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HSC Chemistry Syllabus Summary

Huon Wilson
June 28, 2011
This document is provided as is, the author gives no assurance of quality. It can be
freely modified and distributed, in any form, as long as: it is not used for commercial
or monetary gain; this notice remains visible; and, the author is attributed in some clear
manner.
Preface
I wrote these notes over the course of 3 or 4 months as preparation for my trials and the HSC. I tried
to go through the whole syllabus
1
and give an answer for each point of it (and thought that I might as
well do in such a way that I could use it for revision, hence this document), just so that I know that I
know everything. So most of the syllabus is answered, although some points were particularly easy (in
my opinion at least), or were already ingrained in my head from years of repetition in the junior school
science courses, and I skipped them so someone using these might want to just check that theyve got
everything under control. Also, since these are my notes for me, I only did what was applicable to me,
as in, only the option that we did at school (Industrial Chemistry).
They are personal notes, but I cleaned them up a very little bit (like, the rst chapters formatting
is still completely dierent to the rest) and decided to share them
2
, which would be why you are reading
this. However, being personal notes means that they are imperfect in depth of content (see above),
spelling, formatting, exposition. . . everything, really. So, if you see a mistake, please dont throw your
computer around, or eat the piece of paper in a t of rage. If there is a particularly bad mistake
in the content, or an unclear section of writing, you could email me
3
, preferably with a informative
subject, although I will not answer an email that is asking something along the lines of teach me
chemistry. If I do correct a mistake (no guarantees of it, though), the latest version will be available
via sites.google.com/site/somehscsciencenotes, and the date on the front cover will change, so
you can check youve got the latest and greatest version (if you care about those sort of things).
There are images of questionable copyright status included, but everything that I didnt make
has a link to where I got it from, which will have the image in greater context and with more detailed
information, so have a look, if you are inclined, and the Conquering Chemistry: HSC Course textbook
was pretty helpful as well. If you want to print this, it works best with one-page-per-sheet (otherwise
the text is very small) and double-sided (the layout of the sections and whatever is designed so it works
well as a booklet).
Anyway, have fun (and good luck!) with your HSC.
1
Available at: boardofstudies.nsw.edu.au/syllabus_hsc/chemistry.html
2
If anyone wants the L
A
T
E
X source, and it isnt on the website, just email me
3
and I will probably send it to you
3
At i.have.a.query.or.complaint@gmail.com (No, seriously, I have that email)
3
Contents
Contents 4
1 Production of Materials 5
1.1 Addition polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.2 Condensation Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Renewable sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 Redox reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 Nuclear chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 The Acidic Environment 13
2.1 Indicators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Le Chatelier & Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3 Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
2.4 Acids: take two . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.5 Esterication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3 Chemical Monitoring and Management 21
3.1 Chemists . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
3.2 Haber process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
3.3 Manufactured stu . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3.4 The atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.5 Waterways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4 Industrial Chemistry 33
4.1 Synthetic replacements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.2 Equilibrium reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.3 Sulfuric acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
4.4 Sodium hydroxide and electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.5 Saponication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.6 The Solvay process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Index 45
4
1 Production of Materials
1.1 Fossil fuels provide both energy and raw materials such as ethylene for
the production of other substances
Alkanes (C
n
H
2n+2
)
Catalytic cracking: Large alkane (15 25 carbons) alkane + alkene
C
15
H
32
C
10
H
22
+ C
5
H
10
Steam cracking: Alkane collection of small alkanes + H
2
C
11
H
24
4 C
2
H
4
+ C
3
H
6
+ H
2
Combustion: Alkane + O
2
CO
2
+ H
2
O
e.g. C
3
H
8
+ 5 O
2
3 CO
2
+ 4 H
2
O
With Cl and Br in UV: Alkane + Cl
2
or Br
2
chloro/bromo-alkane + hydro-bromic/-
chloric acid
C
3
H
8
+ Cl
2
C
3
H
7
Cl + HCl
C
4
H
10
+ Br
2
C
4
H
9
Br + HBr
Alkenes (C
n
H
2n
)
Combustion as per alkanes
Substitution reactions (always around double bond)
C
2
H
4
+ H
2
Ni
C
3
H
6
C
2
H
4
+ HCl C
2
H
5
Cl
C
2
H
4
+Br
2
CH
2
BrCH
2
Br (note: can be used as a test for alkene vs. alkane, alkene
decolours bromine solution)
C
2
H
4
+ HOBr CH
2
BrCH
2
CH
2
OH
C
2
H
4
+ H
2
O
H
2
SO
4
CH
3
CH
2
OH (alkene to alkanol)
Industrial conversion ethene to ethanol:
C
4
H
2
+ H
2
O
H
3
PO
4
@ 300

C
C
2
H
5
OH
Forming Ethylene glycol (1,2-ethanediol, however note its structure:
CH
2
CH
2
O
):
C
2
H
4
+
1
2
O
2
Ag @ 250

C
CH
2
CH
2
O
Forming vinyl chloride (chloroethane):
2 C
2
H
4
+ Cl
2
+
1
2
O
2
CuCl
2
@ 150

C
2 CH
2
CHCl + H
2
O
Cracking
Most polymers start with ethene, thus it is needed. A large proportion of a renerys production is
petrol, and other large chains that are not otherwise needed, thus they are cracked to give smaller more
useful molecules. It can be either catalytic or thermal/steam cracking.
5
1. Production of Materials
Catalytic Catalytic cracking splits long chain alkanes (15 25 carbons) into two smaller ones (an
alkane and an alkene). Controlling reaction conditions gives dierent amounts of ethene. Catalysts
used are zeolites which are crystalline aluminosilicates, i.e. aluminium, silicon, oxygen and some other
metal ions. It is done at 500

C without air, at pressure >1 atm. Catalytic is not enough for full
demand.
Steam Steam cracking breaks alkanes are split into lots of dierent small alkenes (14 carbons),
and hydrogen. Uses very hot pipes (700 1000

C) and pressures just >1 atm. The steam is a diluent
that doesnt react, but allows for higher pressure while maintaining optimum reactant concentrations.
Ethene
Ethene is a major part of most polymers, since it can be reacted with various side chains to form dierent
polymers with vastly dierent properties (e.g. all chlorine gives Teon, and styrene gives polystyrene).
The double bond means it is easy for the molecule to react with copies of itself to create an addition
polymer of which ethene is the monomer.
Polyethene
Polyethene is an addition polymer (known as PE). The double bond breaks open and attaches to the
end carbon of another ethene atom. The Gas phase process uses a initiator molecule with an O
2
group, which can be bonded to, to start each hydrocarbon chain, as well as high pressure (1000 3000
atm), and temperature (300

C). Made this way the polymer has high chain branching, which creates
LDPE , low density polyethene (the initiator is contained within the nal polymer). The Ziegler-
Natta process uses lower pressure (a few atm) and temperature (60

C), and a catalyst (mixture
of TiCl
3
and a trialkylaluminium like (CH
3
CH
2
)
3
Al). It forms chains with very little chain branching,
which is HDPE , high density polyethene. In both, the chains are cumulatively grown from one end,
where the initiator/catalyst is. Chains can collide, and exchange a H atom, which means both are
stable (one with a ethene on the end, and the other ethane on the end) and the process stops for these
two chains. LDPE is used for:
milk bottles
soft toys
cling wrap
HDPE is used for:
kitchen equipment (utensils, containers)
rigid toys
rubbish bins
carry bags
Vinyl chloride (chloroethane)
Vinyl chloride is CH
2

CHCl (ethene with Cl replacing one H). It makes PVC (poly(vinyl chloride)),
which is very cheap and very common (maybe second behind PE). PVC is chemically and biologically
resistant. Used for:
electrical insulation
hoses
pipes (including drainage, sewerage, guttering, downpipes)
6
1.2. Condensation Polymers
Styrene (phenylethene)
Styrene is CH
2

CHC
6
H
5
, ethene with a phenyl side group (which is a benzene ring with a single H
missing where the ethene is attached). Creates Polystyrene, which is very hard (thus brittle) and clear
in its solid form, it can be aerated to form a foam (with closed cells) which has low density, low thermal
conductivity. It is used for:
Car battery cases
Handles (of tools)
Furniture
CD cases
Drinking cups (as a foam and as a solid)
Packaging material (as a foam)
Other Addition polymers
Polypropylene (polypropene); CH
2

CHCH
3
; car bumpers, ropes, household goods (inc. chairs,
carpets)
Polyacrylonitrile (acrylics); CH
2

CHC

N; wool substitute (clothing, carpets, blankets etc.)


Poly(vinyl acetate) (PVA); CH
2

CHOCOCH
3
; vinyl coatings, paint, adhesives
polytetrauroethylene PTFE (Teon); CF
2

CF
2
; electrical insulation, non-stick surfaces in cook-
ware, screw thread sealant
Correspondence between structure and properties
Molecular weights. The longer the molecules (and smaller the spread of lengths) the higher the
M.P., and hardness of the polymer
Chain branching. More branching creates an amorphous structure since the molecules cannot
pack as closely, thus low density, softer etc. Less branching allows for a crystalline structure,
which is harder, more dense, high M.P.
Chain stiening. Large side groups on the ethene molecules reduce the exibility of the polymer
by restricting the movement of the chains. Small side chains like the CH
3
of polypropylene have
a small eect but the large styrene side-group of polystyrene makes it much harder.
Cross linking. Links between chains can increase the hardness and elasticity of a polymer.
1.2 Some scientists research the extraction of materials from biomass to
reduce our dependence on fossil fuels
Fermentation of glucose to ethanol: C
6
H
12
O
6
yeast
2 C
2
H
5
OH + 2 CO
2
Need
There is a limited amount of petrochemicals available in the form of fossil fuels, and thus they will run
out. Thus new sources (or alternatives) for these chemicals need to be found. Ethanol is very similar
to ethene, and can be converted into ethene, it can be produced by fermentation of starch/sugars found
in crops. Cellulose is also an alternative, which forms condensation polymers, and can be turned into
petrochemicals. Cellulose is also more abundant than ethanol in plants.
7
1. Production of Materials
Condensation polymers
Condensation polymers are polymers which involve an elimination of another molecule (usually H
2
O) in
their formations. For example Glucose (C
6
H
12
O
6
) forms Cellulose (XOC
6
H
10
O
4
OC
6
H
10
O
4
OX)
by elimination of an OH from one glucose and an H from the other, which forms water.
Nylons (polyamides) Nylons are synthetic condensations polymers. Form between an amine
group (YNH
2
) and a carboxylic acid ground (XCOOH), when the OH of the acid and one H from
the amine are eliminated, making a molecule of the form XCONHY. The link is called an amine
or peptide link. (Proteins form from amino acids which have an amine and a carboxylic acid at opposite
ends). Used in clothing as a bre, as packaging.
Polyesters Polyesters are also synthetic condensation polymers. Formed when a carboxylic acid
(XCOOH) and an alcohol (YOH) react, eliminating H
2
O, forming XCOOY. Used in clothing
as a bre, as PET bottles.
Cellulose
Cellulose is a natural polymer, formed form glucose (see above). Cellulose is very linear, because of
the geometry of the bonds and the glucose ring. It makes up a vast majority of biomass, since it is the
main component of plants. It can be converted to glucose by acid digestion or enzymes, glucose can
be converted to ethanol, which can make ethene. (Starch can also undergo the same process and is a
isomer of cellulose).
Biopolymers
Biopolymers are those made by living organisms (cellulose, and those made by modied bacteria etc.)
Polyhydroxybutyrate (PHB) PHB is made naturally by some bacteria (Alcaligenes eutrophus
and Bacillus megaterium). This is slow but can be accelerated by modifying the bacteria and making
them more like catalysts. PHB is biodegradable (eaten by bacteria), so can be used for medical applica-
tions where the material is left within the body and will slowly disappear. PHB is also water insoluble,
and resistant to UV (although not to acids or bases). It is not toxic, has similar tensile strength to
polypropylene, has a similar melting point. It is very expensive to produce, although improved methods
are being developed.
1.3 Other resources such as ethanol, are readily available from renewable
resources such as plants
Dehydration of ethanol (with heating):
CH
3
CH
2
OH
conc. H
2
SO
4
or H
3
PO
4
C
2
H
4
+ H
2
O
Hydration of ethene (with heating):
C
2
H
4
+ H
2
O
dilute H
2
SO
4
CH
3
CH
2
OH (note: these apply to any alkene alkanol reaction)
Combustion of ethanol:
C
2
H
5
OH + 3 O
2
2 CO
2
+ 3 H
2
O H = 1360 kJ/mol
Ethanol
8
1.4. Redox reactions
# Carbons Prex
1 meth-
2 eth-
3 prop-
4 but-
5 pent-
6 hex-
7 hept-
8 oct-
Table 1.1: IUPAC carbon count prexes
Figure 1.1: Zn

