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Figure 3 If the 6.02 x 10 23 atoms in 12 g of
carbon were turned into marbles, the marbles
could cover Great Britain to a depth of 1500 km!
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Figure 3 The mass spectrometer.
Figure 3 The mass spectrometer.
Figure 7 Variation of first ionisation enthalpy
with atomic number for elements with atomic
numbers 1 to 56.
Figure 8 Successive ionisation enthalpies
for aluminium.
sample inlet
electron gun
magnetic field
(at right anglesto paper)
ion detector
ionisation chamber
accelerating electric field
heavy particles
intermediate
particles
lighter particles
pump maintains
low pressure
He
Li
Ne
Na
Ar
K
Kr
Rb
Xe
Cs
2500
2000
1500
1000
500
Atomic number
50403010 200 I
o n i s a t i o n e n t h a l p y /
k J m o l – 1
Ionisation1st 2nd 3rd 4th 5th 6th 7th 8th
20 000
10 000
0 I o n i s a t i o
n e n t h a l p y / k J m o l – 1
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Figure 9 Successive ionisation enthalpies
for phosphorus.
Energy
Shell Sub-shell
n= 4
n= 3
n= 2
n= 1
444343
3
22
1
f dpdsp
s
sp
s
Figure 10 Energies of electron sub-shells from
n = 1 to n = 4 in a typical many-electron atom.
The energy of a sub-shell is not fixed, but falls as
the charge on the nucleus increases as you go
from one element to the next in the Periodic
Table. The order shown in the diagram is correct
for the elements in Period 3 and up to nickel in
Period 4. After nickel the 3d sub-shell has lower energy than 4s.
1s
2s
3s
3p
2p
3d
Energy
Figure 13 Arrangement of electrons in atomic
orbitals in a ground state sodium atom.
Ionisation1st 2nd 3rd 4th 5th 6th 7th 8th
20 000
10 000
0 I o n i s a t i o n e n t h a l p y / k J m o l –
1
30 000
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F i g u r e 1 4
B u i l d i n g u p t h e P e r i o d i c T a b l e .
s y m b
o l
e l e c t r o n i c c o n f i g u r a t i o n
( o u t e r s u b - s h e l l ( s ) o n l y )
a t o m i c
n u m b e r
K E Y O
8
2 p
4
A c t i n i d e s
L a n t h a n i d e s
P a
N p
P r
T h
U
C e
N d
P m
A c
F r
R a
5 8
5 9
6 0
6 1
9 0
9 1
9 2
9 3
8 7
8 8
8
9
4 5 6 7
3 d
1 4 s
2
3 d
3 4 s
2
4 d 1 5 s
2
4 d 3 5 s
2
5 d
1 6 s
2
5 d
3 6 s
2
3 d
2 4 s
2
3 d
5 4 s
1
4 d 2 5 s
2
4 d 5 5 s
2
5 d
2 6 s
2
5 d
4 6 s
2
4 s
1
5 s
1
6 s
1
7 s
1
4 s
2
5 s
2
6 s
2
7 s
2
4 d 5 5 s
1
3 d
5 4 s
2
5 d
5 6 s
2
3 1 1
1 9
4 1 2
2 0
3 7
5 5
3 8
5 6
2 3
2 5
2
1
3
9
5
7
2 4
4 1
2 2
4 0
7 2
4 3
4 2
7 3
7 5
7 4
L i
B e
N a
M g
K
C a
R b
S r
C s
B a
L a S
c Y
H f
T i
Z r
T a V N
b
W C r
M o
R e
M n
T c
f i l l i n
g d s u b - s h e l l s
f i l l i n g 4 f s u b - s h e l l
f i l l i n g 5 f s u b - s h e l l
3 d
6 4 s
2
4 d 7 5 s
1
5 d
6 6 s
2
3 d
7 4 s
2
4 d 8 5 s
1
5 d
7 6 s
2
3 d
8 4 s
2
5 d
9 6 s
1
3 d 1
0 4 s
1
4 d 1
0 5 s
1
5 d 1
0 6 s
1
3 d
1 0 4 s
2
4 d 1 0 5 s
2
5 d
1 0 6 s
2
2 7
2 9
2 8
4 5
2 6
4 4
7 6
4 7
4 6
7 7
7 9
7 8
3 0
4 8
8 0
6 3
6 2
9 4
6 5
6 4
9 5
9 7
9 6
6 6
9 8
A m
B k
E u
P u
C m
S m
G d
T b
O s
F e
R u
I r C o
R h
P t
N i
P d
A u
C u
A g
C f
D y
H g
Z n
C d
4 d 1 0 5 s
0
4 p
1
5 p
1
6 p
1
4 p
2
5 p
2
6 p
2
4 p
2
6 p
3
4 p
4
5 p
4
6 p
4
4 p
5
5 p
5
6 p
5
3 2
3 4
3 3
5 0
3 1
4 9
8 1
5 2
5 1
8 2
8 4
8 3
3 5
5 3
8 5
6 8
6 7
9 9
7 0
6 9
1 0 0
1 0 2
1 0 1
7 1
1 0 3
F m
N o
E r
E s
M d
H o
T m
Y b
T l
G a
I n
P b
G e
S n
B i
A s
S b
P o
S e
T e
L r
L u
A t
B r I
5 p
3
4 p
6
5 p
6
6 p
6
3 6
5 4
8 6 R
n K r
X e
f i l l i n g p s u b - s h e l l s
3
4
5
6
7
0
2 p
1
3 p
1
2 p
2
3 p
2
3 p
3
2 p
4
3 p
4
2 p
5
3 p
5
6
5 1 3
8
7
1 4
1 6
1 5
9 1 7
T l
B
S i
C
P N
S O
C l
F
2 p
3
1 s
2
2 p
6
3 p
6
2 1 0
1 8
A r
H e
N e
1 s
1
1
H
2 s
1
3 s
1
2 s
2
3 s
2
P e r i o d
1 2 3
f i l l i n g s s u b - s h e l l s
1
2
G r o u p
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Figure 15 Dividing up the Periodic Table.
s block
d block
p block
metals non-metalsf block
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Cl
–
ion
Na+ ion
‘Pool’ of delocalised
electrons
attraction
nucleus
+ +
–
–
shared electrons
Figure 9 In a hydrogen molecule, the atoms are
held together because their nuclei are both
attracted to the shared electrons.
