlorine is +1 in CIO- ions.
O Chlorine is +5 in CIO; ions.
Redox
is a stronger
Chlorine
oxidising
thanbromine,
whichis
agent
thaniodine.
stronger
o Chlorine is a powerful oxidising agent and is reducedto the -1 state.

o The half equationis:
Clr(aq)+ 2e-.. 2Cl-(aq)
and is similar for the other halogens.
o Chlorine disproportionatesin alkali at room temperature:
Cl,(aq) + 2OH-(a9)- Cl-(aq)+ OCI-(aq)+ H,O(l)
(+1)
(0)
(-1)
o Chlorate(I) compounds disproportionatewhen heated:
3OCf+2CI-+ClOr3x(+1) Zx(-L) (+s)
from
seawaterby bubbling in chlorine gaswhich
o Bromine is extracted
the
Bf
ions.
oxidises
LABoRATORY
CH EM ISTRY
I
chemistry
38:Laboratory
[]nit Test
ffi
J this is a written paper,taken by alt candidates.

J tt is designedto assessa candidate'sability (relatedto the topics in
Units 1 and 2) to:
I
ll
C=C group
C-OH group
Decolourises
brown bromine
in hexane
Steamyfumes
with PCl.
Organic halides Warm with

sodium
hydroxide
solution. Acidify
with dilute nitric
acid and then
test as for ionic
halides as on
page 55
evaluate information generated from experiments

describe and plan techniques used in the laboratory.
J Tests
o You should know the testslisted in Unit 3A above.
o You should also know the testsfor alkenes,the OH group and the
halogenin halogenoalkanes.
o You should be able to deducethe identity of a compound from the
resultsof a seriesof tests.
J Techniques
You should be able to describetechniquesusedin:
o titrations and enthalpy changemeasurements
O simple organic proceduressuch as distillation and heating under
reflux.
[l Phnning
You should be able to:
O Plan a seriesof teststo determine the identity of an inorganic or
organic compound.
O Describehow to make up a solution of known concentration for
titrations.
O Plan an experiment to determine the enthalpy of a reaction such as
the combustion of a liquid, or the neutralisation of an acid.
o Plan an experiment to follow the progressof a reaction in which
there is a changein physical state,such as the production of a gas.
[l calculations
You should be able to calculate:
o empirical formulae
O reacting masses
o resultsfrom titration data
o enthalpy changesfrom experimentaldata.
iJ Evaluation
You should be able to criticise:
o an experimental plan or apparatus
o the resultsof an experiment in terms of significant figures,accuracy
or experimentalerror etc.
[J sarety
You should be able to suggestspecificsafetyprecautionswhen a substance
is flammable, toxic or irritating.
tt*,rcruRE,
B o N D T N GA N D M A r N G R o u p c H E M r s r R y
Practlce Test: Unit L

Time allowed Lhr
All questionsare taken from parts of previous EdexcelAdvancedGCE questions.
The answersare on pagesIZ5-t26.
Complete and balancethe following equations.
i Ca+O,
t1I
ii NarO + HrO +
tlI
iii NarO + HCI +
l2l
b Stateand explain the trend in thermal stability of of the carbonatesof the Group 2 elementsas the
group is descended.
t3l
(Totat 7 marks)
[May 2002 Unit Test1 question2]
La
2 a Statethe structure of, and the type of bonding in, the following substances.Draw labelled
diagrams to illustrate your answers.
i
Graphite
t4I
ii Sodium chloride
t3I
b Explain why both graphite and sodium chloride have high melting temperatures.
t3l
c i Explain why graphite is able to conduct electricity in the solid state.
r2l
ii Explain why sodium chloride conducts electricity in the liquid state.
tlI
(Totat 13 marks)
lMay 2002 Unit TestL question6l
3a i
ii
Define the terms atomic number and mass number

t2l
Identify the particle that contains 35 protons, 44 neutrons and 34 electrons.
tlI
Bromine consistsof two isotopesof massnumbers 79 and 81. A sampleof bromine gas,Br, was
examined in a massspectrometer.The massspectrumshowing the molecular ions is given below.
100
Relative
intensity
158
160
162
b i Explain how the moleculesin the sampleare ionised.

ii Statehow the resulting ions are accelerated.
iii Identify the speciesresponsiblefor the peak at mle = 160.
t2l
tll
tl]
(Total 7 marks)
llanuary 2001 CH1 questionL & lune 2001 Unit TestL question3l
Hydrogen forms compounds with most non-metallic elementsand with some metals.
Calculatethe empirical formula of the compound used in the manufactureof artificial rubber,which
has the following composition by mass:
hydrogen
tI.Lo/o
carbon
88.9o/o
t3l
b The boiling temperaturesof hydrogen chloride and hydrogen iodide are:
-85'C
-35 "C
hydrogen chloride
Hydrogen iodide
Explain why hydrogen iodide has a higher boiling temperaturethan hydrogen chloride
l2l
c Draw and explain the shapesof:
i
ii
the PH. molecule

the AIH; ion.
I2l
I2l
El
to"oRAroRY
c H E Mr s r R Y I
i
Explainwhy there is a lossin massas the reactionproceeds.
t2l
Explain the shapeof the curve drawn for experiment 1.
ii
t2l
Draw curveson the graph aboveto representthe resultsyou would expect for experiments2, 3
and 4.
tsl
i
Calculatethe massof calcium carbonatethat exactly reactswith 50.0 cm3of 1.00 mol dm-'
aqueoushydrochloric acid. (Molar massof CaCOr= 100 g mol-')
t3l
Basedon your answerto c part (i), suggesta suitablemassof calcium carbonateto use in the
ii
experiments.Explain your answer.
t2l
(Total 1.2 marks)
[anuary 2002 Unit Test38 question2]
A student was required to determine the enthalpy change for the reaction betweeniron and copper
sulphatesolution. The student produced the following account of their experiment.
A pieceof iron,massabout3 g, was placedin a glassbeaker.Then 50 cm'of 0.5 mol dm-'aqueous
coppersulphatesolutionwas measuredusinga measuringcylinderand addedto the beaker.The
beforethe additionand everyminuteafterwards
temperature
of the mixturewas measuredimmediately
untilno furtherchangetook place
F e + C u S O o-
F e S O o+ C u
Timing
Before
addition
1 min
2 mins
3 mins
4 mins
5 mins
Temperature/'C
16
27
29
26
24
22
Suggesttwo improvementsyou would make to this experiment. Give a reasonfor each of the
improvements suggested.
t4l
oC occurred
b In an improved version of the same experiment a maximum temperaturerise of I5.2
when reacting excessiron with 50.0 cmt of 0.500 mol dm-' aqueouscopper sulphate solution.
i
Using this data and taking the specificheat capacityof all aqueoussolutionsas 4.181 g-' deg',
calculatethe heat change.
ii
Calculatethe number of moles of copper sulphate used.
iii Calculatethe enthalpy changefor this reaction in kJ mol-'
r2l
(Total 8 marks)
[une 2002 Unit Test38 question4]
tu
A student carried out an experiment to find the percentage of calcium carbonate, CaCO, in a sample
of limestone following his own plan. The student's account of the experiment, results and calculations
of the mean titre are given below.
Account
I
Massof pieceof limestone= 5.24 g
acid (an excess)to a
ll
A pipettewas usedto transfer50 cm'of 2.00 mol dm-'aqeoushydrochloric
placed
left
therewas no more
piece
and
until
in
the
beaker
was
limestone
of
100 cm' beaker.The
effervescence.
Equation
Ill
lV
CaCO.(s)+ 2HOl(aq)-
CaOl'(aq)+ CO'(g)+ H,O(l)
The acidicsolutionin the beakerwas filteredinto a250 cm3volumetricflask.A smallamountof the

solidimpurityremainedin the filterpaper.The solutionin the volumetricflaskwas carefullymadeup
to 250 cm'with distilledwater.
A pipettewas usedto tranfer25.0 cm3portionsof the acidicsolutionto conicalflasks.The solution
was then titratedwith 0.100mol dm-'aqueoussodiumhydroxide.
HCI(aq)+ NaOH(aq)-
tttaQl(aq)+ H,O(l)
y, e*Ufrzo*irr
2 OfAA"niL,
l,/Va-/ a.tA VL'771

/
J,VVI
Mkr
Jvvl.v))
u
ar4d,e4uilib r i/,u,t
I
[nergetics
Introduction
o Statesymbolsshould alwaysbe used in equationsin this topic.
O In definitions in this topic, there are three points to note:
1 the chemical changethat is taking place
2 the conditions
3 the amount of substance(reactantor product).
o It alwayshelps to add an equation with statesymbolsas an example,
becausethis may gain marks lost by omission in the word definition.
O It is assumedfor simplicity that the value of LH is an indicator of the
direction of a chemical reaction. The more exothermic the reaction, the
more likely it is to take place,but other factors,such as activation
energy (seepage 44), alsodetermine whether the reaction happens.
Things to learn
It followsfromthisdefinition
that
theenthalpy
offormation
ofan
initsstandard
state,
is
element,
zero.
giveanequation
Youshouldalways
forthisandother
asanexample
enthalpy
definitions.
J Standardconditions are:
O gasesat a pressureof L atmosphere
o a statedtemperature(usually 298 K)
o solutions, if any,at a concentration of 1.00 mol dm-'
o substancesin their most stablestates,e.g. carbon as graphite not
diamond.
[-l Standardenthalpy of formation, AI{'is the enthalpy change,under
standardconditions, when one mole of a compound is formed from
its elements in their standardstates,e.g. AFII'for ethanol is the
enthalpy changefor the reaction:
2C(graphite)+ 3H,(g)+'/,Or(g) - C,H.OH(l)
[f Standardenthalpy of combustion, AF/,'is the enthalpy change,under
standardconditions, when one mole of a substanceis completely
burned in oxyger, .g.AI1.'for ethanol is the enthalpy changefor the
reaction:
C,H'OH(I) + 3O,(g)- ZCO,(g)+ 3H,O0)
AI/:.,, of an acid is the enthalpy
E Standard enthalpy of neutralisation
change,under standardconditions, when the acid is neutralisedby
of sulphuric acid,
baseand one mole of water is produced,e.g.A.Fif;",,
by sodium hydroxide solution, is the enthalpy changefor the reaction:
'/,HrSOn(aq)
+ NaOH(aq)-'l,Na,SO,(aq)+ H'O(l)
E N e R G E T T c sr l
Checklist
Beforeattempting questionson this topic, check that you:
:J Can define enthalpy of atomisation.
iJ Can define enthalpy of hydration.
;J Can define lattice energy.
iJ Can construct a Born-Haber cycle.
IJ Cun use a Born-Haber cycle to calculatelattice energy or electron
affinity.
[] U.tdetstandwhy the value of AF/**from Born-Haber might be more
exothermic than the theoretical value.
[,] Can stateand explain the changein solubilities of the Group 2
sulphatesand hydroxides.
#- -x
Lvve
GT
For the following questions, cover the margin, write your answer, then
check to see if vou are correct.
a MgCO,
b MgCO,
C NAF
I In each of the following state which compound has the larger (more
exothermic) lattice energy:
a MgCO. or BaCO,
b NarCO. or MgCO,
c NaF or NaCl.
Al*>Mg'.rBa'*>Na*
I Arrange the following ions in order of decreasing (less exothermic)

enthalpy of hydration: Na*, Mg'*, Bat* and Alt*
Ba(0H),
o State the formula of the most soluble Group 2 hydroxide.
tothenumbered
Theanswers
questions
132.
areonpage
The following data, in kJ mol-', should be used in this question.

Enthalpies of atomisation: calcium +193; chlorine +LZL.
Ionisation energies for calcium: 1st +590; 2nd +1150
Electron affinity for Cl(g): -364
Lattice energies:for CaClr(s) -2237; for CaCl(s) -650 (estimated).
a
Construct a Born-Haber cycle for:
i the formation of CaCl(s)

ii the formation of CaClr(s).
Calculate the standard enthalpy of formation of:
i CaClr(s)
ii CaCl(s)
iii hence calculate the enthalpy of the reaction:
2CaCl(s) * Ca(s) + CaCl'(s)
and comment on the fact that CaCl(s) does not exist.

Comment on the values of the lattice energies, in kJ mol-', given
below:
NaF
MgI,
Experimental Theoretical
-912
-918
-t944
-2327
EI
euANTrrATrvE EeurLrBR'A AND FUN.TT'NAL GRoup cHEMIsrRy

"r*roDrcrry,
ll
Table
ThePeriodic
'&
Inffoduction
;J you will need to look again at Topic 1.4.

iJ fne elementsbecomemore metallic down a Group. This meansthat
their compounds,such as their chlorides,becomemore ionic and their
oxidesbecomemore basic.
f
fn. elementsbecomeless metallic from left to right acrossa Period.

This meansthat their chloridesbecomemore covalent and their oxides
becomemore acidic.
[-] There are many formulae and equationsthat must be learnt in

this Topic.
[l fne propertiesof elementsand their compounds change steadilyfrom
the top to the bottom of a Group and from left to right acrossa Period.

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:
AI
Si
Mgo
Al2o3
Chlorine NaCl
MgCl,
Alcl, (')
Water
NaOH +
MgO + No
H2
H,tn'
Na
Oxygen
Mg
Na,O or
N a rO,(t)
reaction
sio,
PnO,o
SO,
sicl4
PCI,
(t)
PCl,
SrCl,
No
reaction
No
reaction
No
reaction
CI
Ar
No
reaction
No
reaction
No
reaction
HCI +
HOCI
No
reaction
("
(')
Notes: with excessoxygen sodium peroxideis formed, ''' aluminium chloride is covalent, with excess
(n)with
chlorine,
steam.
Thehydroxides
lessbasicand
become
moreacidicasthesurface
charge
of thecationincreases.
density
is sucha weakacidthat
dioxide
Silicon
molten
hydroxide
is required.
sodium
Theoxides
form
of thenon-metals
increasingly
strongacidsasthe
number
of oxygen
atomsin theacid
increases.
[l uetA
hydroxides
and oxides
alkaline: NaOH(s) + aq - Na-(aq) + OH-(aq)
t NaOH
o Mg(OH), basic: Mg(OH),(s) + 2H.(aQ) - Mg'.(aq) + ZH,OQ)
basic: MgO(s) + 2H-(aq) -- Mg'*(aq) + H,O(l)
o MgO
amphoteric: Al(OH),(s) + 3H.(aQ)- Al'.(aq) + 3H,O(l)
a AI(OH),
Al(OH),(s) + 3OH-(a9) - Al(OH).3-(aq)
amphoteric: AlrO.(s) + 6H.(aQ) - 2Al'.(aq) + 3HrO(l)
o Al2O3
Al,O,(s) + 6OH-(aq) + 3H,O(l) '2Al(OH)6'-(aq)
[] Non-metal
o SiO,
O P4O6
o P4O10
oxides
weakly acidic: SiOr(s) + 2NaOH(l) - NarSiO'(l) + HrO(g)
weakly acidic: PnOu+ 6HrO ' 4H'PO, + 4H-(aq) + 4HrPOrstrongly acidic: PnO,o+6HrO -' 4HrPOn- 4H'(aq) + 4HrPOn-
eNERGErrcs I
Workêi,exiloLf.b
A 0.120g sample
wasburntandtheheatproduced
of ethanol
warmed
250g
'Cto 20.72
'C.The
from17.30
ofwater
specific
heatcapacity
ofwateris4.18
J gto0-t.Calculate
A{omustion
of ethanol.
= 250g x 4.18J gj o6-tx3.42'C = 3574J.
Answer.Heatproduced
g mol-'= 2.61x 10-'mol
Amount
of ethanol = 0.120g146
=
produced
per
Heat
x 10-3
ffi010 3574J12.61
mol= 1370x 10'J mol-'.
= -1370 kJ mol-t
A4omuustion
Calculation
Calculation
of A^tI values from average bond enthalpies
O Draw the structural formulae for all the reactants and all the products.
il Decide what bonds are broken in the reaction and calculate the energy
requiredto breakthe bonds (endothermic).

Decidewhat bonds are made in the reactionand calculate the energy
releasedby making the bonds (exothermic).
Add the positivebond breakingenthalpy to the negative bond making
enthalpy.
Workpi,oxiloLplr,
Calculate
theenthalpy
of thereaction:
H
H
+ H_
t l
--__________+
H_ C - C - H
Given
thefollowing
average
bondenthalpies/kJ
mol-':
C-Cis +348,C=Cis +612,H-His +436,andC-His +412.
(endo)
Answer. break
C=C +612
H-H +436
(exo)
make
-348
c-c
2 x C-H -824
-1172
+1048
-124
=
=
A4,,,rion+1048 1172
kJ mol-'
Checklist
i
Kno* the standard conditions for enthalpy changes.
J Kno* the signs of A,Hfor exothermic and endothermic reactions.

J Can define the standard enthalpies of formation, combustion and
neutralisation.
l-l Understand an energy level diagram.
J Can define and use Hess'sLaw.
li Know how to calculate values of A/{from laboratory data.
iJ Can use bond enthalpies to calculate enthalpies of reaction.
El
o * o A N r c c H E M I s r R y , E N E R G E T T c sK
, rNETrcsAND EeurLrBRruM
ffi
try
Theanswers
tothenumbered
questions
areonpages
126-127.

1 Statethe conditions usedwhen measuringstandard enthalpy changes.
2 Give equations,with statesymbols,which representthe following
enthalpy changes:
i
the enthalpy of formation of ethanoic acid, CH,COOHQ)
ii
iii
the enthalpy of combustion of ethanoic acid

the enthalpy of neutralisation of an aqueoussolution of ethanoic
acid with aqueoussodium hydroxide.
Draw an enthalpy level diagram for the following sequenceof reactions:

I'N,(g)+ O,(g) -.' NO(g) +'t,O,
A,H= +90.3 kJ mol-'
NO(g)+'1,O.(g)' NO,(g)
A,H= -57.L kJ mol-'
and hence calculatethe enthalpy changefor the reaction:

'/,Nr(g)+ or(g) * Nor(g)
4 Given that the standardenthalpiesof formation of NOr(g) and NrOn(g)
are +33.9 kJ mol-' and +9.7 kJ mol-' respectively,calculatethe enthalpy
changefor the reaction:
2NO,(g)- N,O,(g)
5 The standardenthalpy of combustion of lauric acid,
CH3(CHr),'COOH(s),
which is found in someanimal fats,is -7377 kI
mol-'. The standardenthalpiesof combustion of C(s) and Hr(g) are -394
kJ mol-' and-286 kJ mol-1.
Calculatethe standardenthalpy of formation of lauric acid.
6 100 cm' of L.00 mol dm-'HCI was addedto 100 cm'of 1.00 mol dm-'
NaOH in a polystyrenecup, both solutions being initially at 2L.IO'C.
On mixing the temperaturerose to 27.9OoC.Determine the enthalpy of
neutralisation and statewhether the reaction is exothermic or
endothermic. You may assumethat the polystyrenecup has a negligible
heat capacity,the solution has a density of L.00 g cm-t and that the final
solution has a specificheat capacityof 4.18 J g-' oC-'.
7 Calculatethe enthalpy changefor the reaction:
CrH,(g)+ HrO(g)- CHTCHTOH(g)
given the following averagebond enthalpies in kJ mol-':
C-C +348; C=C +612; C-H +41,2;H-O +463; C-O +360.
oRGANrc cHEMrsrRY I
I
0rganicchemistry
da
LN
Introduction
i.J Organiccompoundsconsistof a chain of one or more carbonatoms
and contain functional groups(seeTable2.1).The functional group
givesthe compound certainchemicalproperties.For instancethe C=C
group (exceptin benzenerings) reactsin a similar way in all
compounds.Thus knowledgeof the chemistryof ethene,H,C=CH,
enablesyou to predict the reactionsof all compoundscontaining the
C=C group.
Substance
Alcohol
Aldehvde
Group
- CI - O H
I
H.tC:o
Ketone
R tc:o
.
R'/
R/
Acid
_C
..O
\oH
Ester
arO
R_C
to-R'
*
Acid
chloride
_C
,aO
tcl
*
Amide
_C
,ro
\NHZ
Nitrile
Amine
_C =N
-C-NHz
I
group.
Toble 2.1 Functionolgroups.*Thesewill only be met at A2. R is o carbon-contoining
E you must learn the equationsand conditions for the reactionsin the
specification.
tfa
LN
youwritestructural
When
formulae,
that:
check
atomhasfourbonds
carbon
oevery
hastwobonds
and
oevery
oxygen
andevery
halogen
oeveryhydrogen
have
onlyonebond.
Thingsto learn
o Homologous series: a seriesof compoundswith the samefunctional

group, the samegeneralformula, and where one member differs from
the next by CHr.
r Emplrical formula: showsthe simplestwhole number ratio of the
atoms presentin one molecule.
I Molecular formula: showsthe actual number of atoms presentin
one molecule, e.g. propane is CrHr.
o Structural formula: shows each atom in the molecule separatelyand
how it is bonded. A more condensedway is to show the groupings
around each carbon atom, e.g. propane can be written as CHTCH,CH3
and propan-2-ol as CH'CH(OH)CH3.
fl Isomers: two or more compounds with the samemolecular formula.
f Homolytic fission: when a bond breakswith one electron going to
each atom (forming radicals).
ff Heterolytic fission: when a bond breakswith the two electrons going
to one atom.
E Substitution: a reaction in which an atom or group of atoms in one
molecule is replacedby another atom or group of atoms.
[l laaition: a reaction in which two moleculesreact together to form a
single product.
. H E M T . A L E e u r L r B R r u Mr l
All partial pressuresare equilibrium values.
So for the reaction:
CO,(g)+ C(s)+2CO(g)
= p(CO)'"' and its units are atm2=atm
160
in
isa solidit is ignored
Ascarbon
theexpression.
atm
P(co,)*
Colculotionsinvolving K,
o The calculation of Kofrom equilibrium data is done in a similar way to

those involving K.:
i Draw up a table and fill in the initial number of moles,the change
for eachsubstance,the equilibrium number of moles of each
substanceand the total number of molesat equilibrium.
ll
Convert equilibrium molesto mole fraction.
iii Multiply the mole fraction of eachby the total pressure.
lv Statethe expressionfor K'.
Y Substituteequilibrium concentrationsinto the expressionfor Ko.
vl Work out the units for K' and add them to your answer.
oh
oxal,u?12
placed
to 175"C.When
andheated
in avessel
0.080molof PCluwas
was2.0atm
it wasfoundthatthetotalpressure
hadbeenreached,
equilibrium
K,torthereaction:
haddissociated.
Calculate
of thePClu
andthat40o/o
+ PCl,(g)
+ Cl,(g)
PCl,(g)
60%wasleft.Thusat equilibrium:
AnswenAs40%haddissociated,
waspresent
andtherefore
0.60x 0.080= 0.048molof PClu
hadreacted.
0.080- 0.048= 0.032molof PClu
PCI.
PCI,
cr,
Total
0
0
0.080
-0.032
+0.032
+0.032
Change/mol
amount 0.60x 0.080
Equilibrium
= 0.048
0.032 0.112
0.032
/mol
0.032t0.1120.032t0.112
0.04810.112
Molfraction
=0296
=0286
= 0.429
pressure
x2
0.286x 2
0.286
0 . 4 2 x92
Partial
= 0.571
= 0.571
= 0.857
/atm
lnitialamounVmol
= 0.571
p(Cl,),.
atm= 0.38atm
atmx 0.571
l( = p(PCl,),'
Variation
of K with
conditions
thequotient
whenthe
Konlyequals
This is the only factor that alters the value of K.
o Temperature.
lf the
is atequilibrium.
system
i
If a reaction is exothermic left to right, an increase in temperature
quotient
is greater
thanK,the
will lower the value of K. This means that the position of
willmoveto theleftuntil_
reaction
equilibrium will shift to the left (the endothermic direction).
lf thequotient
is
thetwoareequal.
ii
If a reaction is endothermic left to right, an increase in temperature
willmove
lessthanK thereaction
will
increase the value of K. This means that the position of
to therightuntilthetwoareequal.
will shift to the right.
equilibrium
alterthevalue
Temperature
changes
AH=0).Concentration
of K(unless
O Catalyst. This neither alters the value of K nor the position of
changes
alterthevalue
andpressure
equitibrium. It speeds up the forward and the reverse reactions equally.
of thequotient.
Thus it causes equilibrium to be reached more quickly.
oRGANrc cHEMrsrRY I
O Alkenesare oxidised by potassiummanganate(Vll)solution:

CH,CH=CH,+ [O] + HrO - CH'CH(OH)CHTOH
t l
C-C
l
Fig 2.5
Poly(ethene)
lLII
Ftg 2.6
Poly(propene)
conditions: at room temperature,when mixed with sodium hydroxide

solution it producesa brown precipitate.
o Alkenescan be polymerised. Etheneforms poly(ethene)(Figure2.5)
and propene forms poly(propene)(Figure2.6):
n-CHr-Qlf, + -(CH r-CHr)-,
conditions either: a very high pressure(about 2000 atm)
and a temperatureof about 250 "C
or: a catalystof titanium(Iv) chloride and triethyl aluminium
at 50 oCand pressureof about L0 atm.
Halogenoalkanes
(e.9. 2-iodopropane,
CHTCHICH,)
o They substitute with aqueous sodium (or potassium) hydroxide

to give an alcohol:
CH3CHICH,+ NaOH - CH.CH(OH)CH.+ NaI
Therateofallthese
reactions
increases
C-Clto C-Brto C-|,
thebondenthalpy
because
and
hence
thebond
strength
decreases
C-Clto C-Brto C-|.Theweaker
the
bondthelowertheactivation
energy
andhence
thefaster
thereaction.
conditions:boil under reflux with aqueoussodium hydroxide.

o They eliminate with ethanolic potassium hydroxide to give an
alkene:
CH3CHICH,+ KOH - CH,CH-CH'+ KI + H,O
conditions: boil under reflux with a concentratedsolution of potassium
hydroxide in ethanol, and collect the gaseouspropene over water.
o They substitute
with potassium cyanide:
CH3CHICH.+ KCN' CH,CH(CN)CH,+ KI

conditions: boil under reflux with a solution of potassiumcyanide in a
mixture of water and ethanol.
O With ammonia they form amines:
CH3CHICH,+ 2NH, - CH,CH(NHr)CH,+ NH'I
conditions: heat excessof a concentratedsolution of ammonia
in ethanol with the halogenoalkanein a sealedtube.
-C-OH
H
1 0
-cl l
-c-c-oH
t
-C-
-c-c-oH
l
0
t- c - l
I
3o
Ftg 2.7 1", 2" and 3" alcohols
o The test for halogeno compounds:

1 Warm the substancewith aqueoussodium hydroxide.
2 Add dilute nitric acid until the solution is just acidic.
3 Add silver nitrate solution.
Result:
t white precipitate,soluble in dilute ammonia indicateschlorocompound
O cream precipitate,soluble in concentratedammonia indicatesbromocompound
o yellow precipitate,insoluble in concentratedammonia indicatesiodocompound.
AIcohols
Primary (1') alcohols contain the CHrOH group.
Secondary(2') alcohols have two C atoms attachedto the CHOH group.
Tertiary (3') alcohols have three C atoms attachedto the COH group (see
Figare2.7).
ACID-BASE
EQUILIBRIA
Calculatethe value of K for the reaction:

2SO,(g)+ 2SO,(g)+ O,(g)
Theanswers
to thenumbered
questions
133.
areonpage
2 I.O mol of nitrogen(Il) oxide, NO, and 1.0 mol of oxygen were mixed 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 pressurein the vesselwas
4.0 atm. Calculatethe value of K, for the reaction:
2NO(S)+ O,(g) -- 2NO,(g)
3 This questionconcernsthe equilibrium reaction:
2SO,(g)+ O,(g)-- 2SO.(g) AH = -796 kJ mol-l
K. = 3 x 10*mol-t dm3at 450'c
a
2 mol of sulphur dioxide, I mol of oxygen and 2 mol of sulphur

trioxide were mixed in a vesselof volume l0 dmt at 450 "C in the
are initially in
presenceof a catalyst.Statewhether thesesubstances
equilibrium. If not, explain which way the systemwould react.
Stateand explain the effect on the value of K. and on the position of

equilibrium of:
i
decreasingthe temperature
decreasingthe pressure
ii
iii adding more catalyst.
equilibria
(g Acid-base
<ffi
Introduction
o It is essentialthat you can write the expressionfor K" of a weak acid.

O Make surethat you know how to use your calculatorto evaluate
logarithms, and how to turn pH and pK" valuesinto [H-] and K" values.
I This meansusing the lg key for log,oand 10'key for inverselog,o.
o Give pH valuesto 2 decimal places.
O Buffer solutions do not have a constant pH.They resistchangesin pH.
O You may use H-, H-(aq)or HrO- as the formula of the hydrogen ion.
d-a
LN
Thingsto learn
[| A Brsnsted-Lowry
acid is a substancethat donates an H- ion (a
proton) to another species.
tr n monobasic (monoprotic) acid contains, per molecule, one hydrogen
atom which can be donated as an H" ion. A dibasic acid contains two.
tr e Bronsted-Lowry
another species.
base is a substancethat acceptsan H* ion from
E K. = [H-(aq)][OH-(ag)]= 1.0 x 1O" mol' dm* at 25 "C.

f A neutral solution is one where [H-(aq)]= [OH-(aq)].
f
dmt).
pH = -log,o[H.(aq)],'ormore accurately= -log,o([HrO.(aq)]/mot
41,
oRcnrurc cHEMrsrRY I
zCOz+3HrO
cH2oHCH2OH
CH2BTCHTBT
o2
Spark
Brz
KMnOn
NaOH(aq)
cH3cooH
Boil under reflux
KtCtrOrlHrSOn(aq)
conc H2SO4
at 100'C
at l7O"C
Crz
W
NaOH
cH3cH2cl
NH, in ethanol
cH3cH2cN
Fig 2.8 Summory of
orgonic reoctions
cH3cH2NHz
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 alkenes are more reactive than
alkanes and react by addition, whereas alkanes react by substitution.
A C-I bond is weaker than a C-Cl bond, and so iodoalkanes are
rapidly hydrolysed by aqueous sodium hydroxide, unlike
chloroalkanes which react very slowly.
Quantitative
yieldis lessthan100%
Thepercent
because
of competing
reactions
and
handling
losses.
organic
chemistry
unThis involves calculation of empirical formulae from percent data (see

page 6).
w This involves calculation of percentage yield.
First calculate the theoretical yield from the equation (seepage B),
x 10oo/o
then the o/oyield = actual yield in grams
theoretical yield in grams
Applied
organic
chemistry
* Liquid versus gaseous fuels. You should consider the following

points:
L
2
3
4
5
the
the
the
a
easewith which gaseousfuels can be piped into the home

easier handling of liquid fuels at a filling station for cars
extent and type of pollution produced:
the quantity of carbon dioxide and any other greenhouse gases
produced per kilojoule of energy
the emission of oxides of nitrogen and sulphur, and the way in

which these can be limited
the emission of particulates
the energy produced per unit mass of fuel for aeroplanes

the extent to which the world's supply of fossil fuels is limited.
cHEMrsrRy,
"RGANrc
a Polymers. You should realisethat simple polyalkenesare resistantto

breaking down under environmental conditions. This is becauseof the
strength of the C-C and the C-H bonds.
* Organic halogen compounds. There are three main usesof these:
1
DDTis a chlorine-containing
pesticide
andit haseradicated
malaria
fromsomecountries,
butits
hasledto thedestruction
overuse
of
lt is a veryinertchemical
wildlife.
(owing
to thestrength
of theC-Cl
in an
bond)andso persists
organism,
beingstoredin fatty
tissue.
As polymers. PVC is used as a waterproofing material, as an

electricalinsulator and as a stableand maintenancefree material for
window frames.When burnt it producesharmful fumes of
hydrogenchloride.PTFEis usedas a non-stickcoatingfor saucepans
etc. Thesepolymers are very stableowing to the strength of
carbon-halogenand C-C bonds.
As herbicides.Complicatedchlorine compounds,such as 2,4-D and
2,4,5-Tare usedas selectiveweedkillers.They are stableand so
persistin the environment.
Chlorofluorocarbons(CFCs)make excellent refrigerants,but they
are so stablein air and water that they diffuseto the stratosphere
where they are broken down by light energyand form chlorine
radicals.Thesecatalysethe destructionof ozone.New substances
have been developedwhich contain hydrogenaswell as chlorine,
fluorine and carbon,and theseare lessstableand are broken down
by atmosphericoxidation.
Checklist
tJ Can name simple organic molecules.
tf Can write structural formulae of structural and geometric isomers.
lJ Know the reactions of alkanes with air and halogens.
Ll Know the reactions of alkenes with hydrogen, halogens, hydrogen
halides, potassium manganate(Vll) and in polymerisation.
[J Kno* the reactions of halogenoalkanes with potassium hydroxide (both
aqueous and ethanolic), potassium cyanide and ammonia.
[f Kno* the oxidation, dehydration and halogenation reactions of
alcohols.
'J
Can relate reactivity to bond strength and polarity and to the stability
of intermediates.
if Can calculate the empirical formula of a compound.
iJ Understand the advantages and disadvantages of the use of organic
compounds.

