ra enit een neers Telit a aaHow to use this book ‘This book contains a number of great features that will help you Find ‘your way around your AS Chemistry course and support your learning. Introductory pages Unie Theowre princes cheney, ach unit has two introductory pages. giving you an idea of the chemistry to wenisen, Chm te come and linking the content to the chemical ideas, how chemists work end chemistry in action that you will encounter in the unit. HSW boxes How Science Works is 2 key feature of your course. The many HSW boxes \within the text will help yu cover all the new aspects of How Science Works that you need. These include how scientsis investigate ideas and develop theories, how to evaluate data and the design of studies to test their validity and tli ility, and how science affects the real world including informing decisions that need to be taken by individuals and society. Main text ‘The main pert of the bock covers all you need to learn for your course, The text is supported by many diagrarrs and photographs that will help you understand the concepts you need to learn, Key terms in the text are shewn in bold type. These terms are defined in the interactive glossary that can be found on the software using the ‘search elossary’ feature Introductory pages 5 introductory organic chemistry eer ‘Abst egal hey Mainter=. Drea ee nestor ergs eee petit iowa te ioe t et 8 arolse nruO te temo es eae comyect iin malta ots eink Anim =_ Seg = able eel Brant men 13398 Seen ler igi 1 Wha siete eneer dit inert deepen taut mote 2 same ang ras nee Ce Lc ting th et one Fe cep an Exarore: Ut et owes 1 824 ‘xamzone page Practical boxes Your course contains @ number of core practicals that you may be vested ton. These bores indicate links to practical work. Your teacher will give you ‘opportunities to cover these investigations. Worked example boxes “These boxes give example questions and answers taking yu through the calculations step-by-step and showing how you could set cut your answers. Question boxes ‘the end of each section of tex: you wil find a box containing questions that cover what you have just ler. You can use these questions to help you check whether you have understood whet you have just read end whether there is anything that you need to look at again Examzone pages A the end of the book you wil find 9 pages of exam questions fo past papers. You can use these questions to test how flly you have understood ‘the units, aswell 2 0 hep you pracise for your exams. There ae 2 tests for each unit Tre contents lst sows you thet there are two urits nthe Book, etching ‘the Edexcel AS specification for Chemisty. There ore 7 chapters in uit 1 (chapters 1.1 to 1.7) and 11 chapters in unit 2 (chapters 2.1 0 211), Page numbering in the contents st, and inthe index atthe back ofthe book, will help you find what you are coking for.How to use your ActiveBook ‘The ActiveBook is an electronic copy of the book, which you can use on a compatible computer. The CD-ROM will only play while the disc is in the computer. The ActiveBook has these features: Opa Click ths tab ot the top of the screen to access the electronic version ofthe book a= Click on any of the words in bold to see a box with tre word ‘and what It means Clck'play’ to listen to someone read it out for {you to help you pronounce it & Interactive view Click this button to see al the icons on the page that link to electronic files, such as documents ard spreadsheets ‘You have access to all of the features that are useful for you to use at hore on your own. IF you dor't want to see these links you can return to Book: Student Book Lf SS reno Bewais Soor SD 5 Introductory orga ‘rch hte ny slaty get nC ty on (esky ss han [te mod ran fhe hm tts tbe Oa < eae a fot neve butane ie conp (aos sta carne eta Caen gueeen ecient hero eth cowratou eperteg oo ‘Gick on this tab to see menus ‘hich Ist all che electronic fles ‘on the Activedook. chemistry About organic chemistry rene wd oie’ cori etm but ens ed oe sb i Chen mw eae nega temas Ue ay afeaea ‘pai a inp). Co at at ‘ete bg sa rn A ih et fre ‘hy meg est ee fu a P91 ly oe 18 fe eben Owrck oad sontaermax nthe Gg ir See sen gre eed on ron tara ad dre Sepecceetemectety Sentara trophy tte arate incon tne ta om tercheerd one macnn EWS dean pte ee eres corabarntoeconecaeticalityt nisi mrecopencrent mn’ tenis eines ect aOR te an (roveins Opie tokabeweebuselnigeme ed InosRiisiainntesmni cont herent rte Pate ereroanaes ea eeQa) Click this tab to see all of the key words ané what ‘they mean. Click'play’ to listen to someone read ‘them our to help you pronounce them. ‘The vast range of organic compounds bopper rein Enel eteemnempende Te snp nda eed pease bate leg hen uch er rene erie ere Fst === Peedi reer ace ‘see gn ty ove pms om aso ee pe ga ‘edi mie Pet deans pt ‘mes nie nese oe he ee tin i ed eee a eon ‘Nernst yy ms etn a ow Inte nis ac vent nner ‘ga rane cmp ened Sinewed earnest or ae at Pech eerie aati onctmpne omen Spowee wvow oman) ac Sryonse wenger oem ore ge mee esi and nae wget rr ee, Sein eh snes > Sonya seseeoeeee, Ripamivecntars.seennnass ru 7 ocr yas rs ome iy med 2 vie ce tis ty oben ne ‘Slang wpe ong ra ar 2 femora ote ein ernie 1 spp sae 94/95 of 264 Click on this tab at any time to search for help on how to use the ActiveBook, Dye Just click on a section of the page and It wil magnify so that you can read it easily on screen. This also means that you can look closely at photos ‘and diagrams,Sau Bw recowwineesteniy—r® Fonnulzeequatins endarountsofsubsance 10 Bonding 7 Tee eee ‘0 Ere eee ne eter 2 Gir i late 0 Pee eens ‘ peered w@ The male ‘6 late enery w Ling meles 8 aun eae ae eee eed 2 Metalic bonding m Neaurg concentration Pr Nore ways to calculate equations 2 Nee ereter 200 heen geri derisry oh Aboot ote crear 4 fer endkinorgenc chemistry 96 Energetics and enthalpy changes 32 The properties of the carbon atom 100 ery and eerie 2 Naming orgie eleces 14 Neaning eneay changes ethly change 34 Renee aera x Important enthalpy changes 40 ‘The alkanes - a family of saturated Teeter cet cnet eee eS 100 Bond entlplesand mean bond entapes 46 ee amas a Using bond enthalpies 48 Making the most of crude oil V2 ete oper cr eee The renctons of healers ne ‘omic structure and the peiodictable 52 Reacorscl the allans with chive 118 eet eet ee 2 tthe sues 20 Usgéeatonanesseciomre 54 Te eee eee ree eee eae Se ce aera Fling orbits end Ses 6 aeeehens . Representing electrons and orbitals 66 natae’ trecapereatser eaten 22 Electronic ceiiguton and cher eae ne Properties: 68 Reactions of the alkenes 129 The ects the period ale R How do onpricreectns happen? 132 Patterns in the periodic table 74 pees ecient tare reactions ofthe aleres 1 Faber poles and soltons 136‘Shapes of molecules and fons 144 Predicting the shapes of molecules 144 Shapes of simple organic molecules 8 Carbon 150 mers Intermediate bonding and bond polarity 154 Electronegativity 154 Intermediate bonding 156 Polarity of bonds and molecules 158 Chapter 23 a 2 = » ons wee hydroxides 182 Reactions of the halogens and halides Hologens end the water supply 192 194 196 The rate of reacticn 196 ‘Measuring reaction rates 198, ‘Activation energy 200 ee z Pee nes = =o oom ox ST tees |e Identifying and preparing halogenoalkanes 220 = = Nucleophilc substitution of halogencakenes 226 Chemistry in the ozone layer 228 Gres) Mass spectra and IR absorption 230 Using mass spectra with organic compounds 230 Infrared spectroscopy 232 Erorsn Green chemistry 236 Global warring and climate change 236 Carbon neutrality and carbon footprint 238 Reducing hazards and pollution In the chemical industry 240 Increasing efficiency in the chemical industry 244 Examzone: Unit 1 Test 1 248 Exarmzone: Unit Test 2 250 Exarone: Unit 2 Test 1 252 Exaruone: Unit 2 Test 2 254 Index 237 table 262Unit 1 The study of chemistry is basically the study of everything. To understand how matter works, chemists need a set of principles ‘end a toolkit of ideas and techniques. In this unit you ‘are going to be looking at some of the core principles of chemistry, which you ean then apply in ary situation, The core principles of chemistry Chemical ideas Most important ideas in chemistry involve the ways in which different chemicals react with tone another. In this unit you are going to be developing models of atoms, molecales snd ‘ponds which will help you to understend exactly what goes on when they react ‘The making and breaking of chemical honds always involves energy charges. You are going to learn how to measure these changes and use them to understand what is going on during a chemical reaction. You will develop a more complex model of the atom with electrons arranged! into orbitals with different energy levels. This model of atomic structure will help you understund the patterns oF the periodic table, The unit alo uses these models to explain three types of chemical bonding ~ ionic, covalent and metalic, Finally in this unit you will discover the importance of organic chemistry. You will lok at the basic structures of carbon-based compounds and investigate two of the simplest ongunic farniies, the allames and the slleenes. How chemists work Chemists work in a variery of ways to build up theoretical models of the nature of matter and then collect the practical evidence to support or disprove the model. You will be carrying out practical work to build up your experimental skills - and also to demonstrate just how difficult i¢ can be to build up reliable and accurate evidence, Systematic and random errors all (00 often interfere with the sults! Incressingly chemists ray on instrumentation © get the evidence they need 1 support their theories ard you wil be looking at some examples, particularly the mass spectometer. ‘The difference benween ideal (theoretical) measurements and wal, practically based results can be seen clearly when you consider the latice energies of different compounds using Born Haber cycles calculated frem theory snd by experimentation! Chemistry in action Although a lot of the chemistry yout learn in school is sbout madels and theory, chemistry plays an enormous role in the real wor. Tn this unit you will he looking at variety of examples of chemistry in action Which range from detecting athletes who are cheating by using drugs through to recycling polymers and trying to build a more sustainable woric, Chemistry and chemists do not exis n'a vacuum, The work of chemists has a big effect on the life you lead and on the well-being and the economy of the whole planet. Some oF the developments and discoveries of chemists raise ethieal problems which scientists cannot answer, Society as a whole has to decide what is acceptable und what is not, So you will, bye looking at chemical ideas, practical chemistry and the rele of chemistry in societyInchapter 1.3 you will be looking atthe way chemists are Ina constant bale 10 iWenuty athletes who ry towin by cheating \ and using } pefermance eihancirg drugs Accurate chemical measurements are vital in many situations as well as the laboratory. n chapter 1.1 you willbe looting at the way they are used to dlapnose Ilness and ‘monitor the health of the envrerment. For instence, maintaining the correct concentrations of different solutes in body Fuide isan important aspect of medicine particularly for kidney patients on dialysis, Anotler aspect of how science works isto develop an Lunderstancirg of where our scientific knowledge comes from. In this unit you wil begin to see how Ideas emerge — and sometimes clsappear again even though they are correct! And in sorne cases you will se just how difficult it con be to make sense of the ‘evidence, Evidence for bording and the artangement of atoms within @ molecule can be very difficult to interpret. Computers make life eater for usin the 21st century, but when people Fest analysed images like this lysozyme they hac to work it all out for ea Doerrrneyeresnnrenynngerne | Qnrmnrnine ‘Throughout this unit, and particularly in chapter 1.6 and 1.7, you will be ‘how chemists are now trying toTORR ee 1 Formulae, equations and amounts of substance The foundations of z chemistry Te cen prot tet matter mde up of aor wes proaded by Abert Ein n 1905, Heaton shoved how rowan eto ies xlned ater fpr tery of mate The ander movement of micoscec keer pale panies suseended ina 8 oq ue tocalisns betwee Ces pares and te pares of he a rH fig 1.1 Everything ia and on the tarthis made up of chemicals. Cherists investigate the way éitferent elements ard compounds react together in both Uving and noeliving mater. At the heart of chemical theory is the atom 1s the building block of all matter. ‘The first recorded reference we have to the idea of stoms fi 1.1.2 Th dancing tage of ake pris in air 88 basis of matter comes from around 2600 pelt gars ete oeeren eros meyer botnet years ago in ancient India! The idea of atoms in Robert Brown who frst ebserved it 1827. the West can be raced back about 2500 years, tw the Greek philosophers Leueippus and his pupil Democritus, The word atom comes fiom \ hag > the Greek word meaning ‘indivisible’. It is likely at's in an atom? that a similar theory was held by some of the Scientists now believe that the nucle of atoms sre made up great Arab scientists uch as Jubie sho Hayyan of protons ind neutrons. These two components of the during the ninth and tenth centuries, but the cleus are usualy referred 10 as nueleons. ‘The electrons idea was not accepted in Europe until the start in the atom occupy the space outside the mucieus. Each of the nineteenth century when a Manchester proton fus a positive charge and each electron a negative schoolteacher called John Dakon made the case charge. Neutrons have no charge. You will be looking at the for atoms bined on evilence from experiments stsueture of alums in much more detail in chapecr 1.3. with gases. secon at ‘Throughout the nineteenth and early wench ie centuries a body of theory sbout the nature Va “yy cee cee eater SN \ togesher gradually built up. This was based 4 3 on careful observation and experimentation by ie scientists such us Berzelis, Kekule, Rutherford and ‘Thomson, From the 1860s onwasds Dri Mendlzev and others developed the periodic table, which mapped the known elements fig. 1.13 Atoms const of rotors ard neutronsin a mules, sureunded by ncverding to their properties, sdectrons,An eloment is a substance that cannot be broken down chemically into simpler substances. The atoms of an element all contain the same numiser of protons. ‘The number of protons in the nucleus of an atom is ine atomie number of the element, given the symbol %. The number OF proiuns is equal 1 che number of electrons ~ an atom is electrically neutral. The protons and neutrons in an atom have mass, but the electron's _mast is negligible. The number of protons (Z) plus the aumber of neutrons (N) in an stom is known as the mass number (4). Figure 1.1.4 shows hove the data for 2 nucleas sre presented. ZAl umber ofreuirans = 2713 «14 mass nurber 4 Groton metros) cereal symbol forelement storie wirbat (Groton number) 2 fig. 114 How the details ofthe nucleus are written withthe chemical symbole alureium The nuber of netons is the mass number ‘minus tre atomic number. Isotopes |All the atoms of o particular element have the wame atomic number ~ they all have the same number of protons and electrons. It is the number of electrons in the atom that determines its chemical properties However, stoms within the same element may have Uifferent numbers uf neutrons. Neutrons have mass, eee so this means that the atoms making up an element may have different masses. Atoms with the same atomic number but different numbers of neutrons are called isotopes. Most elements are a mixture of isotopes. Sometimes the presence of exira neutrons ‘makes the nucleus unstable, so some ‘heavy’ isuwopes are radivactive, Although different isotopes of the