Edexcel AS Chemistry Guide

7Strurtu,r,o,bo@ al4d,
wgroryMtry t l r
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 nehtive isotopic mass is the massof one atom of an isotope relative
Therelative
molecular
massisalso to lll2th the massof a carbon-L2atom.
called
therelative
formula
mass
especially
forionicsubstances. 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 E fst lonisation energy is the amount of energyrequired per mole
endothermic
andrelate
tothe to remove one electron from each gaseousatom to form a singly
ofa positive
formation ion. positive ion
E(g)*E.(g)+e-
f 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

U !
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
isotopes 15oo/o)and "Br 150o/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 I The relative atomic mass of an element can be calculated from mass
ontheformula
+ charge of a species spectra data as follows:
fora linein a mass
responsible
A, = the sum of (mass of each isotope x percentage of that isotope)/l0O
spectrum.
Work"ei,oxaloLpb
Boronwasanalysedin a massspectrometer.
atomicmassof boronusingtheresults
therelative
Calculate below.
at mleot
Peaks (%)
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.
@otoMrc srRucruRE
F ig l. l Theorderof filling of atomic

orbitals
Electron structurescan be shown in two ways:
o The S,p, d notation. For vanadium (atomic number 23) this is:
rs", 2s' zpu, 3s' 3pu3d" 4st.
o The electronsin a box notation. For phosphorus (Z = 15) this would be:
ruuuuuutrtr
1s 2s 2p, 2p, 2p, 3s 3p, 3p, 3p,
Sizes of atoms and ions

O The atoms becomesmaller going acrossa period from left to right,
becausethe nuclear chargeincreases,pulling the electronsin closer,
though the number of shellsis the same.
lnanatom,theouterelectrons
are o The atoms get btgger going down a group, becausethere are more
fromthepullofthenucleus
shielded shellsof electrons.
bytheelectrons nearer
inshells to
(theinner
thenucleus electrons). O A positive ion is smallerthan the neutral atom from which it was made,
becausethe ion has one shell fewer than the atom.
O A negativeion is bigger than the neutral atom, becausethe extra
repulsion between the electronscausesthem to spreadout.
lst ionisation enerry

O There is a general increase going from left to right across a period (see
Figure 1.2). This is caused mainly by the increased nuclear charge
(atomic number) without an increase in the number of inner shielding
electrons.
2400
ts
I 2200
2000
&' 1800
x 1600
bo
(u 1,400
k
(u 1,200
1000
(€ 800
cn
600
400
15 20
Fig 1.2 The first ionisation energies Atomic number
(kl mol-') of the elements up to krypton
I st*ucruRE, B'NDTNG AND MArN cRoup .HEMrsTRy
O There are slight decreases after Group 2 (this is because,for Group 3, it

Youshould beableto sketchthe is easierto remove an electron from the higher energyp orbital), and
variation
of 1stionisation
energies after Group 5 (this is because,for Group 6, the repulsion of the two
withatomicnumber forthefirst20
elements. electronsin the p, orbital makesit easierto remove one of them).
O There is a decreasegoing down a Group. This is causedby the outer
electron being further from the nucleus.(The extra nuclear chargeis
balancedby the sameextra number of inner shielding electrons.)
Successive ionisation energies

Thefirs!sixionisation
energies/
kJmol ofanelement are: o The 2nd ionisation energy of an element is alwaysbigger than the first,
1st 786 becausethe secondelectron is removed from a positive ion.
2nd 1580 O When there is a very big jump in the value of successive ionisation
3rd 3230
energies,an electron is being removed from a lower shell, e.g.if this
4th 4360
sth 16000 iump happensfrom the 4th to the 5th ionisation energy,four electrons
6th 20000 have been removed from the outer shell during the first four
Thereis a bigjumpafterthefourth, ionisations, and so the element is in Group 4.
sotheelement is inGroup4.
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.
otoMrc srRUcruRE 5
@
and understanding
Testingyour knowledge
For the following set of questions,cover the margin, write down your
answer,then check to seeif you are correct. (You may refer to the Periodic
Tableon the inside back cover)
' M a s s1 ,c h a r g+e1 I Statethe massesand charges(relativeto a proton) of:
Mass1,charge 0 a proton (p)
Mass1i1860, charge -1
a neutron (n)
2 3( p + n-) 1 1 p = 1 2 f i an electron(e).
o How many neutrons are there in an atom of ?iXa ?
- 56n= 43.
99(p+n)
o What is the atomic number of an elementwhich has an atom of mass
number 99 and contains56 neutrons?
N a ( g*)N a - ( g )+ e - I Write equationswith state symbolsfor:
C l ( g-)C l - ( g )+ e - a the 1st ionisation energyof sodium
Mg-(g) -Mg'-(g)+e- b the 1st ionisation energyof chlorine
c the 2nd ionisation energyof magnesium.
O Using the ls, 2s 2p. . notation, give the electronicstructuresof the
1s',2s',2p'
elements:
1s',2s',2pu,
3s'.
a u C
1s',2s',2pu,3s"
3pu,
3du,4s'
b ,rM8
c ,uF€.
Explain the difference between relative isotopic mass and relative

to thenumbered
Theanswers atomic mass. Illustrate your answer with reference to a specific element.
questions
areonpage 121.
Lithium has naturally occurring isotopes of mass numbers 6 and 7.
Explain why its relative atomic mass is 6.9 not 6.5.
Magnesium was analysed in a mass spectrometer.
Peaks were found at three different mle ratios.
mle (%)
Abundance
24.0 78.6
25.0 10.1
26.0 11.3
Calculatethe relative atomic massof magnesium.
Gallium has a relativeatomic massof 69.8. Its massspectrumshowstwo
peaksatmle of 69.0and 71.0.
Calculatethe percentageof each isotope in gallium.
ionisation energiesof an elementX are given below:
The successive
Ionisation energy 1st Znd 3rd 4th 5th 6th 7th Bth
Value/kJmol-' 1060 1900 2920 4960 6280 2L ZOO2s 900 30 s00
State,giving your reasons,which group the element X is in.
6 a Sketchthe variation of 1st ionisation energyagainstatomic number

for the first LL elements.
b Explain why the ionisation energyis lessfor:
i the elementof atomic number (4 of 5 than that for elementof
Z=4
ii the element of Z -- 8 than that for element of Z = 7
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
electron affinity of i lithium, ii chlorine, iii oxygen.
b Give the equation that representsthe 2nd electron affinity of
oxygen.
c Why is the 2nd electron affinity of oxygen endothermic whereas
the 1st electron affinities of lithium, chlorine and oxygen are all
exothermic?
@ Formulae, andmoles
equations
,-ld
tri Introduction
(H H
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-'.
iJ O.re mole of a substance is the amount of that substance that contains
1 molof NaOH hasa massof 40g
6.O2 x 1023particles of that substance.This means that one mole of a
1 molof 0, hasa massof 32 g.
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 Percentage divided by A,of element Divide each by lowest
Carbon 48.7 48.7+12-4.1 4 . I + 2 . 7= 1 . 5

Hydrogen 8.1 8 . 1+ 1 = 8 . 1 8 . 1+ 2 . 7= 3
Oxygen 43.2 43.2+16-2.7 2 . 7+ 2 . 7= 7
ro*MULAE, EeuATroNS AND MoLEs
@
The last column gives the empirical formula, but if any value in this
column comes to a number ending in .5 or .25, you must multiply all the
values by 2 or 4 to get integers. So here the empirical formula is C3H6O,.
Equations
These must balance. The number of atoms of an element on one side of
the equation must be the same as the number of atoms of that element on
the other side.
Ionic equations
Therearethreerules:
(salts,strong
for solutionsof ionic compounds
o Writethe ionsseparately
acids and bases).
mustalsobalance
lonicequations
o Write full 'molecular' formulae for solids and all covalent substances.
forcharge.
o Spectator ions must be cancelled and so do not appear in the final
equation.
Moles
There are three ways of calculating the amount of substance (in moles):
I For a pure substance X
The amount of X (in moles) = mass of X (in grans)/its molar
rnASS
Workpi, oxaloLpb
Avoiw g o l= 0 . 1 1 . I n s t e a d
d r i t i nm
statethenameor formula of the of H,0in 1.1g of water
theamount
Calculate
substance
e . ga. m o u notf N a= 0 . 1 1m o l . gl18g mol-'= 0.061molof H,0
Answer:1.1
t For solutions:
The amount of solute = concentration (in mol d--') x volume
(in dm')
Thereforeconcentration = moles / volume in dm'
Asyolume indm-= volume in

cm-/1000, thefollowing formulacan Workd,oxiloLpb
beused:
m o l e=sM x W 1 0 0 0
orconcentration = moles x1000lV of NaOH
theamount
Calculate of 0.100moldm-'solution
in 22.2cm3
where M istheconcentration and Answer:0.100 = 2.22x10-'molof Na0H
x 0.0222
t/isthevolume incm-.
O For gases:
Amount of gas (in moles) = volume (in dm')/molar
volume.
The molar volurne of a gas is 24 dm3mol-r,measuredat room
temperature and pressure (RTP).
II tt*ucruRE, B.NDING AND MAIN GRoup cHEMIsrRy
Workêi,oxiloL\-lx'
theamountof H,(g)in 3.2dm"at RTP.
Calculate
Answer'. = 0.13molof H,(g)
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,
thenumber
Calculate ofcarbondioxidemoleculesin3.3g ofC0,.
ofC0,= 3.3144
Amount
Answer: = 0.075mol
Number = 0.075
ofmolecules x 6.02x 10"= 4.5x 10"
thenumber
Calculate ofsodium ionsin5.5g of Na,CO,
Answer: =5.51106
of NarCO,
Amount = 0.0519mol
ofNa-ions= 0.0519
Number x 10"x2 =6.2x10"
x 6.02
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 Step2 Step3

Ma s sA - Mol es A -Mol es B + Mass B
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,,
themass
Calculate hydroxide
ofsodium required with1.23g ofsilicon
to react
In Step2, thestoichiometric
ratiois dioxide.
211asthereare2Na0Hmolecules Answer. SiO,+ 2Na0H---lNa,Si0,
Equation: + H,0
foreach1Si0,molecule in the Step1 amount ofSiO,= 1.23160
mol = 0.0205mol
equation. Step2 amount of NaOH molx 211= 0.0410
= 0.0205 mol
Step3 mass of NaOH= 0.0410x 40 = 1.64g
ro*M u LAE, EeuATroNs AN D M.LES
@
Titrotions (this will only be exomined ot AS in Unit test 38)

The route is much the same:
SteP1 Step2 Step

^ 3 answer
concentration and
v o l u m e o fA + MolesA+MolesB+aboutB
For Steps1 and 3 usethe relationship:

amount (in moles) = M x V/1000
For Step2 usethe stoichiometricratio from the equation:
moles of B = moles of A x ratio B/A
oxalo7.b
Workêi,
25.0cm'ofa solution of sodium hydroxide of concentration 0.212moldm-'
wasneutralised by 23.4cm'ofa solution of sulphuric acid.Calculate the
of thesulphuric
concentration acidsolution.
In Step2 thestoichiometric
ratiois
Answer.Equation: 2Na0H+ H,SO. ---) Na,SOo + 2Hr0
112as thereis 1H2S0o
molecule = 5.3x 10-'mol
in Step1 amount of Na0H= 0.212x25.011000
forevery 2Na0H molecules
theequation. S t e p2 a m o u n0tf H 2 S 0 o 5 . 3x 1 0 - x31 l 2 = 2 . 6 5x 1 0 - ' m o l
=
Step3 concentration of H2S0o = 2.65x 10-'mol/0.0234 dm3
= 0.113 m o ld m - '
Concentrotion of solutions
This is either: amount of solute (in molqs) units: mol dm-"
volume of solution in dm''
or: mass of solute (in grams) units: g dm-'
volume of solution in dm''
Gos volume colculotions

1 For reactions where a gas is produced from solids or solutions,
follow:
Step1 Step2 Step3

Massof A*Moles of A+Moles of gasB + Volumeof gasB
Step 1 use the relationship:

moles = mass/molar mass
Step 2 use the stoichiometric ratio from the equation:
moles of A = moles of B x ratio of B/A
Step 3 use the relationship:
volume of gas B = moles of B x molar volume
lI tt*ucruRE, B.NDTNG AND MAtN GRoup cHEMlsrRy
Workpj,oxu,u?h, L
i-,',-.,;r:,,''
thevolume
Calculate of carbondioxidegasevolved,
measuredatroom
andpressure,
temperature when7.8g ofsodium hydrogencarbonateis heated.
volume
Themolar andpressure
of a gasis 24dmsmol-'atthetemperature of
theexperiment.
AnswenEquation: 2NaHC0, - NarCO, + HrO+ COr(g)
ratiois
lnStep2 thestoichiometric Step1 amount of NaHCO'=7.8184mol= 0.0929mol
ll2asthereis1C0,molecule
for Step2 amount molx 112= 0.0464
of C0,= 0.09286 mol
2NaHCO,
every molecules
inthe Step3 volume of C0,= 0.0464molx 24 dmsmol-'= 1.1dm'
equation.
For calculations involving gasesonly, a short cut can be used. The

volumes of the two gasesare in the same ratio as their
stoichiometry in the equation.
i ,Workti,
ry oxilov-l"o
r:
L$.:i*'q'ffr''
o Youmustshowallthestepsin
yourcalculations volume
What ofoxygen 15.6cm'ofethane?
to burncompletely
isneeded
o Don'tcutdownto two or three AnswenEquation: + 70,(g)- 4C0,(g)+ 6Hr0(l)
2C,Hu(g)
figuresin themiddle
significant ofoxvqen
Calculation:volume oas= 7 = 3.5
of a calculation volume gas 2
ofethane
o Check everycalculationto ensure volumeofoxygeng?s= 3.5x 15.6= 54.6cm'
thatyouhaveentered thedata
correctly
Significant figures
You should alwaysexpressyour answerto the samenumber of significant
figuresas statedin the question or as there are in the data.
If you cannot work this out in an exam, give your answerto 3
significant figures (or 2 decimal placesfor pH calculations),and you are
unlikely to be penalised.Do not round up numbersin the middle of a
calculation. Any intermediate answersshould be given to at least 1 more
significant figure than your final answer.
Checklist
Beforeattempting questionson this topic, check that you can:
iJ Calculatethe empirical formula of a substancefrom the
o/ocomposition.
t-J Write balancedionic equations.

[i Culc.rlatethe number of moles of a pure substancefrom its mass,of a
solute from the volume and concentration of its solution, and of a gas
from its volume.
i] Catculatereacting massesand reactinggasvolumes.
L] Use titration data to calculatethe volume or the concentration of one
solution.
a"RMULAE, EeuATroNs AND MoLEs 11
@
and understanding
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:

a lead nitrate and potassium chloride
a Pb"(aq)+ 2Cl-(aq)-- PbCl,(s) b magnesium chloride and sodium hydroxide
b Mg'-(aq)
+ 20H-(aq)-'Mg(0H),(s) c sodium chloride and silver nitrate
+ Ag'(aq) -- AgCl(s)
c Cl-(aq) d sodium hydroxide and hydrochloric acid.
+ 0H-(aq) --' H,0(l)
d H-(aq) t Calculate the amount (in moles) of:
a Na in I.23 g of sodium metal
a 1.23123= 0.0535 mol b NaCl in 4.56 g of solid sodium chloride
b 4.56/58.5= 0.0779
mol c Cl, in 789 cm'' of chlorine gas at room temperature and pressure
G 0.789124 = 0.0329
mol d NaCl in 32.1 cm'' of a 0.111 mol dm-' solution of sodium chloride.
d 0.111x 0.0321= 3.56x 10-3
mol
I Calculate the volume of a 0.222 mol dm-'' solution of sodium
= 0.205d hydroxide, which contains 0.0456 mol of NaOH.
0.045610.222 m' = 205cm'
t Calculate the number of water molecules in 1.00 g of HrO.
(1.00n8)x 6.02x 10"= 3.34x 10"
o Calculate the number of sodium ions in 1.00 g of NarCO,,.
x 6.02x 1d'x 2 =1.14x1ff
(1.00/106) ) 4.44 g of solid sodium hydroxide was dissolved in water and the
a 4.44g10.250 dm'= 17.8g dm-' solution made up to 250 cmS.Calculate the concentration in
=
E 4 . 4 4 1 4 00 . 1 1 1
mol a g dm-'
Therefore 0.111mol/0.250 dmg b mol dm-'.
= 0.444moldm-'
1.a An organic compound contains 82.760/o carbon and 17.24o/o

Theanswers
tothenumbered hydrogenby mass.Calculateits empiricalformula.
areonpages
questions 121-122.
b It was found to have a relativemolecularmassof 58. Calculateits
molecular formula.
Balance the equations:
a NH.+O,-NO + HrO
b Fe'.(aq) + --
Sn'.(aq) 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 BoNDtNG AND MAtN GRoup cHEMtsrRy
"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 between separateions
Covalent 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
Metallic bonding causedby electronsdelocalised
throughout the solid.
O Intermolecular forces(between covalent molecules)

Hydrogen bonds between 6- H in one molecule and 6 F, O or
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
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.
o-bond 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.
n-bond U n metallic bond is the force of attraction between the sea of
delocalised electrons and the positive ions which are arranged in a
Fig l . 3 o a n d n b o n d s .
_ regular lattice.
iJ the electronegativity of an element is a measure of the attraction its
atom has for a pair of electrons in a covalent bond.
srRucruRE AND B.NDTNG
@
In hydrated
cations,
suchas J n hydrogen bond is an intermolecular force that exists between a 6-
the
[Mg(HrO)r]'', watermolecules hydrogen atom in one molecule and a 6- fluorine, oxygen or
arebondedto themagnesium ionby nitrogen atom in another molecule.
dative
covalent Eachoxygen
bonds. "J van der Waals forces are between covalent molecules and are caused
atombondswithitslonepairinto by dipole/dipole and induced dipole/induced dipole (dispersion) forces.
emptys andp orbitals
in theMg'
ion.
Ionic bonding
o An ionic bond is likely if there is a large difference (greater than about
1.5) in the electronegativities of the two atoms.
o Cations with a small radius and/or high charge have a large charge
lonicsubstances willbewater density, and so are very polarising. Anions with a large radius and/or
solubleif theenergy required to high charge are very polarisable. If either the cation is very polarising or
separatetheionsin thelattice
the anion is very polarisable, the outer electrons in the anion will be
(lattice
energy) is compensated for
pulled towards the cation and the bond will have some covalent
bytheexothermic natureof
hydration. Thisis theenergy character.
releasedwhentheverypolarwater I Ionic bonding gives rise to an ionic lattice, which is a regular three-
molecules areattractedto the+ and dimensional arrangement of ions.
- ions.
* An ionic bond is, on average,the same strength as a covalent bond.
Covalent bonding
Covalent substances are either:
i giant atomic, such as diamond, graphite and quartz (SiOr)
ii simple molecular, such as I, and many organic substances
iii hydrogen-bonded molecular, such as ice, and ethanol
iv non-crystalline, such as polymers like poly(ethene).
Polar covalent bonds may result in polar molecules, but for linear
molecules of formula AB, planar molecules of formula AB, tetrahedral
molecules of formula AB, and octahedral molecules of formula ABu, the
polarities of the bonds cancel out, and the molecule is not polar.
Intermolecular forces
o The strongestintermolecular force is hydrogen bonding. In molecules
with many electrons,such as l, the next strongestare induced
dipole/induced dipole forces(sometimescalled dispersionforces)and, in
most cases,the weakestare permanent dipole/permanent dipole (or
dipole/dipole)forces.
In HCItherearenohydrogen bonds,
thedispersionforcescountfor o The strength of dispersionforcesdependsmainly upon the number of
about80%of thetotal electronsin the molecule.This is why I, with 106 electronsis a solid,
forces,
intermolecular with whereasCl, with 34 electronsis a gas.
dipole/dipole
accountingforthe o This explainsthe trend in boiling temperaturesof the noble gases,as
remaining20%.
the dispersionforcesare lessin helium than in neon than in argon etc.
Likewisethe boiling temperaturesof the Group 4 hydrides increasein
the Group from CHnto PbH4.
o The boiling temperaturesof the hydridesof Groups5, 6 and 7 (see
Figure1. 4) can alsobe explained.Becausethere is hydrogenbonding
betweenHF moleculesbut not betweenthe other hydrides in the group,
HF has the highestboiling temperature.After the drop to HCl, there is a
steadyupward trend in boiling temperaturesfrom HCI to HI (in spite of
a decreasein the dipole/dipole forces)becausethe dispersionforces
increase.
II =t*ucruRE, B.NDTNGAND MA'N GRoup cHEMrsrRy
400 400 400

350 350 3s0
300 300 300
250 2so 250
K ZOO K 200 K 200
150 150 150
100 100 100
50 50 50
0 0 0
NHs PH: AsH3 sbH3 Hzo HzS HrSe H2Te HF HCI HBT HI
Group 5 Group 6 Group 7
Fig 1.4 Boilingtemperatures

of f If the number of electronsin two different substancesis about equal
Groups5, 6 and 7 hydrides 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.
o As the temperaturerisesthe vibrations increaseuntil they becomeso
great that the forcesbetweenthe particlesare overcome,and the regular
Donotsaythattheparticles
startto arrangementin the lattice breaksup. The substanceis then a liquid.
vibrate,
astheyarevibrating
evenat O In an ionic solid, such as NaCl, the vibrating particlesare ions which
verylowtemperatures.
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
Thestrongertheforcebetween melting temperature.
particles,
themoreenergy neededto o In a giant atomic solid, such as diamond, the vibrating particlesare
separate
themandhence thehigher
themelting atoms which are held by strong covalent bonds, and so the solid has a
temperature.
very high melting temperature.
Shapes of molecules
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.
o lt isthebondsnottheatomsthat
repel, ii The repulsion betweenlone pairs is greaterthan that betweena lone
o Don't forget
to countthenumber pair and a bond pair, which is greaterthan that between two bond
of lonepairs. 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.
srRucruRE AND BoNDTNG
@
2 bond pairs
linear
h:r o The total number of pairs of electronsindicatesthe arrangement
the electrons.
of
Lg0'
2 = linear
3 = trianSularplanar
bond pairs
? 4 = tetrahedral
\120'
triangular 5 = trigonal bipyramid
planar tA{- 6 = octahedral
But the shape will differ if any of the pairsare lone pairs (see
v Figure1.5).
I tos't," 4pairs:3bond+1lone:
bond pairs \
molecularshapeis pyramidal,e.g.NHr, or PCl,
tetrahedral o4f\
.^(/ 2bond + 2lone:
molecularshapeis bent or V-shaped,e.g.HrO
6pairs:5bond+1lone:
bond pairs +
1 lone pair o4/b-rc pyramid.
molecularshapeis a square-based
pyramidal
Ot <I07" 4bond+2lone:
molecularshapeis squareplanar.
bond pairs +
2lone pairs
V-shaped
;>-"
6w <lo5'
Shapes of ions
Negativejons have gained 1 electron for each negativecharge.
Thus SO;- has 4 o bonds (and 2 n bonds)and no lone pairsaround the
o ? sulphur,and so the ion is tetrahedral.
noo CO.'- has 3 o bonds (and 1 z bond) and no lone pairsaround the carbon,
s bondpairs Il ^ and so it is triangularplanar.
Trigonal 120"\lre
NO; has one single covalent, one dative covalent and one double covalent
bipyramid bond (i.e. 3 o and 1 z) and no lone pairsaround the nitrogen and so is
o/l
alsotriangularplanar.
Positiveions have lost 1 electronfor eachpositivecharge.
Thus NHn.has 4 o bonds and no lone pairsaround the nitrogen, and so is
bond pairs tetrahedral
octahedral
-H
i )J//l
90"and 180' -?'-

f'-
r
^,.'-
Checklist
Fig 1.5 Shapesof moleculesond ions Before attempting the questions on this topic, check that you understand:
lJ the nature of ionic, covalent and dative covalent bonds
LJ tfre effect of difference in electronegativity on type of bonding

iJ that polar bonds may not give rise to polar molecules
J the effect of size and charge of ions on the type of bonding

J intermolecular forces such as hydrogen bonding and van der Waals
,J the different structures of solids and their properties
J the trends in boiling temperatures caused by intermolecular forces

,J the nature of hydration of ions
iJ the changes in motion and arrangement of particles on change of state
J a metallic bond
J the shapes of molecules and ions.
ll B.NDTNG AND MA'N GRoup cHEMrsrRy
"t*ucruRE,
and understanding
For the first set of questions, cover the margin, write your answers, then
check to see if you are correct.
O State which types of bond are present in a double bond as in O=C=O.

I State the value of the charge on the ions of the following elements:
Al3*,Mgz*,Na*,F, N*, o',- Al, Mg, Na, R N, O.
o State which of the cations above:

a Al" a has the smallest radius
b Al" b has the largest charge density
G AI3- c is the most polarising.
O State which of the anions above is the most polarisable.

O Which ion has the largest radius: Li'or Na- or K-?
o Which of these three ions, Li*, Na* or K*, has:
a the largest surface charge density
b the largest polarising power?
Which is the most electronegative element in each list:

a C,O,N,F
b Cl, Br, I?
Which is the least electronegative element of:
aCa
a Be, Mg, Ca
bNa
b Na, Mg, A1?
a Which is the molecule in each group with the most polar bond:
a hydrogen
fluoride
a HE, HCl, HBr
b hydrogen
fluoride
b HF, HrO, NH3
c water
c HrO, HrS, HrSe
d aluminium
chloride
d Alcl' sicln, PClr?
o List all of the following molecules that are polar:
H2 HCI HrO NH, CHn

HCl,Hro,NH3,
l0l,HrS
CO, ICI H,S BH, CFn
o Rearrange the noble gasesin order of decreasing boiling temperature:

Xe>Kr>Ar>Ne>He Ar, He, Kr, Ne and Xe
o State which of the following has the lowest boiling temperature:
HE HCl, HBr, or HI
o Which of the following form hydrogen bonds between their molecules?
H,O NH, HF HCI CO, CHn

H r O ,NH3,HF ,CH30 HC, H 3 N H ,
cH3oH cH3NH2 cH3F cHCl3 cH2-cH2 poly(ethene)
1 Draw a diagram of two p orbitals overlapping which produce:
Theanswersto thenumbered a aobond

questions
areon pages122-123. b anbond
2 For each pair, state which is the more covalent substance and give a
reason:
a AlF. or AlCl3
b BeCl, or MgClr.
AND BoNDTNG
@sr*.rcruRE
Intermolecular forces can be divided into three types:

a hydrogen bond
b dispersion (induced dipole/induced dipole)
c permanent dipole/permanent dipole.
For all the following substancesstate all the types of intermolecular
forces a, b andlor c that are present:
i HF ii 12 iii HBr iv PH, v Ar
4 Solid structures can be divided into six types:

a metallic, b giant atomic (network covalent), c ionic,
d hydrogen bonded molecular, e simple molecular, f polymeric.
For each of the solids listed below, state the structural type in the solid.
iodine ice, HrO(s) copper

silica (sand), SiO, dry ice, COr(s) calcium oxide, CaO
poly(ethene) graphite sulphur

coppersulphate,CuSOosucrose lithium fluoride. LiF
Explain the processesof melting and boiling in terms of the

arrangement and motion of the particles.
State, for each of the following pairs, which has the stronger forces
between particles and hence has the higher boiling temperature, and
explain why in terms of the types of force present:
a NH, or PH,
b HCI or HBr
c CH3COCH..(propanone) or CnH,o@utane)
d Pnor Su
e NaCl or CCln
In order to work out the shape of a molecule or ion, you should first
evaluate the number of o bond pairs of electrons and the number of
lone (unbonded) pairs of electrons around the central atom.
Construct a table similar to that shown below, and use it to deduce the
shapes of the following species.
SiH4,BFr, BeCl2,PCI3,SFu,XeFn,NHr*, PCl6-
Molecule/ Number of Number of Total number Shape

ion o bond pairs lone pairs of electron pairs
NH, 3 1 4 pyramidal
Explain why solid sodium metal conducts electricity whereassolid

sodium chloride doesnot.
I tt*ucruRE, B.NDTNG AND MArN GRoup qHEMIsrRy
ThePeriodic TableI
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
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
Therearetwoexceptions withthe
outer shells.Theseare called the valenceelectrons.
first40 elements.Because of the
extrastability
of a halffilledor full o Elementsin the samePeriod have the samenumber of shellscontaining
setof d orbitals,
chromium is [Ar] electronsso their outer or valenceelectronsare in the sameshell.
4s',3du,andcopper is [Ar]4s',3d'o 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)
Melting (and boiling) temperatures of the Period 3

elements (Na to Ar)
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.
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
Themoreelectrons
inthemolecule, the lattice are strong and so the solid has a very high melting
thestronger
thedispersionforce temperature.
andthehigherthemeltingor boiling o If the solid is a simple molecular substance:the melting (or boiling)
temperature. 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 ' Checklist
l/H
H
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)() Testingyour knowledgeand understanding

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

to thenumbered
Theanswers following have in common:
questions
areonpage123.
a membersof the samegroup , €.8. Group 2,
b 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 b sodium c silicon d sulphur
e chlorine f argon.
3 Explain the differencein melting temperaturesof the following
elements:
Element Na Mg Si Pn s8 CI,
Melting temperature/O6 98 650 1 4 1 0 44 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
orl Rtc
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.
J,,+
- ^ f"/ ,- |
W Things to understand
!---.-.-l'
Oxidation 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:
Inanoverallequation,
thetotal
increaseinoxidation
number ofone 1 The oxidation number of an uncombined element is zero.
element(increase
x number of 2 A simple monatomic ion has an oxidation number equal to its
atoms ofthatelement)mustequal charge.
thetotaldecrease
inoxidation
number ofanotherelement. 3 The oxidation number of Group 1 metals is always+1, and of
Group 2 metals is +2.
4 Fluorine alwayshas an oxidation number of -1, hydrogen (except
in metallic hydrides) of +1, and oxygen (exceptin FrO and
peroxides)of -2.
5 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.
lNTRoDUcrroN To oxrDATroN AND REDUcrroN 21
@
Workêi,oxal44f-{x,
theoxidation
Calculate numberofchlorine inClr,Cl-,MgCl, andCl0r-.
Cl, = 0
Answers:.in (uncombined element: rule1)
inCl- = -1 (monatomic ion:rule2)
inMgCl, = -1 (Mgis2+;(+2)+ZCl = 0;therefore each Clis-1:
rules 3 and5)
i n C l 0=
; 15 ( C+l 3 x ( - 2 =) - 1 : r u l e s 4 a n d 5 )
Half equations
These are written:
either as reduction with electrons on the left side of the half equation,
e.g. Cl, (g) + 2e ^- zCl- (aq)
Rememberthatanoxidisingagent
here chlorine is being reduced and so is acting as an oxidising agent.
becomesreduced(loses
electrons),
anda reducing
agent becomes or as oxidation with electrons on the right side of the equation,
oxidised. e.g. Fe'- (aq) -.-Fe'- (aq) + e-
mustbalance
Halfequations for
atomsandforcharge. here iron(ll) ions are being oxidised, and thus are acting as a reducing
.
bothsidesof theCr"'
Forexample, agent.
addupto -5.
equation .- Many oxidising agents only work in acid solution. Their half equations
have H. ions on the left hand side and HrO on the right. This is likely
with oxdising agents containing oxygen (such as MnOr-),
e.g. MnO.,-(aq)+ 8H.(aq) + 5e- + Mn'.(aq) + 4HrO(l)
r If a redox system is in alkaline solution, OH- may need to be on one

side and HrO on the other,
e.g. Cr'.(aq) + BOH-(aq) * CrOn2-+ 4H,O(l)+ 3e-
Overall redox equations

t Overall redox equations are obtained by adding half equations together.
I One half equation must be written as a reduction (electrons on the left)
and the other as an oxidation (electrons on the right).
lf thequestion
asksfortheoverall o When they are added the electrons must cancel. To achieve this it may
equationforthereactionof A withB, be necessaryto multiply one or both half equations by integers,
makesurethatbothA andB appear
e.g. for the overall equation for the oxidation of Fe'. ions by MnOn-
ontheleft-handsideof thefinal
overall
equation. lons
add MnOf(aq) + BH-(aq) + 5e- + Mn'-(aq) + 4H,O(l)
to5x Fe' -(aq)+ Fe" (aq)+ e-
+ Mn'z-(aq)+ 4HrO(l) + 5Fe3-(aq)

MnOo-(aq) + 8H-(aq) + SFe2-(aq)
II =t*ucruRE, BONDING AND MAIN GROUP CHEMISTRY
Checklist
Beforeattempting the questionson this topic, check that you can:
[] Define oxidation and reduction.
lJ oefine oxidising agent and reducing agent.
E Calc.tlateoxidation numbers in neutral moleculesand in ions.
fl Write ionic half equations.
I-l Combine half equationsand so deducean overall redox equation.
Testingyour knowledgeand understanding

For the first set of questions, cover the margin, write your answer, then
O In the following equations, state which substance,if any, has been
a iodide
ions oxidised:
b none a 2Cen.(aq) + 2l- (aq) + zce'* (aq) + I, (aq)
c zinc b H. (aq) + OH- (aq) + H,O (l)
d iron(ll)
ions c Zn (s) + 2H. (aq) + Zn'- (aq) + H, (g)
d zFe'* (aq) + 2Hg" (aq) + 2Fe'. (aq) + Hgr2. (aq)
o Calculate the oxidation number of the elements in bold in the
+4 -2 following:
+6 +6 so2, H2s,
-1 +6 Z!1t at+2and2 ar+3; CtOn'-, CtrOr'-,
average
2i) HrO", H2SO4, FerOn
Theanswers
tothenumbered 1 Construct ionic half equationsfor:
questions
areonpages
123-124. a Sn'* ions being oxidised to Snn*ions in aqueoussolution
b Fe'*ions being reducedto Fe2*ions in aqueoussolution.
c Now write the balancedequation for the reaction between Fe3*and
Sn'* ions in aqueoussolution.
2 Construct ionic half equationsfor:

a hydrogen peroxide being reducedto water in acid solution
b sulphur being reducedto hydrogen sulphide in acid solution
c Now write the balancedequation for the reaction between
hydrogen peroxide and hydrogen sulphide in acid solution.
3 Construct ionic half equationsfor:

a PbOr(s)being reducedto PbSOr(s)in the presenceof HrSOn(aq)
b PbSO.(s)being reducedto Pb(s)in the presenceof water
c Now write the balancedequation for the reaction between PbO,
and lead in the presenceof dilute sulphuric acid.
@ 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
i
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: lithium carmine red
sodium yellow
potassium lilac
O Group 2: calcium brick red
strontium crimson red
barium green.
o These colours are caused because:
,A l* I Heat causesthe compound to vaporise and produce some atoms of
light out 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
3rd the form of visible light is emitted. The light that is emitted is of a
characteristic frequency, and hence colour, dependent on the energy
Fig 1,6 Emissionof a spectrolline 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
STRUCTURE, BONDING AND MAIN GROUP CHEMISTRY
becauseas the atoms get larger,the outer electronsare further from the
nucleusand so are held on lessfirmly. The increasein nuclear chargeis
compensatedfor by an increasein the shielding by the inner electrons.
Reactions of the elements with oxygen