Li1.0
Be1.6
B2.0
C2.6
N3.0
O3.4
F4.0
Na0.9
Mg1.3
K0.8
Ca1.0
Rb0.8
Sr 1.0
Al1.6
Si1.9
P2.2
S2.6
Cl3.2
Br 3.0
I2.7
H2.2
Li1.0
Period
symbol
electronegativity
KEY
Group
2
1
1 2 3 4 5 6 7
3
4
5
Figure 2 The sodium chloride lattice, built up
from oppositely charged sodium ions and
chloride ions.
Figure 15 A model of metallic bonding.
Figure 13 Pauling electronegativity values for
some main group elements in the Periodic Table.
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Figure 17 The relative sizes of atoms and ions.
Figure 18 Ions with higher charge densities
attract more water molecules
(ions are only shown in two dimensions).
Na+ ion(charge 1+, radius 0.098nm)
On average, eachNa+ ion is surrounded by
5 water molecules
Mg 2+ ion(charge 2+, radius 0.078nm)
On average, eachMg 2+ ion has 15
water molecules around it
+ 2+
Figure 19 Hydrated ions are much bigger than
isolated ions.
Li+
(g)
isolated Li+ ion(radius = 0.078nm)
Li+ (aq)
hydrated Li+ ion (radius = 1.00nm)
Na+ (g)
Na+ (aq)
isolated Na+ ion(radius = 0.098nm)
Figure 36 Two isomers of alanine.
H
C
HOOC NH2CH3
H
C
COOHH2NH3C
Figure 38 The CORN rule. Look down the
H—C bond from hydrogen towards the central
carbon atom.
COOH COOH
C
H
CORN
L isomer
H2N
R
C
H
CORN
D isomer NH2
R
hydrated Na+ ion (radius = 0.79nm)
Li Li+
Li atom
r atom = 0.152 nm
Li+ ion
r ion = 0.078 nm
Na Na+
Na atom
r atom = 0.186 nm
Na+ ion
r ion = 0.098 nm
Mg Mg2+
Mg atom
r atom = 0.160 nm
Mg2+ ion
r ion = 0.078 nm
F F –
F atom
r atom = 0.071 nm
F – ion
r ion = 0.133 nm
O O2 –
F atom
r atom = 0.073 nm
F – ion
r ion = 0.132 nm
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E n t h a l p y
reactants products
Progress of reaction
chemicalreactants
energy given outto surroundings∆H negative
eg CH4+2O2
products
eg CO2+2H2O
Figure 1 Enthalpy level diagram for an
exothermic reaction, eg burning methane:
CH4 +2O2 g CO
2 + 2H
2O.
thermometer
water
electrically heatedwire to ignite sample
air jacket
oxygen underpressure
crucible containingsample under test
stirrer
Figure 3 A bomb calorimeter for making
accurate measurements of energy changes. The
fuel is ignited electrically and burns in the
oxygen inside the pressurised vessel. Energy istransferred to the surrounding water, whose
temperature rise is measured.
Note that the experiment is done at constant
volume in a closed container. Enthalpy changes
are for reactions carried out at constant pressure ,
so the result needs to be modified accordingly.
energy taken infrom surroundings∆H positive
chemicalreactants
eg CaCO3
E n t h a l p y
reactants
products
Progress of reaction
products
eg CaO+CO2
Figure 2 Enthalpy level diagram for an
endothermic reaction, eg decomposing calcium
carbonate:
CaCO3 g CaO + CO
2.
∆H going this way...
... is the sameas ∆H going
this way
CH4(g)
CO2(g) + 2H2O(I)
C(s) + 2H2(g)
Figure 4 An enthalpy cycle for finding the enthalpy
change of formation of methane, CH 4.
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E n e
r g y
+
breaking bonds(takes in energy)
making new bonds(gives out energy)
H
H
O O
O O
C H
O O O O
H H H
C OOO
HH
O
HH
C
HH
Figure 9 Breaking and making bonds in the reaction between methane and oxygen.
Solid Liquid Gas
particles in fixed positions particles moving around
regular lattice pattern random arrangement
particles close together particles widely separated
volume depends only slightlyon pressure and temperature
volume depends strongly ontemperature and pressure
Figure 14 A comparison of solids, liquids and
gases.
Increasingenergy
each rotationallevel has its own
translational levels
each vibrationallevel has its own
rotational levels
each electroniclevel has its own
vibrational levels
groundelectronicenergylevel
vibrationalenergylevels
rotationalenergylevels
translationalenergylevels
Figure 15 Each electronic energy
level has within it several
vibrational, rotational and
translational energy levels. Note
that the levels are not to scale.
‘stack’ of ‘stack’ of ‘stack’ of
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ionic lattice + solvent solution
gaseous ions+
solvent
∆H solution
∆H LE ∆H hyd(cation)+
∆H hyd(anion)
Figure 21 An enthalpy cycle to show the
dissolving of an ionic solid.
Figure 26 Born–Haber cycle for sodium
chloride.