same clement may have different physieal properties ~ they have a different mass and some may be radioactive = they always have the same chemical properties Ddecause the number of electrons stays the same For example, hydrogen has three isotopes, hydrogen-1, hydrogen-2 and hyrdrogen-3, shown in fig. 1-15, Around 99,985% of dhe atoms in a container of hydrogen will be hydrogen-1. About 0.015% are hydrogen-2, with twice ‘the mass of hydrogen-1. The number of hydrogen 3 atoms in a sample of hydrogen is variable — these nuclei are unstable, and undergo radioactive decay. A shorthand way of representing the isotopes is 'H, 7H. and 7H (ee fig. 11.8) or 1H. 7H and 7H, CN NK "Wlyérozen-t) FH thydrogen-2) *H hydrogen 3) 1 poten ‘proton 1 proton Oo etrons ‘ neuten neato 1 election electron 1 election fig. 1.15 Te tree otopes of hydrogen. a ‘toric rumber 2 3 “ 2 7 2 Mass rumter A 7 8 65 108 28 Nurber of neutrons M (= A~ 2) 4 “ 36 82 16 symbol uw as sgcu ‘hag au table 11.1 Thistable shows how many rotons and neutrans combine to makeup the melo diferent atoms OL 1. An atom has atomic number 26 and mass rumber 56. How many protons, neutrons and electrons does it have? 2 Wore out the number of protans, electrons and ‘neutrons present in the fllowir a HNe be Ske ators: —Formulae and equations Holding atoms together In compounds formed between metals and non-metals, the atoms are ususlly joined by ionic bonding. The atoms lose or gain electrons so that they have a complete outer shell, which is the ‘most stable state for an jon, An atom that loses or gains one or more elecirons forms un fon, An avom dat loses an electron becomes a positive ion, and an atom dist gains an electron becomes 4 negative ion. Strong forces of attraction (ionic bonds) ‘hold the oppositely charged ions in a giant lattice structure. Nav + (an ean ea) tedirmatomn cherie store exduion chlerteien 5,116 The formation of sodium chloride, NaCl — an example of fnic bonding, The dot ex! ross diagrams show the fal ater shel the fons procuce, ‘Many chemical reactions de not invalve ions. Non-metals generally gain electrons to achieve a stable outer shell. When non-metals react together, the atoms achieve full outer shells by sharing clecisons ~ this is known as covalent bonding. ‘The atoms in the molecules are then held together because they are sharing pairs of clectrons. These strong bonds between the atoms are known as covalent bonds, (e} No 0 1) ea (2) ryeegen agen angen so xe moe fig. 1.7 Baamples of covalent bonding, Dt ad cross dagrams show how electrons are shared to achieve 2 fllouter shell. Representing chemical reactions Chemists need to explain what is happening during a chemical reaction as fally, yet as simply as possible. Equations Delp them calculue the amounts of rreuctants they need, predict the yields of products and tell other chemists exactly ‘what experiment they did. When magnesium bums in aiz, ane atom of magnesinm reacts with one atom of oxygen to form magnesium oxide. In theory this reaction can be represented by 1a simple chemical equation: Mg +0 > Mgo However, oxygen normally exists as diatomic molecules, exch containing 10 ‘oxygen atoms, so this equation should rel: Mg + 0; > MgO +0 But now you have an oxygen atom left cover! You need 1 produce a balanced equation showing all the reactants ia the form in which they take part in the 2Mg + 0, > 2MgO ‘This kind of balancing act is performed for every chemical equation. The total mass of the product or products of chemical reaction is alviays equal to the total mass of the reactants, The products have the same aoms us the reactants = bur arranged in a different way. ‘To check if an equation is balanced, count the number of each type of atom con both sides. If the numbers ace equal, sand all the atoms are part of « complete molecale, then the equation is balanced. For example, when nitrogen reacts with hydrogen, ammonia is produced: N+H > NH,But nitrogen and hydrogen are diatomic gases, N, and. H, so, assuming there is one nitrogen molecule: + IH, > NH; +N But you can’t have half molecules of a single nitrogen stom, To balance the equation you need three molecules of hydrogen, which make two ammonia molecules: ) + 3H, > 2NH, Finally acl up the different stoms ~ there are sve nitrogen atoms snd six hycrogen atoms on both sides of the equation, all in complete molecules, 60 it is balanced, The state symbols It is also important to show the state symbols for the reacting chemicals = whether each is a solid (8). a ligaid (1), a ges (g) or in solution in water (aquecus solution, aq). hydrosen sulle oct (ne ‘onutes ns) + H,S0 faa) > ZnSO a) + Hale) fig. 1.18 Zhereacts with slic acid te produce hydrogen. thes to know the state of all the reactants an prodvets when planing the ‘pparatus youneed lons in solution ‘Many reactions involve ions in solution, When substances reat in this way an joni equation is useful. For example, when a sclution of sodium hydroxide is added to 2 solution of magnesium chloride, sodium chloride, NaCl and a solid precipitate of magnesium hydroxide, Mg(OH), are formed: 2N2OH(aq) + MaCl,taa) > 2NaCliag) + Me(OH) 48) 5.1.1.9 Magresum hydonide fprsere fn Mik of Mages canbe ‘mode by adding a soliton of sodium hyeroxgetoaselutien of raagresum eHovde, Re Ca This is a molecular equation, because it shows the complete formula of every substance. However, none of the substances consists of molecules ~ both reactants dissolve in Water to form ions, so an joni equation gives a more accurate picture: 2NaM(aq) + 2OHMIag) + Mp2*(ag) + 2CP(aa) > 2Na"(aq) + 2CI(aq) + Me(OH),(s) The sodium ions and chloride fons appear in exactly the sume way on each Side of the equation, Tons ike this ace ofien called spectator fons, and can be left out of the equation 2Na‘(ag) + 2OH"(ag) + Mg?"(aq) + 2Cr(aq) > Nar tagy + 2€r (ay + MeOH), (8) This produues the much simpler overall Fonte equation: ‘Mg?*(aq) + 2OH-(aq) > Mg(OH),(s) Which type of equation? ‘The type of equation you use depends on what you want to show. A molecular equation gives a complete description of the reactants and the amounts you need in 2 practical experiment. An ionic equation shows what is actually happening in solution, eg when sodium hydroxide and magnesium chloride react together. The power of overall ionic equations is thar dhey let you make generalisations, eg any solution containing magacsium ions will react with any other solution containing hydroxide fons to form a. precipitate of magnesium hydroxide. As you continue through this book you will discover more ways of representing. reactions OED 1. Write balanced chemical equations including state symbcls forthe following word equations. Use the data in the periodic table at the back of the book tohelp you: inc + oxygen > zinc ovide potassium + water > hydrogen and potassium hydroxide © calclum carbonate > calcium oxide + carbon dioxide 2 When sclutions of potassium chloride, KCL and silver nitrate, AgNO, are mixed, a precipitate of silver chloride forms. Write a molecular ané an Jonic equation for ths reaction,TR cd Atoms ure far too small to be seen with an ordinary uptical microscope. However, itis possible tw see atoms using more sophisticated techniques. Figure 1.1.10 shows the tip of a platinum seedile seen through an fon microscope. ‘This Instrument uses helium ions instead of light, giving much, higher magnifications. The adius of an individual aton is around 1 107! ma, fig. 11.10 Then microscape reveas that platiuen consist of layers of platinum atoms, ranged in ‘aighy symmetrical erysal atc. The image produced i stiking. ‘When deaing with ators, you need to use both very small and very large rumbers. Powers of 10 re often wed to expres number ite this For example, the apprenimate distance travelled by light in one year is 1» 1018 m, or 10000000000000000 m.The 15 sealed the index - the power to whieh 10 ie raised ~ and 10 ic the base. Srila the approximate radius of «platinum atom is 1x 10-m, or (1000000000 m.The sgn ofthe index tells you which way the decimal point maves. Numbers are often written in standard form as @ number between 1 and 10 ‘multistied by 10 reised tothe appropriate power. So for example, the belting pont Fricke is 30 103K. ond the wavelength of red light i563 x 1077 m. (Beth of these exemples are quoted to 2 significant figures) Relative atomic mass ‘The mass of aa atom is also tiny, but calculating the masses and numbers cf atoms is essential in practical chemistry. Using actual mass would be cumbersome, so chemists use a relative scale which is easier to handle, ‘Whenever you measure something, you do it by comparing what you are measuring with « known quantity. For example, if you buy 4 kilogram of apples, the mass of the apples has been determined by weighing it against 3 standard 1 kg mass, ‘The eylinder in fig. 11.11 is defined as having a mast of exactly 1 kg. You are effectively comparing the mass of the apples with the mass of this cylinder!fg. 19.11 Tic eyes of metal Parc the standard Kilogram twill be replaced in the fue because Is very slow losing mas a metal som evaporate From its surface. In the same way, chemists compare the masses of atoms with the mass of a standard atom ~ dhe carbon-12 isotope. This ip called the relative atomic mass scale. ‘The relative atomic mass (RAM, given the symbol A,) of an clement is often shown on the periodic table. Relative stomic masses have no units ~ they compare the mass of one atom with that of another. +The relative atomic mass of an element is defined as the average mass of ifs isotopes compared with the mass of an atom of the carbon-12 isotope. ‘The mass number of an element tells you the number of protons and neutrons in a typical atom of thet clement. However, as you have seen, the atoms in aun element do not necessarily all have the sume mass number if there are different isotopes. This is why the relative atomic mass scale is hased on one isotope, On this scale, stoms of the curbon-12 isotope are assigned a relative atomic mass of 12, An atom of the hydrogen-1 isowpe has » relative atumie mass of 1, one-wvelli of the RAM for dhe carbon-12 isotope Mixtures of isotopes Teyou look up the relative atomic mass of carbon in & data book; you will find it given es 12,011 not 12.000. This is because naturally occurring carbon contains mainly atoms of carbon-12, but aso some atoms of carbon-13 and carbon-14, making the average relative atomic mass of a carbon atom slightly greater than 12. The relative atomic mass of every element is an average which reflects the mix of isotopes and their differing masses within the elerment, Most elements have one major isotope and very small propurtions of oth enough to assume that the value of the relative atomic isotopes, and for these itis usually accurate mass is the same as its mvs number, Reet ‘A sample of iron was analysed in a mass spectrometer (eee chapter 1.3). Table 1.1.2 shows the isotopes that it contains. Find the relative atomic mass of thie carpe of iron sz ess) Relative 554 gigs z.17— | O31 abundance, (6) ‘able 112 The relative abundance of fotopes in a samme of ren, ‘To find the ralative atomic mass, you need to calculate the average of these four isotopes. However they are present in different proportions so just acing therm ‘together and dividing by 4 would give a misteacing ‘average. So you multiply the relative atomic mass of inotope by its relative eburdance to calculate @ ‘weighted mean which wll give you the overall relative Aff) = (54 584%) + (56 x 91.68%) + (57 x 2.17%) + (58 x 031%) Affe) = 55.91 For many caletions 56s. close enough approximation to the relive atomic mass of ion, (Thi sth relative atomic mass ofthe most common isctope of iron) OED 1. The element bromine has atomic number 35 and has two isotopes of relative atomic mass 79 and 81, Copy and complete table 1.1.3, rrr Br ae {able 1.1.3 Two isotopes of bromine 2 Calculate the relative atomic mass of each of the following elements: «bromine (50.5% bromine-79, 43.5% bromine-81) b silver (51.3% sliver-107, 48.796 slver-109) chromium (4.3% chromium-50, 838% chromium-£2, 9.69% chromium-$3, 2.39% chromium-4)TR cd The mole Counting and weighing atoms As 2 chemist you often need to ‘coun? and ‘weigh? atoms. You aeed to mix chemicals together in the correct ratio to carry out a reaction. Or you might ‘want (0 find out the composition and formula of the compound you have made, by calculating the ratio of the aumbers of different atoms in your proxluet fiom the amounts of dhe reactants. The mole provides a way’ of doing this, Just Tike relative atomic mass, the mole is based on the carbon-12 isotope as a standard measure, The relative atomic mass of carbon-12 in grams (12.00 2) contains a set number of atoms, From this it follows that for any element, the relative atomic mass in grams contains this same number of atoms, This is the basis of the definition of the mole; the ST unit of the amount of substance. Like other units, the mole has an abbreviation, mol, + A-mole of any substance is defined as the amount of substance that contains as many particles (atoms, ions or molecules) as there are atoms in exactly 12 of earbon-12, The number of wins in exactly 12 g of curbon-12 js found from experiments w be 6.02 * 10% (o 3 significant figures). This mumber is known as the Avogadeo constant, afer the nineteenth-century Italian chemist Amedeo Avogadro, The Avogadro constant has the unit particles per mole (mol) and is sometimes given the symbol J. or Ng. One mole of any substance contains 6.02 x 109 particles. ‘You can work out the number of moles in any amount of aa clement: Number of moles mass in g mor mass in g mort ‘The molar mass (symbol M) is just the numerical value of the relative stomic mass, but with the unit, grams per mole. You cin ako use the Avogadra constent to work cout how many 2 substance. For example, imagine you have 6 g of magnesium and 6 g of carbon-12 and you want to know how many atoms of each you have. oms there are in a certain mass of 7) SO eo eecri How many moles of zine are there in a 16.35 g sample of the metal? A,(Zn) = 654 Number of moles ~_ 16.355 ESagmelt = 025mol of zine in 16.35g ‘You would divide the mass of each element by its molar ‘mass and then multiply by the Avogadro constant: A2C) = 12 Number of moles 6g =0.5 mol 12 g moh ‘Therefore the number of carban-12 atoms = 0.5 * 6.02 x 10° = 3.01 x 10 A,(Ma) = 24.31 Namber of moles 6g = 0.25 mol 243 g molt ‘Therefore the number of magnesium ams = 0.25 6.02 10% = 1,505 = 1025 You cun see from this that 6 g of magnesium hus half as muny atoms as 6 g of curbon-12. This is logical given that the magnesium atom has tice the mass of carbon-12 atom. We can also say that 6 g of magnesium is 0.25 of a mole of magnesium and 6 g of carbon-12 is, 0.5 of a mole of earbon-12. {ig 1172 Counting atomais ite counting these sweets The quickest way fo weigh therm ~ but we need to know how rch each individual scat, oeatom, weighs fisteee ‘A great deal af science is based on measuring physical quantities, The units of mass and density ilustrate how such a lrgth and mats, sing a number combined with sunt. For baze unite and derived units are related. cexzrrple, a length may bs quoted az 25 km of 2500 m.To make commurication between sientits and engineers eae, a cornmien aoe system of urits is now in use in the word of science. This system is A ane nene res ie rest eine are ‘alled the Systeme International (SI), and it consists of a set of seven een ‘base units. The base S nits are the mesre(r, the kilogram (kg) the Volare is expressed as metres cubed (m3). second (the ampere (A) the kelvin (k), the candela (cd) and the smoke (mol All other measurements relate to these in some way, ard 0 they are known as derived urits, + Mass has the unit flogrars (kg) in the SI So the units of ders ae kilograms per metre cubed. This may be rritten es kilogrems/metre3, gin? or kg m3. {in chemistry you are more Uikely to use the smaller derived unit of g ern-3 for density) {tis tempting o assume that bese units such as length and mass ae absolute and unchanging, tut ite that simple. For exarple, as you ‘vf Fig. 1.1.11 the standard kilogram i constantly losing mass There is an identical, cinder stored in London and the two are compared reqarly. The Pars standard has lost 50 pats per illon compared wth the London yliderScerss dnt know i the loss is due to pollutants when it was forged solvents used to clean i or because on rare oczsiors thas been hardled. The quantity i: very small (ess than the mas of again of sug) soit dors matter when you buy a kilogram of apples, but in the scientific world it is very important. Now sclertists are looking at new ways to cere the {ig 1.113 Althoce cs mess ime but do they mesure sng the ‘logyam, including relating i to the mass ofan tat Istana secant? tr. Progress will be reviewed in 2011, aa Use the data in the pericdic table at the back ofthe back to help you. 1. Calculate the number of moles in: 2 BOgof oper 16 ators b 48 of carbon-12 atoms © 888 zof chlorine ators. 