Zn
2+

Cu
2+

Cu
Source: en.wikipedia.org/wiki/File:
Galvanic_Cell.svg
Ethanol is often used as a solvent, since it can dissolve both non-polar
and polar substances. Ethanol has a polar region, the hydrogen bond of
the OH group which can dissolve polar things (and means it is miscible
in water in any proportion), and a non-polar region, the CH
3
CH
2
re-
gion, which can use dispersion forces to dissolve non-polar substances.
Ethanol is used as a solvent in cosmetics, food colourings/avourings,
antiseptics, industry. Ethanol can be used as a fuel since it combusts
easily, e.g. it is used in small stoves, it can be used in small proportions
with petrol ( < 20%) without engine modications, it can be made from
glucose e.g. in sugar cane.
Advantages over fossil fuels Ethanol is far more renewable than
fossil fuels, and can maybe reduce net CO
2
emmissions.
Disadvantages Large agricultural areas taken over for fuel pro-
duction, disposal of fermentation by-products. It was used in the 1970s
and 80s in Brazil, but the program petered out after a few decades;
modern petrol often contains upto 10% ethanol.
1.4 Redox reactions
are increasingly important as a source of energy
N.B. Oxidation is loss, Reduction is gain of electrons. Electrodes
: Anode is where oxidation happens, Cathode is where reduction
happens. These are placed in an electrolyte which is a solution which
conducts electricity.
Displacement
A displacement reaction is an exchange of electrons from a solid metal to one in solution so that the
dissolved one comes out of solution and the solid goes into solution (e.g. Cu
(s)
+2 Ag
+
(aq)
2 Ag
(s)
+
Cu
2+
(aq)
). The solid is oxidised (it loses electrons) and the dissolved one is reduced (it gains electrons).
More reactive metals will displace less reactive ones.
Galvanic cell
A galvanic cell (See Figure 1.1) is a separated redox reactions. The oxidation half-reaction releases
electrons into the circuit at the anode, which travel to the cathode were they reduce the ion in solution,
which deposits on the cathode. The Salt bridge of the galvanic cell is to allow ions to migrate,
allowing electrical neutrality to be preserved, otherwise there is a net charge created by the movement
9
1. Production of Materials
of electrons, which will eventually build up into a potential large enough to stop current ow (the
electrolyte in the salt bridge should not form precipitates with other substances, like KNO
3
or NaCl if
there is no Ag).
Figure 1.2: Lechlanche cell
Source: diracdelta.co.uk/science/source/l/e/
leclanchecell/source.html
Dry cell (Leclanche cell)
The dry cell is a basic cell that is very cheap and widely used
(Illustrated in Figure 1.2). The zinc is oxidised around the
case (anode) (Zn
(s)
Zn
2+
(aq)
+2 e

), and the reduction
reaction on the carbon rod (cathode) is NH
+
4 (aq)
+MnO
2(s)
+
H
2
O + e

Mn(OH)
3(s)
+ NH
3
. That is, zinc goes into
solution, and thus the cell is slightly acidic because of NH
4
Cl.
The cells casing is eaten away in operation, and by the acid
that forms, and it is not particularly energy dense, nor is it
capable of delivering large currents. However, it is cheap, ro-
bust, has a long shelf life, and is not particularly environmen-
tally damaging. The dry cell was the rst cell which could be
used as a portable source of power and has thus changed the
way humans interact with their environment, for example,
allowing communication breakthroughs like small transistor
radios.
Gratzel cell
Figure 1.3: Gratzel cell
Source: energyer.com/Know_How/
dye-sensitized-solar-cell.html
The Gratzel cell (See Figure 1.3) is a solar cell, also known as
a Liquid junction photovoltaic device, or a dye-sensitized so-
lar cell. The cell consists of a transparent electrode through
which light comes and hits the thin layer of TiO
2
doped
with a photosensitive dye which increases the spectrum ab-
sorbed by the TiO
2
. The light releases a photoelectron
from the dye which is conducted through the front elec-
trode into the circuit. This electron is replaced by one from
the I

in solution as an electrolyte. The resulting triiodide


then receives an electron returning along the other electrode.
TiO
2
+hf TiO
+
2
+e

and 3 TiO
+
2
+3 I

3 TiO
2
+I

3
.
The Gratzel cell is a robust device, which can be made very
thin (thin enough to be transparent). It is constructed from
fairly common materials and is thus fairly cheap, as well as
having a very low, even negative environmental impact, since
it replaces fossil fuels in energy generation. The Gratzel cell
along with other forms of renewable energy will revolutionise
society by freeing it from dependence on fossil fuels, and re-
ducing the environmental impact of energy generation.
1.5 Nuclear
chemistry provides a range of materials
Nuclear instability
Elements with too few neutrons and those with too many
will be unstable, as well as those with more than 83 protons
(i.e. past bismuth on the periodic table). The stable pro-
10
1.5. Nuclear chemistry
ton/neutron ratio goes from 1 at helium to 1.5 at uranium.
Too many neutrons = decay, Too few neutrons = decay.
Transuranic elements
Transuranic elements are produced by bombarding large nu-
clei with neutrons so that they undergo decay so their atomic number increases (even larger
transuranic elements can be made by bombarding with larger particles like helium or carbon nuclei).
Detection
Radiation can be detected by:
Photographic lm. The lm is developed by radiation
Cloud chamber. A supersaturated vapour (of water or alcohol), which is acted upon by air ionised
by the radiation, to form trails of condensation
Geiger-M uller counter. Normally measures particles but can do the others. It works by a gas
molecule being ionised by radiation and the electron ying o is directed and accelerated, giving
it enough energy to ionise other gas molecules, cascading until the electrons hit an electrode,
generating an electrical pulse that can be detected.
Scintillation counter. When some materials are irradiated with a specic type of radiation they
emit light, which can be collected, amplied and detected.
Uses/Production
Radioisotopes are produced in nuclear reactors (like technetium-99m and cobalt-60), by bombardment
with neutrons, and cyclotrons (like iodine-123 and uorine-18), by bombardment with helium nuclei.
Benets of radiation: more sensitive equipment for industry, reliability (e.g. sterilisation) and new
possibilities for things (like weld fault detection; non-invasive diagnostic and treatment procedures,
much more eective treatments). Disadvantages: tissue damage, genetic mutation (including cancers).
Industry Sodium-24. Made by neutron bombardment of sodium-23, decays by Made by neutron
bombardment of sodium-23, decays by emission into magnesium-24 with a half life of about 15 hours.
It is used for leak detection in pipes, since the radiation can easily be picked up, and the short half life
means that the uid the sodium-24 is placed in quickly ceases to be radioactive.
Medicine Cobalt-60. Made by netron bombardment of cobalt-59. Decays by emission into
nickel-60, releasing rays in the process, which can penetrate deep enough to kill cancer by destroying
some specic molecules. It has a half life of about 5 years, which is long enough to allow for extended
use, but also short enough to have a useful intensity of radiation.
11
2 The Acidic Environment
2.1 Indicators were identied with the observation that the colour of some
owers depends on soil composition
Acidity
A substance is either acidic (pH < 7), neutral (= 7) or basic (> 7). An acid tastes sour, burns the skin,
conducts electricity, turn blue litmus red. Alkalis are taste bitter, feel soapy, conduct electricity well,
turn red litmus blue.
Indicators
An indicator is a substance that changes colour based on the pH of a substance. They can be used to
test and thus regulate soil pH, which plants require to be in certain ranges for best growth. Similarly,
they can be used to make sure swimming pools are appropriately basic. Also, they can be used to
monitor waste, since it is of
Colour pH range
Indicator Low High Low High
methyl orange red yellow 3.1 4.4
bromophenol blue yellow blue 3.0 4.6
bromocresol green yellow blue 3.8 5.4
methyl red pink yellow 4.4 6.0
litmus red blue 5.0 8.0
bromothymol blue yellow blue 6.2 7.6
phenol red yellow red 6.8 8.4
thymol blue yellow blue 8.0 9.6
phenolphthalein clear red 8.3 10.0
Table 2.1: Common indicators
2.2 While we usually think of the air around us as neutral, the
atmosphere naturally contains acidic oxides of carbon, nitrogen and
sulfur. The concentrations of these acidic oxides have been increasing
since the Industrial Revolution
Oxides
Oxides can be either acidic or basic. Acid oxides are normally those of non-metals, such as CO
2
, and
P
2
O
5
. An oxide is acidic if it reacts with water to create an acid, and/or if it reacts with a base to make
salts (e.g. CO
2
, NO
2
, P
2
O
3
, SO
2
,Cl
2
O, normally non-metals). Basic oxides are those which react with
acids to make salts and do not react with alkali solutions (e.g. Na
2
O, K
2
O, MgO, normally metals).
13
2. The Acidic Environment
An oxide which makes salts in acids, but also react with alkalis is called an amphoteric oxide (e.g.
ZnO, Al
2
O
3
, PbO, SnO). Neutral oxides react with neither acids nor bases (e.g. CO, NO, N
2
O).
Le Chateliers principle
Le Chateliers principle is the statement that a system will react to disturbance in a way that minimises
the disturbance. E.g. if a system is heated it will move in an endothermic direction, to absorb energy;
if a gaseous system is increased in pressure it will move to reduce the pressure (equivalent to volume)
by reducing the number of molecules.
Equilibrium reactions
An equilbrium reaction is a reaction in which does not go to completion, a balance between products
and reactants is reached when the rate of forward reaction and the rate of reverse reaction is equal.
An equilibrium reaction is denoted X Y. The position of equilibrium can be anything, not just
half-half, and for a given set of products it can change depending on factors like temperature, pressure
etc.
Carbon dioxide
Carbon dioxide undergoes an equilibrium reaction in water
CO
2(g)
+ H
2
O
(l)
H
2
CO
3(aq)
This reaction is exothermic, so increasing the temperature will drive it left to absorb heat, so CO
2
has higher solubility at lower temperatures. Increased pressure of CO
2
pushes the equilibrium right
(forcing CO
2
into solution). Adding OH

