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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 syllabus1 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 they’ve 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 first chapter’s formatting is still completely different to the rest) and decided to share them2 , 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 don’t throw your computer around, or eat the piece of paper in a fit of rage. If there is a particularly bad mistake in the content, or an unclear section of writing, you could email me3 , 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 you’ve 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 didn’t 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 2 If

at: boardofstudies.nsw.edu.au/syllabus_hsc/chemistry.html A anyone wants the L TEX source, and it isn’t on the website, just email me3 and I will probably send it to you 3 At i.have.a.query.or.complaint@gmail.com (No, seriously, I have that email)

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Contents
Contents 1 Production of Materials 1.1 Addition polymers . . . 1.2 Condensation Polymers 1.3 Renewable sources . . . 1.4 Redox reactions . . . . . 1.5 Nuclear chemistry . . . 2 The 2.1 2.2 2.3 2.4 2.5 Acidic Environment Indicators . . . . . . . Le Chatelier & Oxides Acids . . . . . . . . . Acids: take two . . . . Esterification . . . . . 4 5 5 7 8 9 10 13 13 13 15 16 19 21 21 22 23 26 28 33 33 33 34 37 39 41 45

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3 Chemical Monitoring 3.1 Chemists . . . . . 3.2 Haber process . . . 3.3 Manufactured stuff 3.4 The atmosphere . . 3.5 Waterways . . . .

and Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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4 Industrial Chemistry 4.1 Synthetic replacements . . . . . . . 4.2 Equilibrium reactions . . . . . . . 4.3 Sulfuric acid . . . . . . . . . . . . . 4.4 Sodium hydroxide and electrolysis 4.5 Saponification . . . . . . . . . . . . 4.6 The Solvay process . . . . . . . . . Index

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1

Production of Materials
1.1 Fossil fuels provide both energy and raw materials such as ethylene for the production of other substances

• Alkanes (Cn H2n+2 ) alkane + alkene – Catalytic cracking: Large alkane (15 – 25 carbons) C15 H32 C10 H22 + C5 H10 collection of small alkanes + H2 – Steam cracking: Alkane C11 H24 4 C2 H4 + C3 H6 + H2 – Combustion: Alkane + O2 CO2 + H2 O e.g. C3 H8 + 5 O2 3 CO2 + 4 H2 O – With Cl and Br in UV: Alkane + Cl2 or Br2 chloro/bromo-alkane + hydro-bromic/chloric acid C3 H8 + Cl2 C3 H7 Cl + HCl C4 H10 + Br2 C4 H9 Br + HBr • Alkenes (Cn H2n ) – Combustion as per alkanes – Substitution reactions (always around double bond) C3 H 6 ∗ C 2 H4 + H 2 ∗ C2 H4 + HCl C2 H5 Cl ∗ C2 H4 +Br2 CH2 Br−CH2 Br (note: can be used as a test for alkene vs. alkane, alkene decolours bromine solution) CH2 Br−CH2 −CH2 OH ∗ C2 H4 + HOBr ∗ C2 H4 + H2 O 2 4 CH3 −CH2 OH (alkene to alkanol) – Industrial conversion ethene to ethanol: H PO @ 300◦ C C 4 H2 + H 2 O 3 4 C2 H5 OH – Forming Ethylene glycol (1,2-ethanediol, however note its structure: C2 H 4 +
Ag @ 250◦ C 1 2 O2
CH2 O CH2

Ni

H SO

):

CH2 CH2 O 2 CH2 CHCl + H2 O

– Forming vinyl chloride (chloroethane): 2 C2 H4 + Cl2 + 1 O2 2 Cracking Most polymers start with ethene, thus it is needed. A large proportion of a refinery’s 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
CuCl2 @ 150◦ C

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 different 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 different small alkenes (1–4 carbons), and hydrogen. Uses very hot pipes (700 – 1000 ◦ C) and pressures just >1 atm. The steam is a diluent that doesn’t 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 different polymers with vastly different properties (e.g. all chlorine gives Teflon, 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 O2 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 final polymer). The ZieglerNatta process uses lower pressure (a few atm) and temperature (60 ◦ C), and a catalyst (mixture of TiCl3 and a trialkylaluminium like (CH3 CH2 )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 CH2 −CH−Cl (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 CH2 −CH−C6 H5 , 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); CH2 −CH−CH3 ; car bumpers, ropes, household goods (inc. chairs, carpets) • Polyacrylonitrile (acrylics); CH2 −CH−C−N; wool substitute (clothing, carpets, blankets etc.) − • Poly(vinyl acetate) (PVA); CH2 −CH−O−CO−CH3 ; vinyl coatings, paint, adhesives • polytetrafluroethylene PTFE (Teflon); CF2 −CF2 ; electrical insulation, non-stick surfaces in cookware, 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 stiffening. Large side groups on the ethene molecules reduce the flexibility of the polymer by restricting the movement of the chains. Small side chains like the CH3 of polypropylene have a small effect 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
yeast