-ene
ethene
andbut-1
-ol
2-chlo
ro-3-methylpentan-1
o Which of the following compounds are membersof the same

homologousseries:
ethene CrHn,cyclopropaneCrHu,but-l-ene CHTCHTCH=CH,
but-1,3-dieneCH'=CHCH=CH',cyclohexeneCuH,o?
Name CH3CHTCH(CH3)CHCICHTOH
EI
euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMtsrRy

"a*roDrcrry,
=
tothenumbered L Calculate the pH of O.22 mol dm-' C2H'COOH which has pK. 4.87.
Theanswers
questions
133-134. 2 25 cm' of a weak acid HX of concentration 0.10 mol dm-t was titrated
areonpages
with 0.10 mol dm-' sodium hydroxide solution, and the pH measuredat
intervals. The results are set out below:
10
T2
20
23
24
25
26
30
Volume NaOH/cm3
pH
4 . 5 4 . 8 4.9 5 . 5 6 . 5 7 . 0 9 . 0 12.o 1 2 . 5
Draw the titration curve and use it to calculate pK, for the acid HX.
Suggest a suitable indicator for the titration.
3 a
b
Define a buffer solution and give the name of two substances that
act as a buffer when in solution.
Explain how this buffer would resist changes in pH, if small
amounts of H- or OH- ions were added.
4 Calculate the pH of a solution made by adding 4.4 g of sodium

ethanoate, CHTCOONa,to 100 cmt of a0.44 mol dm-'solution of
ethanoic acid. K" for ethanoic acid = I.74 x 10-smol dm-'.
ll
chemistry
@ 0rganic
',"'"\
..H
"
(H
fhings to learn and understand
Isomerism
iJ Structural. Therearethreetypes:
a
Carbon chain. Here the isomers have different arrangements of

carbon atoms in a molecule,
e.g. butane, CH.CH TCHTCH,and methyl propane, CH.CH(CHr)CH..
Positional. Here a functional group is on one of two or more

different places in a given carbon chain,
and propan-Z-oI, CH.CH(OH)CH..
e.g. propan-l-ol, CHTCHTCHTOH,
Functional group. Here the isomers have different functional groups,
e.g. ethanoic acid, CH3COOH and methyl methanoate, HCOOCH..

:J Stereoisomerism.
There are two types:
a
Thetwoisomers
arenot
interconvertible
atordinary
there
is no
temperatures
because
rotation
a double
bond.
about
Geometric. This is caused by having two different Sroups on each

carbon atom of a >C=C< group (see Figure 4.4).
H,C
\
/
H
CH,
C-C
/
\
H
cis-but-2-ene
H:C
\
/
H
H
C-C
/
\
CH.
trans-but-Z-ene
Fig . cisond transisomersof but-2-ene
EI
"a*roDrcrry,
euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy
Preparation
They can be made by the oxidation of a primary alcohol. The alcohol is
heatedunder reflux with dilute sulphuric acid and excesspotassium
dichromate(Vl).
Reactions
O + alcohols to produce esters:
+ CH3COOCTH,
+ HrO
CH3COOH+ CTHTOH
ethyl ethanoate
conditions: heat under reflux with a few drops of concentrated
sulphuric acid.
Testfor a carboxylic
acid.When
toaqueous
added
sodium
(orsodium
hydrogencarbonate
it gives
carbonate),
a gas,C0,,
which
turnslimewater
milky.
o + lithium tetrahydridoaluminate(Ill) to produce a primary alcohol:

CH3COOH+ a[H] 'CH'CH,OH + H,O
ethanol
followed
by hydrolysis with H.(aq).
dissolve
in
dry
ether,
conditions:
o + phosphoruspentachlorideto produce an acid chloride:
CH'COOH + PCI' - CH'COCI+ HCI + POCI,
ethanoyl chloride
conditions: dry; observation:steamyfumes given off.
Esters
Thesehave the generalformula RCOORwhere R and R are atkyl or aryl
groups,and which may or may not be different.
o
R-C
/
\
Thisreaction
Theacidisa catalyst.
hasa lowyieldbecause
it isa
reversible
reaction.
Thisreaction
hasa highyield
it is notreversible.
because
o-
R'
Reactionsof ethyl ethanoate

o Hydrolysis with aqueousacid to produce the organic acid and the
alcohol:
+ HrO + CHTCOOH+ CTHTOH
CH3COOCTH,
ethanoic acid
conditions: heat under reflux with dilute sulphuric acid.
o Hydrolysiswith aqueousalkali to produce the salt of the acid and the
alcohol:
+ NaOH - CHTCOONa+ CTHTOH
CH3COOCTH,
sodium ethanoate
with
aqueoussodium hydroxide.
conditions: heat under reflux
Corbonyl compo,unds(oldehydesond ketones)
Thesecontain the C=O functional group. Aldehydeshave the general
formula RCHO,and ketonesthe generalformula RCORwhere R and R are
alkyl or aryl groups, and may or may not be different.
o
R-C
/
\
H
Aldehyde
R-C
/
\
R'
Ketone
KrNErrcs I
ttt
q,)
Notethatthepeakhasmoved
to the
rightfor f,, andthatthetotalareas
thecurves
under
arethesame,
but
theareaunder
totheright
thecurve
thefraction
of E equals
ofthe
molecules
withenergy
2 E^,
which
is
greater
forTrthan
for I,.
(u
(J
fr .
Fig 2.9 Moxwell-Boltzmanndistribution

Catalysts work by providing an alternativeroute with a lower
activationenergy.Thus, at a given temperature,a greaterproportion of
this lower activation energyby
the colliding moleculeswill possess
following the route with the catalyst,and so the reaction will be faster.
This is shown on a Maxwell-Boltzmann diagram (seeFigure2.lO).
The enthalpy profile diagramsfor an uncatalysedand a catalysed
reactionare shown in Figure2.I1.
(t)
(u
I
q)
(J
Energy
E^^. E
Ldt
Fig 2.lO Effectof a catalyst
Do not say that a catalystlowers the activation energy.

Note that the A.Elvaluesare the samefor both paths.
:------- Transi ti on
Intermediate
rrl
Uncatalysed
Fig 2.1| Energyprofilediagrams
Thermodynamic
stability
o This is when the enthalpy level of the products is much higher than the
enthalpy level of the reactants.
o Thus the substanceson the left-hand side of a very endothermic
reaction are said to be thermodynamically stablerelative to those on the
right.
o The substanceson the left-hand side of a very exotherrnic reaction are
said to be thermodynamically unstablerelative to those on the right.
Whether a reaction will then take place dependsupon its kinetic
stability.
Kinetic
stability
If a reaction has such a high value of activation energy that no molecules

possesssufficient energy on collision to react, the system is said to be
kinetically stable. An example is a mixture of petrol and air, which is
El
e u A N T r r A T r v E E e u T L I B R I AA N D F U N c T t o N A L G R o u p c H E M I s r R y
".RroDrcrTy,
Reactions of ethanoyl chloride
O + water to produce the carboxylic acid, ethanoic acid:
CHTCOCI + HrO - CHTCOOH + HCI(g)
observation: steamy fumes of HCl.
o + alcohols to produce an ester:
CH3COCI + CTHTOH- CHTCOOCTH'+ HCI
observation: characteristic smell of the ester, ethyl ethanoate.
o + ammonia to produce the amide, ethanamide:
CHTCOCI + 2NH. - CHTCONH, + NH4CI
I + primary amines to produce a substituted amide:
CHTCOCI + CrHrNH, - CH3CONH(CrH') + HCI
compounds
Nitrogen
Primory omines
o They contain the -NH, group, e.g. ethylamine C2HrNHz.
O They are soluble in water (if the carbon chain is fairly short) because
they form hydrogen bonds with water molecules.
o They are weak bases.
from
Theaminecanberegenerated
thesaltbyadding
a strongalkali.
Reactionsof ethylamine
O + acids,to form an ionic salt that is soluble in water:
C2H'NH2+ H.(aq) + CrHrNHr.(aq)
| + acid chlorides,to form a substitutedamide:
C2H'NH2+ CHTCOCI-'CH'CONHC2H, + HCI
Nitriles
They contain the C=N group, e.g. propanenitrile C,H'CN.
bythe
Nitriles
canbeprepared
with
reaction
ofa halogenoalkane
KCN
inaqueous
ethanol.
by
Hydroxynitriles
canbeprepared
to carbonyl
theaddition
of HCN
inthepresence
ofbase.
compounds
Reationsof propanenitrile
O Hydrolysis either with acid:
+ NHn*
CTH'CN+ H* + zHrO - CTHTCOOH
conditions: heat under reflux with dilute sulphuric acid
or with alkali'
+ NH,
crHscN + oH- + Hro'crHrcooconditions: heat under reflux with dilute sodium hydroxide
O Reductionby lithium tetrahydridoaluminate(Ill):
C'H'CN + a[H] - C2H'CHNH,
conditions: dry ether, followed by addition of dilute acid
Amldes
They contain the CONH, group, .8. ethanamide CHTCONHT.
o
cHg-Q
/
\
NH,
Reactionsof ethanamide
O Dehydration with phosphorus(V)oxide:
CH3CONH,-HzO-CH'CN
distil off the ethanenitrile.
warm
and
conditions:
EI
tr*roDrcrry,
euANTrrATrvE EeurLrBR'A AND FUN.TToNALGRoup cHEMtsrRy
Checklist
Can recognise stereoisomerism (geometric and optical) in organic
compounds.
iJ Know the effect of an optical isomer on plane polarised light.

iJ Understand the nature of a racemic mixture.
li Can recall the preparation and reactions of Grignard reagents,
.J Can recall the reactions of carboxylic acids.
lJ Can recall the reactions of esters.
'J Can recall the reactions of carbonyl compounds (aldehydes and
ketones).
iJ Can recall the reactions of ethanoyl chloride.
iJ Can recall the reactions of amines with acids and with acid chlorides.
J
Can recall the hydrolysis and the reduction of nitriles.
J Can recall the reactions of amides with PnO,oand with BrrlNaOH.

iJ Know that amino acids are both acids and bases.
yourknowledge
andunderstanding
Testing
ffi
check to see if you are correct.
a CH,CH,CH(0H)CH3
b cH,cH,c(0H)(cH3)cH3
c
CHT CHT O H
reflux
withdilute
Heatunder
hydroxide,
thenadd
sodium
dilute
sulphuric
acid.
b Addlithium
Il) indry
tetrahydridoaluminate(l
followed
bydilute
ether,
sulphuric
acid.
a water
b methanol
c ammonia
a
b
ClCH3CH2NH'cH,c0NHcH2cH3
* Write the formulae of the products of the reaction of CH,MgI with:

a propanal
b
butan-2-one
methanal.
o State the names of the reagents and give the conditions for the
following conversions:
a C,H'COOCH, to C,H'COOH + CH,OH in a high yield
b
C2H'COOH to CHTCH,CH,OH.
O State the names of the reagents needed to convert ethanoyl chloride to:
a ethanoic acid
b
methyl ethanoate
ethanamide.
o State the structural formulae of the product obtained by reacting:

a ethylamine with dilute hydrochloric acid
b
ethvlamine with ethanovl chloride.
'RGANrc cHEMrsrRy, ENERGETT.',KrNETrcs AND EeurLrBRruM
2CrOn'z-(aq)
+ 2H.(aq) + Cr,O,'-(aq) + HrO(l)
Addition of alkali will remove the H'ions, causingthe equilibrium to
move to the left.
O Catalyst. This has no effect on the position of equilibrium. What it
doesis to increase the rate of reaching equilibrium, thus a catalyst
allows a reaction to be carried out at a reasonablerate at a lower
temperature.
Optimum industrial
conditions
Temperoture
Many industrial reactions,such as the Haber processfor manufacturing
ammonia, are reversibleand exothermic. For such reactions:
o If a high temperatureis used,the yield at equilibrium is small, but the
rate of reaction is fast.
r If a low temperatureis used,the theoretical yield is higher, but the rate
of reactionis slow.
O In systemssuch as this, a catalystis used to allow the reaction to
proceedrapidly at a temperatureat which the yield is reasonablygood.
This is often called a compromisetemperature,balancing yield with
rate. Any unreactedgasesare then separatedfrom the products and
recycledback through the catalystchamber.
Pressure
processes
Allindustrial
thatinvolve
passing
gases
through
a bedof
catalyst
mustworkabove
pressure
1 atmosphere
inorder
to
force
thegases
through
thesystem.
O High pressuresare extremely expensive,and are only used if the yield at

lower pressuresis too small to be economic.
o Two examplesof manufacturing processesthat usevery high pressures
are the Haber processand the polymerisation of ethene.
Checklist
J Understandthat equilibria are dynamic.
J Can deducethe effect of changesin temperature,pressureand
concentration on the position of equilibrium.
lJ Can predict the economic conditions for an industrial process.
yourknowledge
Testing
andunderstanding
ffi
Theanswers
to thenumbered
questions
areonpage
129.
Considerthe reversiblereaction at equilibrium:

A(g) + B(g)
Which statementsare/is true about this system?
i
ii
There is no further changein the amounts of A or B.
No reactionsoccur, now that it has reachedequilibrium.

iii
The rate of formation of B is equal to the rate of formation of A.
Considerthe equilibrium reaction:
NrOn(B)+ 2NO,(g) NI = +58.1 kJ mol-'
Stateand explain the effect on the position of equilibrium of:
INDU'TRTAL IN.RGANTc cHEMI'TRY
i
ii
halving the volume of the container
adding a catalyst.
Ethanoic acid and ethanol react reversibly:
+ CH.COOCTH,+ HrO NI = 0 kJ mol-'
CHTCOOH+ CTHTOH
iii
Explain the effect of adding an alkali.

What will happen to the position of equilibrium if the
ii
'C?
temperatureis increasedfrom 25 "C to 35
White insoluble lead(Il) chloride reactsreversiblywith aqueouschloride
ions to form a colourlesssolution:
PbCl,(s) + 2Cl-(aq) + PbCl,'(aq)
i
Stateand explain what you would seewhen concentratedhydrochloric

acid is addedto the equilibrium mixture.
In the manufactureof sulphuricacid, the critical reactionis:
2SO,(g)+ O,(g) -- 2SO,(g) Nf = -196 kJ mol-'
The reactionis very slow at room temperature.Why are conditions of
725 K and a catalystof vanadium(V)oxide used?
chemistry
inorganic
Industrial
@
Inffoduction
ffi
Industrial chemistsalwaysneed to keep manufacturing costsdown. They

do this by:
L making the reaction as fast as possible
2 ensuring a high yield
3 keepingthe temperatureand pressureas low as possible.
ffi
Lry
Thingsto learnand understand
The Haber
process
for the manufacture
of ammonia
N,(g) + 3H,(g) + 2NH,(g) NI=-92.4 kJ mol-'

O Becausethis reaction, left to right, is exothermic and the number of gas
the yield and kinetics are affectedaccordingto the
moleculesdecreases,
table below:
on yield
Effect
on rate
Reaction conditions
Increasein temperature
Increasein pressure
Effect
Increase
lncrease
Very slight increase
Addition of catalyst
None
Very large increase
Decrease
O Thus the following conditions are found to be the most economic:

400 "C. A higher temperature would reduce the yield,
Temperafire:
cHEMrsrRy,
"RGANrc
Pressure:
Uses
ofammonia:
I manufacture
ofnitric
acid
t manufacture
offertilisers
suchas
ammonium
nitrate
andurea
o manufacture
ofpolyamides
such
asnylon.
200 atm. The yield at 1 atm is too low, and so a high

pressure is necessary even though it is very expensive.
Catalyst:
Iron.This allows the reaction to proceed at a fast, and
hence economic, rate at a moderate temperature.
Yieldper cycle: 15o/o.The gasesfrom the catalyst chamber are cooled in
order to liquefy the ammonia, and then the unreacted
nitrogen and hydrogen are recycled, giving a final
conversion of nearly lOoo/o.
The oxidation
of ammonia
to nitric
acid
This happensin three stages:

1 The ammonia and air are passedover a platinum/rhodium catalystat
900 "c:
4NH.(g) + 5O,(g)+ 4NO(g) + 6H,O(g)
2 On cooling, the nitrogen(Il) oxide reactswith more air:
aNO(g) + 2O,(g)-* 4NO,(g)
3 The nitrogen(IV) oxide and air are then absorbedinto water:
4NO,(g) + O,(g) + 2H,O(l) + 4HNO,(aq)
The contact
acid
process
for the manufacture
of sulphuric
O This takesplace in three stages:

1 The combustion of sulphur:
S(l)+O,(g)-SO,(8)
Uses
ofsulphuric
acid:
I themanufacture
offertilisers
suchasammonium
sulphate
r themanufacture
of phosphate
fertiliser
r themanufacture
ofpaints
and
detergents.
2 The reversibleoxidation of the sulphur dioxide:

SOr(g)+'lrOr(g)+ So,(g)
3 Absorption by the water in 98o/osulphuric acid.
I The conditions for stagetwo, which is exothermic and has fewer gas
moleculeson the right, are:
Temperature: 425 "C. A higher temperaturewould reducethe yield,
Pressure:
2 atm. This is enough to force the gasesthrough the
plant. A higher pressureis not necessarybecausethe
yield is high under theseconditions.
Catalyst:
Vanadium(v)oxide.
YieId:
per cycle.The gasesfrom the catalystchamber are
960/o
passedinto the absorbercontaining the 980/osulphuric
acid, and all the SO,is removed.The gasesthen go
back through another bed of catalyst,giving a final
conversionof 99.8o/o.
Manufacture
of aluminium
O Aluminium is 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.
o The ore contains aluminium oxide (amphoteric) with large impurities of
iron oxide (basic) and silicon dioxide (weakly acidic). The ore is treated
with a hot 10olosolution of sodium hydroxide, which reacts with the
amphoteric aluminium oxide to form a solution of sodium aluminate.
Iron oxide does not react as it is a base, and silicon dioxide does not
TRANSITTON
METALS,
QUANTTTATTVE KTNETICS AND
APPLTED ORGANIC
CHEMISTRY
Workêi'
exa*np-lo
Theratioof iron(ll)
to
ionsin theequation
manganate(Vll)
is 5:1andsothenumber
of moles
of Fe'-is 5 timesthenumber
of
molesof manganate(Vl
l).
wasacidified,
andtitrated
against
sulphate
25.0cm'ofa solution
of iron(ll)
cm3wererequired
moldm-'potassium
manganate(Vll)
solution.23.4
0.0222
theconcentration
oftheiron(ll)
sulphate
to givea faintpinkcolour.
Calculate
solution.
forthereaction
is:
Answer:
Theequation
- Mn'*(aq)
+ 4H,0(l)+
SFe3.(aq)
MnOi(aq)
+ 8H.(aq)
+ SFe'.(aq)
= 5.195
=0.0222x23.411000
x 1Q mol
Amount
ofmanganate(Vll)
=
= 5.195
x 10-'mol
x 10*x 5/_t
Amount
ofironlillsuldnaie
_?
- 2.597
= 0.104
=2.597
x 10 + 0.0250
moldm
sulphate
Concentration
of iron(ll)
Iodine/thiosulphate
agents
titrations
- estimation
of oxidising
o The procedureis to add a 25.0 cm' sampleof an oxidising agentto

excesspotassiumiodide solution (often in the presenceof dilute
sulphuricacid).
The oxidising agentliberatesiodine, which can then be titrated against
standardsodium thiosulphatesolution. When the iodine has fadedto a
pale strawcolour, starchindicator is added,and the addition of sodium
thiosulphatecontinueduntil the blue colour disappears.
r Iodine reactswith thiosulphateions accordingto the equation:
-' 2I- + S*On'I' + 2S.O,1-
Workêi,oxil44f-lt,
Theratioofiodine
tothiosulphate
ionsis1:2,sothemoles
ofiodine
moles
are'lrthe
ofthiosulphate.
peroxide,
H,0,,wasadded
to anexcess
25.0cm'ofa solution
of
of hydrogen
potassium
iodine
required
23.8cm'
iodide
solution,
andtheliberated
acidified
theconcentration
moldm-'sodium
thiosulphate
solution.
Calculate
of
of0.106
peroxide
thehydrogen
solution.
peroxide
fortheoxidation
ionsbyhydrogen
is:
Answen
Theequation
ofiodide
Hr0r+2H.+21--lr+2Hr0
= 0.106
x 23.8/1000 =2.523
x 10-'mol
Amount
thiosulphate
ofsodium
= 1.261x 10-'mol
produced = 2.523
x 10-'x 112
Amount
ofiodine
= 1.261
peroxide= 1.261
x 10-3x
1/1
x 10-3
mol
Amount
ofhydrogen
= 1.261
+ 0.0250 = 0.0505
x 10-3
moldm-3
of H,0,
Concentration
Disproportionation
A disproportionation reaction can be predicted by using electrode
potentials. Use the data to work out E.",,for the proposed
disproportionation reaction. If it is positive, the reaction will occur.
Reoox EeurLrBRrA
ttWrkpj, oxiloLPb
to copper
and
inaqueous
solution
ionsdisproportionate
Willcopper(l)
ions?
copper(ll)
V
+ e-+ Cu(s) Es= +0.52
Cu-(aq)
V
+
Cu'-(aq)e-+ Cu'(aq)Eo= +0.15
the
andaddit tothefirst.Thisgives
thesecond
equation
AnswenReverse
equation:
- +0.52
- (+0.15)
= +0.37
V
+ Cu*(aq)
+ Cu(s) E*o,,
20u-(aq)
ions
copper(l)
isfeasible,
andsoaqueous
thereaction
F,,,,is positive,
Because
willdisproportionate.
Corrosion
oz(g)
(rusting)
This is an electrolytic process.When iron is stressedor pitted, some areas

become anodic and some cathodic. In the presence of water and oxygen
the following reactions take place (seeFigure 5.2).
a At the anodic areasiron atoms become oxidised and lose 2 electrons:
Fe(s) -* Fe'*(aq) + 2eo The electrons travel through the metal and reduce oxygen :
'lrOr(aq)
+ 2e- + HrO --' 2OH-(ag)
o The Fe'. and the OH- ions meet and iron(Il) hydroxide is precipitated:
Fe'.(aq) + 2OH-(a9) - Fe(OH)'(s)
Fig 5.2 Rusting

steelis ironcontaining
a
Stainless
which
highproportion
of chromium,
formsa protective
layerof Cr,0,
overthewholesurface
of themetal.
lf thesurface
is scratched,
a new
protective
layerof Cr,O,is formed.
I Finally oxygen oxidises the iron(Il) hydroxide to iron(lll) oxide (rust):

2Fe(OH)r1s;+'/,O,(aq) - Fe,O.(s)+ 2H,O(l)
Prevention of corroslon
This can be done by:
O placing a physical barrier between the steel and the environment. Such
barriers are paint, tin or chromium plating.
o adding a sacrificial metal. This can be done by coating with zinc
(galvanising), or by attaching blocks of magnesium at intervals.
Storage
cells
Thesestore electricalenergyas chemical energy.The reactionsmust be

fully reversibleand the chemicalsproduced in the redox reactionsmust be
insoluble.
The leod ocid bottery
When electricity is drawn from the cell (dischargitg), the following
reactionstake place.
At the anode (oxidation) which is negative:
Pb(s)+ SO,'-(aq)'PbSO,(s) + 2e- Eu = +0.36V
for charging
thecell
Thereactions
aretheopposite,
andonlytakeplace
if a potential
>2.05V is applied,
with
theanodebeingconnected
to the
terminal
negative
of thecharging
s0urce.
At the cathode (reduction) which is positive:

+ 2H,O(t)
+ 4H.(aQ)- PbSO.(s)
PbO,(s)+2e- + SO,z-(aq)
E u = + 1 . 6 9V
The overall discharging reaction is:
Pb(s) + PbO,(s) +ZSOn'-(aq)+ 4H.(a9) -ZPbSOn(s) + 2H,O(l)
E' = +1.69 + (+0.36) = +2.05 V
TneNsrTroN
METAL cHEMIsTRY
of transition
Reactions
metal
compounds
Reoctionswith sodium hydroxide ond ommonio solutions

The table givesa summary of thesereactions.
lon
Cr'*
Mn'*
Fe'*
Fe'*
Ni'*
Cu'*
Zn'*
Colour
Addition of
NaOH(aq)
ExcessNaOH(aq)
Addition of
NH.(aq)
ExcessNHr(aq)
Green
Palepink
Palegreen
Brown/yellow
Green
Paleblue
None
Green ppt
Sandypptb
Dirty green ppt'
Foxy red ppt
Green ppt
Blue pptd
White ppt
Green solution
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Colourlesssolution
Greenppt
Sandyppto
Dirty green ppt'
Foxy red ppt
Greenppt
Paleblue ppt
White ppt
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Blue soln
Deepblue soln
Colourlesssoln
" The correct formula for the ions should be the hexa-aquaion, except for zinc, which forms a tetraqua ion.
o
The precipitate of Mn(OH), goesbrown as it is oxidised by air.
'
The precipitate of Fe(OH),goesbrown on the surfaceas it is oxidised by the oxvgen in the air.
o
The precipitate of Cu(OH). goesblack as it loseswater to form CuO.
Deprotonotion
r The aqua ions in solution are partially deprotonated by water. The
greater the surface charge density of the ion the greater the extent of
this reaction, e.g. hexa-aqua iron(III) ions:
[Fe(H,O)u]'.(aq) + H,O + [Fe(H,O),(OH)]'.(aq) + H.O.(aq)
This means that solutions of iron(III) ions are acidic (pH < 7).
hydroxides'redissolve' O When an alkali such as sodium hydroxide is added, the equilibrium is

Amphoteric
e.g.
in excess
strongalkali,
driven to the right, the ion is considerably deprotonated to form a
- [Cr(OH)u]'+ 30H-(aq)
Cr(0H),(s)
neutral molecule which loses water to form a precipitate of the metal
(aq)
hydroxide:
-+ 20H-(aq)
andZn(0H),(s)
lFe(H,O),1'.(aq)+ 3OH-(aq) - Fe(OH),(s)+ 6H,O
[Zn(0H),]"(aq).
If aqueous ammonia is added, the same precipitate is formed:
[Fe(H,O)u]'.(aq)+3NH,(aq) * Fe(OH).(s)+ 3NHn.(aq) + 3H,O
Ligond exchonge
is used
asa testfor:
Thisreaction
withaqueous
ammonia
a nickel(ll):
ionsfirstgivea green
nickel(ll)
precipitate
which
thenforms
a
withexcess
bluesolution
ammonia.
ionsgivea pale
blue
b copper(ll)
precipitate
forms
which
a deep
withexcess
bluesolution
and
ammonia
c zincionsgivea whiteprecipitate
solution
which
formsa colourless
withexcess
ammonia.
O When aqueous ammonia is added to aqua complexes of d block

elements such as those of nickel, copper and zinc, ligand exchange takes
place and a solution of the ammine complex is formed.
reaction:
First the hydroxide is precipitated in a deprotonation
-Cu(OH),(s)
+ 4H,O
+
2NH..(aq)
[Cu(H,O)J'.(aq) + 2NH,(a9)
The hydroxide then ligand exchanges to form an ammine complex with
excessammonia:
Cu(OH),(s) + 4NH,(aq) +ZH,O -- [Cu(NH.)*(H,O)J'. + 2OH-(aq)
The final result is that the NH, ligand has taken the place of four HrO
ligands.
O Addition of cyanide ions to iron(Il) ions produces a solution of
hexacyanoferrate (I I) :
[Fe(H,O).]'.(aq)+ 6CN-(ag) - [Fe(CN)']*(aq) + 6H,O
o A test for iron(III) ions is to add a solution of potassium
thiocyanate,KCNS. Iron(II! ions give a blood red solution:
[Fe(H,O),]'.(aq) + SCN-(ag)t tFe(SCNXH,O).1'.(aq)+ H,O
El
o*.ANIc
cHEMrsrRy, ENERGETT.',KrNETrcsAND EeurLrBRruM
And the structural representationof this is:

H
t
H-C t
H
l
l
C-O-
H + 3O:O
2O-C:O
+ 3H-O
-H
Calculatethe enthalpy changefor this reaction using the averagebond enthalpy valuesgiven below.
t3I
Bond
C-H
c-o
Ot:O
+ 4L2
+ 360
+ 496
Bond
C-C
+ 348
+ 463
+ 743
o-H
c:o
tt Draw and label an enthalpy level diagram to representthis reaction.
I2l
Gotaf 1O marks)
200L
Unit Test2 question5f
lJune
5 a The reaction in the Haber Processthat is used to produce ammonia is:

N,(g) + 3Hr(g) : 2NH,(B)
N:I=-92k1mol-'
i What temperatureis used in the Haber Process?
tl]
ii Justify the use of this temperature.
t3I
lii Name the catalystused in the Haber process.
tll
iv How does a catalyst enable a reaction to occur more quickly?
t2l
b Another industrial processis the one which recoverschlorine from HCl, which often is a by-product in
organic preparations
NI = -115 kJ mol-'
rhisisahomog.-X.:l13)oi'*!?.il,u1*11i1f,1;"3,?:1t'
Statethe meaning of the terms

i homogeneous
ii dynanic equillbrium
Stateand explain the effect on the position of equilibrium of the reaction in b of:
I decreasingthe temperature.
ti decreasingthe volume of the reaction vessel
tlI
l2l
l2l
r2l
(Total 14 marks)
lMay 2002 question3 Unit Test2 & lanuary 2001 question4 Module Test2l
a
b
c
d
e
Aluminium metal is manufactured by a processin which purified bauxite, dissolved in molten cryolite,
is electrolysedat 800'C. Graphite electrodesand a current of about 120 000 amperesare used.
Give the ionic equation for the reaction taking place at the anode.
tlI
Give the ionic equation for the reaction taking place at the cathode.
tlI
Statewhich of thesereactionsis an oxidation process.
tll
Explain why the anodesneed to be replaced frequently.
tzl
Explain why an electrolyte of pure molten bauxite is not used.
r2l
Gotaf 7 marks)
lJune2001 Unit Test2 question7f
[Paper total 6O marks]
s ASlaborator/Mtry
I
Laboratory
chemistry
o The specificationfor thesetestsincludes all of Units L and 2.
O Unit Test38 will contain many of the calculationsfor AS level, and so
Topic t.2 (pages6 to 12) must be thoroughly revised.
ffi
'Lb
of practical
Unit Test3A: Assessment
skiltsI
iJ tfris is either internally assessed

or a practicalexam.
iJ Notesand textbooksare allowedin the tests.
J the practicalexam will contain somequantitativework, probablya
titration or an enthalpy changeexperiment.
J You should know the following gastests:
o H,
I O,
o CO,
burns with a squeakypop

relights a glowing spill
turns lime water milky
o NH3
turns red litmus blue
O Cl,
a NO2
bleachesdamp litmus; turns KBr solution brown

brown gaswhich turns starch/iodidepaper blue-black
turns acidified potassiumdichromate(Vl) solution green.
I SO,
E you should know the testsfor the following ions:

o COr'o HCO3o SOn'-
Ion
Flame colour
Li'
camine red
Na'
yellow
K'
lilac
Ca'*
brick red
crimson red
pale green
Sr'*
Ba"*
Add acid. Testfor COr.