2 Calculate the number of atoms in: a 38g ofcarbon-12 b 4 gof magnesium-24 © 532 gof caesium-133 57 goflead-208TR cd Using moles So far you have used relative atomic mass, the Avogadro constant and the mole for calculations involving atoms and elements. Now you can apply these principles to compounds as well. Relative formula mass and relative molecular mass For a compound, the sum of the relative atomic masses of all the atoms in the chemical formula is called the relative formula mass, In covalent compounds that are made up of molecules, this is referred to as the relative molecular mass (M,) he relative molecular mass can apply to elements as ‘well as compounds, Most gaseous elements exist as diatomic molecules, eg oxygen, 03. Relative molecular ‘mass is used rather than relative atomic mass for practical chemistry: M,(O,) = 32. CColeulate the relative molecular mass of carbon dioxide. A(C) = 120 and A(0) = 160 (to 1 decimal place). M{cO,) = 120+ (2x 160) = 440 For ionic componnils the relative formulls mass is calculated in the same way, using the formula, Relative formula mass for NaCl = 4,(Na) + 4,(CD = 23 +355 = S85 ‘The relative atomic mass can be used for ions because the atoms have simply lost or guined electrons, which have virtually no mass. More about molar mass Like relative atomic mass, the relative molecular mass or relative formula mass does not have units. By eliniion, the relative molecular mass of a substance in grams contains one mole of molecules of the substance ~ so 44 g of carbon dioxide contains 6.02 < 1023 molecules of CO;. Once agsin the molar mass is the relative molecular or Formula mass in grams per mole. It tells you che number of grams of thar substance that makes up one mole, eg the molar mass of carbon dioxide is 44g mol"! and the ‘molar mass of sodium chloride is 58.5 g mol"!. fig. 19.14 One mole looks very eiferent cepending on hich ‘compound you are considering. A student plans an experiment that uses 0.2 mol of ‘calcium phosphate, Ca,(P0,).- How many grams of calcium phosphate need to be weighed out? Adatve formula mas [Ca(?0,)] = A(Ca) «3-4 2x40) +4 A(0)] = (40.1 x3) +2 [310+ (4% 160)] = 1203 +2 x (31 + 64) = 3103 MicafPo,),) = 3103 gre 1 mol of calcium phosphate has a mass of 3103 g,50 02 mol would weigh: 3103 g mol" x 0.2 mol = 62.1 g (to 1 decimal place) Always check that your answer makes sersel A tenth (0.1) of a mole would weigh about 31 g. 0.2 is twice as much as this, so an answer of 62.1 g seems reasonable More about moles and equations In an equation, the symbol for an clement stands for two things ~ un atom of die element and a mole of atoms of the element. For example, when carbon buras in a limited supply of oxygen to produce carbon monoxide, the exjustion tells you the reacting quantities:2C@) + O,@ > — 20%) Zatoms + 1 melccule > 2 molecules 2 mol of atoms + 1 mol of mokcules > 2 mol of molecules I also telly you the state (Gulld, Buu, gas or agueuus ions) of the reactants and products It is important to specify precisely which particle you mean Whenever you use moles, eg does ‘a male of oxygen’ mi Giving the formula or clearly stating the particles, involved avoids this confusion, oxygen atoms or oxygen molecules? From equation to react Using moles sont can work out from a chemics! equation the quantities of reactants vou need to carey out the reaction. For example, how much magnesium and oxygen do you need to make one mole of magnesium oxide? The equation is: 2Ma) + 0, > 2MZOG) 2mol + ima > 2m 2x 243g mur) + G2gmu) > (2 * 40.3 g mot!) So 48.6 g of magnesium needs to be reacted with 22 g of oxygen (in practice, oxygen would be in excess) to make 80.6 g of magnesium oxide fig. 1.15 The bight white light produced when magnesien rects ‘ith oxygens used in reworks and fares. Calculations Tike these are carried out at an industrial level as well as in the school laboratory to determine the quntitics of raucting chemicals needed. For exampl sar one UK-based fertiliser company produced 650 000 tonnes of ammonium nitrate. This is one of the world’s leading fertilisers. ‘The final stage involves reacting ammonia with nitric acid: NH,(@) ~ HNO, (ag) > NH,NO, (sa) fie 11.16 Chemistry on this scale reeds careful sicuation 0 no reoctnes oe wert, ‘The industrial chemists need to know exactly how much ammonia and nitric acid are needed to make 650 000 tonnes of ammonium nitrate, They start off with lab-sized cuantities and work up! | mol of ammonia reacts with 1_mol of nitic acid to produce {mol of ammonium nitrate, Calculating molar masses ives: (MOH) = 17 ¢ mor, M(HNOs) = 63 g mol"!, M(NHNO3) = 80 g mo 17 g of NH, + 63 g of HNO, > 80 g of NH,NO, 17 kg of NH, + 63 kg of HNO, > 80 ke of NH,NO, 138 125 kg of NH, + 511.875 kg of INO, > 650 000 kg of NINO; The mass of nitric acid needed will actually be even Jager because the acid is in aqueous solution, Reactions with gases ‘Many chemical reactions take place between gases, oF involve gases 8 one of the reactants or products Rather than weighing gases, itis more convenient to meesure their volume, Provided that you are carefull to sinte the temperature and preure of the gus wheal you give its volume, this is quite straightforward since + One mole of any gas occupies 24 dm? at 25°C (298 K) and 1 atmosphere pressure.TR cd ‘At the end of the eighteenth cantury, the English scientist Henry CCavendich artablished that whan the gases hydrogen end onygen react to form water, thay always react in the ratio of 2:1 by volume, Ths work was repeated and extended by the French chemist Joseph-Louis Gay-Lussac. In 1805, Gay-Lussac published his fincings. He ciscovered that when gases react, their volumes are simple ratios of whole numbers, proviced that they are ‘measured under che sare conditions of temperature and pressure. Zvclumesot + yolumeot_ «> —_zvalumes of hyogen| oven wiaterapoar woke + Solumescf 2am of snerogen tyrone Semone ig. 12.17 The volemes of roasting gases re always simple ratioe of whole umber. ‘The allan chemist Amedeo Avogadro selzed cn Gay-Lussacs work ‘and jn 1811 published his law (now named for Kim as Avogadro's law) Avogadro's law states thst: Equal volumes ofall gases contain equal rumbers of melecules, ‘provided that they are at the same temperature and pressure. By interpreting Gay-Lussac's workin this way. Avogaxto provided chemists with a very powerful practical tool for meesuring gases. How docs Avogadro's law explain bow gascs reves? ake the synthesis of ammonia from nitrogen and hydrogen as an example. Experiment showed that: 1 volume of nitrogen + 3 volumes of hydrogen > 2 volumes of ammonia Using Avogedto’s ideas, it follows from this that if one volume of any gas coninins 7 molecules, then: Jnr molecules of nitrogen + 3” molecules of hydrogen > 2n molecules of ammonia From which: 1 molecule of nitrogen + 3 molecules of hyuregen > 2 molecules of ammonia So the chemical equation for the reaction ean be written as: NXg) + 3Hy(@) > 2NH3(@) ‘Avogadro's theory was not generally accepted for many years, for 2 rumber of reatons Dalton's atomic ‘theories, on which Avogadto built his ideas, were sill, very new Avogadro's ideas were largely thecretica, vith relatively little laboratory work to back them Uup—and he was not known as 2 careful researcher! He published his ideas in relatively minor scientific Journals which many people dd not read, and he didn’t ite particularly dearly so not everyone Understood what he was tying to say Finally, his ‘ideas vere in confit with some of the best-known sciortists of the day so many people ignored him to avoid rocking the boat It was not until the middle of the nineteenth century that Avogadro's ideas were ‘accepted by the majonty of chemist. og. 1.1.18 Amedeo Avogado, count of Quregna (1776-1856), Avogrea stared out 2 lawyer but quickly ‘turned to chemisty, applying a mathematical approve f0 ‘combining volumes of gases, aorg other things. The power of Avogadso’s law lies in dhe fact dat it allows the masses of the molecules in two gases to be compared simply by teking equal volumes of the gases and comparing their masses, This enables chemists to mesure the relative molecular masses of gases, and so to determine their formulae. Molar volume ‘One of the major implications of Avogadro's law js that one mole of any gas must occupy the same volume under the same conditions ~ this is the molar volume of the 4us, Viq- Scientists use the standard temperature and pressure (STP) t compare molar volumes. The (25°C). Under these conditions, the volume of 1 mel are 1 atm pressure and 298 K of any gus is 24 dm, or very close to it, How can we tise this information about gases snd molar volumes?8 ——————————————————————————Eyy Burning fuels 1 Coal Isa fossil fuel which Is made up of carbon. If 6 g ‘of carbon is burned, what volume of carbon dioxide ‘would you expect to be produced at 25°C? What ‘mass of carbon dioxide would this be? Cs) + O42) > CO,(e) ‘1mol of carbon atoms + 1 mol of axygen molecules 3 1 mol of carbon dioxide molecules A() = 120 (to 1 decial place) so 6g =a5ma Tegmor 5005 mol of carbon reacts; this mears that 0.5 mel of catbon diaxide is produced. (CO) = 24 dm at 25°C and 1 atm Therefore: lume of catbon dose produced = 24 dense 0S = 12m? M(CO) = 12 + 2(16) gmat" = 124 32= 44 gmolt ass of carbon dioxide produces = 44 gmol x05 mol= 22g eee Burning fuels 2 ‘Wren propane, CH, s burned in oxygen, carbon dioxide and water are produced: Hele) + 50,(@) > 3C0,{@) + 44,018) Amal + Smal > 3mal + 4 mol 1 30 em? of propane (measured at 25 °C and 7 atm) is burned in ait, what mass of carbon dioxide would you expect to be produced? 24d? of propene = 1 molar volume of propane 30 dn? of propane is 30/24 = 1.25 molar volumes + molar volume of propane burns to produce 3 molar volumes of catbon ciexde so: 1.25 molat volumes of propane > 3 x 1.25 molar ‘volumes of carbon dioxide = 3.75 molar volumes of carbon cowie This is equivalent to 375 molar masses, therefore Mass ot carbon dioxide produced = 3.75 (120+ 32) = 3.75 440 = 1653, 1. Define carefully relative formula mass. relative molecular mass, mclar mass ‘and molar volume, 2a Summarise Avogadro's law and explain wl is useful bb Explain why It took 50 years for Avogadro's ideas to become generally accepted by scientists 3. Methane (CH, burns in oxygen (0,) to form carbon diosice (CO) and water (4,0). ‘a Write a balanced equation for this reaction b How mary moles of each substence are involved in the reaction? ‘€ What volume of methane, oxygen and carbon dioxide would you expect at25"c? L(OH),{aq) + Hig) Wal disagrees He thinks t should be: Alils} + 2H,0() > 2UIOH(aq) + Hg) ‘They cared out the reaction inthe lab and measured the quantities of some ofthe reacting materials i fig. 1.19 Ts epparetus canbe used to collect the gs produced when itiur rect with water, or any ether reaction that ghee off gas 11 Calculate the mass of one mole ofthe following: 2 As,0, the arsenic of detective stris) bb Pot (uso in explosives to prime the charge] © CalNOy) (used in matches) d_ CalCgH,,NSO,), (calcium cyclamate, an artificial sweetener), 2 Aluminium oxide, ALO end hydrogen iodide, HI, react together as follows A1,04(9) + GH) > zAll,(oq) + 34,0(0) ‘a How many moles of hydrogen iodide would react completely with 0.5 mol of aluminium oxide? bow many moles of aluminium iodide would this reaction form? ‘© What mass of aluminium iodide fs this? ‘d_ What masses of aluminium oxide and hydrogen iodide would be required to produce 102 g of aluminium iocide? ‘Thay reactod C035 g of lithium with water and 60 em? of hydrogen was collected in a ga syringe. Use the data in the periodic table at the end of this book and this information to confirm the correct ‘equation for the reaction, M(Ui) = 69 g mot 0035 g = 0005 mal of lithium atoms 69 g mot 11 mol of hydrogen melecules has a velume of 24 dm? (= 24 000 em?) at 25°C 60 cm? of hycrogen molecuies 60 = 00025 mol of hydrogen molecules 24000 From this you can see thet when 0.005 rol of fhiurn reacts with weter, 00025 mol of hydrogen ges is formed. So when 2 mel of lithium reacts with water, 1 mel of hydrogen ga is formed. Therefore Wills equation is correct. 3. The substance ATP is important for ‘transporting energy in living cells. sample (of 1.6270 g of ATP was enalysed end found to contain 0.3853 g of carbon (105178 g of hydrogen, 02247 g of nitrogen and 0.2581 g ‘of phosphorus. The rest was oxygen. {2 Calculste the rumber of moles of each ‘element prosant in the sample of ATP. Calculate the ratio of the numbers (of moles of each element using the nearest whole numbers. © Write down the empirical formula ot ATP. The relative molecular mass of ATP is S507. What i its molecular formula?TR cd Measuring concentration 5 5(1 mab fect Moles in solution OPN ‘Many chemical reactions occur in solution ~ that is, with a solute (olid, liquid ar pas) dissolved in a solvent. Scientists measure the concentration a ‘of a solution using moles per cubic decimetre (mol dm™), \ ere eee (soos) pdms est eo mn ten ae YY 1 litre = 1000 cm? = (10 em)? = 1 dm? reltodere” weiter” Ta make a solution of ascurate concentration, you do not simply ealeuate the mass of solute you need then add it to 1 dm} of solvent ~ this would make a sohution with a volume greater chan 1 dm?. Tastead you dissolve the weighed solute in a small quantity of solvent, then sd more solvent until the solution has a volume of exactly 1 dm?, ‘The symbol M (for molar) is sometimes used to mean mol dmv, and molarity is another word for 117g (2rrol of NaCl \ ri po \ | concentration in ml \ ) Molaity = moles of vite (= =) - [lane oF schuton Cam) = etree eserserl Tee erm anna eaten ORED Wi wo nats stesoale( canoes ise pees " Si Gee 1M (1 mol dmv), When making up solutions you add solvent up to the pee eee required volume. If the volume you need is not | dm? you calculate the Seeansane ras of solute accordingly Finding the mass of solute Inan experiment you need a 0.150 M solution of sodium chleride. How many grams of sodium chloride ‘would you need to make 500 cm? of 0.150 M sodium chloride solution? (NaCl) = 230+ 355 g mot“! = 535 g mot? (1150 mol of NeClis 58.5 g mot“ x 0.150 mol = 83 (10-1 decimal place) ‘Therefore to mate 1 di? of 0.1S0.M NaC! solution, you need to make 88 g of NaCl up to 1 dm? with water ‘To make 500 cm of 0.150 M NaC! solution you need 44g of NaCl. Finding the molarity IF you weigh out 10.60 g of sodium carbonate, Na,CO,, and make it up to 250 em? in a volumetric flask, what will be the molarity of the resulting solution? First work out how many moles of NezCO3 you have: HM(Na,CO,) = (230 x 2) + 120+ (16 x 3) got = 460+ 120+ 480 g mot" = 106 g mot"? Number of moles = 0.41 mol "Now substitute into the equation: Molarty= moles of solute O1mol =04N volume of solution (dm?) 025 dm?