NaCI(s)Na(s) + ½CI2(g)
Na+(g) + CI-(g)Na(g) + CI(g)
∆H 2
∆H 1
∆H 3
∆H 4
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Figure 27 Born–Haber cycles for sodium chloride and potassium chloride.
Enthalpy/kJmol –1
Na+(g) + Cl(g)
+800
+700
+600
+500
+400
∆H i (1)(Na)
∆H EA(1)(Cl)
Na+(g) + Cl(g)
K+(g) + Cl(g)
∆H i (1)(K)
K+(g) + Cl(g)
K+(g) + Cl –(g)
∆H EA(1)(Cl)
+400
+200
+100
0
+300
–100
–200
–300
–400
–500
Na(g) + Cl(g)
∆H at (Cl)
Na+(g) + 12 Cl2(g)
∆H at (Na)
Na(s) + 12 Cl2(g)
∆H f (NaCl)
NaCl(s)
∆H LE(NaCl)
∆H at (Cl)
K(g) + 12 Cl2(g)
∆H at (K)
K(s) + 12 Cl2(g)
∆H f (KCl) ∆H LE(KCl)
KCl(s)
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Figure 27 Born–Haber cycles for sodium chloride and potassium chloride.
Enthalpy/kJmol –1
Na+(g) + Cl(g)
+800
+700
+600
+500
+400
Na+(g) + Cl(g)
K+(g) + Cl(g)
K+(g) + Cl(g)
K+(g) + Cl –(g)
+400
+200
+100
0
+300
–100
–200
–300
–400
–500
Na(g) + Cl(g)
Na+(g) + 12 Cl2(g)
Na(s) + 12 Cl2(g)
NaCl(s)
K(g) + 12 Cl2(g)
K(s) + 12 Cl2(g)
KCl(s)
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Figure 2 What happens when an ionic substance
such as sodium chloride dissolves in water.
Figure 5 Polar water molecules attract the ions in
a solid lattice.
Figure 11 (a) The structure of diamond and (b)
the structure of graphite.
(a) (b)
Figure 12 Imagine you are inside a diamond. The
regular network structure would repeat in all
directions – as far as the edge of the diamond.
Figure 13 The fullerenes are a recently discovered
molecular form of carbon.
(a) shows C 60 , named buckminsterfullerene.
It is made up of a mixture of 5-membered and 6-
membered rings and looks like a football
(b) is another way of presenting C 60 , showing the
positions of the carbon atoms
(c) shows C 70 , which is shaped like a rugby ball.
(a) (b) (c)
– + –
– –
– –
– –
– –
–
–
+
+ +
+ +
+ +
+
+
+
+
Solid sodium chloridea retular ionic lattice
Cl – Na+ Cl –(aq) Na+(aq) water molecule
Sodium chloridedissolved in water
δ−δ+
solid lattice
polar water molecule
hydrated ions
+
–
+
+
+ +
+ +
+ + +
+ + +
–
– –
– –
– –
– – –
δ−
δ−
δ−
δ−
δ−
δ−
δ−
δ−
δ−
δ−
δ−δ−
δ−
δ−δ+
δ+
δ+
δ+
δ+ δ+
δ+
δ+
δ+
δ+
δ+
δ+
δ+
δ+
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Figure 14 On heating, the molecular substance
(represented by ) changes from a solid to a
liquid and then to a gas. Energy must be supplied
to overcome the intermolecular forces. Note that the covalent bonds within the molecules remain
intact.
heat
m.p.
heat
b.p.
Solid Liquid Gas
δ + δ –
At some instant, more of the electroncloud happens to be at one end of themolecule than the other; moleculehas an instantaneous dipole.
Electron cloud evenlydistributed; no dipole.
Cl Cl Cl Cl
Figure 15 How a dipole forms in a chlorine
molecule.
This atom is not yetpolarised, but itselectrons are repelledby the dipole next to it ...
Xe
This atom isinstantaneouslypolarised
Xeδ + δ – Xeδ + δ –
... so it becomespolarised
Xeδ + δ –
Figure 18 How an induced dipole is formed in a
Xe atom.
B o i l i n g p o i n t / K
400
300
200
100
Period2 3 4 5
H2TeSbH3HISnH4
H2O
HF
NH3
CH4
Group 4Group 5Group 6Group 7
Figure 20 Variation in the boiling points of the
hydrides of some Group 4, 5, 6 and 7 elements.
E n
t h a l p y c h a n g e o f
v a p
o r i s a t i o n / k J m o l - 1
l
40
20
0
Period2 3 4 5
H2TeSbH3HISnH4
H2O
HF
NH3
CH4
Group 4Group 5Group 6Group 7
Figure 21 Variation in the enthalpy changes of
vaporisation of some Group 4, 5, 6 and 7
elements.
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Lone pair;concentratednegative
charge
F
H
H
δ +
Fδ–
Figure 23 The positively charged H atom lines
up with the lone pair on an F atom.
H
HHH
O
Hydrogen bond
Lone pair
O
HH
O
Figure 25 The positively charged H atoms line
up with the lone pairs on the O atoms.
Key
oxygen
hydrogenhydrogen bond
Figure 28 The arrangement of water molecules
in ice.
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HEAT
easily broken by heating; polymer canbe moulded into new shape.
chains cannot be easily broken; polymer keeps shape on heating.
polymer chain
cross–link
Figure 29 Thermoplastics and thermosets.
crystalline region
amorphous region
Figure 32 Crystalline and amorphous regions of
a polymer.
GIANTLATTICEgoes on
indefinitely
STRUCTURES
MOLECULARmade of groups of atoms
COVALENTMOLECULAR
COVALENTNETWORK
METALLICIONIC MACROMOLECULAR(eg polymers)
Figure 36 A summary of the structures of
substances.