into the solution increases solubility of CO


2
, since H
2
CO
3
+
2 OH

2 H
2
O + CO
2
3
, so dihydrogen carbonate is removed from solution, forcing the equilibrium
to move to the right to counteract the changing conditions (by Le Chateliers principle).
Sulfur dioxide
Sulfur dioxide is mostly generated by volcanoes and other geothermal activity, although some comes
from human activities like burning fossil fuels, and extracting metals from ores (which often contain
sulfur). e.g.
2 ZnS + 3 O
2
2 ZnO + 2 SO
2
Sulfur dioxide is a respiratory irritant which is particularly bad for asthma and emphysema (even when
only at 1 ppm). Sulfur dioxide forms acid rain (along with nitrogen dioxide), and it also gives air a bad
smell.
Oxides of nitrogen
Oxides of nitrogen come in three main types N
2
O (nitrous oxide), NO (nitric oxide) and NO
2
(nitrogen
dioxide). Nitrous oxide is formed by some bacteria in soil, human fertiliser increase the amount of
nitrogen in the soil and so facilitate the release of this oxide. Much nitric oxide comes from lighting,
where the high temperatures allow this reaction to happen N
2
+ O
2
2 NO. It is also formed along
with nitrogen dioxide in fossil fuel combustion (in cars and power stations), where the high temperature
again helps. Nitric oxide reacts with oxygen to form nitrogen dioxide, which is an acidic oxide. (The
mixture of NO and NO
2
is called NO
x
). Like sulfur dioxide, nitrogen dioxide is a respiratory irritant,
although it needs a concentration of about 3 ppm to inhibit breathing, which is very rarely reached.
Nitrogen dioxide reacts in sunlight to form ozone in a Photochemical smog, which is very poisonous
even at low concentrations. Nitrogen dioxide also forms acid rain.
14
2.3. Acids
Acid rain
Acid rain is rain which has a pH less than 5 (normal rain has pH between 5 and 6 due to carbonic acid
from CO
2
). It is formed when SO
2
and NO
2
dissolve in rain water, forming sulfuric and nitric acids.
2 NO
2
+ H
2
O HNO
2
+ HNO
3
2 HNO
2
+ O
2
2 HNO
3
2 SO
2
+ O
2
2 SO
3
SO
3
+ H
2
O H
2
SO
4
Acid rain can have a pH as low as 3. The acidity of the rain has many detrimental impacts:
Increased acidity of waterways, which can kill animal and plant life not adapted to the pH, as
well as increasing the ability of the water to leach minerals out of surrounding rocks, increasing
the number of dissolved ions. (Observed in lakes in Scandinavia and North America)
Damage to vegetation, acid rain can strip trees of foliage, destroying large swathes (Observed in
Europe and North America). It can also completely denude an area of vegetation (Queenstown
in Tasmania).
Erosion of CaCO
3
based buildings. Carbonate dissolves in acid, so the acid rain ends up dissolving
buildings and statues, damaging them beyond repair, and sharply accelerating the weathering
process (seen in many old buildings and statues in Europe).
Change soil chemistry, by changing the pH of the soil and the water running through it, acid
rain can leach minerals out of soil, and kill bacteria and other micro-organisms, damaging the soil
ecosystem, possibly even killing larger trees.
Acid rain washes SO
2
and NO
2
out of the atmosphere so these substances rarely spread a long way
from where they were emitted, often restricting the atmospheric problem to a local one, although the
eect on waterways can have far reaching consequences.
2.3 Acids occur in many foods, drinks and even within our stomachs
Acids
An acid is a proton donor, it will react with water to form a hydronium ion H
3
O
+
. e.g.
HBr + H
2
O H
3
O
+
+ Br

pH
pH is a measure of the concentration of hydronium ions, [H
3
O
+
].
pH = log
10
[H
3
O
+
]
pH should have the same number of decimal places as the number of signicant gures in the concen-
tration of hydronium ion.
Strong & weak acids
An acid is described as strong if it completely ionises in water, there is no molecules retaining a hydrogen
atom, e.g. hydrochloric acid. An acid is weak if it doesnt completely ionise in water, the degree of
ionisation is a measure of how much ionises, e.g. citric acid and acetic acid (although citric has a higher
15
2. The Acidic Environment
Acid Formula Comments
Natural
Hydrochloric HCl Aids ecient operation of enzymes, as industrial
cleaner, base neutraliser
Acetic CH
3
COOH Found in vinegar, used to synthesis organic com-
pounds
Citric C
6
H
8
O
7
Found in citrus fruit, used as a food additive
Ascorbic C
6
H
8
O
6
Vitamin C, good for health
Synthetic
Sulfuric H
2
SO
4
Most common acid, used in fertilisers, detergents,
synthetic bres
Nitric HNO
3
Used in fertilisers and explosives
Table 2.2: Examples of Acids
Base Formula Comments
Natural
Ammonia NH
3
Formed in anaerobic decay, used in fertilisers, clean-
ing agents
Amines CH
3
NH
2
Smell like sh, occur in decomposition of organic
matter
Metallic oxides Fe
2
O
3
Used to extract some metals
Carbonates NaCO
3
Used to make glass, paper, as a neutralising acids
Synthetic
Sodium hydroxide NaOH Used to make soap, synthetic bre, as a powerful
cleaning agent
Calcium oxide CaO Quick lime, made by heating limestone, used in ce-
ments
Calcium hydroxide Ca(OH)
2
Slaked lime, used in mortar and plaster
Table 2.3: Examples of Bases
degree of ionisation). Dilute and concentrate are terms which describes the concentration of the acid,
concentrate is more than 4 or 5 M, dilute is less than 2 or 3 M. The reaction of an acid with water is
an equilibrium, in a strong acid the equilibrium is far to the right (dissociation), in a weak acid the
equilibrium lies somewhere in the middle.
Acids as food additives
Acids are often used as food additives because they can improve the taste, and they can act as preser-
vatives because they kill bacteria which cant survive in acidic environments. Common additives are
acetic, citric and phosphoric acids, along with propanoic acid in bread, and ascorbic acid added because
it is vitamin C, for its nutrient value.
2.4 Because of the prevalence and importance of acids they have been
used and studied for hundreds of years. Over time, the denitions of
acid and base have been rened
Denitions of acids
The denition of an acid has changed over time, one of the rst denitions was that of Lavoisier in
1780 who said that acids were substances that contained oxygen, although this was disproved by basic
16
2.4. Acids: take two
Neutral
NaCl KNO
3
Na
2
SO
4
CH
3
COONH
4
Acidic
NaHSO
4
KHSO
4
NH
4
NO
3
Basic
KNO
2
NaHCO
3
CH
3
COONa KCN Na
2
CO
3
Table 2.4: Salts, by acidity and alkalinity
substances such as Na
2
O, and substances like HCl which were acidic without any oxygen.
Davy said in 1815 that acids contained replaceable hydrogen, i.e. substances with a hydrogen
that could be replaced by a metal, to form a salt. Bases reacted with acids to make salt and water.
Arrhenius said in 1884 that acids ionised to produce hydrogen ions. He made the distinction
between complete and equilibrium ionisation. His denition of a base was a substance that ionised to
make hydroxide ions, although this misses some substances.
Bronsted-Lowry theory
The Bronsted-Lowry theory of acid and bases says that acids are proton donors, and bases are proton
acceptors. Thus, a substance can change from basic to acidic and vice-versa when it changes solvents,
if the substance gives up protons to the solvent (as in a greater tendency to lose protons) the it is an
acid. If the substance has a tendency to take protons from the solvent then it is a base.
Conjugate pairs
Bases and acids have what is called their conjugate acid and base, respectively. Conjugate pairs are the
pairs of acids and bases where one has gained a proton and the other lost it (e.g. HCl and Cl

are a
conjufate pair). The strength of a conjugate acid and base is approximately inverse, as in a strong acid
will have a weak conjugate, and a moderate base will have a similarly moderate conjugate acid.
Salts
Salts can be non-neutral, since the ions can be conjugates of acids or bases. If the ion is the conjugate
of an acid, it will accept a proton, so it is acidic. If an ion is the conjugate of a base it will give up a
proton so it is basic. The ions can be weak or strong acids or bases, if a salt consists of two ions of the
same strength (i.e. strong or weak) then it will be approximately neutral, if they are misbalanced then
the strong ion will mean a solution of that salt will be this acidity.
Amphiprotic substances
An amphiprotic substance can donate and accept protons, i.e. it can act as a base or an acid. e.g.
HCO
3
:
HCO

3
+ H
2
O H
3
O
+
+ CO
2
3
HCO

3
+ H
2
O OH

+ H
2
CO
3
Thus, CO
2
3
is the conjugate acid of HCO
3
, and H
2
CO
3
is the conjugate base.
17
2. The Acidic Environment
Neutralisation
Neutralisation is a proton transfer reaction, where the proton given up by the acid replaces the proton
taken from the solvent by the base. In water, the net ionic reaction is often H
3
O
+
+ OH

2 H
2
O.
Other reactions can occur, such as the neutralisation of ammonia H
3
O
+
+ NH
3
NH
+
4
+ H
2
O. All
neutralisation reactions are exothermic, and the energy released is about 56 kJ mol
1
.
Titration
Titration (also called volumetric analysis), is the process by which the concentration of a substance
can be determined by the use of another substance with known concentration. The substance with
known concentration is called the titrant, it is added to the other substance slowly so the volume at
which all the added titrant and all the unknown substance are used can be accurately determined. This
point is called the equivalence point. The equivalence point can be detected by using an indicator,
since the solution will suddenly undergo a large change in pH when the titrant reacts with all of the
substance being titrated with. It is important the concentration of the titrant is accurately known,
the volume used (the titre), and that the volume of the substance being analysed is also accurately
known. Equipment used in titration is: a burette (should be washed with the titre), a ask to hold
the substance being analysed (washed with pure water), a volumetric pipette to accurately measure a
volume of the substance to be analysed (washed with the substance), an indicator.
Primary standard A primary standard is a substance that can be used to make an titrant of
accurately known concentration. A primary standard has to not absorb water, must be stable, and
must be very pure, so that a measured weight of the substance is known to be almost completely that
substance. The purity of a primary standard is important so that volumetric analysis can be accurately
and reliably carried out with it. Examples of primary standards are NaCO
3
and NaHCO
3
, which can
be dried and measured with high purity.
Equivalence point The pH of the equivalence point is the pH of the salt which forms at this
point, so an indicator must be chosen that has a colour change near this.
Buers
A buer solution is a solution which contains similar amounts of a weak acid and its conjugate. These
solutions can maintain a constant pH, since when either OH

or H
3
O
+
ions are added one of the
equilbriums will move (by Le Chateliers principle) to absorb these ions. e.g. for a solution of H
2
CO
3
and HCO

3
:
H
2
CO
3
+ H
2
O H
3
O
+
+ HCO

3
So adding H
3
O
+
will move this equilibrium left, and if there is enough HCO

3
in solution, all the H
3
O
+
will be absorbed, so there will be no change in pH. Adding OH

will neutralise H
3
O
+
, which will force
the equilibrium to the right to replace the hydronium, and if there is enough H
2
CO
3
in solution, all the
OH

will react before the H


2
CO
3
runs out, so there will be no change in pH. It is important that both
acid and base from the conjugate pair are present so the solution can buer against both increases and
decreases in pH. The pH a buer maintains depends on the position of the equilibrium.
Example of buered systems Buers occur in some rivers and lakes. Rainwater has a natural
equilibrium with CO
2
HCO

3
, if there is another source of HCO

3
such as that dissolved out of rocks,
then the equilibrium above will be pushed left. This creates an equilibrium of H
2
CO
3
and HCO