+ messuring out the mass of solute ~ inaccuracies in the balance: mistakes in reading ‘making up the solution ~ reading the levelon the volurnetric flask inaccurately so not adding exactly the right volume of solvent, not washing al of the solute into the solution + changes in temperature ~ the volume ofa solution changes as temperature goes up In any scientific investigetion you need to be aware of any limitations in your technique ard the types of errors and inaccuracies that can ereep in. Then when you evaluate your method you can make realistic suggestions to improve i in future. There 2re a number of sources af inaccuracies and eres when making tp elution: fig. 1.21 When working with 4nd down. You should ote dovin the temperature when you make up a solution and ivtens you need toremember al its concentration will enly be accurate at this temperature ‘the possbie sources of ear. ig. 79.22 For kidney patents, solute ae hep at the correct concentrations in th blood wigan artical ood tering system known as daly. ae dake co xact concentrations are very important in medicine. For example, the concentrations of sodium and pozassium ions in your blood are vital forthe regulation of your blocd pressure and the working of your nervous systern Your kidneys control these concentrations — If levels in your blood are not normal this stows that your kidheys are rot working property. The team at the renal unit at the Royal infirmary of Edinburgh have developed a website “which allows patients to see what doctors are [coking for ina biood test. Table 1.1.5 sows the normal ranges for a number of chemicals found in your blood, The quantities ‘measured are very small They include mleremoles (1 pmol = 10° rrol) ard mrilimotes. (1mmol = 19 ro), Sol mers Cesainine (a ace prosuct of muscle metabclien) 60-170 pmal dev? Urea (¢ waste preeierof protein metabolism) 35-65 mmol dar Na" (sodumiens) 135-149 mmal dar? 1 (potassium ons) 35-50 mmol dir {able 1.1.5 Normal ranges fr some blood solutes. You can use table 1.1.5 to calculate the amount of the citferent substances in your bol. For example, an average person has 5 dof bicod. What is the minimum ‘mass of sodium for in the blood of an average person? | mol of Na has a mass of 23 g I mmol of Na? has a mass of 23/1000 8 Minimum Ne* concentration is 135 rao! dor? So in 1 of blood there wil be 135 x 23 gof sodium ion 7000 3105 g So the minimum mass of sodium ions in 5 cr? of blood Is 3.105 x 5 = 15.5258,eee Sipetabe aia fig 1.1.23 Foo labels can give al of Information but how ahi it? Other units of concentration Percentage by mass Sometimes molarity is aot the hest measure of concentration to tse, eg You muy need » quick comparison rather than calculating the sumber of atoms or roles involved, ‘A simple way of expressing concentration is as @ percentage by mass or volume. To find the percentage by mass, vou divide the mass of the solute by the mass of Ge whole solution and muluply by 100: Percentage by mass = mass of solute x 100% ‘mass of solution For example, if 100 g of solution contains 15 x of sodium chloride, the percentage of sodium chloride by mass fs: 15g 100% = 15% by mass 100g Percentage by volume ‘For a mixture of two liquids or two gases, the percentage by volume can be useful Percentage by volume = volume of one component » 100% Total volume For example if you mix 5 cm? of ethanol with 43 em? uf water, the percentage by volume of ethanol would be: Som? x 100% = 5 x 100% = 10% by volume 5+ 45cm 50 In recent years people have become more aware ofthe role ofa healthy det in reducing the risk of problems such as hear: cisease, diabetes or tooth decay. Food ‘manufacturers now provide lots of information ~ range of food labels may tell, ‘you the percentage of certain nutrients in the food, or the percentage of your daily requirements of diferent nutrients the food provides, or simply the mass in grams cf different nutrients. This information may be presented esa table, a pie chart of a sirple ist — but how scientific, end how much help does it give? Gill Cowburn and Lynn Stockley from the British Heart Foundetion Health Promotion Research Group ar the University of Oxford locked at 103 research papers investigating how useful people found food labelling. They discovered that ‘many people claim to look at the labels, but relatively few actually understand all ‘the information, Pie charts ae of limited use unless the label explains whet they ‘mean. A comparison with the recommended detary inteke was helpful. Mary of the studies were poorly carried cut, and provided only self-reported dt — in other ‘words what people said about themselves and how they read and use labels, rather than the scientists observing what they actually do. They found very litte existing ‘evidence thet food labelling has any impact on the quality of ou diets,eee Parts per million For very small concentrations, percentages become les useful, eg 0.01% solution dificult © visualise, Parts per milfion (ppm) can be useful for aw concentration “To find the concentration in parts per million you divide the mass of the sotute by: the (otal mass oF the solution (or the gas mixture) and muldiply by 2 million (108), Concentration = mass of component 1000000 ppm mass of solution For example, if there is 2g of orgenophoyphate pollution in 1.5 million grams of solution (eg river water), there will be: 2g «1000000 ppm = 1.3 ppm of organophosphate pollution 1500000 2 fig 1.24 Amide scene — but ow clea the a? Some local sexiest he UK, seh 2s “Tameside, provide sir paliton levels on their waits, Parts per million are ofien used for levels of pollutants in the air or in water. Parts per billion and parts per tillion are alo widely ased when measuring polluting chemicals present at very low levels (see table 1.1.6). Sulfur dioxide (po, tess than 100 1c0-198 200-399 400 or more 15-minute averege) Ozone (ppb) less than SD (B-hour 50-89 (hourly average) | 90-179 (hourly 180 armor sunning average) average] (hourty average) Certo monoxide (ppm, ess than 10 10-14 15419 20.0 more hour running average) ngen dioxide (ppb, tes than 150 150-239 300-399 400 or more hourly average) Fine particles (yg m2, fess than $0 sera 1599 oD ormore 24 hour running averse) {able 1.1.6 Parts pr milion (gpm) and pert pr bllon (pb) are cften used forthe evel cf polutant ges, a you can se in these figures fom Tameside. Be 1A stock solution contains 10 ml dr? of hyerochiorc ‘cil 'Mhat volume of this solution should be &ssoive in eter to make 6 dr? of acd of ccneenttien 0.1 mol dr? ‘When solutions of potassium chloride, KCl and siver ritvate AgNO ae mixed together, a precipitate of siver chloride forms. ‘2 Wirte down a balanced molecular equation for this reaction. In an experiment, 240 cm? of 005 M siver nitrate solution actly reacts with 15.0 em3 of potassium Chloride colution.Calculate the molar concentration ‘of the potassium chiorde solution, How much KCI would be needed to produce 100 err of a solution of 3 Using the data for the Roya Infirmary of Edinburgh (cable 11.5), calculate the maximum and minimum ‘mess of potessim fons you would expect to find in 1 dm? ofthe blood of ahecltay individual. 2 Why are sel-eported data a poo bass for research evidence? 'b- What studies would be needed to determine i foad labeling has an imoact on detary choices? 5 Using table 1.1.6 42 What isthe minirrum ras of CO you would expect to callect over 24 hours of very high ir pollution? Ie ficult to assess which polutant is the biggest probiem in Tameside. Wnat other factors sma the data more complex? GlTad Equations from precipitation reactions Another way of using calculations to confirm chemical equations is using precipitation reactions. For example, ‘when you mix colourless solutions of potassium indide, KI and lead nitrate, PoQNO3), # bright yellow previpitate forms. This ip lead iodide, Poly. The other product of the resction is soluble potassium nitratc, KNO,, You can filter out the yellow precipitate, ‘then evaporate the solution to dryness to obtain the ‘white solid porassium nitrate. The reaction can be represented by this unbalanced equation: Kea) + PbONO.) (aq) > PbI6) + KNOs(aq) How ean you work out experimentally the proportions in which these compounds react together? Put 5 em} of 1.0 M KI(aq) into each of seven Gifferent tse tuber. Add 0.5 em? of 0 M POGNO;)(ay) W Lube 1 Add 1.0 em? of 0 M PlONO;)a(aa) to tube 2, eliiilll More ways to calculate equations + Add 1.5 cm? of 1.0 M Po(NO,);(aq) to tube 3, etc, +A yellow precipitate of lead iodide forms in each tube, Place each tube in a centrifuge and spin for the same length of time. + Measure the depth of the yellow precipitate in each tatbe. The depth is a eure of the muss of the solid lead indide precipitated in each me. As the volume of lead nitrate added increases, the amount of lead fodide produced increases too, shawn by the increasing depth of the precipiuate. This continues ‘until 2.5 cm? of lead nitrave has been added, alter which, the amount of precipitate produced stays the same. ‘This tells you that all the reacting particles in the potassium iodicle have been used up. So $ * 103 mal of KT just rencts with 2.5 x 10° mol af Pb(NO3)> ‘The reactants are in the proportion 2:1 — so 2 mol of potassium iodide reacts with 1 mol of lead nitrate. You know the overall equation for the reaction, so from this information you ean work ut the balanced eguation. 2KItaq) + Po(NO;),(2a) > PbI;{s) + 2KNO5(za) ‘This is a very simple example for which ‘you could have writen a balanced ‘equation from first principles. However, it shows hew the method is used for more complicated reactions witen you do not know the products or the proportions in which the reactants reuet. tase tle ‘Bete nae ‘Siatonses inaitese ete fig, 1125 Youcanuse the dopth of precipitate Peon produce os @ measure ofthe mass of notable product. — SS SSS) 5 5 5 5 5 5 5 Number of moles of Kt 5x13 | 5x10? | Sx103 | 5103 | sx103 | Sx103 Sx 103 Volume of 10M Pb(NO,), (em!) | os 10 15 20 25 30 35 "Number of moles of Pb(NOs)_ 0Sx104) 10x10 18x10) 20x10) 25x 103] 30x 107 35x 107 Depth of precipitate (mm) 5 6 8 10 2 w w table 11.7 The depths of preiitate produced when diffrent voimes of 1.9 M PEIN.) (eq) are added toS crn? of 10M Kil)aD pa ard ‘You can carry out a similar investigation {yourself to determine the aqustion {or the reaction between potarslum chromate and berium chleride : ) eee Pie acute ) | Yaj]_—_————— Many errors might cast doubt on the validity ofthe results oF this ‘experiment, eg the height of a preciptate is affected by the shape of the tube (coe Fig. 1.1.26). Once the pracipitate rascher the straight part of the tube, the results become much mare reliable ~ but ven then factors sich as packing of the precipitat= and whether the test ‘tube is upright could cause unreliable results to creep in Us oT 2S fig, 1128 The depth of precitate must be tneesuted ot the sme place in eae tube for Fobable rete elle ‘The labels of medicines show the ermourts of the diferent ingredients eg ron tablets may contain 200 mg of ion, or & painkiller may contain 500 mg of paracetamol How accurate are they? You can check the iron content of, inon tablets by grinding up a couple of tables, dissolving ‘them in dilute sufurc ac and then titrating the solution ‘against very dilute potassium mangenate(V/) solution, The lend point of the experiment is when the frst permanent purple colour appears. Comparing class results after such an investigation, you will probably see considerable variation in the amount of ron ‘ound inthe tablets. This alses several questions. + How much ofthis variation is due to experimental eror, and how much to variation in the tablets? Think of possible experimental ero. + Hon euch variation do you think fe acceptable in the tablets? In the pharmaceutical industry the amount of variation tolerated changes from chug to drug, from 99-1019% of the stated value of active ingredient present ‘to 95-105%. This latter igure gives quite a wide range. How can you have 101% —or 1059 ~of the stated dose? ‘Most quality control in the pharmaceutical industry oes not involve titrations or other simple laboratory techniques. They are simply not reliable encugh ~ particularly when working with medicines that are needed in micrograms or where an overdose might be harmful. Quality contol is ensured in a number of ways. ‘The precise quantities of ingredients for any batch of ‘medcone are measured and recorded. Then random samples from each batch ~ 10-20 tablets for example ~ are selected and tested, The tablets or other medicines are crushed if necessary, and disslved in a known solvent {often methanol). This is filtered ané then diluted, Standard solutions are made accurately using pure active drug to a precise cancentration. Bath the random samples and the standerd solution are passed through a high-performance liquid chromatograph (HPLC) and the quantities compared HPLC 's widely used to check the quantities of active Jngredients in medicines. The results of chis process show I the average content oF the medicine Les within the accepted limits of variation. QOD 1. Using table 1.1.7, draw a graph of depth of precipitate ‘explain how your graph can help you write a balanced ‘equation for the reaction. 2. Why might a wider level of variaticn be acceptable ‘over-the-counter medicines than in prescribed drugs such as cancer treatments? volume of lead ritrate solution added andThe yield of a reaction Suppose you wanted to make $0 g of capper by reacting black copper(I) oxide with hydrogen: CxO@ + Hye) > Cuvs) + HOM Looking up molar mases and the molar volume of a fg3s, yinu shoal be able to ealeulate that tor make 50g. of copper you would react 62.6 g of black copper(Il) oxide with 18.9 dm? of hydrogen. However, this calculation assumes that all of the copper(I) oxide will be curned into copper ~ that the yield of the reactioa will be 100%. Yiells approaching 100% are very rare in practical chemical reactions for various reasons. The reactants may aot be pure. The reaction may not continue until all the reactants are used up because it is an equilibrium reaction (vou will look at this later in the book). Some product is always left behind on the zpparatus. Volatile products may evaporate. And human error is often 2 factor! The yield is very important. In this example, if dhe practical yield was likely to be 50% (only half of the copper(I) oxide was converted into copper), you would need twice as emuck copper(M) aside as you have ealeulated to make 50 ¢ of copper ‘You can find the yield of a chemical reaction very simply ~ eg the formation of copper sulfate from this reaction: CuOG) + H,SO,(eq) 3 CaSO,(eq) + H,00) As black solid copper(II) oxide is added to the sulfuric acid, it reacts to form a solution of copper sulfate, which is blue. Eventually all of the sulfuric acid is used up, and any further copper oxile added simply remains us a black solid, which is insoluble in water. The solid copper(II) oxide ean then be filtered out, leaving a solution of copper sulfate. ‘The water ean be removed from this solution by evaporation, leaving blue crystals of copper sulfate, CuSO,.5H,O. 7 Cee A student reacted 6.4 g of copper(l) oxide with ‘excess sulfuric acid and obtained 14,7 of blue ‘copper suifate crystals. Calculate the yield, The balanced equation shows that 1 mol af copper) ‘oxide shoul produce 1 mol of copper sulfate enystals M(Cu0) = 635 + 160 g mot" = 79.5 g mot M(CuSO, SHO) = 635 + 32.1 + (4x 160) + (8x 180) grrot* = 2495 got So 795 of copperil) oxide would produce 249.6 g of blue copper sulfate crystas if the yield of the reaction was 100%, The number of moles in 64 got copper) oxide = 64g = 008 mol 795 gor Fer a yield of 100%, this weld produce 0.03 mol oF copper subate crystal. 