• Fermentation of glucose to ethanol: C6 H12 O6 Need

2 C2 H5 OH + 2 CO2

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 H2 O) in their formations. For example Glucose (C6 H12 O6 ) forms Cellulose (X−O−C6 H10 O4 −O−C6 H10 O4 −O−X) 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 (Y−NH2 ) and a carboxylic acid ground (X−COOH), when the OH of the acid and one H from the amine are eliminated, making a molecule of the form X−CO−NH−Y. 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 fibre, as packaging. Polyesters Polyesters are also synthetic condensation polymers. Formed when a carboxylic acid (X−COOH) and an alcohol (Y−OH) react, eliminating H2 O, forming X−CO−O−Y. Used in clothing as a fibre, 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 modified 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 applications 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
CH3 CH2 OH − − − 2− − − − −4 C2 H4 + H2 O − − − −4 − −3 − →
conc. H SO or H PO

• Dehydration of ethanol (with heating):

• Hydration of ethene (with heating): C2 H 4 + H 2 O
dilute H2 SO4

CH3 CH2 OH (note: these apply to any alkene ↔ alkanol reaction)

• Combustion of ethanol: C2 H5 OH + 3 O2 2 CO2 + 3 H2 O ∆H = −1360 kJ/mol Ethanol 8

1.4. Redox reactions

# Carbons 1 2 3 4 5 6 7 8

Prefix methethpropbutpenthexheptoct-

Table 1.1: IUPAC carbon count prefixes

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 CH3 CH2 region, which can use dispersion forces to dissolve non-polar substances. Ethanol is used as a solvent in cosmetics, food colourings/flavourings, 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 modifications, 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 CO2 emmissions. Disadvantages Large agricultural areas taken over for fuel production, disposal of fermentation by-products. It was used in the 1970’s and 80’s in Brazil, but the program petered out after a few decades; modern petrol often contains upto 10% ethanol.

Figure 1.1: Zn Zn 2+ Cu 2+ Cu
Source: en.wikipedia.org/wiki/File: Galvanic_Cell.svg

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) + 2+ Cu (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 flow (the electrolyte in the salt bridge should not form precipitates with other substances, like KNO3 or NaCl if there is no Ag). Dry cell (Leclanch´ cell) e 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+ (aq) +MnO2 (s) + 4 Mn(OH)3 (s) + NH3 . That is, zinc goes into H2 O + e – solution, and thus the cell is slightly acidic because of NH4 Cl. The cell’s 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, robust, has a long shelf life, and is not particularly environmenFigure 1.2: Lechlanch´ cell e tally damaging. The dry cell was the first cell which could be used as a portable source of power and has thus changed the Source: diracdelta.co.uk/science/source/l/e/ way humans interact with their environment, for example, leclanchecell/source.html allowing communication breakthroughs like small transistor radios. Gr¨tzel cell a The Gr¨tzel cell (See Figure 1.3) is a solar cell, also known as a a Liquid junction photovoltaic device, or a dye-sensitized solar cell. The cell consists of a transparent electrode through which light comes and hits the thin layer of TiO2 doped with a photosensitive dye which increases the spectrum absorbed by the TiO2 . The light releases a photoelectron from the dye which is conducted through the front electrode 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. – TiO2 + hf TiO+ + e – and 3 TiO+ + 3 I – 3 TiO2 + I3 . 2 2 The Gr¨tzel cell is a robust device, which can be made very a 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 Gr¨tzel cell a along with other forms of renewable energy will revolutionise society by freeing it from dependence on fossil fuels, and reducing the environmental impact of energy generation.