(a) Thermoplastic: no cross–linking
HEAT
Weak forces between polymer chains
(b) Thermoset: extensive cross–linking Strong covalent bonds between polymer
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Figure 3 Obtaining a line emission spectrum.
Figure 4 Obtaining a line absorption
spectrum.
electron hasbeen excitedto level 5,drops back tolevel 1
etclevel 5level 4
level 3
level 2
level 1
groundstate
Lyman series
this line
correspondsto electronsdroppingfrom level 5 1
1 2
1 3
1 5
2 1 3 1 4 1
1 4
Frequency
Figure 6 How the Lyman series in the
emission spectrum is related to energy
levels in the H atom.
wire with sampleof element
excited atoms
in hot flameemit light
slit
prism
line emission spectrum(bright lines on a blackbackground)
source of white light
wire with sampleof element
cool flame:most atoms invapour are in their ground state line absorption spectrum (black lines
on a bright coloured background)
slit
prism
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Increasingenergy
Cl
H
ELECTRONICENERGY
VIBRATIONALENERGY
ROTATIONALENERGY
TRANSLATIONALENERGY
Cl H
Cl H
Cl
H
Cl H Figure 7 An HCl molecule has energy associated
with different aspects of its behaviour.
Figure 16 The basic parts of a double beaminfrared spectrometer.
3000 2000 1000
Wavenumber/cm –1
T r a n s m i t t a n c e / %
100
80
60
40
20
Figure 21 Infrared spectrum of butane.
Absorption/cm –1 Bond2970 C—H (alkane)
CH3 CH2 CH2 CH3
sample cell for solution of sample
infrared source(electrically heatedfilament)
reference cellfor solvent only
NaCl prism(or diffraction
grating)
infrareddetector
chart recorder
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3000 2000 1000
Wavenumber/cm –1
T r a n s m i t t a n c e / %
100
80
60
40
20
Figure 23 Infrared spectrum of benzoic acid.
Absorption/cm
–1
Bond3580 O−H3080 C−H (arene)1760 C=O
COHO
Figure 22 Infrared spectrum of methylbenzene.
Absorption/cm –1 Bond3050 C−H (arene)2940 C−H (alkane)
CH3
powerfulmagnet
sample
RF signalgenerator
detector
recorder
SN
Figure 37 A simplified diagram of an n.m.r.
spectrometer.
N S
N S
E2
E1
∆Ealigned against
magnetic field
aligned withmagnetic field
N S
NS
Figure 36 The principle of n.m.r.: a small
magnet in a strong magnetic field can have two
different energies.
100
80
60
40
20
3000 2000 1000
Wavenumber/cm –1
T r a n s m i t t a n c e / %
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Chemical Relative Type of shift no. protons proton0.9 3 CH31.3 4 CH2
CH3 CH2 CH2 CH2 CH2 CH3
A b s o r p t i o n
012345
Chemical shift
8H
6H
TMS
678910
Figure 43 N.m.r. spectrum of hexane.
Chemical Relative Type of shift no. protons proton1.6 3 CH3
5.6 1
C C
H
CH3
H3C
H
H C C H
Figure 44 N.m.r. spectrum of trans-but-2-ene.
A b s o r p t i o n
012345
Chemical shift
3H
2H
2H
1H
TMS
678910
Chemical Relative Type of shift no. protons proton0.9 3 CH3
1.6 2
2.3 1 OH
3.6 2
CH3
CH2
CH2
OH
C CH2 C
C CH2 O Figure 45 N.m.r. spectrum of propan-1-ol.
transparent object,glass or a solution
all wavelengths of visible light transmitted:appears colourless
all wavelengthsof visible lightreflected:appears white
opaque object,eg a piece of chalk
Figure 52 How light behaves with transparent
and opaque objects.
Chemical shift
A b s o
r p t i o n
6H
TMS2H
10 9 8 7 6 5 4 3 2 1 0
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transparent object
absorbsred
transmits wavelengths correspondingto other colours: appears green
reflects wavelengths corresponding toother colours: appears orange
opaqueobject absorbs blue
Figure 53 How colours arise from absorption of
light.
I
n t e n s i t y o f a b s o r p t i o n
ultra violet
visible
infra red
260
300
340
380
420
460
500
540
580
620
660
700
Wavelength/nm
ultra violet visible
violet blue green yellow red
infra red
Figure 57 The absorption spectrum of carotene
(in solution in hexane).
λ /nm
blue light istransmitted
blue light isreflected(Reflectancespectrumshown below)
opaque,colouredobject,eg painting
I n t e n s i t y o f a b s o r p t i o n
absorption spectrum
R e f l e c t a n c e
reflectance spectrum
red and yellow lightis absorbed. (Absorptionspectrum shown below)
transparentcolouredobject, egsolution
600 700500400 600 700500400
paint layer absorbsred and yellowlight
100
0
λ /nm
Figure 59 Absorption and reflectance spectra of
Monastral Blue.
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excitationenergy excited electronic state
energy absorbed corresponds toultraviolet light
excitation energies inthis region correspond to visible radiation
energy absorbed corresponds tovisible light
excited electronic state
ground electronic states
COLOUREDCOMPOUND
COLOURLESSCOMPOUND
Figure 63 The energy needed to excite an
electron in a coloured compound and in a
colourless compound.
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Figure 5 The pH scale.
H+ (aq) +
stays roughlyconstantbecause
plenty of HA to make moreH+ (aq) if some used up by alkali that gets added
plenty of A – to combine
with any H+(aq) that getsadded
A –HA
Figure 6 How a buffer solution keeps the pH
constant.
pH [H+(aq)]/mol dm –3
Moreacidic
Neutral
Morealkaline
0
1
2
3
4
5
6
7
8
9
10
11
12
13
1
10 –1
10 –2
10
–3
10 –4
10 –5
10 –6
10 –7
10 –8
10 –9
10 –10
10 –11
10 –12
10 –13
14 10 –14
–
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Figure 2 The reaction of chlorine with potassium
iodide solution.