0.08 mol x 2496 gmat! = 200g (101 decimal place) But the actual mass of blue copaer sulfate erystals produced was 14,7, a yield of: 147g % 100% = 73.5% 2s Double salts Double salts are crystals that contain so different salts in @ 1:1 ratio. The alums such as KAMSO,),-12H,0 containing hycrated potassium and, aluminium sulphates are one example. Ammoniam iron(ID) sulphate, (NH,),SO ,.FeSO,.6H,0, Is another example of & double salt You can make ammnontum iron) sulphate in the laboratory from frst principles using iron flings, sulfuric aid and and dilute ammonia. You can ‘calculate the thooretical and actual yield of product.The idea of atom economy ‘The concept of atom economy was developed by Professor Barry Trost (1941-) at Stanford University in the USA, He argued that what really mattered in a reaction was not the overall yield, but the number of reacting atoms that ended up in the desired product, Any ather compounds produced are by-products (often waste) which need to be disposed of and are therefore: bau for the environment, A reaction with good ator economy is very efficient at timing reactants into desired preduets with litle waste. Atom economy (“%) mass of atoms in desired product x 100% ‘miss oF atorns in ea is In practice, to compare these masses of atoms ‘we use the relative formula masses OF the chemicals involved. Professor Trost wus warded the Presidential Green Chemistry Challenge Award in 1998 and his ideas are increasingly applied 1 industrial processes around the werkl, ig. 11.20 Gay Trost fist developed the ides of ator economy. OED 1 A.chemist mixed 1200 g of phosphorus with 35.5 of chlorine gas to synthesize phosohorus (I) chloride [phosphonis trichloride) The yild was 42.4 of PCL. Calculate the percentage yield for this action. The equation for the reaction is 2042) + 2Ch(g) > 20c1,() 2 Z-bromo-2-methylpropane, C,Hy6r can be used to produce methyboropere, C,H 2-bromo- rethyloropane rescts with sodium ethoxid, NaOC;H, to produce ethanol, CH,OH and sodium bromide, Nar along with methylpropene. Using the rolative formula macces ofthe reactants and products work cut the ator economy for this reaction, eee eee rk eed Ibuproten s a widely used painkiller. For many years it was made by a sx-ste9 methad developed in the UK in the 1960s, However, the atom econoriy of the process was only 40% —which meant 6O% of the reactants ended up as waste products Relative formula mass of reactants = 514.5, 06 Relative formula mat af ibuprofen Relative formula mass of waste products = 3085 ‘Atom economy = 205 x 100% = 40% 5145 fig. 11.29 Around 13 milion kibgrams of buproten ave made ‘each year The old production method made almost 20 milion ilopoms of worte products - sigh environmental price to ‘ures Reacche! In the mid-1980s scientists worked hard to develop a new, greener way of manufacturing this useful drug By the mi-190s they hed a three-step process in production with an atom economy of 7736,When you ‘also consider that one of the by-products in the fst step isethanoic acid which can be recovered and is itself 4 useful end-product, the atom economy becomes an. Impressive 9956. This new synthes' substantially reduces, the environmental impact as well as inoducing fnarcial economies into the process. Relative formula mass of reactants = 265 Relative formula mass of ibuprofen = 205 Relative formula mass of waste product 1% « Atom economy = 205 x 10 265Unit 1 The core principles of chemistry 2 Energetics and enthalpy changes Energy and energetics Tn this chapwr you are going 1 100k ut one of the most important areas of chemistry ~ the energy changes in reactions, and how these energy changes reflect changes at a molecular level Energetics is the study of energy transfers beeen reacting chemicals and their surraunelings. In chemical systems, the most common way of transferring energy is by heating. Remember that this means the increased jostling of molecules that causes other molecules 19 vibrate more, Tt is not dhe movernent of something called ‘heat’ ~ heat is a form of energy, not a substance. ‘The study of these energy transfers is also Known 35 thermochemistry. Exothermic and endothermic reactions For some chemical reactions to happen, they need energy from heating. Other reactions release energy as heat. A reaction that needs energy from heating to take place is endothermic (‘endo’ means within), and one that releases energy ay heal is exothermic exo" means, out). Whether a reaction takes in or releases energy depends on what happening to the chemical bonds in the reacting particles. Separating atoms or oppositely charged ions requires energy, while joining oppositely charged ions or atoms together releases energy ~ in other words: + Bond breaking requires enemy while bond making releases energy Both bond breaking and bond making happen in any chemical reaction. Whether the reaction is endothermic or exothermic depends on the balance beween the nergy required te breek bonds and the energy released when new bonds are made. Different bonds have different energy requirements for making and breaking, ss you will se. Energy changes in exothermic reactions In un exothermic reaction the energy relewed by bond formation in the praduets is grester than the energy needed to break the bonds in the reactants, In the exothermic reaction of the combustion of methane: CH, + 20,(¢) > CO,(@) + 21,0%) heat is given out. More energy is released when the new bonds sre formed in the products (carbon diowide and water) than is requiredl to break the bonds in the reactants (methane and oxygen) and the reaction’ products store less chemical enengy than the reuctants, ‘Neutralisation reactions between acids and alkalis are also exothermic, and the rise in temperature produced during the reaction can essily be measured in the lab. Energy changes In endothermic reactions Im endothermic reactions the energy required to break the bonds in the eoctants is greater than that released when new bonds are formed in the products, so the difference is absorbed from the surroundings. Fndothermic reactions are less common than exothermic reactions, For example, the thermal dlecompesition of calcium carbonate to caleium oxide and carbon dioxide is an endothermic reaction Photosynthesis ~ the process by which plants make glucose ond oxygen from cerbon dioxide and water using energy from the Sun — is also an endothermic reaction, ‘ig. 12.1 Photosynth perhaps the best krown and most [portant endothermic reaction on EarthEnthalpy changes An exothermic resection releases energy to the surroundings in the form of heat. ‘This energy is known as the enthalpy change of reaction (previously called the heat of reaction). The reaction in which the changes are happening is known as the system. Outside the system, everything else is known as the surroundings. Tn the example of the reaction of hydrochloric acid and sodium hydroxide, the acid, the alkali and the products of their reaction are the system, The test tube containing them, the person holding the test tube and the entie rest of the universe are the surroundings. We think of the system as having a boundary which separates it from its surroundings. Sometimes this is a physical boundary ~ if it prevents particles from cmtecing or leaving the system, the system is said 10 be ‘elosed. IF the boundary also prevents energy from entecing or leaving the system, the system is said 10 be isolated. However, in most cases the boundary does not physically exist but is just « theoretical distinction enween # system and its surroundings. Suroundings—anythingin the Univers tht isnot nthe system ie. 122 Inthennochemisty Boxer thi separates we study the energy the system rom the rest ansterstemeen systen —Sitheurivne adits sercundings. TO Reena All of the energy that leaves a system is transferred to the surroundings (or vive versa). Phe first aw of thermodynamics states that + Energy cannot be created or destroyed, ‘The energy that is transferred to the surroundings is not lost to the universe ~ it is dissipated, or spread ‘through the surroundings. ‘This is an important principle in the behaviour of the universe which is usually called the principle of conservation of energy: + The total energy content of the universe is constant. =D 1 Describe at the particle level what happens when energy Is transferred as heat irom a reaction to the surroundings. 2. What is the differance betwean an endothermic and an exothermic reaction? Explain how this ditterence arises. 3 Use fig. 1.2.3 to help you answer the following ‘Reaction time Reaction time ‘09.122 The temperature changes curing swo chemical ‘a Which of these reactions s exothermic ané Which Is endothermic? Explain your reasoning, What wes the termperature change in the ‘exothermic reaction and the endothermic reaction?TOR Coa How much energy is transferred? ‘The amount of energy transferred in a given chemical reaction depends to some extent on the conditions ‘under which the reaction occurs, Most chemical changes tke place at constane pressure, eg ian open test tube. Chemists define the energy content of a system held at constant pressure as its enthalpy, represented by the letter HL. You cinot measure the enthalpy of 2 system — bat fortunately this does not matter! What you really want to know ss the enthalpy change during a reaction. his is a measure of what the reaction can do for you (or even in some circumstances, what it can do 10 you!) under conditions of constant pressure, When f system reacts at constant pressure and gives out or takes in energy, we say that it undergoes an enthalpy change, represented a5 AF H, AP Frcoduces — YG a 5.12.4 When buring petal in 2 car engine you relly donot care hat the toa enthalpy fs iter before o fer the rescten Al thet ‘matters isthe change in enthaly, since this sth only energy thats ‘ible to you Enthalpy level diagrams For exothermic reactions, the enthalpy of reaction is negative, showing that the energy content of the system hhas decreased ~ some energy has left the system ancl centered the surrounclings as beat, The energy released when bonds form in the products is more than the energy needed to break the bonds in the reactants H, Hrcsctans 50 AIL is positive, Daring an endothermic reaction, enengy’ is transferred from the surroundings and there is a net inerewse in the potential energy af the system. The enthalpy changes involved in reactions can be represented in an enthalpy level diagram. nan exothermic eaction the vernperature ofthe produc higher than the temperate ofthe sartoundngs nergy 26 het transferred to thesrroundings asthe pradicis ol, Exthalpy A = Hpraducte~Hreactarts products Represersing an exothermic reaction using anerthapy level diagram Inanendatheriereseion the temperstrn of the products [Gwes the the termperatre ofthe surounding Energy a est ' wansfered em the sevoundings asthe produ's am Up. produc Enthlpy SH = Hprocuets~ Mreactans reacants Represrcing an endotherricreacton using anerthapy level diagram {ig 125 Enthalpy level diagrams show the enthalpy changes fn reactors,pr raed Hest packs ‘One common example ofan exothermic reaction isthe heat pacts used by sportspeople to relax their muscles. o Enthaloy eee ete patria geese eae Scene furebyiy ont eer een eee eee ener eens nara ning ths od choco bred perforated bag. This is in an initially sealed bag which Tesh op ep aed yee ne earn ae eee ee Seed decal “4Fe(8) + 30.48) > 2Fe,0,(5) Cold packs Cold packs may be used to treat injury One type wes the endothermic reaction that happens when ammonium nitrate and water are mived. NH4NO.(s} > NH4*(eq) + NO- (aq) Nag) NOS Lea) x Fathalpy NHN) io. 12,7 Cold packs canbe ied to help reduce sveling ad halp recovery in spore injuries. They depend on andatheric reactors, DCE Ty “lives? After heart attack, brain cls die within rrinutes because they lack oxygen forrespration. The adds on surviving @ hheatt attack alter becoming comatese ere not very good ~ 7536 die then or soen afterwards but occasionally, when people'drown’ in very cold water, they survive for ‘more than half an hour without breathing, Their cooled brain tissues need alot less oxygen. ‘At the Dandenong Hospital, Australis, doctors recently tested to sc if mild hypothermia (cooling the bod) would help heart attack patients. On odd-numbered days comatose heart attack patients were cooled with ice packs on resuscitation and their core temperature ‘pt low (32-34 °C) forthe next 12 hours. On cever-rumbered days, patien:s were kept warm after resuscitation, Of the 43 patients cooled, 21 (49%) went back home or for rehabilitation compared with only 9 of the 34 patients (26%) who were kept warm. ‘A similar study at 80m University followed 273 patients with an average age of $8. Within 6 months of, their heart attack, 41% of those who received cooling ‘treatment died, compared with 55% of those who were ‘pt at normal body temperature That represents a 145% ‘increase in survival rate for the cooled patients. Among the patients that were cocled, 55% recovered wel ‘enough 10 live independently and work again, compared \with only 39% of those whe had not been cooled. As a result oF these studies and others, there is. a move ‘to design hoods and Blankets using cool-pack chemicals ‘t0-cool the body in emergency situations. OED 1 What ie the difference between enthalpy anc ‘enthalpy change? 2 What isan enthalpy level diagram and wit Ist useful? How does a cool pack work? resent the data on the impact of cooling on heart attack patients in the two studies graphically. How reliable isthe evidence collected? Evaluate the methodology of the trials described. PR ec nc aeTOR Coa Heat capacities and calorimeters ‘You will know by experience that different materials need dilferent amounts of heat to change their temperatures by similar amounts, The same applies to different volumes of the same material ~ it takes more energy to heat « bathful of water eo 35 °C than to heat a cupfil of water to the same temperature. The heat capacity, C of an object (or a bady of Tiquid or air) is the amount of heat required to raise its temperature by 1 K. The SI unit of heat capacity is the joule per Ketvin, JK r= ‘When measuring heat capacities you should use the Kelvin veinperature scale rather than the Celsius scale. ‘The Kelvin scale relates tothe average kinetic energy of ‘the particles and so reflects thelr movement ata given ‘temperature, ‘A absolute 2e10, 0K, the Kinetic energy of the particles is ze and all particle movements cease. the ‘temperature rises, the average kinetic energy gets bigher and particle movernents increase. So 2 ‘temperature change can be understood as a change in the average kiretic energy ofthe particles. Using the Kelvin scale helps build up an effective model of what is. happening when substances are heated. ‘Whilst heat capacity is useful to know in certain circumstances. it applies only to a single object. Specific heat capacity, ¢ gives the hest capacity per ‘unit mass of a particular substance, and is obviously more generally useful, [ty SI unit isthe joule per Ailogram per Kelvin, | ke"! K-!, Sor + Specific heat capacity is the amount of energy in joules @) needled to raise the tempersture of one Jslogram (kg) of a particular substance by 1 kelvin (K). ‘This allows you to calculate the amount of energy needed for a reaction. For example, for an endothermic reaction you can use the specific heat capacities of the substances involved and the enthalpy change of the reaction to find out how much energy ‘you need to transfer to the reaction. So if you represent the amount of heat transferred as [and the temperature change as AT: nergy transferred (J) = mass (kg) x specific heat capacity (J ke! K“)) x remperanure change (K) E=meST for a mast m of a substance with @ specific heat capacity In table 1.2.1 you can see some examples of the specific heat capacity of a number of sutstances. Pray Carton (graphite) orto x10 Copper 0.385 x10 Etharel 2440x107 Gold 129x108 water (bud) A181 x18 “XT Clee TOF ‘ble 121 Specific est eapstes, Measuring energy changes PD mies snail How do you measure the erthaipy change of 2 reaction? One widely used method invelves carrying, ‘out the chemical change in an insulated container called 3 calorimeter, and mossuring the temperature charge that results. simple form of this apparatus is 2 coffee-cup calorimeter’ which is just two expanded polystyrene cups, one inside the other, with ald. Because expanded polystyrene Is an excelent insulator «and also has a very low specific heat capacity, any ‘temperature changes in the calorimeter can easly bbe measured before the heat finds its way out of the «calorimeter. Errors can creep in depending on the ‘uniformity ofthe insulating cups and the insulating, properties of the lid, but the apparatus gives accurate enough results for most situations Figure 1.2.8 shows such a calorimeter, an the box on the rignt shows how Is used to make rreasurements. /we 5-128 Acoffeecup calorimeter Another simple way of ‘measuring energy charges ‘that can be carried cut in the school laboratory is shown in fig. 1.2.9.The heat given ‘ut by the burning fue is sed fo warm a known mass of water Ifyou measure ‘the mass of fuel bumed and the temperature rise of the water, you can work cut the approximate energy change that happens as ‘the fuel burs {the hest of ‘combustion. TO Reena ‘A student placed 25.0 em? of 1.0 M HCLin a coffee-cup calorimeter, and ‘measured its temperature a6 225°C, 25.0 cm3 of 1.0 M NaOH, also at 225°C, was added quickly to the acid. The mixture was sted and the final temperature was recorded as 29.2 °C. If the specific heat capacity of the ‘solutions is 4.2 | ~' K~" and if their densities can be taken as 1.00 g cm™, calculate the enthalpy change for this reaction per mole of HCl assuming ‘that no heat was lst to elther the cup or the surroundings. In the calorimeter. SO cm? of solution increased in temperature from 225°C ‘to 29.2 °C, a rise of 6.7 K (remember that 1 °C is approximately equivalent to. 1k). Taking the total mass of the solutions as SU g, the energy required for this. ‘temperature ses given by: E=meaT =SEx4Z1 ET KK OTK = 107) ‘The student used 25 cm? of a 1.0 M solution of HCl, so the number of moles of HC present fs 25cm? x 10mol 1900 cm? = 0025 mat So the enthalpy charge, Sper mole of HCLis ven by: v= 1407) 025 mol = 56.3) mot" (to 3 sigan gues) ‘The enthalpy chenge fer ths rection fs 56:3 kJ mol~! of HCL used. screen to feduce craps splat burer iui ue ‘ig. 1.29) thse another direc method cf calormetry which particulary users for measuring the nergy changes her Fis barnCSR CR fig. 12:10 Asyou saw in chapter 1, Information on foad packaging usally Inches the enegy ontent of tre food Ink. This erergy content iscalcuated by busing the food in bomb calorimeter “he process of respiration ts asiower verso af the seme reaction More accurate measurements — the bomb calorimeter ‘The calorimeter used to determine the energy change during a reaction accurately is known as a bomb calorimeter (60 calleel hecouse the sealed vessel in which the reactions are carried out looks something like a bomb) “This apparatus is particulsrly useful for studying the enthalpy changes when a fuel burns ~ and itis also used to find out the “calorific value’ (hat is, the ‘energy content) of food. Figure 1.2.11 shows a simplified diagram af a bomb calorimeter and explains how it works. Tn any calorimeter, however good the insulation, some heat ie transferred to the surroundings, which adls an element of inaccuracy and unreliability t0 the results. This heat loss can he estimated and corrections can be calculated to compensate for it. However, the accurscy can be improved in a more sophisticated calorimeter. For example, for a combustion reaction, the substance is burned in a bomb calorimeter and the temperature change is recorded and graphed. Then an elecirical heater is used 1 create exacly the same temperature change in the calorimeter. In this way the electrical energy needed to bring about the same temperature change can be caleulatedl tells you more accurutely the ergy change that actually oceurred during the reaction, because the measured energy change duplicates any heat losses from the calorimeter that occurred during the combustion reaction. So this method avoids the need for any heat lass calculations, Forreatiens tha vole sgisasa ectat lee Soper oreamburion ‘eutbre) the go enter ‘thebor ve tsa, ‘The themonerer . records he She simer ensures teenie the he vaterls of frente sta tniionn ee temper, lnslation The bors sarounded by ‘eater which ‘sorte heat From the reaction, “The hob The reactants ae put The elecea heating device Inhere andthe ber seed farts the reaction 1g. 12.11 The energy olacad by the chal rection inthe bem can be acute frm the tempereture rise ofthe water te speci heat capacity of the water andthe heat capacity of he tbamb and ts contents.RA aa Ga eee 9 ‘The enthalpy change ofa reaction depends on the physical ‘conditions of temperature and pressure, So cherists specify asetof standard coraitions under which enthalpy changes are measured.The standard conditions for ‘thermochemical measurements are agreed os: + 1.aum pressure and 298 & (25 °C). ‘An enthalpy change measured uncer these conditions for ‘a reaction is referred to as a standard enthalpy change Of reaction, nd is represented by the symbol AH® or sometimes aH (298 K) ‘The enthalpy change fora reaction obviously also depends on the quantities of materia reacting — eg if you are bbuming more fuel, the enthalpy change forthe reacticn will be greater. Unlike specific heat capacity, enthalpy changes ate expressed per mole of reaction as you sew in the worked example earlier, nct per Kilogram. ‘s well as temperature and pressure, you need to remember two o:her points about the standard conditions {ora chesnical reaction: PR ec nc ae + The reacting substances must be in thelr normal physical states under the standard conditions. Where ‘wo or mere forms of a substance exist, the most stable one at 1 atm and 298 K is used. So, for example, standard enthalpy changes involving sulfur relate to ‘thombic sulfur which i stable at room temperature, not monoclinic sulfur, which is stable above 95.5 &C + Where solutions are used, they should have a concentration of 1 mel drr-3, ‘so when you are presented with data from thermochemical ‘experiments you can assume that the reaction took place under stardard conditions cf temperature and pressure, that the physical state that is most stable under those conditions was used, and that the quartitos of reacting substances are now. You can alo assure that the measurements have been taken in a calorimeter that Is perfectly insulated so no hheat energy has been transferred elsewhere, Other possibie sources of inaccuracy, eg error in making up solutions or cooling alr currents that might affect reacings ee ignored. So when you consider the validity of any results, you need to beer these assumpticns in mind. \ 11 Why is specitic heat capacty a mich more useful measure than heat, capacity? 2. A gold sng ith a mass of 55 gis warmed up from 25°C to 28.0 °C ‘How much energy has been transferred to the gold? (specific heat cepacity of gold 129 Jg-*K"1) 13. Acoffee-cup calorimeter contains 55.0 em3 of dilute solution of copper) sulfate at 2 temperature of 228°C.A small amount of zine powder also at 228°C is added tothe solution. Copper metal is formed and the ‘emperatue of the solution rises to 32.3 °C. The copper sccllected, tied ‘and weighed, when itis found to have a mass of 0324p. ‘4 Calculate the total amount of energy released inthis eacton, jgnering the heat capacity of the zinc and the calorimeter. Take the specific heat capacity of the solution a5 42 J 7K". bb Calcuiate the enthalpy change forthe eacton per mole of copper formed 4. How might you increase the reliability ofthe data collected using: a acoffee-cup calorimeter the direct calorimeter shown in fig. 1.2.10?Unit 1 The core principles of chemistry Important enthalpy changes Representing standard enthalpy changes ‘You have seen that standard enthalpy changes of rection ure useful meusurements that allow you to ‘compare how much energy is given out or taken in at constant pressure by different reactions. ‘There tare a number of usefil enthalpy changes that we will be looking at here. Some of these can be forind experimentally, eg using a bomb calorimeter to tancard enthalpy of combustion others need to be calculated using data measured from other related reactions. determine the ‘A suundard enthalpy change may be presented like this: AHE{Cigraphite)] = 393.5 Kf mot! “This is what the symbols mean: + AH: enthalpy change + ©: this superscript indicates standard conditions 1 atm pressure, 298 K (25 °C) +: the subscript indicates the iype of enthalpy Change ~ C= combustion, £= formation, + negative numbers: exothermic reactions ~ energy i given out to the surroundings + positive numbers: endothecmic reactions ~ energy’ jg taken in from the surroundings. Fractions of moles Sometimes when you write thermochemical equations you may need to use fractions such as 0," This is so that you have the correct number of moles for the reaction. For example, if you are quoting the standard enthalpy change when carbon bums to form carbon monoxide (see below) you need 10 quowe the enthalpy change for burning, one mole of carbon, To get a balanced equation for the reaction forming carbon monoxide, you need half a mole of oxygen molecules (hich provides one mole of oxygen ators) Pent Standard enthalpy change of combustion Chemists detine the standard enthalpy change of combustion, AF, of x substance as the enthalpy change that happens when one mole of dhe substance ‘oxygen under standard is completely burnt conditions. The term ‘completely burnt’ is important, because many elements form more than one oxide. For example, carbon ean bum to farm two oxides: Cigraphite) + 40,(8) > COC) Cigraphite) + O3(8) > C032) Complete combustion of carbon produces carbon dioxide ~ so it is the enthalpy change in the second process that is the standard enthalpy change of combustion of carbon. In ‘chemist’s shorthand? this i: AH{C(graphite)] = -393.5 KJ mot! (ig. 12.12 Comtion i sual highly exothermic prousl Different fuels have different standard enthalpy changes of combustion (see table 1.2.2) cael ee ‘AHE (KI mot") 8903 41630 ‘able 122 The standard enthalpy changes of ommustin for sore fuels. 7260 13673 3935 2858Why do the standard enthalpy changes of combustion ‘vary so much? When these fuels release energy, they combine with oxygen. The amount of energy involved in this depencls om cwo factors: +The nuniber of bonds that need! tbe broken and made ~ this depends on the size of the molecule. For example, in methane there are just 4 cazbon hydrogen bonds, compared with hexane that has $ carhon-carbon bonds and 14 earbon-hydrogen bonds, a total of 19 bonds, ‘There is a lot more bond-breaking and bonc-forming per mole when ‘hexane is burnt in oxygen than when methane is bburnt, and this is why more energy is released per mole from hexane than methane. Another example compares the combustion of methane and methanol. The same products are formed (CO, + HQ), but methanol already contains an O—F bond. The energy released during combustion comes from the making of bonds with oxygen. If methanol already hes one OH bond made, it will sive out less energy when it bums. As a general rule, the more oxygen a fuel has in its molecule, the Tess energy it will give out when it burns. + The type of bored ireolewd ~ bonds between different clemeaws involve different bond energies. For example, it takes more energy to break & carhon— hydrogen bond than a carbon-carbon bond. You will be looking at this in more detail later in this chapter. It means that the chemical make-up of the fucl and dhe bonds that need 1 be broken or mace affect the enthalpy of combustion, Standard enthalpy change of formation “Another useful enthalpy change i the energy released ‘when a compound is formed. The standard enthalpy change of formation, 4H9 of a compound is the cnthalpy change when one mole of the compound formed from its elements uncer standard conditions. For example, the stancard enthalpy change of formation of methane (CH,) is for the change: Caraphite) + 2H,@) > CHY@ “The accented value for the enthaipy change of this reaction is ~74.8 KJ mol", Once again, we can use “chemist’s shorthand’ AH®CH,(g)] = -748 KJ mot! TR eee ‘The units of enthalpy of formation are kJ mot, as we would expect. Note that ‘per mole” refers to the formation of one mole of tre componnd, not (0 the quantity of elements reacting. If we say Una “the standard enthalpy change 0” formation of sodium carbonate, NaCO, is “1130.7 J anol, this means that for every mole of sodium cerbonate formed from jis elements, the change in enthalpy ix -1130.7 i For an element under standard conditions its enthalpy of formation is zero. “This is sometimes useful in calculations, Clyaphre) + 2+) > cHyis) | -743 Clyaphte) + OQ) > cO,f@) = 2clgrephite) + 21) GH) +522 Clgrphite) + 2H,(a) + 40,l8) > 239 cH.OM(), ‘able 123 The tardard enthalpy changes of formation fora nenber of cempeunds Standard enthalpy change of atomisa’ ‘The standard enthalpy change of atomisation, AHS, of an element iy the enthalpy change when one smoke of ity stom in the gaseous sate is formed from. the clement under standard conditions. The standard enthalpy change of atomisation of carbon (as graphite) $716.7 KJ mot"! ~ this is the enthalpy change for: Cigrephite) > Ca) AHG{[C(graphite)] = +716.7 kJ mol! Note thot the standard enthalpy change of atomisation refers to the formation of one mole of atoms of the element = it is nor the enthalpy change when one mole of the clement is atomised. Atomisation is always endothermic, since it involves increasing the separation between atoms, which requires energy. Standard enthalpy changes of atomisation may be calculated from other measurements (in the case of a solid, from the enthalpies of fusion and vaporisation together with ite specific heat eapucity), or they may be messured by spectroscopic means in the case of gases like oxygenStandard enthalpy change of neutralisation ‘The standard enthalpy change of neutralisation, AHG is the enthalpy change of a reaction where one mole of ci is just neutralised by an alkali in their standard states at 25°C. and in solutions containing {mol drw3 ‘The enthalpy change of neutralisation for dilute solutions of strong acids with strong bases is always close to 58 KI mol". ‘The reason is that these acids anc alkalis are fully ionised, so the reucsion is uke same in every case. Enthalpies of neutralisation can be measured approximately by solutions of acids and elkalis in a coffee-cup calorimeter. HG) + OHGaa) > HAO) AH® = ~57.9 | mor For example HClfag) + NaQH@q) > NaClieq) + HO) sH2 QD “1 For each of the folowing, write an ution forthe reaction in which the enthalpy change Is the standard enthalpy change of combustion. 2 Gre) b chon) 2. For each of the following, write an equstion forthe reaction in which the enthalpy change i the standard enthalpy change of formation, a K,C0,/) b cHycH,OH() 3 The standard enthalpy change of formation Is cefined using the term standard condidons. What does thls mean and why sit necessary to have @ standard set of conditions? 