3
, which
acts as a buer in the water system, so the pH is maintained constant (if lakes are not buered, such
as those in Scandinavia, then acid rain will change the systems pH). The same buer reaction is used
in swimming pools to maintain a pH around 7. Blood is also buered by this equilibrium, since
18
2.5. Esterication
Flavour Ester
apple methyl butanoate & isopentyl pentanoate
banana isopentyl ethanoate
grape ethyl methanoate & ethyl heptanoate
orange octyl ethanoate
pear pentyl ethanoate
raspberry butyl ethanoate
rum ethyl methanoate
jasmine benzyl ethanoate
Table 2.5: Esters as avours
many biological processes require specic pHs, although other buers like hmoglobin are also needed
to buer against pH changing due to CO
2
.
2.5 Esterication is a naturally occurring process which can be performed
in the laboratory
Alkanoic acids
An alkanoic acid is an alkane with a carboxyl group on one end:
RCOOH
It is basically an primary alkanol with an additional double bonded oxygen atom. They are named as
<parent alkane>-oic acid, i.e. methanoic acid, ethanoic acid etc. (In an alkanoic acid R can only
be an alkyl, but in a carboxylic acid R can be any side group). The melting and boiling points of
alkanoic acids are higher than alkanes and alkanols (which is also much higher than the alkanes) of
similar molecular weights, because both the CO and the OH bond is polar, (and the OH bond
forms hydrogen bonding) which means the intermolecular forces are strong.
Esters & esterication
An ester is a compounded formed by the reaction of a carboxylic acid with an alcohol. The OH group
on each molecule reacts to eliminate H
2
O, leaving an O between the original acid and alcohol.
XCOOH + YCHOH XCOOCHY + H
2
O
Esters are named as <alcohol ><acid>-oate e.g. methanol and ethanoic acid forms methyl ethanoate.
Esterication is the name given to the synthesis of an ester. The esterication reaction is an equilibrium
which is slow, so H
2
SO
4
is used as a catalyst, and it absorbs the water produced, so moves the equilib-
rium to completion (if enough H
2
SO
4
is used). Also, the reaction is carried out at a high temperature
(just below the boiling point of the alcohol) to increase the rate of reaction.
Reuxing Reuxing is required to stop the loss of the reactants due to vaporisation. It works by
using an open ask with a long neck, which is surrounded by a water jacket, the hot vapours rise up
through this, and are condensed by the cold water, and so cannot escape from the reaction vessel. This
allows the reaction to be carried out at a high temperature without using a closed vessel, which would
cause pressure build up and thus possible explosions.
Uses of esters
Esters are used for many things, including:
19
2. The Acidic Environment
Food avouring (see Table 2.5), esters are often found in natural foods giving them their avours,
and thus the synthetic avours (and they are non-poisonous)
Perfumes, since they have distinctive odours which can be used.
Solvents, normally ethyl ethanoate (a.k.a. ethyl acetate), which is used in nail polish remover.
Plasticisers, heavy (therefore non-volatile) molecules are used in plastics like PVC to make it
more plastic.
20
3 Chemical Monitoring and Management
3.1 Much of the work of chemists involves monitoring the reactants and
products of reactions and managing reaction conditions
An actual chemist
John Smith
1
is a chemical engineer working for the Shell Chemical Company. He works as a senior
research engineer in the chemical development department. Smith develops washing machine detergents,
attempting to improve and innovate on the products which are currently available. He has to improve
the ecacy of the detergents by improving properties of them such as solubility in both polar and
non-polar substances. The detergents have to be able to dissolve into the water used in the washing
machine, and then dissolve the dirt on the clothing. Since the water is polar, it can dissolve any polar
substances on the clothing, leaving only non-polar dirt, which the soap has to be able to dissolve and
thus lift from the textiles. These requirements mean the soap molecule has to have areas of polarity
and areas of non-polarity, neither of which can be much larger than the other, or else it will reduce the
solubility of the molecule in one of the types of substances. Part of Smiths work is maximising the
molecules solubility in water and in the non-polar dirt, often performing tests, as well as attempting
to ne-tune a detergents properties for a specic type of washing machine, so that it performs as well
as is possible.
Collaboration
Collaboration is need in chemistry since the subject is so broad that people must specialise in specic
areas. However, many problems require detailed knowledge of multiple areas of speciality, this forces
the participating chemists to collaborate so that each person can build of others expertise, extending
the solution to a problem. Also, many problems in chemistry come from, or involve, other areas of
1
Not his real name
Figure 3.1: Branches of Chemistry
21
3. Chemical Monitoring and Management
Use Form
fertilisers ammonium nitrate, urea etc.
plastics (inc. bres) rayon, nylon, acrylics
nitric acid makes fertilisers, dyes, TNT, dynamite
cleaning products/detergents ammonia
Table 3.1: Uses of Ammonia
science, such as biology or physics, so collaboration with people with expertise in these areas is also
needed.
Monitoring
Many chemical process must be monitored so that the products are produced with the greatest yield,
purity, speed etc. For example in the production of ethylene oxide, the reaction is
CH
2

CH
2
+
1
2
O
2
Ag cat. @ 250

C
CH
2
CH
2
O
but ethene can also react with oxygen in a combustion reaction, thus the conditions of the reaction to
form ethene oxide must be monitored to restrict the amount of oxygen, and make sure the reaction is
not too hot. Also, properties such as concentration of CO
2
and the pressure of the reaction would be
monitored.
3.2 Chemical processes in industry require monitoring and management
to maximise production
Synthesis of ammonia
Ammonia can be synthesised from N
2
and H
2
by the equilibrium (its exothermic, releasing 92 kJ mol
1
):
N
2
+ 3 H
2
2 NH
3
Normally this lies to the left, but increasing the pressure and lowering the temperature pushes the
equilibrium position to the right. However, cooling the reactants decreases the rate of reaction, because
a reaction happens when the reactants collide with enough energy to overcome the activation energy of
the reaction, so heating the reaction will mean more of the collisions are high enough energy.
Haber process
The Haber process is the industrial process for the synthesis of ammonia, it is carried out at about
400

C and a pressure of 250 atm, along with magnetite (Fe


3
O
4
) with a pure iron surface as a catalyst.
These conditions are a balance between reaction rate, and yield. With these conditions the equilibrium
lies at about 45%, although the reaction is rarely carried to completion so yields are more usually
around 30%. The process consists of passing a stoichiometric mixture of N
2
and H
2
through a catalytic
reactor. The products are passed into a coolant condenses the NH
3
out of the mixture of ammonia
and the unreacted reactants (its boiling point is -33

C, and the boiling points of the others are below


-180

C). The unreacted N


2
and H
2
are recycled through the catalytic reactor (the mixture always has
a ratio of 1:3 so this can be done without building an imbalance of either reactant).
Monitoring the Haber process
Some parts of the Haber process must be monitor to maximise the products, reaction rate etc and to
ensure safety. The temperature and pressure need to be monitored. Also, the ratio of N
2
and H
2
needs
22
3.3. Manufactured stu
Figure 3.2: A owchart to identify lone cations in a solution
Source: hsc.csu.edu.au/chemistry/core/monitoring/chem943/943net.html
to be maintained at 1:3 as accurately as possible. The presence of O
2
, CO
2
, CO and sulfurs need to be
monitored and minimized since O
2
could cause an explosion, and the other three reduce the ecacy of
the catalyst. Other gases like CH
4
and Ar need to monitored because these reduce the eciency of the
reaction. The output ammonia should be monitored for purity as a double check.
History of the Haber process
Fritz Haber developed his method of synthesis of ammonia in 1908 in Germany. 6 years later this process
was industrialised by Bosch, also German. During WWI, this process allowed Germany independence
from nitrates mined from guano deposits in bat caves in South America. This shielded the agricultural
sector of the German economy from the loss of trade routes, which would have caused a lack of fertilisers.
Also, ammonia can be used to create explosives (TNT, dynamite etc.) so the development of the Haber
process gave the German war eort cheaper and reliable access to the raw materials required for the
manufacture of explosives.
3.3 Manufactured products, including food, drugs and household
chemicals, are analysed to determine or ensure their chemical
composition
Ion tests
The ions in a solution can be determined by precipitation tests, and by ame tests.
Identifying cations The cations in a solution can be identied by testing for precipitates, com-
bined with ame tests to identify metals (see Figure 3.2). Dierent cations precipitate with dierent
anions, and often with dierent colours (see Appendix B for a chart). When some metals are passed
through a ame, they give it a distinctive colour (see Table 3.2)
Identifying anions The anions in a solution can be identied by testing the formation of pre-
cipitates, using the solubility rules found in Appendix B. A sample owchart can be seen in Figure
3.3. CO
2
3
can be identied because it releases CO
2
gas in an acid. Phosphate ion doesnt form a
precipitate with Ba
2+
in a neutral solution because it equilibriums with HPO
2
4
, so that there is very
23
3. Chemical Monitoring and Management
Figure 3.3: A owchart to identify lone anions in a solution
Source: hsc.csu.edu.au/chemistry/core/monitoring/chem943/943net.html
little in a solution to form the precipitate. However, adding a base (such as ammonia) means that there
is sucient phosphate to form insoluble Ba
3
(PO
4
)
2
.
Atomic Absorption Spectroscopy (AAS)
AAS is used to identify low concentrations of metals (in the range of a few ppm, to an accuracy of up
to 0.01 ppm). Every element has a distinct series of wavelengths of light that it emits when excited,
due to electrons moving shells and releasing a photon. When irradiated with the same wavelengths an
element will absorb it, and then reradiate it in any direction (as the electrons are pushed up a shell,
and then fall back down).
AAS works on this principle (See Figure 3.4): an aqueous sample is atomised, light created by
atomic emission of the element being detected is shone through the atomised sample, and the amount
of each of the wavelengths absorbed is recorded. This gives a very accurate and precise measure of the
concentration of trace elements in a sample. AAS can be used to monitor the concentrations of trace
metals in the environment like lead, mercury, cadmium etc. It can also monitor soil health by recording
the concentrations of nutrients in the soil.
Metal Colour
Ca Brick red
Ba Apple green
Cu(I) Blue
Cu(II) Green to blue-green
Fe Gold
Li Dull red
K Lilac
Sr Crimson
Na Intense yellow
Table 3.2: Flame test colours of common metals
24
3.3. Manufactured stu
Figure 3.4: A simple AAS device
Source: en.wikipedia.org/wiki/File:AASBLOCK.JPG
Need to monitor ions
Many ions in the environment are harmful to humans, and the environment, and so their concentrations
need to be monitored and carefully controlled. Lead, for example, is poisonous, causing mental damage,
and developmental problems. Lead in the environment can be absorbed into the food chain and work
its way up to humans, so the concentration should be monitored to minimise the damage due to it.
Sulfate in lawn fertiliser
The sulfate content of lawn fertiliser can be determined by gravimetric analysis. The procedure could
be: dissolve as much of the fertiliser as possible in an acid (HCl) and lter away remaining solids, heat
the solution until it is nearly boiling (e.g. place it in a water bath) and add excess BaCl
2
while stirring,
continue to heat for 30 minutes, and then leave to cool until the precipitate settles at the bottom, then
cool with ice, lter this solution and precipitate through a sintered glass lter. The lter is washed to
remove other ions as much as possible and its dry weight is compared to its original dry weight. This
experiment suers from errors such as:
Loss of BaSO
4
due to dissolution, passage through the lter, remaining in the beaker, or spillage
Contamination of the residue due to other ions or impurities attaching to the surface of precipitate
particles (adsorption)
Measurement errors, such as not fully drying the lter when it is weighed
These errors can be reduced by:
Forming the precipitate slowly at high temperatures so that the precipitate particles are as large as
possible (and allowing it to digest, as in, continue heating it, makes the particles larger) reducing
adsorption (by reducing surface area) and losses through the lter
Cooling with ice reduces the solubility of BaSO
4
so reduces losses due to solubility
Careful washing, with many repetitions with small volumes of liquid, and drying between
The nal drying-then-weighing stage should be done multiple times until the mass is constant
25
3. Chemical Monitoring and Management
160 180 200 220 240 260 280 300
0
10
20
30
40
50
60
70
80
90
100
Temperature (K)
H
e
i
g
h
t
(
k
m
)
Troposphere
Stratosphere
Mesosphere
Thermosphere
Figure 3.5: The layers of the atmosphere and their temperatures
3.4 Human activity has caused changes in the composition and the
structure of the atmosphere. Chemists monitor these changes so that
further damage can be limited
Structure of the atmosphere
The atmosphere consists of 3 main elements nitrogen (78.1%), oxygen (21.0%) and argon (0.9%). There
are other trace elements such as CO
2
and Ne, and the concentration of water vapour varies from about
0.5% to 5%. The atmosphere consists of layers (see Figure 3.5): the troposphere is about 15 km thick
and is closest to the Earths surface; the stratosphere is about 35 km thick and is above the troposphere
(they are separated by the tropopause; the stratopause separates this from the mesopause etc). The
temperature falls as height increases in the troposphere as radiant heat from the Earths surface is
the main source of energy. In the stratosphere temperature rises with altitude due to heating by the
absorbtion of UV light, because of this the stratosphere is very stable, air doesnt mix by convection
because the temperature gradient is backwards.
Pollutant Source
Carcinogens Unleaded petrol, vinyl chloride from plastics, dioxins from chlorine com-
pounds
CFCs Refrigeration, air-con, re extinguishers
Carbon monoxide Combustion (cars, res etc.)
Hydrocarbons Solvents
Lead Lead smelters, paint dust, leaded petrol
NO & NO
2
Combustion
Particulates Combustion, mining, other industrial process, asbestos
O
3
Photochemical smog, printers/photocopiers
SO
2
Combustion, metal smelting
Table 3.3: Pollutants in the lower atmosphere
26
3.4. The atmosphere
O O
2
O
3
Formation UV Photosynthesis UV & electric discharge
Appearance Colourless gas, pale blue
liquid
Colourless gas, blue liquid
Smell Odourless Strong, distinctive smell
Eect on life Easily reacts in living
cells
Vital in diluted form Poisonous (even as low as
0.1 ppm)
Boiling point 183