O Group 1: All burn.
Thevigourof thereaction
increases Lithium forms an oxide: 4Li * O, - zLizO
downthegroup. peroxide: 2Na + Or - NarO,
Sodium forms a
Potassiumand the others form a superoxide: K + O, - KO,
o Group 2: AII burn to form ionic oxides of formula MO, except that in
excessoxygen barium forms a peroxide (BaOr).
ZCa+ Or'ZCaO
Reaction of the elements with chlorine

o Group 1: All react vigorously to form ionic chlorides of formula MCl.
Thesedissolvein water to produce hydrated ions, e.g.
NaCl(s)- Na*(aq) + Cl (aq)
I Group 2: All react vigorously to produce ionic chlorides of formula
MCl, exceptthat BeCl,is covalent when anhydrous.All Group 2
chlorides are soluble in water producing hydrated ions of formula
[M(H,O).]2-.Beryllium chloride givesan acidic solution becauseof
deprotonation:
[Be(H,O)u]'*+H,O + [Be(H,O)'(OH)]. + H,O*
Reaction of the elements with water

o Group 1: All react vigorously with cold water to give an alkaline
solution of metal hydroxide and hydrogen gas,e.g.
Therateof reaction
increases
down 2Na(s)+ 2H,O(l) -- 2NaOH(aq)+ H,(g)
thegroup.
t Group 2: Beryllium doesnot react but magnesiumburns in steamto
produce an oxide and hydrogen:
Mg+HrO-MgO+H,
the others react rapidly with cold water to form an alkaline suspension
of metal hydroxide and hydrogen gas:
Ca + zH,O - Ca(OH)r+H,
Reactions of Group 2 oxides with water

O BeO is amphoteric and doesnot reactwith water.
O MgO is basicand reactsslowly with water to form a hydroxide.
a All the others react rapidly and exothermically to form alkaline
suspensionsof the hydroxide, which have a pH of about 13.
CaO + H,O-- Ca(OH),
Solubilities of Gro$p 2 sulphates and hydroxides

O Sulphates:their solubilities decrease down the group. BeSOo and MgSOo
are soluble;CaSOois slightly soluble,SrSOoand BaSOo are insoluble.
o Hydroxides:their solubilities increase down the group. Be(OH),and
Mg(OH), are insoluble,Ca(OH),and Sr(OH),are slightly soluble,and
Ba(OH),is fairly soluble.
O Addition of aqueoussodium hydroxide to solutions of Group 2 salts
producesa white precipitateof metal hydroxide. (Barium producesa
faint precipitate):
M'.(aq) + 2OH-(a9)- M(OH)'(s)
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 stability of nitrates and carbonates

o Thermal stability increases down both groups:
Thecompound is morelikely to be o Group 2 nitrates all decomposeto give a metal oxide, brown fumes of
decomposedonheating if thecation
polarises
theanion. nitrogen dioxide, and oxygen:
Thus
Group2 compounds (cation 2+) 2Ca(NOr)r- 2CaO+ 4NO, + O,
decomposemorereadily thanGroup O Group 1 nitrates, except lithium nitrate, decomposeto give a metal
1 compounds(cationonly1+). nitrite and oxygen:
Compoundsofmetals higher ina 2NaNO,-- 2NaNO,r O,
group
(smallerionic
radius)
decomposemoreeasily than but 4LiNO,,-- ZLirO+ 4NO, + O,
compoundsof metalslower inthe o Group 2 carbonatesall decompose(exceptbarium carbonatewhich is
Group. 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.
H
' 9 ^ r
â/
H
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?
o What is the oxidation number of:

K is +1,Cais +2 i potassiumin KrCrrO,and
ii calcium in CaCOr?
o Barium compounds normally are poisonous,but barium sulphateis

It is extremely
insoluble. given to people in order to outline their gut in radiography (X-ray
imaging).Why is barium sulphatenot poisonous?
II B.NDING AND MAIN GRoup cHEMtsrRy
"t*ucruRE,
You are given sotid samplesof three chlorides.One is lithium chloride,
to thenumbered
Theanswers one is potassiumchloride and the other is barium chloride. Describethe
areonpage
questions 124.
teststhat you would do to find out which was which.
2 Explain why sodium compounds give a yellow colour in a flame.
3 Exptain why the Lst ionisation energyof sodium is larger than the Lst
ionisation energy of potassium.
4 Write balancedequationsfor the reactionsof:

a calcium with oxygen
b calcium with water
c potassiumwith water
d magnesiumwith steam.
Explain why the addition of dilute sodium hydroxide to a solution of

magnesiumchloride producesa white precipitate,but little or no
precipitatewhen dilute sodium hydroxide is added to a solution of
barium chloride.
6 Stateand explain which Group 2 element forms the leastthermally

stablecarbonate.
Write balancedequationsfor the thermal decomposition of the

following, but if there is no reaction at laboratory temperatures,say so:
a lithium nitrate, sodium nitrate and magnesiumnitrate
b sodium carbonate,magnesiumcarbonateand barium carbonate.
cRouP 7 (caLoRrNE To rooiNre)
@
Group7 (chlorine
toiodine)
<ta
iAl
y-v Introduction
Group 7 chancteristics are that:
r The halogensare oxidising agentswith their strength decreasingdown
the group.
1 Chlorine is the strongestoxidising agent and iodine is the weakest.
2 Chloride ions are the weakestreducing agents,and so are the hardest
to oxidise, whereasiodide ions are the strongestreducing agents,and
so are the easiestto oxidise.
I They form halide ions, such as Cl-, and oxoanions, such as ClO,-.
o Solutionsof the hydrogen halides are strong acids.
ffi Thingsto learnand understand

Lry
Disproportionation
This occurswhen an element is simultaneouslyoxidised and reduced.It
follows that there must be at leasttwo atoms of that element, with the
sarne oxidation number, on the left of the equation, and that the element
must be able to exist in at least three different oxidation states.
Chlorine disproportionatesin alkali:
Cl, + zOH- - Cl- + OCI- + H,O
(0) (-1) (+1)
Physical properties (at room temperature)

o Chlorine is a greenishgas.
O Bromine a brown liquid.
o Iodine is a dark grey lustrous solid which givesa violet vapour on
heating.
o A solution of iodine in aqueouspotassiumiodide is red/brown, and in
non-oxygen-containingorganic solventsit is violet.
Tests for the elements (only examined at AS in Unit

Test 3B)
o First observe the colour of the halogen or its solution.
O Chlorine rapidly bleaches damp litmus paper. It will displace bromine
from a solution of potassium bromide (then test for bromine by adding
a suitable organic solvent such as hexane, which will show the brown
bromine colour).
o Bromine is brown and will (slowly) bleach litmus. It will displace iodine
from a solution of potassium iodide (then test for iodine with starch or
hexane as below).
o Iodine turns a solution of starch blue-black, and it forms a violet
solution when dissolved in suitable organic solvents such as hexane.
II B.NDTNG ^ND MAIN GRoup 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.
o All metal halides are soluble in water, except for silver and lead halides.
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.
Chloride Bromide Iodide

Addition of Ag-(aq) white precipitate cream precipitate yellow precipitate
Addition of
dilute NH, precipitate dissolves no change no change
Addition of
concentrated NH, precipitate dissolves precipitatedissolvesno change
Addition of concentrated sulphuric acid to the solid

halide
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
o Chlorine is a powerful oxidising agent and is reducedto the -1 state.
is a stronger
Chlorine oxidising o The half equationis:
agentthanbromine,whichis Clr(aq)+ 2e-.. 2Cl-(aq)
thaniodine.
stronger
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)
(0) (-1) (+1)
o Chlorate(I) compounds disproportionatewhen heated:
3OCf+2CI-+ClOr-
3x(+1) Zx(-L) (+s)
o Bromine is extracted from seawaterby bubbling in chlorine gaswhich
oxidises the Bf ions.
e Rou P 7 (cHLoRtNE To toDtNE)
@
ffi
l4),
Checklist
Before attempting questionson this topic, check that you can recall:
iJ the physical propertiesof the elements
lJ ttre testsfor the elementsand for the halides
iJ ttre reactionsof concentratedsulphuric acid with the halides
iJ examplesof -1, 0, +1 and +5 oxidation statesof chlorine and the
disproportionationof chlorine and chlorate(I)ions
I ttre relativestrengthsof the halogensas oxidising agents.
<ffi
,rftn Testingyour knowledge
tH'
and understanding
For the first set of questions, cover the margin, write your answer, then
Name the halogen that is a liquid at room temperature.
,r Describe the test for iodine.
* Which of Cl, Br, and I, is the strongest oxidising agent?
O Which of HCl, HBr and HI is the strongest reducing agent?
Theanswersto thenumbered t Why is hydrogen chloride gas very soluble in water?

questions
areon pages124-125. 2 It is thought that a sample of solid sodium carbonate has been
contaminated by some sodium chloride. How would you test for the
presence of chloride ions in this sample?
Explain why hydrogen chloride gas is produced but chlorine is not
when concentrated sulphuric acid is added to solid sodium chloride,
whereas iodine and almost no hydrogen iodide is produced when
concentrated sulphuric acid is added to solid sodium iodide.
Define disproportionation and give an example of a disproportionation
reaction of chlorine or a chlorine compound.
I 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.
La 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]
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 Define the terms atomic number and mass number t2l

ii 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. t2l

ii Statehow the resulting ions are accelerated. tll
iii Identify the speciesresponsiblefor the peak at mle = 160. 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:
hydrogen chloride -85'C Hydrogen iodide -35 "C
Explain why hydrogen iodide has a higher boiling temperaturethan hydrogen chloride l2l
c Draw and explain the shapesof:
i the PH. molecule I2l
ii the AIH; ion. I2l
Pnlctrce
d Calculate the number of molecules in 8.0 cm' of gaseousphosphine, PH. at room temperature
and pressure.
(The molar volume of a gas at room temperature and pressure should be taken as 2.4 x lOn cm' mol-t.
The Avogadro constant is 6.0 x 10" mol-'.) t2l
(Total L1 marks)
ffanuary 2001 CH1 question 2]
5 a Hydrogen sulphide is produced when concentrated sulphuric acid is added to solid sodium iodide, but
sulphur dioxide is produced when concentrated sulphuric acid is added to solid sodium bromide.
i Complete the following table:
Compound Formula Oxidation stateof sulphur in the compound
Sulphuric acid HzSO'
Hydrogen sulphide H,S
Sulphur dioxide SO,
tsl
ii Useyouranswers
to a parti to suggest
whichof the ions,iodideor bromide,hasthe greater
reducing
power. t2l
i Write an ionic half-equation to show the oxidation of chloride ions, Cl-, to chlorine, Cl,. tU
ii Write an ionic half-equation to show the reduction of chlorate(l) ions, OCf, to chloride ions, in
acidic solution. I2l
iii Bleach is a solution of chlorate(l) ions and chloride ions. Combine the two ionic half-equations
above to produce an equation which shows the effect of adding acid to bleach. tll
(Total 9 marks)
[May 2002 Unit Test 1 question 7l
6 a Complete the following for the element sulphur

Number of electrons in the 1st shell =
Number of electrons in the 2nd shell =
Number of electrons in the 3rd shell = t1l
b Write one equation in each caseto represent the change occurring when the following quantities are
measured.
i The first electron affinity of sulphur r2l
ii The first ionisation of sulphur. tll
c The graph below shows the logarithm of the successiveionisation energies of sulphur plotted against the
number of the electron removed. Account for the form of the graph in terms of the electronic structure
of sulphur.
6.00
$ s.so
H s.oo
! +.so
€ 4.oo
A 3.so
I E.oo
3oz.so
2.00
o 2 4 6 8 1 0 1 2 1 4 1 6 1 8
Number of electron removed
t3I
One of the chlorides of sulphur is sulphur dichloride, SClr. It is a liquid at room temperature; the
electronegativity of S is 2.5 and that of chlorine is 3.0
i Draw a dot and cross diagram to show the bonding in SClr. r2l
ii The shape of the molecule is bent (V-shaped).Explain why the molecule has this shape. r2l
iii State, with reasons,whether SCl, is a polar molecule overall. r2l
(Total L3 marks)
fJanuary2002 CHl question 2 & May 2002 Unit Test 1 question4l
2 OfAA"niL, l,/Va-/ a.tA VL'771 y, e*Ufrzo*irr
,
J,VVI / Jvvl.v))
Mkr ar4d,e4uilib r i/,u,t

u
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
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
It followsfromthisdefinition
that
theenthalpy offormation
ofan standardconditions, when one mole of a compound is formed from
element, initsstandardstate,is its elements in their standardstates,e.g. AFII'for ethanol is the
zero. 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)
Youshouldalwaysgiveanequation
asanexampleforthisandother E Standard enthalpy of neutralisation AI/:.,, of an acid is the enthalpy
enthalpy
definitions. change,under standardconditions, when the acid is neutralisedby
baseand one mole of water is produced,e.g.A.Fif;",, of sulphuric acid,
by sodium hydroxide solution, is the enthalpy changefor the reaction:
'/,HrSOn(aq) + NaOH(aq)-'l,Na,SO,(aq)+ H'O(l)
O EneRGETrcs r
for hydrochloric acid the enthalpy changeis for the reaction:

HCI(aq)+ NaOH(a9)- NaCl(aq)+ H,O(l)
for any strong acid being neutralisedby any strong base,the
enthalpy changeis for the reaction:
H-(aq)+ OH-(aq)- H,O(l) Aff" = -57 kJ mol-'
E Aoerage bond enthalpy. This is the average quantity of energy
required to break one mole of covalent bonds in a gaseous species
(at one atmospherepressure).It is always endothermic, e.g. the
C-H bond enthalpy in a gaseouscompound is the enthalpy changefor
the reaction:
C-H(in compoundxs) - C(8) + H(g)
E nn exothermic reaction gets hot, so that heat is then given out to the
surroundings.For all exothermic reactions A^tIis negative (see
Figure2.1).This meansthat chemicalenergyis being convertedinto
_ thermal (heat) energy.
[J An endothermic reactiongetscold, so that heat is then taken in from
the surroundings.For all endothernic reactions AII is positive
(seeFigure2.2).
t
I
1 *..ctants I Products
t - I
Enthalpy Enthalpy
Products
Fig 2.1 Enthalpydiagromfor an Fig 2.2 Enthalpydiogramfor on

exothermicreoction endothermicreoction
Route 1
E Hess's Law. The enthalpy changefor a given reaction is independent

of the route by which the reactionis achieved(seeFigure2.3).
Thus the enthalpy changeproceedingdirectly from reactantsto
products is the sameas the sum of the enthalpy changesof all the
reactionswhen the change is carriedout in two or more steps.
NI = A.FI,+ NIr+ AJI.,
Route 2 ffi Thingsto understand

Fig 2.3 A reaction cycle
Lry
Calculation of A.ff*.ooo from A^tI, data
You can usethe expression:
Afl"uoio,,= the sum of Aflo,rnation

of products - the sum of AI{o,-u,ionof reactants
O Rememberthat if you have two moles of a substance,you must double

the value of its AId.
O The enthalpy of formation of an element (in its standardstate)is zero.
H cHEMrsrRy, ENERGETT.', KrNETrcs AND EeurLIBRruM
"RGANrc
Workri, oxiloq-lr'
thestandard
Calculate enthalpychange forthereaction:
4NH,(g)+ 50,(g)-- 4N0(9)+ 6H,0(g)
giventhefollowing
AHelkJmol-':
NH,(g)= -46.2,N0(g)= +90.4,H,0(g)= -242.
AHf,o",= SUITI
AnSwer. Aff of produCtS- SumAH,Fof reactants
= 4 x(+90.a)+ 6 x (-242)-4x (-46.2)-5x (0)= -906kJ mol-'
Calculation of LII, from A^f["data

To do this you use the alternative route:
LH,
Elemen 1 mol of substance
LH2=- LH"because aH,represents
thereverseof combustion.
\
LH'\ /o,.
lf anequationis reversed,
thesign /
of itslH mustbechanged. combustionproductsof the elements
where AH, = the sum of the enthalpies of combustion of the elements

taking into account the number of moles of each element,
and A^H,= - the enthalpy of combustion of I mol of the substance.
= LH, + A,H,
Thereforer Aflo,-u,,on
Workz,oL
oxiloLf./*,
thestandard
Calculate enthalpy of propan-1-ol,
of formation given
C2H'CH,0H,
thefollowing
aH+,..ou*on :
/kJ mol-1
= -2010,C(graphite)
propan-1-ol(l) = -394,H,(g)= -286
Answer. 3C(s)+ 4H,(g)+ 10,(g)- C,H'CH,OH(|)

(sraphite)
3x AH. m"fi1c,HscH,0H)
I \+ "
+ 4H,0(l)'
3C0,(g)
AH*,=4H",of elements - aH", of compound
= 3 x (-394)+ 4 x(-286)- (-2010)= -316 kJmol-'
Calculation of AII values frorn laboratory data (only

Themassin thisexpression
is the examined at AS in unit test 38)
totalmassof thesystem(usually
water)notthemassof thereactants. I Calculation of heat change from temperature change:
heat produced = rl?SS x specific heat capacity x rise in temperature
I Then heat produced per mole = heat produced in experiment
the number of moles reacted
o Then enthalpy change, AFI, is minus the heat produced per mole (for an
exothermic reaction A/{is a negative number).
O For an endothermic reaction, calculate the heat lost per mole. This
equals A,H,a positive number.
:
-t rl
@ eNERGErrcs I
Workêi,exiloLf.b
A 0.120g sample wasburntandtheheatproduced
of ethanol warmed 250g
ofwaterfrom17.30'Cto 20.72
'C.The
specific
heatcapacity
ofwateris4.18
J gto0-t.Calculate
A{omustion
of ethanol.
Answer.Heatproduced= 250g x 4.18J gj o6-tx3.42'C = 3574J.

of ethanol = 0.120g146
Amount g mol-'= 2.61x 10-'mol
produced
Heat per =
ffi010 3574J12.61x 10-3mol= 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 H
+ H_ H --__________+
t l
H_ C - C - H
H H H
r H
l
Giventhefollowing
averagebondenthalpies/kJ
mol-':
C-Cis +348,C=Cis +612,H-His +436,andC-His +412.
Answer. break
(endo) make(exo)
C=C +612 c-c -348
H-H +436 2 x C-H -824
+1048 -1172
= -
A4,,,rion+1048 1172 = -124 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.
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 Testingyour knowledgeand understanding
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 the enthalpy of combustion of ethanoic acid
iii 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.
* *
Acid
Substance Alcohol Aldehvde Ketone Acid Ester Amide Nitrile Amine
chloride
H.tC:o R tc:o
. ..O arO ,aO ,ro
- CI - O H _C I
Group R_C _C _C _C =N -C-NHz

I R'/ \oH to-R' tcl \NHZ I
R/
Toble 2.1 Functionolgroups.*Thesewill only be met at A2. R is o carbon-contoining

group.
E you must learn the equationsand conditions for the reactionsin the
specification.
€tfa
LN 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.
Whenyouwritestructural
formulae, fl Isomers: two or more compounds with the samemolecular formula.
that:
check
atomhasfourbonds f Homolytic fission: when a bond breakswith one electron going to
oeverycarbon
oeveryoxygenhastwobondsand each atom (forming radicals).
oeveryhydrogen
andeveryhalogen ff Heterolytic fission: when a bond breakswith the two electrons going
haveonlyonebond. 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.
E cHEMrsrRy, ENERGETT.', KrNETrcs AND EeurLrBRruM
"RGANrc
U nnmination: a reaction in which the elementsof a simple molecule

such as HBr, HrO etc. are removed from the organic molecule and not
replacedby any other atom or group of atoms.
[l nyArolysis: a reaction in which water (often catalysedby aqueousacid
or aqueousalkali) splits an organic molecule into two compounds.
f Free radical: a specieswhich has a single unpaired electron, e.g. Cl'
f Nucleophile: a specieswhich seeksout positive centres,and must
have a lone pair of electronswhich it donatesto form a new covalent
bond.
[l nlectrophile: a specieswhich seeksout negative centres,and acceptsa
lone pair of electronsto form a new covalent bond.
Isomerism
There
arethreestructural
isomers
of O Structural isomers may have:
formula
CrHu0:
o propan-1-olCH3CH,CH,OH i different carbon chains (straight or branched)
r propan-2-olCH'CH(0H)CH3 tt the functional group in different placesin the carbon chain
I methoxyethaneCH3OCH,CH3 iii different functional groups.
O Geometric lsomerism
cHa cH,
I Geometricisomerismoccurswhen there is a C=C in the molecule,
\ /
cis C-C and both carbon atoms have two different atoms or groups attached.
/ \ ii Geometricisomersare not easilyinterconvertedbecauseof the
H H difficulty of rotating about the n bond.
cHs H Alkanes (e.9. methane, CHJ

\ /
trans C- C O Alkanes burn in excessoxygen to form carbon dioxide and water:
/ \ CHn+ 2Or-' CO, + zHzO
H CHs
Ftg 2.4 Geometricisomersof O Alkanes react with chlorine (or bromine) in the presenceof UV light in
but-2-ene a stepwisesubstitution reaction:
CHn+ Clr- CH3CI+ HCI
CH3CI+Clr-CHrClr+HCl
Nkenes (e.g. propene, CIITCH=CH,)

Thedecolourisation
ofa brown O Alkenes add hydrogen:
solution
of bromine
isa testfora
C=Cgroup ina molecule. CH3CH=CH,+ H, - CH:CHTCH'
conditions: passgasesover a heatednickel catalyst
O Alkenesadd bromine (or chlorine):
CH3CH=CH,+ Br, - CHTCHBTCHTBT
conditions: at room temperaturewith the halogen dissolvedin hexane.
Withunsymmetrical alkenes,the O Alkenes add hydrogen halides, e.g. HI
hydrogengoesto thecarbon that CH3CH=CH,+ HI' CH3CHICH3
already
hasmorehydrogen atoms
directly
bonded to it.Thisis conditions: mix gasesat room temperature.
Markovnikov's
rule.
@ oRGANrc cHEMrsrRY I
O Alkenesare oxidised by potassiummanganate(Vll)solution:

H H CH,CH=CH,+ [O] + HrO - CH'CH(OH)CHTOH
t l
lLII
conditions: at room temperature,when mixed with sodium hydroxide
C-C solution it producesa brown precipitate.
l l o Alkenescan be polymerised. Etheneforms poly(ethene)(Figure2.5)
H H and propene forms poly(propene)(Figure2.6):
Fig 2.5 Ftg 2.6 n-CHr-Qlf, + -(CH r-CHr)-,
Poly(ethene) Poly(propene) 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
conditions:boil under reflux with aqueoussodium hydroxide.
o They eliminate with ethanolic potassium hydroxide to give an
Therateofallthese reactions alkene:
increases
C-Clto C-Brto C-|,
becausethebondenthalpy CH3CHICH,+ KOH - CH,CH-CH'+ KI + H,O
and
hencethebond strengthdecreases conditions: boil under reflux with a concentratedsolution of potassium
C-Clto C-Brto C-|.Theweakerthe hydroxide in ethanol, and collect the gaseouspropene over water.
bondthelowertheactivationenergy o They substitute with potassium cyanide:
andhence thefasterthereaction.
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.
o The test for halogeno compounds:
1 Warm the substancewith aqueoussodium hydroxide.
H 2 Add dilute nitric acid until the solution is just acidic.
3 Add silver nitrate solution.
-C-OH
I Result:
t white precipitate,soluble in dilute ammonia indicateschloro-
H -c- compound
1 0 O cream precipitate,soluble in concentratedammonia indicatesbromo-
l l
-c-c-oH compound
t l o yellow precipitate,insoluble in concentratedammonia indicatesiodo-
compound.
H
-C-
l
-c-c-oH
i 2 0 AIcohols
Primary (1') alcohols contain the CHrOH group.
t- c - l Secondary(2') alcohols have two C atoms attachedto the CHOH group.
I Tertiary (3') alcohols have three C atoms attachedto the COH group (see
3o
Figare2.7).
Ftg 2.7 1", 2" and 3" alcohols

E }RGANrc cHEMrsrRy, ENERGETI.', KtNETtcs AND EeutLtBRtuM
o Oxidation reaction with aqueous orange potassium

dichromate(Vl), KrCrrO, acidified with dilute sulphuric acid.
a 1' alcohols are oxidised via an aldehyde to a carboxylic acid. The
solution turns green ([Cr(HrO)u]'. ions formed).
CH,CH,OH + [O] - CH,CHO + H,O
then CH3CHO + [O] - CH,COOH
conditions: to stop at the aldehyde: add potassium dichromate(Vl)
in dilute sulphuric acid to the hot alcohol and allow the aldehyde to
distil off.
to prepare the acid: boil the alcohol with excess acidified oxidising
agent under reflux.
b 2" alcohols are oxidised to a ketone. The solution turns green.
ln equations
in organic
chemistry, CH3CH(OH)CH3+ [O] 'CH.COCH, + H,O
anoxidisingagentcanbewrittenas
conditions: boil the alcohol and the acidified oxidising agent under
[0] anda reducingagentasIH],but
theequationmuststillbalance. reflux.
c 3'alcohols are not oxidised and so do not turn the solution green.
o Dehydration of an alcohol to an alkene:
worksforall
Notethatthisreaction
andisomers
alcohols, of thealkene CTH'OH-HrC=CHr+HrO
maybeproduced. conditions: add excess concentrated sulphuric acid (or concentrated
phosphoric acid) to the alcohol and heat to 170'C.
o Ilalogenation Io,2" and 3'alcohols react with:
1. Phosphorus pentachloride, PCI' to form a chloroalkane:
Thisisa testforan0Hgroup. CTH.OH + PCl, - CrHrCl + HCI + POCI,
Steamy acidicfumesaregiven
off conditions: at room temperature and the alcohol must be dry.
whenphosphorus pentachloride
is
added tothedryorganicsubstance. Solid sodium bromide and 50o/osulphuric acid to give a
bromoalkane:
NaBr + HrSOn-- HBr + NaHSO,
then HBr + CTH'OH - CrHrBr + HrO
conditions: add the sulphuric acid mixed with the alcohol to solid
sodium bromide at room temperature.
Phosphorus and iodine to give the iodoalkane:

2P + 3lr- 2Pl,
then 3CrHrOH + PI, -- 3CrHrI + H.PO,
conditions: add the alcohol to a mixture of moist red phosphorus
and iodine at room temperature.
A summary of reactions is shown in Figure 2.8.
oRcnrurc cHEMrsrRY I 41,
@
zCOz+3HrO CH2BTCHTBT cH2oHCH2OH cH3cooH
o2 Brz KMnOn Boil under reflux

Spark NaOH(aq) KtCtrOrlHrSOn(aq)
conc H2SO4
at 100'C at l7O"C
Crz NaOH
W
cH3cH2cl
NH, in ethanol
cH3cH2cN cH3cH2NHz
Fig 2.8 Summory of

orgonic reoctions
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.
b 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 organic chemistry

unThis involves calculation of empirical formulae from percent data (see
Thepercentyieldis lessthan100% page 6).
because
of competing reactions
and
w This involves calculation of percentage yield.
handling
losses.
First calculate the theoretical yield from the equation (seepage B),
then the o/oyield = actual yield in grams x 10oo/o
theoretical yield in grams
Applied organic chemistry

* Liquid versus gaseous fuels. You should consider the following
points:
L the easewith which gaseousfuels can be piped into the home
2 the easier handling of liquid fuels at a filling station for cars
3 the extent and type of pollution produced:
a the quantity of carbon dioxide and any other greenhouse gases
produced per kilojoule of energy
b the emission of oxides of nitrogen and sulphur, and the way in
which these can be limited
c the emission of particulates
4 the energy produced per unit mass of fuel for aeroplanes
5 the extent to which the world's supply of fossil fuels is limited.
"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 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
DDTis a chlorine-containing etc. Thesepolymers are very stableowing to the strength of
pesticideandit haseradicated
carbon-halogenand C-C bonds.
malariafromsomecountries, butits
hasledto thedestruction 2 As herbicides.Complicatedchlorine compounds,such as 2,4-D and
overuse of
lt is a veryinertchemical
wildlife. 2,4,5-Tare usedas selectiveweedkillers.They are stableand so
(owingto thestrength of theC-Cl persistin the environment.
bond)andso persists in an 3 Chlorofluorocarbons(CFCs)make excellent refrigerants,but they
organism, beingstoredin fatty are so stablein air and water that they diffuseto the stratosphere
tissue. 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.
For the first set of questions,cover the margin, write your answer,then
o Which of the following compounds are membersof the same

homologousseries:
ethene -ene
andbut-1 ethene CrHn,cyclopropaneCrHu,but-l-ene CHTCHTCH=CH,
but-1,3-dieneCH'=CHCH=CH',cyclohexeneCuH,o?
2-chlo -ol
ro-3-methylpentan-1 Name CH3CHTCH(CH3)CHCICHTOH
@ oRGANrc cHEMrsrRy I
O What product is obtained if a large excess of chlorine is mixed with

methane and exposed to diffused light?
O A compound X contained 54.5olocarbon, 36.40/ooxygen and9.Io/o
tetrachloromethane,
CClo
hydrogen by mass. Calculate its empirical formula.
c2H4o
1 Write the structural formulae of:

Theanswers
tothenumbered
questions
areonpages
127-128. a 1,l-dibromo-I,2-dichloro-2,3-difluoropropane
b 1-chlorobutan-2-ol.
2 Write out the structural formulae of the isomers of:
a C3H8O(alcohols only)
b CrH,,
c CoH, (no cyclic compounds).
3 Define:
a free radical
b homolytic fission.
4 Define:
a an electrophile
b heterolytic fission.
5 Write equations and give conditions for the reaction of:
a ethane + chlorine
b ethane + oxygen.
6 Write equations and give conditions for the reaction of propene with:
a hydrogen
b bromine *
c hydrogen iodide
d potassium manganate(Vll) solution *
For reactions marked *, state what you would see.
7 Write equations and name the products obtained when 2-iodopropane
is:
a shaken with aqueous dilute sodium hydroxide
b heated under reflux with a concentrated solution of potassium
hydroxide in ethanol
c heated in a sealed tube with a concentrated solution of ammonia in
ethanol.
8 Write the equation and give the conditions for the reaction of
propan-Z-ol with sulphuric acid.
9 Write the structural formula of the organic product formed, if any, give
its name and say what you would see when:
a propan-l-ol is heated under reflux with dilute sulphuric acid and
excessaqueous potassium dichromate(Vl)
b 2-methylpropan-2-ol is heated under reflux with dilute sulphuric
acid and aqueous potassium dichromate(Vl)
c phosphorus pentachloride is added to propan-2-ol.
1O Why does bromine react rapidly with ethene at room temperature but
only slowly with ethane?
ORCAI\|IC CHEMtSTRy, ENERGETTCS, KINETICS AND EQUILIBRIUM
L1 Why does L-bromopropanereact more slowly than l-iodopropane with

water?
12 When 5.67 g of cyclohexene,CuH,o, reactedwith excessbromine, 15.4 g
was obtained. Calculatethe theoretical yield of CuH,oBr,and
of CuH,oBrz
hence the percentageyield of the reaction.
13 Explain why compounds such as CClrF,are harmful to the
environment.
KineticsI
o The rate of a reaction is determinedby:
1 the rate at which the moleculescollide
2 the fraction of the colliding moleculesthat possess
enough kinetic
energy 'to get over the activation energybarrier'
3 the orientation of the moleculeson collision.
Things to learn
[] ^Lctivation energy is the minimum energythat the reactant
moleculesmust have when thev collide in order for them to form
product molecules.
[l Factors which control the rate of a reaction are:
1. the concentration of a reactant in a solution
2 the pressure,if the reactantsare gases
3 the temperature
4 the presenceof a catalyst
5 the surfaceareaof any solids
6 light for photochemical reactions.
Collision theory
o The effect of an increasein concentration of a solution, or the

increasein pressureof a gas,is to increasethe frequency of collision
of the molecules,and hence the rate of reaction.
O The effect of heating a gasor a solution is to make the moleculesor
ions:
Anincrease in temperature
also 1 move fasterand so have a greateraveragekinetic energy
causes anincreasein therateof 2 which increasesthe fraction of colliding moleculeswith a combined
butthisis unimportant
collision, energygreaterthan or equal to the activation energy
compared withtheincrease in the
3 which resultsin a greaterproportion of successfulcollisions.
of molecules
fraction withthe
necessary energy.
activation o The effect of heating can be shown by the Maxwell-Boltzmann
distribution (seeFigure2.9) of molecular energiesat two temperaturesT,
and T, where T, is > 7,.
@ KrNErrcs I
ttt
q,)
Notethatthepeakhasmoved to the I
(u
rightfor f,, andthatthetotalareas
under thecurves arethesame, but
theareaunder thecurve totheright
of E equals thefractionofthe
molecules withenergy 2 E^,which is (J
greaterforTrthan for I,. fr .
Fig 2.9 Moxwell-Boltzmanndistribution
(t)
(u Catalysts work by providing an alternativeroute with a lower
I
activationenergy.Thus, at a given temperature,a greaterproportion of
q)
the colliding moleculeswill possessthis lower activation energyby
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
(J
reactionare shown in Figure2.I1.
Energy E^^. E
Do not say that a catalystlowers the activation energy.
Ldt d
Note that the A.Elvaluesare the samefor both paths.