4. Which of the combustion reactions shawn in table 1.2.2 i a the most excthermic b the least exothermic? © How would you explain the iference? In table 1.2.3,.shich revetion is endothermic? b_ Wit are all standard enthalpy changes of atomisation endothermic, ‘when only a minority of standard enthalpy changes of formation are ‘endothermic? ———Working with enthalpy changes of reaction Enthalpy changes for ‘difficult’ reactions ‘You have seen that the standard enthalpy change of combustion of carbon is ~393.5 KJ mol“!: ) + On{@) 9 CO,(e) AH? = -393.5 Ky mor! CG@raphi Suppose you wanted to know the enthalpy change for the decomposition of carbon dioxide to its elements: CO,(@) > Cigraphite) + O,te) AHS = This reaction would be very difficult to carry out. Fortunately the law of conservation of energy comes 10 our rescue ~ because the first reaction, w make carbon dioside, has a standard enthalpy change of 393.5 KJ mol", the enthalpy change for the reverse reaction must be +393.5 Kf moll, If it were diflerent the implication would be that energy had either ippeared somewhere ar sppeared out of nowhere. So the law of conservation of energy tells yo that the enthalpy change for a reverse reaction has the same numerical value as the enthalpy chunge for the forwarel reaction, but the opposite sign. You cannot et energy out of nowhere ~ 30 the enthalpy chat for forward and reverse reactions must add together to give zero, ‘Taking this idea 2 bit further, think about the possible reactions of carhon with oxygen — carhon forms nwo oxides. You can draw a “triangle of reactions’ in which carbon reacts with oxygen to form carbon monoxide, which reacis with more oxygen to form carbon dioxide, which then decomposes to form carbon and oxygen again. This is shown in fig, 1.2.12(6). ‘Can you work out the energy changes involved here? ‘The standard enthalpy of formation of carbon dioxide is -393.5 bf mot", while the standard enthalpy of reaction for carbon monoxide and oxygen forming 83.0 KJ mot!. On the basis of these figures, the law of conservation of energy tells you that the standard enthalpy of formation of carbon monoxide is: [2393.5 Kf mol" ~ (-283.0 kJ mol") 110.5 kj mor carbon dioside is TO Reena ‘The enthalpy level diagram in fig. 1.2.13(6) makes this clearer. This is exactly the figure you get if you measure the enthalpy change for the formation of carbon monoxide experimentally under standard conditions. Notice how the enthalpy change is zero if wwe go round a closed loop in this eycle, eg from +0, 3 CO +40, > CO, > C +0, again ‘There are many cases where the law of conservation of energy can be used to combine enthalpy changes like this. ’ rosie! clamp +096) POU cop) evox os mo om cont) 6 elves)» 2160 -r08tjmat™ Cty + Hote 5 -za20Ksmot" Y wel) (ig 12.13 The energy changes inthis celica! process ave governed by the lw of corservation of energy it ike al ether energy changesHess's law "The chemist and doctor Germin Henri Hess used the law of conservation of energy to find 2 way of working out the enerzy changes in a reaction. He developed Hess's law which states that: + ‘The total enthalpy change for a reaction is independent of the route taken, In other words, if we have 2 reaction: AtB9CHD ddeectroite y= My + ay (ig. 1.2.14 The ow which chemists use when corrbiningerthaly changes for ferent reactions was named for the Sie Ruston “chemist, German Hen Hess (1802-50), it does not matter whether you go directly from A + B to C + D, or whether you go via some intermediate compound X ~ the standard enchalpy change for the overall reaction will always be the same, HSW Using Hess's law and energy cycles to calculate enthalpy changes Hote’ law is an example of a mathematical model that enables ‘you to calculate standard enthalpy changes of formation for substances that might otherwise be dificult to measure. ‘This might seem unnecessary ~ but in fact itis very useful {or determining haw stable compounds will be. This type of information pericularly useful for substences such Fuels. (One example of using Hess's law is for the formation of sucrose (table sugar) trom carton, hycrogen and oxygen: 12C(grapite) + 11H,lg) + SHO pIg) > CyHe20 8) [No chemist has ever been able to get ths reaction to heppen, 50 you cannot -neesure the enthalpy change directly. However, \you can maazure the standard enthalpy change of combustion of sucrose, and this can lead you to the standard enthalpy change for this reaction, as fig. 1.2.15 shows. AtfiCaHaO v6 s2clgapte) + 1H) ie Cutt ul) oviose ahs sex ate Sian cecal secofal + 114,01) 1g.12.15 By measuring the standard enthalpy change of formation of carbon dioxse and water, and the standard erthalay change of combustion of sucrose you can calculate the enthalpy change you want to hnew forthe formation o sucrose. The extra oxygen is needed to baance the cc Looking atthe cycie of reactions in fig. 1.2.15, ‘you can see that the standard enthalpy change of formation of sucrose can be calculated by applying Hess's law: ABFIC He 20 (6) = 12 « ANFICO,L)] + 11x ARGH OU ~ MAPLE 2H220 1 1)) ‘The figures for the enthalpy changes on the fight-hand side of this equation are: ‘AH®{CO,{g)] = -3935 kj mol"? 4H 9{4,0(0] - 2858 KJ met? HOC; Hy, 0 (8) = 9638.7 kj molt Substituting these into the equation we get AAFC Hg: y(0] = 12 x (3895) + 11 (2858) - (-$639.7) kl mot? = 4722 + -3143.8 + 5639.7 kj mot 2226.1 kj mot! So the standard enthalpy of formation of sucrose (to 4 signtticant fures) is ~2226 kj mot’. In this way Hess's law allows you to combine known data to calculate enthalpy changes that ‘cannot be measured directly, eg the standard enthalpies of formation of hydrocarbon fuels.Tiydrogen peroxide is 2 powerful oxiising agent which is used to bleach puper and cloth, and also to turn hair blonde. Hydrogen peroxide decomposes slowly t form, Water and oxygen: 10,0) > 1,00 + 40,66) Figure 1.2.16 shows the eyele of reactions that can be used to calculate AH® for this reaction, ic v4i9+049 “220. oy aefH.0(0) H,OU) 4 o5t) 5 12:16 You ean ne these rections to ealulate AH for the ‘composition of hydrogen pero. “The standard enthalpy charge of formation of hydrogen peroxide from its elements is -187.8 KJ mot"!, and that for water from its elements is ~285.8 KJ mo!, Remember that the enthalpy change of formation of an clement in its standard state is zero, by cefinition, Applying Hess's law, the value of 4H for the decomposition of H03() is given by: SH® = -AHE[H,O,0)] + AHPIELOG)] + YAHF(O,()] = = (-187.8) + (-285.8)+ 0 WJ mat! = -98.0 J mot So the standard enthalpy change for the decomposition of hydrogen peroxide to warer and oxygen is -98 KJ mor Using Hews law in this way, you can find AHP for any process using standard enthalpies of formation, In general, for any chemical process the standard enthalpy change A#® is given by: AH® = sum of standard enthalpy changes of formation of products ~ sum of stundard enthalpy changes of formation of reactants TO Reena r= EE Ifthe standard enthalpy changes of formation of, nitogen(l) oxide, NO and nitrogen(IV) oxide, NO, {are 490.2 Kj mol! and 433.2 kj mol"! respectively, ‘calculate AH? forthe change: NO(g) + %40,(g) > NOs) The standard erthalpy change for this pracess is sven by. AWE ~ AHPINO ial] - AHFINO(g)] (Note that te stenderd enthalpy change of formation ‘of oxygen is zero, by definition) Substituting the deta ges AHO = 433.2 (490.2) mor = -570) mot forthe eacton shown, AH® is -57.0 kj mot a 1. Define the term’standard enthalpy change of combustion; Explain how the standard enthalpy change of combustion may be used to calculate the stenderd enthalpy change of formation of a sven compound indirectly. 2. Hydrogen chloride, HCI can be made by heating potessiurn chloride with concentrated sulfur acid: H,SO,(U) + 2KCi(s) > ZHCILg) + K,S0,3) Given the infermetion: H,S0,(U) + 2KOH|s) > K,S0,(5) + 24,0(0) AyP = 342K} HIG) + KOH) > KCI) + H,0(0 AHP = 204K) calculate the standard enthalpy change for the formation of hydrogen chloride from potassium chloride and concentrated sulfuric acd. 3 The standard enthalpy change of combustion of propancic acid is -1527.2kj mot". Given thatthe standerd enthalpy change of formation of water 15-2858 kJ mot” and that of carbon code is 393.5 KJ mot", calculate the standard enthalpy change of formation of propanoic acid.TOR Coa ‘The idea of bond enthalpy is useful in calculating the energy change in a reaction invalving covalent bonds. You have already seen that breaking bends is endothermic and making bonds is exothermic. Bond enthalpy data ean tell you which bond wall break first in a meaction, how easy or difficult this bond breaking is and therefore how rapidly reaction will take place at room temperature. ‘The enengy needed to break a particular covalent bond, or the energy released when the bond is formed, is called the bond dissociation enthalpy (sometimes called bond energy). HH) > H@) +H) +4359 Kf mort Scientists have found that the bond enthalpy for a ven bond does aot wary much in diffrent compounds. For instance, the C—C bond is ery similar in ethane (C,H,) and butane (CyHo). These compounds behave in similar ‘wavs, 60 it isnot surprising that their bonds are similar, However, the same type of bord in different compounds can have slighly differen bond enthalpies depending on the combinations of other atoms in the molecule and their effect on the bonds Mean bond enthalpy mists use the ides of mean bond enthalpy ~ the mean (average) value of the bord dissociation enthalpy of a particular type of bond over a wide range of different compounds ‘Mean bond enthalpies can be used to work cout the enthalpy change in a reaction using Hess's law. Because they use average values taken from many different compourals, enthalpy changes calculated in this way are usually slightly different from these obtained experimentally. As you can see in the equation above, bond enthalpies apply to substances in the gaseous state. Many reactions involve solids, Tiquids or aqueous solutions, so this is another possible source of inaccuracy in your calculations, Bond enthalpies and mean bond enthalpies As an example, consider methane, CH, which contains four C—H bonds. The bond enthalpy of the C—H bone in methane can be found from the change: CHy(g) > Cig) + 4F(@) which is sometimes called atomisation - in this case, the satomisation of methane, The enthalpy change for the atomisation of methane can also be found by applying Hess's law to the series of changes shown in fig. 1.2.17 4 cia) +440) x xan 244121801 nar) cy +2448) swfelgaphie) =sfier iat" Chpertite + 240) amicHitell 748 mat AHH = ee) cnthaoy chute) Vig: 12.17 Calealatng the bend enthelpy ofthe C—H bord in methane. Figure 1.2.17 shows that AA for the atomisation of ethane is ~C148) +167 +4 x 2180 K) mor 1063.5 Kj mot ‘This process involves the breaking of four C—HT bonds, s0 the CII bone enthalpy in methane, written as E(C—HD or HC, is (CAND = 1663.5 1 molt 4 4415.9 KI molt “This is the enerpy released when one mole of carbon atoms and one mole of hydrogen atoms combine to form one mole of CH bonds, or it isthe eneray required w break one mete of C—H bonds. The calculation assumes that all four C—H bonds in methane are the tame, so we have exleulated the 2 HCH), meaning ‘the average CH bond enthalpy’. Rond enthalpy values wll vary slightly depending on where thes are found, ce the CAH bend ethaipy in methane will be slightly diferent from the value of the CH bord in ethane ba hese variations are overcome by using the eserage bond enthalpy average C—H bond enthalpy. This is why we verTR en nay Peron Bond cu | an ca 6 cee | 6 Non | 163 co | 358 HH 6 cc aa Newt | 945 co | 743 Ho 468 CN 26 Hoe | 565 ce | 27 HON 38 c+ | 467 re | ise ‘ble 12.6 These bond ental ae the average valves calculated for 3 number ot polystomic(many-atom) mleciles. ‘The value for the C—H bond enthalpy calculated opposite For methane is very dese to the CH bond enthalpy average over a number of compounds in table 1.24. Using the bond enthalples in ble 1.2.4, estimate the enthalpy change of formation of methanol vapour from its elements. To cry out this calculation you a0 need to know the enthalpy changes of atomization cf the cloments in methanol. These ae as folows: aeiclgratite) = +716,7 4) mot ‘Ff H(@)) = #2180 4) mot! AG) 0218) = +2492k) mor ‘The enthalpy level diagram int. 1.2.18 shows ‘be ently changes inthe formation of methane From the enthalpy dagram,the enthalpy of formation of methanol can be calculated frome AHP = 47167 + (42180) + 2492 — (3 413) + 358 4 463] kj mol-1 = -222 kj mo“? The enthaly change of formation of methanol ‘vapour from its elements is ~222 kj mol-", (Note that this nat @ standard enthalpy change, since we are forming methancl nthe opour state, whereas methenol is actualy @ liquid under standard conditions) ——— rd ) Enthalpy change of formation from bond enthalpies Cla) + 4Hig) + Ole) artslO,48)] =:2002K) ot" Clas dal + Wake) 4 SHSIHA(e)) = 4x (4278.0 Kj mol!) Cle) +244) + Wont) axe(—¥) | +Ee—9) § +e) g . #3. 4130 ot! aiclgapht) T3:aK)me™ = +7167 kj) mot! 4463 kj mat" lacie + 248) + WOxE) | ary ICHsOH) (ig, 12.19 Eethalpy agra forthe Formation of methanol. CoHala) + Hale) > CaHele) The enthalpy change ofthis reacton can be found by experiment to be 136 kj mot, Calculate the enthalsy change using the mean bond enthebpies given in table 1.24 The values wil be diferent. Why i this? Sketch a fuly labelled enthalpy lve diagram for this reaction. 4TOR Coa Using bond enthalpies Although bond enthalpies are a theoretical concept, they are a valuable tool for chemists + ‘They allow you to estimate the enthalpy changes in reactions. + They can be used 1 compare the strengths of bonds henveen different atoms (see below) + They help in building up an understanding of the seracture and bonding of compounds. + ‘They ako help in deveioping an understanding of the mechanisms of chemical reactions However, as you have already seen, bonel enthalpies tre average values and they apply to the goseous state. So sometimes the results from practical investigations dier from the expected theoretical bond enthalpies. Practical work can show differences in the bone cnthalpies of some bonds in different molecules ~ og the carbon-carbon single bond ranges from 330 ta 346 UJ mot”. This difference, ahough senall, woul be significant if yom gone calculating the enthalpy of formation of 2 compound containing a large number of carbon-carbon bonds, such as a large organic molecule. So if vou use bord enthalpies in Hess evcle calculations, beer in mind that there may be some small discrepancies in the answers that you seach. On the other hand, sometimes the differences between thooretcal values and experimental values can drive forward the development of new chemical ideas. Benzene (CH) Was fist Isolated in 1825 by Michael Faraday from whale oll Over te years much was Wf) IL) Is 2s 2p Ne 1s72872p? NJ I) LY LL ls 2s Op Te Reena ‘Write down the electronic configuration of a vanadium ‘atom (Z = 23), and represent this diagrammatically, showing how electron spins are palred ‘Vanadium hes 23 protons ints nuceus so the atom will hve 23 electrons, following fig. 7.3.21 (and remembering Hund’ ‘ue toc) we can fill subehal In order of creasing energy unt We tun out of electons. This gives the configuration V 1s2es?opha5?3p3d4s? The arengeret of electrons in orbitals can be represented lagarrratcaly as BO) fe ie) Ce oe Cd ) Is 2s 2p 3s 3p 3d 4s The 45 orbital is at @ lower energy level than the 3¢ orbitals, 0 the ds obit fle fist: However when you write this, he otbitals are grouped together in their shells ..2d4s2 The three clecrons in the 34 subshel gp into separate orbital sa t0 mavimise the numter of unpaire electrons. SY Using the rules cudined above, the electronic configuration of « polonium atom (Z = 84) is written as follows: Bo 1:2 2<22phalaptaalgzaphualOasc2sphsaMGeept Writing electronic configurations for ions For an ion, you simply add or subtract the right number of electrons from the cuter shell ~ taking clectrans for 2 positive jon, adding them for a negative ion, When removing electrons from an atom with a complete orbital as well as an incomplete one in the outer shell, the first electron will come from the complete orbital. For example, dhe oxygen iv, 07° iy 1572s?2p5, and the calcium ion Cs?