1.5 Nuclear chemistry provides a range of materials
Figure 1.3: Gr¨tzel cell a
Source: energyer.com/Know_How/ dye-sensitized-solar-cell.html

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-

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1.5. Nuclear chemistry

ton/neutron ratio goes from 1 at helium to 1.5 at uranium. Too many neutrons = β decay, Too few neutrons = α decay. Transuranic elements Transuranic elements are produced by bombarding large nuclei with neutrons so that they undergo β 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 film. The film 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¨ller counter. Normally measures β particles but can do the others. It works by a gas u molecule being ionised by radiation and the electron flying off 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 specific type of radiation they emit light, which can be collected, amplified 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 fluorine-18), by bombardment with helium nuclei. Benefits 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 effective treatments). Disadvantages: tissue damage, genetic mutation (including cancers). Industry Sodium-24. Made by neutron bombardment of sodium-23, decays by β Made by neutron bombardment of sodium-23, decays by β 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 fluid the sodium-24 is placed in quickly ceases to be radioactive. Medicine Cobalt-60. Made by netron bombardment of cobalt-59. Decays by β emission into nickel-60, releasing γ rays in the process, which can penetrate deep enough to kill cancer by destroying some specific 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.

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2

The Acidic Environment
2.1 Indicators were identified with the observation that the colour of some flowers 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 Low High red yellow yellow blue yellow blue pink yellow red blue yellow blue yellow red yellow blue clear red pH range Low High 3.1 4.4 3.0 4.6 3.8 5.4 4.4 6.0 5.0 8.0 6.2 7.6 6.8 8.4 8.0 9.6 8.3 10.0

Indicator methyl orange bromophenol blue bromocresol green methyl red litmus bromothymol blue phenol red thymol blue phenolphthalein

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 CO2 , and P2 O5 . 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. CO2 , NO2 , P2 O3 , SO2 ,Cl2 O, normally non-metals). Basic oxides are those which react with acids to make salts and do not react with alkali solutions (e.g. Na2 O, K2 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, Al2 O3 , PbO, SnO). Neutral oxides react with neither acids nor bases (e.g. CO, NO, N2 O). Le Chatelier’s principle Le Chatelier’s 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. Y. The position of equilibrium can be anything, not just An equilibrium reaction is denoted X 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 CO2 (g) + H2 O(l) H2 CO3 (aq)

This reaction is exothermic, so increasing the temperature will drive it left to absorb heat, so CO2 has higher solubility at lower temperatures. Increased pressure of CO2 pushes the equilibrium right (forcing CO2 into solution). Adding OH – into the solution increases solubility of CO2 , since H2 CO3 + 2 2 OH – 2 H2 O + CO3 – , so dihydrogen carbonate is removed from solution, forcing the equilibrium to move to the right to counteract the changing conditions (by Le Chatelier’s 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 O2 2 ZnO + 2 SO2 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 N2 O (nitrous oxide), NO (nitric oxide) and NO2 (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, 2 NO. It is also formed along where the high temperatures allow this reaction to happen N2 + O2 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 NO2 is called NOx ). 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 CO2 ). It is formed when SO2 and NO2 dissolve in rain water, forming sulfuric and nitric acids. 2 NO2 + H2 O 2 HNO2 + O2 2 SO2 + O2 SO3 + H2 O HNO2 + HNO3 2 HNO3 2 SO3 H2 SO4

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 CaCO3 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 SO2 and NO2 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 effect on waterways can have far reaching consequences.

2.3
Acids

Acids occur in many foods, drinks and even within our stomachs

An acid is a proton donor, it will react with water to form a hydronium ion H3 O+ . e.g. HBr + H2 O pH pH is a measure of the concentration of hydronium ions, [H3 O+ ]. pH = − log10 [H3 O+ ] pH should have the same number of decimal places as the number of significant figures in the concentration 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 doesn’t 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 H3 O+ + Br−

2. The Acidic Environment

Acid Natural Hydrochloric Acetic Citric Ascorbic Synthetic Sulfuric Nitric

Formula HCl CH3 COOH C 6 H8 O 7 C 6 H8 O 6 H2 SO4 HNO3

Comments Aids efficient operation of enzymes, as industrial cleaner, base neutraliser Found in vinegar, used to synthesis organic compounds Found in citrus fruit, used as a food additive Vitamin C, good for health Most common acid, used in fertilisers, detergents, synthetic fibres Used in fertilisers and explosives Table 2.2: Examples of Acids

Base Natural Ammonia Amines Metallic oxides Carbonates Synthetic Sodium hydroxide Calcium oxide Calcium hydroxide

Formula NH3 CH3 NH2 Fe2 O3 NaCO3 NaOH CaO Ca(OH)2

Comments Formed in anaerobic decay, used in fertilisers, cleaning agents Smell like fish, occur in decomposition of organic matter Used to extract some metals Used to make glass, paper, as a neutralising acids Used to make soap, synthetic fibre, as a powerful cleaning agent Quick lime, made by heating limestone, used in cements 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 preservatives because they kill bacteria which can’t 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 definitions of acid and base have been refined