C 111

C
Density Similar to air 1.5 air
Solubility Slightly soluble more than O
2
Reactivity Very high Moderate oxidant, reacts
with most things into ox-
ides
More reactive, stronger
oxidant than O
2
Uses Medical, rocket fuel,
steel-making, cutting
tools (oxy-acetylene)
Sterilisers, water puri-
er, paper/textile bleach-
ing agent
Table 3.4: Comparison of properties of allotropes of oxygen
Co-ordinate covalent bonds
A co-ordinate covalent bond is just like a normal covalent bond except both electrons are supplied by
the one atom, i.e. it is sharing both electrons in a pair to make up for another atom missing 2 electrons.
Examples of co-ordinate covalent bonds are the one in ozone (O
OO), the one in C

=O, and the one


in ammonium (H
3
N(H
+
)).
Ozone
Ozone is molecule made from three oxygen atoms, it is normal O
2
with an additional O co-ordinate
covalently bonded to form a bent shape. Ozone is a poison to life, and as such is a pollutant in the
troposphere, but it is involved in the absorption of UV light in the stratosphere so it is vital for life
when it is in the stratosphere.
Chlorouorocarbons & Halons
A chlorouorocarbon (CFC) are compounds with only chlorine, uorine and carbon. A halon is a
compound with carbon and bromine, possibly with other halogens. CFCs come from refrigeration,
aerosol cans and foaming agents in the making of plastics like polystyrene. CFCs were also used to
clean electronic circuit boards. Halons are used in re extinguishers (BCF re extinguishers, as in
bromine, chlorine, uorine). CFCs are very stable, and are not destroyed by sunlight, so they last for
a long time in the atmosphere, long enough to spread into the stratosphere by dispersion, and they are
insoluble in water so are not washed out by rain.
Naming haloalkanes
The prexes for F, Cl, Br and I are uoro-, chloro-, bromo-, iodo- respectively. Its positions and
multiplicities are given in the form <carbon numbers>-<number prex><element prex>, e.g. 1,2,3-
trichloro . The numbers are counted from the end that minimises their sum. The elements are listed
alphabetically. (If there is multiple ways of counting to minimise the sum, then it is counted to minimise
the most electronegative element).
27
3. Chemical Monitoring and Management
Problems with CFCs
CFCs destroy ozone in the stratosphere. When a CFC is hit by high energy UV light, a chlorine atom
is broken o. This Cl reacts with O
3
, converting it into an ozone and a ClO radical.
CFCl
3
UV light
CFCl
2
+ Cl
Cl + O
3
ClO + O
2
ClO + O
3
Cl + 2 O
2
Thus, chlorine is a catalyst, and so can destroy many ozone molecules. Thus CFCs are detrimental
to the atmosphere, so measures have been taken against them. The Montreal Protocol was signed in
1987 which agreed to phase out halons, CFCs, and HCFCs in a short period of time (although some
countries were given extensions). So far there has not been any improvement in the concentration of
ozone in the stratosphere, but the slow speed with which particles move in the stratosphere mean that
this is not too surprising.
Measuring ozone
Ozone is measured in Dobson Units (DU), and is a measure of the thickness of the ozone if it were
at ground pressure. Ozone can be measured by observing the amount of the frequencies it absorbs
compared to surrounding frequencies in the light coming through the atmosphere. This is done with a
UV spectrophotometer. Satellite based instruments can also be used to give worldwide map of ozone
concentration (as well as ozone concentration at specic altitudes). A balloon can also be used to obtain
a concentration prole at a specic location on the Earths surface .
Alternatives for CFCS
There are several alternatives to CFCs for almost all the uses:
Hydrochlorouorocarbons (HCFCs), these are more volatile and thus a larger proportion breaks
down in the lower atmosphere, well away from the ozone layer. However, a signicant proportion
still reaches the stratosphere, where it breaks down, releasing a chlorine atom, resulting in similar
damage to a CFC.
Hydrourocarbons (HFC) are even more volatile that HCFCs and very few reach the stratosphere,
although they contain no CCl bond to be broken and so cannot destroy ozone any way. HFCs
are used in almost all the areas where CFCs were used, including refrigeration (some plain
hydrocarbons are also used, and these have similarly little impact on ozone levels) and aerosols,
although they are slightly less ecient compared to CFCs.
However where they were used in laboratories for research, CFCs have had to be replaced by other
methods, since CFCs are often used to deplete ozone in a laboratory environment. Also, all these
alternatives are greenhouse gases so more research is still required to nd more environmentally friendly
alternatives.
3.5 Human activity also impacts on waterways. Chemical monitoring and
management assists in providing safe water for human use and to
protect the habitats of other organisms
Water quality
Water quality describes its appropriateness for uses, e.g. for drinking, washing, agriculture, recreation,
environmentally etc. Thus, a denition of good water quality depends on its use, but a measure of
quality can be obtained by measuring a few properties:
28
3.5. Waterways
Acidity, as in pH, it should be around 6.58.5
Concentration of ions the each ion has a dierent safe range (e.g. [NO

3
] < 0.1 ppm &
[PO
2
4
] < 0.03 ppm)
Biological oxygen demand is a measure of the amount of dissolved oxygen that would be used
to decompose all the organic material in the water, measured in ppm, and should be less than 5
ppm. A high BOD means that water will use more dissolved oxygen as the stu in it decomposes.
Dissolved oxygen is a measure of the amount of oxygen dissolved in the water, which is necessary
for life, it should be 7-9 ppm
Hardness, a measure of the concentration of Ca
2+
and Mg
2+
Total dissolved solids, the mass of solids dissolved in the water, (can be either mg L
1
or
ppm), should be less than 500 ppm for drinking, it includes the mass of any salts (sea water has a
TDS of 35,000 ppm), which often make up the bulk of the solids, so conductivity is often a good
approximation.
Turbidity is a measure of the cloudiness of water, as in, the amount of suspended particles. It
is measure in NTU (nephelometric turbidity units), and should be less than 3 NTU. It can be
measured with a sechhi disk or a graduated calibrated tube, both processes involve adding more
water until the disk cant be seen, or a cross at the bottom of the tube disappears.
Factors aecting ion concentrations
There are several factors which can aect the concentration of ions in water bodies. Rain is pretty much
free of ions (a small amount of CO
3
and sea spray etc.) but it can pick up ions as it runs on the ground,
picking up nitrate, phosphate, calcium and magnesium. If the water enters an underground aquifer
it will pick up many more ions from the rocks and soil (calcium, magnesium, sulfate, chloride, carbonate
etc.). If it goes to an artesian basin, it will pick up other ions like iron, manganese, copper, and zinc,
which can push TDS to over 1000 ppm. Acid rain can leach metal ions like calcium, magnesium and
iron from the soil better, pushing TDS up again. Human activity such as land clearing and other
agriculture can also aect TDS, land clearing increases turbidity and helps the dissolution of ions
like sodium, potassium, calcium, magnesium, sulfate, chlorine and carbonate. Agriculture puts more
nitrate and phosphate into the environment (in fertilisers) and thus increases the concentration of these
ions in run o. Discharged sewage contains high levels of phosphate and nitrate and many other
ions, even if it has been treated well sewage can have TDS of 200 ppm. Industrial waste can contain
more exotic ions, like lead, mercury, cadmium, chromium, copper and zinc. Rubbish tips can contain
high concentrations of common ions (nitrate, phosphate), and others like lead, cadmium, mercury (in
batteries), zinc (from galvanised iron), if the tip is not properly designed then water running though it
can leach these minerals out.
Treatment
Water can be treated (see Figure 3.6) to improve its quality and often is, in a multistage process basi-
cally involving clarication (making it look/taste better) and sanitisation (making it safe for humans).
Clarication can be done by precipitating the particles out of the water, this process is called Floccu-
lation or Coagulation. It works by adding FeCl
3
to the water, which allow the suspended solids to
group into large and larger particles, eventually getting large enough to be ltered by a coarse lter like
sand or anthracite (which also lters out organic matter), for better results though, a membrane lter
can be used. The FeCl
3
needs to be added to an alkaline solution (so the pH is often adjusted with
NaOH) so that the insoluble Fe(OH)
3
can form. (Sometimes Al(OH)
3
is used instead of Fe(OH)
3
). The
water is sanitised by dissolving Cl gas in the water, this kills bacteria and some viruses, with careful
monitoring, enough is added to last for long enough to keep the water disinfected until it reaches the
29
3. Chemical Monitoring and Management
Catchment Add NaOH
Add FeCl
3
to coagu-
late/precipitate
suspended
solids
Filter to
remove pre-
cipitate (using
sand/anthracite
or a mem-
brane lter)
Add Cl
2
gas
to sanitise
Add F

for
tooth health
Storage Consumer
Figure 3.6: A process to treat water
consumer. Fluoride is often also added (at 1 ppm) as it is good for tooth health, it has no eect on
water quality/safety. Monitoring has to be used to make sure the concentrations of everything is with
the required ranges. Most water suppliers uses sand or anthracite lters even though membrane lters
are much superior, since the current lters are much cheaper.
Membrane lters
A membrane lter consists of a thin lm of a polymer (polypropylene, teon, polysuplone) with very
small holes in it (these holes are uniformly sized). This lm can be pleated and placed in a cylinder,
the area outside the membrane is lled with dirty water, and the clean water comes out on the inside
of the membrane. Another method is to make the lm into a large number of thin capillaries (called
hollow bre membrane lter), which is hollow, so that dirty water ows over the outside and clean
comes out of the passage in the capillary. A bre lter is made from many of these so that it has a
large surface area. The ltrate is left on the outside of the membrane/capillary in each method, and it
can be cleaned by back ushing, by blowing air through it from the clean side. A membrane lter can
be made with holes of a custom size, so they can lter dierent things. A membrane lter can stand
pressure so they can be sped up by forcing the water onto them.
Heavy metals
The presence of heavy metals in a solution can be determined by testing with H
2
S, in acidic and in
alkaline solutions. In acid the equilibrium
S
2
+ 2 H
3
O
+
H
2
S + 2 H
2
O
lies well to the right, but PbS and other very insoluble precipitates (like copper) can still form, this
takes out some S
2
so the equilibrium removes to the left, providing more S
2
until all the insoluble
precipitates come out of solution, however, more soluble precipitate, like zinc and iron, dont form
precipitates. In an alkaline solution the equilibrium lies on the left, so there is enough S
2
to form
precipitates with the more soluble elements. Once their presence is determined the actual elements
present can be more accurately determined (see Table 3.5)
Eutrophication
Eutrophication is when a water body becomes so nutrient laden that an algal bloom is likely. Eu-
trophication is accelerated by human activity which increases the concentrations of, most importantly,
phosphate and, secondarily, nitrate. Human activity such as agriculture with fertilisers and sewage
30
3.5. Waterways
Metal Test
Ba
2+
White precipitate with SO
2
4
, none with OH