Add to almost boiling water.Testfor COr.
Giveswhite precipitatewhen dil HCI and BaClr(aq)are
added to the solution.
above.
Solution is acidic to litmus, then test as for SOn2Add dil acid to solid and warm. Testfor SOr.
o HSO4o SO32o Halide ion: To solution add dil HNO3then AgNOr(aq).White

precipitate soluble in dil ammonia indicateschloride;
cream precipitateinsoluble in dil but soluble in conc
ammonia indicatesbromide; pale yellow precipitate
insoluble in conc ammonia indicatesiodide.
Heat solid. All nitrates give off Or. All but sodium and
a NO3potassiumnitrates also give off NOr. Alternatively add
aluminium powder and sodium hydroxide solution.
Nitrates give off ammonia gas.
Add dil NaOH and warm. Testfor ammonia.

Giveswhite precipitatewhen dil ammonia is added
to a solution.
O You must know how to carry out a flame test and the colours obtained.
a NHn.
o Mg'.
LABoRATORY
CH EM ISTRY
I
chemistry
38:Laboratory
[]nit Test
ffi
J this is a written paper,taken by alt candidates.

J tt is designedto assessa candidate'sability (relatedto the topics in
Units 1 and 2) to:
I
ll
C=C group
C-OH group
Decolourises
brown bromine
in hexane
Steamyfumes
with PCl.
Organic halides Warm with

sodium
hydroxide
solution. Acidify
with dilute nitric
acid and then
test as for ionic
halides as on
page 55
evaluate information generated from experiments

describe and plan techniques used in the laboratory.
J Tests
o You should know the testslisted in Unit 3A above.
o You should also know the testsfor alkenes,the OH group and the
halogenin halogenoalkanes.
o You should be able to deducethe identity of a compound from the
resultsof a seriesof tests.
J Techniques
You should be able to describetechniquesusedin:
o titrations and enthalpy changemeasurements
O simple organic proceduressuch as distillation and heating under
reflux.
[l Phnning
You should be able to:
O Plan a seriesof teststo determine the identity of an inorganic or
organic compound.
O Describehow to make up a solution of known concentration for
titrations.
O Plan an experiment to determine the enthalpy of a reaction such as
the combustion of a liquid, or the neutralisation of an acid.
o Plan an experiment to follow the progressof a reaction in which
there is a changein physical state,such as the production of a gas.
[l calculations
You should be able to calculate:
o empirical formulae
O reacting masses
o resultsfrom titration data
o enthalpy changesfrom experimentaldata.
iJ Evaluation
You should be able to criticise:
o an experimental plan or apparatus
o the resultsof an experiment in terms of significant figures,accuracy
or experimentalerror etc.
[J sarety
You should be able to suggestspecificsafetyprecautionswhen a substance
is flammable, toxic or irritating.
Practice Test: Unit 38

Time allowed t hr
All questions,except5, are taken from partsof previousEdexcelAdvancedGCEquestions.
The answersare on pagesl3O-I32.
1
Complete the table below.

Gas
Reagents
or test
Hydrogen
Burning splint
Oxygen
Glowing splint
Observationexpectedfor a positiveresult
Carbon dioxide
Sulphur dioxide
Potassiumdichromate(VI )
solution acidified with dilute
sulphuric acid.
Solution turns from orange to .
Moist blue litmus paper
Turns red and is then bleached white
t6I
(Total 6 marks)
2002
Unit
Test 38 question 2l
llune
In a series of experiments to investigate the factors that control the rate of a reaction, aqueous
hydrochloric acid was added to calcium carbonate in a conical flask placed on an electronic balance.
The loss in mass of the flask and its contents was recorded for 15 minutes.
CaCO,(s) + 2HCl(aq)
CaCl,(aq) + H,O(l) + CO,(g)
Four experiments
were carried out.
. Experiments L, 3 and 4 were carried out at room temperature (20"C).
o The same mass of calcium carbonate (a large excess)was used in each experiment.
o The pieces of calcium carbonate were the same size in experiments 1, 2 and 4.
Experiment
Calcium carbonate
Hvdrochloric acid
Small pieces
Small pieces
One large piece
Small pieces
50.0cm' 1.00mol dm-'

50.0 cm' 1.00 mol dm-' heatedto 80 "C
50.0 cm' 1.00mol dm-'
50.0cm'2.00 mol dm
a The resultsof experiment I give the curve shown on the graph below.
Massloss/g
1.50
1.00
0.50
15
Time/min
El
to"oRAroRY
c H E Mr s r R Y I
i
Explainwhy there is a lossin massas the reactionproceeds.
t2l
Explain the shapeof the curve drawn for experiment 1.
ii
t2l
Draw curveson the graph aboveto representthe resultsyou would expect for experiments2, 3
and 4.
tsl
i
Calculatethe massof calcium carbonatethat exactly reactswith 50.0 cm3of 1.00 mol dm-'
aqueoushydrochloric acid. (Molar massof CaCOr= 100 g mol-')
t3l
Basedon your answerto c part (i), suggesta suitablemassof calcium carbonateto use in the
ii
experiments.Explain your answer.
t2l
(Total 1.2 marks)
[anuary 2002 Unit Test38 question2]
A student was required to determine the enthalpy change for the reaction betweeniron and copper
sulphatesolution. The student produced the following account of their experiment.
A pieceof iron,massabout3 g, was placedin a glassbeaker.Then 50 cm'of 0.5 mol dm-'aqueous
coppersulphatesolutionwas measuredusinga measuringcylinderand addedto the beaker.The
beforethe additionand everyminuteafterwards
temperature
of the mixturewas measuredimmediately
untilno furtherchangetook place
F e + C u S O o-
F e S O o+ C u
Timing
Before
addition
1 min
2 mins
3 mins
4 mins
5 mins
Temperature/'C
16
27
29
26
24
22
Suggesttwo improvementsyou would make to this experiment. Give a reasonfor each of the
improvements suggested.
t4l
oC occurred
b In an improved version of the same experiment a maximum temperaturerise of I5.2
when reacting excessiron with 50.0 cmt of 0.500 mol dm-' aqueouscopper sulphate solution.
i
Using this data and taking the specificheat capacityof all aqueoussolutionsas 4.181 g-' deg',
calculatethe heat change.
ii
Calculatethe number of moles of copper sulphate used.
iii Calculatethe enthalpy changefor this reaction in kJ mol-'
r2l
(Total 8 marks)
[une 2002 Unit Test38 question4]
tu
A student carried out an experiment to find the percentage of calcium carbonate, CaCO, in a sample
of limestone following his own plan. The student's account of the experiment, results and calculations
of the mean titre are given below.
Account
I
Massof pieceof limestone= 5.24 g
acid (an excess)to a
ll
A pipettewas usedto transfer50 cm'of 2.00 mol dm-'aqeoushydrochloric
placed
left
therewas no more
piece
and
until
in
the
beaker
was
limestone
of
100 cm' beaker.The
effervescence.
Equation
Ill
lV
CaCO.(s)+ 2HOl(aq)-
CaOl'(aq)+ CO'(g)+ H,O(l)
The acidicsolutionin the beakerwas filteredinto a250 cm3volumetricflask.A smallamountof the

solidimpurityremainedin the filterpaper.The solutionin the volumetricflaskwas carefullymadeup
to 250 cm'with distilledwater.
A pipettewas usedto tranfer25.0 cm3portionsof the acidicsolutionto conicalflasks.The solution
was then titratedwith 0.100mol dm-'aqueoussodiumhydroxide.
HCI(aq)+ NaOH(aq)-
tttaQl(aq)+ H,O(l)
El
t*oNsrrroN
METALS, euANTrrATrvE
Energy profile
KrNETrcs AND AppLtED .RGANtc
cHEMIsrRy
diagrams
The first diagram is for a reaction that takes place in a single step, and the
second diagram is for this reaction with a catalyst (seeFigure 5.6).
:-------- Transition
Intermediate
>.
bo
bo
tr
q.)
rtl
Catalysed
Fig 5.6 Energyprofile diagroms
An example of a reaction with a transition state is the S*2 reaction of

bromoethane with hydroxide ions.
An example of a catalysed reaction forming an intermediate is Fez*ions as
a catalyst in:
SrOrz-(aq)+ 2l-(aq) - 2SOn'-(a9) + Ir(aq)
In this mechanism the catalyst first reduces the SrO.'- ions:
ZFe'.(aq) + SrOr'-(a9) - 2Fe'.(aq) + 2SO.,'-(aq)
then the Fe"*ions are reduced back to Fe2*ions:
2Fe3.(aq)+ Zl-(aq)'- ZFe'*(aq)+ Ir(aq)
H
c , g
*4-
Checklist
Beforeattemptingthe questionson this topic, checkthat you:

J Can define rate constant,order of reactionand half-life.
iJ Can deducerate equationsfrom initial rate data.
iJ U.tderstandthe concept of activation energy and its relation to the rate
constant.
E Understandthat information about mechanismscan be deducedfrom
the partial ordersof the reactants.
iJ Can recall the energyprofiles of reactionswith and without catalysts.
ff Ca.r suggestsuitablemethods for following reactions.
f
Can deducethe order of a reaction from concentration/time graphs.
c n e M r c A L K r N E T r c st l
and understanding
1 and2, order
a Fromexperiments
withrespect
to N0,= |
1 and3, order
b Fromexperiments
withrespect
to C0 = 0
is 2 + 0 = 2
c 0rderof reaction
d Rate=k[N0,]'
For the following set of questions, cover the margin before you answer,
O The following results were obtained from a study of the reaction:
NO,(g) + CO(g) -' NO(8) + CO,(g)
Experiment
NO,l/mol dm-"
lCol/mol dm-'
Relative rate
1
2
3
o.o2
0.04
0.o2
0.o2
o.o2
0.04
1
4
1
a
b
c
d
What is the order with respect to NOr?

What is the order with respectto CO?
What is the order of reaction?
Statethe rate expression.
o Reaction A has a high value of E., and reaction B has a lower E. r'alue.
Which reaction has the larger rate constant?
a
Which is the faster reaction?
b
o A reaction takes place in 3 steps. The E^lkI mol-' for each step are:
E,,value
Step2 asit hasthelargest
step 1: 32,
step 2: 51,
step 3: 20
Which step determines the rate?
100to 6.25= 4 half-livee,

therefore
time= 4x25= 100minutes
Theanswers
to thenumbered
questions
areonpage
138.
O The decomposition of NrO, is first order. At 200 "C the reaction has a
half-life of 25 minutes. Calculate how long it will take for the
concentration of NrO, to fall to 6.250/oof its original value.
L The rate of the second order reaction:
2HI(g) -- H,(g) + I,(8)
is 2.0 x 10' mol dm-' s-' when [HI] = 0.050 mol dm-' at 785 K. Calculate
the value of the rate constant, giving its units.
'C,
the rate of the reaction:
Describe how you would follow, at 60
+ H,O(l).
+
CH,COOCH.(|)
CH3COOH(aq) CH'OH(aq)
The decomposition of 3-oxobutanoic acid, CH3COCHTCOOH,was
studied:
CHTCOCHTCOOH- CH.COCH. + CO,
The results, at 40'C, are tabulated below.
Time/min
0
26
52
78
[3-oxobutanoic acid]/mol dm-'
t.6
0.8
0.4
o.2
Deduce the order of the reaction.
E N e R G E r r c st l
energies for the formation of the cation, the electron affinity for the
formation of the anion and the lattice energy of the ionic substance.
O This can either be drawn as a Hess's Law cycle, or as an enthalpy level
diagram (seeFigures 4.1 and 4.2).
Mg'.(g) + 2cl(g)
4,ti
t osn
I vg2.(g)+ ctr(gt
zcr(g)
Mg-(g) + Clr(g)
ll * * . l1
+
C l z (g )-M g C l r(s )
+ zCf (g)
Nrz
Mg(S) + Clz(g)
NIl
Mg(s) + Clr(g)
MgC l r{s)
Fig 4.2 Enthalpyleveldiagram

AH, of MgCl, = NI^ of Mg (AH,) + lst ionisation energy of Mg (NIr) + 2nd ionisation energv of Mg (aH,) + 2 x
A , F / " oC
f l ( A H r ) + 2 x e l e c t r o n a f f i n i t y o f C l ( A H r ) + A / { , , , , o fM g C l r ( A F l r ) = A H , + A , H . + A H , + l H , + l H . + - \ H "
Any one value can be calculated when all the others are known.
Lattice enerry
lf a bondis partially
covalent,
the
(from
latticeenergy
experimental
(more
BornHaber)
willbebigger
thanthevalue
exothermic)
froma purely
ionic
calculated
model.
Thegreater
thedifference
between
theexperimental
andtheoretical
thegreater
theextentof
values,
Thiswillhappen
if the
covalency.
(smallor
cationis verypolarising
highlycharged)
or theanionis very
polarisable
(large).
Seepage13.
O Lattice energy is always exothermic.

o Its value depends upon the strength of the force of attraction
(sometimes called the ionic bond) between the ions.
O The strength of this force depends upon the value of the charges and
the sum of the radii of the ions:
i the larger the charge on either or both of the ions, the larger (more
exothermic) the lattice energy
ii
the larger the sum of the ionic radii, the smaller (lessexothermic)
the lattice energy.
o Theoretical values of lattice energy can be calculated assuming that the

substance is 100o/oionic.
Voriotion of lottice energies in o Group
O Group 2 sulphates. As the radius of the cation increases down the
Group, the lattice energy decreases.But because the radius of the
sulphate ion is much larger than the radii of any of the Group 2
cations, the sun of the radii of the cation and the anion alters only
slightly, and so the lattice energy only decreasesslightly.
As the radius of the cation increases down the
O Group 2 hydroxides.
Group, the lattice energy decreases.But because the anion is small, and
matches the size of the cation (the ionic radii of Ba'* and OH- are about
and so the lattice
the same), the surn of the radii alters significantly,
energy decreasesby a large amount.
El
t*oNsrrroN
METAL', euANTrrATrvE
KrNETrcs AND AppLrED .RGANrc
cHEMrsrRy
100
s
O
U
g s o
(a
(t)
Lr
t-
Fig 5.8 lnfroredspectrumof ethonol
Thechemical
shiftis thedifference
theabsorption
between
frequencies
nucleiin the
of thehydrogen
compound
andthosein the
reference
compound.
1000
2000
1s00
Wavenumber
/ cm-r
O NMR spectra
o The phenomenon of nuclear magnetic resonance occurs when nuclei
'H
such as
are placed in a strong magnetic field and then absorb
applied radio frequency radiation.
t The nuclei of hydrogen atoms in different chemical environments
within a molecule will show up separately in a NMR spectrum. The
values of their chemical shift, 6, are different.
o The hydrogen nuclei in a CHr group will have a different chemical
shift from those in a CH, or in an OH group. The value of d of the
peak due to the hydrogen in OH (or in NH) depends upon the
solvent.
* In low resolution
NMR, each group will show as a single peak, and
the area under the peak is proportional to the number of hydrogen
atoms in the same environment. Thus ethanol, CH.CHTOH will have
three peaks of relative intensities 3:2:1 and methyl propane
CH.CH(CH3)CH3,will have two peaks with relative intensities of 9:1.
NMR spin coupling is observed. This is caused
O In high resolution
by the interference of the magnetic fields of neighbouring hydrogen
nuclei. If an adiacent carbon atom has hydrogen atoms bonded to
it, they will cause the peaks to split as follows:
1 neighbouringH atom
2 neighbouringH atoms
n neighbouring H atoms
peaksplits into 2lines (a doublet)

peaksplits into 3 lines (a triplet)
peaksplitsinto (n + 1) lines.
Thus ethanol gives three peaks (see Figure 5.9):

1 peak due to the OH hydrogen, which is a single line
(as it is hydrogen bonded)
1 peak due to the CH, hydrogens, which is split into four lines
by the three H atoms on the neighbouring CH, group.
1 peak due to the CH, hydrogens, which is split into three lines
by the two H atoms on the neighbouring CHr group.
Fig 5.9 High resolution NMR spectrum

of ethonol
E N e R G E T T c sr l
Checklist
:J Can define enthalpy of atomisation.
iJ Can define enthalpy of hydration.
;J Can define lattice energy.
iJ Can construct a Born-Haber cycle.
IJ Cun use a Born-Haber cycle to calculatelattice energy or electron
affinity.
[] U.tdetstandwhy the value of AF/**from Born-Haber might be more
exothermic than the theoretical value.
[,] Can stateand explain the changein solubilities of the Group 2
sulphatesand hydroxides.
#- -x
Lvve
GT
check to see if vou are correct.
a MgCO,
b MgCO,
C NAF
I In each of the following state which compound has the larger (more
exothermic) lattice energy:
a MgCO. or BaCO,
b NarCO. or MgCO,
c NaF or NaCl.
Al*>Mg'.rBa'*>Na*
I Arrange the following ions in order of decreasing (less exothermic)

enthalpy of hydration: Na*, Mg'*, Bat* and Alt*
Ba(0H),
o State the formula of the most soluble Group 2 hydroxide.
tothenumbered
Theanswers
questions
132.
areonpage
The following data, in kJ mol-', should be used in this question.

Enthalpies of atomisation: calcium +193; chlorine +LZL.
Ionisation energies for calcium: 1st +590; 2nd +1150
Electron affinity for Cl(g): -364
Lattice energies:for CaClr(s) -2237; for CaCl(s) -650 (estimated).
a
Construct a Born-Haber cycle for:
i the formation of CaCl(s)

ii the formation of CaClr(s).
Calculate the standard enthalpy of formation of:
i CaClr(s)
ii CaCl(s)
iii hence calculate the enthalpy of the reaction:
2CaCl(s) * Ca(s) + CaCl'(s)
and comment on the fact that CaCl(s) does not exist.

Comment on the values of the lattice energies, in kJ mol-', given
below:
NaF
MgI,
Experimental Theoretical
-912
-918
-t944
-2327
EI
euANTrrATrvE EeurLrBR'A AND FUN.TT'NAL GRoup cHEMIsrRy

"r*roDrcrry,
ll
Table
ThePeriodic
'&
Inffoduction
;J you will need to look again at Topic 1.4.

iJ fne elementsbecomemore metallic down a Group. This meansthat
their compounds,such as their chlorides,becomemore ionic and their
oxidesbecomemore basic.
f
fn. elementsbecomeless metallic from left to right acrossa Period.

This meansthat their chloridesbecomemore covalent and their oxides
becomemore acidic.
[-] There are many formulae and equationsthat must be learnt in

this Topic.
[l fne propertiesof elementsand their compounds change steadilyfrom
the top to the bottom of a Group and from left to right acrossa Period.

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:
AI
Si
Mgo
Al2o3
Chlorine NaCl
MgCl,
Alcl, (')
Water
NaOH +
MgO + No
H2
H,tn'
Na
Oxygen
Mg
Na,O or
N a rO,(t)
reaction
sio,
PnO,o
SO,
sicl4
PCI,
(t)
PCl,
SrCl,
No
reaction
No
reaction
No
reaction
CI
Ar
No
reaction
No
reaction
No
reaction
HCI +
HOCI
No
reaction
("
(')
Notes: with excessoxygen sodium peroxideis formed, ''' aluminium chloride is covalent, with excess
(n)with
chlorine,
steam.
Thehydroxides
lessbasicand
become
moreacidicasthesurface
charge
of thecationincreases.
density
is sucha weakacidthat
dioxide
Silicon
molten
hydroxide
is required.
sodium
Theoxides
form
of thenon-metals
increasingly
strongacidsasthe
number
of oxygen
atomsin theacid
increases.
[l uetA
hydroxides
and oxides
alkaline: NaOH(s) + aq - Na-(aq) + OH-(aq)
t NaOH
o Mg(OH), basic: Mg(OH),(s) + 2H.(aQ) - Mg'.(aq) + ZH,OQ)
basic: MgO(s) + 2H-(aq) -- Mg'*(aq) + H,O(l)
o MgO
amphoteric: Al(OH),(s) + 3H.(aQ)- Al'.(aq) + 3H,O(l)
a AI(OH),
Al(OH),(s) + 3OH-(a9) - Al(OH).3-(aq)
amphoteric: AlrO.(s) + 6H.(aQ) - 2Al'.(aq) + 3HrO(l)
o Al2O3
Al,O,(s) + 6OH-(aq) + 3H,O(l) '2Al(OH)6'-(aq)
[] Non-metal
o SiO,
O P4O6
o P4O10
oxides
weakly acidic: SiOr(s) + 2NaOH(l) - NarSiO'(l) + HrO(g)
weakly acidic: PnOu+ 6HrO ' 4H'PO, + 4H-(aq) + 4HrPOrstrongly acidic: PnO,o+6HrO -' 4HrPOn- 4H'(aq) + 4HrPOn-
THE PERroDrc rABLE rl

weakly acidic: SO, + HrO --*H2SO3+ H.(aq) + HSO.strongly acidic: SO. + HrO -- HzSOn-- H'(a9) + HSO,-
I SO,
t SO,,
iJ cntorides
lonicchlorides
in waterto
dissolve
formhydrated
ions.
Thesehydrated
ionsmay
if thesurface
deprotonate,
charge
density
of themetalionis high.
(ofPeriod
Covalent
chlorides
3)
reactwithwaterto formHCIand
either
theoxideor theoxoacid.
o NaCl ionic solid, dissolves in water:

NaCl(s) f ?q--+Na-(aq) + Cl-(aq)
o MgCl, ionic solid, dissolves in water:
MgCl,(s) + ?q--+ Mg'.(aq) + 2Ct-(aq)
Hydrated
ionic
AlCl,
solid, deprotonated by water:
I
-[AI(H,O)"]'.(aq) + H,O
[A1(H,O),(OH)]'.(ag)+ H,O-(aq)
r Anhydrous AlCl, covalent solid, reacts with water:
AlCl,(s) + 3H,O(l) -'Al(OH),(s) + 3HC|(aq)
w SiCl.,covalent liquid, reacts with water:
Sicl,(l) + 2H'O(l) -- SiO,(s)+ aHCl(aq)
*r PCll covalent liquid, reacts with water:
P C l ,(l )+ 3H .O(l )-- H ,P O,(aq)+ 3H C l (aq)
, PCl. covalent solid, reacts with water:
PCl.(s)+ 4HrO(l) - H,PO.,(aq)+ SHCl(aq)
Variation
Thetrendin metallic
character
is
caused
bythedecrease
in ionisation
energy
astheradius
of theatom
increases,
making
it energetically
fortheformation
favourable
of ionic
bonds.
of properties
down Group 4
-l The metallic character increases down the Group:

carbon and silicon are non-metallic (not malleable; only graphite
conducts electricity)
germanium is semi-metallic (semi-conductor).
tin and lead are metallic (malleable and electrical conductors).
iJ fne +2 oxidation
state becomes more stable relative to the +4
state. Lead(IV) is oxidising and is itself reduced to lead(Il), whereas
tin(Il) is reducing and is itself oxidised to tin(IV). This is illustrated by:
o lead(IV) oxide oxidises concentrated hydrochloric acid to chlorine:
PbO, + 4HCl - PbClz + Cl, + HrO
o tin(Il) ions are oxidised to tin(IV) ions by chlorine:
Sn'*+ Cl, -- Sn'.+ zcr
lJ Tetrachlorides.
Both CCl, and SiCln are covalent and are tetrahedral
molecules owing to the repulsion of the four bond pairs of electrons.
SiCl4is rapidly hydrolysed by water. A lone pair of electrons from the
oxygen in the water forms a dative bond into an empty 3d orbital in
the silicon atom. The energy released is enough to overcome the
activation energy barrier involved in the breaking of the Si-Cl bond.
Carbon's bonding electrons are in the 2nd shell and there are no 2d
orbitals. The empty orbitals in the 3rd shell are of too high an energy to
be used in bonding, and equally important is that carbon is such a
small atom that water molecules are prevented from reaching it by the
four much larger chlorine atoms arranged tetrahedrally around it.
if .q.ciaity of the oxides. This decreasesdown the Group:
o Carbon dioxide is weakly acidic, and reacts with metal oxides and
alkalis:
CO,(g) + 2OH-(a9) - CO,'-(aq) + H,O(l)
O Silicon dioxide is very weakly acidic, and reacts with molten sodium
hydroxide:
SiO,(s) + 2NaOH(l) - Na,SiO.(l) + H'O(g)
O Lead oxides (and hydroxide) are amphoteric, and react with aqueous
acids and alkalis, but lead(Il) oxide is the strongest base of the Group
4 oxides:
PbO(s) + 2H-(aq) -- Pb'.(a9) + H,O(l)
PbO(s) + 2OH-(aq) + H,O - Pb(OH)*'-(aq)
EI
trRroDrcrry,
e u A N T r r A T r v E E e u T L T B R I AA N D F U N . T I . N A L G R o u p c H E M I s T R y
Before attempting the questions on this topic, check that, for the Period 3
elements, you:
i
Can write equations for the reactions of the elements with oxygen and
with chlorine.
J Can write equations for the reaction of the elements with water.
J Can state and explain the acid/base nature of the metal hydroxides.
J Can state and explain the acid/base nature of the non-metal oxides.
J Know the formula of their chlorides and their reactions with water, and
can relate the reactions to their bonding.
Before attempting the questions on this topic, check that, for the Group 4
elements, you:
iJ Kno* why the elements become more metallic down the Group.
[J Kno* that the +2 oxidation state becomes more stable down the
Group.
l-f Know why SiCln is rapidly hydrolysed by water, whereas CCln is
unreactive with water.
E Can write equations to show the acid/base character of the oxides of
carbon, silicon and lead.
-.________.-]fl,
O
,t17i Testingyour knowledgeand understanding
a. t'For the following questions,cover the margin, write your answer,then

PbOandPb0,
o Statethe formulaeof lead(Il)oxide and lead(IV)oxide.
Pb0
o Statethe formula of the most basic Group 4 oxide.

1 a
tothenumbered
Theanswers
questions
areonpages
132-133.
Write equations for the changescausedby the addition of water to:
i
sodium chloride
ii
silicon tetrachloride
iii phosphorus pentachloride.
b Relate these reactions to the bonding in the chlorides.
Explain why silicon tetrachloride, SiCln, reacts rapidly with water,
C
but tetrachloromethane, CCln, does not react even when heated with
oC.
water to 100
Write two ionic equations to show that aluminium hydroxide is
2
amphoteric.
Write ionic equations for the reactions, if any, of:
3
aqueous acid with:
magnesium hydroxide
i
lead monoxide
ii
iii sulphur dioxide
aqueous alkali with:
i
magnesium hydroxide
ii
lead monoxide
iii sulphur dioxide.
4 a Write an equation to show lead(IV) oxide acting as oxidising agent.
b Write an equation to show aqueous tin(Il) ions acting as a reducing
agent.
6A
h,borator/
Ma'y
Laboratory
II
chemistry
O The specification (syllabus) for the tests on this module includes all the
AS and A2 material.
o The Unit Test 68 is a synoptic paper, taken by all candidates, and will
also assessthe candidate's quality of written communication.
=1
..
'- , 4,Ki
of practical
.t#
skills II
E ftris is either internally assessed

or a practical exam.
f
Notes and books may be used in the tests.
E ffre practical exam will be broadly qualitative in its approach.

[l You should be able to:
i
observeand interpret details of the chemistry of the elementsand

compounds listed in Units 4 and 5.
ii recognizethe resultsof experimentsto identify functional groups in
organic compounds.
iii carry out the techniquesdescribedin Topic 5.5 and those used in
volumetric analysis,kinetics and equilibria.
iv presentand interpret quantitative and qualitative results.
v deviseand plan simple experimentsbasedon the chemistry and
techniquesas above.
K+a
All candidates will do this paper
The Unit
Test question
(exam)
paper
I Section A will consist of a compulsory question and will assessa

candidate'sability to interpret data from laboratory situations.
O Section B will consist of three questionsand the candidatemust
answertwo of the three questions.
I Thesequestionswill require candidatesto make connectionsbetween
different areasof chemistry,for exampleby applying knowledgeand
understandingof principles to situations in contexts new to them.
EI
"t*toDlctry'
euANTITATtvE
EeurLrBRrA AND FUN.TT.NAL
GRoup
cHEMrsrRy
Colculotion of K,
This must be done using equilibrium concentration values,not initial
concentration values.The calculation is done in 5 steps:
i Draw up a table and fill in the initial number of moles, the change
for each substanceand the equilibrium number of moles of each
substance.
ii convert equilibrium moles to concentration in mol dm-r.
iii Statethe expressionfor K..
iv Substituteequilibrium concentrationsinto the expressionfor K..
v work out the units for K. and add them to your answer.
WorkpoL
oxiloLf.b
o C(s)doesnotappear
in theK.
expression
because
it is a solid.
o Theamount
of C0 madeis twice
theamount
of C0,reacted.
Animportant
reaction
intheblastfurnace
is theformation
of carbonmonoxide
fromcarbon
andcarbon
dioxide.
Thisreaction
isanexample
ofa
heterogeneous
equilibriu
m.
when1.0molof carbon
dioxide
washeated
withexcess
carbon
to a
temperature
of700'c ina vessel
ofvolume20dm',g5%ofthecarbon
dioxide
reacted
fo formcarbon
monoxide.
calculate
K,tor
C(s)
+CO,(g)
+2C0(g)
Answer.
C0,(g)
co(s)
Units
Initialamount
1.0
0
mol
-0.95
Change
+0.95x 2
mol
Equilibrium
amount
1.0-0.95=0.05 1.9
mol
Equilibrium
concentration
= 0.0025 1.9120
0.05120
= 0.095 moldm-'
= 3.6motdm-3
K = t!91,*= (0.095),(moldm-s),
reo;i; ffi
Partial pressure
o The partial pressureof a gasA, po,in a mixture is the pressurethat the
gaswould exert if it alone filled the container.It is calculatedfrom
the
expression:
partial pressureof a gas= mole fraction of that gasx total pressure
where the mole fraction = the number of moles of that gas
the total number of moles of gas

o The total pressure,P, is equal to the sum of the partial pressuresof each
gasin the mixture.
The equilibrium
constant
K"
The equilibrium constant, measuredin terms of partial pressure,only

appliesto reactionsinvolving gases.solids or liquids do not appear
in
the expressionfor K".
For a reaction:
mA($ =*xB(g) + ZC(g)
where m, x and y arethe stoichiometric numbers in the equation:
K, = (p).-t_(pJ *_
(Po)^
"n
. H E M T . A L E e u r L r B R r u Mr l
All partial pressuresare equilibrium values.
So for the reaction:
CO,(g)+ C(s)+2CO(g)
= p(CO)'"' and its units are atm2=atm
160
in
isa solidit is ignored
Ascarbon
theexpression.
atm
P(co,)*
Colculotionsinvolving K,
o The calculation of Kofrom equilibrium data is done in a similar way to

those involving K.:
i Draw up a table and fill in the initial number of moles,the change
for eachsubstance,the equilibrium number of moles of each
substanceand the total number of molesat equilibrium.
ll
Convert equilibrium molesto mole fraction.
iii Multiply the mole fraction of eachby the total pressure.
lv Statethe expressionfor K'.
Y Substituteequilibrium concentrationsinto the expressionfor Ko.
vl Work out the units for K' and add them to your answer.
oh
oxal,u?12
placed
to 175"C.When
andheated
in avessel
0.080molof PCluwas
was2.0atm
it wasfoundthatthetotalpressure
hadbeenreached,
equilibrium
K,torthereaction:
haddissociated.
Calculate
of thePClu
andthat40o/o
+ PCl,(g)
+ Cl,(g)
PCl,(g)
60%wasleft.Thusat equilibrium:
AnswenAs40%haddissociated,
waspresent
andtherefore
0.60x 0.080= 0.048molof PClu
hadreacted.
0.080- 0.048= 0.032molof PClu
PCI.
PCI,
cr,
Total
0
0
0.080
-0.032
+0.032
+0.032
Change/mol
amount 0.60x 0.080
Equilibrium
= 0.048
0.032 0.112
0.032
/mol
0.032t0.1120.032t0.112
0.04810.112
Molfraction
=0296
=0286
= 0.429
pressure
x2
0.286x 2
0.286
0 . 4 2 x92
Partial
= 0.571
= 0.571
= 0.857
/atm
lnitialamounVmol
= 0.571
p(Cl,),.
atm= 0.38atm
atmx 0.571
l( = p(PCl,),'
Variation
of K with
conditions
thequotient
whenthe
Konlyequals
This is the only factor that alters the value of K.
o Temperature.
lf the
is atequilibrium.
system
i
If a reaction is exothermic left to right, an increase in temperature
quotient
is greater
thanK,the
will lower the value of K. This means that the position of
willmoveto theleftuntil_
reaction
equilibrium will shift to the left (the endothermic direction).
lf thequotient
is
thetwoareequal.
ii
If a reaction is endothermic left to right, an increase in temperature
willmove
lessthanK thereaction
will
increase the value of K. This means that the position of
to therightuntilthetwoareequal.
will shift to the right.
equilibrium
alterthevalue
Temperature
changes
AH=0).Concentration
of K(unless
O Catalyst. This neither alters the value of K nor the position of
changes
alterthevalue
andpressure
equitibrium. It speeds up the forward and the reverse reactions equally.
of thequotient.
Thus it causes equilibrium to be reached more quickly.
euANTrrATrvE
EeurLrBRrA AND FUN.TT.NAL
GRoup
cHEMrsrRy
"aRroDrcrry,
O Concentration. A changein the concentration of one of the

substancesin the equilibrium mixture will not alter the value of K, but
it will alter the value of the quotient. Thereforethe reaction will no
longer be at equilibrium. It will reactuntil the value of the quotient
once again equalsK. If the concentration of a reactanton the left hand
sideof the equation is increased,the position of equilibrium will move
to the right.
o Pressure. A changein pressuredoesnot alter K. If there are more gas
moleculeson one side than the other, the value of the quotient will be
alteredby a change in pressure.Thereforethe reaction will no longer be
at equilibrium, and will react until the value of the quotient once again
equalsK. If there are more gasmoleculeson the right of the equation
and the pressureis increased,the position of equilibrium will move to
the left. For example,if the pressureis increasedon the equilibrium
NrOn(B)+ 2NOr(g),the position of equilibrium will shift to the left as
there are fewer gasmoleculeson the left side of the equation.
Checklist
[i Can define the partial pressureof a gas.
[l Can deducethe expressionfor K. and its units given the equation.
E Can deducethe expressionfor Koand its units given the equation.
E Can calculatethe value of K. given suitabledata.
|J Ca.r calculatethe value of K, given suitabledata.
fl Kt o* not to include valuesfor solids and liquids in the expression
for Ko.
I] Knot" that only temperaturecan alter the value of K, and how it will
affect the position of equilibrium.