Fig 2.lO Effectof a catalyst
:------- Transi ti on
Intermediate
rrl
Fig 2.1| Energyprofilediagrams Uncatalysed
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
E cHEMrsrRy, ENERGETT.', KrNETrcs AND EeuILrBRruM
"RGANrc
thermodynamically unstablebut kinetically stable.No reaction occurs
unlessthe mixture is ignited.
Checklist
Beforeattemptingthe questionson this topic, checkthat you:
iJ Can recall the factorswhich effect the rate of reaction.
J Can explain theserate changesin terms of collision theory.
[i Can draw the Maxwell-Boltzmann distribution of molecular energiesat
two different temperatures.
,J Can use this to explain the effect of a change of temperatureand the
addition of catalyst.
J Understandthe conceptsof thermodynamic and kinetic stability.
and understanding
For the following questions, cover the margin, write your answer, then
O For a reaction involving gases,state three factors that control the rate of
Pressure,
temperature,
andcatalyst the reaction.
O For a reaction carried out in solution, state three factors that control the
rate of the reaction.
e For the reaction of a solid with a gas or with a solution, state one other
Thesurlace
areaof thesolid
factor that controls the rate of reaction.
Fe(Haber),
orV,Ou (Contact),
or Ni o Give an example of a solid catalyst used in a gas phase reaction.
or Pt(addition
of hydrogen
to C=C)
L Define
Theanswers
to thenumbered i activation energy
questions
areon page128.
ii catalyst.
2 Explain, in terms of collision theory, why changes in temperature and
in pressure and the addition of a catalyst alter the rate of a gas phase
reaction.
3 Draw the Maxwell-Boltzmann distribution of energy curve for a gas:
i at room temperature (mark this T,) and
ii at 50 "C (mark this [).
Now mark in a typical value for the activation energy of a reaction that
proceedssteadilyat room temperature.
Explain, in terms of activation energy,why animal products such as
meat and milk stay fresherwhen refrigerated.
Draw energyprofile diagramsof:
i an exothermic reaction occurring in a single step
ii the samereaction in the presenceof a suitablecatalyst
iii a reaction where the reactantsare thermodynamically stable
iv a reaction where the reactantsare both thermodynamically and
kineticallyunstable.
@ G H E M T c A LE e u r L r B R r A I
Chemical I
equilibria
<ffi
W Introduction
Many reactionsdo not go to completion becausethe reaction is reversible.
As the rate of a reactionis dependenton the concentrationof the
reactants,the reaction will proceedup to the point at which the rate of the
forward reaction equalsthe rate of the reversereaction, when there is no
further changein concentrations.The systemis then saidto be at
equilibrium.
ffi Thingsto learnandunderstand

Lry
Dynalnic equilibrium
O At equilibrium, the rate of the forward reaction equals the rate of the
reverse reaction.
O Both products and reactants are constantly being made and used up,
but their concentrations do not change.
O This can be demonstrated by using isotopes. For the reaction:
CH3COOH(I) + C,HsOH(l)+CH,COOC,H,(I) + H,O(l)
Mix the four substances in their equllibrium concentrations, but
have the water made from the isotope tto. After some time the "O
isotope will be found (by means of a mass spectrometer) in both the
ethanoic acid and the water, but the concentrations of the four
substances will not have changed.
Effect of changes in conditions on position of

equilibrium
O Le Chatelier'sprinciple may help you to predict the direction of the
changein the position of equilibrium, but it doesnot explain it.
O Temperature. An increase in temperaturewill move the position of
principle
LeChatelier's states that equilibrium in the endothermic direction. Likewisea decreasein
whenoneof thefactorsgoverning temperaturewill move the equilibrium in the exothermic direction:
theposition
ofequilibrium is
theposition
changed, willalterin N,(g) + 3H,(g) =. 2NH,(g) LH - -92.4 kJ mol-'
sucha wayasif to restore
the As this reaction is exothermic left to right, an increasein temperature
original
conditions. will causeless ammonia to be made, thus lowering the yield.
O Pressure. This appliesonly to reactionsinvolving gases.An increasein
pressurewill drive the equilibrium to the side with fewer gasmolecules.
Thus, for the reaction above,an increasein pressurewill result in more
Donotsay'the ammonia in the equilibrium mixture, i.e. an increasedyield. This is
sidewitha smaller
asa gaswillalways
volume', fillits becausethere are only two gasmoleculeson the right of the equation
container. and four on the left.
O Concentration. This appliesto equilibrium reactionsin solution. If a
substanceis physically or chemically removed from an equilibrium
system,the equilibrium will shift to make more of that substance:
E 'RGANrc cHEMrsrRy, ENERGETT.',KrNETrcs AND EeurLrBRruM
+ 2H.(aq) + Cr,O,'-(aq) + HrO(l)

2CrOn'z-(aq)
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 O High pressuresare extremely expensive,and are only used if the yield at
passinggases
through
a bedof lower pressuresis too small to be economic.
catalyst
mustworkabove
pressure
1 atmosphere inorder to o Two examplesof manufacturing processesthat usevery high pressures
forcethegases
through
thesystem. 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
Considerthe reversiblereaction at equilibrium:
Theanswers
to thenumbered
questions
areonpage 129. A(g) + B(g)
Which statementsare/is true about this system?
i There is no further changein the amounts of A or B.
ii 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 decreasingthe temperature
ii halving the volume of the container
iii adding a catalyst.
Ethanoic acid and ethanol react reversibly:
CHTCOOH+ CTHTOH + CH.COOCTH,+ HrO NI = 0 kJ mol-'
i Explain the effect of adding an alkali.
ii What will happen to the position of equilibrium if the
'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)
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?
@ Industrial chemistry
inorganic
ffi Inffoduction
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 Thingsto learnand understand

Lry
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
moleculesdecreases, the yield and kinetics are affectedaccordingto the
table below:
Reaction conditions Effect on yield Effect on rate

Increasein temperature Decrease lncrease
Increasein pressure Increase Very slight increase
Addition of catalyst None Very large increase
O Thus the following conditions are found to be the most economic:

Temperafire: 400 "C. A higher temperature would reduce the yield,
and a lower one would make the reaction
uneconomically slow.
"RGANrc
Pressure: 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
Usesofammonia: hence economic, rate at a moderate temperature.
I manufacture
ofnitric
acid Yieldper cycle: 15o/o.The gasesfrom the catalyst chamber are cooled in
t manufacture
offertilisers
suchas order to liquefy the ammonia, and then the unreacted
ammonium nitrate nitrogen and hydrogen are recycled, giving a final
andurea
conversion of nearly lOoo/o.
ofpolyamides
o manufacture such
asnylon. 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 process for the manufacture of sulphuric

acid
O This takesplace in three stages:
1 The combustion of sulphur:
S(l)+O,(g)-SO,(8)
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.
Usesofsulphuric
acid: Pressure: 2 atm. This is enough to force the gasesthrough the
I themanufacture
offertilisers plant. A higher pressureis not necessarybecausethe
suchasammonium sulphate yield is high under theseconditions.
of phosphate
r themanufacture Catalyst: Vanadium(v)oxide.
fertiliser YieId: 960/oper cycle.The gasesfrom the catalystchamber are
ofpaints
r themanufacture and passedinto the absorbercontaining the 980/osulphuric
detergents. 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
INDUSTRIAL INORGANIC CHEMISTRY
react becauseof its giant atomic structure.Thesesolids are filtered off,

and carbon dioxide is blown through the solution precipitating
aluminium hydroxide. This is obtained by filtration and heatedto
produce pure aluminium oxide.
Aluminium isprotected from o The purified aluminium oxide is dissolvedin molten cryollte, NarAlFu,
corrodingbyits layerof oxidewhich at 900'C.
reformswhenit isscratched. lt is
alsolessdense thaniron.These O The solution is electrolysed using carbon anodesdipping into a steel
properties
make it ideal
asa material cell lined with carbon, which is the cathode.
foraeroplane wings andfuselage a At the cathode, aluminium ions are reduced:
andfordrinkcans(even though it is
Al'*+3e--Al(l)
moreexpensive thaniron). lt isalso
anexcellentconductor ofelectricity, O The molten aluminium sinks to the bottom of the cell and is siphoned
andsois usedinoverhead power off.
cablesbecause ofthese three o At the carbon anode, oxygen ions are oxidised and reactwith the
properties. anode:
Astheelectrolytic method of
manufacture isveryexpensive, it is 2O'- + C(s)-' CO'(g) + 4e-
economically sensible to recycle o Becauseof the expenseof this method of manufacture,it is economic to
aluminium objects. recyclealuminium drink cans.
The production of chlorine

o This is done by the electrolysisof an aqueoussolution of sodium
chloride (brine).
At the titanium anode (+): NaCl contains Cl- ions and theseare
Chlorineis usedfor: oxidised to Clr:
i water sterilisation zCl-(aq)-Cl,(g) +2{
ii themanufacture oforganic
chlorine
compounds, suchasthe chlorine gasis produced.
plastic
PVCandtheherbicide o At the steel cathode (-): water is ionised in an equilibrium reaction:
2,4-D H,O[) + H-(aq)+ OH- (aq)
iii themanufactureof HCl.
Na* ions are very hard to reduce, and so H* ions are preferentially
reduced:
2Hr(aq)+2e--Hr(g).
The removal of the H- ions drives the water equilibrium to the right,
producing OH ions. The overall equation for the reaction at the
cathode is:
zHrO + 2e- - ZOtf(aq) + Hr(g)
Thus sodium hydroxide and hydrogen are produced.
The anode and cathode compartments are separatedby an ion-exchange
membranewhich allows Na. ions to passthrough but keepsthe
chlorine separatedfrom the hydroxide ions that are produced at
the cathode.
Manufacture of sodium chlorate(I)

If the electrolysisof sodium chloride solution is carried out with the
Sodium is used:
chlorate(l) solution being stirred, sodium chlorate(I) and hydrogen are obtained. The
i asa domesticbleach chlorine produced at the anode disproportionateswhen in contact with
ii asa disinfectant. the alkali from the cathode:
Cl,(aq) + 2OH-(aQ)- OCI-(aq)+ Cl-(aq)+ H,O(l)
OnceNIc cHEMISTRY, ENERGETICS, KINETICS AND EQUILIBRIUM
Checklist
."j Know the conditions for the manufacture of ammonia.
*i Know the conditions for the manufacture of nitric acid.
.-- Know the conditions for the manufacture of sulphuric acid.
.-; Can iustify the conditions in terms of the economics and the chemistry
of these processes.
; Know some of the uses of ammonia, nitric acid and sulphuric acid.
-.,1Know the conditions and electrode reactions used in the manufacture
of aluminium.
J Can recall the details of the production of chlorine and sodium
chlorate(l) and their uses.
o- - lH
q rrl
t-----!
,i.:. Testingyour knowledge
and understanding
o State the conditions used in the manufacture of ammonia.
of350to 450'C,a
A temperature
pressure
of 200to 250atmandan
ironcatalyst O State two uses of ammonia.
Tomakefertllisers,
andto make
nylon(ornitricacid) o State the conditions used for the oxidation of ammonia in the
manufacture of nitric acid.
A temperatureof900'Canda
platinum/rhod
ium catalyst
O State the conditions used for the oxidation of sulphur dioxide in the
A temperature
of 400to 450'C,a Contact process.
vanadium(V)
oxide catalyst
anda
pressure
of2 atm
O State two uses of sulphuric acid.
Tomake andpaints
fertilisers, (or
detergents)
It isamphoteric. o What property of aluminium oxide is the basis of its purification from
bauxite?
f What is the essential condition used in the manufacture of aluminium?
Al'-+ 3e-- Al
Cathode O Write the equations for the reactions at the cathode and at the anode in
A n o d e :2 0 ' - + C - C O z + 4 e - the manufacture of aluminium.
Explain the economic reasonsfor the choice of the conditions used in

Theanswers
to thenumbered the Haberprocess.
questions
areonpage 129.
In the Haber processwhy is the gasmixture cooled after it has left the
catalystchamber?
Write the equationsfor the reactionsat the anode and at the cathode in
the manufactureof chlorine.
PRAGTIcE:
Practice Test: Unit 2

Time allowed Lhr
All questionsare taken from parts of previous EdexcelAdvancedGCE questions.
The answersare on pagesI29-I3O.
La Propene,C.Hu,and but-2-ene,CH.CH=CHCH3, are in the samehomologousseries.Explain the term

homologous series. t3l
b Draw a representativelength of the polymer chain of poly(propene) r2l
c i Draw the geometricisomersof but-2-ene. r2l
ii Explain how geometricisomerismarises. t1I
(Total 8 marks)
llune 2001 Unit Test2 question2 & May 2002 Utrit Test2 qtestion 5l
The rate of any chemical reaction is increasedif the temperatureis increased.

a Draw a diagram to representthe Maxwell-Boltzmann distribution of molecular energiesat a
temperatureT, and at a higher temperatureTr. t3l
b Useyour diagram and the idea of activation energyto explain why the rate of a chemical reaction
increaseswith increasingtemperature. t4l
(Total 7 marks)
llune 2001 Unit Test2 questiott3)
Considerthe following reaction scheme:
step 1
CrHu CrHrBr(maior product)
propene S
I
aqueousNaOH
KMnOn
II I
I
in alkali I t
* c3H8o
a P
*.0 3 (oxidation)
|
V
cH3cocH3
a i Give the reagentand the conditions neededfor step 1. r2l

ii Give the structural formula of S. tu
b i Give the structural formula of P. tlI
ii Statethe type of reaction in:
step 1 r2l
the conversionof S to P. r2l
c i Give the reagentand the conditions neededfor step 2. r2l
ii Give the reagentand the conditions neededfor step 3. t3l
d Give the structural formula of compound Q. tlI
(Total 14 marks)
IMay 2002 Unit Test2 question4l
4a State Hess's Law. I2l

b Define the term standard enthalpy change of combustion. t3I
c The equation for the combustion of ethanol in air is
CrHsOH[) + 3O,(g) - 2CO,(E) + 3H,O0)
El o*.ANIc cHEMrsrRy, ENERGETT.',KrNETrcsAND EeurLrBRruM
And the structural representationof this is:
H H
t l
H-C - C-O- H + 3O:O # 2O-C:O + 3H-O -H
t l
H H
Calculatethe enthalpy changefor this reaction using the averagebond enthalpy valuesgiven below.
t3I
Bond Averagebond energy/kJmol-' Bond Averagebond energy/kJmol-'
C-H + 4L2 C-C + 348
c-o + 360 o-H + 463
Ot:O + 496 c:o + 743
tt Draw and label an enthalpy level diagram to representthis reaction. I2l

Gotaf 1O marks)
lJune200L Unit Test2 question5f
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 tlI
ii dynanic equillbrium l2l
Stateand explain the effect on the position of equilibrium of the reaction in b of:
I decreasingthe temperature. l2l
ti decreasingthe volume of the reaction vessel r2l
(Total 14 marks)
lMay 2002 question3 Unit Test2 & lanuary 2001 question4 Module Test2l
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.
a Give the ionic equation for the reaction taking place at the anode. tlI
b Give the ionic equation for the reaction taking place at the cathode. tlI
c Statewhich of thesereactionsis an oxidation process. tll
d Explain why the anodesneed to be replaced frequently. tzl
e 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
Laboratory I
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, burns with a squeakypop
I O, relights a glowing spill
o CO, turns lime water milky
o NH3 turns red litmus blue
O Cl, bleachesdamp litmus; turns KBr solution brown
a NO2 brown gaswhich turns starch/iodidepaper blue-black
I SO, turns acidified potassiumdichromate(Vl) solution green.
E you should know the testsfor the following ions:

o COr'- Add acid. Testfor COr.
o HCO3- Add to almost boiling water.Testfor COr.
o SOn'- Giveswhite precipitatewhen dil HCI and BaClr(aq)are
added to the solution.
o HSO4- Solution is acidic to litmus, then test as for SOn2-
above.
o SO32- Add dil acid to solid and warm. Testfor SOr.
o 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.
Ion Flame colour a NO3- Heat solid. All nitrates give off Or. All but sodium and
potassiumnitrates also give off NOr. Alternatively add
Li' camine red
aluminium powder and sodium hydroxide solution.
Na' yellow Nitrates give off ammonia gas.
K' lilac a NHn. Add dil NaOH and warm. Testfor ammonia.
Ca'* brick red o Mg'. Giveswhite precipitatewhen dil ammonia is added
Sr'* crimson red to a solution.
Ba"* pale green O You must know how to carry out a flame test and the colours obtained.
LABoRATORY CH EM ISTRY I
38:Laboratory
[]nit Test I
chemistry
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 evaluate information generated from experiments
ll describe and plan techniques used in the laboratory.
J Tests
C=C group Decolourises
brown bromine o You should know the testslisted in Unit 3A above.
in hexane
o You should also know the testsfor alkenes,the OH group and the
C-OH group Steamyfumes halogenin halogenoalkanes.
with PCl.
Organic halides Warm with o You should be able to deducethe identity of a compound from the
sodium resultsof a seriesof tests.
hydroxide
J Techniques
solution. Acidify
with dilute nitric You should be able to describetechniquesusedin:
acid and then o titrations and enthalpy changemeasurements
test as for ionic O simple organic proceduressuch as distillation and heating under
halides as on reflux.
page 55
[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.
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 Observationexpectedfor a positiveresult
Hydrogen Burning splint
Oxygen Glowing splint
Carbon dioxide
Sulphur dioxide Potassiumdichromate(VI ) Solution turns from orange to .

solution acidified with dilute
sulphuric acid.
Moist blue litmus paper Turns red and is then bleached white
t6I
(Total 6 marks)
llune 2002 Unit Test 38 question 2l
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

1 Small pieces 50.0cm' 1.00mol dm-'
z Small pieces 50.0 cm' 1.00 mol dm-' heatedto 80 "C
3 One large piece 50.0 cm' 1.00mol dm-'
4 Small pieces 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

ii Explain the shapeof the curve drawn for experiment 1. 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
ii Basedon your answerto c part (i), suggesta suitablemassof calcium carbonateto use in the
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
temperature beforethe additionand everyminuteafterwards
of the mixturewas measuredimmediately
untilno furtherchangetook place
F e + C u S O o- F e S O o+ C u
Timing Before 1 min 2 mins 3 mins 4 mins 5 mins

addition
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. tu
iii Calculatethe enthalpy changefor this reaction in kJ mol-' r2l
(Total 8 marks)
[une 2002 Unit Test38 question4]
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
ll A pipettewas usedto transfer50 cm'of 2.00 mol dm-'aqeoushydrochloric acid (an excess)to a
100 cm' beaker.The pieceof limestonewas placed in the and
beaker left untiltherewas no more
effervescence.
Equation
CaCO.(s)+ 2HOl(aq)- CaOl'(aq)+ CO'(g)+ H,O(l)
Ill The acidicsolutionin the beakerwas filteredinto a250 cm3volumetricflask.A smallamountof the
solidimpurityremainedin the filterpaper.The solutionin the volumetricflaskwas carefullymadeup
to 250 cm'with distilledwater.
lV 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)

O uNrr TEsrBB
Results
1 2 3
Burettereading(final) 14.90 15.40 30.25
Burettereading(at start) 0.00 0.05 15.40
Titre/cm3 14.90 15.35 14.85
1 4 . 9 0 + 1 5 . 3 5 + 1 4=. 8 5
Meantitre= 15.033cm'
The accuracyof the student'smethod was judged to be poor by his teacher.The teachersuggestedthat
the procedurein II could be improved, and that the titres used to calculatethe mean were incorrectly
chosen.
i Suggest,with a reason, one improvement to the student's procedure in II. I2l
ii Recalculate a value of the mean making clear which titres you choose. r2l
b i Using your answerto a part (ii), calculatethe amount in moles of sodium hydroxide in the mean
titre. tlI
ii Hence state the amount in moles of hydrochloric acid in a 25.0 cm' portion of the acidic solution
transferredin IV. tll
lll Hence calculate the amount in moles of hydrochloric acid remaining after the reaction in II. tll
lv Calculate the amount in moles of hydrochloric acid transferred to the beaker in II. tU
v Hence calculate the amount in moles of hydrochloric acid used in the reaction. tl]
vt Hence calculate the amount in moles of calcium carbonate and the mass of calcium carbonate in
the sampleof limestonelM, (CaCOr)= 100) I2l
vii Hence calculatethe percentageof calcium carbonateby massin the sampleof limestone. tU
The burette used in the titrations had an uncertainty for each reading of +0.05 cm'.
i Which of the following should be regardedas the actual value of the titre in titration 3?
A between 14.80 and 14.90cm':
B between L4.825and 14.875cm3:
C between 14.75 and 14.95cm'. tlI
ii Suggestone reasonwhy a student may obtain volumes outside the uncertainty of the burette when
carrying out a titration. tll
(Total L4 marks)
fJune2001 Unit Test38 question4]
Propan-Z-ol(molar mass60 g mol-1 and boiling temperature82 "C) can be preparedby the reaction
between 6.15 g of 2-bromopropane(molar mass I23 g mol-' and boiling temperature59 "C) and excess
aqueous2.0 mol dm-' sodium hydroxide. This reaction is slow at room temperature.
Describethe procedure,identifying the apparatusthat you would use,to preparea pure sampleof
propan-2-olfrom 6.15 g of 2-bromopropane. tsl
b Calculatethe minimum volume of sodium hydroxide solution that must be taken to ensurecomplete
reaction of the 2-brompropane. r2l
Your teachersuggestedthat an 80o/oyield would be an excellent result. Calculatethe massof pure
propan-Z-olthat you would need to prepareto obtain this yield. r2l
Suggestone reasonwhy your yield will be below 1,00o/o. tu
(Total 1O marks)
4 ?erinry, qMttatun'
e4rulibrrn,arud,
Win nAl
lroryMny
E n e r g e tlilc s
- H.l
C '
\
I
.a- t
Introduction
(H
J This topic extendsthe useof Hess'sLaw to reactionsinvolving ions.

iJ yon must be able to construct a Born Haber cycle.
f] Lattice energyis crucial to the understandingof ionic bonding, because
it is this releaseof energythat makesthe formation of an ionic
substancethermodynamically favourable.
fl Oefinitions of enthalpy changesmust include:
i the chemical changetaking place
ii the conditions
iii the amount of substance(reactantor product)
iv an example of an equation with statesymbols,as this may gain
marks lost through omission in your word definition.
Things to learn
,J fne sign of the value of AIltells you the direction of the movement of
heat energy:
a,H^torchlorine is theenthalpy o positive (endothermic) for heat flowing into the system
change for: o negative (exothermic)for heat flowing out of the system.
%Cl,(g)- Cl(g)
AHn,ofor the Na-ion is the enthalpy [J nntnalpy of atomisation, A.f,Iu,is the enthalpy change for the
change for: production of one mole of atoms in the gas phase from the
Na-(g)+ itQ--+Na-(aq) element in its standardstate.It is alwaysendothermic.
Af{.nfor sodium chloride is the ;J nntnApy of hydration, A.f,foru,is the enthalpy changewhen one
enthalpy change for: mole of gaseous ions is added to excesswater. It is alwaysexothermic.
Na-(g)+ Cl-(g)-- NaCl(s)
[i fattice energy, LII""', is the energy change when one mole of
ionic solid is made from its separategaseousions. It is always
exothermic.
<ffi
LH Thingsto understand
Born-Haber cycle
o This relates the enthalpy of formation of an ionic solid to the
enthalpies of atomisation of the elements concerned, the ionisation
O 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 zcr(g) |
t osn
I vg2.(g)+ ctr(gt
Mg-(g) + Clr(g)
+ zCf (g)
ll * * . l1
Nrz
Mg(S) + Clz(g)
NIl
Mg(s) + Clr(g)
+
I N
C l z (g )-M g C l r(s )
I f I 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
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 "
A , F / " oC
Any one value can be calculated when all the others are known.
Lattice enerry
O Lattice energy is always exothermic.
lf a bondis partially
covalent,the o Its value depends upon the strength of the force of attraction
experimental (from
latticeenergy (sometimes called the ionic bond) between the ions.
BornHaber) willbebigger (more O The strength of this force depends upon the value of the charges and
exothermic) thanthevalue the sum of the radii of the ions:
calculatedfroma purely ionic i the larger the charge on either or both of the ions, the larger (more
model. exothermic) the lattice energy
Thegreater thedifferencebetween
theexperimental andtheoretical ii the larger the sum of the ionic radii, the smaller (lessexothermic)
values,thegreater theextentof the lattice energy.
covalency.Thiswillhappen if the o Theoretical values of lattice energy can be calculated assuming that the
cationis verypolarising(smallor substance is 100o/oionic.
highlycharged) or theanionis very
polarisable(large).Seepage13.
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.
O Group 2 hydroxides. As the radius of the cation increases down the
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
the same), the surn of the radii alters significantly, and so the lattice
energy decreasesby a large amount.
El rrRroDrcrry, quANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMIsTRy
Enthalpy of hydration
o Enthalpy of hydration is alwaysexothermic.
O For a cation it is the result of the force of attraction betweenthe ion
YoumustnotuseaHhyd when
to a compound.
referring to
lt refers and the 6 oxygen in the water.
ions.
separate Theenthalpychange O For an anion it is the result of the force attraction between the ion and
+ ?Q+ Na+(aq)
forNaCl(s) + Cl-(aq) the 6- hydrogen in the water.
theenthalpy
iscalled ofsolution. I The value of enthalpy of hydration will depend upon the value of the
chargeon the ion and its radius:
i the larger the charge,the larger (more exothermic) the enthalpy of
hydration,
ii the larger the ionic radius,the smaller (lessexothermic) the
enthalpy of hydration.
Vorlotion of entholpies of hydrotion in o Group

The value will becomelessexothermic as the radius of the cation increases
down the Group.
Solubility
The direction of a chemical reaction is partially determined by the value of
the enthalpy change.When discussingsolubilities,it is assumedthat the
more exothermic the enthalpy of solution, the more soluble the substance
is likely to be. The enthalpy of solution can be estimatedfrom a
considerationof lattice energiesand enthalpiesof hydration of the two
ions as can be seenfrom a Hess'slaw diagram.
M-(g) + rG)
Notethatbothlatticeandhydration l t
enthalpies numbers,
arenegative
-Aff.nis positive
so
l*'a l*u
MX(s)+ aq
l
(aq)
t
x-(aq)
A H,"rn= - (lattice energy) + (hydration enthalpy of each cation + hydration enthalpy of each anion)
o Solubility of Group 2 sulphates

i The enthalpy of hydration becomesmuch less as the cations
becomebigger.
ii Becausethe radius of the sulphateion is much bigger than the
radius of any of the cations,the lattice energyonly decreases
slightly - seeabove.
iii (i) and (ii) together mean that the enthalpy of solution becomes
considerablyless exothermic and causesthe solubility of the
sulphatesto decrease down lhe Group.
r Solubtlity of Group 2 hydroxides
i The enthalpy of hydration becomesless as the cations become
bigger.
ii Becausethe radius of the hydroxide ion is a similar sizeto that of
the cations,the lattice energydecreases considerably.
iii (i) and (ii) together mean that the enthalpy of solution becomes
considerablymore exothermic and causesthe solubility of the
hydroxides to increase down the Group.
O 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
check to see if vou are correct.
I In each of the following state which compound has the larger (more
exothermic) lattice energy:
a MgCO, a MgCO. or BaCO,
b MgCO, b NarCO. or MgCO,
C NAF 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.
The following data, in kJ mol-', should be used in this question.

tothenumbered
Theanswers
questions
areonpage132. 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).
b 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:
Experimental Theoretical
NaF -918 -912
MgI, -2327 -t944
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.
Things to learn and understand

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:
Na Mg AI Si P S CI Ar
Oxygen Na,O or Mgo Al2o3 sio, PnO,o SO, No No
N a rO,(t) reaction reaction
Chlorine NaCl MgCl, Alcl, (') sicl4 PCI, SrCl, No
(t)
PCl, reaction
Water NaOH + MgO + No No No No HCI + No
H2 H,tn' reaction reaction reaction reaction HOCI reaction
(') ("
Notes: with excessoxygen sodium peroxideis formed, ''' aluminium chloride is covalent, with excess
(n)with
chlorine, steam.
[l uetA hydroxides and oxides

t NaOH alkaline: NaOH(s) + aq - Na-(aq) + OH-(aq)
Thehydroxidesbecome lessbasicand o Mg(OH), basic: Mg(OH),(s) + 2H.(aQ) - Mg'.(aq) + ZH,OQ)
moreacidicasthesurface charge o MgO basic: MgO(s) + 2H-(aq) -- Mg'*(aq) + H,O(l)
of thecationincreases.
density a AI(OH), amphoteric: Al(OH),(s) + 3H.(aQ)- Al'.(aq) + 3H,O(l)
Al(OH),(s) + 3OH-(a9) - Al(OH).3-(aq)
o Al2O3 amphoteric: AlrO.(s) + 6H.(aQ) - 2Al'.(aq) + 3HrO(l)
Al,O,(s) + 6OH-(aq) + 3H,O(l) '2Al(OH)6'-(aq)
[] Non-metal oxides
dioxide
Silicon is sucha weakacidthat
moltensodium hydroxideis required. o SiO, weakly acidic: SiOr(s) + 2NaOH(l) - NarSiO'(l) + HrO(g)
Theoxides of thenon-metals form O P4O6 weakly acidic: PnOu+ 6HrO ' 4H'PO, + 4H-(aq) + 4HrPOr-
strongacidsasthe
increasingly o P4O10 strongly acidic: PnO,o+6HrO -' 4HrPOn- 4H'(aq) + 4HrPOn-
number of oxygen atomsin theacid
increases.
@ THE PERroDrc rABLE rl
I SO, weakly acidic: SO, + HrO --*H2SO3+ H.(aq) + HSO.-

t SO,, strongly acidic: SO. + HrO -- HzSOn-- H'(a9) + HSO,-
iJ cntorides
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)
I Hydrated AlCl, ionic solid, deprotonated by water:
--
[AI(H,O)"]'.(aq) + H,O [A1(H,O),(OH)]'.(ag)+ H,O-(aq)
lonicchlorides in waterto
dissolve r Anhydrous AlCl, covalent solid, reacts with water:
formhydrated ions. AlCl,(s) + 3H,O(l) -'Al(OH),(s) + 3HC|(aq)
Thesehydrated ionsmay w SiCl.,covalent liquid, reacts with water:
deprotonate,if thesurfacecharge Sicl,(l) + 2H'O(l) -- SiO,(s)+ aHCl(aq)
densityof themetalionis high. *r PCll covalent liquid, reacts with water:
Covalentchlorides (ofPeriod3) P C l ,(l )+ 3H .O(l )-- H ,P O,(aq)+ 3H C l (aq)
reactwithwaterto formHCIand
, PCl. covalent solid, reacts with water:
either
theoxideor theoxoacid.
PCl.(s)+ 4HrO(l) - H,PO.,(aq)+ SHCl(aq)
Variation of properties down Group 4

-l The metallic character increases down the Group:
carbon and silicon are non-metallic (not malleable; only graphite
Thetrendin metalliccharacter is conducts electricity)
causedbythedecrease in ionisation germanium is semi-metallic (semi-conductor).
energyastheradius of theatom tin and lead are metallic (malleable and electrical conductors).
increases,
making it energetically
iJ fne +2 oxidation state becomes more stable relative to the +4
fortheformation
favourable of ionic
bonds. 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 -
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 Write equations for the changescausedby the addition of water to:

Theanswerstothenumbered i sodium chloride
questions
areonpages ii silicon tetrachloride
132-133. iii phosphorus pentachloride.
b Relate these reactions to the bonding in the chlorides.
C Explain why silicon tetrachloride, SiCln, reacts rapidly with water,
but tetrachloromethane, CCln, does not react even when heated with
oC.
water to 100
2 Write two ionic equations to show that aluminium hydroxide is
amphoteric.
3 Write ionic equations for the reactions, if any, of:
aqueous acid with:
i magnesium hydroxide
ii lead monoxide
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.
@ c H E M T c A LE e u r L r B R t u M l l
ll
equilibria
Chemical
ffi Introduction
Lry
[l Concentration, in the context of equilibrium, is alwaysmeasuredin
mol dm-', and the concentration of a substanceA is written as [A].
E fne common errors in this topic are to use moles not concentrations
and initial valuesnot equilibrium valueswhen substitutedin
expressionsfor K..
iJ Calculationsof K must be set out clearly,showing eachstep.
J A homogeneousequilibrium is one in which all the substancesare in
the same whereas
phase, in a heterogeneous equilibrium there are two
or more phases.
Thingsto learn and understand

The equilibrium constant K"
The equilibrium constant, measuredin terms of concentrations,is found

from the chemical equation.
o For a reactiont
*A + nB+ rC + yD
where ffi, fl, x and y arc the stoichiometric numbers in the equation:
K. = [C]'"q[D]/"q
[A]'"0[B]'",
Thevalue of ( isspecific
to a
- andto theequation
reaction used All the concentrationsare equilibrium values.
- andcan
thatreaction
to represent
onlybealtered the
bychanging O In a heterogeneousequilibrium a solid substancedoesnot appearin the
temperature. expressionfor K..
o K. is only equal to the quotient [C]' [D]'
tAr tBr
when the systemis at equilibrium.
O If the quotient doesnot equal K., the systemis not in equilibrium and
will react until it reachesequilibrium when there will be no further
changein any of the concentrations.
o K. has units. For the reaction:
Nr+3Hr+2NH.
K. = [NHJr"o
Nrl"o [HJ'"'
the units of K. are (mot d--')' 1

= mol-2 dm6
(mol dm*) (mot d--')'
EI euANTITATtvE EeurLrBRrA AND FUN.TT.NAL GRoup
"t*toDlctry' 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
Animportant
reaction
intheblastfurnace
is theformation
of carbonmonoxide
fromcarbon
andcarbon dioxide.
Thisreaction isanexample ofa
heterogeneous
equilibriu
m.
when1.0molof carbondioxide
washeated withexcesscarbon to a
of700'c ina vessel
temperature ofvolume20dm',g5%ofthecarbon
dioxide
reacted
fo formcarbonmonoxide.calculateK,tor
C(s)+CO,(g) +2C0(g)
o C(s)doesnotappear in theK. Answer.
expression
because it is a solid.
o Theamount of C0 madeis twice C0,(g) co(s)Units
theamountof C0,reacted. Initialamount 1.0 0 mol
Change -0.95 +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-'
K = t!91,*= (0.095),(moldm-s),
= 3.6motdm-3
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
O . 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)
in
isa solidit is ignored
Ascarbon = p(CO)'"' and its units are atm2=atm
160
theexpression.
P(co,)* atm
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
0.080molof PCluwasplaced
in avesselandheated to 175"C.When
it wasfoundthatthetotalpressure
hadbeenreached,
equilibrium was2.0atm
haddissociated.
of thePClu
andthat40o/o K,torthereaction:
Calculate
+ PCl,(g)
PCl,(g) + Cl,(g)
AnswenAs40%haddissociated, 60%wasleft.Thusat equilibrium:
0.60x 0.080= 0.048molof PClu
waspresent
andtherefore
0.080- 0.048= 0.032molof PClu
hadreacted.
PCI. PCI, cr, Total

lnitialamounVmol 0.080 0 0
Change/mol -0.032 +0.032 +0.032
amount 0.60x 0.080
Equilibrium
/mol = 0.048 0.032 0.032 0.112
Molfraction 0.04810.112 0.032t0.1120.032t0.112
= 0.429 =0286 =0296
pressure
Partial 0 . 4 2 x92 0.286x2 0.286x 2
/atm = 0.857 = 0.571 = 0.571
l( = p(PCl,),' = 0.571
p(Cl,),. atm= 0.38atm
atmx 0.571
Variation of K with conditions
Konlyequals thequotient whenthe o Temperature. This is the only factor that alters the value of K.
system is atequilibrium. lf the i If a reaction is exothermic left to right, an increase in temperature
quotientis greaterthanK,the will lower the value of K. This means that the position of
reactionwillmoveto theleftuntil_
equilibrium will shift to the left (the endothermic direction).
thetwoareequal. lf thequotientis
lessthanK thereaction willmove ii If a reaction is endothermic left to right, an increase in temperature
to therightuntilthetwoareequal. will increase the value of K. This means that the position of
Temperature changes alterthevalue equilibrium will shift to the right.
of K(unless AH=0).Concentration
O Catalyst. This neither alters the value of K nor the position of
andpressure changes alterthevalue
equitibrium. It speeds up the forward and the reverse reactions equally.
of thequotient.
Thus it causes equilibrium to be reached more quickly.
H 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
Beforeattempting questionson this topic, check that you:
[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
P(N,) x 104= 81.2kNm-' o Dry air at a pressureof 104 kN m-'contains 78.Io/onitrogen 2I.Oo/o
= x 104=21.8kNm-'
P(0,) 0.210 oxygen and 0.9o/oargon by moles. Calculatethe partial pressuresof
= x 104= 0.9kNm-'
P(Ar) 0.009 eachgas.
O Write the expressionfor K., stating its units, for the following reactions:
8 K= [S0J' = mofl dmg
^ 2SO,(g)+ O,(B)+ 2SO,(g)
tsortoJ b zHcl(g) +'1,o,(g)+ H,o(g) + cl,(g)
b K= [H,0][Cl,] = mofz dmil2
lHctit
ro,r O Write the expressionfor Ko,stating its units, for the following reactions:
a CO($ + 2H,(g)+ CH,OH(g)
d 6=p(CH,0H) atm-' b Fe,O,(s)+ CO(g)+ 2FeO(s)+ CO,(g)
p(CO)
x p(H,))'
b K,=499)no.units 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
p(c0) was found to be presentafter equilibrium had been reached.
ACID-BASE EQUILIBRIA
Calculatethe value of K for the reaction:

Theanswers
to thenumbered
questions
areonpage 133. 2SO,(g)+ 2SO,(g)+ O,(g)
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
presenceof a catalyst.Statewhether thesesubstances are initially in
equilibrium. If not, explain which way the systemwould react.
b Stateand explain the effect on the value of K. and on the position of
equilibrium of:
i decreasingthe temperature
ii decreasingthe pressure
iii adding more catalyst.
(g Acid-base
equilibria
<ffi
W 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 base is a substancethat acceptsan H* ion from
another species.
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 pH = -log,o[H.(aq)],'ormore accurately= -log,o([HrO.(aq)]/mot
dmt).
EI euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy
"r*roDrcrry,
E pOH = -log,olOH-(aq)1.
E pH + pOH - !4 at Z|'C.
tr e strong acid is totally ionised in aqueoussolution, and a weak acid
is only partially ionised in aqueoussolution.
f K, for a weak acid, HA, = tHl tAl / tHAl.
f PK. = -log'o K".
tr e buffer solution is a solution of known pH which has the ability to
resistchanging pH when small amounts of acid or baseare added.
Gffi
1ru, Thingsto understand
t--------!
Coniugate acid,/base pairs

f Theseare linked by an H- ion:
Acid - H' - its coniugatebase:
CH3COOH(acid)- H* + CHTCOO-(coniugatebase)
Base + H* - its coniugate acid:
NH, (base) + H* + NHn*(coniugateacid)
E When sulphuric acid is added to water, it acts as an acid and the water
acts as a base:
HrSOn+HrO- HrO* + HSO*-
acid base coniugateacid of HrO conjugatebaseof HrSOn
J Uydtogen chloride gasacts as an acid when addedto ammonia gas:

HCI+NHr- NHn' + C f
acid base conjugate acid of NH. coniugate base of HCI
pH scale
lf theacidity increases, f Waterpartiallyionises
ofa solution
[H-] increases
butthepHdecreases.
HrO+ H'(aq) + OH-(aq)
As the [HrO] is very large and so is effectivelyconstant, its value can be

incorporated into the K for the reaction:
The2ndionisationofa dibasic
acid K* = tH-] tOH-]= L.0 x LO'nmol' dm* at 25'C
suchasH2S04 isweak. So[H-]for or pH + pOH = \4at25"C
0.321moldm-'H,Soo isnot0.642
moldm-',butis only0.356moldm-' f So at 25 "C:
o A neutral solution is one where [H-] = [OH-], and the pH = 7.
oAnacidicsolutionisonewhere[H]>[oHl,andthepH<
oAnalkalinesolutioniswhere[H]<[oHl,andthepH>
Foranalkaliwith2 0H performula, E pH of strong acids and bases

the[0H-]is 2 x the[alkali].
ThepHof a 0.109moldm-'solution I For a strong monobasicacid:
of Ba(OH),
is pH - -log,o[acid]
pOH= -log,o(2 x 0.109)= 0.66 Thereforethe pH of a O.321mol dm-' solution of
pH= 14- 0.66= 13.34
Therefore HCI = -log,o(0.321)- O.49
Remember thatacidshavea pH< 7 O For a strong alkali with one OH- ion in the formula:
a pH> 7.
andalkalis pOH = -log,o[alkali]and
'
pH =L4- pOH
@ 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)
=/+.SO = 2.37x 10-'mol
x 10*x 0.123) dm-3
pH = -log,o(2.37x10-')
= 2.63
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.
Starting End point Vertical pH Final

pH pH range pH
At halfwayto theendpoint(12.5
Strong acid/strongbase 1 7 3 . 5t o 1 0 . 5 13
cm'if theendpointis at 25cm3),
thecurvefora weakacidanda Weak acid/strongbase 3 9 7 to 10.5 13
strongbasewillbealmosthorizontal Strong acid/weakbase 1 5 3.5 to 7 11
at a pHof about5. Thisis whenthe
solution and[HA]= [A].
is buffered 1 3 Weak acid/ 13
Strong acid/
Thusat thehalfwayPH,FK.= PH
fortheweakacid. 11 1L
9 9
7 7
5 5
3 3
0 2 5 0 2 s 0 2 5
Fig 4.3 Titrationcurves Volumeof alkali/cm3 Volume of alkali/ cm3 Volume of alkali/ cm3
-|l
5il PenroDrcrTy, euANTtTATtvE EeurLrBR|A AND FUNGTToNAL GRoup cHEMTSTRY
Indicators
O For use in a titration, an indicator must change colour within the pH of

the vertical part of the titration curve.
Vertical range of pH Suitable indicator

Strongacid and base 3.5 to 10.5 Methyl orange or phenolphthalein
Weak acid/strongbase 7 to 10.5 Phenolphthalein
Strong acid/weakbase 3.5 to 7 Methyl orange
Buffer solutions
o Theseconsistof an acid/baseconjugatepair, e.g.a weak acid and its salt

such as CH.COOH/CHTCOONa, or a weakbaseand its salt, e.g.
NH3/NH4CI.
o To be able to resist pH changes, the concentration of both the acid and

its conjugate base must be similar.
I Consider a buffer of ethanoic acid and sodium ethanoate. The salt is

ftrlly ionised:
CH3COONa(aq)- CH'COO-(aq) + Na-(aq)
The weak acid is partially ionised:

CH3COOH(aq) + H'(aq) + CH,COO-(aq)
The CHTCOO- ions from the salt suppress most of the ionisation of the
acid, and so both [CH.COOH(aq)] and [CH,COO-(aq)] are large.
If H' ions are added to the solution, almost all of them are removed by
reaction with the large reservoir of CH.COO- ions from the salt:
H-(aq) + CH,COO-(aq) - CHsCOOH(aq)
If OH- ions are added, almost all of them are removed by reaction with
the large reservoir of CHTCOOH molecules of the weak acid:
OH-(aq) + CH,COOH --' CH,COO-(aq) + H,O(l)
Calculotion of the pH of o buffer solution

Consider a buffer made from a weak acid, HA, and its salt NaA.
The acid is partially ionised:
HA(aq)+H.(aq)+A(aq)
Thus K^ = [H-(aq)] [A (aq)]
IHA(aq)l
The saltis totally ionised,and suppresses
the ionisationof the acid,
Therefore[A-(aq)]= [salt]
and [HA(ag)]= [weakacid]
Thus 16.= [H-(aq)] [salt]

lf theconcentrations
of theweak
acidanditssaltarethesame, then: tweakacldf
[H-(aq)]= K^, and = K. trygg&gql
or [H-(aq)]
pH= pK,.
[salt]
pH = -loglH.(aq)l
@ AcrD-BA'E Eeur.-rBR'A
Workpi,oxiloLf.h'
thepH0f 500cm3of a solution
Calculate containing
0.121m01 of ethanoic
acid
and0.100molof sodium ethanoate.
pK^torethanoicacid= 4.76
Answer. gK, = 4.76,
Therefore/( = inverselog(-p0 = 1.74x 10-umoldm-'
[weakacid]= 0.121+0.500 = 0.242moldm-3
[salt] = 0.100+ 0.500 = 0.200moldm-3.
= (.
[H-(aq)] [weakacid] = 1.74x 10u x0.242=2j0x 10-u moldm-'
Isalt] 0.200
pH = -log,o[H-(aq)]
= 4.68
Enthalpy 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 -
E IJ)'I
;
i //,-r.--t---)a
H
Before attempting the questions on this topic, check that you:

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,-
O Calculate the pH of:
a 0.96 a 0 .1 1 mol dm* H C I
b 13.04 b 0.1 1 mol dm-' LiOH
c 13.34 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
areonpages
133-134. 2 25 cm' of a weak acid HX of concentration 0.10 mol dm-t was titrated
with 0.10 mol dm-' sodium hydroxide solution, and the pH measuredat
intervals. The results are set out below:
Volume NaOH/cm3 5 10 T2 20 23 24 25 26 30
pH 4 . 5 4 . 8 4.9 5 . 5 6 . 5 7 . 0 9 . 0 12.o 1 2 . 5
a Draw the titration curve and use it to calculate pK, for the acid HX.
b Suggest a suitable indicator for the titration.
3 a Define a buffer solution and give the name of two substances that
act as a buffer when in solution.
b 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
(H
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..
b 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,
c 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 Geometric. This is caused by having two different Sroups on each

carbon atom of a >C=C< group (see Figure 4.4).
arenot
Thetwoisomers
interconvertible
atordinary
temperatures
because is no
there
rotation a double
about bond. H,C CH, H:C H
\ / \ /
C-C C-C
/ \ / \
H H H CH.
cis-but-2-ene trans-but-Z-ene
Fig . cisond transisomersof but-2-ene
@ oRcANtc cHEMtsrRY tl
Optical. Optical isomers are defined as isomers of which one is the

I
Having grouPs
fourdifferent non-superimposable mirror image of the other.
to onecarbon
attached atomwill
Thus lactic acid (2-hydroxypropanoicacid), cH3cH(oH)cooH'
cause atomis
this.Thiscarbon
a chitalcentre.
called existsas two optical isomers.Thesemust be drawn three
dimensionally so as to show that one is the mirror image of the
other (seeFigure4.5).
COOH COOH
I I
A 50/50mixtureof thetwoisomers
,t\ . F-.-
Hsc /l oH
HO \\ CH,
willhavenoeffect
onPlane H H
polarised Thistypeofmixture
light.
a racemic
iscalled andis
mixture Fig 4.5 Opticol isomersof loctic ocid
often when
theresult chiral
One isomer will rotate the plane of polarisation of plane polarised
substancesareproduced bya
reaction. monochromatic light clockwise and the other will rotate it anti-
chemical
clockwise.
Further reactions
Grignord reagenfs
Thesehave the formula R-Mg-halogensuch as C,HuMgl.They are usedto
increasethe carbon chain length, becausethey are nucleophiles and
contain a 6-carbonatom which will attacka 6'carbon atom in other
compounds.
Preparation
Halogenoalkane+ magnesium
Conditions: dry ether solvent (flammable,thereforeno flames),under
reflux with a trace of iodine as catalyst:e.g.
C2H'I+Mg-CrHrMgI
Reactions
produces
Methanal a PrimarY O + aldehydesto produce (after hydrolysis with dilute hydrochloric acid) a
alcohol. secondary alcohol:
C,H,MgI + CH,CHO- CH:CH(OH)C'H'
butan-2-ol
O + ketones to produce (after hydrolysis) a tertiary alcohol:
C,H,MgI + CH.COCH,- CH3C(CH3)(OH)CrH'
2-methyl butan-2-ol
O + solid carbon dioxide (dry ice) to form (after hydrolysis)a carboxylic
acid:
CrHrMgI+ COr(s)-'CTHTCOOH
propanoic acid
O Grignard reagentsreactwith water to form alkanes:
CrHrMgI+HrO-CrHu
which is why they must be preparedand used in dry conditions.
Corboxylic ocids
Thesehave the functional grouP:
o
/
-C
o-H
EI euANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMIsrRy
"a*roDrcrry,
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:
CH3COOH+ CTHTOH + CH3COOCTH, + HrO
ethyl ethanoate
conditions: heat under reflux with a few drops of concentrated
sulphuric acid.
o + lithium tetrahydridoaluminate(Ill) to produce a primary alcohol:

Testfor a carboxylic
acid.When CH3COOH+ a[H] 'CH'CH,OH + H,O
added toaqueous sodium ethanol
hydrogencarbonate (orsodium conditions: dissolvein dry ether, followed by hydrolysis with H.(aq).
carbonate),it gives
a gas,C0,,
which turnslimewater milky. 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
\
o- R'
Reactionsof ethyl ethanoate
o Hydrolysis with aqueousacid to produce the organic acid and the
alcohol:
CH3COOCTH, + HrO + CHTCOOH+ CTHTOH
Thisreaction
Theacidisa catalyst. ethanoic acid
hasa lowyieldbecause
it isa conditions: heat under reflux with dilute sulphuric acid.
reversible
reaction.
o Hydrolysiswith aqueousalkali to produce the salt of the acid and the
alcohol:
CH3COOCTH, + NaOH - CHTCOONa+ CTHTOH
sodium ethanoate
conditions: heat under reflux with aqueoussodium hydroxide.
Thisreaction hasa highyield
becauseit is notreversible.
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 o
/ /
R-C R-C
\ \
H R'
Aldehyde 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
conditions: dissolve in dry ether, followed by hydrolysis with H-(aq).
Or reduction with sodium tetrahydridoborate(Ill), also to produce an
alcohol:
Theformationofanorange orred
precipitate
with2,4-DNP is a testfor CH3CHO + 2[H] 'CHTCH,OH
carbonylcompounds,i.e.forboth CH3COCH. + 2[H] - CH,CH(OH)CH,
aldehydesandketones. conditions: aqueous solution, followed by hydrolysis with H-(aq).
a Reaction with Z,4-dinitrophenylhydrazine (2,4-DNP) to give an
orange/red precipitate:
NOt NO,
2,4.DNP
Specificreactionof aldehydes
Theformationof thesilvermirror Aldehydesare oxidised to carboxylic acidsby a solution of silver nitrate in
withammoniacal silvernitrateis the dilute ammonia. On warming the silver ions are reducedto a mirror of
testwhichdistinguishesaldehydes, metallic silver.
whichgivea positiveresult,from
Aldehydesare also oxidised by warming with Fehling'ssolution, which is
ketones,whichhaveno reaction.
Aldehydesarealsooxidised by reducedfrom a blue solution to a red precipitateof copper(I) oxide:
potassiummanganate(Vl l) or C H . C H O + [ O ]- C H ' C O O H
potassium
acidified dichromate(Vl).
Iodoform reoction
o This is a reaction which producesa pale yellow precipitate of iodoform,
to dothisis
Theonlyaldehyde CHI3,when an organic compound is addedto a mixture of iodine and
ethanal,
CH3CH0.
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.
CHTCOCTH, producesCTHTCOONa + CHI.(s)
Thisreactionis oftenusedin a All ketonescontaining the CH.C=O group will give this precipitate.
organic'problem' questions.The
O This reaction is also undergoneby alcohols containing the CH.CH(OH)
paleyellow precipitate
produced on
hydroxide and group. They are oxidised under the reaction conditions to the CH.C=O
additionofsodium
iodineistheclue.Theorganic group, which then reactsto give iodoform.
compound thatproduces this Acid chlortdes
precipitate
willeither
bea carbonyl
witha CH,C=Q groupor analcohol Thesehave the generalformula RCOCI,and the functional group is:
witha CH.CH(0H) group.lt is nota
generaltestforketones. 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
Nitrogen compounds
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.
Reactionsof ethylamine
O + acids,to form an ionic salt that is soluble in water:
C2H'NH2+ H.(aq) + CrHrNHr.(aq)
Theaminecanberegenerated from | + acid chlorides,to form a substitutedamide:
a strongalkali.
thesaltbyadding C2H'NH2+ CHTCOCI-'CH'CONHC2H, + HCI
Nitriles
They contain the C=N group, e.g. propanenitrile C,H'CN.
Reationsof propanenitrile
O Hydrolysis either with acid:
CTH'CN+ H* + zHrO - CTHTCOOH + NHn*
canbeprepared
Nitriles bythe conditions: heat under reflux with dilute sulphuric acid
reaction with
ofa halogenoalkane or with alkali'
KCN inaqueous ethanol. crHscN + oH- + Hro'crHrcoo- + NH,
canbeprepared
Hydroxynitriles by
theadditionof HCNto carbonyl conditions: heat under reflux with dilute sodium hydroxide
compounds inthepresenceofbase. 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
conditions: warm and distil off the ethanenitrile.
@ oRGANrc cHEMrsrRY rl
o Hofmann degradation reaction:

CHTCONH, + Br, + 2NaOH - CHTNHT+ COr+ 2NaBr + ZH'O
Amidescanbeprepared fromacid conditions: add liquid bromine to the amide at room temperature, and
+ ammonia.
chlorides then add concentrated aqueous sodium hydroxide solution and warm.
Amidescanbeconverted intoan The amine distils off.
amineeitherwiththesame number Amino ocids
ofcarbonatoms (reduction)
orwith
oneless(Hofmann degradation). These contain an NH, and a COOH group (usually bonded to the same
carbon atom). They react both as acids and bases.
They are water-soluble ionic solids because they form a zwitterion.
NHTCH.COOH + NH,.CHTCOO-
Reactions
o With acids:
NHTCHsCOOH+ H'(aq) - NH,'CH.COOH(aq)
Aminoacidscanbeprepared from t With bases:
chloroacidsbyheating
themin a NH'CH'COOH + OH-(aq) - NH.CH.COO-(aq) + H.O
tubewithanethanolic
sealed
solution
of ammonia.
Figure 4.6 summarises the reactions of organic substances.
CO2.-----------C2H'COOH
HCHO ---------------- C2H5CH2OH
Grignard
CrHrMgBr CH3CHO -------+ C2H'CH(OH)CH3 H2O-CH3COOH
CH3COCH3 + C2H'C(CH,)zOH
Acid C2H'OH ---) CH3COOCzHs
HzO-CrHu chlorides
cH3cocl NH3-CH3CONH2
C2H5OH - CH3COOCTHs CH3NH2+ CH3CONHCH3
Acids
LiAlHn- CH3CH2OH
cH3cooH
H * -C 2H sN H ;
PCl, -----_+ CH3COCI
Amines
c2HsNH2
CH3COCI- CH:CONHC,H'
H- CH3COOH+ CTHTOH
Esters l-
CH"COOC"H.
J I'
OH- ___---_-+ CH3COO- + CTHTOH t- P+Oto- CH3CN
Amides I
CH.CONH, I
H C N -> C (OH )C N L Brr(r)lNaoH-+CH3NH2
Aldehydes and
ketones
2,4-DNP .-+ red precipitate
>C=O
lHl - >CH(OH) H*---+CH3COOH
Nitriles OH --C H 3C OO-
Ag'lNH3---+ CH3COO-+ silver mirror CH3CN
Aldehydes only l-
LiAlHa--+ CH3CH2NH,
CH.CHO I
Fehling's ---------------
CH3COO- + red precipitate
Fig 4.6 Summaryof organicreactions

EI tr*roDrcrry, euANTrrATrvE EeurLrBR'A AND FUN.TToNALGRoup cHEMtsrRy
Checklist
i 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
Testing andunderstanding
ffi
a CH,CH,CH(0H)CH3 * Write the formulae of the products of the reaction of CH,MgI with:
a propanal
b cH,cH,c(0H)(cH3)cH3
b butan-2-one
c CHT CHT O H
c methanal.
a Heatunder reflux
withdilute o State the names of the reagents and give the conditions for the
sodium hydroxide,
thenadd following conversions:
dilute
sulphuricacid.
a C,H'COOCH, to C,H'COOH + CH,OH in a high yield
b Addlithium
Il) indry
tetrahydridoaluminate(l b C2H'COOH to CHTCH,CH,OH.
followed
ether, bydilute
sulphuric
acid.
O State the names of the reagents needed to convert ethanoyl chloride to:
a water a ethanoic acid
b methanol b methyl ethanoate
c ammonia c ethanamide.
o State the structural formulae of the product obtained by reacting:

a Cl-
CH3CH2NH'- a ethylamine with dilute hydrochloric acid
b cH,c0NHcH2cH3
b ethvlamine with ethanovl chloride.
O oRGANrccHEMrsrRYrl
a HeatunderrefluxwithNaOH(aq) O State the conditions for the conversion of:

thenacidify. a ethanenitrile, CHTCN, to ethanoic acid, CH3COOH
b AddLiAlH4 followed
in dryether, b ethanenitrile, CH3CN, to ethylamine, CzHsNHz
bydilutealkali.
c propanamide, CTHTCONH2,to ethylamine, C2HsNHz.
c Warmwithliquidbromine and
concentratedaqueoussodium
hydroxide.
it formsthe,ryitterion
Because O Explain why aminoethanoic acid is a solid that is soluble in water.
-NHrCHS00-
L Draw the stereoisomersof:

Theanswers
to thenumbered
questions
areonpage 134. a CH,CH=C(CI)CH,
b cH.cH(oH)F.
2 Outline how you would prepare2-methylpropanoicacid from
2-iodopropane.
3 Describethe teststhat you could do to distinguish between:
a ethanoic acid and ethanoyl chloride
b propanal and propanone.
EI euANTrrATrvE EeurLrBRrA AND FUNcTtoNAL GRoup cHEMI'TRY
"r*roDrcrry,

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
calculate the lattice energy of magnesium chlodde. [5]
AIflkJ mol-'
-364
lst electron affiniW of chlorine
1st ionisation energyof magnesium +736
2nd ionisation energyof magnesium +1450
Enthalpy of atomisation of chlorine +LZL
Enthalpy of atomisationof magnesium +150

-642
Enthalpy of formation of MgClr(s)
b Use the following to answer the questions in this section.
AfflkJ mol-'
-1480
Enthalpyof hydration of Sr'.
-1360
Enthalpy of hydration of Ba'.
-460
Enthalpy of hydration of OH-
Lattice energy of Sr(OH)'(s) -r894
-L768
Lattice energy of Ba(OH)r(s)
I Explain why the lattice energyof strontium hydroxide is different from that of barium hydroxide.[2]
ll fxplain why the hydration *tfrutpy of a cation is exothermic. l2l
lll Use the lattice .n.igy and hydration enthalpy values to explain why barium hydroxide is more
soluble in water than strontium hydroxide. t4l
(Total 13 marks)
lJanuary2001 CH 3 question4l
2 a i Give the structural formula of a nitrile, CnHrN,that has an unbranched chain tll
ii primary amines can be made by reducing nitriles. Suggesta reagentthat could be used for this
purpose. tlI
iii Draw the structural formula of the amine producedby reducing the nitrile given in a part i. tU
i What feature of an amine molecule makesit both a baseand a nucleophile? tlI
ii Give, by writing an equation, an example of an amine acting as a base tll
Ethanoyl chloride, CHTCOCI,reactswith both amines and alcohols
i Give the full structural formula of the compound producedwhen ethanoyl chloride reactswith
ethylamine, CrHrNHr. tll
ii Name the type of the compound producedin c part i. tU
iii Stateone of ihe advantagesof reacting ethanoyl chloride with ethanol to make an esterrather than
reacting ethanoic acid with ethanol. tU
iv Write the full structural formula of the estermade in c part iii tll
(Total 9 marks)
-
ffanuary2002 Unit Test4 question5 modified]
PRACTICE
3 Compound X is a secondaryalcohol which has a molecular formula of CnH,oO.

X exhibits optical isomerism.
a Draw the structural formulae of the two optical isomersof X. l2l
b Suggestreagentsand conditions which would enable its preparationvia a reaction involving a
Grignard reagent.(You are not expectedto describehow you would preparea Grignard reagent) t3I
c Compound Y is obtained by oxidising the secondaryalcohol X with potassiumdichromate(Vl)
acidified with dilute sulphuric acid.
i Draw the structural formula of Y. t1l
ii To which classof compoundsdoesY belong? t1I
iii Describethe testsyou would do on Y, and the resultsyou would expect,to show that your
classificationis correct. t4I
iv Both X and Y give a yellow precipitatewhen treatedwith iodine in the presenceof sodium
hydroxide solution. Write the structuralformulaeof the organicproductsof this reaction. l2l
(Total 13 marks)
lJwte2OO1CH I questiotr1- modiftefl
At about 1000oC,when aluminium chloridevapour is heatedwith solid aluminium, the following

equilibrium is set up:
AlCl.(g)+ 2Al(s)-'3AlCl(g)
a Give the expression for the equilibrium constant, Kr, for this reaction. IU
b At a particular temperature,a mixture of the above systemat equilibrium was found to contain 0.67 g
of AlCl, and 0.63 g of AlCl vapoursat an equilibrium pressureof 2.0 atm. Calculatethe value of the
equilibrium constant,Ko,at this temperature,statingits units. t4l
c The position of equilibrium moves to the right as the temperatureis raised.Statewhat this suggests
about the enthalpy changefor the forward reaction. tll
d State,with reasoning,the effect of an increasein the pressureon the systemon the value of the
equilibrium constant and on the position of the equilibrium. t3I
e Suggesthow this reversiblereaction could be used in a processto recyclealuminium by extracting it
from impure aluminium. r2l
(Total LL marks)
lJune2001 CH3 question3l
S a i Write an equation for the reaction betweenmagnesiumoxide and dilute sulphuric acid, including
the statesymbols. r2l
ii Describewhat you would seeduring this reaction. r2l
b i Write an equation for the reaction between phosphorus(V) oxide and aqueous sodium hydroxide
solution. r2l
ii With the aid of two equations, show how aluminium hydroxide exhibits amphoteric behaviour.
t3I
c With reference to the reactions in a and b, describe the variation in the metallic character of the
elements across Period 3 of the Periodic Table (sodium to argon) tzl
d Suggest,with reasoning,the acid-basecharacterof Indium(III) oxide, InrOr. Indium is the fourth
element down Group 3 of the PeriodicTable. I2l
(Total L3 marks)
llune 2002 Unit Test4 question4l
EI quANTrrATrvE EeurLrBR'A AND FUN.TT.NAL GRoup cHEMrsrRy
"a*roDlcrry,
6a In the context of Brdnsted-Lowryacid-basebehaviour,explain the terms:

acid weak acid dilute acid. t3l
b i Define pH tll
ii 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
c 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
d The concentration of hydrogen ions in a 0.100 mol dm-' solution of sulphuric acid is 0.105 mol
dm-t.
I Write equationsto show the two successive
ionisations of sulphuric acid, H2SO,,in water. tzl
ll 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
5 Tt'a*actn k(/t44"etal,r,
qMrtatttv MiLr ar4d,
orgaJ,ur,Mtty
@ R edox
equi l i bri a
t-fi Inftoduction
i rtl.--1
H
t You must revise Topic 1.5 (lntroduction to oxidation and reduction).

* The sign of E' indicates the direction of spontaneous reaction.
t A useful mnemonic is OIL RIG. When a substance is Oxidised It Loses
one or more electrons, and if Reduced It Gains one or more electrons.
o A half equation always contains electrons.
o Half equation data are usually given as reduction potentials, i.e. with
the electrons on the left-hand side.
o An oxidising agent becomes reduced when it reacts.

The standard hydrogen electrode
z(g)
+_ This consistsof hydrogen gasat 1 atm pressurebubbling over a platinum
atm electrodeimmersedin a 1 mol dm-' solution of H'ions, at a temperature
of 25 "C. By definition the potential of a standardhydrogen electrodeis
zero(seeFigure5.1).
Standard electrode potential, E'

f This is the electricpotential (EMF)of a cell composedof the standard
H*(aq) electrodeconnectedto a standardhydrogen electrode,measuredwhen
1 mol dm-3 the concentrationsof all the ions are 1 mol dm-3,the temperatureis
25 "C and any gasesare at 1 atm pressure.
Fig 5.1 A stondord hydrogen electrode O for a metal the standardelectrodepotential is when the metal is
immersedin a solution of its ions at a concentrationof 1 mol dm-t.
For the reaction:
Zn'.(aq)+2e-- Zn(s)
it is for a zinc electrodeimmersedin a 1 mol dm-' solution of Zn2'
ions at 25 "C.
o for a non-metal the standardelectrodepotential is when the non-
metal at 1 atm pressure(or a solution of it at a concentrationof
1 mol dm*) is in contactwith a platinum electrodeimmersedin a
EI t*oNsrrroN 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 ' - tE D . R G A N t c c H E MI s r R y
solution of the non-metal's ions at a concentration of 1 mol dm-'

at 25 "C.
For the reaction:
'lrcl,(g)+e +Cl-(aq)
it is for chlorine gas,at 1 atm pressure,being bubbled over a

platinum electrodedipping into a 1 mol dm-'solution of Cl- ions
at 25 "C.
o for a redox system of two ions of an element the standard
electrodepotential is when a platinum electrodeis immersedin a
solution containing all the ions in the half equation at a
concentration of 1 mol dm-t.
For the reaction:
Fet.(aq)+e+Fe'.(aq)
it is for a platinum electrodeimmersedin a solution which is 1 mol
dm-t in both Fet*and Fe'*ions at 25 "C.
O The equationsare alwaysgiven as reduction potentials, i.e. with the
'lr}l,+ e-+ Cl-E+= +1.36V
electronson the left.
'lr}f,+ e-+ Bi E+= + 1.07V
O Comparing substanceson the left of two half equations,the one with
As+1.36> +1.07, is a
chlorine
stronger than
agent
oxidising the larger positive value of E'is the more powerful oxidising agent (it
bromine. is the most easily reduced).
o Comparing substanceson the right of two half equations,the one with
the smaller positive (or more negative) value of E'is the more
powerful reducing agent.
Sno* + 2e-=.Sn'-E* = +0.15V Calculation of -8..".,"" (E""o)

F e t * + e - + F e f' * = + 0 . 7 7 V
As+0.15< +0.77, Sn"ionsarea The value can be deducedin one of three ways:
betterreducing agentthanFe'-ions. L From a cell diagram:
E = Eright-hand electrode - Et"rt-n"na electrode
"tt
If E""uworks out to be a negativevalue, |ou have written the cell
diagram backwards,and so the reaction will go right to left.
2 From an overall equation: write both half reactionsas reduction
potentials, i.e. with electronson the left.
is calculatedas:
E,"".tio.
= (E of half equation of the reactant being reduced) - (E of

E,"u.tio,
half equation of reactant being oxidised.
Thus for the reaction:

Zn(s)+ Cu'*(aq)+Znz*(aq)+ Cu(s)
The half equationsare:
Cu2.(aq)+ 2e--- Cu(s) E' = +0.34 V
Zn'.(aq) + 2e-=. Zn(s) E' = -0.76 V
In the reaction the Cu2*ions are being reduced(electrongain), and the
zinc atoms are being oxidised (electronloss):
Et,""*.n= +0'34 - (-O'76)= +1'10 V
3 From half equations:
To do this one of the half equationshas to be reversed(seeWorked
examplebelow). This processaltersthe sign of its Eo.
.:r,i"{FF.;
ri;.
E
rag'
REDox EeurLrBRrA
O
oxiloLph,
WorkêoL
Whena redoxhalfequation is
reversed,itssignmustbechanged. datato deduce
Usethefollowing andthevalueof E*,,.o.n
equation
theoverall
Thenumber of electrons ontheleft- forthereaction
between potassium
acidified andiron(ll) ions.
manganate(Vll)
handsideof onehalfequation must i MnOi(aq) + 5e--- Mn"(aq)
+ 8H-(aq) + 4H,0(aq) Es = +1.52V
equalthenumber ontheright-hand + e-+ Fe'-(aq)
ii Fe&(aq) f = +0.77V
sideof theotherhalfequation.
Whena redoxhalfequation is
multiplied,itsE+valueis not
Answer.
Reverse (ii)andmultiply
equation it by5.Then (i):
addittoequation
altered. V)= -0.77
thatthereactants
+ 5Fe'-(aq)
5Fe'-(aq) + 5e- f =-(+0.77 V
Always ensure
+ 8H-(aq)
Mn0i(aq) + 4H,0(l) E+= +1.52V
+ 5e-+ Mn"(aq)
thatarespecified in thequestion
(heretheyareiron(ll) and -- Mn"(aq)
(aq)+ AH;1aq;
MnO, + 5Fe'-(aq) + Sre'-(aqi
+ 4H,O(l)
manganate(Vll) ions)are0ntheleft-
f,*t, = 4J7 + 1'52= +0'75
V
handsideofthefinaloverall
equation.
Stoichiometry of an overall equation
The total increasein oxidation number of one element must equal the
total decreasein another.
Inthereaction
above,theoxidation
number ofthemanganesedecreases Spontaneous change
by5 from+7lo +2,andastheiron
increasesby1,theremustbe5 O Electrode potential data can be used to predict the feasibility of a
ionsto eachMnOo-
iron(ll) ionin the chemical 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.
reaction takes place.
Potassium manganate(Vll) titrations - estimation of

reducing agents
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
25.0cm'ofa solution of iron(ll)
sulphatewasacidified,andtitrated
against
0.0222 moldm-'potassium manganate(Vll) cm3wererequired
solution.23.4
Theratioof iron(ll)to to givea faintpinkcolour. theconcentration
Calculate oftheiron(ll)
sulphate
manganate(Vll) ionsin theequation solution.
is 5:1andsothenumber of moles Answer: Theequation forthereaction is:
of Fe'-is 5 timesthenumber of MnOi(aq) + 8H.(aq) - Mn'*(aq)
+ SFe'.(aq) + 4H,0(l)+SFe3.(aq)
molesof manganate(Vl l). Amount ofmanganate(Vll) =0.0222x23.411000 = 5.195 x 1Q mol
= 5.195 =
x 10*x 5/_t x 10-'mol
Amount ofironlillsuldnaie - 2.597 _?
-
Concentrationof iron(ll)
sulphate=2.597 x 10 + 0.0250 = 0.104moldm
Iodine/thiosulphate titrations - estimation of oxidising

agents
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,
25.0cm'ofa solution peroxide,
of hydrogen H,0,,wasaddedto anexcessof
potassium
acidified iodide andtheliberated
solution, iodine
required23.8cm'
of0.106moldm-'sodium thiosulphate
solution. theconcentration
Calculate of
thehydrogenperoxide
solution.
Theratioofiodine
tothiosulphate
ionsis1:2,sothemolesofiodine Answen fortheoxidation
Theequation ofiodide peroxide
ionsbyhydrogen is:
moles
are'lrthe ofthiosulphate. Hr0r+2H.+21--lr+2Hr0
Amount
ofsodium = 0.106
thiosulphate x 23.8/1000 =2.523 x 10-'mol
Amount produced = 2.523
ofiodine x 10-'x 112 = 1.261x 10-'mol
ofhydrogen
Amount peroxide= 1.261
x 10-3x 1/1 = 1.261x 10-3
mol
of H,0,
Concentration = 1.261 + 0.0250 = 0.0505
x 10-3 moldm-3
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
O
ttWrkpj, oxiloLPb
inaqueous
ionsdisproportionate
Willcopper(l) to copper
solution and
ions?
copper(ll)
+ e-+ Cu(s) Es= +0.52
Cu-(aq) V
Cu'-(aq)e-+ Cu'(aq)Eo= +0.15
+ V
AnswenReverse thesecond andaddit tothefirst.Thisgives
equation the
equation:
20u-(aq)+ Cu*(aq) - +0.52
+ Cu(s) E*o,, - (+0.15)= +0.37 V
BecauseF,,,,is positive, isfeasible,
thereaction andsoaqueous ions
copper(l)
willdisproportionate.
Corrosion (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).
oz(g) a At the anodic areasiron atoms become oxidised and lose 2 electrons:
Fe(s) -* Fe'*(aq) + 2e-
o 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)
I Finally oxygen oxidises the iron(Il) hydroxide to iron(lll) oxide (rust):
Fig 5.2 Rusting 2Fe(OH)r1s;+'/,O,(aq) - Fe,O.(s)+ 2H,O(l)
Prevention of corroslon
Stainlesssteelis ironcontaining a
highproportion of chromium, which This can be done by:
formsa protective layerof Cr,0, O placing a physical barrier between the steel and the environment. Such
overthewholesurface of themetal. barriers are paint, tin or chromium plating.
lf thesurfaceis scratched, a new o adding a sacrificial metal. This can be done by coating with zinc
protectivelayerof Cr,O,is formed. (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
At the cathode (reduction) which is positive:
Thereactions for chargingthecell PbO,(s)+2e- + SO,z-(aq) + 4H.(aQ)- PbSO.(s)
+ 2H,O(t)
aretheopposite, andonlytakeplace
E u = + 1 . 6 9V
if a potential
>2.05V is applied, with
theanodebeingconnected to the The overall discharging reaction is:
negativeterminal of thecharging Pb(s) + PbO,(s) +ZSOn'-(aq)+ 4H.(a9) -ZPbSOn(s) + 2H,O(l)
s0urce. E' = +1.69 + (+0.36) = +2.05 V
l. I
92 Ei t*oNsrrroN METAL', quANTrrATrvE KTNETIcs AND AppLtED oRGANtc cHEMISTR'
o .rH
-; I Checklist
.,-H
(H
Beforeattemptingthe questionson this topic, checkthat you can:

iJ Define standardelectrodepotential.
-J Describethe construction of a standardhydrogen electrode.