+
–
–
Cu2+ ion+
–
–
–
+
–
+
+
+
+
SO42– ion
–
Zn atom
Cu atom
– –
–
– –
–
+
+
+ +
+
SO42– ion –
+
Zn2+ ion+
Figure 4 The reaction of zinc with
copper(II) sulphate solution:
Zn(s) + Cu2+
(aq) g Cu(s) + Zn2+
(aq)
Figure 5 The general arrangement for an
electrochemical cell.
Velectronflow
ELECTRONSRELEASED
ELECTRONS ACCEPTED
oxidationreaction
reductionreaction
Figure 6 An ordinary dry cell – the kind you use
in a torch.
– + I – ion
I2 molecules
Cl – ion
K+ ionK+ ion
Cl2
molecules
–
– –
– –
–
– –
– –
– –
–
++
+
+ ++
++ +
++
+
+
seal+
electronflow alongexternalwire
mixture of chemicalscontaining ammoniumchloride which acceptselectrons and isreduced
card covering
zinc container (–) terminalzinc supplies
electrons and isoxidised
carbon rod(+) terminal
–
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platinum electrode
solution containing
equal concentrationsof Fe2+(aq) andFe3+ (aq)
Figure 12 A standard half-cell for the
Fe3+
(aq)/Fe2+
(aq) half-reaction.
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Figure 2 Enthalpy profile for an exothermic
reaction.
N u m b
e r o f m o l e c u l e s w i t h
k i n e t i c e n e r g y E
Kinetic energy (E )
300 K
310 K
Figure 4 Distribution curves for molecular
kinetic energies in a gas at 300 K and 310 K.
Figure 5 Distribution curve showing collisions
with energy 50 kJ mol –1
and above.
Figure 6 Distribution curves showing the effect
on the proportion of collisions with energy
50 kJ mol –1 and above of changing the
temperature from 300 K to 310 K.
X
Activation enthalpy
Reactants∆H
Products
Progress of reaction
E n t h a l p y
Activation enthalpyE a= 50 kJ mol
–1
Kinetic energy (E )
N u m b e r o f c o l l i s i o n s w i t h
k i n e t i c e n e r g y E
300 K
310 K
Number of collisions withenergy greater than50 kJ mol –1 at 310 K
Number of collisions withenergy greater than50kJ mol–1 at 300 K
Kinetic energy (E )
Activation enthalpyE a= 50 kJ mol
–1
N u m
b e r o f c o l l i s i o n s w i t h
k i n e t i c e n e r g y E
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invertedburette
water
yeastsuspension+ hydrogen
peroxidesolution
Figure 8 Apparatus for investigating the rate of
decomposition of hydrogen peroxide. The yeast
provides the enzyme catalase.
Figure 10 The decomposition of hydrogen
peroxide solutions of differing concentrations.
Figure 11 The initial rate of decomposition of
hydrogen peroxide plotted against concentration
of hydrogen peroxide.
[H2O2] =0.40 mol dm –3
[H2O2] =0.40 mol dm –3
[H2O2] =0.40 mol dm –3
[H2O2] =0.40 mol dm –3
[H2O2] =0.40 mol dm –3
V o l u m e O 2 / c m
3
Time /s
262422
201816
14121086
42
0 20 40 60 80 100 120 140 160 180
R a t e o
f r e a c t i o n / c m
3 ( O 2 ) s – 1
0.5
0.4
0.3
0.2
0.1
0 0.1 0.2 0.3 0.4
Concentration of hydrogenperoxide/mol dm –3
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Second bondforms, and productdiffuses away fromcatalyst surface,leaving it free toadsorb freshreactants.
4
H H H
C
H C
H
H
H
H
New bond forms.
H
C
H C
H
3
HH H
H
H
C
H
C
H
H
H
HH HH
Bonds break.2
Reactants get
adsorbed ontocatalyst surface.Bonds are weakened.
1
HH CH
C
H
H
H
HH
catalyst surface
H H
C
H
C H
H
H
C H C
H
H
H
H H
Figure 18 An example of heterogeneous
catalysis. The diagrams show a possible
mechanism for nickel catalysing the reaction
between ethene and hydrogen to form ethane.
activation enthalpyuncatalysed reaction
activation enthalpycatalysed reaction
uncatalysedreaction
catalysedreaction
reactants
products
∆H
E n t h a l p y
Progress of reaction
Figure 19 The effect of a catalyst on the enthalpy
profile for a reaction.
E n t h a l p y
Progress of reaction
Figure 19 The effect of a catalyst on the enthalpy
profile for a reaction.
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D e n s i t y / g c m – 3
2
1
3
0Li Be B C N O F Ne Na Mg Al Si P S Cl Ar
Figure 3 Densities of elements in Periods
2 and 3.
Figure 4 Melting and boiling points of elements
in Period 3.
M e l t i n g a n d b o i l i n g
p o i n t s /
K
Na Mg Al Si P S Cl Ar
m.p.
Key
b.p.
1000
0
2000
3000
Figure 5 Variation in atomic size across Period 3.
A t o m i c r a d i u s
/ n m
Na Mg Al Si P S Cl Ar
0.2
0.1
0
F i r s t i o n i s a t i o n e n t h a l p y / k J m o I – 1
1000
0H He Li Be B C N O F Ne NaMg Al Si P S Cl Ar K Ca
2000
Figure 6 First ionisation enthalpies of elements
1–20.