Definitions of acids The definition of an acid has changed over time, one of the first definitions 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

NaCl

KNO3 NaHSO4

KNO2

NaHCO3

Neutral Na2 SO4 CH3 COONH4 Acidic KHSO4 NH4 NO3 Basic CH3 COONa KCN

Na2 CO3

Table 2.4: Salts, by acidity and alkalinity

substances such as Na2 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 definition of a base was a substance that ionised to make hydroxide ions, although this misses some substances. Br¨nsted-Lowry theory o The Br¨nsted-Lowry theory of acid and bases says that acids are proton donors, and bases are proton o 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. HCO3 : HCO− + H2 O 3 HCO− + H2 O 3
2− H3 O+ + CO3

OH− + H2 CO3

2 Thus, CO3 – is the conjugate acid of HCO3 , and H2 CO3 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 H3 O+ + OH – 2 H2 O. Other reactions can occur, such as the neutralisation of ammonia H3 O+ + NH3 NH+ + H2 O. All 4 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 flask 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 NaCO3 and NaHCO3 , 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. Buffers A buffer 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 H3 O+ ions are added one of the equilbriums will move (by Le Chatelier’s principle) to absorb these ions. e.g. for a solution of H2 CO3 – and HCO3 : H2 CO3 + H2 O H3 O+ + HCO− 3

– So adding H3 O+ will move this equilibrium left, and if there is enough HCO3 in solution, all the H3 O+ – will be absorbed, so there will be no change in pH. Adding OH will neutralise H3 O+ , which will force the equilibrium to the right to replace the hydronium, and if there is enough H2 CO3 in solution, all the OH – will react before the H2 CO3 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 buffer against both increases and decreases in pH. The pH a buffer maintains depends on the position of the equilibrium.

Example of buffered systems Buffers occur in some rivers and lakes. Rainwater has a natural – – HCO3 , if there is another source of HCO3 such as that dissolved out of rocks, equilibrium with CO2 – then the equilibrium above will be pushed left. This creates an equilibrium of H2 CO3 and HCO3 , which acts as a buffer in the water system, so the pH is maintained constant (if lakes are not buffered, such as those in Scandinavia, then acid rain will change the system’s pH). The same buffer reaction is used in swimming pools to maintain a pH around 7. Blood is also buffered by this equilibrium, since 18

2.5. Esterification

Flavour apple banana grape orange pear raspberry rum jasmine

Ester methyl butanoate & isopentyl pentanoate isopentyl ethanoate ethyl methanoate & ethyl heptanoate octyl ethanoate pentyl ethanoate butyl ethanoate ethyl methanoate benzyl ethanoate Table 2.5: Esters as flavours

many biological processes require specific pH’s, although other buffers like hæmoglobin are also needed to buffer against pH changing due to CO2 .

2.5

Esterification 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: R−COOH 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 C−O and the O−H bond is polar, (and the O−H bond forms hydrogen bonding) which means the intermolecular forces are strong. Esters & esterification 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 H2 O, leaving an −O− between the original acid and alcohol. X−COOH + Y−CHOH X−CO−O−CH−Y + H2 O

Esters are named as “<alcohol > <acid >-oate” e.g. methanol and ethanoic acid forms methyl ethanoate. Esterification is the name given to the synthesis of an ester. The esterification reaction is an equilibrium which is slow, so H2 SO4 is used as a catalyst, and it absorbs the water produced, so moves the equilibrium to completion (if enough H2 SO4 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. Refluxing Refluxing is required to stop the loss of the reactants due to vaporisation. It works by using an open flask 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 flavouring (see Table 2.5), esters are often found in natural foods giving them their flavours, and thus the synthetic flavours (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 Smith1 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 efficacy 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 Smith’s work is maximising the molecule’s solubility in water and in the non-polar dirt, often performing tests, as well as attempting to fine-tune a detergent’s properties for a specific 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 specific 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 other’s 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 fertilisers plastics (inc. fibres) nitric acid cleaning products/detergents

Form ammonium nitrate, urea etc. rayon, nylon, acrylics makes fertilisers, dyes, TNT, dynamite 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
1 CH2 −CH2 + 2 O2 Ag cat. @ 250◦ C