iJ Write half equationsand usethem to deduceoverallequations.
,J Predictthe feasibilityof redox and disproportionationreactions.
J Deduceoxidation numbersand usethem to balanceredox equations.

rJ Recallthe principlesof manganate(Vll)and thiosulphatetitrations.
ii Recallthe corrosionof iron and its prevention.
'J Understandthe chemistry of the tead/acidbattery.
and understanding
For the following set of questions, cover the margin before you answer,
I Write the equation representing the reaction that takes place in a
'/, H,(g)+ H-(aq)
+ e-. standard hydrogen electrode.
Statesymbols areessential.
f What are the conditions, other than temperature, for this electrode?
H,(g)at1 atmpressure,
=1moldm-'
[H-(aq)] * What are the oxidation numbers of manganese in MnOn- and in Mn'.?
+7 and+2 and in SOn'-?
What are the oxidation numbers of sulphur in SO-,2-
.r, What is the ratio of SOr'- to MnOn- in the reaction between them?
numbers
5:2Sothatoxidation of
bothchangeby10 O Why is it not necessaryto have an indicator present in potassium
manganate (VII) titrations?
ionsare
themanganate(Vll)
Because
intensely
coloured. L a Write ionic half equations for the reduction of:
i CrrOrt to Crt* in acidic solution E' = +1.33 V
tothenumbered
Theanswers Eu = +0.15 V
questions ii Snn*to Snr*
areonpages
136-137.
iii Iodate(V) ions, (IOr) to I, in acidic solution E'= +1.19 V
iv I, to I- E ' = + 0 . 5 4V
b values and hence
Write overall ionic equations, calculate E,"u.,,o,
comment on the feasibility of the reactions between:
i potassium dichromate(Vl) and tin(Il) chloride in acid solution
ii potassium iodate(V) and potassium iodide in acid solution.
2 1.32 g of mild steel filings was reacted with excessdilute sulphuric acid,
and the resulting solution made up to a volume of 25O cm'. 25.0 cm'
samples of this were titrated against 0.0200 mol dm-' potassium
manganate(Vll) solution. The mean titre was 23.5 cm'. Calculate the
percentage of iron in the steel.
3 Write the half equations for the redox reactions involved in the
corrosion of iron.
T n a r u s r r r o N M E T A Lc H E M r s r R Y
@
i ;;';rnistrY
ITf;t,ir
@ Transition
Introduction
'..J You should know the colour of the aqua complex ions and of the
hydroxides of the d block elements scandium to zinc.
iJ you must be able to link the reactions in this topic to the theory of
redox equilibria, Topic 5.1.
g -,tHr o
H
, &-- Things to learn
which the highest occupied energy
" d block elements are those in
Neither
scandium norzincis a levelisadorbital.
theyarein
metalalthough
transition
c A transition element is one that has at least one of its ions with a
thed block,becausetheirionshave
partly filled d shell.
[Ar]3do,4so
structure
theelectronic
4sorespectively.
and[Ar],3d'0, *' Electron structure of the atoms
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Notethatthenumber ofd electrons 3d 1 2 3 J 5 6 7 8 10 10
thatCr
leftto right,except
increases
andCuhave 4s'electron structures, 4s 2 z 2 1 2 2 2 2 I 2
whereastheothers have is
4s'.This
becausestabilityisgainedwhen the Electron structure of the ions. The element first loses its 4s
ishalffullorfull.
d shell electrons when forming an ion. Thus the electron structures of iron and
its ions are:
Fe [Ar], 3d6, 4s2
Fe'* [Ar], 3d6, 4so
Fet* [Ar], 3ds, 4sn
Properties of transition metals
Complex ion formotion

o Bonding in complex ions. The simplestview is that the ligands form
dative covalent bonds by donating a lone pair of electronsinto empty
orbitalsof the transition metal ion. Thesecould be empty 3d, 4s, 4p or
4d orbitalsin the ion (e.g.seethe arrangementof electronsin boxesin
Figure5.3).
3d 4s 4p
| | | | t l Fl--T'f
\E
Fig 5.3 Electronarrongement in the
hexo-aquoiron(ll)ion Fe2*electron
/ \ ,rrurro electrons: ,i* puir,/
TRANSTTTON METALS, QUANTTTATTVE KTNET|CS AND APPLTED ORGANTC CHEMISTRY
Typical ligands are:

neutral molecules: HrO (aqua), NH. (ammine)
anions: F- (fluoro), Cf (chloro), (CN)- (cyano).
o Shapesof complex ions (seepages 14-15). If the complex ion has 6 pairs
of electrons donated by ligands, the complex will be octahedral. This
is so that the electron pairs in the ligands will be as far apart from each
other as possible.
Coloured complex ions

a If the ion has partially filled d orbitals, it will be coloured. Sc'* and Ti'*
have d0 structures, and Cu. and Zn'* have dto and so are not coloured.
o d orbitals point in different directions in space, and so interact to
different extents with the electrons in the ligands.
O This causes a splitting of the d orbitals into two of higher energy and
isturquoise
[Cu(H,O)r]'. blue, three of lower energy.
[Cu(NH.)*(H,0),1'. blue,
isdeep and I When white light is shone into the substance, a d electron is moved
isyellow.
[CuCl.]'- from the lower energy to the higher energy level.
o The frequency of the light that causesthis iump is in the visible range,
so that colour at this frequency is removed from the white light.
t The colour depends on the size of the energy gap which varies with the
metal ion and with the type of ligand.
Vorioble oxidotion stote

Hydrated cations
ofcharge4+or o Successiveionisation energies increase steadily until all the 4s and the
moredonotexistbecause thesum
3d electrons have been removed, after which there is a large jump in
ofalltheionisation istoo
energies
the value.
largeto becompensatedforbythe
hydrationenergy. o Formation of cations. The increase between successiveionisation
Copper formsCu.andCu'*, and energies is compensated for by a similar increase in hydration energies.
chromium Cf. andCr'.. Thus cations in different oxidation states are energetically favourable for
all transition metals.
O Formation of covalent bonds. Transition metals can make available a
variable number of d electrons for covalent bonding. The energy
required for the promotion of an electron from a 3d to a higher energy
orbital is compensated for by the bond energy released.
o Formation of oxoions. In ions such as MnOi, VOr-, VOi and VO2-,the
oxygen is covalently bonded to the transition metal which uses a
varying number of d electrons.
O Manganese exists:
in the +2 state as Mnt*
in the +4 state as MnO,
in the +6 state as MnOn'-
in the +7 state as MnOn-.
Catalytic octlvity
Tlansition metals and their compounds are often good catalysts.
O Vanadium(V) oxide is used in the oxidation of SO, to SO, in the contact
process for the manufacture of sulphuric acid.
o Iron is used in the Haber process for the manufacture of ammonia.
O Nickel is used in the addition of hydrogen to alkenes (hardening of
vegetable oils).
I
TneNsrTroN METAL cHEMIsTRY
@
Reactions of transition metal compounds
Reoctionswith sodium hydroxide ond ommonio solutions

The table givesa summary of thesereactions.
lon
a
Colour Addition of ExcessNaOH(aq) Addition of ExcessNHr(aq)
NaOH(aq) NH.(aq)
Cr'* Green Green ppt Green solution Greenppt Ppt remains

Mn'* Palepink Sandypptb Ppt remains Sandyppto Ppt remains
Fe'* Palegreen Dirty green ppt' Ppt remains Dirty green ppt' Ppt remains
Fe'* Brown/yellow Foxy red ppt Ppt remains Foxy red ppt Ppt remains
Ni'* Green Green ppt Ppt remains Greenppt Blue soln
Cu'* Paleblue Blue pptd Ppt remains Paleblue ppt Deepblue soln
Zn'* None White ppt Colourlesssolution White ppt 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).
Amphoterichydroxides'redissolve' O When an alkali such as sodium hydroxide is added, the equilibrium is
strongalkali,
in excess e.g. 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:
andZn(0H),(s)+ 20H-(aq)
[Zn(0H),]"(aq). lFe(H,O),1'.(aq)+ 3OH-(aq) - Fe(OH),(s)+ 6H,O
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
O When aqueous ammonia is added to aqua complexes of d block
is used
Thisreaction asa testfor: elements such as those of nickel, copper and zinc, ligand exchange takes
withaqueous
a nickel(ll): ammonia place and a solution of the ammine complex is formed.
ionsfirstgivea green
nickel(ll) reaction:
First the hydroxide is precipitated in a deprotonation
precipitate
which thenforms a
bluesolutionwithexcess [Cu(H,O)J'.(aq) + 2NH,(a9) -Cu(OH),(s) + 2NH..(aq) + 4H,O
ammonia. The hydroxide then ligand exchanges to form an ammine complex with
ionsgivea pale
b copper(ll) blue excessammonia:
precipitate
whichforms a deep
bluesolutionwithexcess Cu(OH),(s) + 4NH,(aq) +ZH,O -- [Cu(NH.)*(H,O)J'. + 2OH-(aq)
ammonia and The final result is that the NH, ligand has taken the place of four HrO
c zincionsgivea whiteprecipitate ligands.
which formsa colourlesssolution
O Addition of cyanide ions to iron(Il) ions produces a solution of
withexcess ammonia.
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 chemistry
o Vanadium 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: yellow caused by VO'.(aq)ions (+5 state)
then: green caused by a mixture of yellow VOr.(aq) and blue
VO'z.(aq)
then: blue caused by VO'z.(aq)ions (+4 state)
then: green caused by V't(aq) ions (+3 state)
finally: 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 E€values
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 VO,* +5
V O r * + 2 H *+ e + V O ' . + H r O E € = + 1 . 0V A
Fe'* +e --Fe'* E' = +O.77Y Fet* CT,
'lrclr+e- +cl- E ' = + 1 . 3 6V V
+4 VO,' +4
vo'* +2H*+e-+vt*+Hro Eu = +0.34V AFe'*
Snn* +2e- +Sn2* E ' = + 0 . 1 5V Sn'*
Fet* +e +Fet* Eu = +O.77Y V
+3 V,* +3
Vt* +e +V'* E' = -0.26 V ' 4.H'
Z r' t' * + 2 e - + Z n E' = -0.76V II znlH.
H* + e- +'lrH, Eu = 0.00 V V
+2 v'* +2
8t..,, for the reduction of: Et for the oxidation of:

",, -
VOr*by Fe'. = +1.0- (+0.77) - +O.23Y V'* by H. = o.o (-0.26) - +0.26Y
VO'* by Sn'*= +0.34- (+0.15)= +0.19V V3*by Fe3* = +O.77- (+0.3a) = +0.43V
v'. by Zn - -0.26 - (4.7 6) = +0.50V VO'* by Cl, = +1.36 - (+1.0) = +0.36V
'?\i
-H
l//H
t Checklist
H
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
o
," .Testing
- o - ( your knowledge
and understanding
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.
v is [Ar],3d',4s'. v'- is 1Ar1,
3d'
turquoise-blue,
ICu(H,0),]'- State the formula and colour of the aqua complex of copper(ll).
H,),(H,0),1'.
[Cu(N darkblue * State the formula and colour of the ammine complex of copper(ll).
Dative
covalent(ligand
to ion)and o Name the types of bonding in the aqua complex of iron(Il).
(withinthewatermolecule)
covalent
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).
o State the type of reaction that occurs when excess aqueous ammonia is
Ligand
exchange added to a solution of the aqua complex of copper(Il).
+5,V0r*,yellow.+4,V0'-,blug. o What are the oxidation states of vanadium? Give the formula and the
+3,V'*,green.+2,\f*,lavgndgr. colour of the cation for each oxidation state.
process
lronintheHaber to o Give an example of the use of iron as an industrial catalyst.
manufacture
ammonia o Give an industrial use of a vanadium compound as a catalyst.
oxideintheContact
Vanadium(V)
process
to manufacture
sulphuric
acid
tothenumbered 1
Theanswers Explain why the [Cu(H,O)u)'. ion is coloured.
questions
areonpages
137-138. 2 Give the equations for the reactions caused by small additions of
sodium hydroxide solution, followed by excessto:
a a solution of the aqua complex of chromium(Ill)
b a solution of the aqua complex of iron(Il)
c a solution of the aqua complex of zinc(Il).
Give the equations for the reactions caused by small additions of
ammonia solution, followed by excessto:
a a solution of the aqua complex of iron(III)
b a solution of the aqua complex of copper(Il).
4 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 Thingsto learnand understand
lry
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 of compounds with a carbon-containing side

chain
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:
CuHsCzHs + 6[0] + OH-- C'HTCOO-+ CO, + 3HrO
conditions: heat under reflux with potassiummanganate(Vll)and
aqueoussodium hydroxide.
oncerurc cHEMrsrRY lll
@
Phenol
OH
isa weaker Although it forms some hydrogen bonds with water, it is only partially
Phenol acidthan
carbonic andsoit willnot
acid, soluble and forms two layerswhen addedto water at room temperature.
C0,fromsodium
liberate hydrogen o + alkali. Phenol is a weak acid and it forms a colourlesssolution with
carbonate,
unlike
carboxylicacids aqueoussodium hydroxide:
whichwill. C6HsOH(l) + OH-(a9)- CuH'O-(aq) + H,O(l)
O + bromine water. The presenceof the OH group makessubstitution
into the benzenering much easier.No catalystis required:
OH OH
nr--r\',,nr
A +
(aq)+3Brr(aq) (s)+3HBr(aq)
|!|J
V
Br
observation: when brown bromine water is added, a white precipitate is

rapidly formed.
I + acid chlorides. Phenol reacts as an alcohol, and an ester is formed:
C6H'OH + CHTCOCI' CHTCOOC'H, + HCI
Phenylamine
Phenylaminehas a NH, group attachedto the benzenering.
Preporotion
Nitrobenzeneis reducedby tin and concentratedhydrochloric acid when
heatedunder reflux. Then sodium hydroxide is addedto liberate the
phenylamine, which is removed by steamdistillation.
Reoctions
O + acid
C6H'NH2+ H.(aq) - CuHTNH'.(aq)
o + nitrous acid
Thesolutionof diazoniumionscan C6H'NH2 +2H* +NOr--CuHrNr.+ZH.O
withphenol.
react A yellow
precipitate
ofdiazo compound is conditions: add dilute hydrochloric acid to phenylamine and cool the
'C. Sodium nitrite solution is then added,keepingthe
obtained. solution to 5
temperafurecloseto 5 "C and above0'C.
El t*oNsrTroN METAL', euANTrrATrvE KrNETrcs AND App'tED .RGANIc cHEMtsrRy
Mechanisms
A curly arrow (fJ ) representsthe movement of a pair of electrons,either
from a bond or from a lone pair. A half-headedarrow (f\) representsthe
movement of a single electron.
Ensurethatthecurlyarrowstarts
froma bondor anatomwitha lone Homolytic, free radical substitution
pairofelectrons.
Ensurethatthearrowpoints Reoction befrnreenon olkone ond chlorlne or bromine
towardsanatomeither forming
a O An exampleis shown of reaction betweenmethane and chlorine.
ionor a newcovalent
negative bond.
O There are three stagesin this type of reaction:
1 Initiation: light energycauseshomolytic fission of chlorine:
Clr- 2g,1'
2 Propagation: each propagation step involves a radical reacting
with a molecule to produce a new radical:
CHn+ Cl'- CHr' + HCl
then CHr' + Cl, - CH.CI + Cl' etc.
3 Termirtation: involves two radicalsioining with no radicalsbeing
produced,€.S.
CHr'+CHr'tCrHu
Homolytic, free radical addition
Polymertsotlon of ethene
wayof polymerising
Another ethene
titanium
isbyusing tetrachloride The conditions are a very high pressure(1000 atm) and a trace of oxygen.
andaluminium butthisis
triethyl, The conditions produce radicals,R', which attack an ethene molecule:
mechanism.
nota homolytic R' + H,C=CH,- R-CH2-CH''
then R-CHr-CH 2' * H2C=CH, -- R-CH'-CHr-CH,-CHr' etc
Heterolytic, electrophilic addition
Reoctlonsof olkenes wlth hologens or hydrogen holldes

The reaction takes place in two steps:
1 The electrophileacceptsthe n electronsto form a new bond with
ofa hydrogen
Withtheaddition one of the carbon atoms and at the sametime the Br-Br bond
halide
to anunsymmetricalalkene, breaks.
thehydrogenatomaddstothe 2 The intermediate carbocationthen bonds with a Bf ion.
carbon which
alreadyhasmore
hydrogenatoms bonded
directly to
it. A
Thisis because
carbocation,
t t l
thesecondary
\
Br- Br
H,C - CH,
lT'fl]
L"r.
- C*HrJ
Br
t
H2C-
Br
CHz
l
-C-C-C-
e.o.
-
l @ l
thana primary
is morestable one.
t t l Heterolytic, electrophilic substitution
- -C-C-O
e,o. t t Ol
Nltratlon of benzene
1 Sulphuric acid is a strongeracid than nitric and so protonatesit:
HrSOn+ HNO, - HrNOr'+ HSO;
then the cation loseswater:
H2NO3*tHrO+NOr*
o R c a r u t c c H E Mr s r n v i l l
O
2 The Nor. ion is the electrophile and attacks the benzene ring.
3 The HSon- ion pulls off a H. and reforms H2son (the catalystf
Similarmechanisms occurfor
bromination,wherethecatalyst
reactswithbromine to providethe
electrophile
Br-,andin theFriedel-
Craftsreaction
wherethecatalyst
reactswiththehalogen compound
to provideelectrophiles
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 t{' -l-
bondformsastheC-Brbond 9H, t ,cH,
breaks.
Thetransition
statehasa
Ho:' 'Q ------+
l l - .ur l /
chargeof-1. .:-g s' lno- I Ho-c.
l---------+ :Bi
H l | /\ | l "
H t*u.rr?rro., H
tu*'
o with tertiary (3") halogenoalkanesthe gl mechanism is dominant.
This happensin two steps:
1 The halogenoalkaneionisesin the relativelyslow,and hencerate
determining step,to form an intermediate carbocation.
CHt CH,
Anyoptical activity
is maintained
in
I r-r I
cHr-C-Br CHr-a" + :Br-
a Sr2reaction.
lf themechanism is Sr1,a reactant I I
whichis anoptical CH, CHt
isomer wilt
produce a racemicmixture, asthe
carbocationcanbeattacked from 2 This then rapidly forms a bond with the nucleophile, oH-.
eitherside.
CH, CHt
CH?-
tr\
C* t OH- CHe-C
I-OH
I I
CHg CHt
Heterolytic, nucleophilic addition
TheCN-ionis a catalyst,
andthe Reaction between o corbonyl compound and hydrogen cyonide
conditions mustbesuchthatthere o Although the reaction is the addition of HCN, the first step is the
is a significant
amount
of bothHCN nucleophilic attack by the cN- ion on the 6+ carbon atom in the
molecules andCN-ionspresent,
i.e. carbonyl group.
a mixtureof HCNandKCN.
El t*oNsrTroN METAL=, euANTrrATrvE KrNETrcs AND App'rED .RGANIc cHEMrsrRy
O The negatively charged oxygen in the anion then removes an H* from

an HCN molecule. This produces another CN- ion, which reacts with
another carbonyl group and so on.
-oAt A
aot u-cN o-H
*'/ -+
I +
I
R-C R_C_H R-C-H + CN-
r-\
\ H
I
CN
I
CN
cN-
o The conditions for this reaction are either HCN and a trace of baseor
KCN and a small amount of dilute sulphuric acid.
Reactionsof aromaticsubstances (Figure5.4) and mechanisms(Figure5.5)
are summarisedschematically.
conc HNO3 ----------+ C6H'NO2 OH-(aq)-CoHsg

conc H2SO4
Phenol
c6l{soH Brr(aq)--> CuHrBr.OH
Brt CuHrBr
Fe catalyst
cH3cocl -------------->
cH3cooc6Fls
c2Hscl
AlClrcatalyst
rf(aq) -------------->
c6IlNHJ
Phenylamine [-
c6HsNH2 |
cH3cocl c6Hscocl{3 HNO2- CoI{sNz-
AlCl3catalyst at 5oC
Fig 5.4 Summaryof reactionsof oromaticsubstances
Substitution Addition
Freeradical: alkanes + Cb Freeradical: polymerisation of alkenes
Nucleophilic: halogenoalkanes + OH-(aq) Nucleophilic: carbonyl + HCN

compounds
+ CN-
Electrophilic: benzene + HNq Electrophilic: alkenes + ClrlBr,
+ Brr(l) + HCI/HBr/ HI
+ RCI
+ RCOCI
Fig 5,5 Summoryof mechonisms
ffiChecklist
[J Understandthe structure of benzeneand why it reactsby substitution
rather than by addition.
oRclrurc cHEMrsrRY lll
O
U Can recallthe reactionsof benzenewith nitric acid,bromine and

halogencompounds.
r.J Can recallthe product of oxidising sidechains.
U Can recall the reactionsof phenol with alkali, bromine and acid
chlorides.
i.l Can recall the preparation of phenylamine and its reaction with nitrous
acid and the coupling of the product with phenol.
iJ Understandthe mechanismsof free radical substitution and addition.
tJ Understandthe mechanismsof electrophilic substitution and addition.
if Understandthe mechanismsof nucleophilic substitutionand addition.
-H
|I.;g'
and understanding
"4.
* State the structural formulae of the organic product obtained by the
a cuHuc00- reaction of:
b CuHuO-
Na-
c c,Huc00cuHu a propylbenzene with alkaline potassium manganate(Vll)
b phenol with sodium hydroxide solution
c phenol with propanoyl chloride.
Thebrownbrominewaterwouldgo o What would you observe if bromine water were added to aqueous
and
colourless a precipitate
white phenol?
wouldform.
withtinand O State the conditions for the conversion of nitrobenzene to
Heatunderreflux
hydrochloric
concentrated acid,cool phenylamine.
andthenaddaqueous sodium
hydroxide.
tothenumbered
Theanswers a Describe the mechanism for the reaction of bromine with benzene.
areonpage
questions 138. b Why does benzene undergo a substitution reaction with bromine
rather than an addition reaction?
In the reaction between propanone and hydrogen cyanide no reaction
occurs unless a small amount of a base such as sodium hydroxide is
added. Explain these observations.
When benzenediazonium chloride is prepared, the reaction is carried
out at about 5 "C.
a Why are these conditions chosen?
b What is the formula of the product obtained by the reaction of the
benzene diazonium chloride solution with phenol in alkaline
solution?
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 Thingsto learn
f fne rate equation for the reaction:
Theunitsof k are:
I fora zero-orderreaction: xM + /N - products,is:
moldm-'s-' -
Rateof reaction k tMlj [N]bwhere a and b areintegersand are
t fora first-order
reaction:
s-' experimentally determined.
I fora second-orderreaction: i The rate constant, & is the constant of proportionality in the rate
mol-t dmts' 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 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
of a first-order
Thehalf-life reaction
is constant. selectedvalue to half that value.
ffi Thingsto understand

iry
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.
C H E M T . A LK r N E T r c st l
@
Experiment tAl tBl tcl Relative rate
1 1 1 1 1
2 z 1 1 z
3 1 2 1 4
4 1 2 2 4
o From experimentsl- and 2: [A] doublesand rate doubles.Therefore

order with respectto A = 1
o From experimentsL and 3: [B] doublesand rate x 4. Thereforeorder
with respectto B = 2
o From experiments3 and 4: [C] doublesand rate unaltered.Therefore
order with respectto C = 0
I Rateof reactiorr= k [A]' [B]' [C]0,and the reactionis 3rd order.
Experimental techniques for following a reaction

1 Titration method. Mix the chemicalsand start the clock. At intervals
withdraw a sample,add it to iced water to slow the reaction.Then
graph,
Notethatforthefirst-order
thehalf-life
remains constant titrate one of the substances in the reaction.This method can be usedif
throughoutthereaction,
whereasfor an acid, an alkali or iodine is a reactantor a product.
thesecond-orderthehalf-life 2 Colorimetricmethod. This can be usedwhen either a reactantor a
increases
astheconcentrationfalls. product is coloured(iodine or potassiummanganate(Vll)are examples).
The colorimeter must first be calibratedusing solutions of the coloured
substanceof known concentrations.Then the reactantsare mixed and
the clock started.The intensity of the colour is measuredas a function
of time. The concentration of the coloured substanceis proportional to
the amount of light absorbed.
3 Gasvolume method. If a gasis producedin the reaction, its volume can
be measuredat intervals of time. The gascan be collectedin a
100 * Zeroorder horizontal gassyringe or by bubbling it into an inverted measuring
* Lstorder cylinder filled with water.
* Znd order
Graphs of results
E60
If the concentration of a reactant is plotted against time, three shapes of
0,)
graph are likely depending on the order of the reaction.
H 4 0
-l
20 Mechanisms
A suggestedmechanism must be consistentwith the order of reaction. The
partial order of any specieswhich occursin the mechanismafter the rate
determining step will be zero.The rate-determiningstep is the slowest
step,e.g.
Nor(g) + Co(g) -' No(g) + Cor(g) has the rate expression:
Rate=kD{O,l'[CO]"
A suggestedmechanism is:
o Step1 (slow):
NOr+ NO, -- NOr + NO
o Step2 (fast):
NOr+CO-NOr+CO,
As the CO entersthe mechanismaftter the rate determining step,the
mechanism is consistentwith the fact that the reaction is zero order with
respectto CO.
El t*oNsrrroN METALS, euANTrrATrvE KrNETrcs AND AppLtED .RGANtc cHEMIsrRy
Energy profile 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
O
and understanding
O The following results were obtained from a study of the reaction:
NO,(g) + CO(g) -' NO(8) + CO,(g)
a Fromexperiments 1 and2, order
withrespectto N0,= |
b Fromexperiments 1 and3, order
withrespectto C0 = 0 Experiment NO,l/mol dm-" lCol/mol dm-' Relative rate
is 2 + 0 = 2
c 0rderof reaction
d Rate=k[N0,]' 1 o.o2 0.o2 1
2 0.04 0.o2 4
3 o.o2 0.04 1
a What is the order with respect to NOr?

b What is the order with respectto CO?
c What is the order of reaction?
d Statethe rate expression.
o Reaction A has a high value of E., and reaction B has a lower E. r'alue.
a Which reaction has the larger rate constant?
b Which is the faster reaction?
o A reaction takes place in 3 steps. The E^lkI mol-' for each step are:
Step2 asit hasthelargest

E,,value step 1: 32, step 2: 51, step 3: 20
Which step determines the rate?
O The decomposition of NrO, is first order. At 200 "C the reaction has a
100to 6.25= 4 half-livee,
therefore half-life of 25 minutes. Calculate how long it will take for the
time= 4x25= 100minutes
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)
Theanswers
to thenumbered
questions
areonpage 138. 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,
Describe how you would follow, at 60 the rate of the reaction:
+
CH3COOH(aq) CH'OH(aq) - CH,COOCH.(|) + H,O(l).
The decomposition of 3-oxobutanoic acid, CH3COCHTCOOH,was
studied:
CHTCOCHTCOOH- CH.COCH. + CO,
The results, at 40'C, are tabulated below.
Time/min [3-oxobutanoic acid]/mol dm-'

0 t.6
26 0.8
52 0.4
78 o.2
Deduce the order of the reaction.

i
T I
I
I El t*oNsrrroN 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 t c c H E Mt s r R y
lV
chemistry
Organic
@
Introduction
I Questionson this topic will form part of the synopticassessment in
Unit Test5.
I This Topic brings together all the organic chemistry that has been
coveredin earliertopics,so you will need to reviseTopics2.2, 4.5
and 5.3.