For the following questions,cover the margin, write your answer,then
= 0.781
x 104= 81.2kNm-'
P(N,)
=
x 104=21.8kNm-'
P(0,) 0.210
=
x 104= 0.9kNm-'
P(Ar) 0.009
8 K= [S0J'
= mofl dmg
tsortoJ
o Dry air at a pressureof 104 kN m-'contains 78.Io/onitrogen 2I.Oo/o

oxygen and 0.9o/oargon by moles. Calculatethe partial pressuresof
eachgas.
O Write the expressionfor K., stating its units, for the following reactions:
^ 2SO,(g)+ O,(B)+ 2SO,(g)
b
zHcl(g) +'1,o,(g)+ H,o(g) + cl,(g)
b K= [H,0][Cl,] = mofz dmil2
lHctit
ro,r
d 6=p(CH,0H) atm-'
p(CO)
x p(H,))'
b K,=499)no.units
p(c0)
O Write the expressionfor Ko,stating its units, for the following reactions:
a CO($ + 2H,(g)+ CH,OH(g)
b
Fe,O,(s)+ CO(g)+ 2FeO(s)+ CO,(g)
L When a 0.0200 mol sampleof sulphur trioxide was introduced into a

vesselof volume I.52 dm3at 1000'C, 0.01,42mol of sulphur trioxide
was found to be presentafter equilibrium had been reached.
ACID-BASE
EQUILIBRIA
Calculatethe value of K for the reaction:

2SO,(g)+ 2SO,(g)+ O,(g)
Theanswers
to thenumbered
questions
133.
areonpage
2 I.O mol of nitrogen(Il) oxide, NO, and 1.0 mol of oxygen were mixed 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 pressurein the vesselwas
4.0 atm. Calculatethe value of K, for the reaction:
2NO(S)+ O,(g) -- 2NO,(g)
3 This questionconcernsthe equilibrium reaction:
2SO,(g)+ O,(g)-- 2SO.(g) AH = -796 kJ mol-l
K. = 3 x 10*mol-t dm3at 450'c
a
2 mol of sulphur dioxide, I mol of oxygen and 2 mol of sulphur

trioxide were mixed in a vesselof volume l0 dmt at 450 "C in the
are initially in
presenceof a catalyst.Statewhether thesesubstances
equilibrium. If not, explain which way the systemwould react.
Stateand explain the effect on the value of K. and on the position of

equilibrium of:
i
decreasingthe pressure
ii
iii adding more catalyst.
equilibria
(g Acid-base
<ffi
Introduction
o It is essentialthat you can write the expressionfor K" of a weak acid.

O Make surethat you know how to use your calculatorto evaluate
logarithms, and how to turn pH and pK" valuesinto [H-] and K" values.
I This meansusing the lg key for log,oand 10'key for inverselog,o.
o Give pH valuesto 2 decimal places.
O Buffer solutions do not have a constant pH.They resistchangesin pH.
O You may use H-, H-(aq)or HrO- as the formula of the hydrogen ion.
d-a
LN
Thingsto learn
[| A Brsnsted-Lowry
acid is a substancethat donates an H- ion (a
proton) to another species.
tr n monobasic (monoprotic) acid contains, per molecule, one hydrogen
atom which can be donated as an H" ion. A dibasic acid contains two.
tr e Bronsted-Lowry
another species.
base is a substancethat acceptsan H* ion from
E K. = [H-(aq)][OH-(ag)]= 1.0 x 1O" mol' dm* at 25 "C.

f A neutral solution is one where [H-(aq)]= [OH-(aq)].
f
dmt).
pH = -log,o[H.(aq)],'ormore accurately= -log,o([HrO.(aq)]/mot
ANswERs
NaCl(s) the electrons are localised on the ions, not
loosely held and the ions are fixed in their
positions in the lattice and so are not free to move.
4 a i
ll
Topic7.4 ThePeriodicTableI
b i
1 a
b
2 a
b
c
d
e
f
They all have the same number of electrons in

their outer shell. For Group 2 this number is 2.
This period is Period 4, and so all the members
have electrons in four shells.
H, is simple molecular
Na is metallic
Si is giant atomic
S*is simple molecular
Cl, is simple molecular
Ar is simple molecular (argon is monatomic).
ll
T h ea n s w e r ' h y d r obgoennd eodr' ' i o n i c 'a n n oatp p ltyo

elements.
Sodium and magnesium are metals. Magnesium is
2+ and has a smaller ionic radius. therefore it will
have stronger metallic bonds and a higher melting
temperature. Silicon forms a giant atomic structure
with each silicon atom ioined covalently to four
other silicon atoms. These strong covalent bonds
have to be broken. This requires a huge amount
of energy and so the melting temperature is very
high.
C a r b o inn,t h ef o r mo f d i a m o nhda, sa s i m i l asrt r u c t u r e ,

b u ta st h es m a l l ecra r b oant o mf o r m s t r 0 n g e
b ro n d s
t h a ns i l i c o nd,i a m o n dm' se l t i ntge m p e r a t u
i sreev e n
higher.
White phosphorus, sulphur and chlorine all form
simple molecular solids. The melting temperatures
depend upon the strengths of their intermolecular
forceswhich are dispersion (induced dipole/induced
dipole) forces.The strength of this force depends
upon the number of electrons in the molecule.
Nuclear charge is equal to the number of

protons in the nucleus.
Screeningor shielding occurs when an outer
electron is insulated from the pull of the
positive nucleus by electrons in inner shells.
The 1st ionisation energy of sodium is for
the removal of the 3s el ectron. S odium has a
nucl ear chargeof + 11, but the 3s e lect r on is
shi el dedby the 10 el ectronsi n the 1st and
2nd shel l s.The secondel ectron that is
removed comes from the Znd shell (it is a 2p
el ectron).Thi s el ectron i s shi el dedf r om t he
nucl eus onl v bv el ectronsw hi ch ar e in a
l ow er shel l , rvhi ch i n thi s casei s by t he t wo
1s el ectronsand so i t i s hel d much m or e
strongl v bv the nucl eus.It i s al so n ear ert o
t h e n u c l e u s ,r v h i c h m a k e si t e v e n h a r d e r t o
remoV e.
S o d i u m h a s a n u c l e a rc h a r g eo f + 1 1 a n d i t s
3 s e l e c t r o ni s s h i e l d e db v t h e i n n e r 1 s t a n d
2 n d s h e l l e l e c t r o n s \. l a g n e s i u m h a s a
n u c l e a rc h a r g eo f + 1 2 ( o n e n l o r e t h a n
sodi um), but i ts 3s el ectron i s shi eldedby
the same i nner el ectrons.Thus i ts 3s
electrons are pulled more strongly to the
nucleus and are harder to remove.
I t i s b e c a u soef t h i se x t r a
o u l tl h a ta m a 0 n e s i u m
a t o mi s s m a l l et hr a na s o d i u m
atom.
Topic7.5 Introductionto
oxidationand reduction
1 a
Sn"(aq) -- Sn'.(aq)+ 2e
E l e c t r o nasr e0 n r i g h tb e c a u sSen ' .i s o x i d i s e d2 :e i s n e e d ebde c a u soex i d a t i onnu m b ecrh a n g ebsy 2 .

b
c
T h es i m p l e swt a yi n w h i c ht o w o r kt h i so u t i s t o a d d
t o g e t h et rh ea t o m i cn u m b e rosf a l lt h ea t o m si n t h e
mo l e cul e .
Pnhas 4 x 15 = 60, S*has 8 x 16 = 128 and Cl, has
2 x I 7 = 34 electrons per molecule. Thus sulphur
has the strongest intermolecular forces and the
highest melting temperature and chlorine has the
weakestintermolecular forces and the lowest
123
F e ' - 1 a q+) e --'Fe"-(aq)

S n ' - ( a q )+ 2Fe''.(aq)-- Snn.(aq)+ 2Fe'.(aq)
E q u a t i obnh a st o b e d o u b l e ds,o t h a tt h ee l e c t r o n s
c a n c ewl h e n2 t i m e sb i s a d d e dt o a .
2 a
HrOr(aq)+ 2H.(aq) + 2e- -. 2HrO(l)
H . 0 ,i s r e d u c e ds ,o e l e c t r o nasr e0 n t h el e f t .
AcrD-BAsEEeurLrBRrA
Therefore the pH of a 0.109 mol dm-' solution of NaOH is calculated:
pOH = -log,o(0.109) = 0.96
fherefore pH = 14 - 0.96 = 13.04
pH of weok ocids
o Weak acids are partially ionised. A general equation for this is:
HA(aq)+H-(aq)+A-(aq)
o The acid produces eqrral amounts of H- and A-, so that:
lH'(aq)l = [A-(aq)]
O This enables either the pH of a weak acid solution or the value of K. of a
weak acid to be calculated.
Worktl'oxarorylt,
thepHof a 0.123moldm'solutionof anacidHAwhichhas
Calculate
K. = 4.56x 10'moldm{:
HA(aq)+H'(aq)+A(aq)
= U'(aQl:
Answer: ( = [H-(aq)][A(a_q)]
IHA(aq)l [HA(aq)]
lH'(aq)l= 7'j( JHA(aq)l)
= 2.37x 10-'mol
=/+.SO
dm-3
x 10*x 0.123)
-log,o(2.37x10-')
= 2.63
pH =
Titration
curves
o These are drawn either for the addition of base to 25 cm' of a 0.1 mol
dm-' solution of acid until the base is in excess,or for addition of acid
to a base (seeFigure 4.3).
a If the acid and base are of the same concentration, the end point is at
25 cm'.
t There are several pH values to remember.
At halfwayto theendpoint(12.5
cm'if theendpointis at 25cm3),
thecurvefora weakacidanda
strongbasewillbealmosthorizontal
at a pHof about5. Thisis whenthe
is buffered
and[HA]= [A].
solution
Thusat thehalfwayPH,FK.= PH
fortheweakacid.
Fig 4.3 Titrationcurves
Starting
pH
End point
pH
Vertical pH
range
Final
pH
1
3
1
7
9
5
3 . 5t o 1 0 . 5
7 to 10.5
3.5 to 7
13
13
11
Strong acid/strongbase
Weak acid/strongbase
Strong acid/weakbase
Strong acid/
1 3 Weak acid/
13
11
1L
0
2
5
0
2
s
0
2
5
Volumeof alkali/cm3 Volume of alkali/ cm3 Volume of alkali/ cm3
ANsweRs 125
iodide, HI is produced by the protonation of the
iodide ions, but the HI is a very strong reducing
agent, and so it will reduce the sulphuric acid and
itself become oxidised to iodine.
ll
4 Disproportionation is a reaction in which an

element is simultaneously oxidised and reduced.
Chlorine disproportionates when added to alkali:
Cl, + ?OH- - Cl- + CIO- + H,O
( 0)
(-1 ) (+ 1 )
Also, chlorate(I) disproportionates when heated:
3ClO- -- ZCl- + ClO,,
(+1)
(-1) (+5)
Answersto PracticeTestUnit 1
The allocation of marks follows Edexcelmark
sc hem es .
The marks that you will need for each grade are
approximately:
A
7Oo/o
B
6lo/o
C
52o/o
D
44o/o
E
360/o
= [1]
Z C a +O r - Z C a O
= [1]
NarO + HrO ---+2NaOH
Na,O + ZHCI ---; 2NaCl + H,O
= l2l
Species[.], balancing [.]
b The thermal stability increasesdown the group
[f.] as the cation size increases[1] and so the
carbonate ion is distorted (or polarised) less tll
_ t3l
b Graphite has covalent bonds between atoms that

have to be broken [1]; sodi um chl ori d e has
el ectrostati cforcesbetw een the i ons [1 ] . I n bot h
these forcesare strong and so a l ot of e ner gy is
= [ 31
neededto break them [1]
c i
Graphi te has del ocal i sedel ectronsabove and
bel ow the pl ane of he.ragons[1], which can
ii
iii
2 a i
Graphite has a giant atomic (or giant

covalent) structure [1]. The bonding between
atoms is covalent [U.
Your diagram must show several interlinked
= [4]
hexagons [1] in layers tU
The l atti ce i s broken don' n i n the l iquid and

so the i ons are free to nl ove
=[u
a S t r u c t u rmee a n gs r a nat t o m i ci .o n i cl a t t i c e ,
s i m p l oe r h ,d r o g e bn o n d em
d o l e c u loarra
l a t t i coef m e t arl o n si n a s e ao f e l e c t r o n s .
c A s u b s t a n c, e' r, l lc o n d u cet l e c t r i c iitfyi t h a s
d e l o c a l r seel d
e c t r o nt hs r o u g h otuhtes t r u c t u r e
o r i o n s ' , ' . , har rcehf r e et o m o v e .
L ai
b Donotattempt
to answer
thistypeof question
in
termsof sizematch.
= f2l
flow (which are mobilet [1]

ll
3 a i
A tomi c number i s the number of prot ons in

the nucl eus [1] Mass number i s the t ot al ( or
sum of the) number of protons and neut r ons
tu
= l2l
= [1]
High energy electrons bombard the Br,
molecules [1] and knock out an electron [1]
= [2]
ll
They are acceleratedby charged plates (or
= [1]
an
across
-" B r-' ' B
r. electric field)
= [U
iii
ii
b i
,.gt-
has1 fewerelectrons
than
a ii Astheparticle
p r o t o nist ,w i l lb ea p o s i t i vi o
en .
a i i i I na m a s s p e c t r o m emt eorset l e m e n t s
p r o d u ci o
e n sc o n t a i n ionngea t o mb, u t
d i a t o mei cl e m e nst us c ha sN , ,0 , a n dt h e
h a l o g eg
n isv em o l e c u liaorn ss u c ha sB 1 2
w h i c hm a yc o n t a it nw od i f f e r einsto t o p e s .
It
Sodium chloride has a lattice structure t l l .

The bonding is ionic [l.].
Your diagram must show a 3-D arrangement
= [3]
of ions, Na. alternating with Cl-. [1]
4 a
Divide each o/oby their A, values [L] and then divide
by the smallest [1]
H
L 1 . L* 1 = L 1 . 1 t h e n * 7 . 4 = 1 . 5
C
88.9* 12 = 7.4 then + 7.4= 1
Multiply both by 2 to get whole numbers
= [3]
.'. E.F.is CrH. tll
.l
AcrD-BA'E Eeur.-rBR'A
Workpi,oxiloLf.h'
Calculate
thepH0f 500cm3of a solution
containing
0.121m01
of ethanoic
acid
and0.100molof sodium
ethanoate.
pK^torethanoic
acid= 4.76
gK, = 4.76,
Answer.
Therefore
/( = inverse
log(-p0 = 1.74x 10-umoldm-'
[weakacid]= 0.121+0.500 = 0.242moldm-3
= 0.100+ 0.500 = 0.200moldm-3.
[salt]
=
= 1.74x 10u x0.242=2j0x 10-u
(.
moldm-'
[H-(aq)] [weakacid]
Isalt]
= 4.68
pH = -log,o[H-(aq)]
Enthalpy
0.200
of neutralisation
=
When a strong acid is neutralised by a solution of a strong base,A.FI,,",,,
-57 kJ mol-', becausethe reaction for strong acids n'ith strong basesis:
H -(aq)+ OH -(aq)= H ,O(l l
The value for the neutralisation of a weak acid is less becauseenergv has to
be used to ionise the molecule to form H- ions.
a
IJ)'I
i //,-r.--t---)a
H

lJ Can identify acid/base coniugate pairs.
*l Can define pH and K-.
u.J Can define K" and pK" for weak acids.
U Understand what is meant by the terms strong and weak as applied to
acids and bases.
iJ Can calculate the pH of solutions of strong acids, strong basesand weak
acids.
iJ Can recall the titration curves for the neutralisation of strong and weak
acids.
tl Can use the curve to calculate the value of K" for a weak acid.
if Understand the reasons for the choice of indicator in an acid/base
titrations
[J Can define a buffer solution, explain its mode of action and calculate its pH.
j.ld
t,XE),Testingyour knowledgeand understanding
L/.-
,-
For the following questions, cover the margin, write your answer, then check
to see if you are correct.
AcidH,S0o:
itsconjugate
baseHSO.- o Identify the acid/base conjugate pairs in the reaction:
BaseCH,COOH:
itsconjugate
acid
HrSOn + CH,,COOH + CH.COOH2- + HSO,-
cH,c00H,-
a 0.96
b 13.04
c 13.34
O Calculate the pH of:

a 0 .1 1 mol dm* H C I
b 0.1 1 mol dm-' LiOH
c 0.11 mol dm-' Ba(OH),
EI
euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMtsrRy

"a*roDrcrry,
=
tothenumbered L Calculate the pH of O.22 mol dm-' C2H'COOH which has pK. 4.87.
Theanswers
questions
133-134. 2 25 cm' of a weak acid HX of concentration 0.10 mol dm-t was titrated
areonpages
with 0.10 mol dm-' sodium hydroxide solution, and the pH measuredat
intervals. The results are set out below:
10
T2
20
23
24
25
26
30
Volume NaOH/cm3
pH
4 . 5 4 . 8 4.9 5 . 5 6 . 5 7 . 0 9 . 0 12.o 1 2 . 5
Draw the titration curve and use it to calculate pK, for the acid HX.
Suggest a suitable indicator for the titration.
3 a
b
Define a buffer solution and give the name of two substances that
act as a buffer when in solution.
Explain how this buffer would resist changes in pH, if small
amounts of H- or OH- ions were added.
4 Calculate the pH of a solution made by adding 4.4 g of sodium

ethanoate, CHTCOONa,to 100 cmt of a0.44 mol dm-'solution of
ethanoic acid. K" for ethanoic acid = I.74 x 10-smol dm-'.
ll
chemistry
@ 0rganic
',"'"\
..H
"
(H
fhings to learn and understand
Isomerism
iJ Structural. Therearethreetypes:
a
Carbon chain. Here the isomers have different arrangements of

carbon atoms in a molecule,
e.g. butane, CH.CH TCHTCH,and methyl propane, CH.CH(CHr)CH..
Positional. Here a functional group is on one of two or more

different places in a given carbon chain,
and propan-Z-oI, CH.CH(OH)CH..
e.g. propan-l-ol, CHTCHTCHTOH,
Functional group. Here the isomers have different functional groups,
e.g. ethanoic acid, CH3COOH and methyl methanoate, HCOOCH..

:J Stereoisomerism.
There are two types:
a
Thetwoisomers
arenot
interconvertible
atordinary
there
is no
temperatures
because
rotation
a double
bond.
about
Geometric. This is caused by having two different Sroups on each

carbon atom of a >C=C< group (see Figure 4.4).
H,C
\
/
H
CH,
C-C
/
\
H
cis-but-2-ene
H:C
\
/
H
H
C-C
/
\
CH.
trans-but-Z-ene
Fig . cisond transisomersof but-2-ene
136 AxsweRs
c An increase in temperature shifts the equilibrium
in the endothermic direction. .'.AH is
positive = [1]
d Ko stays constant [1] The position of equilibrium
moves to the side with fewer gas molecules [1],
= [3]
which is to the left [1]
Mix scrap aluminium metal with AlCl, and heat
to form AlCl [U, remove from excessAl, then
cool (or increase pressure)and pure Al and AlCl3
are formed. The latter is then used again [1] = [2]
t4
12
10
pH8
6
4
2
0
25
a S o l i ddson o ta p p e ai nr K oe x p r e s s i 0 n s .
pressure
x totalpressure.
is molefraction
b Partial
c K i s o n l ya l t e r ebdyt e m p e r a u r e .
-- MgSO.,(aq)
+ H,O(l)
MgO(s)+ H,SOn(aQ)
Correctequation [1] statesymbols[L] = lz'J
ii A white solid [1] reactsto form a colourless
5 a i
= fz'l
solution [1.]
b i PnO,o+ L2NaOfl ---+4NarPOn+ 6HrO
or PrO.,+ 6NaOH ---+2NasPOn+ 3HrO
= I2f
All speciescorrect [l.], balanced [1]
(or
HCI)
ii For having 2 equations, one with H'
and the other with OH- (or NaOH) [1,] and:
AI(OH)3 + 3H* -- Al''* + 3HrO or
AI(OH)3+ 3HCl --' AICIr + 3H,O [1.] plus
AI(OH), + 3OH- -r Al(OH)u'-or
= [3]
AI(OH), + 3NaOH -'Na,Al(OH). [1]
is
MgO is basic, AI(OH). is amphoteric and PnO,o
acidic [L] showing the metallic character of the
= f2l
element decreasingacrossthe period tll
get
more
As a Group is descendedthe oxides
basic [1]. Indium is in the same Group as
amphoteric aluminium, so indium oxide will be
= I2l
basic [1]
equations.
areverybadatwriting
Manystudents
t ake
s u r et h a yt o ul e a r tnh ee q u a t i oinns
Y o um u s m
T o p i4c . 2o l t h es p e ci icf a t i o n .
youareasked
to statewhatyouwould
a Whenever
s e ey, o um u s dt e s c r i bt heea p p e a r a nbceef o raen d
afterreaction.
6 a An acid is a proton donor [,],
Weak means that it is incompletely dissociated
(ionised) [L], but dilute means that its
= [3]
concentration is small [1]
b i pH = -log,u [H.]
ii Ku = 3.72 x lO-" = [H.]tOCl-l
Vol. NaOH/cmE
Shape of curve correct [L], start at pH = 4 llf,
vertical at 25 cm' [1] and at a pH of between 7 and
= [5]
11 [f.], curve flattening off at pH 13 [1]
i
HrSOl --' H* + HSO.,- [L]

HSO.*-+ H* + SOn^ [1]
ii
The second ionisation is incomplete and is

suppressedby the H. from the first ionisation,
= [1]
and so produces very few H. ions
= [2]
withdilute
a Don'tconfuseweak(howionised)
( h o wm a n ym o l e s ) .
b T og e tf r o mp Ht o [ H - ]u, s et h e1 0 "b u t t oonn
y o u rc a l c u l a t o r .
d S u l p h u rai c i di s o n l ys t r o n ign i t s1 s t
i o n i s a t i osnot, h i ss o l u t i ohna sa p Ho f 0 . 9 8n o t
0.699.
U n i5t
Topic5 .7 Redoxequilibria
1 a i
ii
iii
iv
CrrOr'- (aq) + 14H'(aq) + 6e- -- 2Cr"(aq) +

THrO
Snn.(aq)+ 2e- -- Sn'.(aq)
IO, (aq) + 6H .(aq) + 5e- -' 1,1,+ 3H rO
l, + 2e- -- Zl-(ag)
=[u
lHocll
= 5 .8 9 x 1 0 -' mo l d m
[ H] = 10- o n
-r
lHl = [octl tl]

.'. tHOCll= (5.89x 10-')'* 3.72x 1 0 *
= 0.0932 mol dm-' [1]
tU
tll
= [41
nn
st h el e f t .
A l la r er e d u c t i oannsds oh a v e l e c t r o o
n
nq
s u a lt sh et o t acl h a n gi e
T h en u m b eorf e l e c t r o e
o x i d a t i onnu m b e r .
EI
"a*roDrcrry,
euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy
Preparation
They can be made by the oxidation of a primary alcohol. The alcohol is
heatedunder reflux with dilute sulphuric acid and excesspotassium
dichromate(Vl).
Reactions
O + alcohols to produce esters:
+ CH3COOCTH,
+ HrO
CH3COOH+ CTHTOH
ethyl ethanoate
conditions: heat under reflux with a few drops of concentrated
sulphuric acid.
Testfor a carboxylic
acid.When
toaqueous
added
sodium
(orsodium
hydrogencarbonate
it gives
carbonate),
a gas,C0,,
which
turnslimewater
milky.
o + lithium tetrahydridoaluminate(Ill) to produce a primary alcohol:

CH3COOH+ a[H] 'CH'CH,OH + H,O
ethanol
followed
by hydrolysis with H.(aq).
dissolve
in
dry
ether,
conditions:
o + phosphoruspentachlorideto produce an acid chloride:
CH'COOH + PCI' - CH'COCI+ HCI + POCI,
ethanoyl chloride
conditions: dry; observation:steamyfumes given off.
Esters
Thesehave the generalformula RCOORwhere R and R are atkyl or aryl
groups,and which may or may not be different.
o
R-C
/
\
Thisreaction
Theacidisa catalyst.
hasa lowyieldbecause
it isa
reversible
reaction.
Thisreaction
hasa highyield
it is notreversible.
because
o-
R'
Reactionsof ethyl ethanoate

o Hydrolysis with aqueousacid to produce the organic acid and the
alcohol:
+ HrO + CHTCOOH+ CTHTOH
CH3COOCTH,
ethanoic acid
conditions: heat under reflux with dilute sulphuric acid.
o Hydrolysiswith aqueousalkali to produce the salt of the acid and the
alcohol:
+ NaOH - CHTCOONa+ CTHTOH
CH3COOCTH,
sodium ethanoate
with
conditions: heat under reflux
Corbonyl compo,unds(oldehydesond ketones)
Thesecontain the C=O functional group. Aldehydeshave the general
formula RCHO,and ketonesthe generalformula RCORwhere R and R are
alkyl or aryl groups, and may or may not be different.
o
R-C
/
\
H
Aldehyde
R-C
/
\
R'
Ketone
oRGANrc cHEMrsrRY rl
Reactionsin common
a Addition of hydrocyanic acid, HCN, to produce a hydroxynitrile:
CH,CHO + HCN - CH,CH(OH)CN
2 -hy dr oxypr o p an en i t ri I e
conditions: there must be both HCN and CIS present,
e.g. HCN + a trace of KOH, or KCN(s) + some dilute sulphuric acid.
o Reduction with lithium tetrahydridoaluminate(Ill) to produce an
alcohol:
C H 3C H O+ 2[H ] -C H TC H TOH
CH'COCH, + 2[H] - CH.CH(OH)CH3
Theformation
ofanorange
orred
precipitate
is a testfor
with2,4-DNP
i.e.forboth
carbonyl
compounds,
aldehydes
andketones.
conditions: dissolve in dry ether, followed by hydrolysis with H-(aq).