CH2 CH2 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 CO2 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 N2 and H2 by the equilibrium (its exothermic, releasing 92 kJ mol –1 ): N2 + 3 H2 2 NH3 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 (Fe3 O4 ) 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 N2 and H2 through a catalytic reactor. The products are passed into a coolant condenses the NH3 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 N2 and H2 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 N2 and H2 needs 22

3.3. Manufactured stuff

Figure 3.2: A flowchart 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 O2 , CO2 , CO and sulfurs need to be monitored and minimized since O2 could cause an explosion, and the other three reduce the efficacy of the catalyst. Other gases like CH4 and Ar need to monitored because these reduce the efficiency 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 effort 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 flame tests. Identifying cations The cations in a solution can be identified by testing for precipitates, combined with flame tests to identify metals (see Figure 3.2). Different cations precipitate with different anions, and often with different colours (see Appendix B for a chart). When some metals are passed through a flame, they give it a distinctive colour (see Table 3.2) Identifying anions The anions in a solution can be identified by testing the formation of precipitates, using the solubility rules found in Appendix B. A sample flowchart can be seen in Figure 2 3.3. CO3 – can be identified because it releases CO2 gas in an acid. Phosphate ion doesn’t form a 2 precipitate with Ba 2+ in a neutral solution because it equilibriums with HPO4 – , so that there is very 23

3. Chemical Monitoring and Management

Figure 3.3: A flowchart 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 sufficient phosphate to form insoluble Ba3 (PO4 )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 Ca Ba Cu(I) Cu(II) Fe Li K Sr Na

Colour Brick red Apple green Blue Green to blue-green Gold Dull red Lilac Crimson Intense yellow

Table 3.2: Flame test colours of common metals 24

3.3. Manufactured stuff

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 filter away remaining solids, heat the solution until it is nearly boiling (e.g. place it in a water bath) and add excess BaCl2 while stirring, continue to heat for 30 minutes, and then leave to cool until the precipitate settles at the bottom, then cool with ice, filter this solution and precipitate through a sintered glass filter. The filter is washed to remove other ions as much as possible and its dry weight is compared to its original dry weight. This experiment suffers from errors such as: • Loss of BaSO4 due to dissolution, passage through the filter, 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 filter 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 filter • Cooling with ice reduces the solubility of BaSO4 so reduces losses due to solubility • Careful washing, with many repetitions with small volumes of liquid, and drying between • The final drying-then-weighing stage should be done multiple times until the mass is constant 25

3. Chemical Monitoring and Management

100 90 80 70 Height (km) 60
Mesosphere Thermosphere

50 40 30 20 10
Troposphere Stratosphere

0 160 180 200 220 240 260 280 300 Temperature (K) 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 CO2 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 Earth’s 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 Earth’s 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 doesn’t mix by convection because the temperature gradient is backwards.

Pollutant Carcinogens CFCs Carbon monoxide Hydrocarbons Lead NO & NO2 Particulates O3 SO2

Source Unleaded petrol, vinyl chloride from plastics, dioxins from chlorine compounds Refrigeration, air-con, fire extinguishers Combustion (cars, fires etc.) Solvents Lead smelters, paint dust, leaded petrol Combustion Combustion, mining, other industrial process, asbestos Photochemical smog, printers/photocopiers Combustion, metal smelting Table 3.3: Pollutants in the lower atmosphere

26

3.4. The atmosphere

Formation Appearance Smell Effect on life Boiling point Density Solubility Reactivity

O· UV — — Easily reacts in living cells — — — Very high

O2 Photosynthesis Colourless gas, pale blue liquid Odourless Vital in diluted form −183◦ C Similar to air Slightly soluble Moderate oxidant, reacts with most things into oxides Medical, rocket fuel, steel-making, cutting tools (oxy-acetylene)

O3 UV & electric discharge Colourless gas, blue liquid Strong, distinctive smell Poisonous (even as low as 0.1 ppm) −111◦ C 1.5× air more than O2 More reactive, stronger oxidant than O2 Sterilisers, water purifier, paper/textile bleaching agent

Uses

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−O→O), the one in C←O, and the one = in ammonium (H3 N→(H+ )).

Ozone Ozone is molecule made from three oxygen atoms, it is normal O2 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.

