Professional Documents
Culture Documents
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
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
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
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
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 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
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
Pb
2+
Yellow precipitate with I
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
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
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