Or reduction with sodium tetrahydridoborate(Ill), also to produce an
alcohol:
CH3CHO + 2[H] 'CHTCH,OH
CH3COCH. + 2[H] - CH,CH(OH)CH,
conditions: aqueous solution, followed by hydrolysis with H-(aq).
a Reaction with Z,4-dinitrophenylhydrazine (2,4-DNP) to give an
orange/red precipitate:
NO,
NOt
2,4.DNP
Theformation
of thesilvermirror
is the
withammoniacal
silvernitrate
testwhichdistinguishes
aldehydes,
result,
from
whichgivea positive
whichhaveno reaction.
ketones,
Aldehydes
arealsooxidised
by
potassium
l) or
manganate(Vl
potassium
dichromate(Vl).
acidified
to dothisis
Theonlyaldehyde
ethanal,
CH3CH0.
Thisreaction
is oftenusedin
questions.
The
organic'problem'
yellow
precipitate
produced
pale
on
hydroxide
and
addition
ofsodium
iodine
istheclue.
Theorganic
this
thatproduces
compound
precipitate
willeither
bea carbonyl
groupor analcohol
witha CH,C=Q
group.lt is nota
witha CH.CH(0H)
general
testforketones.
Specificreactionof aldehydes
Aldehydesare oxidised to carboxylic acidsby a solution of silver nitrate in
dilute ammonia. On warming the silver ions are reducedto a mirror of
metallic silver.
Aldehydesare also oxidised by warming with Fehling'ssolution, which is
reducedfrom a blue solution to a red precipitateof copper(I) oxide:
C H . C H O + [ O ]- C H ' C O O H
Iodoform reoction
o This is a reaction which producesa pale yellow precipitate of iodoform,
CHI3,when an organic compound is addedto a mixture of iodine and
dilute sodium hydroxide (or a mixture of KI and NaOCI).
t The group responsiblefor this reaction is the CH'C=O group, and the
reaction involves breaking the C-C bond betweenthe CH, group and
the C=O group.
+ CHI.(s)
producesCTHTCOONa
CHTCOCTH,
give
group
will
this precipitate.
a All ketonescontaining the CH.C=O
the CH.CH(OH)
containing
O This reaction is also undergoneby alcohols
reaction
conditions
to the CH.C=O
group. They are oxidised under the
give
iodoform.
group, which then reactsto
Acid chlortdes
Thesehave the generalformula RCOCI,and the functional group is:
o
-C
/
CI
e.g.ethanoyl chloride,CH.COCI,and propanoyl

chloride,CrHrCOCl.
El
e u A N T r r A T r v E E e u T L I B R I AA N D F U N c T t o N A L G R o u p c H E M I s r R y
".RroDrcrTy,
Reactions of ethanoyl chloride
O + water to produce the carboxylic acid, ethanoic acid:
CHTCOCI + HrO - CHTCOOH + HCI(g)
observation: steamy fumes of HCl.
o + alcohols to produce an ester:
CH3COCI + CTHTOH- CHTCOOCTH'+ HCI
observation: characteristic smell of the ester, ethyl ethanoate.
o + ammonia to produce the amide, ethanamide:
CHTCOCI + 2NH. - CHTCONH, + NH4CI
I + primary amines to produce a substituted amide:
CHTCOCI + CrHrNH, - CH3CONH(CrH') + HCI
compounds
Nitrogen
Primory omines
o They contain the -NH, group, e.g. ethylamine C2HrNHz.
O They are soluble in water (if the carbon chain is fairly short) because
they form hydrogen bonds with water molecules.
o They are weak bases.
from
Theaminecanberegenerated
thesaltbyadding
a strongalkali.
Reactionsof ethylamine
O + acids,to form an ionic salt that is soluble in water:
C2H'NH2+ H.(aq) + CrHrNHr.(aq)
| + acid chlorides,to form a substitutedamide:
C2H'NH2+ CHTCOCI-'CH'CONHC2H, + HCI
Nitriles
They contain the C=N group, e.g. propanenitrile C,H'CN.
bythe
Nitriles
canbeprepared
with
reaction
ofa halogenoalkane
KCN
inaqueous
ethanol.
by
Hydroxynitriles
canbeprepared
to carbonyl
theaddition
of HCN
inthepresence
ofbase.
compounds
Reationsof propanenitrile
O Hydrolysis either with acid:
+ NHn*
CTH'CN+ H* + zHrO - CTHTCOOH
conditions: heat under reflux with dilute sulphuric acid
or with alkali'
+ NH,
crHscN + oH- + Hro'crHrcooconditions: heat under reflux with dilute sodium hydroxide
O Reductionby lithium tetrahydridoaluminate(Ill):
C'H'CN + a[H] - C2H'CHNH,
conditions: dry ether, followed by addition of dilute acid
Amldes
They contain the CONH, group, .8. ethanamide CHTCONHT.
o
cHg-Q
/
\
NH,
Reactionsof ethanamide
O Dehydration with phosphorus(V)oxide:
CH3CONH,-HzO-CH'CN
distil off the ethanenitrile.
warm
and
conditions:
A,NSwERS 141
lv
Mix the blue Cr'* solution separately with

bromine and iodine [1], the solution goes
green and stays green with excesshalogen
tll
= [2]
t h a n3 d o ,
a R e m e m b tehr a t3 d ' ,4 s ' i s m o r es t a b l e
4 s ' ( a n ds i m i l a r lfyo r C uw h i c hi s 3 d ' 04, s ' ) .A l s o
t he4 s e l e c tro nasrel o s tfi rs tw h e nc ati onsare
fo r m e d .
c i A l lt r a n s i t i om
n e t ailo n sa r eh y d r a t eidn
s o l u t i o nw, i t h6 w a t e rm o l e c u l ecso o r d i n a t e l y
b o n d e od n .
iv Chromium
i s a m p h o t e r iIcC. r ( 0 H ) ,w
] -o u l db e
a n a c c e p ta bal en s w e r.
v A d d i t i oonf a c i dw i l lf i r s tp r e c i p i t atthee
h y d r o x i dweh i c ha, s i t i s b a s i cw, i l lt h e nr e a c t
w i t he x c e sas c i dt o f o r ma s o l u t i o o
nf t h e
h y d ra tem
d e ta il o n s .
The allocation of marks follow Edexcel mark schemes.
approximately:
a D o n ' ft o r g etto m u l t i p l by y 1 0 t o g e tt h et o t a l
a m o u not f t h eN H , ' i o n sa,n dt h e nh a l v ei t a st h e r e
i s I a m o l eo f a m m o n i u smu l p h a tpee r1 m o lo f
N H .i o n s .
F o r g e t t i nt og d i v i d eb y 2 g i v e st h ea n s w e9r 7 . 3 Y o
( o b t a i n ebdy a b o u 't/ ,o f t h ec a n d i d a t ewsh) i c h
score4
s marks.
c i I n a p r e c i p i t a t i roena c t i otnh e r ea r ej u s tt w o i o n s
o n t h el e f ta n dt h ef u l lf o r m u l oa f t h es o l i do n
t f t h ee q u a t i o n
t h er i g h o
t i v ea g r 0 u p1 c a r b o n a tneo, r B a C Oa, ,s i t
d Don'g
n h e a t i nign t h el a b ,n o r
t decompo0
se
doesn
B e C 0b e c a u si ted e c o m p o sbees l o wr o o m
temoerature.
Answer any two of the section B questions

2 a A ny tw o of : i t i s consi derabl ycheape r[ 1] ;
l essri sk of l eachi ng tU
it does not effect the pH of the soil [1]
= [21
it releasesthe nitrogen slowly [L]
b The smaller the K" of the conjugate acid, the
stronger the base [1]. Therefore ammonia is the
= I2l
stronger base [.]
Polymerisation occurs when many molecules ioin
to form a long chain [1]; condensation is with
the elimination of water or a small inorganic
molecule such as HCI [L].
A polyamide contains the -CONH- link [1] as in:
O
/ll ,
1 a Amount of NaOH = 0.100 mol dm-' x 0.0280 dm'

= 0.00280 mol [f.] = moles of H.
Ratio H. to NHn*= 1 : 1".
Amount of NH.,.in 25 cm' = 0.00280 mol.
Amount in 250 cm' = 0.0280 mol [L]
'1,
, O.o280= 0.0140 mol
Amount of (NHr)rSOn[ 1] ,
- 0.0140 mol x 132 g mol-' =
mass of (NHn)rSOn
1. 848 I [ 1] ,
o/o(NH*)'SO.*
in fertiliser = 1".848x 100/3.80 =
= [5]
48.60/ofaf
b Any two of: not all ammonia driven off [1];
ammonia incompletely absorbed by the HCI [f,];
= I2l
some ammonia gas escapes[1]
i Ba'.(aq)+ SOn'-(aq) - BaSO.(s)
= f2l
Species[1], state symbols [1.]
ions
were
ii To ensure that all the sulphate
= [U
precipitated
d Many carbonateswill decomposeon heating [L],
and the CO, gas evolved will result in a lower
mass being recorded [1]. An example is CaCO. [1]
= [4]
CaCO, - CaO + CO, [1]
d i
ll
e l
ii
ll |
l\
-(
n,),-*+
cH,)--i*-(.
tu
+.
The reagentsare : liquid bromine [1] and

concentrated sodium hydroxide [1]. The
= [3]
condition is that it must be heated [1]
= [u
NH.NH,
Solids are not included in Ko expressionsand
= [1]
ammonium nitrate is a solid.
As the reaction is endothermic, the energy
level of the products is higher than that of the
reactants [1], therefore the reaction is said to
a T h ed i s a d v a n t aogf eu s i n gu r e aa r et h a ts o m eu r e a
if thereis norainwithin4 daysof
evaporates
especially
l tnc .a n n obteb l e n d ewdi t hp h o s p h antoer
applicatio
p o t a s s i uf emr t i l i s e ar sn,di t i s l e s ss u i t a bol enc h a l k y
e s e e d l i n gl tsd. o e sn o tw o r k
s o i l sl.t c a nc a u sdea m a gt o
i f t h es o i li s t o oc o l d .
thebase,
theweaker
itsconjugate
acid.
c Thestronger
t ai cb i l i itsyt o d ow i t hA Ha n dk i n e t i c
d T h e r m o d y n asm
is to dowiththerateof thereaction.
stabilitv
EI
tr*roDrcrry,
euANTrrATrvE EeurLrBR'A AND FUN.TToNALGRoup cHEMtsrRy
Checklist
Can recognise stereoisomerism (geometric and optical) in organic
compounds.
iJ Know the effect of an optical isomer on plane polarised light.

iJ Understand the nature of a racemic mixture.
li Can recall the preparation and reactions of Grignard reagents,
.J Can recall the reactions of carboxylic acids.
lJ Can recall the reactions of esters.
'J Can recall the reactions of carbonyl compounds (aldehydes and
ketones).
iJ Can recall the reactions of ethanoyl chloride.
iJ Can recall the reactions of amines with acids and with acid chlorides.
J
Can recall the hydrolysis and the reduction of nitriles.
J Can recall the reactions of amides with PnO,oand with BrrlNaOH.

iJ Know that amino acids are both acids and bases.
yourknowledge
andunderstanding
Testing
ffi
check to see if you are correct.
a CH,CH,CH(0H)CH3
b cH,cH,c(0H)(cH3)cH3
c
CHT CHT O H
reflux
withdilute
Heatunder
hydroxide,
thenadd
sodium
dilute
sulphuric
acid.
b Addlithium
Il) indry
tetrahydridoaluminate(l
followed
bydilute
ether,
sulphuric
acid.
a water
b methanol
c ammonia
a
b
ClCH3CH2NH'cH,c0NHcH2cH3
* Write the formulae of the products of the reaction of CH,MgI with:

a propanal
b
butan-2-one
methanal.
o State the names of the reagents and give the conditions for the
following conversions:
a C,H'COOCH, to C,H'COOH + CH,OH in a high yield
b
C2H'COOH to CHTCH,CH,OH.
O State the names of the reagents needed to convert ethanoyl chloride to:
a ethanoic acid
b
methyl ethanoate
ethanamide.
o State the structural formulae of the product obtained by reacting:

a ethylamine with dilute hydrochloric acid
b
ethvlamine with ethanovl chloride.
APPENDIX
o ethanoic acid ----ran alcohol

lithium aluminium hydride (lithium tetrahydridoaluminate(III))
Reactant:
CH,COOH + a[Hl - CH,CH'OH + H'O
Equation:
dry ether solution then hydrolyse with dilute acid
Conditions:
Classification: reduction
. ethanoic acid ---+an acid chloride
phosphorus pentachloride (or PCl, or SOCIr)
Reactant:
CH.COOH + PCI, -J CH,COCI + POCI, + HCI
EqUAtiON:
dry
Conditions:
. ethanoic acid ---+a salt
sodium carbonate
Reactant:
2CH,COOH(aq)+ Na'CO,(s)
Equation:
---+
2CH,CooNa(aq) + Co,(g) + H,o(l)
Classification: neutralisation
o ethanoic acid - a salt
sodium hydrogencarbonate
Reactant:
CH.COOH(aq)+ NaHCO,(s)t
Equation:
CH,COONa(aq)+ CO.(8) + H'O(l)
Esters, e.g. ethyl ethanoate

o ethyl ethanoate --+ acid + alcohol
any aqueous stront acid such as dilute sulphuric acid
Reactant:
+ C'H.OH
CH,COOC'H, + Hp-CH,COOH
Equation:
heat under reflux
Conditions:
Classification: reversible hydrolysis
o ethyl ethanoate ----rsalt + alcohol
aqueous sodium hydroxide
Reactant:
CH,COOCTH,+ NaOH - CH,COONa + C,H.OH
Equation:
heat under reflux
Conditions:
Classification: hydrolysis (saponification)
Carbonyl compounds aldehydcs, e.g. CHTCHO, and ketones, e.g. CHtCOCH3
o Both react with:
2,4-dinitrophenylhydrazine
Reactant:
+ H'o
+ NH.NHC.H,(NO.): ---+>c:N-NHC6H'(No')'
>c{
Equation:
observed
precipitate
oranSe
solutions:
mix
conditions:
o Both react with:
hydrogen cYanide
Reactant:
+ HCN -+ >C(OH)CN
>C{
Equation:
potassium
cyanide + some dilute sulphuric acid
conditions:
Classification: nucleophilic addition
o Both react with:
lithium aluminium hydride (or sodium borohydride)
Reactant:
cH,CHo + 2[Hl - CH'CH'OH (a primary alcohol)
Equation:
CH.coCH, + 2[Hl - CH'CH(OH)CH. (a secondaryalcohol)
dry ether, then hydrolyse with dilute acid
Conditions:
o Aldehydes only react with:
Fehling's solution or ammoniacal silver nitrate
Reactant:
CH,CHO + [Ol + OH- ---rCH'COO- + H,O
Equation:
warm
Conditions:
Classification: oxidation
o Carbonyl compounds with a CH,CO group give a yellow precipitate of iodoform
with:
Reactant:
Equation:
iodine and sodium hydroxide solution

cH,cocH, + 31,+ 4OH- ---+CH3COO-+ CHI, + 3I- + 3HrO
Acid chlorldes, .8. ethanoyl chloride

o ethanoyl chloride ---'ethanoic acid
water
Reactant:
CH,COCI + H.O --- CH.COOH + HCI
Equation:
Classification: hYdrolYsis
o ethanoyl chloride ---tan ester
an alcohol
Reactant:
CH,COCI + C.H.OH --- CH.COOCTH'+ HCI
Equation:
rapid reaction at room temperature
Conditions:
Classification: esterification
EI
euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMI'TRY

"r*roDrcrry,
Practice Test: Unit 4

Time allowed 1. hr 3O min
All questionsare taken from parts of previous EdexcelAdvancedGCE papers
The answersare on pages134-136.
1 a Draw a Born-Haber cycle for the formation of magnesium chlodde, Mgcl, and use the values below to
[5]
calculate the lattice energy of magnesium chlodde.
AIflkJ mol-'
lst electron affiniW of chlorine
-364
1st ionisation energyof magnesium
+736
2nd ionisation energyof magnesium
+1450
Enthalpy of atomisation of chlorine
+LZL
Enthalpy of atomisationof magnesium
+150
Enthalpy of formation of MgClr(s)
-642
b Use the following to answer the questions in this section.
AfflkJ mol-'
Enthalpyof hydration of Sr'.
-1480
Enthalpy of hydration of Ba'.
-1360
Enthalpy of hydration of OH-
-460
Lattice energy of Sr(OH)'(s)

Lattice energy of Ba(OH)r(s)
I
ll
lll
-r894
-L768
Explain why the lattice energyof strontium hydroxide is different from that of barium hydroxide.[2]
l2l
fxplain why the hydration *tfrutpy of a cation is exothermic.
is
more
hydroxide
why
barium
explain
to
values
Use the lattice .n.igy and hydration enthalpy
t4l
soluble in water than strontium hydroxide.
(Total 13 marks)
lJanuary2001 CH 3 question4l
tll
Give the structural formula of a nitrile, CnHrN,that has an unbranched chain
primary amines can be made by reducing nitriles. Suggesta reagentthat could be used for this
tlI
purpose.
part
i.
given
in
a
nitrile
the
tU
iii Draw the structural formula of the amine producedby reducing
nucleophile?
a
tlI
i What feature of an amine molecule makesit both a baseand
base
as
a
tll
ii Give, by writing an equation, an example of an amine acting
Ethanoyl chloride, CHTCOCI,reactswith both amines and alcohols
i Give the full structural formula of the compound producedwhen ethanoyl chloride reactswith
tll
ethylamine, CrHrNHr.
tU
ii Name the type of the compound producedin c part i.
iii Stateone of ihe advantagesof reacting ethanoyl chloride with ethanol to make an esterrather than
tU
reacting ethanoic acid with ethanol.
tll
iv Write the full structural formula of the estermade in c part iii
(Total 9 marks)
ffanuary2002 Unit Test4 question5 modified]
2 a i
ii
EI
6a
b i
ii
c
quANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMrsrRy

"a*roDlcrry,
In the context of Brdnsted-Lowryacid-basebehaviour,explain the terms:

acid
weak acid
dilute acid.
Define pH
t3l
tll
Calculate the concentration, in mol dm-t, of a solution of chloric(I) acid, HOCI, which has a pH of
4.23. Chloric acid is a weak acid with K^=3.72 x 10* mol dm-t.
t4I
Sketch, on a grid of pH (y-axis) versus volume of alkali added / cm' (x-axis), the titration curve for
the titration of 25 cm' of the chloric(I) acid solution in b part ii with 50 cm' of a solution of
sodium hydroxide of equal concentration.
tsI
The concentration of hydrogen ions in a 0.100 mol dm-' solution of sulphuric acid is 0.105 mol
dm-t.
I
ll
Write equationsto show the two successive

ionisations of sulphuric acid, H2SO,,in water.
tzl
Suggestwhy the concentration of hydrogen ions is not 0.20 mol dm-'in 0.100 mol dm-' sulphuric
acid.
t1I
(Total L6 marks)
llanuary2001 CH2 question4 & lanuary 2002 CH2 question2l
.:r,i"{FF.;
ri;.
E
rag'
REDox EeurLrBRrA
oxiloLph,
WorkêoL
is
Whena redoxhalfequation
itssignmustbechanged.
reversed,
Thenumber
of electrons
ontheleftmust
handsideof onehalfequation
thenumber
equal
ontheright-hand
sideof theotherhalfequation.
is
Whena redoxhalfequation
multiplied,
itsE+valueis not
altered.
thatthereactants
Always
ensure
in thequestion
thatarespecified
(here
theyareiron(ll)
and
ions)are0ntheleftmanganate(Vll)
handsideofthefinaloverall
equation.
andthevalueof E*,,.o.n
equation
theoverall
datato deduce
Usethefollowing
potassium
andiron(ll) ions.
manganate(Vll)
acidified
forthereaction
between
+ 4H,0(aq) Es = +1.52V
+ 5e--- Mn"(aq)
+ 8H-(aq)
i MnOi(aq)
f = +0.77V
ii Fe&(aq)
+ e-+ Fe'-(aq)
Answer.
(i):
(ii)andmultiply
addittoequation
it by5.Then
Reverse
equation
V)= -0.77
V
+ 5Fe'-(aq)
f =-(+0.77
+ 5e5Fe'-(aq)
+ 4H,0(l) E+= +1.52V
+ 5e-+ Mn"(aq)
+ 8H-(aq)
Mn0i(aq)
-- Mn"(aq)
+ Sre'-(aqi
+ 4H,O(l)
(aq)+ AH;1aq;
+ 5Fe'-(aq)
MnO,
V
f,*t, = 4J7 + 1'52= +0'75
Stoichiometry
of an overall equation
The total increasein oxidation number of one element must equal the
total decreasein another.
theoxidation
Inthereaction
above,
decreases Spontaneous change
number
ofthemanganese
by5 from+7lo +2,andastheiron
O Electrode potential data can be used to predict the feasibility of a
increases
by1,theremustbe5
ionin the
iron(ll)
ionsto eachMnOochemical reaction. A reaction is feasible (thermodynamically unstable) if
overall
equation.
E.",,is positive.
o However the rate of the reaction may be so slow that the reaction is not
observed (kinetically stable).
Non-stondord cells
O Non-standard conditions may result in a reaction taking place even if
the standard electrode potential is negative.
I The reaction:
ZCu'.(aq) + 4l-(aq) + 2CuI(s) + I,(aq)
should not work becauseE' (assuming all speciesare soluble) = -9.39 y.
However copper(I) iodide is precipitated and this makes [Cu'(aq)] very
much less than 1 mol dm-'. The equilibrium is driven to the right by
becomes positive and the
the removal of Cu. (aq) ions, so that E,"u.tio.
place.
reaction takes
Potassium manganate(Vll)
reducing agents
titrations
- estimation
of
o Acidified potassium manganate(Vll) will quantitatively oxidise many

reducing agents.
r The procedure is to pipette a known volume of the reducing agent into
a conical flask and add an excessof dilute sulphuric acid.
O The potassium manganate(Vlf solution of known concentration is put
in the burette and run in until there is a faint pink colour.
f This shows that there is a minute excessof the manganate(Vll) ions.
o If the stoichiometry of the reaction is known, the concentration of the
reducing agent can be calculated. No indicator is needed as the
manganate(vll) ions are very intensely coloured.
TRANSITTON
METALS,
QUANTTTATTVE KTNETICS AND
APPLTED ORGANIC
CHEMISTRY
Workêi'
exa*np-lo
Theratioof iron(ll)
to
ionsin theequation
manganate(Vll)
is 5:1andsothenumber
of moles
of Fe'-is 5 timesthenumber
of
molesof manganate(Vl
l).
wasacidified,
andtitrated
against
sulphate
25.0cm'ofa solution
of iron(ll)
cm3wererequired
moldm-'potassium
manganate(Vll)
solution.23.4
0.0222
theconcentration
oftheiron(ll)
sulphate
to givea faintpinkcolour.
Calculate
solution.
forthereaction
is:
Answer:
Theequation
- Mn'*(aq)
+ 4H,0(l)+
SFe3.(aq)
MnOi(aq)
+ 8H.(aq)
+ SFe'.(aq)
= 5.195
=0.0222x23.411000
x 1Q mol
Amount
ofmanganate(Vll)
=
= 5.195
x 10-'mol
x 10*x 5/_t
Amount
ofironlillsuldnaie
_?
- 2.597
= 0.104
=2.597
x 10 + 0.0250
moldm
sulphate
Concentration
of iron(ll)
Iodine/thiosulphate
agents
titrations
- estimation
of oxidising
o The procedureis to add a 25.0 cm' sampleof an oxidising agentto

excesspotassiumiodide solution (often in the presenceof dilute
sulphuricacid).
The oxidising agentliberatesiodine, which can then be titrated against
standardsodium thiosulphatesolution. When the iodine has fadedto a
pale strawcolour, starchindicator is added,and the addition of sodium
thiosulphatecontinueduntil the blue colour disappears.
r Iodine reactswith thiosulphateions accordingto the equation:
-' 2I- + S*On'I' + 2S.O,1-
Workêi,oxil44f-lt,
Theratioofiodine
tothiosulphate
ionsis1:2,sothemoles
ofiodine
moles
are'lrthe
ofthiosulphate.
peroxide,
H,0,,wasadded
to anexcess
25.0cm'ofa solution
of
of hydrogen
potassium
iodine
required
23.8cm'
iodide
solution,
andtheliberated
acidified
theconcentration
moldm-'sodium
thiosulphate
solution.
Calculate
of
of0.106
peroxide
thehydrogen
solution.
peroxide
fortheoxidation
ionsbyhydrogen
is:
Answen
Theequation
ofiodide
Hr0r+2H.+21--lr+2Hr0
= 0.106
x 23.8/1000 =2.523
x 10-'mol
Amount
thiosulphate
ofsodium
= 1.261x 10-'mol
produced = 2.523
x 10-'x 112
Amount
ofiodine
= 1.261
peroxide= 1.261
x 10-3x
1/1
x 10-3
mol
Amount
ofhydrogen
= 1.261
+ 0.0250 = 0.0505
x 10-3
moldm-3
of H,0,
Concentration
Disproportionation
A disproportionation reaction can be predicted by using electrode
potentials. Use the data to work out E.",,for the proposed
disproportionation reaction. If it is positive, the reaction will occur.
Reoox EeurLrBRrA
ttWrkpj, oxiloLPb
to copper
and
inaqueous
solution
ionsdisproportionate
Willcopper(l)
ions?
copper(ll)
V
+ e-+ Cu(s) Es= +0.52
Cu-(aq)
V
+
Cu'-(aq)e-+ Cu'(aq)Eo= +0.15
the
andaddit tothefirst.Thisgives
thesecond
equation
AnswenReverse
equation:
- +0.52
- (+0.15)
= +0.37
V
+ Cu*(aq)
+ Cu(s) E*o,,
20u-(aq)
ions
copper(l)
isfeasible,
andsoaqueous
thereaction
F,,,,is positive,
Because
willdisproportionate.
Corrosion
oz(g)
(rusting)
This is an electrolytic process.When iron is stressedor pitted, some areas

become anodic and some cathodic. In the presence of water and oxygen
the following reactions take place (seeFigure 5.2).
a At the anodic areasiron atoms become oxidised and lose 2 electrons:
Fe(s) -* Fe'*(aq) + 2eo The electrons travel through the metal and reduce oxygen :
'lrOr(aq)
+ 2e- + HrO --' 2OH-(ag)
o The Fe'. and the OH- ions meet and iron(Il) hydroxide is precipitated:
Fe'.(aq) + 2OH-(a9) - Fe(OH)'(s)
Fig 5.2 Rusting

steelis ironcontaining
a
Stainless
which
highproportion
of chromium,
formsa protective
layerof Cr,0,
overthewholesurface
of themetal.
lf thesurface
is scratched,
a new
protective
layerof Cr,O,is formed.
I Finally oxygen oxidises the iron(Il) hydroxide to iron(lll) oxide (rust):

2Fe(OH)r1s;+'/,O,(aq) - Fe,O.(s)+ 2H,O(l)
Prevention of corroslon
This can be done by:
O placing a physical barrier between the steel and the environment. Such
barriers are paint, tin or chromium plating.
o adding a sacrificial metal. This can be done by coating with zinc
(galvanising), or by attaching blocks of magnesium at intervals.
Storage
cells
Thesestore electricalenergyas chemical energy.The reactionsmust be

fully reversibleand the chemicalsproduced in the redox reactionsmust be
insoluble.
The leod ocid bottery
When electricity is drawn from the cell (dischargitg), the following
reactionstake place.
At the anode (oxidation) which is negative:
Pb(s)+ SO,'-(aq)'PbSO,(s) + 2e- Eu = +0.36V
for charging
thecell
Thereactions
aretheopposite,
andonlytakeplace
if a potential
>2.05V is applied,
with
theanodebeingconnected
to the
terminal
negative
of thecharging
s0urce.
At the cathode (reduction) which is positive:

+ 2H,O(t)
+ 4H.(aQ)- PbSO.(s)
PbO,(s)+2e- + SO,z-(aq)
E u = + 1 . 6 9V
The overall discharging reaction is:
Pb(s) + PbO,(s) +ZSOn'-(aq)+ 4H.(a9) -ZPbSOn(s) + 2H,O(l)
E' = +1.69 + (+0.36) = +2.05 V
TneNsrTroN
METAL cHEMIsTRY
of transition
Reactions
metal
compounds
Reoctionswith sodium hydroxide ond ommonio solutions

The table givesa summary of thesereactions.
lon
Cr'*
Mn'*
Fe'*
Fe'*
Ni'*
Cu'*
Zn'*
Colour
Addition of
NaOH(aq)
ExcessNaOH(aq)
Addition of
NH.(aq)
ExcessNHr(aq)
Green
Palepink
Palegreen
Brown/yellow
Green
Paleblue
None
Green ppt
Sandypptb
Dirty green ppt'
Foxy red ppt
Green ppt
Blue pptd
White ppt
Green solution
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Colourlesssolution
Greenppt
Sandyppto
Dirty green ppt'
Foxy red ppt
Greenppt
Paleblue ppt
White ppt
Ppt remains
Ppt remains
Ppt remains
Ppt remains
Blue soln
Deepblue soln
Colourlesssoln
" The correct formula for the ions should be the hexa-aquaion, except for zinc, which forms a tetraqua ion.
o
The precipitate of Mn(OH), goesbrown as it is oxidised by air.
'
The precipitate of Fe(OH),goesbrown on the surfaceas it is oxidised by the oxvgen in the air.
o
The precipitate of Cu(OH). goesblack as it loseswater to form CuO.
Deprotonotion
r The aqua ions in solution are partially deprotonated by water. The
greater the surface charge density of the ion the greater the extent of
this reaction, e.g. hexa-aqua iron(III) ions:
[Fe(H,O)u]'.(aq) + H,O + [Fe(H,O),(OH)]'.(aq) + H.O.(aq)
This means that solutions of iron(III) ions are acidic (pH < 7).
hydroxides'redissolve' O When an alkali such as sodium hydroxide is added, the equilibrium is

Amphoteric
e.g.
in excess
strongalkali,
driven to the right, the ion is considerably deprotonated to form a
- [Cr(OH)u]'+ 30H-(aq)
Cr(0H),(s)
neutral molecule which loses water to form a precipitate of the metal
(aq)
hydroxide:
-+ 20H-(aq)
andZn(0H),(s)
lFe(H,O),1'.(aq)+ 3OH-(aq) - Fe(OH),(s)+ 6H,O
[Zn(0H),]"(aq).
If aqueous ammonia is added, the same precipitate is formed:
[Fe(H,O)u]'.(aq)+3NH,(aq) * Fe(OH).(s)+ 3NHn.(aq) + 3H,O
Ligond exchonge
is used
asa testfor:
Thisreaction
withaqueous
ammonia
a nickel(ll):
ionsfirstgivea green
nickel(ll)
precipitate
which
thenforms
a
withexcess
bluesolution
ammonia.
ionsgivea pale
blue
b copper(ll)
precipitate
forms
which
a deep
withexcess
bluesolution
and
ammonia
c zincionsgivea whiteprecipitate
solution
which
formsa colourless
withexcess
ammonia.
O When aqueous ammonia is added to aqua complexes of d block

elements such as those of nickel, copper and zinc, ligand exchange takes
place and a solution of the ammine complex is formed.
reaction:
First the hydroxide is precipitated in a deprotonation
-Cu(OH),(s)
+ 4H,O
+
2NH..(aq)
[Cu(H,O)J'.(aq) + 2NH,(a9)
The hydroxide then ligand exchanges to form an ammine complex with
excessammonia:
Cu(OH),(s) + 4NH,(aq) +ZH,O -- [Cu(NH.)*(H,O)J'. + 2OH-(aq)
The final result is that the NH, ligand has taken the place of four HrO
ligands.
O Addition of cyanide ions to iron(Il) ions produces a solution of
hexacyanoferrate (I I) :
[Fe(H,O).]'.(aq)+ 6CN-(ag) - [Fe(CN)']*(aq) + 6H,O
o A test for iron(III) ions is to add a solution of potassium
thiocyanate,KCNS. Iron(II! ions give a blood red solution:
[Fe(H,O),]'.(aq) + SCN-(ag)t tFe(SCNXH,O).1'.(aq)+ H,O
El
t*oNsrrroN
M E T A L S ,e u A N T r r A T r v E K r N E T r c s A N D A p p ' r E D . R G A N r c c H E M r s r R y
Vanadium
o Vanadium
chemistry
compounds
exist in four
oxidation
states:
+5: VOr-(aq) which is colourless, but in acid solution reacts to form a

yellow solution of VOr.(aq) ions:
VO;+2H* + VOr*+HrO
+4: VO'.(aq), which is blue.
+3: V'.(aq) which is green and is mildly reducing.
+2: V'.(aq) which is lavender and is strongly reducing.
o Reduction by zinc.lf zinc and dilute hydrochloric acid are added to a
solution of sodium vanadate, NaVO' the colour changes in distinct
sequence,as it is steadily reduced from the +5 to the +2 state:
start:
then:
then:
then:
finally:
yellow caused by VO'.(aq)ions (+5 state)

green caused by a mixture of yellow VOr.(aq) and blue
VO'z.(aq)
blue caused by VO'z.(aq)ions (+4 state)
green caused by V't(aq) ions (+3 state)
lavender caused by V'.(aq) ions (+2 state)
t Redox reactions
Vanadium compounds can be oxidised or reduced by suitable reagents. For
a redox reaction to work, the E'.",, value must be positive. A list of Evalues
for the half reactions of vanadium in its various oxidation states and for
some oxidising and reducing agents is given below. These values show, for
instance, that vanadium(V) will be reduced only to vanadium (IV) by Fe'*
ions, whereas Snt* ions will reduce it first to vanadium (lV) and then
to vanadium (lll).
+5
V O r * + 2 H *+ e + V O ' . + H r O
Fe'* +e --Fe'*
'lrclr+e- +cl-
Fet* +e
+Fet*
Eu = +0.34V
E ' = + 0 . 1 5V
Eu = +O.77Y
VO,'
+4
AFe'*
Sn'*
V
+3
E' = -0.26 V
E' = -0.76V
Eu = 0.00 V
+V'*
Vt*
+e
Z r' t' * + 2 e - + Z n
H*
+ e- +'lrH,
CT,
Fet*
+4
vo'* +2H*+e-+vt*+Hro
Snn* +2e- +Sn2*
+5
VO,*
E = + 1 . 0V
E' = +O.77Y
E ' = + 1 . 3 6V
V,*
+3
4.H'
'
II znlH.
+2
v'*
+2
8t..,, for the reduction of:

VOr*by Fe'. = +1.0- (+0.77) - +O.23Y
Et
= o.o (-0.26)
- +0.26Y
VO'* by Sn'*= +0.34- (+0.15)= +0.19V
V3*by Fe3* = +O.77- (+0.3a)
= +0.43V
VO'* by Cl, = +1.36 - (+1.0)
= +0.36V
v'. by Zn
- -0.26 - (4.7 6) = +0.50V

-H
'?\i
l//H
H
for the oxidation of:

",,
-
V'* by H.
t Checklist
Beforeattempting the questionson this topic, checkthat you:

E Can define d block and transition elements.
[,] Cun write the electronicstructureof the d block elementsand their ions.
T R r N s r r r o N M E T A Lc H E M r s r R Y
rJ Can recall the characteristic properties of the transition elements.
J Understand the nature of the bonding in complex ions, the shape of
the ions and their colour.
lJ Can recall the action of aqueous sodium hydroxide and ammonia on
solutions of their aqua ions.
J Understand deprotonation and ligand exchange reactions.
rJ Can recall the oxidation states of vanadium, and the colours of its ions.
J Know reactions to interconvert the oxidation states of vanadium.
Can recall examples of vanadium, iron and nickel and their compounds
as catalysts.
IH
your knowledge
and understanding
," .Testing
o
(
-
v is [Ar],3d',4s'. v'- is 1Ar1,

3d'
For the following set of questions, cover the margin of the page before vou
answer, then check to see if you are correct.
r' Write down the electronic structure of a vanadium atom and a \''- ion.
turquoise-blue,
ICu(H,0),]'-
State the formula and colour of the aqua complex of copper(ll).
H,),(H,0),1'.
darkblue
[Cu(N
* State the formula and colour of the ammine complex of copper(ll).
(ligand
to ion)and
Dative
covalent
(withinthewatermolecule)
covalent
o Name the types of bonding in the aqua complex of iron(Il).

o What is the shape of the iron(Il) aqua complex ion?
o State the type of reaction that occurs when aqueous sodium hydroxide
is added to a solution of the aqua complex of copper(Il).
Ligand
exchange
o State the type of reaction that occurs when excess aqueous ammonia is
added to a solution of the aqua complex of copper(Il).
+5,V0r*,yellow.+4,V0'-,blug.
+3,V'*,green.+2,\f*,lavgndgr.
o What are the oxidation states of vanadium? Give the formula and the
colour of the cation for each oxidation state.
process
to
lronintheHaber
manufacture
ammonia
o Give an example of the use of iron as an industrial catalyst.

o Give an industrial use of a vanadium compound as a catalyst.
Vanadium(V)
oxideintheContact
process
to manufacture
sulphuric
acid
Theanswers
tothenumbered 1
questions
areonpages
137-138. 2
Explain why the [Cu(H,O)u)'. ion is coloured.