or F

Ca
2+
White precipitate with SO
2
4
and F

Cu
2+
Blue precipitate with OH

, which dissolves to deep blue in NH


3
Fe
2+
Green or white precipitate with OH

that may go brown


Fe
3+
Brown precipitate with OH

, deep red with SCN

Pb
2+
Yellow precipitate with I

Table 3.5: Tests for heavy metals


(including water used to wash clothes) are the major contributors to this. Eutrophication can be de-
tected by monitoring the concentration of phosphate, in a still water body like a lake the concentration
should be less than 0.05 ppm, but in moving water (river, stream) it can be as high as 0.1 ppm.
The concentration of phosphate can be determined colorimentrically: a known volume of ammonium
molybdate is added to the solution, then solid ascorbic acid. The solution will have a blue colour, the
absorbance of this solution can be compared against a reference solution given the same treatment so
that a quantitative measure is obtained.
Town water supply
The catchment of a water supply is the area from which water drains into the dams of that town. A
catchment should have minimal human activity, no agriculture, settlement, mining etc since these will
contaminate the water supply. However, contaminants will still nd their way into the supply, but these
can be detected (e.g. ions can use precipitation/ame tests) and measured (AAS) to determine whether
they are in a safe range. After the water has made it to the catchment dam, it can be puried and
claried, using lters, occulation etc to increase its quality. Afterwards, chemicals like chlorine (as a
disinfectant) or uorine (for tooth health) can be added.
31
4 Industrial Chemistry
4.1 Industrial chemistry processes have enabled scientists to develop
replacements for natural products
Rubber s a natural resource derived from rubber trees that has had synthetic replacements developed.
Rubber is used in tyres, and in fabrics, among others. The most important properties of rubber are
its elasticity, as well as the way in which the chemical structure allows the properties to be modied
signicantly (e.g. vulcanisation). Natural rubber is time consuming and eort intensive to obtain, so
with increased demand due to car tyres and population increase alternative had to be developed to keep
prices low. Also, people can have allergies to latex which is a natural form of rubber, so alternatives
with hypo-allergenic properties are needed.
Alternatives to rubber include styrene butadiene and polyurethane, which have taken over most
of the applications where rubber was used. The synthetic compounds often have more suitable properties
for the specic applications they are being used for since the manufacturing process can be ne tuned
to optimise certain things. For example, rubbers that retain their elasticity better in cold weather, or
that remain elastic for a longer period of time, or even are just cheaper for everyday applications.
Overall, research to replace natural rubber has lead to myriad substances, with dierent prop-
erties which can be used in dierent situations. These include as in tyres, as a straight replacement for
natural rubber (styrene butadiene), or as foams in shoes, mattress (polyurethane). The production of
natural rubber is very labourful in that each tree has to be tapped individually and the latex collected,
after which it needs to be adjusted (e.g. vulcanised) to give the desired properties. Rubber substitutes
are manufactured by chemical reactions (normally polymerisation) which allows it to be automated so
that the process can occur without much human interaction, which reduces costs, and the conditions
can be controlled to maximise the eciency of production of the rubber, unlike natural rubber. There-
fore, research has progressed the rubber manufacture process so that natural rubber is now a minor
constituent of the global rubber consumption.
4.2 Many industrial processes involve manipulation of equilibrium
reactions
Equilibrium constant
The equilibrium constant is a quantitative measure of the equilibrium point of a reaction, it is denoted
K. A value of K between 0.1 and 10 means the reaction has what could be called an equilibrium. If K
is very small it means that the reaction barely starts. If it is very large, then the reaction goes almost
to completion. The value of K for any given reaction can only be changed by the temperature at which
the reaction occurs, all other variables do not change K. K is a quotient of the concentrations of the
products (P) and reactants (R), for a reaction a
1
R
1
+a
2
R
2
+ b
1
P
1
+b
2
P
2
+ , the equilibrium
constant is given by:
K =
[P
1
]
b
1
[P
2
]
b
1

[R
1
]
a
1
[R
2
]
a
1

33
4. Industrial Chemistry
Use Comments
In manufacture
Fertiliser Used to break down some compounds to form superphosphate
Ethene Used as a catalyst to dehydrate ethanol
Synthetic bres Used to neutralise the NaOH used in the manufacturing process (and some other
things as well)
Direct uses
Car batteries Used as the electrolyte in lead acid batteries
Metal cleaning Used to pickle steel before applying a surface coating
Metal extraction Used to dissolve metals out of their ores
Table 4.1: Some uses for sulfuric acid
Factors aecting equilibrium reactions
Pressure, volume and concentration Changing the pressure or volume of an equilibrium reac-
tion will cause the reaction to move to counteract this change, by absorbing moles, for example. This
change does not aect the nal ratios of products to reactants, i.e K remains constant, as the whole
system moves equally. Similarly, changing the concentration of a single reactant or product will cause
the system to move to either provide more of this compound (if it was removed) or to convert it into
other things (if more was added), but K will still be the same at equilibrium, because the concentration
of every participant in the reaction will change.
Temperature Changing the temperature of an equilibrium reaction can move the equivalence
point, by Le Chateliers principle, the reaction will move to absorb added heat, or release removed heat
to try to minimise the disturbance to the system.
4.3 Sulfuric acid is one of the most important industrial chemicals
Extraction of sulfuric acid
The Frasch process is the predominant method of extracting sulfur from deposits of pure sulfur. When
a deposit is located underground, three pipes are connected to it (see Figure 4.1), the external pipe
pushes superheated water (160

C) down to the deposit to melt the sulfur. Compressed air is forced


down the centre pipe, so that the combination of the water pressure and the air pressure pushes the
molten sulfur (along with the air and the water) up the third pipe. This method works with sulfur
because the melting point of sulfur is only 113

C, and it easily forms an emulsion (when molten) with


Sulfur deposit
Superheated water
Compressed air
Molten sulfur/water emulsion
Figure 4.1: A simplied diagram of the Frasch process
34
4.3. Sulfuric acid
Oxygen
Combustion
Sulfur
SO
2
Catalytic
conversion
SO
3
Passed through
sulfuric acid
Oleum
(H
2
S
2
O
7
)
Reacted
with water
H
2
SO
4
Figure 4.2: A similied ow chart of the contact process
water. However, it is insoluble so, when it cools, it solidies out of the emulsion leaving behind very
pure (>99%) sulfur. Sulfur is also low density so the the compressed air is an eective way of bring it
to the surface. The fact that the only materials used to extract the sulfur are water and air means that
the whole process is fairly cheap.
However, the Frasch process has a variety of environmental issues. The water used cannot be
discharged into the environment without being processed because it will dissolve impurities (such as
metal ions) in the sulfur and so becomes contaminated. Also, sulfur forms dangerous oxides, so oxidation
of the sulfur must be kept to an absolute minimum. Signicantly, the sulfur deposit occurs as a large
block, so it leaves behind a large hole in the ground which can cause ground subsidence and thus possible
damage the environment above.
Production of sulfuric acid
Sulfur by itself is not particularly useful, so once it is extract it undergoes further processing to obtain
more useful compounds. One such compound is sulfuric acid, which is produced by the contact process.
The contact process has three basic steps: oxidation of sulfur to sulfur dioxide; oxidation of sulfur
dioxide to sulfur trioxide; and, the conversion of sulfur trioxide and water to sulfuric acid. The basic
steps of the contact process are outlined in Figure 4.2.
Production of SO
2
Sulfur dioxide is produced by spraying molten sulfur into dry air so that it
combusts. Since it is combustion, the reaction is exothermic and it can heat the air up to more than 2
times the desired temperature for the next stage, so it has to be cooled. The reaction for this stage is:
S
(s)
+ O
2(g)
SO
2(g)
Sulfur dioxide can also be produced by roasting metal sulfates, which is commonly done to
extract metals such as zinc and copper from their ores.
35
4. Industrial Chemistry
Production of SO
3
The mixture of air and sulfur dioxide is cooled to 400

C and pushed into a


catalytic converter. The reaction is:
2 SO
2(g)
+ O
2(g)
2 SO
3(g)
It is an exothermic equilibrium reaction, so to obtain a commercially viable yield many factors need to
be considered and optimised. Since it is exothermic, lowering the temperature will increase the yield
of SO
3
, but this slows the reaction down, so a compromise between yield and rate is required. For this
reaction, the optimal temperature is about 400

C. A catalyst (V
2
O
5
) is also used to increase the rate
of reaction. This catalyst is a surface layer on a highly porous material, to increase its surface area.
The mixture of air and SO
2
is passed over a bed of this catalyst at a high temperature (550

C) which
converts the majority of the dioxide into trioxide, after this it is run over the another bed of catalyst
at 400

C to try to maximise the yield. The mixture is then redirected into an absorber tower (where
H
2
SO
4
is produced) to remove the SO
3
, and the remaining SO
2
is run over another catalyst bed, which
converts the almost all the remaining gas into SO
3
. This is then run through another absorber tower
to extract the most sulfuric acid possible.
Production of H
2
SO
4
The last stage of the process is to convert the SO
3
into sulfuric acid.
Sulfur trioxide reacts directly with water to form sulfuric acid, but this reaction is very exothermic, so
it can not be done in a safe and economic way. However, SO
3
reacts with sulfuric acid to form oleum
(H
2
S
2
O
7
), which reacts with water to form 2 H
2
SO
4
. This second reaction can easily be controlled, since
water is the limiting reagent, and so this method is both safe and economic, since the sulfur trioxide is
dissolved into the sulfuric acid as it bubbles through, and the rate of heat release is controllable.
Reactions of sulfuric acid
Oxidation Sulfuric acid can oxidise other substances, since it contains a hydrogen atom. The
reaction when sulfuric acid acts as a oxidant is:
H
2
SO
4
+ 2 H
+
+ 2 e

SO
2
+ 2 H
2
O
Or, when the sulfuric acid is concentrated:
2 H
2
SO
4
+ 2 e

SO
2
+ SO
2
4
+ 2 H
2
O
Dehydration Sulfuric acid is hygroscopic when it is concentrated, so it readily absorbs water from
its environment and other substances. Sulfuric acid even pulls H
2
O molecules out of other molecules
(such as alcohols), and so is used as a catalyst for the production of ethene from ethanol, for example.
Sulfuric acid dehydrates hydrated molecules, and can dry gases.
C
2
H
5
OH
H
2
SO
4
C
2
H
4
+ H
2
O
Sulfuric acid ionisation
Concentrated sulfuric acid is almost completely molecular, since it contains very little water (which is
what ionises the molecules), and much of what water there is not in a state to ionise the acid (since it
is in hydrate form, like H
2
SO
4
H
2
O). Thus, when sulfuric acid is diluted it will be completely ionised,
from H
2
SO
4
to H
2
SO