Chlorofluorocarbons & Halons A chlorofluorocarbon (CFC) are compounds with only chlorine, fluorine 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 fire extinguishers (BCF fire extinguishers, as in bromine, chlorine, fluorine). 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 prefixes for F, Cl, Br and I are fluoro-, chloro-, bromo-, iodo- respectively. It’s positions and multiplicities are given in the form “<carbon numbers>-<number prefix ><element prefix >”, e.g. 1,2,3trichloro· · · . 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 off. This Cl· reacts with O3 , converting it into an ozone and a ClO· radical. CFCl3 Cl· + O3 ClO· + O3
UV light

CFCl2 + Cl

ClO· + O2 Cl· + 2 O2

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 specific altitudes). A balloon can also be used to obtain a concentration profile at a specific location on the Earth’s surface . Alternatives for CFCS There are several alternatives to CFCs for almost all the uses: • Hydrochlorofluorocarbons (HCFCs), these are more volatile and thus a larger proportion breaks down in the lower atmosphere, well away from the ozone layer. However, a significant proportion still reaches the stratosphere, where it breaks down, releasing a chlorine atom, resulting in similar damage to a CFC. • Hydroflurocarbons (HFC) are even more volatile that HCFCs and very few reach the stratosphere, although they contain no C−Cl bond to be broken and so cannot destroy ozone any way. HFCs are used in almost all the areas where CFC’s 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 efficient 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 find 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 definition 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 6.5–8.5 • Concentration of ions the each ion has a different safe range (e.g. [NO− ] < 0.1 ppm & 3 2− [PO4 ] < 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 stuff 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 can’t be seen, or a cross at the bottom of the tube disappears. Factors affecting ion concentrations There are several factors which can affect the concentration of ions in water bodies. Rain is pretty much free of ions (a small amount of CO3 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 affect 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 off. 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 basically involving clarification (making it look/taste better) and sanitisation (making it safe for humans). Clarification can be done by precipitating the particles out of the water, this process is called Flocculation or Coagulation. It works by adding FeCl3 to the water, which allow the suspended solids to group into large and larger particles, eventually getting large enough to be filtered by a coarse filter like sand or anthracite (which also filters out organic matter), for better results though, a membrane filter can be used. The FeCl3 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 FeCl3 to coagulate/precipitate suspended solids

Filter to remove precipitate (using sand/anthracite or a membrane filter)

Consumer

Storage

Add F – for tooth health

Add Cl2 gas to sanitise

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 effect 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 filters even though membrane filters are much superior, since the current filters are much cheaper. Membrane filters A membrane filter consists of a thin film of a polymer (polypropylene, teflon, polysuplone) with very small holes in it (these holes are uniformly sized). This film can be pleated and placed in a cylinder, the area outside the membrane is filled with dirty water, and the clean water comes out on the inside of the membrane. Another method is to make the film into a large number of thin capillaries (called hollow fibre membrane filter), which is hollow, so that dirty water flows over the outside and clean comes out of the passage in the capillary. A fibre filter is made from many of these so that it has a large surface area. The filtrate is left on the outside of the membrane/capillary in each method, and it can be cleaned by back flushing, by blowing air through it from the clean side. A membrane filter can be made with holes of a custom size, so they can filter different things. A membrane filter 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 H2 S, in acidic and in alkaline solutions. In acid the equilibrium S 2− + 2 H3 O+ H2 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, don’t 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. Eutrophication 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 Ba 2+ Ca 2+ Cu 2+ Fe 2+ Fe 3+ Pb 2+

Test 2 White precipitate with SO4 – , none with OH – or F – 2– White precipitate with SO4 and F – Blue precipitate with OH – , which dissolves to deep blue in NH3 Green or white precipitate with OH – that may go brown Brown precipitate with OH – , deep red with SCN – 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 detected 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 find their way into the supply, but these can be detected (e.g. ions can use precipitation/flame 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 purified and clarified, using filters, flocculation etc to increase its quality. Afterwards, chemicals like chlorine (as a disinfectant) or fluorine (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 modified significantly (e.g. vulcanisation). Natural rubber is time consuming and effort 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 specific applications they are being used for since the manufacturing process can be fine 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 different properties which can be used in different 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 efficiency of production of the rubber, unlike natural rubber. Therefore, 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 b1 P1 + b2 P2 + · · · , the equilibrium products (P ) and reactants (R), for a reaction a1 R1 + a2 R2 + · · · constant is given by: K= [P1 ]b1 × [P2 ]b1 × · · · [R1 ]a1 × [R2 ]a1 × · · · 33

4. Industrial Chemistry

Use In manufacture Fertiliser Ethene Synthetic fibres Direct uses Car batteries Metal cleaning Metal extraction