Give the equations for the reactions caused by small additions of
sodium hydroxide solution, followed by excessto:
a a solution of the
b a solution of the
c a solution of the
Give the equations
ammonia solution,
aqua complex of chromium(Ill)

aqua complex of iron(Il)
aqua complex of zinc(Il).
for the reactions caused by small additions of
followed by excessto:
a a solution of the aqua complex of iron(III)

b a solution of the aqua complex of copper(Il).
Write the half equations for the following changes in oxidation state:
a vanadium(V) to vanadium(Il)
b vanadium(V) to vanadium (IV)
c vanadium(Ill) to vanadium(IV)
lrl
El
TnnNstrtoN
METALS, euANTrTATrvE KrNETrcs AND Appl-lED oRGANlc cHEMISTRY
lll
chemistry
@ Organic
ffiI
lry
Thingsto learnand understand
The structure of benzene and reactions of aromatic

compounds
o The benzenering doesnot consist of alternatedouble and single bonds.
o All the bond lengths are the sameand the molecule is planar.
t There is an overlap of p orbitals aboveand below the plane of the
molecule, forming a continuous or delocalised n system.
o This givesstability to the benzenestructurewhich is why it undergoes
substitution rather than addition reactions.
o Benzenecan be representedeither by:
Reactions
of benzene
Benzenereactsmainly by electrophilic substitution:

O Nitration. Benzenereactswith a mixture of concentratednitric and
sulphuric acidsto form nitrobenzene:
CuHu+ HNO, - CuHrNO.,+HrO
I Bromination. Benzenereactswith liquid bromine in the presenceof a
catalystof anhydrous iron(III) bromide (made in situ from iron and
liquid bromine) or of anhydrous aluminium bromide:
CuHu+ Brr(l)'CuHrBr + HBr
o Friedel-Crafts reaction. Benzenewill react with halogenoalkanesor
with acid chlorides in the presenceof a catalystof anhydrous
aluminium chloride:
CuHu+ CrHrCl + CuHrCrH,+ HCI
ethylbenzene
CuHu+ CHTCOCI- C'HTCOCH,+ HCI
phenylethanone (a ketone)
Reactions
chain
of compounds
with
a carbon-containing
side
o Compounds such as methyl benzeneC6H'CH3and ethyl benzene

C6HsC2Hs
can be oxidised, and the product will contain a COO-group
on the benzenering, regardlessof the number of carbon atoms in the
chain. On acidification benzoic acid is produced:
+ 6[0] + OH-- C'HTCOO-+ CO, + 3HrO
CuHsCzHs
conditions: heat under reflux with potassiummanganate(Vll)and
o R c a r u t c c H E Mr s r n v i l l
2
3
The Nor. ion is the electrophile and attacks the benzene ring.
The HSon- ion pulls off a H. and reforms H2son (the catalystf
Similar
mechanisms
occurfor
bromination,
where
thecatalyst
reacts
withbromine
to provide
the
electrophile
Br-,andin theFriedelCraftsreaction
wherethecatalyst
reacts
withthehalogen
compound
to provide
electrophiles
suchas
CH3C'0
or C,Hu-.
The lossof H. resultsin the reforming of the benzenering and the gain in
stability associated
with the ring.
Heterolytic,
nucleophilic
substitution
Reoction between hologenoolkonr ond hydroxide or cyonide ions

' Thereare two mechanismsdepending
on the type of halogenoalkane.
with primary (1")halogenoalkanes,
an S*2 mechanismis dominant.
' Reactionproceedsvia a transition statewhen the lone
pair of electrons
on the nucleophileattacksthe halogenoalkane.
Inthetransition
state,
thenew0-C
bondformsastheC-Brbond
breaks.
Thetransition
statehasa
charge
of-1.
-l9H,
'Q ------+
l
l - .ur l
Ho:'
Ho-c.
.:-g s'
lno- I
l---------+
t{'
H l
| /\
|
t*u.rr?rro.,
tu*'
o with tertiary (3") halogenoalkanesthe gl

This happensin two steps:
1
CHr-a"
mechanism is dominant.
I
+ :Br-
CHt
This then rapidly forms a bond with the nucleophile, oH-.

CH,
tr\
C* t
OH-
I
Heterolytic,
CHt
CHe-C
I-OH
CHg
TheCN-ionis a catalyst,
andthe
conditions
mustbesuchthatthere
is a significant
amount
of bothHCN
molecules
andCN-ionspresent,
i.e.
a mixture
of HCNandKCN.
l "
CH,
CH?-
:Bi
CH,
I r-r
cHr-C-Br
,cH,
The halogenoalkaneionisesin the relativelyslow,and hencerate

determining step,to form an intermediate carbocation.
CHt
Anyoptical
activity
is maintained
in
a Sr2reaction.
lf themechanism
is Sr1,a reactant
whichis anoptical
isomer
wilt
produce
a racemic
mixture,
asthe
carbocation
canbeattacked
from
either
side.
CHt
nucleophilic
addition
Reaction between o corbonyl compound and hydrogen cyonide

o Although the reaction is the addition of HCN, the first step is the
nucleophilic attack by the cN- ion on the 6+ carbon atom in the
carbonyl group.
El
t*oNsrrroN
METAL', euANTrTATrvE KrNETrcs AND AppLIED .RGANrc cHEMIsrRy
ll
kinetics
Chemical
ffi
b
Introduction
You must also reviseTopic 2.3 in Chapter 2, page44 and especiallyhow
the changesin the Maxwell-Boltzmann distribution of energywith
increasein temperatureaffect the rate of reaction.
da
LN
Theunitsof k are:
reaction:
I fora zero-order
moldm-'s-'
reaction:
s-'
t fora first-order
reaction:
I fora second-order
mol-t
dmts'
Thingsto learn
fne rate equation for the reaction:
xM + /N - products,is:
Rateof reaction k tMlj [N]bwhere a and b areintegersand are
determined.
experimentally
i The rate constant, & is the constant of proportionality in the rate
equation:
I Its value dependson the activation energyof the reaction and the
temperature.
o Reactionswith a large activation energywill have small valuesof k.
E fne order with respect to one substance is the power to which
the concentration of that substanceis raisedin the rate equation. In the
example abovethe partial order of the chemical M is a.
E fne order of reaction is the sum of the partial orders.In the
example above,the order of the reaction is a + b.
f
reaction
Thehalf-life
of a first-order
is constant.
fne activation enert[y, Eo,is the total kinetic energy that the
moleculesmust have on collision in order for them to be able to react.
E naff-life, tr,r, is the time taken for the concentration to fall from any
selectedvalue to half that value.
ffi
iry
Thingsto understand
Determination
of rate equation
from
initial
rates
Considerthe reaction:
A+B+e+products
The initial ratesof reaction with different concentrationsof A, B and C are
found, and by taking the experimentstwo at a time, the order with respect
to each substancecan be found.
Look for two experimentswhere the concentration of only one substance
varies.If doubling that concentration causesthe rate to double, the order
with respectto that substanceis 1.
El
t*oNsrrroN
METALS, euANTrrATrvE
Energy profile
KrNETrcs AND AppLtED .RGANtc
cHEMIsrRy
diagrams
The first diagram is for a reaction that takes place in a single step, and the
second diagram is for this reaction with a catalyst (seeFigure 5.6).
:-------- Transition
Intermediate
>.
bo
bo
tr
q.)
rtl
Catalysed
Fig 5.6 Energyprofile diagroms
An example of a reaction with a transition state is the S*2 reaction of

bromoethane with hydroxide ions.
An example of a catalysed reaction forming an intermediate is Fez*ions as
a catalyst in:
SrOrz-(aq)+ 2l-(aq) - 2SOn'-(a9) + Ir(aq)
In this mechanism the catalyst first reduces the SrO.'- ions:
ZFe'.(aq) + SrOr'-(a9) - 2Fe'.(aq) + 2SO.,'-(aq)
then the Fe"*ions are reduced back to Fe2*ions:
2Fe3.(aq)+ Zl-(aq)'- ZFe'*(aq)+ Ir(aq)
H
c , g
*4-
Checklist
Beforeattemptingthe questionson this topic, checkthat you:

J Can define rate constant,order of reactionand half-life.
iJ Can deducerate equationsfrom initial rate data.
iJ U.tderstandthe concept of activation energy and its relation to the rate
constant.
E Understandthat information about mechanismscan be deducedfrom
the partial ordersof the reactants.
iJ Can recall the energyprofiles of reactionswith and without catalysts.
ff Ca.r suggestsuitablemethods for following reactions.
f
Can deducethe order of a reaction from concentration/time graphs.
c n e M r c A L K r N E T r c st l
and understanding
1 and2, order
a Fromexperiments
withrespect
to N0,= |
1 and3, order
b Fromexperiments
withrespect
to C0 = 0
is 2 + 0 = 2
c 0rderof reaction
d Rate=k[N0,]'
For the following set of questions, cover the margin before you answer,
O The following results were obtained from a study of the reaction:
NO,(g) + CO(g) -' NO(8) + CO,(g)
Experiment
NO,l/mol dm-"
lCol/mol dm-'
Relative rate
1
2
3
o.o2
0.04
0.o2
0.o2
o.o2
0.04
1
4
1
a
b
c
d
What is the order with respect to NOr?

What is the order with respectto CO?
What is the order of reaction?
Statethe rate expression.
o Reaction A has a high value of E., and reaction B has a lower E. r'alue.
Which reaction has the larger rate constant?
a
Which is the faster reaction?
b
o A reaction takes place in 3 steps. The E^lkI mol-' for each step are:
E,,value
Step2 asit hasthelargest
step 1: 32,
step 2: 51,
step 3: 20
Which step determines the rate?
100to 6.25= 4 half-livee,

therefore
time= 4x25= 100minutes
Theanswers
to thenumbered
questions
areonpage
138.
O The decomposition of NrO, is first order. At 200 "C the reaction has a
half-life of 25 minutes. Calculate how long it will take for the
concentration of NrO, to fall to 6.250/oof its original value.
L The rate of the second order reaction:
2HI(g) -- H,(g) + I,(8)
is 2.0 x 10' mol dm-' s-' when [HI] = 0.050 mol dm-' at 785 K. Calculate
the value of the rate constant, giving its units.
'C,
the rate of the reaction:
Describe how you would follow, at 60
+ H,O(l).
+
CH,COOCH.(|)
CH3COOH(aq) CH'OH(aq)
The decomposition of 3-oxobutanoic acid, CH3COCHTCOOH,was
studied:
CHTCOCHTCOOH- CH.COCH. + CO,
The results, at 40'C, are tabulated below.
Time/min
0
26
52
78
[3-oxobutanoic acid]/mol dm-'
t.6
0.8
0.4
o.2
Deduce the order of the reaction.
oRclluc
cHEMrsrRY lv
To distinguish between aldehydes and ketones:
Warm with ammoniacal silver nitrate solution.
Test:
Observation: Aldehydes give a silver mirror, ketones have no reaction.
reaction
Gentlv warm with a solution of sodium hydroxide and
iodine.
pale yellow precipitate of CHI,
A
Observation:
This test works with carbonyl compounds containing the
CH,C=O and alcohols containing the CH'CH(OH) groups.
acids, COOH group
I Carboxylic
Add to a solution of sodium hydrogen carbonate.
Test:
O Iodoform
Test:
of gas,whichturn lime watermilky.

Observation:Bubbles
Interpretation
Thesolidmustbepurified
by
inorder
to have
a
recrystallisation
melting
sharp
andaccurate
temperature.
thatcause
When
identifying
species
givea
lines
inthespectrum,
always
formulafortheionandits
structural
+ charge.
of data
You should be able to deducestructuralformulaeof organicmolecules

given data obtainedfrom:
r Chemical methods
Carry out testsas aboveto determine the functional groups in the
molecule.Measurethe melting point of the substance.Make a solid
derivative (such as the 2,4-DNPderivative from carbonyl compounds),
purify it, and measureits melting temperature.Checkthe melting
temperaturevalueswith a data bank to identify the substance.
o Mass spectra (seeFigure5.7)
o Observethe fragmentsobtained and look for the value of the
molecular ion (M)+, if any.
o Seeif there is a peak at (M-15)+.If so the substanceprobably had a
CH, group which is lost forming the (M-15)+ peak.
I If there is a peak at (M-28)+,the substanceprobably had a CO group.
Other fragmentswill help to identify the structure.
100
b 8 0
(tt
9 6 0
.E 40
&, 20
10
Fig 5.7 Massspectrumof ethonol
Thepeaksgivenby0-HandN-Hare
to hydrogen
usually
broad
owing
bonding.
15
20
25 30
m/z
3 5 40
45
O Infrared spectra (seeFigure5.8)

o Theseare used to identify functional groups in the substance,and
also to comparethe spectrumof the unknown with a data bank of
spectra('finger printing').
O Peaksto look for are at:
given bY C=O
1650to 1750 cm-'
given by O-H
2500 to 3500 cm-'
given by N-H
3300 to 3500 cm-'
given by C-O
1000 to 1300 cm-'
El
t*oNsrrroN
METAL', euANTrrATrvE
KrNETrcs AND AppLrED .RGANrc
cHEMrsrRy
100
s
O
U
g s o
(a
(t)
Lr
t-
Fig 5.8 lnfroredspectrumof ethonol
Thechemical
shiftis thedifference
theabsorption
between
frequencies
nucleiin the
of thehydrogen
compound
andthosein the
reference
compound.
1000
2000
1s00
Wavenumber
/ cm-r
O NMR spectra
o The phenomenon of nuclear magnetic resonance occurs when nuclei
'H
such as
are placed in a strong magnetic field and then absorb
applied radio frequency radiation.
t The nuclei of hydrogen atoms in different chemical environments
within a molecule will show up separately in a NMR spectrum. The
values of their chemical shift, 6, are different.
o The hydrogen nuclei in a CHr group will have a different chemical
shift from those in a CH, or in an OH group. The value of d of the
peak due to the hydrogen in OH (or in NH) depends upon the
solvent.
* In low resolution
NMR, each group will show as a single peak, and
the area under the peak is proportional to the number of hydrogen
atoms in the same environment. Thus ethanol, CH.CHTOH will have
three peaks of relative intensities 3:2:1 and methyl propane
CH.CH(CH3)CH3,will have two peaks with relative intensities of 9:1.
NMR spin coupling is observed. This is caused
O In high resolution
by the interference of the magnetic fields of neighbouring hydrogen
nuclei. If an adiacent carbon atom has hydrogen atoms bonded to
it, they will cause the peaks to split as follows:
1 neighbouringH atom
2 neighbouringH atoms
n neighbouring H atoms
peaksplits into 2lines (a doublet)

peaksplits into 3 lines (a triplet)
peaksplitsinto (n + 1) lines.
Thus ethanol gives three peaks (see Figure 5.9):

1 peak due to the OH hydrogen, which is a single line
(as it is hydrogen bonded)
1 peak due to the CH, hydrogens, which is split into four lines
by the three H atoms on the neighbouring CH, group.
1 peak due to the CH, hydrogens, which is split into three lines
by the two H atoms on the neighbouring CHr group.
Fig 5.9 High resolution NMR spectrum

of ethonol
oRclrurc cHerarsrnYIV
a Visible and fIV spectra

o z bonds will absorblight energyas an electron is promoted from a
bonding to an anti-bonding n orbital.
O The energygap is in the near UV or visible range,and the group
causingthis is calleda chromophore.
O If the n bonded electronsare linked to a conjugatedsystem(alternate
double and single carbon-carbonbonds), the absorption will shift to
a lower frequency,and the substancemay be coloured.The colour
observedwill be the complementarycolour of that absorbed.
Organic synthesis
Reogents ond conditions for the preporatlon oJ substonce B from A
A common
erroris to thinkthat
KCN
willreact
with
orHCN
to formRCN.
Youmust
alcohols
firstconvertROHto R-halogen.
questions
Many
onorganic
in
require,
synthesis
somewhere
theconversion
of
thesequence,
to a
thestarting
substance
compound
ora
carbonyl
halogenoalkane.
If the number of carbon atoms in the chain is:

o increased by one, consider:
a halogenoalkanewith KCN
b carbonyl with HCN
c the Grignard reagentCHrMgBr
d a Grignard reagentaddedto CO, or methanal
o increased by more than one, consider:
a a Grignard reagentwith more than one carbon atom
b Friedel-Craftsreaction for aromatic substances
o decreased by one, consider:
a the Hofmann degradation
b the iodoform reaction.
Practical
for
Recrystallisation
isonlysuitable
purifying
solids.
precaution
is
When
a specific
safety
give
the
for,
do
not
useof
asked
glasses,
labcoats
etc.as
safety
isprobably
Theanswer
examples.
'nonaked
(ether
or
flames
solvent)'
'carry
ina fume
outtheexperiment
inwhich
thespecific
case
cupboard',
mustbe
hazard
suchastoxicity
stated.
(u
l-r
E
T 1
H
C,.'
tr 17
.a)
loOo/o X
A
O Recrystallisation. Dissolvethe solid in a minim m of hot solvent.

Filter the hot solution through a preheated funnel using fluted filter
paper.Allow to cool. Filter under reduced pnsssurle (Buchnerfunnel),
wash with a little cold solvent and allow to dry. The solid should have
a sharpmelting temperature.
o Heating under reflux is necessarywhen either the reactanthas a low
boiling temperatureor the reaction is slow at room temperature.
r Safety precaution. You must use a fume cupboardwhen a reactantor
product is toxic, irritant or is carcinogenic.
o Fractional distillation. This is used to separatea mixture of two
liquids. Thesemixtures can usually be separatedinto pure samples,but
if the boiling points are too close,a good separationwill be difficult.
'C
If a liquid of composition X is heated,it will boil at Tr to give a vapour
of compositionY (seeFigure5.10).If this is condensedand reboiled,it will
'C giving a vapour of composition Z. Eventually
boil at a temperatureof T,
pure B will distill off the top and pure A will be left in the flask.
Applied
Liquid
Z TOOo/o
B
Fig 5.lO Boiling

temperoture/ compositiondiagrom
techniques
organic
chemistry
o Targeting pharrnaceutical compounds. Those which are ionic or

have severalgroups that can form hydrogen bonds with water, will tend
to be retained in aqueous(non-fatty) tissue.Compounds with long
hydrocarbon chains and with few hydrogen bonding groupswill be
retained in fatty tissue.The latter will be storedin the body, whereas
water-solublecompounds will be excreted.
o Nitrogenous fertilisers are of three types:
1 quick release,such as those containing NO; and NHn.ions
2 slow release,such as urea, NHTCONH,
3 nafural, such as slurry, compost and manure.
The first two are water-solubleand can be leachedout. The last is bulky
and contains little nitrogen.
El
METAL', euANTrrATrvE KrNETrcsAND AppLrED .RGANtc cHEMIsrRy
t*oNsrrroN
o Esters, oils and fats. Simple estersare used in food flavourings,

perfumesand as solventsfor glues,varnishesand spray paints. Animal
fats are estersof propan-t,2,3-triol and saturated acids such as stearic
acid C,'H3'COOH.When hydrolysedby boiling with aqueoussodium
hydroxide, they produce soapwhich is the sodium salt of the organic
acid.
Vegetableoils are liquids which are estersof propan-I,Z,3-triol and
unsaturated acids.
Margarineis made from polyunsaturatedvegetableoils by partial
hydrogenation (addition of hydrogen) so that only a few double bonds
remain.
O Polymers are of two distinct chemical types:
1 Addition. The monomers contain one or more C=C groups.
Polymerisationis the addition causedby breaking the n bonds, and
the polymer and the monomer have the sameempirical formula.
Examplesare poly(ethene),poly(tetrafluoroethene)(PTFE)and
poly(propene).
2 Condensation. Both the monomers have two functional groups,
one at each end. Polymerisationinvolves the loss of a simple
molecule (usually HrO or HCI) as each link forms. Examplesare
nylon, a polyamide (seeFigure5.11),and terylene,a polyester.
Polymers
overa
usually
soften
rather
than
range
oftemperatures
have
melting
temperature.
a sharp
Themainreason
forthisisthatthe
polymer
is a mixtureof molecules
of
lengths.
different
chain
/H C l
cr
(
i- (.n,)-r
\
\
/
lil
N\- (cH,)u\
/
"
\
/
a diacid chloride
Fig 5.ll A polyamide
\ i/ /
l-(
ts
\' lol
- (.",)..n,),i T- iii
a diamine
O
H
a polyamide
Synthetic polymers are not easilybiodegradedand can causean

environmental problem of disposal.One answeris for them to be recycled.
da
rX,=r Checklist
\/'/J-I
t-------!

c.J Can recallthe testsfor C=C, C-Hal, COH, C=O, CHO and COOH groups.
iJ Can deducethe functional gtoupspresentfrom resultsof chemicaltests.
t.l Can interpret mass,IR, NMR and UV spectra.
*J Can deducepathways for the synthesisof organic molecules.
*J Rppreciatehow the structure of a pharmaceuticalaffectsits solubility.
i-l Can distinguish between types of polymer and understand
polymerisation.

Theanswers
tothenumbered I How would you distinguish between:
questions
138-139.
areonpages
a
pentan-3-oneand pentanal
t*oNsrrroN
El
M E T A L ' , e u A N T r r A T r v E K r N E T r c s A N D A p p ' r E D . R G A N r c c H E Mr s r R y
Practice Test: Unlt 5

Time allowed thr 3O min
All questionsare taken from parts of previous EdexcelAdvancedGCE papers
The answersare on pagesI39-14L.
1, a The kinetics of the hydrolysis of the halogenoalkane(where R is an alkyl group) RCHTCIwith aqueous
sodium hydroxide was studied at 50 "C. The following resultswere obtained:
loH-l
Initial rate/mol dm-' s-'
lRCHrcll
0.0s0
0.10
4.0 x 10"
0.15
0.10
1.2 x I0-3
0.10
o.20
1.6 x 1O3
Experiment
Deducethe order of reaction with respectto the halogenoalkane,RCHrCl,and with respectto the
hydroxide ion, OH-, giving reasonsfor your answers.
t4l
ii Hencewrite the rate equation for the reaction.
tU
iii Calculatethe value of the rate constant with its units for this reaction.
tzl
iv Using your answerto part ii, write the mechanism for this reaction.
t3I
(Total LO marks)
lJanuary2001CH6question1l
i
Benzene,CuHu,reactswith ethanoyl chloride, CH3COCI,by an electrophilic substitution reaction in the

presenceof aluminium chloride as catalyst.
a Identify the electrophileinvolved in this reaction and write the equation to show its formation.
l2l
b Draw the mechanism for the electrophilic substitution of benzeneby ethanoyl chloride.
t3l
c Suggesta reaction scheme,stating reagentsand conditions, to convert the product of the reaction in
OH
b into
I
CuH,-c -COOH
I
tsI
Ethanoyl chloride can be used to prepareesterst:* as 3-methylbutyl ethanoate,

(CH,)TCHCHTCHTOOCCH3,
which is a bee alarm pheromone that signalsdanger to a honey bee. If this
compound is warmed with aqueoussodium hydroxide, a slow reaction takesplace to produce sodium
ethanoateand 3-methylbutan-1-ol.The reaction is first order with respectto both 3-methylbutyl
ethanoateand the aqueoushydroxide ion. Explain the term first orderand give experimental details
showing how this information could be obtained.
t8I
(Totat L8 marks)
lJune2001 CH6 questions2 & 4
PRACTIC E
Study the reaction scheme beloq and then answer the questions that follow.
+D
step 1
--+CrHrMgB
CrHrBr
--+
oH- (aq)
KrCrrOr/HrSOn
C4H,'O
E
step2
CTH'OH
-----+C2H4O
a Give the reagentsand conditions necessaryfor step 1

b Compound D reactswith ammoniacal silver nitrate solution to give a silver mirror.
i Give suitablereagentsfor the conversionof B to D.
l2l
tzl
ii
shouldbe takento ensurethat B wasconvertedmainly to D and did not react

What precautions
tll
turther?
iii
Give the name or the structural formula of the organic compound formed when D reacts with
tll
ammoniacal silver nitrate solution.
tzl
c Give the structural formula of compound E (C4Hr,O).
d Compound F reactswith 2,4-dinitrophenythydrazinesolution but has no effect upon ammoniacal
silver nitrate solution. F will also undergo the iodoform reaction.
i Explain the significanceof the resultsof the test with ammoniacal silver nitrate and 2,4r2l
dinitrophenyl hydrazine concerning the functional group in F.
ii What structural featurein F is identified by the iodoform reaction?Give the formula of the
products of the reaction.
t3t
r2l
iii Give the structural formula of F.
e The massspectrumof F showedmajor peaksat mle valuesof 72,43 and 29. ldentify the species
t3l
responsiblefor thesepeaks.
(Total 18 marks)
[anuary 2002 CH4 question1]
4 a Describe how you would measure the standard electrode (reduction) potential of the Fe'.(aq)/ Fe'.(aq)
tsl
system.
oc.
electrodeis connectedto a standardgold electrode,Au'-(aq)/Au(s),at 25
b A standardFe3.(aq)/Fe'.(aq)
The gold electrodeacts as the cathode and the electronsflow, in the external circuit, from the
electrodeto the gold electrode.
Fe3.(aq)/Fe'.(aq)
i Write the half equationsfor the reactionsthat take place at each electrodewhen an electric current
l2l
is drawn from the cell.
tll
ii Hencewrite the overall ionic equation for the reaction that takesplace.
iii The potential of this cell is +O.73V and the standardelectrodepotential for a Fe3.(aq)/Fe'.(aq)
tzl
electrodeis +0.77 V. Calculatethe standardelectrodepotential of the gold electrode.
(Total LO marks)
ffanuary2001 CH3 question3]
6A
h,borator/
Ma'y
Laboratory
II
chemistry
O The specification (syllabus) for the tests on this module includes all the
AS and A2 material.
o The Unit Test 68 is a synoptic paper, taken by all candidates, and will
also assessthe candidate's quality of written communication.
=1
..
'- , 4,Ki
of practical
.t#
skills II
E ftris is either internally assessed

or a practical exam.
f
Notes and books may be used in the tests.
E ffre practical exam will be broadly qualitative in its approach.

[l You should be able to:
i
observeand interpret details of the chemistry of the elementsand

compounds listed in Units 4 and 5.
ii recognizethe resultsof experimentsto identify functional groups in
organic compounds.
iii carry out the techniquesdescribedin Topic 5.5 and those used in
volumetric analysis,kinetics and equilibria.
iv presentand interpret quantitative and qualitative results.
v deviseand plan simple experimentsbasedon the chemistry and
techniquesas above.
K+a
All candidates will do this paper
The Unit
Test question
(exam)
paper
I Section A will consist of a compulsory question and will assessa

candidate'sability to interpret data from laboratory situations.
O Section B will consist of three questionsand the candidatemust
answertwo of the three questions.
I Thesequestionswill require candidatesto make connectionsbetween
different areasof chemistry,for exampleby applying knowledgeand
understandingof principles to situations in contexts new to them.
PRAcrrcE TEsr: Utqrr 6E} (SYNoPTtc)
Practice Test: Unlt 6B (Synoptic)

Time allowed
L hour 3O min
All questionsare taken from previous EdexcelAdvancedGCE questions.

The answersare on pagesI4I-I42.
SectionA
1
A fertiliser is known to contain ammonium sulphate, (NHn)rSOn,as the only ammonium salt. This
question concerns methods for the determination of the ammonium and sulphate ions.
a A sample weighing 3.80 g was dissolved in water and the volume made up to 250 cm'. To 25.0 cm'
portions of this solution about 5 cm' (an excess)of aqueous methanal was added. The following
reaction took place:
4NHn.(aq) + 6HCHO(aq) ---; CuH',N*(aq) + 4H.(aq) + 6HrO(l)
The liberated acid was titrated directly with 0.100 mol dm-'' aqueous sodium hydroxide. The average
volume required was 28.0 cm'. Calculate the percentage of ammonium sulphate in the fertiliser.
ts]
b In a second determination of the ammonium ion content, the same mass of fertiliser (i.e. 3.80 g) was
treated with excesssodium hydroxide and heated. The ammonia liberated was passedinto a known
excess of hydrochloric acid. The unreacted hydrochloric acid was then titrated with standard aqueous
sodium hydroxide.
The calculation of the percentage composition of the fertiliser gave a value that was 5ololower than the
value obtained by the method in a. Suggest reasons for this error other than those arising from the
measurement of volumes.
tzl
c To determine the sulphate ion concentration of the fertiliser, aqueous barium chloride was added in
excess to the fertiliser solution. The precipitate produced was filtered off and dried by strong heating.
i
ii
Give the ionic equation, with statesymbols,for the precipitation reaction.