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Element Atomic number Electronic arrangement
3d
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
21
22
23
24
25
26
27
28
29
30
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
[Ar]
building up of inner3d sub-shell
outer shell
4s
Figure 20 Arrangement of electrons in the
ground state of elements of the first row of the d
block. [Ar] represents the electronic
configuration of argon.
force
(a) (b)
force The open circles representatoms of iron. The blackcircles are the larger atomsof a metal added to make analloy.
Figure 22 The arrangement of metal
atoms in a crystal (a) before and (b) after
slip has taken place. The shaded circles
represent the end row of atoms.
Figure 23 The arrangement of metal
atoms in an alloy.
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+1
+5
+7
+4 +4 +4
+2 only+2+2 +2 +2 +2 +2 +2
+6 +6 +6
+3 only +3 +3 +3 +3 +3 +3 +3 +3
Figure 24 Oxidation states shown by elements inthe first row of the d block. The most important
oxidation states are in boxes.
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Figure 27 An octahedral complex of Fe(III). Coordination number 6.
Figure 28 A tetrahedral complex of Ni(II). Coordination number 4.
Figure 29 A square planar complex of Ni(II). Coordination number 4.
Figure 30 A linear complex of Ag(I).
Coordination number 2.
Figure 32
(a) Edta4– , a hexadentate ligand.
(b) The nickel–edta complex ion [Ni(edta)]2 –
.
octahedral complex of FE(III)coordination number 6
CN
CN
CN
CN
NC
NC
Fe
3–
shape
CN
NC
Fe
NC
NC
NC
Fe
CN
CN
CN
CN
CN
CN
CN
ClCl
ClCl
Cl Cl
ClCl
Cl Cl Cl
Cl
NiNiNi
tetrahedral complex of Ni(II)
coordination number 5shape
2–
Ni Ni Ni
NC
NC
NC
NC NC
NC
CN
CN
CN
CN
CN
CN
2–
square planar complex of Ni(II)
coordination number 4
shape
H3N Ag NH3+
O
CO
O O
O
OO
O
O
O
O
O
O
O
O
C
C
CH2
C
C
C
C
C
CH2 CH2
CH2
CH2
CH2
CH2 CH2
CH2
CH2
H2C
H2C
2–
Ni
(a)
(b)
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Figure 33 Relative energy levels for the five 3d
orbitals of the hydrated Ti 3+ ion.
Figure 36 The cis and trans isomers of
[Co(NH 3 )
4Cl
2 ]+ have different colours.
energy
Average energy
of 3d orbitals in[Ti(H2O)6]
3+
if there was no
splitting [Ti(H2O)6]3+
ground state
3d level split
[Ti(H2O)6]3+
excited state
light
hv ∆E
cis isomer: violet trans isomer: green
NH3
NH3
NH3
H3N
NH3 NH3
NH3
NH3
Cl
Cl
Cl
Cl
Co Co
++
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Name Molecular Full structural Shortened Further formula formula structural shortened
formula to
methane
ethane
propane
Table 2 Structural formulae of alkanes.
CH4CH4 H C H
H
H
C2H6 H C C
H
H
H
H
H
CH3CH3CH3 CH3
C3H8 H C C C
H
H H H
H H
H CH3CH2CH3CH3 CH2 CH3
109°
represents a bond inthe plane of the paper
represents a bond ina direction behindthe plane of the paper
represents a bond ina direction in front ofthe plane of the paper
H
C
H H
H Figure 5 The three-dimensional shape of
methane.
a simpler way of drawingethane which shows theshape less accurately
C C
H
H
H
H
H
H
Figure 6 The three-dimensional shape of ethane.
C C
H
HH
HH
H
Figure 7 The three-dimensional shape of butane.
C
C
C
C
H
HH
HH
H
H
H
H
H
skeletal formulaof butane
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A L K A N E S
I s o m e r i s a t i o n
R e f o r m i n g
C r a c k i n g
S t e a m c r a c k i n g
C a t a l y t i c c r a c k i n g
F e e d s t o c k
C
4 – C 6 a l k a n e s
n a p
h t h a
n a p h t h a / k e r o s e n e
g a s o i l
P r o d u c t
s a m e m o l e c u l a r f o r m u l a a s
s a m
e n u m b e r o f C
a t o m s a s r e a c t a n t s ;
m o r e m o l e c u l e s ;
m o r e m
o l e c u l e s ;
m o l e c u l e s
r e a c t a n t s ;
c y c
l i c
f e w e r C
a t o m s t h a n r e a c t a n t s ;
f e w e r C
a t o m s t h a n r e a c t a n t s ;
b r a n c h e d
s m a l l m o l e c u l e s , s u c h a s
s o m e u
n s a t u r a t e d ;
C 2 H 4 ,
C 2 H 6 ,
C 3 H 6 ,
C 3 H 8 ,
s o m e b
r a n c h e d ;
C 4 a n d C 5 a l k e n e s a n d
s o m e c
y c l i c
a l k a n e s
C o n d i t i o n s
P
t / A l 2 O 3 ;
P t / A
l 2 O 3 ;
n o c a t a l y s t ;
z e o l i t e ;
1 5 0 ° C
5 0 0
° C ;
9 0 0 ° C ;
5 0 0 ° C
h y d
r o g e n i s r e c y c l e d t h r o u g h m i x t u r e t o
s h o r t r e s i d e n c e t i m e ;
r e d u c e ‘ c o k i n g ’
s t e a m i
s a d i l u t e n t t o p r e v e n t
‘ c o k i n g ’
E x a m p l e
U s e s o f
t o
i m p r o v e o c t a n e r a t i n g o f p e t r o l
t o i m p r o v e o c t a n e r a t i n g o f p e t r o l
t o m a n u f a c t u r e p o l y m e r s
t o i m p r
o v e o c t a n e r a t i n g o f p e t r o l
p r o d u c t s
F u r t h e r
D
e v e l o p i n g F u e l l s s t o r y l i n e ,
D e v e l o p i n g F u e l s s t o r y l i n e ,
T h e P o l y m e r R e v o l u t i o n
D e v e l o
p i n g F u e l l s s t o r y l i n e ,
d e t a i l s
S e c t i o n D F 4
S
e c t i o n D F 4
s t o r y l i n e ,
S e c t i o n s P R 3
S e c
t i o n D F 4
C h e m i c a l I d e a s 1 5 . 2
a n d P R 4
C h e m i
c a l I d e a s 1 5 . 2
C h e m i c a l I d e a s 1 5 . 2
T a b l e 5
T h e a c t i o
n o f h e a t o n a l k a n e s . S k e l e t a l f o r m u l a e a r e
u s e d i n t h e e x a m p l e s .