Comments Used to break down some compounds to form superphosphate Used as a catalyst to dehydrate ethanol Used to neutralise the NaOH used in the manufacturing process (and some other things as well) Used as the electrolyte in lead acid batteries Used to pickle steel before applying a surface coating Used to dissolve metals out of their ores Table 4.1: Some uses for sulfuric acid

Factors affecting equilibrium reactions Pressure, volume and concentration Changing the pressure or volume of an equilibrium reaction will cause the reaction to move to counteract this change, by ‘absorbing’ moles, for example. This change does not affect the final 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 Chatelier’s 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 Compressed air Molten sulfur/water emulsion Superheated water

Sulfur deposit

Figure 4.1: A simplified diagram of the Frasch process 34

4.3. Sulfuric acid

Oxygen

Catalytic conversion

SO3

Combustion

SO2

Passed through sulfuric acid

Oleum (H2 S2 O7 )

Sulfur

H2 SO4

Reacted with water

Figure 4.2: A similified flow chart of the contact process

water. However, it is insoluble so, when it cools, it solidifies out of the emulsion leaving behind very pure (>99%) sulfur. Sulfur is also low density so the the compressed air is an effective 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. Significantly, 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 SO2 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) + O2 (g) SO2 (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 SO3 The mixture of air and sulfur dioxide is cooled to 400◦ C and pushed into a catalytic converter. The reaction is: 2 SO2 (g) + O2 (g) 2 SO3 (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 SO3 , 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 (V2 O5 ) 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 SO2 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 H2 SO4 is produced) to remove the SO3 , and the remaining SO2 is run over another catalyst bed, which converts the almost all the remaining gas into SO3 . This is then run through another absorber tower to extract the most sulfuric acid possible. Production of H2 SO4 The last stage of the process is to convert the SO3 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, SO3 reacts with sulfuric acid to form oleum (H2 S2 O7 ), which reacts with water to form 2 H2 SO4 . 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: H2 SO4 + 2 H+ + 2 e− Or, when the sulfuric acid is concentrated: 2 H2 SO4 + 2 e−
2− SO2 + SO4 + 2 H2 O

SO2 + 2 H2 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 H2 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. C2 H5 OH 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 H2 SO4 · H2 O). Thus, when sulfuric acid is diluted it will be completely ionised, – 2 from H2 SO4 to H2 SO4 and SO4 – . 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
H2 SO4

C2 H 4 + H 2 O

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 protection 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 H3 O+ + energy), so dilution should be done by adding the acid to the water, so that (H+ + H2 O 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

Difference 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 fibres (rayon etc.). It is produced by the overall equation: 2 NaCl(aq) + 2 H2 O(l) 2 NaOH(aq) + Cl2 (g) + H2 (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 flow of mercury along the bottom. Highly concentrated salt water (almost saturated) is fed into the first 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 indefinitely, 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 first 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 continuously 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 off, leaving behind most of the small portion of chlorine that crosses the diaphragm. Some hydroxide also migrates into the first chamber, but this is reduced by having a pressure gradient from the first 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 (Teflon) which has been modified so that has the properties stated above. The Teflon 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 Cl2 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) + Cl2 (g)

Concentrated NaCl(aq) If the sodium chloride is aqueous, but concentrated, then the reaction at the anode still forms Cl2 (g) but the cathode splits water into hydroxide and hydrogen gas, the compete reaction is: 2 NaCl(aq) + 2 H2 O(l) Cl2 (g) + H2 (g) + 2 NaOH(aq)

Dilute NaCl(aq) If the sodium chloride is aqueous and dilute, then the ions are in very concentrations, 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. Saponification

reactions are: Cathode Anode Overall 2 H2 O(l) + 2 e− 2 H2 O(l) 2 H2 O(l) H2 (g) + 2 OH−(aq) + + O2 (g) 4 H (aq) + 4 e− 2 H2 (g) + O2 (g)

4.5

Saponification is an important organic industrial process

Saponification Saponification 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. saponification is just the process of breaking the alcohol off an ester, leaving a carboxylic acid which is missing the hydrogen on the −COO group. An example of saponification with methyl propanoate: CH3 CH2 COOCH3 + OH− CH3 CH2 COO− + CH3 OH