4
and SO
2
4
. This ionisation reaction is very exothermic, which accounts for the
huge amounts of energy released (H = 90 kJ/mol). The reason the dilution of sulfuric acid is much
more exothermic than the dilution of other acids is the fact that concentrated sulfuric acid is molecular,
while other acids are at least partially ionised, even in concentrated form.
36
4.4. Sodium hydroxide and electrolysis
Safety considerations with sulfuric acid
Sulfuric acid is a strong acid, so the normal safety precautions apply to it, such as appropriate pro-
tection etc. However, sulfuric acid is a dehydrating agent, so especial care needs to be taken to avoid
contact with skin and eyes as it can cause serious damage to living tissues. Also, the dilution of
concentrated sulfuric acid (from almost 100% molecular to almost 100% ionic) is highly exothermic
(H
+
+ H
2
O H
3
O
+
+ energy), so dilution should be done by adding the acid to the water, so that
there is more thermal mass of water to absorb any heat, and so that the reaction cannot get out of
control, since it is regulated by the amount of acid added, which can be easily stopped. The storage
vessel of the sulfuric acid is also important, the vessel must be contained in a second vessel, or on a
tray, which can hold the whole volume of sulfuric acid in the vessel. Also, dilute sulfuric acid must be
kept in a glass container (since glass is very resistant to acids), but concentrated sulfuric acid can be
kept in a metal container (since the acid is mostly molecular when concentrated).
4.4 The industrial production of sodium hydroxide requires the use of
electrolysis
Dierence between electrolytic and galvanic cells
An electrolytic cell is basically a galvanic cell in reverse, by providing a negative voltage gradient (i.e.
opposite to the direction of the voltage which the galvanic cell produces) the reactions at each electrode
can be reversed. Obviously, an external voltage source is required to overcome this natural voltage
gradient and provide the energy to make the reactions happen in their unnatural directions. As such,
the signs of electrodes change (since reduction always happens at the cathode, and oxidation at the
anode) so the anode is positive and the cathode is negative in an electrolytic cell. It is as if the
cathode is full of electrons (giving it a negative charge) which it pushes out into the electrolyte to reduce
the ions in solution, while the anode is sucking electrons (since it has a positive charge, provided by the
external voltage source) from the particles in the electrolyte, oxidising them.
Production of sodium hydroxide through electrolytic methods
Sodium hydroxide is an important industrial chemical: being a strong base it in (or to make) soaps,
detergents, and other heavy-duty cleaners. Also it is important in the production of some materials
such as paper, plastics and other synthetic bres (rayon etc.). It is produced by the overall equation:
2 NaCl
(aq)
+ 2 H
2
O
(l)
2 NaOH
(aq)
+ Cl
2(g)
+ H
2(g)
Thus, any process producing NaOH also produces chlorine and hydrogen, which can be (and are) used
for other industrial processes. However, these gases also present a safety issue as they react violently
(and form HCl).
Mercury process The mercury process uses liquid mercury as an electrode and as a catalyst. The
process consists of two chambers, each with a ow of mercury along the bottom. Highly concentrated
salt water (almost saturated) is fed into the rst chamber, where plates of metal (such as titanium)
act as the anode and remove the chlorine from solution. The cathode is the mercury, which creates
a solution of sodium in mercury. This mixture is pushed into the second chamber where the sodium
naturally reacts with the pure water in the chamber to form sodium hydroxide and hydrogen gas. The
mercury can theoretically be reused indenitely, but some mercury is lost into the water, so it needs to
be replaced.
Industrially, plants can use one mercury cell, which is very large, as the plates and the mercury
can be close together, and have a large surface area, so the current (i.e. the creation and movement of
ions) can be very high (many thousands of amps). The sodium hydroxide produced by the mercury
process is very pure since the chlorine is completely separate from the sodium hydroxide (no chlorine
is transported by the mercury). However, safety and environmental concerns surrounding the use of
37
4. Industrial Chemistry
mercury (which is released into the environment at a few hundred grams per tonne of NaOH) have
prompted legislation placing very very low limits on the release of mercury into the environment so that
mercury cells are becoming less and less common.
Diaphragm process The diaphragm process was the rst industrial method of extracting sodium
hydroxide. A diaphragm cell consists of two chambers separated by a thin sheet of a porous material
(normally asbestos since it is immune to hydroxide). Highly concentrated sodium chloride is contin-
uously fed into one chamber, where there is a titanium electrode. This electrode acts as the anode
and so the NaCl is broken down, the sodium stays in solution, it migrates through the diaphragm into
the other chamber where hydroxide is produced by an iron mesh electrode. This solution of sodium
hydroxide is drawn out of the cell, where much of the water is evaporated o, leaving behind most of
the small portion of chlorine that crosses the diaphragm. Some hydroxide also migrates into the rst
chamber, but this is reduced by having a pressure gradient from the rst to the second chamber.
Industrially, each cell is small so that the current (i.e. the production of the ions) is maximised,
but a plant will have many individual cells, so that they can drawn thousands of amps of current.
The diaphragm process is relatively cheap, but the NaOH it produces is contaminated by very small
amounts of chlorine so it is not suitable for applications requiring very high purity.
Membrane process The membrane process is very similar to the diaphragm process except it
replaces the diaphragm with a much better membrane that only allows the passage of cations (like Na
+
)
and blocks anions (like Cl

or OH

). The membrane is normally made from PTFE (Teon) which


has been modied so that has the properties stated above. The Teon is very unreactive and so as
immune to the high pH of hydroxide solutions as asbestos. Other than the changing the diaphragm for
a membrane, a membrane cell is identical to a diaphragm cell.
The membrane process produces almost completely pure NaOH, and there is no risk of the waste
water developing a high pH as no OH

can leach through the membrane (as it can in a diaphragm cell).


A membrane cell is also much safer than either cell above, since there is neither mercury nor asbestos,
which means that almost all new cells built are of this type.
Electrolysis of sodium chloride
When sodium chloride undergoes electrolysis there are three possible reactions, depending on the state
of the sodium chloride.
Molten NaCl If the sodium chloride is molten then electrolysis forms Cl
2
gas at the anode (which
is oxidation) and pure Na (in liquid form since the temperature of NaCl
(l)
is above the melting point
of Na) at the cathode (it is reduction).
2 NaCl
(aq)
2 Na
(l)
+ Cl
2(g)
Concentrated NaCl
(aq)
If the sodium chloride is aqueous, but concentrated, then the reaction at
the anode still forms Cl
2(g)
but the cathode splits water into hydroxide and hydrogen gas, the compete
reaction is:
2 NaCl
(aq)
+ 2 H
2
O
(l)
Cl
2(g)
+ H
2(g)
+ 2 NaOH
(aq)
Dilute NaCl
(aq)
If the sodium chloride is aqueous and dilute, then the ions are in very concen-
trations, so they are replaced by water (at both electrodes), since water has comparable oxidability to
chlorine (so the one with the most is most oxidised, i.e. water), and water has much higher reducability
that sodium, so it replaces sodium even when the sodium has a high concentration (as above). The
38
4.5. Saponication
reactions are:
Cathode 2 H
2
O
(l)
+ 2 e

H
2(g)
+ 2 OH
(aq)
Anode 2 H
2
O
(l)
O
2(g)
+
4
H
+
(aq)
+ 4 e

Overall 2 H
2
O
(l)
2 H
2(g)
+ O
2(g)
4.5 Saponication is an important organic industrial process
Saponication
Saponication is the process of making soap from lipids. The process is the reaction of an ester with an
hydroxide ion (normally provided by sodium hydroxide, hence the need for it), which forms an alcohol
and a carboxylate ion i.e. saponication is just the process of breaking the alcohol o an ester, leaving
a carboxylic acid which is missing the hydrogen on the COO group. An example of saponication
with methyl propanoate:
CH
3
CH
2
COOCH
3
+ OH

CH
3
CH
2
COO

+ CH
3
OH
In the school laboratory Saponication can be conducted in a laboratory by boiling the ester
and sodium hydroxide solution together (since the ester is insoluble in water so another method of
combining the two is needed). This will produce the carboxylate anion and the alcohol, which (in most
instances in the laboratory) are soluble in water. The products can be separated by some form of
distillation, depending on the ester. If the alcohol has a boiling point distant from 100

C then normal
distillation suces, otherwise more complicated fractional distillation is necessary. Also, since solubility
of alcohols decreases with temperature, the alcohol may separate from the water just by cooling the
solution.
Industrially Industrial saponication rarely just makes a carboxylate anion, the process is carried
through until soap is made. The soap is made from fats and oils (triglycerides) rather than esters.
Tryglycerides consist of a backbone of 3 carbons, with carboxyclic acid side chain attached to each one.
The reaction with hydroxide is almost identical for triglycerides and esters, except a single triglyceride
forms one glycerol molecule (which is 1,2,3-trihydroxyl-propane) and three carboxylate anions. The
resulting solution of glycerol and carboxylate anions can be separated by cooling it and mixing in
saturated salt water which separates sodium carboxylate into a solid layer on top of a glycerol solution
(which itself is further puried by multiple distillations). In an industrial context the fats and oils used
are highly contaminated with things such as blood, muscle tissue etc. since many of the fats and soaps
used are animal fats, which is very dierent to the pure reactants used in a laboratory.
Common oils and fats used in an industrial context for saponcation include: olive oil, which is
cheap and produces a hard, durable soap; beef fat, from butchers and abbotoirs, although it is normally
contaminated, so care needs to be taken to remove the unwanted things; coconut and palm oil, which
are very cheap, but often cause environmental damage.
Explanation for the cleaning action of soap
Soap cleans things by allowing things that would otherwise be insoluble to be soluble in water, so that
they can be washed away. Soap consists of a polar end (the end of the COO group) and a non-polar
end (the long carbon chain), which means that it is soluble in both types of substance. When soap
comes into contact with a non-polar substance (like dirt) the non-polar end will burrow into it, while
the polar end will remain outside dissolved in the water. When there are enough soap molecules, the
dirt will become soluble in water because it is surrounded by many polar charges. An substance which
does this, including soap, is called a surfactant.
39
4. Industrial Chemistry
N
+
(a) Cationic detergent

(b) Soap, or anionic detergent

O C C

n
OH
(c) Non-ionic detergent
Figure 4.3: Schematics of the molecular structures of dierent types of surfactants (Note: almost all
hydrogens have been omitted, and a wavy line represents a hydrocarbon chain of arbitrary length)
Soap, water and oil is an emulsion
An emulsion is a mixture of two liquids where one liquid is suspended in the other in lots of little drops.
Water and oil are insoluble normally and so dont form an emulsion without an emulsier. Soap acts
as an emulsier in a mixture of water and oil (by a process explained above).
Comparison between soaps and some types of detergents
Synthetic detergents can have very dierent properties to soap, which normally derives from the dierent
structures of their molecules (visual representations of the structures can be seen in Figure 4.3). Each
type of detergent has dierent properties, and so commercial products will contain multiple types of
detergents.
Soap Soap is shaped like a tadpole, with a non-polar tail, and a negatively charged head. The
tail is a normal hydrocarbon chain, and the head is COO

. In hard water (water with high


concentrations of Ca
2+
and Mg
2+
ions), soaps eectiveness is reduced because it precipitates out,
removing soap molecules. Soap is normally used for personal hygiene.
Anionic detergents Anionic detergents are very similar to soaps, since they have a polar and a
non-polar end. However, the polar end is caused by a sulfonate chain (OSO
2
O