Organic analysis
You should know the testsfor:

s Alkenes
Test: Add bromine in hexane.
Observation:The brown bromine becomescolourless.
o llalogenoalkanes
Test: Heat under reflux with sodium hydroxide solution, then
acidify with dilute nitric acid. Add silver nitrate solution.
Observation: Chlorides give a white precipitatethat is soluble in dilute
ammonia.
Bromidesgive a creamprecipitatethat is insolublein
dilute ammonia but dissolvesin concentratedammonia.
Iodides give a yellow precipitatethat is insoluble in
concentratedammonia.
O OH group (in alcohols and acids)
Test: To the dry compound add phosphoruspentachloride.
Observation: Steamyfumes of hydrogen chloride produced.
I Alcohols
Test: Warm with dilute sulphuric acid and potassium
dichromate(Vl)solution.
Observation: Primary (1') and secondary (2')alcohols reducethe
$::i,?i.m:ras,hey
;"""::?
i11i#1HT,::'{:il are
not oxidised.
To distinguish between 1oand 2o rcpeatthe experiment,
but distil the product into ammoniacal silver nitrate
solution:
1' alcohols are oxidised to aldehydes,which give a silver
mirror.
2'alcohols are oxidisedto ketones,which do not react.
I Carbonyl, C=O group (aldehydeor ketone)
Test: Add a solution of 2,4-dinitrophenylhydrazine.
Observation:A red or orangeprecipitateis seen.
oRclluc cHEMrsrRY lv
O
To distinguish between aldehydes and ketones:

Test: Warm with ammoniacal silver nitrate solution.
Observation: Aldehydes give a silver mirror, ketones have no reaction.
O Iodoform reaction
Test: Gentlv warm with a solution of sodium hydroxide and
iodine.
Observation: A pale yellow precipitate of CHI,
This test works with carbonyl compounds containing the
CH,C=O and alcohols containing the CH'CH(OH) groups.
I Carboxylic acids, COOH group
Test: Add to a solution of sodium hydrogen carbonate.
of gas,whichturn lime watermilky.
Observation:Bubbles
Interpretation of data
You should be able to deducestructuralformulaeof organicmolecules
given data obtainedfrom:
r Chemical methods
Thesolidmustbepurified
by Carry out testsas aboveto determine the functional groups in the
inorder
recrystallisation to have
a
molecule.Measurethe melting point of the substance.Make a solid
sharp
andaccuratemelting
temperature. 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.
When identifying
species thatcause o Seeif there is a peak at (M-15)+.If so the substanceprobably had a
lines
inthespectrum,alwaysgivea CH, group which is lost forming the (M-15)+ peak.
formulafortheionandits
structural I If there is a peak at (M-28)+,the substanceprobably had a CO group.
+ charge. Other fragmentswill help to identify the structure.
100
b 8 0
(tt
9 6 0
.E 40
&, 20
10 15 20 25 30 3 5 40 45
Fig 5.7 Massspectrumof ethonol m/z
Thepeaksgivenby0-HandN-Hare O Infrared spectra (seeFigure5.8)

usually
broad owingto hydrogen o Theseare used to identify functional groups in the substance,and
bonding. also to comparethe spectrumof the unknown with a data bank of
spectra('finger printing').
O Peaksto look for are at:
1650to 1750 cm-' given bY C=O
2500 to 3500 cm-' given by O-H
3300 to 3500 cm-' given by N-H
1000 to 1300 cm-' given by C-O
El t*oNsrrroN METAL', euANTrrATrvE KrNETrcs AND AppLrED .RGANrc cHEMrsrRy
100
s
O
U
g s o
(a
(t)
Lr
t-
2000 1s00 1000

Wavenumber
/ cm-r
Fig 5.8 lnfroredspectrumof ethonol
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
Thechemicalshiftis thedifference
theabsorption applied radio frequency radiation.
between frequencies
of thehydrogen
nucleiin the t The nuclei of hydrogen atoms in different chemical environments
compound andthosein the within a molecule will show up separately in a NMR spectrum. The
reference
compound. 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.
O In high resolution NMR spin coupling is observed. This is caused
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 peaksplits into 2lines (a doublet)
2 neighbouringH atoms peaksplits into 3 lines (a triplet)
n neighbouring H atoms 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
O
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
If the number of carbon atoms in the chain is:
o increased by one, consider:
a halogenoalkanewith KCN
A common erroris to thinkthat b carbonyl with HCN
KCN orHCN willreact with c the Grignard reagentCHrMgBr
alcoholsto formRCN. Youmust d a Grignard reagentaddedto CO, or methanal
firstconvertROHto R-halogen. o increased by more than one, consider:
Many questions onorganic
synthesisrequire, somewhere in a a Grignard reagentwith more than one carbon atom
thesequence, theconversion of b Friedel-Craftsreaction for aromatic substances
thestarting substance to a o decreased by one, consider:
carbonylcompound ora a the Hofmann degradation
halogenoalkane. b the iodoform reaction.
Practical techniques
O Recrystallisation. Dissolvethe solid in a minim m of hot solvent.
Filter the hot solution through a preheated funnel using fluted filter
Recrystallisation for
isonlysuitable paper.Allow to cool. Filter under reduced pnsssurle (Buchnerfunnel),
purifying
solids. 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
When a specific precaution
safety is product is toxic, irritant or is carcinogenic.
askedfor,
do notgive
the useof
glasses, o Fractional distillation. This is used to separatea mixture of two
safety labcoatsetc.as
examples.Theanswer isprobably liquids. Thesemixtures can usually be separatedinto pure samples,but
'nonakedflames (ether or
solvent)' if the boiling points are too close,a good separationwill be difficult.
'carry
outtheexperiment ina fume 'C
cupboard',inwhichcasethespecific If a liquid of composition X is heated,it will boil at Tr to give a vapour
hazardsuchastoxicitymustbe of compositionY (seeFigure5.10).If this is condensedand reboiled,it will
'C giving a vapour of composition Z. Eventually
stated. boil at a temperatureof T,
pure B will distill off the top and pure A will be left in the flask.
Liquid Applied organic chemistry
(u o Targeting pharrnaceutical compounds. Those which are ionic or
l-r
have severalgroups that can form hydrogen bonds with water, will tend
E T 1
H
C,.'
to be retained in aqueous(non-fatty) tissue.Compounds with long
tr 17 hydrocarbon chains and with few hydrogen bonding groupswill be
.a) 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
loOo/o X Y Z TOOo/o 2 slow release,such as urea, NHTCONH,
A B 3 nafural, such as slurry, compost and manure.
Fig 5.lO Boiling The first two are water-solubleand can be leachedout. The last is bulky
temperoture/ compositiondiagrom and contains little nitrogen.
El t*oNsrrroN METAL', euANTrrATrvE KrNETrcsAND AppLrED .RGANtc cHEMIsrRy
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.
Polymersusually softenovera O Polymers are of two distinct chemical types:

rangeoftemperatures rather
than 1 Addition. The monomers contain one or more C=C groups.
havea sharp meltingtemperature. Polymerisationis the addition causedby breaking the n bonds, and
Themainreason forthisisthatthe the polymer and the monomer have the sameempirical formula.
polymeris a mixtureof molecules
of Examplesare poly(ethene),poly(tetrafluoroethene)(PTFE)and
different
chain lengths. 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.
/H C l
lil H
cr
\ \ / \ i/ / \ / l-( - (.",).-
n
/
i- (.n,)--
\ r -
(
\ /
\- (cH,)u-
\ / "
N-
\
ts .n,),-
i T- iii
o o H H
\' lol O H H
a diacid chloride a diamine a polyamide
Fig 5.ll 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 V
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
areonpages
138-139.
a pentan-3-oneand pentanal
O oRGANrccHEMrsrRYrv
b 2-bromopropaneand2-chloropropane
c methylpropan-2-ol, methylpropan-l-ol and butan-2-ol?
The massspectrumof a substanceX of molecular formula C.HrO had
peaksat mass/charge valuesof tZO, 105, and TT.Identify the peaksand
suggesta structural formula for X.
The IR spectrumof aspirin showedpeaksat32OO,I72O and 1150cm-'.
Use the data on page L09 to identify the groupswhich causethese
peaks.
Low-resolutionNMR spectraof two aromatic isomerswith molecular
formula C.H,owere obtained. Isomer Y had three peaksof relative areas
5:2:3, and isomer Zhad two peaksof relative areas6:4. Suggest
structural formulae for Y and Z.
El t*oNsrrroN 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:
Experiment lRCHrcll loH-l Initial rate/mol dm-' s-'

1 0.0s0 0.10 4.0 x 10"
2 0.15 0.10 1.2 x I0-3
3 0.10 o.20 1.6 x 1O3
i 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
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
b into OH
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
3 Study the reaction scheme beloq and then answer the questions that follow.
step 1 +D KrCrrOr/HrSOn
CrHrBr --+CrHrMgB --+ C4H,'O
E
oH- (aq) step2
CTH'OH -----+C2H4O
B D
a Give the reagentsand conditions necessaryfor step 1 l2l

b Compound D reactswith ammoniacal silver nitrate solution to give a silver mirror.
i Give suitablereagentsfor the conversionof B to D. tzl
ii shouldbe takento ensurethat B wasconvertedmainly to D and did not react
What precautions
turther? tll
iii Give the name or the structural formula of the organic compound formed when D reacts with
ammoniacal silver nitrate solution. tll
c Give the structural formula of compound E (C4Hr,O). tzl
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 2,4-
dinitrophenyl hydrazine concerning the functional group in F. r2l
ii What structural featurein F is identified by the iodoform reaction?Give the formula of the
products of the reaction. t3t
iii Give the structural formula of F. r2l
e The massspectrumof F showedmajor peaksat mle valuesof 72,43 and 29. ldentify the species
responsiblefor thesepeaks. t3l
(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)
system. tsl
oc.
b A standardFe3.(aq)/Fe'.(aq) electrodeis connectedto a standardgold electrode,Au'-(aq)/Au(s),at 25
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
is drawn from the cell. l2l
ii Hencewrite the overall ionic equation for the reaction that takesplace. tll
iii The potential of this cell is +O.73V and the standardelectrodepotential for a Fe3.(aq)/Fe'.(aq)
electrodeis +0.77 V. Calculatethe standardelectrodepotential of the gold electrode. tzl
(Total LO marks)
ffanuary2001 CH3 question3]
El t*oNsrrroN METAL=,euANTrrATrvE KrNETrcs AND App.rED .RGANrc cHEMIsrRy
Iron and chromium are very important industrial metals.

a Complete the boxesbelow to show the electronic configurations of:
3d 4s
Fe: tA4 E E t_l E E E
Cr: tArl E E E E E t_l
Cr't: lArl t_l t_l E E E E t3l
b Chromite, FeCrOnor FeO.CrO' is a mixed oxide of iron and chromium that is used in the manufacture
of stainlesssteel. It can be reducedby heating with carbon to produce iron, chromium and carbon
monoxide.
Write an equation to representthe reduction of chromite. I2l
c The mixture of metalsthat resultsfrom the reduction in b was reactedwith excessdilute sulphuric
acid to give a solution of iron(Il) sulphateand chromium(Ill) sulphate. Sodium hydroxide solution
was addedto the mixture until in excess.The mixture was then filtered to give a precipitate Q,
containing all the iron, and a filtrate R, containing all the chromium.
i What is the formula of the iron-containing ion in the aqueousiron(Il) sulphate solution? tU
ii Write an ionic equation for the reaction between sodium hydroxide solution and this ion. State
what type of reaction is taking place. tsI
iii State the colour of the precipitate Q. tll
iv Give the formula of the chromium-containing ion in R. l2l
v State what you would see if solution R was slowly acidified with dilute sulphuric acid until there
was no further change. r2l
Electrodereaction trlv Electrodereaction Elv
'lrEr+ +
e F +2.87
-0.41 tlrclr+e-+Cl-
Crt*+e-+Crt* +1.36
'lrcrror'- + 7H* 'lrBtr+
+ 3e-+ Cr3*+ 3tlrHro +L.33 e- + Br +1.07
'lrrr+ e- + I- +0.54
Use the standardelectrode(reduction) potentials of the chromium ions and the halogensshown below
to answerthe questionsthat follow.
i Define the term standardelectrode potential. tzl
ii List those halogenswhich will oxidise chromium(Il) to chromium(Ilf . tlI
iii List those halogenswhich will oxidise chromium(Il) to chromium(Ill) but not to chromium(Vl).[1]
iv Chromium(Il) in aqueoussolution is sky blue whereasaqueouschromium(Il! solution is dark
green. Describehow you would show that your prediction in d part ii actually worked in practice.
r2l
(Totat L9 marks)
llanuary 2002 CHl question3 & lune 2001 CH3 question5l
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.
'- , 4,Ki
=1 ..
Unit Test6A: Assessment
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 oorrANcED LAB.RAT.RY cHEMrsrRY
t Questions will be set on any of the topics in the AS and A2

specification.
o The questions will require much less factual recall than those in earlier
unit tests. Much more emphasis will be placed upon application of
knowledge.
o Questions will test a candidate's ability to analyse information from
several different areas of the specification.
'deduce'will occur more often in questions
o The words 'suggest' and
'state' or 'recall'.
than
Tackling the paper

* Spendsometime looking through SectionB and decidewhich questions
you are going to attempt. Readall of the questionbeforereiectingit.
You may be able to answerall but the first part and so still scoregood
marks.If you are getting nowherein a question,abandonit and try
another, but do not cross out what you have written, becauseyou
might scoremore for it than for the other question.The examinerwill
count your better mark.
o Do not be put off by unusualcompoundsor situations.In these
questionsyou are not expectedto know the answer,but to be able to
work it out, using your knowledgeand understandingof similar
compoundsor situations.
O Synopticquestionswill contain materialfrom severaltopics.This is
done by using the links that exist betweendifferent branchesof
chemistry.
O Eachquestion should have a thread or link connecting the different
parts.Identificationof this thread will help you to focuson the relevant
chemistry.So do not treat eachpart of a questionin isolation from the
other partsof it.
o For examplein the questionsin the Unit Test6B on pageslI9 and LZO.
o Question2 is basedon organicand inorganicnitrogen compounds,
with questionson fertilisers,pK",polymers,amine preparation,and
K,,for ammonium nitrate linked to thermodynamicand kinetic
stability.
o Question3 is a reactionschemewhere the carbonchain is increased
leadingto a carboxylicacid,then a pH and buffer questionabout that
acid.
O Question4 is about the chemistryof iron, linking bonding, transition
mental properties,Bronsted-Lowrypairs,testsfor Fe'. and redox
titrations.
O To do well in this paperyou must revisethe entire specification
(syllabus)and especiallyTopic I.2. Do not becomeput off by this load
as many of the Topicsin A2 are extensionsof those in AS.For example:
o Topic 4.1 with 2.1 - Energetics
o Topic 4.2 with I.4, 1.6 and I.7 - The PeriodicTable
o Topic 4.3 and 4.4 with 2.4 and 2.5 - Equilibrium
o Topic4.5, 5.3 and 5.5 with 2.2 - Organicchemistry
O Topic5.1 with 1.5 - Redox
O Topic 5.4 with 2.3 - Kinetics
This leavesTopics1.1 (Atomic stmcture),I.2 (Formulae,equationsand moles)
and 1.3 (Structureand bonding) all of which are fundamentalto chemistryand
much of thesetopicswill,have beenrevisedby your teacherduring the A2 year.
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 Give the ionic equation, with statesymbols,for the precipitation reaction. r2l
ii Suggestwhy the aqueousbarium chloride was added in excess. 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
polymerisation.With the aid of diagrams,define the terms condensation andpolyamide.
polyrnerisation
t4l
d Ethanamide,CH3CONH, can be convertedto methylamine, CHrNHr.
i Statethe reagentsand conditions for carrying out this conversion. t3l
ii Suggestthe formula of the likely product if urea were used instead of ethanamide in this
conversron. tu
e Ammonium nitrate can explode when heated strongly.
NHnNO.(s)- N,O(g) + ZH,O(g) NI = -23 kJ mol-'
ADVANCED LABORATORY CH EM ISTRY
With moderateheating the ammonium nitrate volatilisesreversibly

NHnNO,(s) + NH,(g) + HNO.(g) NI = +L77 kJ mol-'
i Statewhy the expressionfor Ko for the reversiblechangedoesnot include ammonium nitrate. tl]
ii Explain the conceptsof thermodynamicand kineticstabilitywith referenceto thesetwo reactions.
tsI
(Total 18 marks)
lJune2001CH6 question4l
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
HCI(aq) conc. HzSOn
cH(oH)cN
cH.cH,cH,cH(cH3) cTHrno3 + heat
CrHrzOz
c D 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 iii Although the element with Z = 11 has 8 more
isotope of an element (relative to 1172th the mass protons, it also has 8 more shielding electrons,but as
of a carbon 12 atom), whereas the relative atomic the 3s electron is further from the nucleus than a 2s
mass is the averagemass taking into account the electron, so lessenergy is required to remove it.
isotopes of the element. The relative isotopic The el ectron i n a box notati on for chl ori ne is:
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
2 There are many more
tli
atoms than "Li atoms in
natural lithium, so the averageis closer to 7.
muruuunnun
1s 2s 2p,2p,2p,3s 3 p . *3 p , , 3 p ,
3 A, of magnesium 8 All have one electron in their outer shells, but K is

= ( 2 4 . Ox 7 8 . 6 + 2 5 . Ox 7 O . I + 2 6 . Ox 7 7 . 3 )= 2 4 . 3 bigger (larger atomic radius) than Na, which is
100 bigger than Li. Therefore the outer electron is held
4 Let the o/oof "ncabe x, on less firmly (the extra nuclear charge is balanced
and so the o/oof "Ga = (100 _ x) by the same extra number of shielding electrons)
69. 8 = [6 9 .0 x+ 7 1 .0 (1 0 0- x )J and so is the easiestto remove from potassium and
100 the hardest to remove from Li. This makes
Therefore6980 = 69x + 7100 - 77x potassium the most reactive.
Therefore2x = l2O and x = 60.0 9 a i Li (g) + e --+Li- (S)
of the ""Gaisotope.
Gallium contains 6O.Oo/o ll cl (g) + e -+ Cl- (g)
iii o (g) + e --+o- (g)
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.
N otethatthespeci es onthel efthandsi dei s a gaseous
6 a zsoo 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 .
>\
bo
t-<
2000
b O- (S) + e- - O- (g)
1500 c For the 1st electron affinity, the (negative)
+) electron is brought closer to the positive
.A 1000 nucleus in a neutral atom, and so energy is
released.For the 2nd electron affinity, the
500 negative electron is brought towards a
v)
negative ion, and so repulsion has to be
0 overcome, which requires energy.
| 2 t^ti*tt e 10 11
":-l.r* Topic7.2Formulae,equations
b i A 2p electron, which is in a higher energy
level, is being removed. So less energy is and moles
required to remove it compared to that o/o
1 a +6.9O
required to remove a 2s electron.
C 82.76 + L2 = 6.9O 1
ll There are two electrons in the 2p, orbital
H 17.24+1=17.24 2.5
which repel one another, so less energy is
Therefore the empirical formula is CrH.
required to remove one of the pair than if
b Mass of CrH, is 29, but M, - 58,
there had only been one electron in that
Therefore the molecular formula is C.,H,u
orbital.
2 a 4NHr+5Or-4NO+6HrO
b 2Fet.(aq)+ Sn'.(aq)-- ZFe"(aq) + Sn'.(aq)
122 ANsweRs
copper a metallic
sio, b giant atomic
solid CO, e simple molecular
H.e r e CaO c ionic
n su sat l s ob a l a n ci nec h a r g e
l o n i ce q u a t i om
poly(ethene) f polymeric
bothsidesare8+.
graphite b giant atomic
sulphur e simple molecular
CuSOn c ionic
Equation: HrPOn+ 3NaOH - Na.,.POn + 3HrO
sucrose d H-bonded molecular
A m ount of H. P O , = 2 .3 4 1 9 8= 0 .0 2 3 8 8 m o l
LiF c ionic
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 Melting: on heating, the molecules or ions vibrate
more until the intermolecular forces (in molecular)
Equation: 2KOH + HrSOn= KrS9n+ ZHrO
or ion/ion forces (in ionic) substancesare overcome
Amount of HrSOn= 0.0125 dm'.x 0.0747 mol dm-'
= 9 . 3 3 8x 1 0 - ' m o l and the lattice breaks down.
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 or ionsstartto vibrate.
Donotsaythatthemolecules
O.l O 7 m o l d m -'
= 0 . 0 1 7 5d m ' = 1 7 . 5c m '
Boiling: on heating the average kinetic energy ot
5 Am ount of B i( N O,), = 0 .0 2 5 d m' x 0 .5 5 mo l dm-' the molecules increases.Those with a large enough
= 0 . 0 L 3 8m o l kinetic energy and hence speed escape,not only
Amount of HrS = 0.0L38 x 312 from the surface but also from the body of the
= 0 .0 2 0 6 mo l liquid, forming bubbles.
Volume of HrS gas = rlol x molar volume
= 0 .O2 0 6x 2 4 = 0 .5 0 d m' a NH.. There are stronger intermolecular forces
in NH. as it forms H bonds and PH. does not.
6 Ratio mol of H,(g):mol of CH.(g) = 3:1
b HBr. It has more electrons in its molecule, and
Volume of Hr(g):volume of CHr(g) = 3:L
so it has stronger dispersion forces (which
Volume of Hr(g) = 3 x 33 = 99 dm'
outweigh the difference in dipole/dipole
Topic7.3Structureand bonding 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.
d 58.It has about twice as many electrons as Pn,
and so has stronger dispersion forces.
o-bond NaCl. It has ion/ion forces that are very much
stronger than the weak intermolecular
dispersion forces between CCln molecules.
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
Number of Number Total Shape
is more polarisable than the smaller F- ion.
o bond of lone number of
BeCl, becauseeither there is less difference in
pairs pairs electron
electronegativity between Be and Cl than pairs
between Mg and Cl
or Be'* is smaller than Mg'. and so is more siHn 4 0 4 Tetrahedral
polarising. BF. 3 0 3 Triangular
planar
a Hydrogen b Dispersion c Dipole BeCl, 2 0 2 Linear
bon d /dipole PCl3 3 1 4 Pyramidal
HF Yes Yes Yes SFu 6 0 6 Octahedral
r2 No Yes No XeFn 4 2 6 Square
No Yes Yes planar
HBr
P H, No Yes Yes NHn' 4 0 4 Tetrahedral
Ar No Yes No PClu- 6 0 6 Octahedral
4 iodine e simple molecular 8 In Na (s) there are loosely held delocalised

ice d H bonded molecular electrons that can move through the lattice. In
ANswERs 123
NaCl(s) the electrons are localised on the ions, not 4 a i Nuclear charge is equal to the number of
loosely held and the ions are fixed in their protons in the nucleus.
positions in the lattice and so are not free to move. ll Screeningor shielding occurs when an outer
electron is insulated from the pull of the
Topic7.4 ThePeriodicTableI positive nucleus by electrons in inner shells.
b i The 1st ionisation energy of sodium is for
1 a They all have the same number of electrons in the removal of the 3s el ectron. S odium has a
their outer shell. For Group 2 this number is 2. nucl ear chargeof + 11, but the 3s e lect r on is
b This period is Period 4, and so all the members shi el dedby the 10 el ectronsi n the 1st and
have electrons in four shells. 2nd shel l s.The secondel ectron that is
removed comes from the Znd shell (it is a 2p
2 a H, is simple molecular el ectron).Thi s el ectron i s shi el dedf r om t he
b Na is metallic nucl eus onl v bv el ectronsw hi ch ar e in a
c Si is giant atomic l ow er shel l , rvhi ch i n thi s casei s by t he t wo
d S*is simple molecular 1s el ectronsand so i t i s hel d much m or e
e Cl, is simple molecular strongl v bv the nucl eus.It i s al so n ear ert o
f Ar is simple molecular (argon is monatomic). 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.
ll 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
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 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
elements. sodi um), but i ts 3s el ectron i s shi eldedby
the same i nner el ectrons.Thus i ts 3s
Sodium and magnesium are metals. Magnesium is electrons are pulled more strongly to the
2+ and has a smaller ionic radius. therefore it will nucleus and are harder to remove.
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 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
of energy and so the melting temperature is very a t o mi s s m a l l et hr a na s o d i u m atom.
high.
Topic7.5 Introductionto
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 ,
oxidationand reduction
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 1 a Sn"(aq) -- Sn'.(aq)+ 2e
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 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 -
depend upon the strengths of their intermolecular 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 .
forceswhich are dispersion (induced dipole/induced
dipole) forces.The strength of this force depends b F e ' - 1 a q+) e --'Fe"-(aq)
upon the number of electrons in the molecule. c S n ' - ( a q )+ 2Fe''.(aq)-- Snn.(aq)+ 2Fe'.(aq)
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 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

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 c a n c ewl h e n2 t i m e sb i s a d d e dt o a .
mo l e cul e .
2 a HrOr(aq)+ 2H.(aq) + 2e- -. 2HrO(l)
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 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 .
melting temperature.
124 ANswERs
b S(s)+ zH'(aq) + 2e---'H,S(aq) 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
andits
S is reduced atom, becausesodium has three shells of electrons
2e-areneeded ontheleftbecause
and potassium has four. Thus sodium's outer s
o x i d a t i onnu m b egro e sf r o m0 t o - 2 .
electron is held on more firmly, and more energy is
required to remove it.
c H,O,(aq) + H,S (aq) - zH,O(l) + S(s)
Thisis thecasein spiteof thefactthatpotassium has

BothH,SandH,0,mustbe0ntheleftbecause theyare
e i g hmt 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
thereactants; equation b is reversed to a;
andadded
e i g hmt o r ee l e c t r 0 b
nes t w e et hnen u c l e uasn dt h eo u t e r
n o t et h a t h eH -i o n sc a n c eolu t . 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.
3 a PbOr(s)+ 2H,SOo(ag)+ 2e- - PbSOo(s)
+ 2H,O(l)
+ SOo'-(aq)
4 a 2C a + O, - ZC aO (or C a * ' l rO, -- C aO)
b Ca + zH,O - Ca(OH), + H,
c 2K + ZH.O -- 2KOH + Hz
d Mg(s) + H,O(g) - MgO(s) + H,(g)
2e-areneeded ontheleftasPbO,is reduced andits The white precipitate is the insoluble magnesium
o x i d a t i onnu m b ecrh a n g ef rso m+ 4t o + 2 . hydroxide. Barium hydroxide is soluble and so is
not precipitated.
b PbSOo(s)+ 2e--- Pb(s) + SOo'-(aq)
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
2e-ar eneeded on th e l e ftb e c a u sPe b S0 i, s re d u c edand they are larger.
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 . 7 a 4LiNO3 -- ZLizO + 4NO, + O,
2N aN O. - 2N aN Or* O,
2Mg(NO,),- 2MgO + 4NO, + O,
c - 2PbSOo(s)
PbOr(s)+ Pb(s) + 2H,SOo(ag) + NarCO. --' no reaction
b
2H,O(t) MgCO,-MgO+CO,
BaCO, --+no reaction
Topic7.7 Group7
BecausePbis a reactant,equationii hasto bereversed
andthenadded thattakesplace
to i. Thisis thereaction Covalent HCI ionises when added to water, and the
whencurrentis drawn froma lead-acid batterv. 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:
Topic7.6 Group1 and Group2 HCI(g) + H,O(l) -- H,O.(aq) + Cl-(aq)
L Dip a hot platinum (or nichrome) wire in clean First a solution has to be made. The sample can be
concentrated HCI and then into the solid. Place in a dissolved either in water or in dilute nitric acid. (If
hot bunsen flame. The substance that turns the water is chosen, dilute nitric acid must then be
flame carmine red is LiCl, the one which turns the added to destroy the carbonate).To this slightly
flame lilac is KCI and the one that turns the flame acidic solution, add silver nitrate solution. If there
apple green is BaClr. is chloride present, there will be a white precipitate
that will dissolve in dilute aqueous ammonia.
2 The heat of the flame vaporisesthe sodium
chloride, producing some Na and Cl atoms. HrSOnis a stronger acid than HCI (or HI), and so it
Electrons are promoted into the 4th shell in some will protonate the Cl- ions in the sodium chloride
of the sodium atoms. These electrons then fall back producing HCI gas. HCI is not a strong enough
to the ground state, which is the 3s orbital, and reducing agent to reduce sulphuric acid, and so
energy is given out in the form of light. The flame no further reaction will take place. With sodium
ANsweRs 125
iodide, HI is produced by the protonation of the ll

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.
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,, b Graphite has covalent bonds between atoms that
(+1) (-1) (+5) have to be broken [1]; sodi um chl ori d e has
el ectrostati cforcesbetw een the i ons [1 ] . I n bot h
Answersto PracticeTestUnit 1 these forcesare strong and so a l ot of e ner gy is
neededto break them [1] = [ 31
The allocation of marks follows Edexcelmark c i Graphi te has del ocal i sedel ectronsabove and
sc hem es . bel ow the pl ane of he.ragons[1], which can
The marks that you will need for each grade are flow (which are mobilet [1] = f2l
ll The l atti ce i s broken don' n i n the l iquid and
approximately:
A 7Oo/o so the i ons are free to nl ove =[u
B 6lo/o
C 52o/o
D 44o/o
E 360/o
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 ai Z C a +O r - Z C a O = [1] 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 .
iiNarO + HrO ---+2NaOH = [1] 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
Na,O + ZHCI ---; 2NaCl + H,O
iii 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
Species[.], balancing [.] = l2l o r i o n s ' , ' . , har rcehf r e et o m o v e .
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 3 a i A tomi c number i s the number of prot ons in
_ t3l 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
ii ,.gt- = [1]
b i High energy electrons bombard the Br,
b Donotattempt thistypeof question
to answer in
molecules [1] and knock out an electron [1]
termsof sizematch. = [2]
ll They are acceleratedby charged plates (or
2 a i Graphite has a giant atomic (or giant an = [1]
across
-" B r-' ' B r. electric field)
covalent) structure [1]. The bonding between iii = [U
atoms is covalent [U.
Your diagram must show several interlinked
hexagons [1] in layers tU = [4]
a ii Astheparticle has1 fewerelectrons than

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 .
4 a
Divide each o/oby their A, values [L] and then divide
by the smallest [1]
It Sodium chloride has a lattice structure t l l . H L 1 . L* 1 = L 1 . 1 t h e n * 7 . 4 = 1 . 5
The bonding is ionic [l.]. C 88.9* 12 = 7.4 then + 7.4= 1
Your diagram must show a 3-D arrangement Multiply both by 2 to get whole numbers
of ions, Na. alternating with Cl-. [1] = [3] .'. E.F.is CrH. tll = [3]
.l
:1ffi A r q s w e n s
b HI has more electrons tll .'. induced dipole d i [L] for the electrons around S and [1] for the
or dispersion or London or v.d.Waals electrons around both Cl atoms. = l2l
are stronger [1] = I2f t a
3 bond pairs and 1 lone pair repel to get

a t
c i S
as far apart as possible [1] see diagram ** *. .* ..
= l2l
below [1] ++CI ++ ++CI ++
ii 4 bond pairs around Al repel to get as
far apart as possible [1] see diagram
below [t] = I2l The 2 bond pairs and the 2 lone pairs [L]
(i) (ii)i repel each other to get as far apart as
possible [.] = I2l
Tj lll Cl is more electronegative than S, so the
t/l---t
@
Moles of gas = volume + molar volume
F-h U n i2t
bonds are polar [1], but as the molecule is
bent, the polarities do not cancel [1] = fzl
= 8.0 ,mt/2.4 x 10ncm' mol-' = 3.33 x 10" mol
Itr"o., of molecules= 6.0 x 10" x numberof

= fzl
I
Topic2.1- Energetics
moles = z.o x 1o'o1t1
Gasesat a pressure of t atmosphete, a stated
temperature (298 K) and all solutions of
concentration 1".00mol dm-'. Substancesin their
b Donotsaybecause themolarmassof Hl is larger. most stable state.
c R e m e m bt hea r ti t i st h ee l e c t r opna i r sn o tt h e
s o rt h eb o n dtsh a tr e p et lo g i v em a x i m u m
a t o mn i zC(s) + ZH,(g) + O,(8) - CHaCOOH(I)
separation. ii CH,COOH(I) + 2O,(g) - 2CO,(8) + 2H,O(l)
iii CH3COOH(aq)+ NaOH(aQ)- CH,COONa(aq)
+ H,O(l)
5 a i The oxidation number of sulphur: in HrSOnis or CH,COOH(aq) + OH-(aq) - CH,COO-(aq)
+6 [1], in H,S is +2 [1], in SO, is +a [1] = [3] + H,O(l)
ll The I- ion is the stronger reducing agent
becauseit reduces sulphur from +6 to +2 fAl,
whereas Br- only reduces it to +4 [1] = l2f
'lrcl,
b i ZCl- - Cl, + 2e- or Cl- - * e- = [1]
ll OCI-+2H-+2e--Cl-+HrO Notethatethanoic acidis a weakacid,andso its
species[1], balance [t] = I2l
a u s bt ew r i t t einn f u l la n dn o ta sH ' .
f o r m u lm
lll OCf + 2H. + Cl- -'Cl, + HrO = [1]
No(g) +tboz(g)
i & ii Foranoxidation
ontheright,andfor reduction
reaction, theelectrons
theyareontheleft.
are
t
i i i Y o uw o u l dn o tb ep e n a l i sfeodrf a i l i ntgo c a n c e l
o n eo f t h eC l -i o n si,. e .h a v i ntgh ee q u a t i o n .
I
Enthalpy
O C l+- 2 H .+ 2 C l - C l , + H , 0+ C l -
6 a 2,8,6 = [1] t/,

Nr(g) + oz(g)
b i S(S)+ e --+S-(g) trl
ii S(g)- S.(g)+ e- [1]
and [1] for state symbols in both equations MI,= +90.3 kJ + (-57.1) kJ = +33.2 kJ mol-'
= [3]
A big jump in ionisation energy means that an
electron has been removed from a new shell [1]
The first big jump is after 6 electrons and so
there are six electrons in the outer shell [1] N o t et h a t h e+ s i g ni s g i v e n
i nt h ea n s w ei nr o r d e r
The second big jump is after 8 electrons and so t o e m p h a s itshea t h er e a c t i oi sne n d o t h e r m i c .
there are 8 in the 2nd shell [1] = [3]
ANswERs 127
Nf,
H H H H
2NOr(g) ---------------+ NzOn(g) \ /
\
r--r-
/ t l
\ / \--\- f H- O-H-+ H-C-C-O-H
\ / // \\ l l
*'\ H H H H
,/*,
Break (endo) Make (exo)
20zG)
Nz(g) + zOzG)
1 x C = C = + 6" 12kJ x C-C = -348 kJ
1 x H-O = +463 kJ x C-H = -4I2 kJ
LH, = AH, + LH, = -2 x (+33.9) + (+9.7) = -58.1 kJ mol-' x C-O = -360 kJ
Total = +1075 kJ Total = - 1120 kJ
NI = net result of bonds broken and bonds made
= + 1075 - 1720 = -45 kJ mol -' .
L H ,= m i n u s2 t i m e st h ee n t h a l poyff o r m a t i oonf
N 0 , ( g )b,e c a u st heer e a c t i or e
npresen t ht se Topic2.2 OrganicchemistryI
f o r m a t i oonf N 0 , ( gr)e v e r s eadn d L H 2 =e n t h a l po yf L a b
f o r m a t i oonf N , 0 , ( g ) . B r F F CI OHH H
l l l t t t l
Br-C-C-C-H H-C-C-C-C-H
aHr
l l l t l l l
C I C I H H H H H
12C(s)+ lZHr(g) + Oz(g)------------>CH3(CHTt6COOH(s)
2 a and CH,CH(OH)CH,.
CH,,CH.CH,OH
Nf1
r2COr(g) + rzHzo(l)
T h i st y p eo f u n a m b i g uf00ur m s u lias a l l o w eudn l e sas
where A-FI,= 12 x enthalpy of combustion of carbon o lr m u lias a s k efdo r .
f u l ls t r u c t u rf a
(graphite) + 12 x enthalpy of combustion of hydrogen
and cH.cHrcH.cH.cH,, and
cH3c(cHr)rcH,
LH, = minus the enthalpy of combustion of lauric acid. cH.cH=cH(cH,)cH.
LH,= 12x(-394) +12x(-286) -(-7377) = -783 kJ mol-'. c C H ,C H = C H C H ,(both the ci s and tr ans
i somers),(C H ,).C = C H ,and C H .C H TCH=CH,
6 HCI + NaOH -- NaCl + HrO
3 a A free radical is a specieswith a single unpaired
Amount of HCI = corC(mol dm-') x vol(dm') e l e c t r o n ,e . g . C l . .
= 1 .0 0x 1 0 0 b Homolytic fission is when a bond breaks with
one electron going to each atom.
1000
= 0.100mol 4 a An electrophile is a specieswhich seeksout
negative centres and acceptsa lone pair of
Ris ein t em p e ra tu r€= + 6 .8 0 ' C
electrons to form a new covalent bond.
Heat produced when 0.100 mol reacts
= total mass x specific heat capacity x rise in b Heterolytic fission is when a bond breaks with
the two electrons going to one atom.
temperature
=2OOgx4.18Jg-' x 6 .8 0 " C = 5 6 8 5 J 5 a C.Hn+ Cl, -* CrH.Cl + HCI
= 5 . 6 8 5k J then: CrH.Cl + Cl, - CrH*Cl, + HCI etc
Heat produced when 1 mol reacts conditions: ultraviolet light
= 5 . 6 8 5 / 0 . 1 0 0= 5 6 . 9 k J m o l - ' b c.H ,,+ 3' l ror- ZC o, + 3H ro
therefore AFI"",,= -56.9 kJ mol-' (exothermic). conditions: flame or a spark
6 a C H ,C H = C H ,+ H , - C H .C H TC H ,
conditions: heat and Pt catalyst
b CH.CH=CH, + Br, -' CH3CHBTCHTBT
conditions: solution in hexane
Because themixture became hotter, thereaction is
observation: goes from brown to colourless
e x o t h e r mTi ch .em a s su s e di s t h em a s so ft h ew h o l e
= 2 0 0c m ' = 2 0 0g , n o t h e c CH.,CH=CH,+ HI - CH..CHICH.
m0' +1 0 0c m 3
s o l u t i o n , 1c 0
conditions: mix gasesat room temperature
m a s so ft h eH C l .
d CH,CH=CH, + [O] + H,O -- CH.,CH(OH)CH,OH
condition: aqueous
observation: goes from purple to brown
precipitate
r rsrr
128 ANswERs
7 a C H .C H (O H )C H ,+ N aI
CH. CHI CH. + N a OH ' Pressure. As the pressure is increased, the number
propan-2-ol of molecules in a given volume increases,and the
b CH3CHICH.+ KOH--'CH.CH=CHz + KI + HrO frequency of collision increasesand hence the rate
propene of reaction, which is dependent upon this
c CH3CHICH, + ZNH, - CH.CH(NHr)CH3 + NH4I frequency of collision, increasestoo.
2-aminopropane
Temperature. If the temperature is increased, the
8 CH.CH(OH)CH, - H,O -'CH.CH-CH, average kinetic energy of the molecules is also
conditions: concentrated acid at l7O "C increased. This means that a greater proportion of
the colliding molecules will have, between them,
9 a energy greater than or equal to the activation
H H o energy. There will be a larger number of successful
l t / - collisions and a faster rate of reaction.
H- C-C-C
l l \ Catalyst. This increasesthe rate of reaction by
H H O - H providing an alternative path with a lower
Propanoic acid activation energy, thus a greater proportion of the
observation: solution goes from orange to green colliding molecules have energy greater than or
b No reaction equal to the lower catalysed activation energy.
observation: solution stays orange
c CH3CHCICH3 ttt
(u
2-chloropropane
U
observation: steamy fumes q.)
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. (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. Ea
Energy
L2 C6H1o + Br, - CuH,oBr,
5. 67 g of CuH, o= 5 .6 7 1 8 2= 0 .0 6 9 1 m o I Bacterial and enzyme reactions are also slowed
Becausethe reaction is a L:L reaction, the amount down by a decreasein temperature for exactly the
of product is also 0.0691 mol. same reason as ordinary chemical reactions, which
Therefore the theoretical yield of CuH,oBr, is that fewer colliding molecules will have the
= 0. 0691 x 242 = 1 6 .7 g necessaryactivation energy to react on collision. So
The o/oyield = 15.4 g x 100 = 92o/o. the low temperature in the refrigerator will slow
1 6 . 7g down the biological decay reactions.
13 They are stable in air owing to the strong C-Cl i i i
and C-F bonds.
They then diffuse into the stratosphere where
they form radicals and destroy the ozone layer. >.
@
Tonic2.3 KineticsI
I
OJ
1 i The activation energy is the minimum energy