i s t h e s k
e l e t a l f o r m u l a f o r a b e n z e n e r i n g .
+
+
+
H 2
+
3 H 2
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C–C bond length0.139 nm
120°
C
CC
C
CCH
H
H
H
H
H
Figure 11 The structure of the benzene ring.
Scale 0.1nm0
Figure 14 An electron density map for benzene
at –3 °C. The lines are like contour lines on a
map: they show parts of the molecule with equal
electron density.
Figure 15 Enthalpy changes for the
hydrogenation of benzene and the hypothetical
Kekulé structure.
regions of higher electrondensity above and belowthe benzene ring
Figure 16 The regions of higher electron density
above and below the benzene ring.
E n t h a l p y
Progress of reaction
∆H = –360 kJ mol –1
(estimated enthalpy change
for Kekulé’s benzane)
C6H12 cyclohexane
+ 3H2
+ 3H2
∆H = –208 kJ mol –1
measured enthalpy
change for benzane)
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Full structural Skeletal Nameformula formula
1-chloropropane
1,2-dichloropropane
3-bromo-1-chlorobutane
Table 1 Naming halogenoalkanes.
Cl
H
C
H
H C C
H
H
Cl
H
H
Cl
ClH
C
H
H C C
Cl
H
Cl
H
H
Cl
BrH
C
H
H C C
Br
H
C
H
H
Cl
H
H
Table 3 Some common nucleophiles.
Full structural Skeletal Nameformula formula
propan-1-ol
propan-2-ol
pentan-3-ol
Table 4 Naming alcohols.
H
C
H
H C C OH
H
H
H
H
OH
H
C
H
H C C H
OH
H
H
H
OH
H
C
H
H C C C
H
H
OH
H
C H
H
H H
H
OH
Name and Structure, showingformula lone pairs
hydroxide ion,OH –
cyanide ion,CN –
ethanoate ion,CH3COO
–
ethoxide ion,C2H5O
–
water molecule,H
2O
ammoniamolecule,NH3
H
H H
H HH
O
O
O
O
O
N
CH3
CH3CH2
N C
C
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Table 6 Some examples of acid derivatives.
Acid derivative Dealt with in Section(s) Example
13.5 and 14.2
13.5 and 14.2
13.8
13.5 and 14.2
ester
acyl chloride
amide
acid anhydride
C
O
OR
C
O
Cl
C
O
NH2
C
O
O
C
O
ethyl ethanoate
ethanoyl chloride
ethanamide
ethanoic anhydride
CH3 C
O
O
CH3 C
O
Cl
CH3 C
O
NH2
CH3 C
O
O
CCH3
O
CH2CH3
Type of alcohol Position of —OH Examplegroup
primary at end of chain: propan-1-ol
secondary in middle of chain: propan-2-ol
tertiary attached to a carbonatom which carriesno H atoms: 2-methylpropan-2-ol
CH3CH2 C OH
H
H
CH3 C CH3
H
OH
CH3 C CH3
CH3
OH
Table 7 Primary, secondary and tertiary alcohols.
H
C
H
R OH
H
C
OH
R R'
R'
C
OH
R R''
Figure 6 How to name an ester.
ethyl ethanoate
This part comes from
the alcohol and is
named after it
This part comes
from the acid and
is named after it
O
OCH3
CH3
CH2
C
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H
CH O C
C
O
H
C
O
H
H
O
C
C
O
O
R1 (long carbon chain)
R2
R3
glycerol part −
always the same
fatty acid parts − R1, R2 and R3
may be different or the same
Figure 7 The general structure of the triesters
found in fats and oils.
O
O
O
O
O
Unsaturated triglyceride
O
O
O
O
O
O
O
Saturated triglyceride
Figure 9 Representations of triglycerides.
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carboxylic acid amine amide group
C
O
N C
O
H
+ H2ON
O
H
H
H
Figure 18 Making a secondary amide.
acid groupamino group
α-carbon: the first carbon atomattached to the –COOH group
H
R
H2N C COOH
Figure 20 The generalised structure of an α-amino acid.
Figure 21 How an amino acid forms a zwitterion.
C
R
H
C
O
OH
N
H
H
C
R
H
C
O
O−
N
H
H
H
receives H+ froma COOH group
H+ donated toan NH2 group
a zwitterion
+
+
azo compound
N + H+N
diazonium ion
NN+
coupling agent
H
Figure 22 A generalised coupling reaction.
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+ HCl(g)sunlight
Cl2(g)
room temp alkene
naddition polymer
trace O2(g)
200 oC and
1500 atm.
H2O(g)
phosphoric
acid catalyst
300 oC and 60 atm.
HBr
conc H2SO4followedby H2O
or
organic solvent
Br2
organic solvent
H2(g)
finely divided Ni
at 150 oC and 5 atm.