Suggestwhy the aqueousbarium chloride was added in excess.
r2l
tll
d Many carbonates are also insoluble, and can be precipitated, dried and weighed in experiments similar
to c. However the strong heating needed to drive off all the water can cause a problem in determining
the mass of the carbonate precipitated. Suggestwhat this problem is, and, choosing a suitable example,
write an equation for a reaction that might occur when the precipitate is heated.
t4I
(Total 14 marks)
[June2002 Urtit Test68 question1]
SectionB
Answer TIIVO questions only
2 a The covalentcompound urea,(NHr)rC= O, is commonly usedas a fertiliserin most of the European
Union, whereasin the UK the most popular fertiliseris ionic ammonium nitrate, NH4NO'.Apart from
its nitrogen content suggesttwo advantagesof using urea as a fertiliser comparedwith using
ammonium nitrate.
I2l
b The ammonium ion in water has an acid dissociationconstantK^ = 5.62 x 10-tomol dm-'' The
conjugateacid of urea has K" = O.66mol dm-'. Usethis data to explain which of ammonia or urea is the
strongerbase.
t2l
c Someorganic nitrogen compounds are usedto manufacturepolyamidesby condensation
polyrnerisation
andpolyamide.
polymerisation.With the aid of diagrams,define the terms condensation
t4l
d Ethanamide,CH3CONH, can be convertedto methylamine, CHrNHr.
i Statethe reagentsand conditions for carrying out this conversion.
ii Suggestthe formula of the likely product if urea were used instead of ethanamide in this
conversron.
e Ammonium nitrate can explode when heated strongly.
NI = -23 kJ mol-'
NHnNO.(s)- N,O(g) + ZH,O(g)
t3l
tu
ADVANCED
LABORATORY
CH EM ISTRY
With moderateheating the ammonium nitrate volatilisesreversibly

NI = +L77 kJ mol-'
NHnNO,(s) + NH,(g) + HNO.(g)
i
ii
Statewhy the expressionfor Ko for the reversiblechangedoesnot include ammonium nitrate. tl]
Explain the conceptsof thermodynamicand kineticstabilitywith referenceto thesetwo reactions.
tsI
(Total 18 marks)
question4l
2001CH6
lJune
The principal sourceof the odour in sweatis the organic acid IIA, CTHnOz.Itwill decolourisebromine
water immediately, and it showsgeometricisomerism.
a IIA can be made by the following sequenceof reactions:
cH3cHzcHrcH(cH3)cHroH
2-methylpentan-L-ol
I
Y
cH3cH2cHrcH(cH3)cHo
conc. HzSOn
HCI(aq)
cH(oH)cN
cH.cH,cH,cH(cH3)
cTHrno3
D
+ heat
CrHrzOz
HA
i Give the reagentsand conditions for the oxidation of 2-methylpentan-1-olto B.

t3l
ii Statethe conditions and write the mechanism for the reaction of HCN with B to give C.
t4l
iii Give the equation for the hydrolysis of C to D, and hence draw the structural formula of D.
t2l
iv Draw the structure of HA.
t2l
b HA has a dissociationconstantK" = 4.50 x 1Osmol dm-', and is a monobasic(monoprotic)acid which
dissociatesaccordingto the equation:
HA(aq) + H,OQ) + HrO.(aq)+ A(aq)
i Write the expressionfor K" and calculatethe pH of a solution of HA of concentration 0.0100 mol
dm-'.
t3l
ii The pH of skin is almost constant. Explain how in principle, this could be achievedby using HA
and one of its salts.(Given its smell, it is perhapsfortunate that skin doesnot use this compound
as a pH regulator)
I4l
(Total L8 marks)
fJanuary2002 CH6 question3]
Iron(III) chloride existsin two forms, the covalent anhydrous chloride and the ionic hydrated chloride.
a Explain why anhydrous iron(III) chloride is covalent whereassodium chloride is ionic.
t4I
b Hydrated iron(III) chloride is soluble in water and its solution is acidic.
i Write an ionic equation to show why its solution is acidic and identify the acid-baseconjugate
pairs in this reaction.
t3I
ii Describewhat you would seewhen a solution of sodium hydroxide is addeduntil in excessto a
solution of iron(III) chloride.
Write an ionic equation for this reaction and identify the type of reaction.
t4l
iii A test for Fe'*ions is to add a solution of thiocyanate ions, SCN-(aq),which react to form a blood
red ion of formula [FeSCN(H'O)J'..What is the bonding betweenthe SCN-ion and the Fe3.ion,
and what is the causeof the colour of the ion?
t3l
c Iron also forms the intensely red coloured anion, FeOn'-.In acidic solution this is a powerful oxidising
agent, and is itself reducedto Fe3*ions.
Calculatethe oxidation number of iron in FeOn'.Suggest,in outline, how you could determine the
concentration of a solution of FeOo'-ions.
t4l
(Total 1"8marks)
ffanuary2001 CH6 question6l
ANSwERS
Arcr,tters
U n i1t
Tonic1.1 Atomic structure
^ v r 7 v
L . 1
t The relative isotopic mass is the mass of a single

isotope of an element (relative to 1172th the mass
of a carbon 12 atom), whereas the relative atomic
mass is the averagemass taking into account the
isotopes of the element. The relative isotopic
m as s esof t he tw o c h l o ri n e i s o to p e sa re 3 5 and 37,
b ut t he r elat iv e a to m i c m a s s o f c h l o ri n e i s 35.5
tli
2 There are many more
atoms than "Li atoms in
natural lithium, so the averageis closer to 7.
3 A, of magnesium
= ( 2 4 . Ox 7 8 . 6 + 2 5 . Ox 7 O . I + 2 6 . Ox 7 7 . 3 )= 2 4 . 3
100
4 Let the o/oof "ncabe x,
and so the o/oof "Ga = (100 _ x)
69. 8 = [6 9 .0 x+ 7 1 .0 (1 0 0- x )J
100
Therefore6980 = 69x + 7100 - 77x
Therefore2x = l2O and x = 60.0
iii Although the element with Z = 11 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 lessenergy is required to remove it.
The el ectron i n a box notati on for chl ori ne is:
muruuunnun
1s
9 a i
ll
iii
5 Gr oup 5. T here i s a b i g i u m p b e tw e e n th e 5th and

6th ionisation energies.Therefore the 6th electron
i s being r em ove d fro m a l o w e r s h e l l (n e a re rto the
nucleus) than the first five electrons.
>\
bo
t-<
2000
b
c
1500
1000
500
v)
e 10 11
| 2 t^ti*tt
":-l.r*
b i
ll
Li (g) + e --+Li- (S)

cl (g) + e -+ Cl- (g)
o (g) + e --+o- (g)
N otethatthespeci es
onthel efthandsi dei s a gaseous
a t o ma n dt h eo n eo nt h er i g h it s a n e g a t i vi eo n .
zsoo
+)
.A
3 p . *3 p , , 3 p ,
8 All have one electron in their outer shells, but K is

bigger (larger atomic radius) than Na, which is
bigger than Li. Therefore the outer electron is held
on less firmly (the extra nuclear charge is balanced
by the same extra number of shielding electrons)
and so is the easiestto remove from potassium and
the hardest to remove from Li. This makes
potassium the most reactive.
of the ""Gaisotope.
Gallium contains 6O.Oo/o
6 a
2s 2p,2p,2p,3s
A 2p electron, which is in a higher energy

level, is being removed. So less energy is
required to remove it compared to that
required to remove a 2s electron.
There are two electrons in the 2p, orbital
which repel one another, so less energy is
required to remove one of the pair than if
there had only been one electron in that
orbital.
O- (S) + e- - O- (g)
For the 1st electron affinity, the (negative)
electron is brought closer to the positive
nucleus in a neutral atom, and so energy is
released.For the 2nd electron affinity, the
negative electron is brought towards a
negative ion, and so repulsion has to be
overcome, which requires energy.
Topic7.2Formulae,equations
and moles
o/o
+6.9O
1
C
82.76 + L2 = 6.9O
17.24+1=17.24 2.5
H
Therefore the empirical formula is CrH.
b Mass of CrH, is 29, but M, - 58,
Therefore the molecular formula is C.,H,u
2 a 4NHr+5Or-4NO+6HrO
b 2Fet.(aq)+ Sn'.(aq)-- ZFe"(aq) + Sn'.(aq)
1 a
122 ANsweRs
copper
sio,
H.e r e
l o n i ce q u a t i om
n su sat l s ob a l a n ci nec h a r g e
bothsidesare8+.
+ 3HrO
Equation: HrPOn+ 3NaOH - Na.,.POn
A m ount of H. P O , = 2 .3 4 1 9 8= 0 .0 2 3 8 8 m o l
A m ount of NaO H = 0 .0 2 3 8 8 x 3 /1 = 0 .0 7 L 6 3 mol
M a s so f N a O H = 0 . 0 7 L 6 3x 4 O = 2 . 8 7 g
Equation: 2KOH + HrSOn= KrS9n+ ZHrO
Amount of HrSOn= 0.0125 dm'.x 0.0747 mol dm-'
= 9 . 3 3 8x 1 0 - ' m o l
A m ount of K O H = 9 .3 3 8 x 1 0 a x 2 l l
= 1 .8 6 8 x 1 0 r mo l
Volume of KOH solution = mol/conc
= 1 .9 6 9 x 1 0 -,m g l
O.l O 7 m o l d m -'
= 0 . 0 1 7 5d m ' = 1 7 . 5c m '
5 Am ount of B i( N O,), = 0 .0 2 5 d m' x 0 .5 5 mo l dm-'
= 0 . 0 L 3 8m o l
= 0.0L38 x 312
Amount of HrS
= 0 .0 2 0 6 mo l
= rlol x molar volume
Volume of HrS gas
= 0 .O2 0 6x 2 4 = 0 .5 0 d m'
6 Ratio mol of H,(g):mol of CH.(g) = 3:1
Volume of Hr(g):volume of CHr(g) = 3:L
Volume of Hr(g) = 3 x 33 = 99 dm'
solid CO,
CaO
poly(ethene)
graphite
sulphur
CuSOn
sucrose
LiF
Melting: on heating, the molecules or ions vibrate

more until the intermolecular forces (in molecular)
or ion/ion forces (in ionic) substancesare overcome
and the lattice breaks down.
or ionsstartto vibrate.
Donotsaythatthemolecules
Boiling: on heating the average kinetic energy ot
the molecules increases.Those with a large enough
kinetic energy and hence speed escape,not only
from the surface but also from the body of the
liquid, forming bubbles.
a
b
Topic7.3Structureand bonding
d
o-bond
2 a
AlCl, becauseeither there is less difference in

electronegativity between Al and Cl than
between Al and F
or A13.is very polarising and the bigger Cl- ion
is more polarisable than the smaller F- ion.
BeCl, becauseeither there is less difference in
electronegativity between Be and Cl than
between Mg and Cl
or Be'* is smaller than Mg'. and so is more
polarising.
HF
r2
HBr
P H,
Ar
4 iodine
ice
a Hydrogen
bon d
Yes
No
No
No
No
b Dispersion
Yes
Yes
Yes
Yes
Yes
e simple molecular
d H bonded molecular
c Dipole
/dipole
Yes
No
Yes
Yes
No
a metallic
b giant atomic
e simple molecular
c ionic
f polymeric
b giant atomic
e simple molecular
c ionic
d H-bonded molecular
c ionic
NH.. There are stronger intermolecular forces

in NH. as it forms H bonds and PH. does not.
HBr. It has more electrons in its molecule, and
so it has stronger dispersion forces (which
outweigh the difference in dipole/dipole
forces).
Propanone. Both have about the same strength
of dispersion forces becausethey have about
the same number of electrons,but propanone is
polar and so has dipole/dipole forces as well.
58.It has about twice as many electrons as Pn,
and so has stronger dispersion forces.
NaCl. It has ion/ion forces that are very much
stronger than the weak intermolecular
dispersion forces between CCln molecules.
Number of
o bond
pairs
Total
Number
of lone number of
pairs
electron
Shape
pairs
siHn
BF.
4
3
0
0
4
3
BeCl,
PCl3
SFu
XeFn
2
3
6
4
0
1
0
2
2
4
6
6
NHn'
PClu-
4
6
0
0
4
6
Tetrahedral
Triangular
planar
Linear
Pyramidal
Octahedral
Square
planar
Tetrahedral
Octahedral
8 In Na (s) there are loosely held delocalised

electrons that can move through the lattice. In
ANswERs
NaCl(s) the electrons are localised on the ions, not
loosely held and the ions are fixed in their
positions in the lattice and so are not free to move.
4 a i
ll
Topic7.4 ThePeriodicTableI
b i
1 a
b
2 a
b
c
d
e
f
They all have the same number of electrons in

their outer shell. For Group 2 this number is 2.
This period is Period 4, and so all the members
have electrons in four shells.
H, is simple molecular
Na is metallic
Si is giant atomic
S*is simple molecular
Cl, is simple molecular
Ar is simple molecular (argon is monatomic).
ll
T h ea n s w e r ' h y d r obgoennd eodr' ' i o n i c 'a n n oatp p ltyo

elements.
Sodium and magnesium are metals. Magnesium is
2+ and has a smaller ionic radius. therefore it will
have stronger metallic bonds and a higher melting
temperature. Silicon forms a giant atomic structure
with each silicon atom ioined covalently to four
other silicon atoms. These strong covalent bonds
have to be broken. This requires a huge amount
of energy and so the melting temperature is very
high.
C a r b o inn,t h ef o r mo f d i a m o nhda, sa s i m i l asrt r u c t u r e ,

b u ta st h es m a l l ecra r b oant o mf o r m s t r 0 n g e
b ro n d s
t h a ns i l i c o nd,i a m o n dm' se l t i ntge m p e r a t u
i sreev e n
higher.
White phosphorus, sulphur and chlorine all form
simple molecular solids. The melting temperatures
depend upon the strengths of their intermolecular
forceswhich are dispersion (induced dipole/induced
dipole) forces.The strength of this force depends
upon the number of electrons in the molecule.
Nuclear charge is equal to the number of

protons in the nucleus.
Screeningor shielding occurs when an outer
electron is insulated from the pull of the
positive nucleus by electrons in inner shells.
The 1st ionisation energy of sodium is for
the removal of the 3s el ectron. S odium has a
nucl ear chargeof + 11, but the 3s e lect r on is
shi el dedby the 10 el ectronsi n the 1st and
2nd shel l s.The secondel ectron that is
removed comes from the Znd shell (it is a 2p
el ectron).Thi s el ectron i s shi el dedf r om t he
nucl eus onl v bv el ectronsw hi ch ar e in a
l ow er shel l , rvhi ch i n thi s casei s by t he t wo
1s el ectronsand so i t i s hel d much m or e
strongl v bv the nucl eus.It i s al so n ear ert o
t h e n u c l e u s ,r v h i c h m a k e si t e v e n h a r d e r t o
remoV e.
S o d i u m h a s a n u c l e a rc h a r g eo f + 1 1 a n d i t s
3 s e l e c t r o ni s s h i e l d e db v t h e i n n e r 1 s t a n d
2 n d s h e l l e l e c t r o n s \. l a g n e s i u m h a s a
n u c l e a rc h a r g eo f + 1 2 ( o n e n l o r e t h a n
sodi um), but i ts 3s el ectron i s shi eldedby
the same i nner el ectrons.Thus i ts 3s
electrons are pulled more strongly to the
nucleus and are harder to remove.
I t i s b e c a u soef t h i se x t r a
o u l tl h a ta m a 0 n e s i u m
a t o mi s s m a l l et hr a na s o d i u m
atom.
Topic7.5 Introductionto
oxidationand reduction
1 a
Sn"(aq) -- Sn'.(aq)+ 2e
E l e c t r o nasr e0 n r i g h tb e c a u sSen ' .i s o x i d i s e d2 :e i s n e e d ebde c a u soex i d a t i onnu m b ecrh a n g ebsy 2 .

b
c
T h es i m p l e swt a yi n w h i c ht o w o r kt h i so u t i s t o a d d
t o g e t h et rh ea t o m i cn u m b e rosf a l lt h ea t o m si n t h e
mo l e cul e .
Pnhas 4 x 15 = 60, S*has 8 x 16 = 128 and Cl, has
2 x I 7 = 34 electrons per molecule. Thus sulphur
has the strongest intermolecular forces and the
highest melting temperature and chlorine has the
weakestintermolecular forces and the lowest
123
F e ' - 1 a q+) e --'Fe"-(aq)

S n ' - ( a q )+ 2Fe''.(aq)-- Snn.(aq)+ 2Fe'.(aq)
E q u a t i obnh a st o b e d o u b l e ds,o t h a tt h ee l e c t r o n s
c a n c ewl h e n2 t i m e sb i s a d d e dt o a .
2 a
HrOr(aq)+ 2H.(aq) + 2e- -. 2HrO(l)
H . 0 ,i s r e d u c e ds ,o e l e c t r o nasr e0 n t h el e f t .
124 ANswERs
b S(s)+ zH'(aq) + 2e---'H,S(aq)
andits
S is reduced
ontheleftbecause
2e-areneeded
o x i d a t i onnu m b egro e sf r o m0 t o - 2 .
c H,O,(aq) + H,S (aq) - zH,O(l) + S(s)
is yellow becausethe energy difference between the

4th shelt and the 3s orbital is equivalent to the
yellow line in the spectrum.
The sodium atom is smaller than the potassium
atom, becausesodium has three shells of electrons
and potassium has four. Thus sodium's outer s
electron is held on more firmly, and more energy is
required to remove it.
has
Thisis thecasein spiteof thefactthatpotassium
e i g hm
t o r ep r o t o nt sh a ns o d i u mb,e c a u si tea l s oh a s
ne
s t w e et hnen u c l e uasn dt h eo u t e r
e i g hm
t o r ee l e c t r 0 b
e ydt h e
n u c l e ac rh a r gies b a l a n c b
e l e c t r osno,t h ee x t r a
extra
shielding.
theyare
BothH,SandH,0,mustbe0ntheleftbecause
to a;
andadded
b is reversed
equation
thereactants;
n o t et h a t h eH -i o n sc a n c eolu t .
3 a
+ 2H,O(l)
PbOr(s)+ 2H,SOo(ag)+ 2e- - PbSOo(s)
+ SOo'-(aq)
andits
ontheleftasPbO,is reduced
2e-areneeded
o x i d a t i onnu m b ecrh a n g ef rso m+ 4t o + 2 .
b
PbSOo(s)+ 2e--- Pb(s) + SOo'-(aq)
and
e b S0 i, s re d u c ed
2e-ar eneeded
on th e l e ftb e c a u sP
t h eo x i d a t i onnu m b eor f l e a dc h a n g efsr o m+ 2 t o 0 .
- 2PbSOo(s)
+
PbOr(s)+ Pb(s) + 2H,SOo(ag)
2H,O(t)
4 a
b
c
d
2C a + O, - ZC aO (or C a * ' l rO, -- C aO)

Ca + zH,O - Ca(OH), + H,
2K + ZH.O -- 2KOH + Hz
Mg(s) + H,O(g) - MgO(s) + H,(g)
The white precipitate is the insoluble magnesium

hydroxide. Barium hydroxide is soluble and so is
not precipitated.
Beryllium, as BeCO. is the least thermally stable of
the Group 2 carbonates.It decomposesvery easily
on heating becausethe Be'* ion is very polarising.
The other Group 2 ions are less polarising because
they are larger.
7 a
4LiNO3 -- ZLizO + 4NO, + O,

2N aN O. - 2N aN Or* O,
2Mg(NO,),- 2MgO + 4NO, + O,
NarCO. --' no reaction
MgCO,-MgO+CO,
BaCO, --+no reaction
Topic7.7 Group7
ii hasto bereversed
Pbis a reactant,
equation
Because
thattakesplace
to i. Thisis thereaction
andthenadded
batterv.
froma lead-acid
is drawn
whencurrent
Topic7.6 Group1 and Group2

L Dip a hot platinum (or nichrome) wire in clean
concentrated HCI and then into the solid. Place in a
hot bunsen flame. The substance that turns the
flame carmine red is LiCl, the one which turns the
flame lilac is KCI and the one that turns the flame
apple green is BaClr.
2 The heat of the flame vaporisesthe sodium
chloride, producing some Na and Cl atoms.
Electrons are promoted into the 4th shell in some
of the sodium atoms. These electrons then fall back
to the ground state, which is the 3s orbital, and
energy is given out in the form of light. The flame
Covalent HCI ionises when added to water, and the

hydration energy given out by the ions bonding
with the water molecules is greater than the energy
required to break the covalent H-Cl bonds:
HCI(g) + H,O(l) -- H,O.(aq) + Cl-(aq)
First a solution has to be made. The sample can be
dissolved either in water or in dilute nitric acid. (If
water is chosen, dilute nitric acid must then be
added to destroy the carbonate).To this slightly
acidic solution, add silver nitrate solution. If there
is chloride present, there will be a white precipitate
that will dissolve in dilute aqueous ammonia.
HrSOnis a stronger acid than HCI (or HI), and so it
will protonate the Cl- ions in the sodium chloride
producing HCI gas. HCI is not a strong enough
reducing agent to reduce sulphuric acid, and so
no further reaction will take place. With sodium
ANsweRs 125
iodide, HI is produced by the protonation of the
iodide ions, but the HI is a very strong reducing
agent, and so it will reduce the sulphuric acid and
itself become oxidised to iodine.
ll
4 Disproportionation is a reaction in which an

element is simultaneously oxidised and reduced.
Chlorine disproportionates when added to alkali:
Cl, + ?OH- - Cl- + CIO- + H,O
( 0)
(-1 ) (+ 1 )
Also, chlorate(I) disproportionates when heated:
3ClO- -- ZCl- + ClO,,
(+1)
(-1) (+5)
The allocation of marks follows Edexcelmark
sc hem es .
approximately:
A
7Oo/o
B
6lo/o
C
52o/o
D
44o/o
E
360/o
= [1]
Z C a +O r - Z C a O
= [1]
NarO + HrO ---+2NaOH
Na,O + ZHCI ---; 2NaCl + H,O
= l2l
Species[.], balancing [.]
b The thermal stability increasesdown the group
[f.] as the cation size increases[1] and so the
carbonate ion is distorted (or polarised) less tll
_ t3l
b Graphite has covalent bonds between atoms that

have to be broken [1]; sodi um chl ori d e has
el ectrostati cforcesbetw een the i ons [1 ] . I n bot h
these forcesare strong and so a l ot of e ner gy is
= [ 31
neededto break them [1]
c i
Graphi te has del ocal i sedel ectronsabove and
bel ow the pl ane of he.ragons[1], which can
ii
iii
2 a i
Graphite has a giant atomic (or giant

covalent) structure [1]. The bonding between
atoms is covalent [U.
Your diagram must show several interlinked
= [4]
hexagons [1] in layers tU
The l atti ce i s broken don' n i n the l iquid and

so the i ons are free to nl ove
=[u
a S t r u c t u rmee a n gs r a nat t o m i ci .o n i cl a t t i c e ,
s i m p l oe r h ,d r o g e bn o n d em
d o l e c u loarra
l a t t i coef m e t arl o n si n a s e ao f e l e c t r o n s .
c A s u b s t a n c, e' r, l lc o n d u cet l e c t r i c iitfyi t h a s
d e l o c a l r seel d
e c t r o nt hs r o u g h otuhtes t r u c t u r e
o r i o n s ' , ' . , har rcehf r e et o m o v e .
L ai
b Donotattempt
to answer
thistypeof question
in
termsof sizematch.
= f2l
flow (which are mobilet [1]

ll
3 a i
A tomi c number i s the number of prot ons in

the nucl eus [1] Mass number i s the t ot al ( or
sum of the) number of protons and neut r ons
tu
= l2l
= [1]
High energy electrons bombard the Br,
molecules [1] and knock out an electron [1]
= [2]
ll
They are acceleratedby charged plates (or
= [1]
an
across
-" B r-' ' B
r. electric field)
= [U
iii
ii
b i
,.gt-
has1 fewerelectrons
than
a ii Astheparticle
p r o t o nist ,w i l lb ea p o s i t i vi o
en .
a i i i I na m a s s p e c t r o m emt eorset l e m e n t s
p r o d u ci o
e n sc o n t a i n ionngea t o mb, u t
d i a t o mei cl e m e nst us c ha sN , ,0 , a n dt h e
h a l o g eg
n isv em o l e c u liaorn ss u c ha sB 1 2
w h i c hm a yc o n t a it nw od i f f e r einsto t o p e s .
It
Sodium chloride has a lattice structure t l l .

The bonding is ionic [l.].
Your diagram must show a 3-D arrangement
= [3]
of ions, Na. alternating with Cl-. [1]
4 a
Divide each o/oby their A, values [L] and then divide
by the smallest [1]
H
L 1 . L* 1 = L 1 . 1 t h e n * 7 . 4 = 1 . 5
C
88.9* 12 = 7.4 then + 7.4= 1
Multiply both by 2 to get whole numbers
= [3]
.'. E.F.is CrH. tll
.l
128
ANswERs
7 a
CH. CHI CH. + N a OH '
C H .C H (O H )C H ,+ N aI
propan-2-ol
CH3CHICH.+ KOH--'CH.CH=CHz + KI + HrO
propene
CH3CHICH, + ZNH, - CH.CH(NHr)CH3 + NH4I
2-aminopropane
b
c
8 CH.CH(OH)CH, - H,O -'CH.CH-CH,

conditions: concentrated acid at l7O "C
9 a
H
H-
l t / -
C-C-C
b
c
H O - H
Propanoic acid
observation: solution goes from orange to green
No reaction
observation: solution stays orange
CH3CHCICH3
2-chloropropane
observation: steamy fumes
1O The n carbon-carbon bond in ethene is weaker

than the o carbon-carbon bond in ethane. This
makes the activation energy less, and so the
reaction is faster.
Pressure. As the pressure is increased, the number

of molecules in a given volume increases,and the
frequency of collision increasesand hence the rate
of reaction, which is dependent upon this
frequency of collision, increasestoo.
Temperature. If the temperature is increased, the
average kinetic energy of the molecules is also
increased. This means that a greater proportion of
the colliding molecules will have, between them,
energy greater than or equal to the activation
energy. There will be a larger number of successful
collisions and a faster rate of reaction.
Catalyst. This increasesthe rate of reaction by
providing an alternative path with a lower
activation energy, thus a greater proportion of the
colliding molecules have energy greater than or
equal to the lower catalysed activation energy.
ttt
(u
U
q.)
(|{
(J
1,1 The C-Br bond is stronger than the C-I bond. This
makes the activation energy more, and so the
reaction is slower.
+ Br, - CuH,oBr,
L2 C6H1o
5. 67 g of CuH, o= 5 .6 7 1 8 2= 0 .0 6 9 1 m o I
Becausethe reaction is a L:L reaction, the amount
of product is also 0.0691 mol.
Therefore the theoretical yield of CuH,oBr,
= 0. 0691 x 242 = 1 6 .7 g
The o/oyield = 15.4 g x 100 = 92o/o.
1 6 . 7g
They are stable in air owing to the strong C-Cl
13
and C-F bonds.
They then diffuse into the stratosphere where
they form radicals and destroy the ozone layer.
Ea
Energy
Bacterial and enzyme reactions are also slowed
down by a decreasein temperature for exactly the
same reason as ordinary chemical reactions, which
is that fewer colliding molecules will have the
necessaryactivation energy to react on collision. So
the low temperature in the refrigerator will slow
down the biological decay reactions.
i
>.
@
Tonic2.3 KineticsI
OJ
1 i
ii
The activation energy is the minimum energy

that the reacting molecules must have when
they collide in order for them to react. It is
measured in kJ mol-'.
A catalyst is a substance that speedsup a
chemical reaction without being used up. It
works by providing an alternatlve route with a
smaller activation enetgy.
tll
lv
bo
q)
ar-l
energy.
lowers
theactivation
Never
saythata catalyst
it is nota substance
because
Lightis nota catalyst,
formof energy.
andit is usedup.lt is justa specific
R is the reactant and P is the product.
ANswERs 133
3 a i
ii
iii
b i
ii
iii
Mg(OH),(s) + 2H.(ae) * Mg'.(aq) + 2H,O(l)

PbO(s)+ 2H.(aq) --'Pb'.(aq) + H,O(l)
SO, + acid: no reaction.
Mg(OH), + alkali: no reaction
PbO(s) + ZOH-(aq) + H,O(l) - Pb(OH),'-(aq)
SO,(g) + ZOH-(aq)* SO,'-(aq)+ H,O(l)
b i
Becausereaction L*R is exothermic, a

decrease in temperature causesK. to
increase,and so the position of equilibrium
moves to the right.
As the reaction going from right to left
causesan increasein the number of moles of
gas, a decreasein pressurewill causethe
position of equilibrium to shift from right to
left. K. is unaltered.
There will be no effect on either. A catalyst
speedsup the rate of both forward and back
reactions equally, and so equilibrium is
reached sooner.
ii
PbO, + 4HCl -' PbCl, + ZH'O + Cl,