In the school laboratory Saponification 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 suffices, 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 saponification 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 purified 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 different to the pure reactants used in a laboratory. Common oils and fats used in an industrial context for saponfication 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
(c) Non-ionic detergent

n

OH

Figure 4.3: Schematics of the molecular structures of different 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 don’t form an emulsion without an emulsifier. Soap acts as an emulsifier 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 different properties to soap, which normally derives from the different structures of their molecules (visual representations of the structures can be seen in Figure 4.3). Each type of detergent has different 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 effectiveness 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 (−OSO2 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 affected 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 different 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 doesn’t 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 efficiacy 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% effective 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 emulsifier 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 affect 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 (80–90% CaCO3 ) 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): CaCO3 (s) + 2 NaCl(aq) Na2 CO3 (s) + CaCl2 (aq)

Brine purification The first 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), flocculated, and removed before the brine is used Solvay process (the flocculation step will also remove other suspended solids, such as dirt). Sodium hydrogen carbonate precipitation The process decomposes the limestone to get CO2 and CaO, the carbon dioxide is then used directly to produce Na2 CO3 as it is bubbled through a the brine saturated with ammonia, which causes carbonic acid (H2 CO3 ) to form, which reacts with the ammonia to produce hydrogen carbonate ions (HCO3 ) and ammonium. Sodium hydrogen carbonate is in soluble so it precipitates from solution. The net equation for this stage is: NaCl(aq) + NH3 (aq) + CO2 (g) + H2 O(l) NaHCO3 (s) + NH4 Cl(aq) 41

4. Industrial Chemistry

Limestone (CaCO3 )

CaO

Reacted with water in a lime slaker

Ca(OH)2

Limestone decomposed in a kiln

CO2

Heated to recover NH3 (CaCl2 waste)

NH4 Cl

Saturated with NH3

Carbon dioxide bubbled through liquid

NaHCO3 (s) & NH4 Cl(aq)

Separated by filtration

Purified brine

Na2 CO3 CO2

Decomposed by heating

NaHCO3

Figure 4.4: A flow chart outlining the key steps of the Solvay process

Sodium carbonate production This mixture of NaHCO3 and NH4 Cl is filtered 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 NaHCO3 (s) Na2 CO3 (s) + CO2 (g) + H2 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 decomposition of limestone calcium oxide, is slaked, (reacted with water) to produce Ca(OH)2 . This is mixed with the NH4 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: NH4 Cl(aq) + Ca(OH)2 (s) NH3 (g) + CaCl2 (aq) + 2 H2 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 significant 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 Glass-making Saponification Water treatment Paper making Sulfur dioxide capture As a base To make NaHCO3

Comments Major use of Na2 CO3 , used to make normal glass Used as an alternative to NaOH since it is cheaper Used to precipitate metal ions to soften water (including as an alternative to phosphorus in washing powders) Used to make NaHSO3 From power station waste gases, to comply with environmental regulations It is cheap, and it is basic so it is often used as an industrial base By bubbling CO2 through a solution of it, pure NaHCO3 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 CaCl2 solution can have a high temperature, and so it needs to be cooled or diluted to a point where it won’t 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 artificial ponds. Smaller, although not insignificant, 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 specifically, 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 CaCO3 solution is a significant 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).

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Index
α decay, 11 Acid rain, 15 Acidity, 13 Acids, 15 Conjugate, 17 Definitions, 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 Teflon, 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 β 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 Br¨nsted-Lowry theory, 17 o Branches of Chemistry (largest branches are circled), 21 Buffers, 18 Real-world example, 18 Carbon dioxide Solubility, 14 Cathode, 9 Chlorofluorocarbons, 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¨ller counter, 11 u Photographic film, 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 Esterification, 19 Refluxing, 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 Gr¨tzel cell, 10 a Haber process, 22 History, 23 Monitoring, 22 Haber, Fritz, 23 Halons, 27 Hardness, 29 HDPE, 6 Hydrochlorofluorocarbons, 28 Hydroflurocarbons, 28 i, 33 Indicators, 13 Ion tests, 23 Anions, 23 Cations, 23 Lavoisier, Antoine, 16 LDPE, 6 Le Chatelier’s principle, 14 Leclanch´ cell, 10 e Liquid junction photovoltaic device, 10 Membrane filters, 30 Membrane process, 38 Mercury process, 37 Mesosphere, 26 Monitoring, 22 46

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 stiffening, 7 Cross linking, 7 Molecular weights, 7 Radioisotopes Cobalt-60, 11 Production, 11 Sodium-24, 11 Uses, 11 Reduction, 9 Salt bridge, 9 Saponification, 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

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 affecting ion concentrations, 29 Flocculation, 29 Hardness, 29 Heavy metals, 30 Total dissolved solids, 29 Treatment, 29 Turbidity, 29 Zeolites, 6 Ziegler-Natta process, 6

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