(or Pt at room tempand 1 atm.)
HC CH
CH2 CH2
HC CH
H Br
HC CHHC CH
H OH
HC CH
Br Br
CH2 CH
Cl
Figure 2 Reactions of alkenes.
Figure 3 Reactions of halogenoalkanes.
alcohol
heat in asealed tube
halogenoalkane
c. NH3(aq)
H2O(l)
NaOH(aq)
amine
alcohol
slow
reflux
R OH
R HalR NH2
R OH
R CH2 O C R'
O
R CH2 OH
R CHO R COOH
R CH2 Br
R CH2 Cl
R CH CH2
ester
bromoalkane
chloroalkane
carboxylic acid aldehyde
alkene primary alcohol
R'−COCl
or (R'CO)2O
anhydrous
conditions
R'−COOH
c. H2SO4 catalyst
reflux
c. HCl
HBr(aq)
(NaBr(s) + c. H2SO4)
reflux
Cr2O72− /H+(aq)
reflux
Cr2O72− /H+(aq)
reflux
NaBH4
Al2O3(s), 300 °C
or c. H2SO4reflux
Figure 4 Reactions of primary alcohols.
room temp
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R
O
C
H
carboxylate ion
carboxylic acid
NaOH(aq) HCl(aq)
R'
O –
O
R
O
C
OHc. H2SO4 catalyst
reflux with
aqueous acid or alkali*
R
O
C
O
R C
O
acid anhydride
R' OH
anhydrous
conditions
reflux
R
O
C
O R'
ester
R' OHroom
temperature
acyl chloride
R
O
C
Cl
R' NH2
room
temperature
room
temperature
primary amide
R
O
C
NH2
c. NH3(aq)
RO
C
NH R'
secondary amide
R C
O
H
aldehyde
C
OH
H
CN
RC
OH
H
H
R
primary alcohol a cyanohydrin
R C
O
OH
carboxylic acid
HCN
(+ alkali)
NaBH4
Cr2O72− /H+(aq)
reflux
or heat with
Fehling's
solution
R C
O
R'
ketone
C
OH
R'
CN
RC
OH
R'
H
R
secondary alcohol a cyanohydrin
HCN
(+ alkali)
NaBH4
Figure 6 Reactions of ketones.
Figure 5 Reactions of aldehydes.
Figure 7 The reactions of carboxylic acids and some related compounds.
Note Esters and amides are both hydrolysed by heating with aqueous acid or aqueousalkali. Alkaline hydrolysis gives the salt of the corresponding carboxylic acid. The freecarboxylic acid is formed on acidification of the solution.
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Figure 8 Reactions of arenes.
Cl
Cl2(g) AlCl3
room
temperature
NO2c. HNO3
c. H2SO4
< 55 °C
alkylation
R
R Cl AICI3
reflux
Friedel-Crafts
reactions
R COCl or (RCO)2O
acylation
O
CR
finely divided Ni
H2(g)
300 °C, 30 atm.
Br 2(l)FeBr 3 (or FE)
room
temperature
Br
SO2OH
c. H2SO4reflux
AICI3reflux
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Feedstock(reactants)
Feedstockpreparation
Energy in or out
REACTION
Temperature, pressure, catalyst
Separation
Products
Co-products
Recycle loop Unused feedstock
Input or removal of energy may be required at any stage
(and by-products)
Figure 1 Sequence of unit operations in a
chemical plant.
Startingmixture
Batch reactor At start Reactants in Some time later
Productmixture
Continuous (stirred tank) reactor
Stirrer
Product mixturecontinuously removed
Reactants added continuously
(a) (b)
Figure 2 Comparison of (a) batch and
(b) continuous tank reactors.
LiverpoolManchester
Castner/Kellner
Works
Lancaster
Durham
Newcastle
SunderlandCarlisle
Annan
Dumfries
Selkirk
Jedburgh
Peebles
Lanark
Stirling
Kelso
Hawick
Glasgow
Edinburgh
STRATHCLYDE
DUMFRIES &
GALLOWAY
Kendal
Chester
Hillhouse Works
CLWYD CHESHIRE
LANCASHIRE
CUMBRIA
NORTH WESTERN
ETHENE PIPELINE
SOLWAY FIRTH
WILTON
GRANGEMOUTH
TRANS PENNINE
ETHENE PIPELINE
NORTH
YORKSHIRE
NORTHUMBERLAND
FIRTH OF FORTH
ETHENE
PIPELINE
Wilton Works
MOSSMORRAN
GRANGEMOUTH
Figure 3 Pipelines from BP, Grangemouth, and Exxon, Mossmorran, for the distribution of
ethene.
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OIL
Fractionaldistillation
LPG Naphtha
Steamcracking
Ethene,propene
Steamcracking
Ethene,propene
Reforming
Branched alkanes, cycloalkanesand aromatic hydrocarbons
for high-grade petrol
Catalyticcracking
Gas Oil
Ethene, propene,high-grade petrol
ResidueKerosene
Figure 5 Feedstocks from oil.
Figure 4 Feedstocks from natural gas.
NATURAL GAS
Fractionaldistillation
Steamcracking
Methane Ethane
Ethene,propene
Steamcracking
Propane
Ethene,propene
Steamcracking
Butane
Ethene,propene
Figure 6 (a) An example of how energy can be used in a chemical process. (b) A diagram to illustrate a heat exchanger.
(a)
Reactants
at 20°C
(a)Heat exchanger
Reactants
at 20°C
Reactants
at 180°C
Reactor
at 200°C
Products at 200°C
Products at about 60°C
(b) Steamin Steamout Hotfeed out
Cold
feed in
Cross section:Condensed
steamSteam pipe
A single-pass tubular heat exchanger
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