Sn'.(aq) + 2Fe'.(aq)-* Snn.(aq)+ 2Fe'.(aq)
4 a
b
iii
Topic4.3 ChemicalequilibriaII
1,
2SO3+
Start(moles)
0.0200
Change(moles) -0.0058
2SO, +
0
+0.0058
o,
0
+0.0029
1 m o l eo f S 0 ,g i v e s1 m o l eo f S 0 ,a n d' / , m o l eo f 0 ,
Equilib.moles 0.0142
0.0058
0.0029
0.074217.52 0.0058/1.s20.002917.s2
il*/mol dm= 0 .0 0 9 3 4
= 0.00382 = 0.00191
^
4= [SOJ" x [O,]
rsoT
Topic4.4 Acid-baseequilibria
1. C,H.COOH + H . + C T H . C O O PK,,= 4'87
ThereforeK , = i n v e r s e l o g ( - 4 . 8 7 ) = 7 . 3 5 x 1 0 - ' m o l
dm-'
[ H - ] = [ C , H . C O OI
K " = [H -l x [C .H .C OO I
lc.H.cooHl
[Hl'
= 1 . 3 5x 1 0 ' m o l d m '
Ic.H.cooHl
[H]= (K"x[C,H'COOH])
--l.7zx1o-'moldm-'
=@
= (0.00382)'zx
0..00191
(0.00e34)'
= 3.L9x 10" mol dm-''
pH=trtoslHt= 2.76
2 a End poi nt i s at 25 cm' N aOH .
Start (moles)
Change (moles)
Equilib. (moles)
Equilib. mole
fraction
zNO(g)+O,(g) + 2NO,(g)
1.0
1.0
0
Total = 2 mol
-0.60
-0.30
+0.60
0.40
0.70
0.60
Total= 1.7 mol
l2
11
9
O.4Oll.7
= 0 .2 3 5
Partial
pr es s ur e/ a tm O .2 3 5x 4
^=o.g4
Kn = (p of NOr)'
O . 7 O | I . 7 0.6011..7
= 0 .4 ' 1 ,2 = 0 . 3 5 3
7
O .4 1 2x 4
= L.65
0.353 x 4
= I.4l
6
5
(p of No) x p o f O ,
20
(oe4)TT.6s
H al f w ay to end poi nt i s 12.5 cm' ,

which is when [HA] = [A-].
pH at this point is 4.95.
ThereforepK = 4.95.
ISOr],"no,'
(q.2\,
( o . 2 ) "x 0 . 1
= 10 mol-t dm'
which is not equal to K., so it is not at equilibrium.
As the quotient <K., the reaction moves left to
right, until equilibrium is reached.
T h e[ ] t e r mo n l ye q u a lKsw h e nt h es y s t e m
isin
equilibrium.
25
VolumeNaOH/cm3
= 1. 4 at m - '
ffi
Half way
p H 8
= (1.41)'
3 a
End point
10
b
3 a
P henol phthal ei n.
A buffer is a solution of known pH, which will
T h i si s a s u i t a b lien d i c a t obre c a u siet s r a n g eo f p H

f o r i t s e n t i r ec o l o u cr h a n g ies w i t h i nt h ev e r t i c apl a r t
o f t h eg r a p h .
136 AxsweRs
c An increase in temperature shifts the equilibrium
in the endothermic direction. .'.AH is
positive = [1]
d Ko stays constant [1] The position of equilibrium
moves to the side with fewer gas molecules [1],
= [3]
which is to the left [1]
Mix scrap aluminium metal with AlCl, and heat
to form AlCl [U, remove from excessAl, then
cool (or increase pressure)and pure Al and AlCl3
are formed. The latter is then used again [1] = [2]
t4
12
10
pH8
6
4
2
0
25
a S o l i ddson o ta p p e ai nr K oe x p r e s s i 0 n s .
pressure
x totalpressure.
is molefraction
b Partial
c K i s o n l ya l t e r ebdyt e m p e r a u r e .
-- MgSO.,(aq)
+ H,O(l)
MgO(s)+ H,SOn(aQ)
Correctequation [1] statesymbols[L] = lz'J
ii A white solid [1] reactsto form a colourless
5 a i
= fz'l
solution [1.]
b i PnO,o+ L2NaOfl ---+4NarPOn+ 6HrO
or PrO.,+ 6NaOH ---+2NasPOn+ 3HrO
= I2f
All speciescorrect [l.], balanced [1]
(or
HCI)
ii For having 2 equations, one with H'
and the other with OH- (or NaOH) [1,] and:
AI(OH)3 + 3H* -- Al''* + 3HrO or
AI(OH)3+ 3HCl --' AICIr + 3H,O [1.] plus
AI(OH), + 3OH- -r Al(OH)u'-or
= [3]
AI(OH), + 3NaOH -'Na,Al(OH). [1]
is
MgO is basic, AI(OH). is amphoteric and PnO,o
acidic [L] showing the metallic character of the
= f2l
element decreasingacrossthe period tll
get
more
As a Group is descendedthe oxides
basic [1]. Indium is in the same Group as
amphoteric aluminium, so indium oxide will be
= I2l
basic [1]
equations.
areverybadatwriting
Manystudents
t ake
s u r et h a yt o ul e a r tnh ee q u a t i oinns
Y o um u s m
T o p i4c . 2o l t h es p e ci icf a t i o n .
youareasked
to statewhatyouwould
a Whenever
s e ey, o um u s dt e s c r i bt heea p p e a r a nbceef o raen d
afterreaction.
6 a An acid is a proton donor [,],
Weak means that it is incompletely dissociated
(ionised) [L], but dilute means that its
= [3]
concentration is small [1]
b i pH = -log,u [H.]
ii Ku = 3.72 x lO-" = [H.]tOCl-l
Vol. NaOH/cmE
Shape of curve correct [L], start at pH = 4 llf,
vertical at 25 cm' [1] and at a pH of between 7 and
= [5]
11 [f.], curve flattening off at pH 13 [1]
i
HrSOl --' H* + HSO.,- [L]

HSO.*-+ H* + SOn^ [1]
ii
The second ionisation is incomplete and is

suppressedby the H. from the first ionisation,
= [1]
and so produces very few H. ions
= [2]
withdilute
a Don'tconfuseweak(howionised)
( h o wm a n ym o l e s ) .
b T og e tf r o mp Ht o [ H - ]u, s et h e1 0 "b u t t oonn
y o u rc a l c u l a t o r .
d S u l p h u rai c i di s o n l ys t r o n ign i t s1 s t
i o n i s a t i osnot, h i ss o l u t i ohna sa p Ho f 0 . 9 8n o t
0.699.
U n i5t
Topic5 .7 Redoxequilibria
1 a i
ii
iii
iv
CrrOr'- (aq) + 14H'(aq) + 6e- -- 2Cr"(aq) +

THrO
Snn.(aq)+ 2e- -- Sn'.(aq)
IO, (aq) + 6H .(aq) + 5e- -' 1,1,+ 3H rO
l, + 2e- -- Zl-(ag)
=[u
lHocll
= 5 .8 9 x 1 0 -' mo l d m
[ H] = 10- o n
-r
lHl = [octl tl]

.'. tHOCll= (5.89x 10-')'* 3.72x 1 0 *
= 0.0932 mol dm-' [1]
tU
tll
= [41
nn
st h el e f t .
A l la r er e d u c t i oannsds oh a v e l e c t r o o
n
nq
s u a lt sh et o t acl h a n gi e
T h en u m b eorf e l e c t r o e
o x i d a t i onnu m b e r .
ANswERs 137
b i
CrrO,'-(aq)+. 14H.(ag) + 3Sn'.(aq) - zCr'.(aq) +

TH.,O+ 3Snn"(aq)
= +1.33 - 0.15 = +1.18 V.
E,"".tio.
Feasible as E,"u.tion
> 0.
Equatio
a ni i i s m u l t i p l i e
bd
y3 , r e v e r s e
ad
nd
added
to equation
a i.
Ior(aq) + 6H.(aq) + Sl-(aq)- 3I, + 3H,O
= *1.19 - 0.54 = +0.65 V.
E,"u.tion
Feasibleas E"u..,o.
> 0.
Topic5.2 Transitionmetal
chemistry
t The water ligands split the d orbitals into two of
higher energy and three of lower energy. When
white light shines on the solution, an electron
absorbs visible light energy and moves (jumps)
from the lower to the higher energy level,
absorbing some of the red/green light and leaving
blue light.
2 a
[C r(H ,O).]" (aq)+ 3OH -(ag)-C r(OH ) , ( s) + 6H, O
T h i sr e a c t i oi snd e p r o t o n a t i o n .
then Cr(OH),(s+
) 3 O H - ( a Q+) C r ( O H ) . ' - ( a q )
Equatio
a ni v i s m u l t i p l i e
bd
y 5 1 2r,e v e r s e
ad
nd
a d d etdo e q u a t i oani i i .
Equations are:
Fe(s^)
+ 2H.(aq) * Fe'*(aq)+ H,(g)
SFe"(aq)+ MnOf(ae) + 8H'(aq) - SFe*(aq)+
Mn'.(aq) + 4HrO
Amount of MnOn- = 0.0235 x 0.0200
= 4 . 7 Ox 1 0 * m o l
Amount of Fe'*in 25 cm' sample = 4.70 x 10* x 5/1
= 0.00235 mol
,/
T h i so c c u r b
s e c a u sCer ( l l l i, sy a m p h o t e r i c
c
3 a
+ ZOH -(aq)- Fe(OH) : ( s)+ 6H, O

[Fe(H ,O)u]" -(aq)
then no further reaction.
[Zn(H,O),]'.(aq)+ ZOH-(ag)'Zn(OH).(s) + 4H.O
then Zn(OH),(s) + 2OH-(aq) - Zn(OH),r (aq)
[Fe(H,O),]'.(aq)+ 3NHr(ag) * Fe(OH),(s)+
3NH; (aq) + 3H,o
5/ 1 bec austeh e rea re5 F e 2to- 1 M n 0 oi -n th e e quati on.

Amount of Fe" in 250 cm' sample = 0.0235 mol
Mass of Fe'*= rl?ss of Fe = 0.0235 x 56 = 1.316 g
Purity of iron in steel = 1.316 x L00 = 99.7o/o
132
Thisreaction
is deprotonation.
then no further reaction.

+ 2NH.(ae)- Cu(OH),(s)+
[Cu(H,O)J'.(aq)
2NH; (aq) + 4H"O
Anode area: Fe(s)-- Fe'.(aq) + 2e-
Thisreaction
is alsodeprotonation.
0xidation
attheAnode,
soelectrons
ontheright.
Cathode area:
'lrOr(aq)
then Cu(OH),(s)+ 4NH,(aq) + 2H,O(l) --'

[Cu(NH,)o(H,O)J'.(ag)+ 20H-(aq)
+ HrO + 2e- -' 2OH-(ae)
Theoveralreacti
l
on
i s l i gandexchange.
Reduction
attheCathode,
soelectrons
ontheleft.
Between anode and cathode:
ZFe(OH),(s)+ 2OH-(aq) - Fe,O,(s)+ 3H,O(l) + 2e
'|,O,(aq)
+ H,O(l) + 2e- - 2OH-(ag)
4 a
VOI(aq) + 4H.(aq) + 3e--- V'.(aq) + ZH,O
Vanadium(V)
is reduced,
soelectrons
areontheleft.The
o x i d a t i onnu m b ecrh a n g ebsy3 , s ot h e r em u s b
t et h r e e
electrons.
-t
a
138 ANsweRs
b
c
d
'C),
the
If the temperature is too high (>5
benzene diazonium chloride will decompose.
VOI(aq)+ ZH.(aq)1 e - VO"(aq)+ H,O

V"(aq) + HrO -- VO'.(aq)+ 2H.(ae)+ eVO"(aq) + H,O -- VOi (aq) + 2H.(aq)+ e-
Topic5.3 OrganicchemistryIII
C.H.N=NC6H*O-but C.H'N=NC.H.,OH is
acceptable.
Tonic5.4 ChemicalkineticsII
L v r P v v . ^
1 a
The bromine reacts with the iron catalyst to

form FeBr.:
ZFe + 3Br, --' 2FeBr,
The FeBr. then reacts with more bromine to
form Br'(the electrophile) and FeBrn.
Rate = klHll'
k = rate.
tHI]"
= 2.0 x 10' mol dm-' s-'
= 0.080 s' mol' dm'
The intermediate cation loses H. to the FeBr".
t- \ st
l-
GyB'l,,rl.-,,
1
v / l t l
L
O-u'*
nu,+FeBr,
2 Cany out the following procedure:

s* Placeequal volumes of solutiorl, e.8. 50 cm'of 0.1.0
mol dm-'ethanoic acid and methanol in flasks in a
thermostatically controlled tank at 60 "C.
,,,:'
Mix, start the clock and replace in the tank.
'ii:iAt intervals of time, pipette out 10 cmt portions
and add to 25 cm'iced water in a conical flask.
+ Rapidly titrate with standard sodium hydroxide
solution using phenolphthalein as the indicator.
.# Repeat several times.
llr Plot a graph of the titre (which is proportional to
the amount of ethanoic acid left) against time.
3 Time taken for the concentration to halve from 1.6
to 0.8 mol dm-' = 26 minutes.
Time taken to halve again to 0.4 mol dm-'= 26
minutes.
Time taken to halve again to O.2 mol dm-'= 26
minutes.
tr,ris a constant, therefore reaction is 1st order.
Topic5.5 OrganicchemistryIV
that:
Check
,s.thearrowstartsonthedelocalised
ringandgoes
theBr-(andnotto the+ of Br-)
towards
.'ffi
ring
delocalised
hasa broken
theintermediate
witha+insideit
.r thearrowstarts
fromtheo bondof thering/H
g
o
e
s
i n s i dteh eh e x a g o( bn u tn o t
a t o ma n d
to the+).
directly
It is energetically favourable for the intermediate

cation to lose an H* and gain the stability of the
benzene ring, rather than add Br- as happens with
alkenes.
The first step is the addition of a CN- ion. HCN is
too weak an acid to produce a significant amount
of CN- ions. NaOH will deprotonate HCN
molecules, producing the necessaryCN- ions.
'C),
the rate is
3 a If the temperature is too low (<5
too slow.
1 a
Add 2,4-dinitrophenylhydrazine. Both give an

orange precipitate.
Add ammoniacal silver nitrate solution. Only
pentanal will give a silver mirror on warming.
g i v ea
s r e dp r e c i p i t a t e ,
F e h l i n gs'osl u t i ow
n ,h i c h
silvernitrate.
of ammoniacal
couldbeusedin place
Heat under reflux with aqueous sodium
hydroxide.
andso mustfirstbe
arecovalent
Halogenoalkanes
h y d r o l y steodp r o d u chea l i dieo n s .
Cool and acidify with dilute nitric acid, then
add silver nitrate solution.
140 ANswERs
CHs
CsHs-
C -CN
oH
tll
Now add aqueous sulphuric acid (or any

named acid) [L] and heat under reflux [1]
_
= [51
oHand
of
ester
amounts
d Mix known
[1]
remove sample [t]
at known time [1.]
quench the reaction by adding ice cold water [1,]
titrate unreacted OH- with acid [t]
Calculate rate = change in [OH-] + time [1]
Repeat with double [ester] and the same tOHl tll
Repeat with double [OHl and the same[ester]-tl]
= [8]
4 a Dip a platinum elec-trode[1] into a solution

which is L mol dm-'in both Fe'*and Fe'. ions [1].
This is connected via a salt bridge (containing
potassium chloride solution) [U to a standard
hydrogen electrode [1]. The potential is measured
with a high resistancevoltmeter (or a
= [5]
potentiometer) [L]
Au
b i Au''* + 3e[1]
= l2l
Fe" -t Fe"*+ e- [1]
= tll
ii Au" + 3Fett- Au + 3Fet'
E (gold)
iii Au'. + 3e- - Au
E ' = -0 . 77 v
3Fe' *-- 3Fet' + 3eadding the two half-equations gives E cell
E (gold) + (-0.77) = E' (cell) = + 0.73 [U
E (gold)= * 0.73+ O.77= + 1.50V[1]
= [21
(gainof electrons)
takesplace
atthe
Reduction
goldelectrode
it actsasthecathode.
because
T h u sA u ' .i o n sg a i ne l e c t r o tnhsa ft l o w eidn t h e
e x t e r ncailr c u fi rt o mF e "i o n sw h i c hl o s t h e m .
y3nd o e sn o t
. a l f - e q u a tbi o
i i i M u l t i p l y itnhgeF e ' h
a l t eirt sF v a l u e .
t h ec a l c u l a t i os tno u s e
A n o t h ewra yo f d o i n g
potentials
thus:
reduction
thestandard
F o f o x i d i s i nagg e n(tg o l d-) f o f r e d u c i n g
a g e n(ti r o n=) P o f t h ec e l l .
b i
theC of theC0nolthe
b Thecurlyarrowmustgotowards
a broken
t ave
a tues h
C o f t h eC H g, r o u pT. h ei n t e r m e d im
a c r o sasl lb u tt h eC a t o mw h i c h a sf o r m e d
r i n gg o i n g
t h eb o n dw i t ht h eC H , Cg0r o u p .
d T h ep Hw o u l dh a r d lcyh a n g seo, a m e t h oidn v o l v i n g
score
a
m e a s u r itnhgep Hc h a n goev e tri m ew o u l d
m a x i m uomf 6 .
3 a The reagent for step 1 is magnesium [1], and the
= l2l
conditions are dry ether [1]
Potassiumdichromate(Vl) [1] and sulphuric
b i
= f2l
acid [1]
= [1]
ii Distil off D as it is formed [1]
iti Ethanoic acid (CH.COOH) or ethanoate ions
(cH3coo) tll
= [1]
E is CHTCH,CH(OH)CH. [f.] for any secondary

= f2l
alcohol and [.] for the correct formula
F is a carbonyl compound as it reacts with
d i
Z,4-dinitrophenyl hydrazine [U, but it must
be a ketone and not an aldehyde as it does
not react with ammoniacal silver nitrate [1]
= I2l
In order to do the iodoform reaction F must

have the CH.CO group [1] and the products
= t3l
are CHI,. [1] and CH.CH,COO- [U
= r2l
iii F is CH,CH,COCH. [2]
=
e The speciesare: (CH.CHTCOCH..).for m/e 72 [1],
(COCH.). for 43 [1] and (CH3CH,)' for 29 tll
_ t3l
ii
b i i i T h ea l d e h y dDe i s o x i d i s etdo a n a c i db y t h e
s i l v e r / a m m o cn oi am p l eixo n s .
re a c w
t i tha n a l d e h y dto
e g i v ea
c G r ignar rdeag e n ts
s e c o n d aa
r yl c o h o l .
are
d ii T heonlys u b s ta n c etos d o th e i o d o fo rmre a c ti on
g r) o u pk, e t o n ews i t ha
a l c o h o lws i t ha C H , C H ( 0 H
C H , , Cg0r o u pa n de t h a n a l .
o nth es p e c i eisn a ma s ss pectrum.
e Don' ft or gett hec h a rg e
5 a
3d
Fe:rArlrutrntrtr
4s
cr: rA4trtrtrtrtr
cr3*:
rArltrtrnII
b FeCrOn+ 4C - Fe + Cr + 4CO
= f2l
species [1], balancing of equation [1]
= [1]
i [Fe(HrO)u]"
ii [Fe(H,O).)'.+ ZOH- Fe(OH), + 6H,O
or [Fe(H,O)u]'.+ ZOH- -' [Fe(OH),(H,O)J + ZH.O
correct iron speciesin product [1] balance
tll
= fzf
= [1]
iii The precipitate's colour is pale green
= [1]
iv [Cr(OH)J'v The solution of R would first give a Sreen
precipitate [1], which forms a green solution
= I2l
with excessacid [1]
d i The standard electrode potential is the
potential difference between a standard
hydrogen electrode and the half-cell [1] where
all concentrations are 1-mol dm-'and the
= I2l
pressure of all gasesis 1 atm. [L]
= [l]
ii All four halogens will oxidise Cr'*
iii Both bromine and iodine will not oxidise Cr''*
'
= [1]
further
A,NSwERS 141
lv
Mix the blue Cr'* solution separately with

bromine and iodine [1], the solution goes
green and stays green with excesshalogen
tll
= [2]
t h a n3 d o ,
a R e m e m b tehr a t3 d ' ,4 s ' i s m o r es t a b l e
4 s ' ( a n ds i m i l a r lfyo r C uw h i c hi s 3 d ' 04, s ' ) .A l s o
t he4 s e l e c tro nasrel o s tfi rs tw h e nc ati onsare
fo r m e d .
c i A l lt r a n s i t i om
n e t ailo n sa r eh y d r a t eidn
s o l u t i o nw, i t h6 w a t e rm o l e c u l ecso o r d i n a t e l y
b o n d e od n .
iv Chromium
i s a m p h o t e r iIcC. r ( 0 H ) ,w
] -o u l db e
a n a c c e p ta bal en s w e r.
v A d d i t i oonf a c i dw i l lf i r s tp r e c i p i t atthee
h y d r o x i dweh i c ha, s i t i s b a s i cw, i l lt h e nr e a c t
w i t he x c e sas c i dt o f o r ma s o l u t i o o
nf t h e
h y d ra tem
d e ta il o n s .
The allocation of marks follow Edexcel mark schemes.
approximately:
a D o n ' ft o r g etto m u l t i p l by y 1 0 t o g e tt h et o t a l
a m o u not f t h eN H , ' i o n sa,n dt h e nh a l v ei t a st h e r e
i s I a m o l eo f a m m o n i u smu l p h a tpee r1 m o lo f
N H .i o n s .
F o r g e t t i nt og d i v i d eb y 2 g i v e st h ea n s w e9r 7 . 3 Y o
( o b t a i n ebdy a b o u 't/ ,o f t h ec a n d i d a t ewsh) i c h
score4
s marks.
c i I n a p r e c i p i t a t i roena c t i otnh e r ea r ej u s tt w o i o n s
o n t h el e f ta n dt h ef u l lf o r m u l oa f t h es o l i do n
t f t h ee q u a t i o n
t h er i g h o
t i v ea g r 0 u p1 c a r b o n a tneo, r B a C Oa, ,s i t
d Don'g
n h e a t i nign t h el a b ,n o r
t decompo0
se
doesn
B e C 0b e c a u si ted e c o m p o sbees l o wr o o m
temoerature.
Answer any two of the section B questions

2 a A ny tw o of : i t i s consi derabl ycheape r[ 1] ;
l essri sk of l eachi ng tU
it does not effect the pH of the soil [1]
= [21
it releasesthe nitrogen slowly [L]
b The smaller the K" of the conjugate acid, the
stronger the base [1]. Therefore ammonia is the
= I2l
stronger base [.]
Polymerisation occurs when many molecules ioin
to form a long chain [1]; condensation is with
the elimination of water or a small inorganic
molecule such as HCI [L].
A polyamide contains the -CONH- link [1] as in:
O
/ll ,
1 a Amount of NaOH = 0.100 mol dm-' x 0.0280 dm'

= 0.00280 mol [f.] = moles of H.
Ratio H. to NHn*= 1 : 1".
Amount of NH.,.in 25 cm' = 0.00280 mol.
Amount in 250 cm' = 0.0280 mol [L]
'1,
, O.o280= 0.0140 mol
Amount of (NHr)rSOn[ 1] ,
- 0.0140 mol x 132 g mol-' =
mass of (NHn)rSOn
1. 848 I [ 1] ,
o/o(NH*)'SO.*
in fertiliser = 1".848x 100/3.80 =
= [5]
48.60/ofaf
b Any two of: not all ammonia driven off [1];
ammonia incompletely absorbed by the HCI [f,];
= I2l
some ammonia gas escapes[1]
i Ba'.(aq)+ SOn'-(aq) - BaSO.(s)
= f2l
Species[1], state symbols [1.]
ions
were
ii To ensure that all the sulphate
= [U
precipitated
d Many carbonateswill decomposeon heating [L],
and the CO, gas evolved will result in a lower
mass being recorded [1]. An example is CaCO. [1]
= [4]
CaCO, - CaO + CO, [1]
d i
ll
e l
ii
ll |
l\
-(
n,),-*+
cH,)--i*-(.
tu
+.
The reagentsare : liquid bromine [1] and

concentrated sodium hydroxide [1]. The
= [3]
condition is that it must be heated [1]
= [u
NH.NH,
Solids are not included in Ko expressionsand
= [1]
ammonium nitrate is a solid.
As the reaction is endothermic, the energy
level of the products is higher than that of the
reactants [1], therefore the reaction is said to
a T h ed i s a d v a n t aogf eu s i n gu r e aa r et h a ts o m eu r e a
if thereis norainwithin4 daysof
evaporates
especially
l tnc .a n n obteb l e n d ewdi t hp h o s p h antoer
applicatio
p o t a s s i uf emr t i l i s e ar sn,di t i s l e s ss u i t a bol enc h a l k y
e s e e d l i n gl tsd. o e sn o tw o r k
s o i l sl.t c a nc a u sdea m a gt o
i f t h es o i li s t o oc o l d .
thebase,
theweaker
itsconjugate
acid.
c Thestronger
t ai cb i l i itsyt o d ow i t hA Ha n dk i n e t i c
d T h e r m o d y n asm
is to dowiththerateof thereaction.
stabilitv
APPEN DIX
A
ffi
reactions
organic
1. AS and A2 (synoptic)
Alkanes, e.g. ethane CIITCII,
. Ethane ---+carbon dioxide and water
oxygen (air)
Reactant:
Equation:
2CH,CH, + 7Or- 4CO, + 6H,O
burn / spark
Conditions:
Classification: combustion
o Ethane ---rchloroethane
Reactant:
chlorine
CH,CH, + Cl, - CH,CHTCI+ HCI
Equation:
Conditions:
sunlight
Classification: free radical substitution
Alkenes, e.g. ethene, H'C{H,
. Ethene ---+ethane
hydrogen
Reactant:
Equation:
H2C={H, + Hr -+ CH,CH,
heated nickel (or platinum) catalyst
Conditions:
Classification: addition or reduction or hydrogenation
. Ethene + I,2-dlbromoethane
bromine
Reactant:
HrC<H2 + Br, - CHTBTCH'Br
Equation:
bubble ethene into bromine dissolved in hexane
Conditions:
Classification: electrophilic addition
a Ethene -> bromoethane
hydrogen bromide
Reactant:
HrC<H, + HBr - CHTCHTBT
Equation:
mix gasesat room temperature
Conditions:
Classification: electrophilic addition
o Ethene ---;ethan-1,2-diol
potassium manganate(Vll) solution
Reactant:
HrC:CH, + [Ol + HrO - CHr(OH)CHTOH
Equation:
a solution made alkaline with sodium hvdroxide
Conditions:
. Ethene -+ poly(ethene)
Reactant:
ethene
---+fCHr-CHr),,
n HrCdH,
Equation:
2000 atm pressure,250 "C
Conditions:
Classification: addition polymerisation
e.g. l-bromopropane
Halogenoalkanes,
o l-bromopropane ---+propan-l-ol
Reactant:
sodium (or potassium) hydroxide
+ NaOH --- CHTCHTCHTOH
CH3CHTCHTBT
Equation:
heat under reflux in aqueous solution
Conditions:
Classification: nucleophilic substitution
o l,-bromopropane ---' propene
potassium hydroxide
Reactant:
Equation:
CH,CH,CHTBT+ KOH --r CHrCH:CH, + KBr + HrO
heat under reflux in ethanolic solution
Conditions:
Classification: elimination
o L-bromopropane --+ butanenitrile
potassium cyanide
Reactant:
CH3CH,CH,BT+ KCN --+ CH.CH2CH2CN+ KBr
Equation:
heat under reflux in a solution of ethanol and water
Conditions:
o L-bromopropane ---;1-aminopropane
Reactant:
ammonia
+ NHnBr
+ 2NH, + CH.CH2CH2NH2
Equation:
CH.CHTCHTBT
heat a solution of ammonia in ethanol in a sealedtube
Conditions:
APPENDIX
o ethanoic acid ----ran alcohol

lithium aluminium hydride (lithium tetrahydridoaluminate(III))
Reactant:
CH,COOH + a[Hl - CH,CH'OH + H'O
Equation:
dry ether solution then hydrolyse with dilute acid
Conditions:
. ethanoic acid ---+an acid chloride
phosphorus pentachloride (or PCl, or SOCIr)
Reactant:
CH.COOH + PCI, -J CH,COCI + POCI, + HCI
EqUAtiON:
dry
Conditions:
. ethanoic acid ---+a salt
sodium carbonate
Reactant:
2CH,COOH(aq)+ Na'CO,(s)
Equation:
---+
2CH,CooNa(aq) + Co,(g) + H,o(l)
o ethanoic acid - a salt
sodium hydrogencarbonate
Reactant:
CH.COOH(aq)+ NaHCO,(s)t
Equation:
CH,COONa(aq)+ CO.(8) + H'O(l)
Esters, e.g. ethyl ethanoate

o ethyl ethanoate --+ acid + alcohol
any aqueous stront acid such as dilute sulphuric acid
Reactant:
+ C'H.OH
CH,COOC'H, + Hp-CH,COOH
Equation:
heat under reflux
Conditions:
Classification: reversible hydrolysis
o ethyl ethanoate ----rsalt + alcohol
aqueous sodium hydroxide
Reactant:
CH,COOCTH,+ NaOH - CH,COONa + C,H.OH
Equation:
heat under reflux
Conditions:
Classification: hydrolysis (saponification)
Carbonyl compounds aldehydcs, e.g. CHTCHO, and ketones, e.g. CHtCOCH3
o Both react with:
2,4-dinitrophenylhydrazine
Reactant:
+ H'o
+ NH.NHC.H,(NO.): ---+>c:N-NHC6H'(No')'
>c{
Equation:
observed
precipitate
oranSe
solutions:
mix
conditions:
o Both react with:
hydrogen cYanide
Reactant:
+ HCN -+ >C(OH)CN
>C{
Equation:
potassium
cyanide + some dilute sulphuric acid
conditions:
Classification: nucleophilic addition
o Both react with:
lithium aluminium hydride (or sodium borohydride)
Reactant:
cH,CHo + 2[Hl - CH'CH'OH (a primary alcohol)
Equation:
CH.coCH, + 2[Hl - CH'CH(OH)CH. (a secondaryalcohol)
dry ether, then hydrolyse with dilute acid
Conditions:
o Aldehydes only react with:
Fehling's solution or ammoniacal silver nitrate
Reactant:
CH,CHO + [Ol + OH- ---rCH'COO- + H,O
Equation:
warm
Conditions:
Classification: oxidation
o Carbonyl compounds with a CH,CO group give a yellow precipitate of iodoform
with:
Reactant:
Equation:
iodine and sodium hydroxide solution

cH,cocH, + 31,+ 4OH- ---+CH3COO-+ CHI, + 3I- + 3HrO
Acid chlorldes, .8. ethanoyl chloride

o ethanoyl chloride ---'ethanoic acid
water
Reactant:
CH,COCI + H.O --- CH.COOH + HCI
Equation:
Classification: hYdrolYsis
o ethanoyl chloride ---tan ester
an alcohol
Reactant:
CH,COCI + C.H.OH --- CH.COOCTH'+ HCI
Equation:
rapid reaction at room temperature
Conditions:
Classification: esterification

A Level - Chemistry, George Facer

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A Level - Chemistry, George Facer

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7Strurtu,r,o,bo@

iJ Atomic numbet (4 of an element is the number of protons in the

nehtive isotopic mass is the massof one atom of an isotope relative

f] Rehtive molecular mass (MJ of a substanceis the sum of all the

E fst lonisation energy is the amount of energyrequired per mole

Zna ionisation energy is the energychangeper mole for the

BoNDtNG AND MAtN GRoup cHEMtsrRy

*i lst electron affinity is the energychangeper mole for the addition

I The relative atomic mass of an element can be calculated from mass

A,=( 10.0x 18.7+ 11.0x 81.3)/ 100 = 10.8

B'NDTNG AND MArN cRoup .HEMrsTRy

after Group 2 (this is because,for Group 3, it

o The 2nd ionisation energy of an element is alwaysbigger than the first,

o The 1st electron affinity valuesare alwaysnegative(exothermic),as a

Deducean element'sGroup from successive

E Work out the electronic structureof the first 36 elements.

B'NDTNG AND MArN cRoup .HEMrsTRy

after Group 2 (this is because,for Group 3, it

o The 2nd ionisation energy of an element is alwaysbigger than the first,

o The 1st electron affinity valuesare alwaysnegative(exothermic),as a

Deducean element'sGroup from successive

E Work out the electronic structureof the first 36 elements.

AND MAIN GRoup

The number of particlescan be calculatedfrom the number of moles.

Thesecan only be done if a correctlybalancedequation is used.

For Steps1 and 3 usethe relationship:

B.NDTNG AND MAIN GRoup

iii the element of Z = 11 than that for element of Z = 3.

Give the equation, with state symbols, that representsthe 1st

Give the equation that representsthe 2nd electron affinity of

Why is the 2nd electron affinity of oxygen endothermic whereas

The keysto this topic are:

iJ O.re mole of a substance is the amount of that substance that contains

of substance is the number of moles of that substance.

[] fne empirical formula is the simplest whole number ratio of the

It is best calculated using a table.

Element Percentage of element

Percentage divided by A,of element

Divide each by lowest

BoNDtNG AND MAtN GRoup cHEMtsrRy

solution of bismuth nitrate, Bi(NO3)r?The molar volume of a gas is 24

You should be able to distinguish between:

O Intermolecular forces(between covalent molecules)

between all molecules. Their strength

between 6- atoms in one molecule and 6

E en ionic bond is the electrostatic attraction that occurs between an

AND MAIN GRoup

The number of particlescan be calculatedfrom the number of moles.

Thesecan only be done if a correctlybalancedequation is used.

For Steps1 and 3 usethe relationship:

B.NDTNG AND MArN GRoup

Things to learn and understand

O The elementsin the PeriodicTableare arrangedin order of atomic

O The melting temperaturedependsupon the strength of the forces

o If the solid is metallic: the greaterthe chargedensity of the ion in the

Solids conduct electricity by the flow of delocalised electrons.

Beforeattemptingthe questionson this topic, checkthat you can:

Testingyour knowledgeand understanding

L What, in terms of electronic structure,are the featuresthat the

2 Statethe type of solid structureof the elementslisted. Give your

3 Explain the differencein melting temperaturesof the following

4 The ionisation energies of sodium and magnesium are listed below:

lst ionisation energy/kJmol-' 2nd ionisation energy/kJmol-'

Explain the meaning of: i nuclearcharge,ii screening(or shielding)