that the reacting molecules must have when
they collide in order for them to react. It is
lv
measured in kJ mol-'. tll
ii 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. bo
q)
ar-l
Never saythata catalyst lowerstheactivation energy. R is the reactant and P is the product.
Lightis nota catalyst, becauseit is nota substance
andit is usedup.lt is justa specificformof energy.
AusweRs 129
Topic2.4 ChemicalequilibriaI L a It is a seriesof compounds with the same general

formula [1] which differ by CH, [L], and have
the same functional group [1] = [3]
i true
b -(C H (C H ,)C H r).-: correct carbon cha in [ 1] wit h
ii false
extension bonds at both ends [.] = l2l
iii true
c i SeeFig 2.4 on page 38. [1] for each
i Position moves R-L, becausethat is the
isomer = I2l
exothermic direction.
ii Rotation around the z bond is restricted = [1]
ii Pressureincreases,therefore position moves
R-L as fewer gas moles on left
iii None, catalyst speedsup the forward and
reverse reactions equally, reducing the time
taken to reach equilibrium.
3 i Alkali removes ethanoic acid, therefore position
b Donothavethe3 carbon atomsin a straight
moves R--L.
c h ani.
ii No change becauseAH is zero
c D on o td r a wt h es t r u c t uw
r ei t ha b o n da n g l eosf
9 0 ' a r o u nt d
h eC = Cgroup.
4 Solid dissolvesbecausehigh [Cll drives equilibrium
L-R.
5 Too high a temperature produces too low a yield. 2 a SeeFig 2.9 on page 45: [1] for having the axes
Too low a temperature produces too slow a rate correct (y-axis labelled fraction of molecules,
Catalyst allows reaction to proceed at a fast rate at x-axis energy), [1] for having the curves with the
a temperature where the yield is high. correct shape, and [1] for having the T, curve
flatter with the peak moved to the right = [3]
b Draw the activation energy on the graph to the
Topic2.5 Industrialinorganic ri ght of both peaks [1,],expl anati on t hat t he ar ea
under the curve to the ri ght of the E . line
chemistry measuresthe number of mol ecul esw it h E > E. ,
L Reaction is slow at moderate temperatures. [1], w hi ch i s l arger at T, than at T,[1] , so t her e
Therefore a catalyst is used which allows a fast rate are a greaterproporti on of successfucollisions
l
and reasonableyield at 400 "C, that is, an economic tu = [4]
rate and yield. A very high pressure (200 atm) is
used, even though this is very expensivebecause
the yield at ordinary pressuresis very low. A very
high pressure drives the equilibrium L'R to the
side with fewer gas moles. After NH, is separated, a T h et o t aal r e au n d etrh et w oc u r v essh o u lbdet h e
the unreacted gasesare recycled. same.
2 The ammonia liquefies under the high pressureand b M e n t i omn u s b t em a d o e fc o l l i s i o n s .
is removed from the unreacted nitrogen and
hydrogen, which are then put back through the
3 a i The reagent is HBr [1] and the conditions are
reaction chamber.
in the gas phase [l.] = I2f
3 Anode: zcl-(aq) - Cl,(B) + 2e- i i S i s C H ,C H B TC H , = [ 1]
Cathode: 2H,O(1) + 2e- -- ZOH-(aq) + H,(g) b i P i s C H .C H (OH )C H , = [ 1]
or 2H'(aq) + 2e- - H,(B) ii The type of reaction in step 1 is electrophilic
lr,l addition [L] = l2l
in the conversion of S to P the type is
Answersto PracticeTestUnit 2 nucleophilic [1] substitution [1] = [21
i For step 2, the reagent is conc sulphuric (or
The allocation of marks follows Edexcelmark phosphoric) acid or aluminium oxide [1] and
schemes. the condition is heat [L] = f?l
The marks that you will need each grade are ii For step 3, the reagentsare potassium
approximately: dichromate(Vl) [1] and sulphuric acid [1] and
the conditions are heat under reflux [1] = [3]
d Q is CH,CH(OH)CH,OH [r.] = [1]
rtul
130 Auswens
tl Dynamic means that the reaction is occurring

in both directions [1] and equilibrium means
that there is no change in concentrations
tlI = l2f
a l f t h ef u l ls t r u c t u rf a
o lr m u lhaa db e e n a s k e dy ,o u
C I A lower temperature will move the position
mustthenshoweachatomseparately, withall
to the right [1], becausethat is the
b o n dssh o w n .
youmustmake exothermic direction (or this produces heat)
b Asthereare2 marks foreach, = fzl
2 points. tll
ll Decreasingthe volume increasesthe pressure
c i i P o t a s s i umma n g a n a t e (i sVal ln)a l t e r n a t ti ove
and so moves the equilibrium to the right [1]
p o t a s s i udm i c h r o m a t e (AVl lw) .a ygsi v ee i t h et rh e
as the right has fewer gas molecules [1] = [2]
f u l ln a m eosrt h e f u l lf o r m u l aee.,g .n o t
'acidified dichromate' n0r'Crr0,'-lHr'. Also'reflux'
b yi t s e ldf o e sn o ti m p l yh e a t .
4 a Hess'slaw statesthat the enthalpy change for a a ii Inindustria p lr o c e s s etsh,ec h o i c eo f

reaction [1] is independent of the route [1] = [2] t e m p e r a t udr e p e n dosn r a t e( h i g h
b The definition is the enthalpy (or heat but not t e m p e r a t ugr e
o o d )a n dp o s i t i o on f
energy) change when 1 mole [1] of a substance is equilibrium ( h i g ht e m p e r a t ubr ea df o r
completely burnt in oxygen (or burnt in excess exothermireacti c ons).A catal yst al l owsa
oxygen) [.] under standard conditions (at L atm fastrateat a l ow ertemperature.
pressure) [1] = [3]
i Bonds broken bonds made
1xC-C =+348 4 x C=O =-2972 6 a ZOt- - O, + 4e-(or Ot- --'lrO, + 2e-) = [1]
5xC-H =+206O 6xO-H =-2778 b Al'. + 3e-'Al = [1]
1xC-O =+360 Total = -5750 kJ tll c The reaction at the anode. = [1]
1xO-H =+463 d The oxygen produced at the anode reacts with
3 Q=O=l-1-a88 the carbon anode and eats it away = [1]
"
Total = + 47L9 kJ tU e Aluminium oxide (pure bauxite) has an
extremely high melting temperature [.], and so
L,H = + 47t9 - 5750 = -103t kJ mol-' [t] = [3]
= l2l
the process would be too expensive [1]
ii S eeF ig. 2.1 o n p a g e 3 3 .
Labelling of reactants and products [1],
with energy of reactants higher than
products and AFI shown [L] = f2l
a R e m e m bt h ea r t h eo x i d e i o nh a sa c h a r goef 2 - .
b I n b o t he l e c t r o l yasni sdc e l l so, x i d a t i o nc c u rast
t h ea n o d (eoa n da a r eb o t hv o w e l s ) .
c i R e m e m bt h ea r tb o n db r e a k i ni sga l w a y s
endothem ( +i c)a n db o n dm a k i negx o t h e r m i c
(-)
ii lf thereaction profile hadbeenasked for, Answersto PracticeTest Unit 38
t h e ny o um u sst h o wa ne n e r gbya r r i e( rt h e
activation energy) in yourenthalpy level The marks that you will need for each grade are
diagram. approximately:
5 a i Your answer for the temperature should be

between 350 and 500 "C (623 and 773K) = [1]
ll A high temperature favours a high rate of
reaction [1], but gives a low yield [1], so a
temperature is chosen which gives a balance
between rate and yield [1] = [3]
Hydrogen: burns with a squeaky pop [1]
tll The catalvst used is iron = [1]
Oxygen: relights splint [1]
lv A catalyst provides an alternative pathway
Carbon dioxide turns lime-water [f.] milky [1]
[1], which has a lower activation energy [1] Sulphur dioxide: the solution turns green [1]
= I2l
The gas which turns moist litmus red then bleaches
b i Homogeneous means that all the substances it is chlorine [1] = [6]
are in the same phase (here all are in the 2 a i There is a loss in mass becauseCO, gas [1] is
gaseousstate) = [U = I2l
lost from the flask [1]
ii At first the slope of the graph is steep, so the
. reaction is fast, then as the slope gets less it
ArusweRs 131
slows down [1], when the line is horizontal

(after 6 or 7 minutes) the reaction has
stopped (all the acid has been used up) [1]
= f2f
b T h et e m p e r a t ugr e 0 e sL . r ps ,0 h e a ti s p r o d u c e d
a ,n d
b For experiment 2: your graph should initially be
t h er e a c t i oins e x o t h e r m i.c' .;A H i s n e g a t i v e .
steeperthan in 1 but is horizontal earlier, but
with the same mass loss (1 B) as in 1. [1]
For experiment 3: your graph should initially be 4 a i Any one of:
less steep. It should become horizontal later, but use a larger beaker [1] as this will prevent
at t he s a me m a s s l o s s a s i n 1 . [1 ] acid spray escaping [1];
For experiment 4: your graph should be steeper powder the limestone [1] as this speedsup
than in 1 and become horizontal at twice the the reaction [1,];
mass loss (2 8) as in 1. [f.] = [3] use more acid [L] as this gives larger and
c i Amount of HCI = 1.00 mol dm-" hence more accuratetitres [,]. = [21
x 50/1 0 0 0 d m' = 0 .0 5 0 0 mo l [L ], ll Choose titres 1 and 3 [1];
' 1,
a m o u n t o f C a C O 3= ' 1 , , 0 . 0 5 0 0 m o l mean = (14.9O+ 14.85) = 14.8 75 cm ' 1L1
= 0. 0 2 5 0 mo l [L ]: mass of CaCO, = -- r2l
0.0250 mol x 100 g mol-' = 2.5O g tll = [3] b i A mount of N aOH i n ti tre = 0.100 m ol dm - ''x
ii As the amount of acid in experiment 4 1 4 . 8 7 5 1 7 0 0d0m ' = 0 . 0 0 1 4 8 7 5m o l = [1]
is twice that of the other experiments ll A mount of H C I i n porti on = 0.001488m o1
[1], the mass of CaCO. must be at least = [1]
2x2.50=5.009tl] =[2] iii Total amount of HCI remaining =
10 x 0.001488= 0.0L488 mol = [ 11
iv Original amount of HCI = 2.0 mol dm-' x
50/1000 dm" = 0.100 mol = [ 1]
v A mount of H C I used = 0.100 - 0 . 01488
a T oa n s w et hr i sy o uh a v e t o w o r ko u ti f t h e = 0.08512 mol = [1]
r e a c t i oi snf a s t eor r s l o w et rh a ni n 1 a n dw h e t h e r ' 1r
vi A mount of C aC O. = r 0.085L2 = O . O 4256
t h em a s so f C 0 ,l o s ti s t h es a m em, o r eo r l e s s mol [1] = 0.04256 mol x 100 g mol- ' = 4. 256g
t h a ni n 1 . = l2l
tll
c i Youhaveto halve themoles of HCIbecause viiPurity= 100x 4.256915.249=8t.2o/o = [1]
there a r eh a l af sm a n vm o l eos f C a C 0a,s i C w hi ch i s betw een I4.75 and 14 . 95 = [ 1]
m o l eosf H C l . ii One of:
not reading from bottom of meniscus, not
3 a Any two of: reading meniscus at eye level, burette not
use a pipette to measure out the CuSO, solution vertical, air bubble below tap, funnel left in
[1] as the volume is measuredmore accurately; top of burette = [U
[1] use smaller piecesof iron [1] as there will be
less heat loss in a faster reaction [1];
use a polystyrene (or plastic) cup [f.] as this
reducesheat loss [1];
measure temperature for several minutes before a i l f p o s s i b ltei t r a t i o en x p e r i m e nsths o u l db e
addition of iron [f.] as this allows for a more d e s i g n et do g i v et i t r e so f a b o u 2t 5 c m ' .
accuratedetermination of the initial i i Y o us h o u l do n l yc h o o s tei t r a t i o vna l u e tsh a t
temperature [1,]; a r el e s st h a n0 . 2c m 3a p a r t .
measure temperature more frequently [1] as this b vi D on' tforgetthatthe rati oof H CIt o CaCOis,
makes the extrapolation more accurate [1]; 2 ' .1 .
use a thermometer which reads to 0.5 or 0.1 O C
[1] as this gives a more accurate temperature [1]; 5 a Place the chemicals in a round bottomed flask
stir the reaction mixture gently [1] as this
[1], fitted with a reflux condenser [1]. Heat for
ensures an even temperature in the liquid [1]. severalminutes [1]. Distil off the propan-2-ol
= [4]
-' d .g-' [1]. Collect the fraction that boils off around
b i Heat given out = 50.09 x 4.18Jg x 15.2' C 82 "C [1] = [5]
= 3 L 8 0J o r 3 . 1 8 k J = [1]
b A mount = 6.15 g + 123 g mol -' = 0.0500 m ol [ 1]
ii Amount of CuSOn= 0.500 mol d m - ' x 5 0 / 1 0 0 0 vol of NaOH = 0.0500 mol * 2.O mol dm-' =
dm'= 0.025mol = [1]
0.025 dm' = 25 cm' [L] = f}l
iii -3.18 kJ + 0.025 mol = -L27 kJ mol-' = [zl c 100o/oyield would give 0.0500 mol of propan-2-
(Lmark for the negative sign and 1.for the ol = 0.0500 mol x 60 g mol -' = 3.00 g t ll.
number) 80o/oyield = 3.00 x 80/1,00 = 2.4 g [1] = I2-l
d One of: the reaction did not go to completion;
it is an equilibrium reaction;
some propene was formed by elimination. = [1]
lll ,uErr
132 AnsweRs
ii AH, of CaCl(s)
= + 193 + 590 + LZt + (-36a) + (-650) = - 110 kJ
mol-t
(a)Thereaction is slow,so it mustbeheated. iii AH, of (ZCaCl(s) -' CaCl,(s) + Ca(s))
= -790 -2 x (-L10) = -57O kJ mol-'
s vnoel a t i lseo, a r e f l ucxo n d e n s e r
1 - b r o m o p r 0 pi a
m u sb y ep r o d u cmt u s bt ed i s t i l l e d
t eu s e dF. i n a ltl h Therefore products are more
offto separate it fromthereaction mixure. thermodynamically stable than reactants.
Thus CaCl will disproportionate.
2 NaF: Experimental lattice energy
= theoretical lattice energy.
Therefore it is nearly t0oo/oionic.
Unit4 MgIr: Experimental >> theoretical.
Therefore it is considerably covalent, becausethe
doubly charged Mg"'ion is much more polarising
II
Topic4.7 Energetics than the singly charged Na- ion.
Also the much bigger I- ion is more polarisable than
1 a i Ca*(g) + Cl(g) the smaller F- ion.
-364
Topic4.2 The PeriodicTableII
|.'no Ca*(g) + CI(g)
Ca(g) + Cl(g) l a i NaCl(s) + aq - Na'(aq) + Cl-(aq)
lt S i c l n+ Z H r O - S i O z + 4 H C l
l+nt lll PCl, + H.,O-' HrPOn+ 5HC1.
ca(g)+lrcb1sy
| +res
Ca(s)+'lrclr(g)
d g i v et h et o t a l lw
D on o tb et e m p t et o y rong
equation:
CaCl(s) N a C+l H , 0 - -N a O +HH C l .
It
ca'*(g) + 2cl(g)
.,,,0 NaCl is ionic and so iust dissolves

Sicln and PCl, are covalent and so react to give
J
Ca-(g)+ 2cl(g)
-364 x 2 H C I.
A lone pair of electrons on the oxygen atom of
l
HrO forms a dative bond into the empty 3d
| +seo ca'*(g)+ zcl-(g) orbital in the silicon atom. This releases
Ca(g) + 2Cl(g) enough energy to break the Si-Cl bond.
+ In CCln, the carbon atom has no 2d orbital and
x2 so a dative bond cannot form before the C-Cl
l+I2I bond breaks, and the four large chlorine atoms
Ca(g) + Clr(g)
+ around the small carbon atom sterically hinder
+1e3 the approach of a water molecule.
|
Ca(s)+ Clr(g)
As a base:
Al(OH).(s) + 3H.(aq) -'Al'.(aq) +3H,O(|)
CaClr(s) and as an acid:
A t(OH ),(s)+ 3OH -(aq)' [A I(OH ),]' -(aq)
is
Not et hatth e e n th a l poyf a to m i s a ti oonf c h l ori ne
f or t he r e a c ti o'n/,C 1 ,(g
--) C l (g ). Forthereactions of oxides andhydroxides, ionic
equations areusually easier. Basic oxides/hydroxides
r e a cwt i t hH -i o n st o g i v es i m p lpeo s i t i vi o
e n sa, n da c i d i c
b i NIr of CaCl,(s) oxides/hydroxides react with0H-ionsto givenegative
= + L93 + 5 9 0 + 1 L 5 0 + 2 x I2 ' 1 .+ 2 x (-3 64) + ions.
(-2237)
= -79O kJ mol-'
ANswERs 133
3 a i Mg(OH),(s) + 2H.(ae) * Mg'.(aq) + 2H,O(l) b i Becausereaction L*R is exothermic, a

ii PbO(s)+ 2H.(aq) --'Pb'.(aq) + H,O(l) decrease in temperature causesK. to
iii SO, + acid: no reaction. increase,and so the position of equilibrium
b i Mg(OH), + alkali: no reaction moves to the right.
ii PbO(s) + ZOH-(aq) + H,O(l) - Pb(OH),'-(aq) ii As the reaction going from right to left
iii SO,(g) + ZOH-(aq)* SO,'-(aq)+ H,O(l) causesan increasein the number of moles of
gas, a decreasein pressurewill causethe
4 a PbO, + 4HCl -' PbCl, + ZH'O + Cl, position of equilibrium to shift from right to
b Sn'.(aq) + 2Fe'.(aq)-* Snn.(aq)+ 2Fe'.(aq) left. K. is unaltered.
iii There will be no effect on either. A catalyst
Topic4.3 ChemicalequilibriaII speedsup the rate of both forward and back
reactions equally, and so equilibrium is
1, 2SO3+ 2SO, + o, reached sooner.
Start(moles) 0.0200 0 0
Change(moles) -0.0058 +0.0058 +0.0029 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
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 , dm-'
[ H - ] = [ C , H . C O OI
Equilib.moles 0.0142 0.0058 0.0029 K " = [H -l x [C .H .C OO I
il*/mol dm- 0.074217.52 0.0058/1.s20.002917.s2 lc.H.cooHl
= 0 .0 0 9 3 4 = 0.00382 = 0.00191 = [Hl' = 1 . 3 5x 1 0 ' m o l d m '
^
4= [SOJ" x [O,] Ic.H.cooHl
rsoT [H]= (K"x[C,H'COOH])
= (0.00382)'zx
0..00191 =@ --l.7zx1o-'moldm-'
(0.00e34)' pH=trtoslHt= 2.76
= 3.L9x 10" mol dm-''
2 a End poi nt i s at 25 cm' N aOH .
zNO(g)+O,(g) + 2NO,(g)
Start (moles) 1.0 1.0 0 l2
Total = 2 mol
Change (moles) -0.60 -0.30 +0.60 11
Equilib. (moles) 0.40 0.70 0.60 End point
10
Total= 1.7 mol
Equilib. mole 9 Half way
fraction O.4Oll.7 O . 7 O | I . 7 0.6011..7 p H 8
= 0 .2 3 5 = 0 .4 ' 1 ,2 = 0 . 3 5 3
Partial 7
pr es s ur e/ a tm O .2 3 5x 4 O .4 1 2x 4 0.353 x 4 6
^=o.g4 = L.65 = I.4l
Kn = (p of NOr)' 5
(p of No) x p o f O , 4
= (1.41)' 20 25
(oe4)TT.6s VolumeNaOH/cm3
= 1. 4 at m - '
H al f w ay to end poi nt i s 12.5 cm' ,
3 a which is when [HA] = [A-].
ISOr],"no,'
pH at this point is 4.95.
ffi ThereforepK = 4.95.
= (q.2\,
( o . 2 ) "x 0 . 1
b P henol phthal ei n.
= 10 mol-t dm'
3 a A buffer is a solution of known pH, which will
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 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
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 o f t h eg r a p h .
equilibrium.
134 ANswERS
resist change in pH when contaminated with

(b) cHs CHs
small amounts of either acid or base. It consists
of any weak acid and its coniugate base, such as I I
ethanoic acid and sodium ethanoate. --c(-'-- .-';c\
F U O H HO(/ F
H H
'Nearly
DonotsaythatthepHis constant. constant'
is acceotable.
l f t h e r ei s a d o u b lbeo n dl ,o o kf o rg e o m e t ri si co m e r s .
The salt is fully ionised: Drawthemwiththecorrect bondangles, not90".
CH'COONa(aq) - CH,.COO-(aq)+ Na-(aq) L o o kf o rf o u rd i f f e r egnrt o u pasr o u nadc a r b oant o m
The weak acid is partially ionised: f o ro p t i c ai sl o m e r i s m .
CH.COOH(aq) + H.(aq) + CH.COO-(aq)
The CHTCOO-ions from the salt suppressmost
of the ionisation of the acid.
Ms/drv ether
If H- ions are added to the solution, almost all CH3CHICHT----:---------+ CH3CH(MgI)CH3
of them are removed by reaction with the large
reservoir of CH.COO- ions from the salt, thus CO2(s)then
the pH hardly alters. HCI(aq)
H.(aq) + CH.COO-(aq)-* CH.COOH(aq) CH3CH(MgI)CH, CH3CH(CHJCOOH
If OH- ions are added, almost all of them are
or KCN
removed by reaction with the large reservoir
CH3CHICH: + CH3CH(CH3)CN
of CHTCOOH molecules from the weak acid,
thus the pH hardly alters. heat under reflux
OH-(aq) + CH,COOH -' CH.COO-(aq) + HrO(l) with HCI(aq)
CH 3cH(cH3)cooH
F ourequa ti o nasren e c e s s a fo ry r a g o o da n s w er, A n i n c r e a si en t h en u m b eor f c a r b o na t o m si n a c h a i n

w i t ho n eo f t h e ma s a n e o u i l i b r i urm
eaction. s eu s eo f a G r i g n a rrde a g e notr a c y a n i d e .
i n d i c a t et h
3 a Add water to each: ethanoyl chloride gives off

[H] = K" x [weak acid]/[salt]
steamy fumes of HCI; ethanoic acid shows no
[weak acid] = 0.44 mol dm-'
visible reaction.
A m ount of s alt = 4 .4 1 8 2= 0 .0 5 3 7 m o l .
1 -
T her ef or e [ s alt ] = 0 .0 5 3 7 /0 .L= 0 .5 3 7 m o l om
3 Add PCl, to each: ethanoic acid gives off steamy
fumes of HCI; ethanoyl chloride shows no
[H] = I.74xlO-s x0.44
0.537 visible reaction.
= 1.43 x 10-' mol dm-' b Add to a solution of iodine and sodium
Therefore pH = -log (1.43 x 1,0*;= 4.85. hydroxide: propanone gives a pale yellow
precipitate; propanal gives no precipitate.
Add ammoniacal silver nitrate solution and
warm: propanal gives a silver mirror;
propanone gives no mirror.
T h ec o n c e n t r a tni o ntt h en u m b eorf m o l essh o u lbde
u s e di n b u f f ecra l c u l a t i o n s . Answersto PracticeTestUnit 4
The allocation of marks follows Edexcel mark
schemes.
The marks that you will need for each grade are
Topic4.5 OrganicchemistryII approximately:
1 a
(a) H CI H CH"
\ / \ /
C-C C-C
/ \ / \
CHs CHs cHs ct
1t vet 5
ArusweRs
1.a iii One of: the reaction is faster, or no catalyst is

required, or with ethanol the reaction is an
equilibrium = [1]
Mg'.(g) zcl- (g
r
Ms"(g) zcl(s)
t I \
H
I
r H
l
H
r o - ?| - c| - H
l
r
Mg(s) +
t
Cl,(g) -* MgClr(s)
H-C-f
i
H
\
o
H H
Correct cycle with all state symbols [2]

Mfo,.ution = SU[l Of all Othef ChangeS
- 6 4 2 = + L 5 0 + 7 3 6 + 1 4 5 0+ 2 x 1 2 1
+2x(-364)+LE[2]
a A s a f u l ls t r u c t u r a
f ol r m u l a
w a sn o ta s k e dv, 0 un e e d
LE = -2492 kJ mol-' [1,] = [5]
n o ts h o wa l lt h ea t o m s .
b i The ionic radius of Sr'* is < that of Ba'' [1],
b A n ya m i n er , v o u dl do .
and so there is a stronger force of attraction
c F u l sl t r u c t u rfaolr m u l aver e r ea s k e ds.o a l la t o m s
bet ween c a ti o n a n d a n i o n i n S r(O H ) .than i n
a n db o n d sm u s tb es h o u r n .
Ba(OH),[r.] = l2'l
ii Energy is releasedwhen the d-oxygen atom in
water [1] is attracted to the positive cation [.]
3 a
= I2l CtH.t C.Ht
= -L?ttice energy + A-F1n,.,,o,inn
iii A.Ff,oru,,on of cation + I
Mhyd,u,ionof the anions [.] C.
I
'..
'oH ...c_
-.n,
AI1,,, Ba(OH), = +2228 - 1360 - 92O = -52kJ CHs t Ho I
tll H H
AI1,.,Sr(OH), = +2354 - 1480 - 920 = -46kJ
tll b Reagents:C,H.CHO[l] and CH.MgBr [1] or
so A-F/,o,u,,u.
of Ba(OH), is 6 kJ more exothermic CH*CHO [1] and C,H,MgBr [1]
and so it is more soluble [,] = l4l Conditions; dry ether solvent [1] = [3]
ci YiSCH,CHTCOCH, =[1]
ii Yisaketone =[1]
iii Add 2,4-dinitrophenylhydrazine [1] which
gives an orange ppt. [1]
a R e m e m bt h ear tl a t t i ceen e r g i e
a sr en e g a t i v e . Add Fehling's solution (or ammoniacal silver
b i i i l f y o uf o r g otto m u l t i p-l y4 6 0b y2 ( t h e r e nitrate) [1] which stays blue (does not give a
a r e2 0 H -i o n sy) o uw o u l dl o s e1 m a r k . silver mirror) [L] = [4]
Another wayto score the3rdand4th iv CH[,, [f.] and C,H.COONa [1] = IZf
m a r kiss :f r o mS r - - B a t, h el a t t i ceen e r g y
decreases by 126kJ [1],butAHnro,,,,o. of the
cation onlydecreases by120kJ [1]
a Y o um u s m t ake a na t t e m pa t a 3 - Dd r a w i nagn d
2 a i cH.cHrcHrc=N = [1] t h et w oi s o m e rms u s bt em i r r oirm a g eosf e a c h
ii LiAlHn or NaBHn = [1] other.
iii cH3cH2cHzcHzNH2 = [1] b i i i Y o um u s st h o wt h a ti t i s a c a r b o n y l
b i The lone pair of electrons on the N atom comooun adn dt h e nt h a ti t i s n o ta n
make it a base = [1] a l dhey de .
ii RNH, + H* - RNH3. = [1] b i v C , H . C 0 0wHo u l db ea c c e p t e adst h eo t h e r
c I organp i cr o d u c t .
H H H
H
\ l
-C-C-H
l 4 a = [1]
N
I / l l
H - C - (^
t \ H H b Amount of AtCl = 0.63g162.5g mol-' = 0.01 mol
I \ Amount of Alcl, = 0.67 9/133.5 $ rnol-' =
H o 0.005mo1 [1] total moles = 0.015
mole fractions: AlCl = O.667,AlCl, = 0.333 [1]
ii It forms a substituted amide = [1] partial pressures:p(AlCl) = O.667 x 2 = 1.33 atm
P (A l C l .) = 2 x 0.333 = 0.667 atm [L]
K " = (1.33 atm)' 10.667atm = 3.56 atm' 1f 1 = 1+1
--
, -e;
e A '
tal
\- ir
136 AxsweRs
c An increase in temperature shifts the equilibrium

in the endothermic direction. .'.AH is t4
positive = [1] 12
d Ko stays constant [1] The position of equilibrium
moves to the side with fewer gas molecules [1], 10
which is to the left [1] = [3]
Mix scrap aluminium metal with AlCl, and heat pH8
to form AlCl [U, remove from excessAl, then 6
cool (or increase pressure)and pure Al and AlCl3
are formed. The latter is then used again [1] = [2] 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 .
b Partial pressure is molefraction x totalpressure. Vol. NaOH/cmE
c K i s o n l ya l t e r ebdyt e m p e r a u r e .
Shape of curve correct [L], start at pH = 4 llf,
5 a i MgO(s)+ H,SOn(aQ) -- MgSO.,(aq) + H,O(l) vertical at 25 cm' [1] and at a pH of between 7 and
Correctequation [1] statesymbols[L] = lz'J 11 [f.], curve flattening off at pH 13 [1] = [5]
ii A white solid [1] reactsto form a colourless i HrSOl --' H* + HSO.,- [L]
solution [1.] = fz'l HSO.*-+ H* + SOn^ [1] = [2]
b i PnO,o+ L2NaOfl ---+4NarPOn+ 6HrO ii The second ionisation is incomplete and is
or PrO.,+ 6NaOH ---+2NasPOn+ 3HrO suppressedby the H. from the first ionisation,
All speciescorrect [l.], balanced [1] = I2f = [1]
and so produces very few H. ions
ii For having 2 equations, one with H' (or HCI)
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
AI(OH), + 3NaOH -'Na,Al(OH). [1] = [3] a Don'tconfuseweak(howionised) withdilute
MgO is basic, AI(OH). is amphoteric and PnO,o is ( h o wm a n ym o l e s ) .
acidic [L] showing the metallic character of the b T og e tf r o mp Ht o [ H - ]u, s et h e1 0 "b u t t oonn
element decreasingacrossthe period tll = f2l y o u rc a l c u l a t o r .
As a Group is descendedthe oxides get more 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
basic [1]. Indium is in the same Group as 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
amphoteric aluminium, so indium oxide will be 0.699.
basic [1] = I2l
Manystudents
Y o um u s m t ake
areverybadatwriting equations.
s u r et h a yt o ul e a r tnh ee q u a t i oinns
U n i5t
T o p i4c . 2o l t h es p e ci icf a t i o n . Topic5 .7 Redoxequilibria
a Whenever youareasked to statewhatyouwould
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
1 a i CrrOr'- (aq) + 14H'(aq) + 6e- -- 2Cr"(aq) +
afterreaction.
THrO
ii Snn.(aq)+ 2e- -- Sn'.(aq)
6 a An acid is a proton donor [,], iii IO, (aq) + 6H .(aq) + 5e- -' 1,1,+ 3H rO
Weak means that it is incompletely dissociated iv l, + 2e- -- Zl-(ag)
(ionised) [L], but dilute means that its
concentration is small [1] = [3]
b i pH = -log,u [H.] =[u
ii Ku = 3.72 x lO-" = [H.]tOCl-l
lHocll -r tU A l la r er e d u c t i oannsds oh a v e l e c t r o onn st h el e f t .
[ H] = 10- o n
= 5 .8 9 x 1 0 -' mo l d m tll
T h en u m b eorf e l e c t r o e s u a lt sh et o t acl h a n gi e
nq n
lHl = [octl tl] o x i d a t i onnu m b e r .
.'. tHOCll= (5.89x 10-')'* 3.72x 1 0 *
= 0.0932 mol dm-' [1] = [41
ANswERs 137
b i CrrO,'-(aq)+. 14H.(ag) + 3Sn'.(aq) - zCr'.(aq) +

TH.,O+ 3Snn"(aq)
Topic5.2 Transitionmetal
= +1.33 - 0.15 = +1.18 V.
E,"".tio. chemistry
Feasible as E,"u.tion
> 0.
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)
Equatioa ni i i s m u l t i p l i e
bdy3 , r e v e r s e
adnd from the lower to the higher energy level,
added
to equation a i. absorbing some of the red/green light and leaving
blue light.
Ior(aq) + 6H.(aq) + Sl-(aq)- 3I, + 3H,O 2 a [C r(H ,O).]" (aq)+ 3OH -(ag)-C r(OH ) , ( s) + 6H, O
= *1.19 - 0.54 = +0.65 V.
E,"u.tion
Feasibleas E"u..,o.
> 0.
T h i sr e a c t i oi snd e p r o t o n a t i o n .
Equatio a ni v i s m u l t i p l i e
bdy 5 1 2r,e v e r s e
adnd ) 3 O H - ( a Q+) C r ( O H ) . ' - ( a q )
then Cr(OH),(s+
a d d etdo e q u a t i oani i i .
,/ I
Equations are:
Fe(s^) + 2H.(aq) * Fe'*(aq)+ H,(g) 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
SFe"(aq)+ MnOf(ae) + 8H'(aq) - SFe*(aq)+
Mn'.(aq) + 4HrO + ZOH -(aq)- Fe(OH) : ( s)+ 6H, O
[Fe(H ,O)u]" -(aq)
Amount of MnOn- = 0.0235 x 0.0200 then no further reaction.
= 4 . 7 Ox 1 0 * m o l c [Zn(H,O),]'.(aq)+ ZOH-(ag)'Zn(OH).(s) + 4H.O
Amount of Fe'*in 25 cm' sample = 4.70 x 10* x 5/1 then Zn(OH),(s) + 2OH-(aq) - Zn(OH),r (aq)
= 0.00235 mol
3 a [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.
Thisreaction
is deprotonation.
Amount of Fe" in 250 cm' sample = 0.0235 mol
Mass of Fe'*= rl?ss of Fe = 0.0235 x 56 = 1.316 g
then no further reaction.
Purity of iron in steel = 1.316 x L00 = 99.7o/o
b [Cu(H,O)J'.(aq) + 2NH.(ae)- Cu(OH),(s)+
132 2NH; (aq) + 4H"O
Anode area: Fe(s)-- Fe'.(aq) + 2e-
Thisreaction
is alsodeprotonation.
0xidation
attheAnode,
soelectrons
ontheright.
then Cu(OH),(s)+ 4NH,(aq) + 2H,O(l) --'
[Cu(NH,)o(H,O)J'.(ag)+ 20H-(aq)
'lrOr(aq)
Cathode area: + HrO + 2e- -' 2OH-(ae)
Theoveralreacti
l on
i s l i gandexchange.
Reduction
attheCathode,
soelectrons
ontheleft.
4 a VOI(aq) + 4H.(aq) + 3e--- V'.(aq) + ZH,O
Between anode and cathode:

ZFe(OH),(s)+ 2OH-(aq) - Fe,O,(s)+ 3H,O(l) + 2e
'|,O,(aq) Vanadium(V) is reduced, soelectrons
+ H,O(l) + 2e- - 2OH-(ag) 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.
I
--
t
a
t
a
138 ANsweRs
'C),
b VOI(aq)+ ZH.(aq)1 e - VO"(aq)+ H,O If the temperature is too high (>5 the
c V"(aq) + HrO -- VO'.(aq)+ 2H.(ae)+ e- benzene diazonium chloride will decompose.
d VO"(aq) + H,O -- VOi (aq) + 2H.(aq)+ e- C.H.N=NC6H*O-but C.H'N=NC.H.,OH is
b
acceptable.
Topic5.3 OrganicchemistryIII
Tonic5.4 ChemicalkineticsII
L v r P v v . ^
1 a The bromine reacts with the iron catalyst to

form FeBr.: I Rate = klHll'
ZFe + 3Br, --' 2FeBr,
The FeBr. then reacts with more bromine to k = rate.
form Br'(the electrophile) and FeBrn. tHI]"
= 2.0 x 10' mol dm-' s-'
@
= 0.080 s' mol' dm'
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.
The intermediate cation loses H. to the FeBr". ,,,:'
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.
H t- \ st l- + Rapidly titrate with standard sodium hydroxide
GyB'l,,rl.-,,
v / l t l
1 solution using phenolphthalein as the indicator.
.# Repeat several times.
llr Plot a graph of the titre (which is proportional to
L B r I 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.
nu,+FeBr, Time taken to halve again to O.2 mol dm-'= 26
minutes.
O-u'* tr,ris a constant, therefore reaction is 1st order.
Topic5.5 OrganicchemistryIV
Check that:
1 a Add 2,4-dinitrophenylhydrazine. Both give an
,s.thearrowstartsonthedelocalised ringandgoes
orange precipitate.
towards theBr-(andnotto the+ of Br-) Add ammoniacal silver nitrate solution. Only
.'ffi
theintermediate hasa broken delocalised ring pentanal will give a silver mirror on warming.
witha+insideit
.r thearrowstarts fromtheo bondof thering/H
a t o ma n dg o e s
i n s i dteh eh e x a g o( bn u tn o t
directly to the+). s r e dp r e c i p i t a t e ,
g i v ea
F e h l i n gs'osl u t i ow
n ,h i c h
couldbeusedin place of ammoniacal silvernitrate.
It is energetically favourable for the intermediate
cation to lose an H* and gain the stability of the Heat under reflux with aqueous sodium
benzene ring, rather than add Br- as happens with hydroxide.
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 Halogenoalkanes arecovalent andso mustfirstbe
molecules, producing the necessaryCN- ions. h y d r o l y steodp r o d u chea l i dieo n s .
'C),
3 a If the temperature is too low (<5 the rate is
too slow. Cool and acidify with dilute nitric acid, then
add silver nitrate solution.
ANswERs 139
The 2-bromo compound gives a cream approximately:

precipitate insoluble in dilute ammonia but
soluble in concentrated ammonia.
The 2-chloro compound gives a white
precipitate which dissolvesin dilute ammonia.
Warm with dilute sulphuric acid and potassium

dichromate(VI) solution and distill off any
product into ammoniacal silver nitrate
a i C onsi der experi ments1 & 2: w hen [ RCHr Cl]is
s olut ion. i ncreased3 ti mes, rate al so i ncreas es3 t im es
Methylpropan-Z-ol does not change the colour
[U , .' . 1st order w i th respectto [R CHr Cl] .t ll
of the potassium dichromate(VI). C o n s i d e re x p e r i m e n t s1 & 3 : w h e n
Methylpropan-1-ol turns it from orange to
concentrati onsof both are doubl ed, t he r at e is
green and the distillate gives a silver mirror.
i ncreased-l ti mes [1], .' .1storder w it h r espect
Butan-2-ol turns it from orange to green and to [OH ] as n' el l [1] = [4]
the distillate has no effect on the silver nitrate i i R a t e= k [ R C H . C l lx [ o H ] = [1]
solution. To confirm, add a few drops of the i i i k = r a t e / ( [ R C H - C lxl [ O H - ] )
butan-2-ol to iodine and aqueous sodium = - 1 . 0x l 0 ' m o l d m ' s '
hydroxide and warm gently. A yellow 0 . 0 5 0m o l d m x 0 . 1 0 r n o l d m - '
precipitate of iodoform will be produced. = 0.080 [r] mol ' clm s ' [U = l2'l
i v A s i t i s l st order i n both, i t i s a S ,,2m echanism
tu.
_ R
R
T h e1 ' a l c o h oi sl p a r t i a l ol yx i d i s et d
o a na l d e h y d e . \ I
T h e2 " a l c o h oi ls o x i d i s etdo a k e t o n e . /--\ ^ I
H - ()' Cl ----------------H - () ----C---- Cl ----------------

T h e3 " a l c o h oi ls n o to x i d i s e d . ,(:- D r
H l / \ :
B u t a n - 2 -cool n t a i ntsh eC H , C H ( 0 H g r)o u pa n ds o
H - H H - J
g i v e sa p o s i t i vieo d o f o r m
test.
R
/
/
HO-C^ CI
The substanceis probably aromatic (> 6 carbon r\
atoms and about the same number of hydrogen l H
H
at om s ) .
120 is the molecular ion. Curlv arrows from O of OH- to C and from C-Cl o
105 is 15 less than 12O and is probably causedby bond to Cl [1], correct transition state [L] = [3]
loss of CH,..
77 is probably causedby the (CuH,).group (77 is 43
less than 720 and is probably caused by loss of
cocH.).
X is probably C.H.COCH..
The 120 peak is causedby (C.H.COCH3)., i Y oumustmakei t cl earw hatdatayouar e
the 105 peak by (C.H.CO)', u s i n ga n dh o wy o ua r r i v ea t e a c ho r d e r .
and the 77 peak by (CuH,).. i v Makesurethatal l yourcurl yarowsst ar t
e i t h ear t a b o n da n dg o t o a n a t o m0 r a t a n
32OOcm-' is due to O-H, 1720 cm-' is due to C=O, a t o ma n dg o t o a b o n d .
and 1L50 c m -' i s d u e to C -O .
Six of the carbon atoms are in a benzene ring. The 2 a The el ectrophi l ei s C H .C O* [1].The equat ion is:
remainder are either CrH, group or 2 x CH, groups. CH,COCI + AlCl,,--+ CH,,CO.+ AICI*- [t] = I2l
Y is C.H,CHrCH..
b
[5 H's in CoH.,2 H's in CH, and 3 H's in CH..] H i
Z is CoH,(CH.)r.
i At
c+ _-_+ l ( * . I t .--.-} ^v\
l( )l cH,
\
CH,
v/\ -
CH,
v + H *
[6 H's in 2 x CH, groups, 4 H's in CuHr.]
Curly arrow from ring to C of CO' [1], correct
intermediate [,], curly arrow from C-H o bond to
Answersto PracticeTestUnit 5 ring [L] = [3]
Reactthe phenylethanone, C.HTCOCH3, with
The allocation of marks follows Edexcel mark HCN [1], with a trace of base (or in a solution
schemes. buffered anywhere between pH 5 to 9 or add a
The marks that you will need for each grade are mixture of HCN and KCN) tll. This produces
i
140 ANswERs
4 a Dip a platinum elec-trode[1] into a solution

CHs
which is L mol dm-'in both Fe'*and Fe'. ions [1].
I This is connected via a salt bridge (containing
CsHs- C -CN potassium chloride solution) [U to a standard
I hydrogen electrode [1]. The potential is measured
oH tll with a high resistancevoltmeter (or a
potentiometer) [L] = [5]
Now add aqueous sulphuric acid (or any -
b i Au''* + 3e- Au [1]
named acid) [L] and heat under reflux [1]
_
= [51 Fe" -t Fe"*+ e- [1] = l2l
ii Au" + 3Fett- Au + 3Fet' = tll
d Mix known amounts of ester and oH- [1]
iii Au'. + 3e- - Au E (gold)
remove sample [t]
3Fe' *-- 3Fet' + 3e- E ' = -0 . 77 v
at known time [1.]
adding the two half-equations gives E cell
quench the reaction by adding ice cold water [1,]
E (gold) + (-0.77) = E' (cell) = + 0.73 [U
titrate unreacted OH- with acid [t] = [21
E (gold)= * 0.73+ O.77= + 1.50V[1]
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]
b i Reduction (gainof electrons) takesplace atthe

goldelectrode because it actsasthecathode.
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
b Thecurlyarrowmustgotowards theC of theC0nolthe 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 .
C o f t h eC H g, r o u pT. h ei n t e r m e d ima tues h
t ave a broken i i i M u l t i p l y itnhgeF e ' h y3nd o e sn o t
. a l f - e q u a tbi o
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 a l t eirt sF v a l u e .
t h eb o n dw i t ht h eC H , Cg0r o u p . A n o t h ewra yo f d o i n g t h ec a l c u l a t i os tno u s e
thestandard reduction potentials thus:
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
m e a s u r itnhgep Hc h a n goev e tri m ew o u l d score a 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
m a x i m uomf 6 . a g e n(ti r o n=) P o f t h ec e l l .
3 a The reagent for step 1 is magnesium [1], and the 5 a 3d 4s

conditions are dry ether [1]
b i
= l2l
Potassiumdichromate(Vl) [1] and sulphuric
acid [1] = f2l
Fe:rArlrutrntrtr m
ii Distil off D as it is formed [1] = [1]
iti Ethanoic acid (CH.COOH) or ethanoate ions
(cH3coo) tll
E is CHTCH,CH(OH)CH. [f.] for any secondary
= [1] cr: rA4trtrtrtrtr
alcohol and [.] for the correct formula = f2l
d i F is a carbonyl compound as it reacts with
Z,4-dinitrophenyl hydrazine [U, but it must
be a ketone and not an aldehyde as it does
cr3*:
rArltrtrnII
not react with ammoniacal silver nitrate [1]
= I2l b FeCrOn+ 4C - Fe + Cr + 4CO
species [1], balancing of equation [1] = f2l
ii In order to do the iodoform reaction F must = [1]
i [Fe(HrO)u]"
have the CH.CO group [1] and the products -
= t3l ii [Fe(H,O).)'.+ ZOH- Fe(OH), + 6H,O
are CHI,. [1] and CH.CH,COO- [U
= r2l or [Fe(H,O)u]'.+ ZOH- -' [Fe(OH),(H,O)J + ZH.O
iii F is CH,CH,COCH. [2]
= correct iron speciesin product [1] balance
e The speciesare: (CH.CHTCOCH..).for m/e 72 [1], = fzf
(COCH.). for 43 [1] and (CH3CH,)' for 29 tll tll
_ t3l iii The precipitate's colour is pale green = [1]
iv [Cr(OH)J'- = [1]
v The solution of R would first give a Sreen
precipitate [1], which forms a green solution
with excessacid [1] = I2l
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 d i The standard electrode potential is the
s i l v e r / a m m o cn oi am p l eixo n s . potential difference between a standard
c G r ignar rdeag e n ts t i tha n a l d e h y dto
re a c w e g i v ea hydrogen electrode and the half-cell [1] where
s e c o n d aa r yl c o h o l . all concentrations are 1-mol dm-'and the
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 are pressure of all gasesis 1 atm. [L] = I2l
a l c o h o lws i t ha C H , C H ( 0 H g r) o u pk, e t o n ews i t ha ii All four halogens will oxidise Cr'* = [l]
C H , , Cg0r o u pa n de t h a n a l . iii Both bromine and iodine will not oxidise Cr''*
o nth es p e c i eisn a ma s ss pectrum. ' further = [1]
e Don' ft or gett hec h a rg e
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]
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
a R e m e m b tehr a t3 d ' ,4 s ' i s m o r es t a b l e t h a n3 d 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
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 score4 s marks.
t he4 s e l e c tro nasrel o s tfi rs tw h e nc ati onsare 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
fo r m e d . 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
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 t h er i g h o t f t h ee q u a t i o n
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 d Don'g 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
b o n d e od n . doesn t decompo0 sen h e a t i nign t h el a b ,n o r
iv Chromium i s a m p h o t e r iIcC. r ( 0 H ) ,w ] -o u l db e B e C 0b e c a u si ted e c o m p o sbees l o wr o o m
a n a c c e p ta bal en s w e r. temoerature.
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 Answer any two of the section B questions
h y d ra tem d e ta il o n s .
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]
Answersto PracticeTestUnit 68 it releasesthe nitrogen slowly [L]
b The smaller the K" of the conjugate acid, the
= [21
The allocation of marks follow Edexcel mark schemes. stronger the base [1]. Therefore ammonia is the
The marks that you will need for each grade are stronger base [.] = I2l
approximately: 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 O H H
/ll , \
l\ ll | , \
+. -( cH,)--i-
*-(.n,),-*+ tu
1 a Amount of NaOH = 0.100 mol dm-' x 0.0280 dm' \ l
= 0.00280 mol [f.] = moles of H.
Ratio H. to NHn*= 1 : 1". d i The reagentsare : liquid bromine [1] and
Amount of NH.,.in 25 cm' = 0.00280 mol. concentrated sodium hydroxide [1]. The
Amount in 250 cm' = 0.0280 mol [L] condition is that it must be heated [1] = [3]
'1,
Amount of (NHr)rSOn- , O.o280= 0.0140 mol ll NH.NH, = [u
[ 1] , e l Solids are not included in Ko expressionsand
mass of (NHn)rSOn - 0.0140 mol x 132 g mol-' = ammonium nitrate is a solid. = [1]
1. 848 I [ 1] , ii As the reaction is endothermic, the energy
o/o(NH*)'SO.* in fertiliser = 1".848x 100/3.80 = level of the products is higher than that of the
48.60/ofaf = [5] reactants [1], therefore the reaction is said to
b Any two of: not all ammonia driven off [1];
ammonia incompletely absorbed by the HCI [f,];
some ammonia gas escapes[1] = I2l
i Ba'.(aq)+ SOn'-(aq) - BaSO.(s)
Species[1], state symbols [1.] = f2l 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
ii To ensure that all the sulphate ions were evaporates especially if thereis norainwithin4 daysof
precipitated = [U applicatio l tnc .a n n obteb l e n d ewdi t hp h o s p h antoer
d Many carbonateswill decomposeon heating [L], 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
and the CO, gas evolved will result in a lower s o i l sl.t c a nc a u sdea m a gt o e s e e d l i n gl tsd. o e sn o tw o r k
mass being recorded [1]. An example is CaCO. [1] i f t h es o i li s t o oc o l d .
CaCO, - CaO + CO, [1] = [4] c Thestronger thebase, theweaker itsconjugate acid.
d T h e r m o d y n asm t ai cb i l i itsyt o d ow i t hA Ha n dk i n e t i c
stabilitv is to dowiththerateof thereaction.
142 ANswERs
be thermodynamically stable [1] and the

equilibrium lies to the left [U.
As the reaction proceeds on moderate heating,
the activation energy is fairly small [1] and so a i Carehasto betakenif youwishto stoptheoxidation
the reaction is kinetically unstable [1] o f a p r i m a rayl c o h o a ltt h ea l d e h y d e .
3 a i The reagents are potassium dichromate(Vl) [1] ii Asalways makesurethatyourcurlyarowsstarton
and sulphuric acid [1]. The conditions are a na t o ma n dg ot o f o r ma b o n do r s t a rot na b o n d
careful heating and distil off the aldehyde as it a n dg ot o a na t o m .
is formed [.]. = [3] i i i t h er e a c t i oi sns i m p lRy - C N- R C O 0 H .
ii The conditions for the addition of HCN to a i v t h ec o n cs u l p h u rdi ce h y d r a t h ee t ol a C = C .
sa l c o h o
carbonyl compound are KCN in aqueous Y o uw e r et o l di nt h es t e mt h a tH Ad e c o l o u r i s e d
ethanol at a pH of 8 (or a mixture of KCN and b r o m i nwea t ear n ds oi t i s u n s a t u r a t e d .
HCN) [1] b ii Thisis thestandard answer to themodeof action of
The mechanism is: a buffer andmustbelearnt.
H H
4 a The Fe ion is 3+ whereas the Na ion is only 1+ [1]
/ I The Fe'*ion is much more polarising than the Na.
R- i {-'cN=----------n- C-CN €
l n ion [L], and so it draws the electrons [.] from the
/\ I t t large Cl- ion towards itself and the bond becomes
\.--o o- H-cN = f4l
H \-/
+H,o* H,o*
o ;""tXt:,'ii;iil" + [Fe(H,o),oH]*
[r]^
I acid [Fe(HrO)J'.' coniugate base[Fe(HrO).OH]'.
R- C -CN tll
I
OH
base HrO: coniugate acid H.O. [1] = [3]
ii a red precipitate will form [.]
which stayswith excessNaOH [1]
[1] for a curly arrow going from the C in CN- --
[Fe(HrO),]'.+ 3OH- Fe(OH). + 6HrO [1] or
[1] for a curly arrow going from the C:O z bond [Fe(H,O)u]".+ 3OH- -.
[Fe(H,O).(OH).]+ 3H,O
to the oxygen atom The reaction is deprotonation. [L] = [4]
[1] for the intermediate with its - charge = [4]
iii The bonding is dative covalent (coordinate)[1]
iii CH,CH,CH,CH(CH.)CH(OH)CN+ HCI + zH,O The ligands split the d-orbitals into two levels
-- CH.CH,CH,CH(CH3)CH(OH) COOH
tll
+ NH'CI [.], The light is absorbed and a d electron
correct formula of organic product [1] = l2l promoted from the lower to the higher level.
iv cH, H tll = [3]
\.-./ c Each oxygen is -2, :. 4 oxyg€rrs= -8. The ion is
o 2-, and so the Fe is +6 (6+ and 8- make 2-) tll
/ \/ There are two ways. The first is: add excess
cHs- cHz- cHz c.
acidified potassium iodide solution to an aliquot
O-H of the FeOn'-solution [1], then titrate the
HA liberated iodine against standard sodium
= [1] thiosulphate solution [1], adding starch when the
solution becomespale yellow and stopping when
b i K. = [H,O.] x [A-] or [H] instead of [H,O.] [1] it is colourlesss[1]
IHA] The second method is: add excessacid to an
lH.ol=[Al=./-(rrl=@ aliquot [1], then titrate against standard FeSOo
= 6. 71x L 0 " m o l d m-' [1 ] solution [1] until the solution becomes very pale
pH = -log (6.7L x LO') = 3.L7 lll = [3] pink [1] = [4]
ll The acid is partially ionised: HA =. H* + A-
The salt is totally ionised: NaA - Na. + A- tll
This suppressesthe ionisation of the acid and
so both [HA] and [Al are large compared to
any H* or OH- that may be added. [1] a A c o m p a r i swo int hN a Cm l u sb t em a d e .
When H'is added, it is removed by the b i Makesurethatyouidentify bothacid-base pairsand
reaction: l a b et lh e mc l e a r l y .
H. + A--- HA [1] i i l r o ni s n o ta m p h o t ear incds ot h ep p ts t a y isn e x c e s s .
If OH- is added, it is removed by: iii Aftertheelectrons havebeenexcited theygradually
OH- + HA -- A- + H,O [1.] = [4] fallbackto thelowerlevelgiving outheat, andare
thenready to absorb photons.
c FeO.,'- is verylikeMn0.,- in colour andin oxidising power.
Soyoucanuseeither thestandard method of estimating
o x i d i s i nagg e n t(si o d i ntei t r a t i o o
n r)t h em a n g a n a t e ( V l l )
m e t h owdh i c hi s d i r e ct ti t r a t i owni t hi r o n ( l li)o n s .
APPEN DIX
A
ffi reactions
organic
1. AS and A2 (synoptic)
Alkanes, e.g. ethane CIITCII,
. Ethane ---+carbon dioxide and water
Reactant: oxygen (air)
Equation: 2CH,CH, + 7Or- 4CO, + 6H,O
Conditions: burn / spark
Classification: combustion
o Ethane ---rchloroethane
Reactant: chlorine
Equation: CH,CH, + Cl, - CH,CHTCI+ HCI
Conditions: sunlight
Classification: free radical substitution
Alkenes, e.g. ethene, H'C{H,
. Ethene ---+ethane
Reactant: hydrogen
Equation: H2C={H, + Hr -+ CH,CH,
Conditions: heated nickel (or platinum) catalyst
Classification: addition or reduction or hydrogenation
. Ethene + I,2-dlbromoethane
Reactant: bromine
Equation: HrC<H2 + Br, - CHTBTCH'Br
Conditions: bubble ethene into bromine dissolved in hexane
Classification: electrophilic addition
a Ethene -> bromoethane
Reactant: hydrogen bromide
Equation: HrC<H, + HBr - CHTCHTBT
Conditions: mix gasesat room temperature
Classification: electrophilic addition
o Ethene ---;ethan-1,2-diol
Reactant: potassium manganate(Vll) solution
Equation: HrC:CH, + [Ol + HrO - CHr(OH)CHTOH
Conditions: a solution made alkaline with sodium hvdroxide
. Ethene -+ poly(ethene)
Reactant: ethene
Equation: n HrCdH, ---+fCHr-CHr),,
Conditions: 2000 atm pressure,250 "C
Classification: addition polymerisation
Halogenoalkanes, e.g. l-bromopropane
o l-bromopropane ---+propan-l-ol
Reactant: sodium (or potassium) hydroxide
Equation: CH3CHTCHTBT + NaOH --- CHTCHTCHTOH
Conditions: heat under reflux in aqueous solution
Classification: nucleophilic substitution
o l,-bromopropane ---' propene
Reactant: potassium hydroxide
Equation: CH,CH,CHTBT+ KOH --r CHrCH:CH, + KBr + HrO
Conditions: heat under reflux in ethanolic solution
Classification: elimination
o L-bromopropane --+ butanenitrile
Reactant: potassium cyanide
Equation: CH3CH,CH,BT+ KCN --+ CH.CH2CH2CN+ KBr
Conditions: heat under reflux in a solution of ethanol and water
o L-bromopropane ---;1-aminopropane
Reactant: ammonia
Equation: CH.CHTCHTBT + 2NH, + CH.CH2CH2NH2 + NHnBr
Conditions: heat a solution of ammonia in ethanol in a sealedtube
APPENDIx
. 1-bromopropane ---+Grignard reagent (A2 only)

Reactant: Magnesium
Equation: CH,CHTCH,BT+ Mg ---' CH,CH,CH,MgBT
Conditions: warm (in water bath) under reflux in dry ether
Alcohols, €.S. ethanol
o ethanol ---;ethanal
Reactant: potassium dichromate(Vl) + dilute sulphuric acid
Equation: C,H,OH + [O] ----rCH.CHO + HrO
Conditions: heat carefully and distil out the aldehyde as it is formed
Classification: oxidation
o ethanol ---+ethanoic acid
Reactant: potassium dichromate(Vl) + dilute sulphuric acid
Equation: CTH,OH + 2lO) ---+CH,COOH + H,O
Conditions: heat under reflux
NOTE: Secondaryalcohols are oxidised to ketones and tertiary alcohols are not
oxidised.
CH3CH(OH)CH,+ [O] - CH,COCH. + H,O
(CH.).COH + [O]----rno reaction; potassium dichromate solution stays orange
o ethanol --+ ethene
Reactant: concentrated sulphuric (orphosphoric) acid or aluminium
oxide
Equation: CTH'OH - HrO ---+HrC:CH,
Conditions: heat
Classification: dehydration
a ethanol -> chloroethane
Reactant: phosphorus pentachloride
Equation: CTH'OH + PClr --- CrHrCl + POCI. + HCI
Conditions: dry
o ethanol ---+bromoethane
Reactant: hydrogen bromide
Equation: C,H.OH + HBr - CrH.Br+ H,O
Conditions: HBr made in sitttfrom 50(%sulphuric acid and solid potassium
bromide
o ethanol ----r
iodoethane
Reactant: hydrogen iodide
Equation: CTH.OH+ HI ---+C,H.l + H,O
Conditions: HI made in situ from iodine and moist red phosphorus
2. A2 only
Grignard reagents, e.8. ethylmagnesium bromide
o Ethylmagnesium bromide ---+ethane
Reactant: water
Equation: CrHrMgBr + HrO - CrHu+ Mg compounds
o Ethylmagnesium bromide ---' a secondary alcohol
Reactant: an aldehvde such as ethanal
Equation: CrH,MgBr + CH.CHO --+ CH,CH(OH)C,H.
Conditions: dry ether solution, then hydrolyse with dilute acid
Classification: nucleophilic addition to the aldehyde
o Ethylmagnesium bromide ---+a tertiary alcohol
Reactant: a ketone such as propanone
Equation: CrHrMgBr+ CH,COCH. - (CH.),C(OH)C,H,
Classification: nucleophilic addition to the ketone
o Ethylmagnesium bromide ---;a carboxylic acid
Reactant: (solid) carbon dioxide
Equation: CrHrMgBr + CO, ---tCTHTCOOH
Carboxylic acids, e.g. ethanoic acid
o ethanoic acid ---+an ester
Reactant: ethanol
Equation: CH,COOH + C,H,OH:CH.COOC,H, + H,O
Conditions: heat under reflux with a few drops of concentrated sulphuric acid
Classification: esterification
APPENDIX
o ethanoic acid ----ran alcohol

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

o ethyl ethanoate --+ acid + alcohol
Reactant: any aqueous stront acid such as dilute sulphuric acid
Equation: CH,COOC'H, + Hp-CH,COOH + C'H.OH
Classification: reversible hydrolysis
o ethyl ethanoate ----rsalt + alcohol
Reactant: aqueous sodium hydroxide
Equation: CH,COOCTH,+ NaOH - CH,COONa + C,H.OH
Classification: hydrolysis (saponification)
Carbonyl compounds aldehydcs, e.g. CHTCHO, and ketones, e.g. CHtCOCH3

o Both react with:
Reactant: 2,4-dinitrophenylhydrazine
Equation: >c{ + NH.NHC.H,(NO.): ---+>c:N-NHC6H'(No')' + H'o
conditions: mix solutions: oranSe precipitate observed
o Both react with:
Reactant: hydrogen cYanide
Equation: >C{ + HCN -+ >C(OH)CN
conditions: potassium cyanide + some dilute sulphuric acid
Classification: nucleophilic addition
o Both react with:
Reactant: lithium aluminium hydride (or sodium borohydride)
Equation: cH,CHo + 2[Hl - CH'CH'OH (a primary alcohol)
CH.coCH, + 2[Hl - CH'CH(OH)CH. (a secondaryalcohol)
Conditions: dry ether, then hydrolyse with dilute acid
o Aldehydes only react with:
Reactant: Fehling's solution or ammoniacal silver nitrate
Equation: CH,CHO + [Ol + OH- ---rCH'COO- + H,O
Conditions: warm
o Carbonyl compounds with a CH,CO group give a yellow precipitate of iodoform
with:
Reactant: iodine and sodium hydroxide solution
Equation: cH,cocH, + 31,+ 4OH- ---+CH3COO-+ CHI, + 3I- + 3HrO
Acid chlorldes, €.8. ethanoyl chloride

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

Reactant: ammonia
Equation: CH.COCI + 2NH. -+ CH,CONH, + NH'CI
ethanoyl chloride ---+a substituted amide
Reactant: an amine
Equation: CH.COCI + CrH.NHr --+CH.CONHCTH.+ HCI
Amines, e.g. CrHrNH,
o ethylamine --+ a salt
Reactant: any acid such as hydrochloric
Equation: C2H.NH2+ HCI ---tCrHrNHr.Cl-
o ethylamine ---Ja substituted amide
Reactant: an acid chloride
Equation: C2H.NH2+ CH.COCI ---+CH.CONHCTH.+ HCI
Nitrlles, e.g. CIITCN
o ethanenitrile ----rethanoic acid
Reactant: dilute sulphuric acid (or sodium hydroxide followed by
acidification)
Equation: CH.CN + H* + zHrO ---+CH,COOH + NHn.
Classification: hydrolysis
. ethanenitrile --+ethylamine
Reactant: lithium aluminium hydride
Equation: CH3CN + a[H] --+ CH.CHTNH,
Conditions: dry ether then hydrolyse with dilute acid
Amides, e.g. CHTCONH,
o ethanamide ---+methvlamine
Reactant: bromine and sodium hydroxide
Equation: CHTCONH, + Br, + 2NaOH ---+CH.NH, + 2NaBr + HrO + CO,
Conditions: liquid bromine and conc sodium hydroxide
Classification: Hofmann degradation reaction.
o ethanamide --+ ethanenitrile
Reactant: phosphorus(V)oxide
Equation: CH,CONH, - HrO ---+CH.CN
Conditions: warm
Classification: dehydration
Benzene
o benzene---+nitrobenzene
Reactant: concentrated nitric acid
Equation: CuHu+ HNO. -- CuHrNO,+ HrO
Conditions: mix with concentrated sulphuric acid at 50 'C
Classification: electrophilic substitution
a benzene ---;bromobenzene
Reactant: bromine
Equation: C.H. + Br, ----rCuHrBr+ HBr
Conditions: liquid bromine with an iron catalyst
o benzene --+ ethylbenzene
Reactant: chloroethane
Equation: C.Hu+ CrHrCl ----tCuHrCrH,+ HCI
Conditions: anhydrousaluminiumchloridecatalyst
o benzene ---+phenylethanone
Reactant: ethanovl chloride
Equation: CuHu+ CH.COCI ---,C.HTCOCH,+ HCI
Conditions: anhydrous aluminium chloride as catalyst
Alkylbenzenes, e.g ethylbenzene
o ethylbenzene ---)ethanoate ions
Reactant: potassium manganate(Vll) + sodium hydroxide
Equation: C5H'C2H,+ 6[0] + OH- ---' C.HTCOO-+ 3H,O + CO,
APPENDIX
Phenol
o phenol' sodium phenate
Reactant: sodium hydroxide
Equation: C.HTOH+ NaOH --- CuHrONa+ HrO
. phenol -"+ 2,4,6-tribromophenol
Reactant: bromine
Equation: C'H.OH + 3Br, -r HOCuHrBr.+ 3HBr
Conditions: aqueous; orange bromine water forms a white precipitate
o phenol -+ phenyl ethanoate
Reactant: ethanoyl chloride
Equation: C.H.OH + CH,COCI --+CH,COOC.H. + HCI
Nitrobenzene
Nitrobenzene ---)phenylamine
Reactant: tin and concentrated hydrochloric acid
Equation: C'H,NO, + 6[Hl - C"H'NHr+ 2H.O
Conditions: heat under reflux, then add sodium hydroxide
Phenylamine
Phenylamine --r diazonium ion + azo dye
'C; step 2: phenol
Reactant: step 1: nitrous acid at 5
Equation: CuHsNH2 + 2H' + NO, - C.H.N,' + 2H.O
CoHrN2'+C"H.OH - HOC.H.-N:N-C"H. + H.O
Conditions: mix phenylamine with sodium nitrite and hydrochloric acid at
5 "C, then add phenol in sodium hvdroxide solution.

Edexcel AS Chemistry Guide

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7Strurtu,r,o,bo@ al4d,

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

ixj Thingsto understand

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

F ig l. l Theorderof filling of atomic

Sizes of atoms and ions

lst ionisation enerry

O There are slight decreases after Group 2 (this is because,for Group 3, it

Successive ionisation energies

Explain the difference between relative isotopic mass and relative

State,giving your reasons,which group the element X is in.

6 a Sketchthe variation of 1st ionisation energyagainstatomic number

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

The keysto this topic are:

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

Carbon 48.7 48.7+12-4.1 4 . I + 2 . 7= 1 . 5

Asyolume indm-= volume in

Calculation of number of particles

Calculations based on reactions

Reocting moss questions

Step1 Step2 Step3

For Steps1 and 3 usethe relationship:

Titrotions (this will only be exomined ot AS in Unit test 38)

SteP1 Step2 Step

For Steps1 and 3 usethe relationship:

Gos volume colculotions

Step1 Step2 Step3

Step 1 use the relationship:

For calculations involving gasesonly, a short cut can be used. The

t-J Write balancedionic equations.

Chlorides All solubleexceptfor AgCl and PbCI,

Hydroxides All insolubleexceptfor Group 1 and

Write ionic equations for the reactions of solutions of:

1.a An organic compound contains 82.760/o carbon and 17.24o/o

O Intermolecular forces(between covalent molecules)

400 400 400

Fig 1.4 Boilingtemperatures

Effect of heat (melting)

90"and 180' -?'-

LJ tfre effect of difference in electronegativity on type of bonding

J the effect of size and charge of ions on the type of bonding

J the trends in boiling temperatures caused by intermolecular forces

O State which types of bond are present in a double bond as in O=C=O.

o State which of the cations above:

O State which of the anions above is the most polarisable.

Which is the most electronegative element in each list:

o List all of the following molecules that are polar:

H2 HCI HrO NH, CHn

o Rearrange the noble gasesin order of decreasing boiling temperature:

o Which of the following form hydrogen bonds between their molecules?

H,O NH, HF HCI CO, CHn

1 Draw a diagram of two p orbitals overlapping which produce:

Theanswersto thenumbered a aobond

Intermolecular forces can be divided into three types:

4 Solid structures can be divided into six types:

iodine ice, HrO(s) copper

poly(ethene) graphite sulphur

Explain the processesof melting and boiling in terms of the

Molecule/ Number of Number of Total number Shape

Explain why solid sodium metal conducts electricity whereassolid

Things to learn and understand

Melting (and boiling) temperatures of the Period 3

T)() Testingyour knowledgeand understanding