). This means that


anionic detergents are much better at cleaning than soaps. They are used in most cleaning instances.
However, the negative end means that anionic detergents are aected by hard water, although less than
soap.
Cationic detergents Cationic detergents are built around an ammonium ion, with hydrocarbon
chains instead of just hydrogen atoms. Thus they can end up being a X (although the branches can
have dierent lengths). Just like in the other detergents, the carbons chains are the bits that dissolve
in non-polar substances, but the charged section is the N atom, which doesnt have to be at the end
of the molecule. Cationic detergents act as antiseptics, and also have good properties for use as hair
conditioner or fabric softener. Cationic detergents cannot precipitate in hard water, as they are a
positively charged ion, so they retain complete eciacy in hard water.
Non-ionic detergents A non-ionic detergent is not an ion, but the molecule is still polar because
of the large number of oxygen atoms towards one end and the hydroxide group at the same end. Since
40
4.6. The Solvay process
non-ionic detergents do not have as high a concentration of charge as the other types of detergents,
they do not form stables bubbles, and hence foam, so easily. This tendency to not foam means that
non-ionic detergents are useful for application which try to avoid foam, such as dishwashing. Also,
non-ionic detergents are used in pesticides, glues, and paints. Since non-ionic detergents are not ions
they cannot precipitate in hard water and so are still 100% eective in hard water.
Examples of emulsiosn
There are many common emulsions. Things like milk, and mayonnaise are emulsions of oil and water
(and other dissolved things). More solid things (like butter and margarine) are the reverse, i.e. little
drops of water dispersed through an oil. All water-oil emulsions need a emulsier to mean that they
are stable, such as casein or lecithin in milk and mayonnaise respectively.
Environmental impact of surfactants
Soap is fair environmentally benign as it is readily broken down by bacteria. However, synthetic
detergents can cause much greater problems. Non-biodegradable detergents have caused a build up
of foam in some water systems since they formed stable bubbles and were not quickly broken down
by natural processes, however, the replacement of these by truly biodegradable detergents mitigated
this problem. Phosphorus can also occur in detergents, not as a surfactant though, but as a builder.
Builders are molecules which remove Ca
2+
and Mg
2+
from the water, allowing anionic detergents
to work properly. The most common builder is sodium tripolyphosphate, which, when released into
the environment, can cause eutriphication of water ways. This problem is serious enough to have laws
controlling the phosphorus content of detergents in many countries. Another, although smaller, problem
is the aect that the antibacterial nature of cationic detergents can have on the good bacteria in sewage
plants, although it only has a big impact at high concentrations.
4.6 The Solvay process has been in use since the 1860s
The Solvay process
The Solvay process is a industrial method of producing sodium carbonate. It takes limestone (8090%
CaCO
3
) and brine (30% NaCl
(aq)
), and produces sodium carbonate and wasted calcium chloride (using
ammonia as a catalyst). The whole process is outlined in Figure 4.4. The overall reaction for the whole
process is (note the relative quantities of each reagent):
CaCO
3(s)
+ 2 NaCl
(aq)
Na
2
CO
3(s)
+ CaCl
2(aq)
Brine purication The rst stage of the process is to obtain brine that is pure and concentrated,
i.e. 30% NaCl and the rest water. Any impurities could precipitate with the sodium hydrogen carbonate,
which will result in the end produce being contaminated. Metal ion impurities such as calcium and
magnesium (which are common in brine obtained from underground reservoirs) can be precipitated out
(with carbonate and hydroxide, respectively), occulated, and removed before the brine is used Solvay
process (the occulation step will also remove other suspended solids, such as dirt).
Sodium hydrogen carbonate precipitation The process decomposes the limestone to get CO
2
and CaO, the carbon dioxide is then used directly to produce Na
2
CO
3
as it is bubbled through a the
brine saturated with ammonia, which causes carbonic acid (H
2
CO
3
) to form, which reacts with the
ammonia to produce hydrogen carbonate ions (HCO
3
) and ammonium. Sodium hydrogen carbonate is
in soluble so it precipitates from solution. The net equation for this stage is:
NaCl
(aq)
+ NH
3(aq)
+ CO
2(g)
+ H
2
O
(l)
NaHCO
3(s)
+ NH
4
Cl
(aq)
41
4. Industrial Chemistry
Limestone
(CaCO
3
)
Limestone
decomposed
in a kiln
CaO
CO
2
Reacted with
water in a
lime slaker
Ca(OH)
2
Heated to
recover NH
3
(CaCl
2
waste)
Carbon dioxide
bubbled
through liquid
Saturated
with NH
3
Puried
brine
NaHCO
3(s)
&
NH
4
Cl
(aq)
Separated
by ltration
NaHCO
3
NH
4
Cl
Decomposed
by heating
CO
2
Na
2
CO
3
Figure 4.4: A ow chart outlining the key steps of the Solvay process
Sodium carbonate production This mixture of NaHCO
3
and NH
4
Cl is ltered to separate the
solid sodium hydrogen carbonate from the rest. This then undergoes heating so that it decomposes
into sodium carbonate, carbon dioxide and water. The carbon dioxide produced at this step can be fed
back into the carbonation step to reduce the materials cost. The net equation for this stage is:
2 NaHCO
3(s)
Na
2
CO
3(s)
+ CO
2(g)
+ H
2
O
(g)
Ammonia recovery The ammonia used to precipitate the sodium hydrogen carbonate can be
recovered and reused, to further reduce the cost of the method. The other product from the decompo-
sition of limestone calcium oxide, is slaked, (reacted with water) to produce Ca(OH)
2
. This is mixed
with the NH
4
Cl solution from the previous step, and heated, which creates calcium chloride (the waste
product of the Solvay process), water and ammonia. The equation for this reaction is:
NH
4
Cl
(aq)
+ Ca(OH)
2(s)
NH
3(g)
+ CaCl
2(aq)
+ 2 H
2
O
(l)
Environmental issues The Solvay process produces two products, but only one is useful, the
majority of the calcium chloride solution is discarded and disposed of. Normally, this disposal occurs into
the sea where the calcium/calcium carbonate equilibrium resists a signicant change in the concentration
of Ca
2+
, so this disposal is fairly harmless in these terms. However, the solution can not be discharged
into a river, since the volume of water is not large enough to be able to dilute the increased concentration
42
4.6. The Solvay process
Use Comments
Glass-making Major use of Na
2
CO
3
, used to make normal glass
Saponication Used as an alternative to NaOH since it is cheaper
Water treatment Used to precipitate metal ions to soften water (including as an alternative
to phosphorus in washing powders)
Paper making Used to make NaHSO
3
Sulfur dioxide capture From power station waste gases, to comply with environmental regulations
As a base It is cheap, and it is basic so it is often used as an industrial base
To make NaHCO
3
By bubbling CO
2
through a solution of it, pure NaHCO
3
can be obtained
(not contaminated by ammonia)
Table 4.2: Uses of sodium carbonate
of calcium and chlorine quickly enough (although the chlorine is the most damaging in fresh water
rivers), even if the output is diluted before disposal.
Another problem is the temperature of the waste liquids. The CaCl
2
solution can have a high
temperature, and so it needs to be cooled or diluted to a point where it wont cause thermal pollution
of the discharge point (even when discharged into the sea). This is another reason why plants distant
to the ocean cannot discharge into rivers or lakes, and forces them to adopt other measures, such as
articial ponds.
Smaller, although not insignicant, problems include the damage that leaked ammonia can cause
as air pollution, and the indirect impacts of the mining, transport, and storage of all the materials
required.
Location of a Solvay process plant
The location of a plant in relation to the reagents, as well as in relation to areas for disposal of the waste
products is an important part of minimising the cost and the environmental impact. For the Solvay
process specically, the cost of transport of the two reagents need to be weighed to decide whether, for
example, the plant should be situated nearer a source of brine, or nearer a limestone mine. Since the
brine is much more dilute (only 30% of its weight is important for the process versus above 80% or even
90% for typical limestone), the amount need to be transported will be higher so its cost of transport is
likely to be much greater which would make positioning the plant near the coast more favourable.
The environmental impacts of the position of the plant also must be considered. For example, the
disposal of the CaCO
3
solution is a signicant problem inland, so a plant would be both economically
and environmentally better near the sea. Also, proximity to built up environments, where ammonia
pollution is particularly bad should be considered, although, the availability of a work force is another
factor which should come into the decision of position.
Other factors could include: the cost and availability of energy (the Solvay process uses fairly
large amounts of energy), the distance, cost and environmental impact of the transport of the products
to their markets (for example, a sodium carbonate plant could be situated next to a glass maker, to
reduce costs).
43
Index
decay, 11
Acid rain, 15
Acidity, 13
Acids, 15
Conjugate, 17
Denitions, 16
Examples, 16
Food additives, 16
Salts, 17
Strong & weak, 15
Table of salts, 17
Addition polymers
List of, 7
Poly(vinyl acetate), 7
Poly(vinyl chloride), 6
Polyacrylonitrile, 7
Polyethene, 6
Polypropylene, 7
Polystyrene, 7
Teon, 7
Alcaligenes eutrophus, 8
Alkalinity, 13
Alkanes, 5
Alkanoic acids, 19
Alkenes, 5
Ammonia
Synthesis, 22
Amphiprotic substances, 17
Anode, 9
Arrhenius, Svante, 17
Atmosphere
Pollutants, 26
Structure, 26
Atomic Absorption Spectroscopy, 24
decay, 11
Bacillus megaterium, 8
Bases
Conjugate, 17
Examples, 16
Salts, 17
Table of salts, 17
Biological oxygen demand, 29
Biopolymers, 8
Polyhydroxybutyrate, 8
Bosch, Carl, 23
Bronsted-Lowry theory, 17
Branches of Chemistry (largest branches are cir-
cled), 21
Buers, 18
Real-world example, 18
Carbon dioxide
Solubility, 14
Cathode, 9
Chlorouorocarbons, 27
Alternatives, 28
Problems, 28
Co-ordinate covalent bonds, 27
Coagulation, 29
Collaboration, 21
Condensation polymers, 8
Cellulose, 8
Nylon, 8
Polyester, 8
Conjugate pairs, 17
Cracking, 5
Catalytic, 6
Steam, 6
Davy, Humphry, 17
Detection of Radiation, 11
Cloud chamber, 11
Geiger-M uller counter, 11
Photographic lm, 11
Scintillation counter, 11
Detergent
Comparison to soap, 40
Environmental impact, 41
Types, 40
Diaphragm process, 38
Displacement, 9
Dissolved oxygen, 29
Dry cell, 10
45
Index
Electrodes, 9
Electrolytic cell
Comparison to galvanic cell, 37
Emulsion
Examples, 41
Emulsions, 40
Equilibrium constant, 33
Equilibrium reactions, 14, 33
Equivalence point, 18
Esters, 19
Esterication, 19
Reuxing, 19
Uses, 19
Ethanol, 8
Ethene, 6
Ethylene glycol, 5
Eutrophication, 30
Flocculation, 29
Galvanic cell, 9
Comparison to electrolytic cell, 37
Gas phase process, 6
Glucose, 8
Gratzel cell, 10
Haber process, 22
History, 23
Monitoring, 22
Haber, Fritz, 23
Halons, 27
Hardness, 29
HDPE, 6
Hydrochlorouorocarbons, 28
Hydrourocarbons, 28
i, 33
Indicators, 13
Ion tests, 23
Anions, 23
Cations, 23
Lavoisier, Antoine, 16
LDPE, 6
Le Chateliers principle, 14
Leclanche cell, 10
Liquid junction photovoltaic device, 10
Membrane lters, 30
Membrane process, 38
Mercury process, 37
Mesosphere, 26
Monitoring, 22
Need to monitor ions, 25
Neutralisation, 18
Nitrogen
Oxides, 14
Di-, 14
Nitric, 14
Nitrous, 14
Nuclear
Instability, 10
Oxidation, 9
Oxides, 13
Oxygen free radical, 27
Ozone, 27
Comparison to oxygen, 27
Destruction, 28
Measurement, 28
pH, 15
Photochemical smog, 14
Primary standard, 18
Properties of addition polymers
Chain branching, 7
Chain stiening, 7
Cross linking, 7
Molecular weights, 7
Radioisotopes
Cobalt-60, 11
Production, 11
Sodium-24, 11
Uses, 11
Reduction, 9
Salt bridge, 9
Saponication, 39
Industrial, 39
Secchi disk, 29
Soap
Cleaning action, 39
Comparison to detergent, 40
Environmental impact, 41
Sodium carbonate
Uses, 43
Sodium hydroxide
Electrolytic extraction, 37
Production, 37
Solvay process, 41
Environmental issues, 42
Stratosphere, 26
Styrene, 7
Sulfate, 25
Sulfuirc acid
46
Index
As a dehydrating agent, 36
Sulfur dioxide, 14
Sulfuric acid, 34
As an oxidising agent, 36
Extraction, 34
Ionisation, 36
Production, 35
Safety, 37
Uses, 34
Surfactant, 39
Titration, 18
Total dissolved solids, 29
Transuranic elements, 11
Troposphere, 26
Tryglycerides, 39
Turbidity, 29
Vinyl chloride, 6
Volumetric analysis, 18
Water quality, 28
Acidity, 29
Biological oxygen demand, 29
Coagulation, 29
Concentration of ions, 29
Dissolved oxygen, 29
Eutrophication, 30
Factors aecting ion concentrations, 29
Flocculation, 29
Hardness, 29
Heavy metals, 30
Total dissolved solids, 29
Treatment, 29
Turbidity, 29
Zeolites, 6
Ziegler-Natta process, 6
47