* is 15?2s?2p°3s?3p6 In the next chapter you will be looking at how you can use clectranic configurations to help you predict haw elements react. aD 1. Use the periodic table atthe back of the book to write down the electronic configurations of the following: a Liatom b atom c Mgatom d Pator e Clatom f Gaatom g Mg ion h Crion. 2. An element has the electonic configuration 1s22s*2ph352 ‘3pP4s?34 dp? Write down its atomic number. | GaUnit 1. The core principles of chemistry eee ed Chemical changes concer only the outer electrons: in the ator, not those inthe inner shel. The inner éectons are strongly atvacted to the nucieus ané they ae not Involved in forming chemical bonds So es Felt to simply electronic configurator to focus on the cuter electrons For exarple the electronic configurations fer potessum and clear are: K 1st2stapas23pbs! co whostapban?apSa? “he core of electrons in she fist tree shel oF both ater are identical ~ it's ony the fourth shell tha 10, sp ate uawap aay 510925 Ky EOF fe:5un Jo sequru @ asneeg 8 Su 1ge: IoURE a. LNOUS IE vos paar spoigd [— sporgs [7 spo saplueuau By ]sa [aw |sH | ya 8s Jad] Ja | |v |og SL LLL | OLL | GOL | BOL Z4OL 9OL | SOL | vOL 68 Uy AW} Od) 1a) Wd} IL do BH] nV] 3d] 41} SO ey M| eL|JH| | 27 ps s9 og SR | pk OER | ZR LB og | 64 | BZ |] ZZ | OL SA oe | EL | AL LS eX 1 | AL| S| US| Ul | dg} PD By] pd] ya} ny IL owl an | uz aN Pp sc bS €S | 25 | LS | OS | 6 Br | db | OF | Sh | be Eh ab | Lb | OOF 6E AA 48] 2S] SV] 2D) PD) dp) UZ) MO] IN | OD) P4/4W) 4D] A] LL} 2S |pe Sp GE se | ve | c€ | ze | LE Oe | 62 | 82 | 42 | 92 82 | vz | E@ | ee Lz Ww DD] S| d]!S| Wa Bt Zt | OL | St | pL | eb e Pe aN A!/O)N/ DO) 9d o 6lelzi{s|s re °®H H SL ae | 049 S bE LUnit 1 The core principles of chemistry CWA rend The history of the develepmert af the paride table is peppered with good ideas that were ignored It ie werth remembering that the madern model af the atom was @ lone way off when these scientists were trying to explain the behaviour of the elements they observed, ard to predict what reactions would take place Early ideas about atomic mass ‘s for back as 1799, joseph Proust showed thet the proportions by mass of the elements were constant in each particuiar compcund he studied. A year later John Dalton propased that elements were made up cf atoms. and that each element is made up of one particular type of atern which differs from all the others by its mass. Unfortunately Daton wasnt very goed at actually working out what ‘hese diferent atomic masses were, When other, more careful scientists tied they often came up with different answers, 50 they were not entirely convinced by his work In 1828 Jins Jacob Beralivs published alist of atomic masses which were quite accurate, but after Dalton’ ear inaccurate efforts no one was interested, Daberviner's triads - the idea of periodicity In 1829 Johann Dobereines showed that many of the known elements could be arranged in groups of three, with al the members of the group showing siniler properties, He called these groups triads This was the fat time elements had bean grouped in this way A number of sclntists continua werking to group the elements In 1852 Alexandre-file Beguyer de Crancourtos developed an early version ofthe prince table, showing strilarties between every eighth element. Unfortunately, when his arte was published the dagrarn was not pinted. Without this visual element the periodiclty ofthe elements wos not clear. As ret of this ero is round breaking work was largely ignored! Newlands’ Law of octaves (One year later John Newlands announced his law of ‘octaves. This involved arranging elements in order of their atomic masses in groups of eight. Although this showec basic ‘periodic table" with similar elements grouped ‘Together, Newands’ work was dismissed because it contained some rrajor flaws. He assumed all the elements hhad been discovered, even though new ones were turning, ‘up each year. He put two elements inthe same place several times to male things fit. He even put dssirilar clements lke copper, lithium and sodium tegether when hhe couldn't decide where else they fitted in. Yet again the scientific community was unimpressed with the whole idea of periodicity. t was even suggested that arranging the elements alphabetically might well produce as many circumrstential sii jes as Newlands’ cereflly eranged Fig, 1.3.25 One example of Dabereber’s tds the group of cherve, bromine and fodine lererts we stil recognise as related toy.Mendeleev’s periodic table Finally, in 1869/70 Dritsi Merdeleey and Julius Mayer published dear representations of periodicity in the elements. Meyer plotted various physical properties of the known elements against their atomic masses and produced curves that demonstrated the periodic relationships. However, Mendeleev published fst, ard scored a major publicity coup by producing a table with gaps in t for as yet undiscovered clements. Based on his table he predicted the properties of ‘these missing elements. Then iv 1895 and 1896 gollium anc germanium were discovered, two of zhe elements predicted by Mendeleev. perimental evidence confirmed that they showed exactly the properties he had deduced from his periodic table. This corvinced any remaining sceptics of the periodicity ofthe chemical elements based on ther atomic mass, and the name Mendeleev became associated with the modern periodic teble, fie 15.27 Dre Mendleey founded the modem perce table = Predicted ound experiment €ka-alurinium altium elativ atomicrmans | 68 9 Density (em) 60 59 Mating temperature low 298°C kxasiicon Germanium Felatveatomiemase 72 723 Onide 0p deity 47 g cn? 0p density 423, chlonde Esl, bog temperature < 100%, ec, bong temperature 84°C, ancy 19g o> ensty 184g or table 1.2.6 Mendelee’s predicted properties for some usdscoveredelment {which called cheeks feared ‘ekaslico), and th experimental avdence which confirmed his ideas when gallum and germanium were discovered. QD “The gases helium te radon are sometimes known as the inert gases. Why is is? 2 What isthe basis of the vertical groups and horizontal periods of the periodic table in terms of the electronic structure ofthe atoms? 3 In which block (sp, d orf) in the periodic table would you tind the follownng elements? abe bN ccs ds ek 4. Discuss the role of hurnan error. experimental inaccuracy and creative ‘thinking in the development of the pertadic table. CR a aiUnit 1 The core principles of chemistry One useful aspect of the periodic table is the way it can be divided into blocks determined by the electron orbitals which are being filed, The four main blocks of 25 by different shading, and examples are shown in figs, 1.3.28-31 clements are shown ia fig. The s-block elements ‘The s block contains the elements of groups 1 and 2. They are known as the ¢-bleck elements becouse the outermost electrons are in the s subshells. These electrons are exsily lost to form positive ions. The s block includes the metals sodium, potassium, calcium and magnesium which are very reactive, forming stabie ionic compounds with non-metals. Indeed, they are ofiea referred w as the reacdve metals, ‘They have lower mel temperatures and lower densities than most other metals, Like all metals, they conduct electricity as a result of metallic bonding with its sex of elec:rons, enween the atoms. You will look more closely at bonding in the next chapter, and the properties of sroup 2 elements in unit 2. ing temperatures and boiling Helium and hydroge Electrons are filing Uhe 1s shell in both, but the are also s-black elements, characteristics of these two elements ~ a reactive gas and an unre ctive gus, both non-metals - ane so different from all the ather s-black elements tht many scientists reat them as a separate group. fig, 13.28 The block metas ae very reactive asthe behaviour ofthis lece of rodum with cold water demonstrator. The blocks of the periodic table The d-block elements ‘The d block lies between groups 2 and 3 and contains elements with successive electrons being added in d orbitals. The d-block elements are often called the transition metals, though some of them, such 3s zine, do aot fit this description well. They include familiar everyday metals such 3s copper, iron, silver and chromium, and they aro much less reactive than the clements in groups 1 and 2 becuuse inner d orbitals are being filled while the outer s subshel is full The transition metals all conduct electricity and heat and many are shiny and hard and can be pulled and hammered into shape. Mercury is a sirkking exception, ‘with such a low meling temperature dhac it iS a Tiquid at room temperature, ‘ig 1529 The é-block elements are much less react than the black ements and ae useful ke this copper ed sliver, os the uncembined flements The f-block elements In the f*block elements suecessive electrons are being added in the f subshells. ‘The top row of 14 elements (Whe kanthanides) are all very similar metals, The seconel row (the actinides) are all radioactive. Ouly the actinides up to uranium are naturally occurring, ‘The others have all been synthesised by chemists and are very unstable, often with half-lives of only milliseconds.The p-block elements ‘The p-block elements are those in groups 3, 4, 5, 6,7 and 8 For these elements electrons are being added to orbitals in the outer shell. The p block contains all the non-metals (apart from hydrogen and helium) and metalloids as well as some metal, Tin and lead are p-block metals, and they form posiuve ions and form ionic bonds with non-metals, However, many of dhe metals in the p block do not have strong metalic characteristics, although they alll conduct clectricity and heat. These post-transition metals are relatively tmnresctive and many of their reactions resemble those of non-metals, The metalloids occur in a diagonal block. Although they act like non-metals in most ways, they have one important property which is metalic in nauare. ‘They are conduaturs of elecwity, albeit poor ones. Ln particular, che metulloids silicon and germanium have been responsible for the microchip revolution of the late twentieth century The non-metals all form covslent bonds with other nnon-metals snd ionic bonds with metals, Carbon (Solid), oxygen (gas) and bromine (liquid) are all examples of non-meuils, The majority of them do not conduct electricity, although some forms of carbon do, Some non-metals, eg carbon, form giant covalent stractures with atoms linked by strang covalent bonds. However, many non-metals exist as small molecules You will be looking the halogens, in unit 2 group 7 of the peblack elements, 5-18.20 Many poco of tchrology which sveryoe takes for _gantedretyon microchips to wort, and many of thes chips are made from the metal steam CR ce ae ae a, ‘ig 1331 Although few non-metal (Uke the sulfur shown her) sre olds the mojorty re goes ke the enlorine weds 9 cher \wespon inthe Fst Wed Wr The auble gases ia group 8 ace exircmey unreactive as a result of their completely filled shells. ee eee ed Ie was originally thought thatthe noble geses were completely chemically unreactive or inert (they used ‘to be caled the inert gates). Ac the model of atoms \withcholls of electrons developed, it snemed obvious that the noble gases. with ther complete outer shells of electrons, would not bond icncally or covalent with ‘other atoms, In 1933 the Nobel prize-winning chemist Linus Pauling precicted that the heavier nate gases would make ‘compounds, but it wasnt until the 1950s that the theory became reality, In 1952 Neil Bartlett, a British herist working in the US, managed 10 produce venon hrexefluoroplatinate, using avery powerful oxidising ‘agent. Since then a nuriber of noble gas compounds have been made, but few of them have proved very Useful Xenon makos the most compounds ~ the lightest noble gases renain completely nen, thaugh chorists are still tying to persuade them to react! oD 1. Why are the transition metals so different in chemical character from the s-block elements? 2 Thec-block alements and nable gates have one crucial cifference in their electronic structure Explain what this diference is and how it affects the reactivity of the elements.Unit 1 The core principles of chemistry Patterns in the periodic table ‘You have seen how the periodic table was built up Grom observations relating: ‘the atomic numbers and the properties of the elements. The electronic structure of the elements and the way they react allow us to group them in blocks. Now you are going to look at how repeating trends of properties appear in the elements of the periodie table. These repeating patterns ane Jnown as the periodicity of the elements and the properties are known as periodic properties. The readiness with which an atom loses or gains electrons determines the way it bonds with other stoms, and that in turn has a big effect on many of its physical propertics. Trends in the periodic table ‘Moving across the periodic table, elements gain electrons, Moving down a group, elements gain electron shells. This changes the size of the atoms, which in curn obviously affocts both their physical and chemical properties. ‘You are going w look at dhe way the atoms change in diameter, and then tt how this affects some of the pattems in properties of the elementy using periods 2 and 3 as an example. soar (Na) argon (at) van der Waals ——=> van eer Waals raus0.239 om sede 0190 9m ‘asthe postive charge on thenuciees nreses acossperedz,1he our lector ae held mre cosely andthe atomic race dace eu (4) metalic air 0.57 a sodur Na) metal air 0391 mm Potassium i) ‘Av ext electro shel ae ade metalic Inpassing down group 1, the outer 0235 nm lectrens ate futher avy and Increasingly screened fromthe » poste nati Theatr cas suit (0) frees metalic asus 0250 mr caesten (63) metallic asus 0279 mm ig. 1.2.22 The trod inthe atomic ea ofthe alorents ae crectly lated to thi letrare Ree Rea +The atonnie ravtius generally decreases acrose a period ~ as yoo can soe from fig. 13.32, as you move across period the nuclear charge becomes, increasingly positive as the number of protons in the nucieus increases. Although the number of electrons also increases, the outer electrons are all in the same shell This means dat they are attracted more strongly 10 we nucleus, Gus reducing the atomic radius across a period. + The atom vases generally increases doc at group ~ the outer electrons enter new energy levels passing down a group, so although the auclens also gains positive protons, the electrons are both further away and screened by more ctectron shells. As a result they are not held so tightly and the atomic radius increases (see fig. 1.3.32) ‘The atomic radius changes when atoms form ions. A positive ion always has & smaller fonic raciuy than the original atom, This because the loss of electrons ‘means that the remaining clectrons cach have a grcater share of the positive charge of the nucleus 90 are more tightly bound, ancl when the ion is formed a whole electron shell is usually lost. Conversely a negative ion has a larger radius thon that of the parent acom. Even though the additional electrons are in the same shell as existing electrons, the addition of extra negative charge ‘means that the electrons are less tightly bound to the nucleus and so the radius is larger. ‘The term ionic radius is used to describe the size of ions, and you will read about trends in ionic radii in chapter 1.4. Periodic trends in ionisation energy ‘One of the most important periodic properties is fonisation energy. This ‘measures the energy change associated with, for example: Na(g) > Natig) + As you saw earlier, the first ionisation energy of an element is directly related Whe attraction of the muckus for the most loosely bound of ue cuter clecuons. The more tightly held the outer ekeetrons, the higher the first ionisation energy. There are three main factors that alfect the jenisation energy of an atom: +The attraction beteceen the nucleus and the outermost electron ~ clecreases (reducing Ue ionisation energy’) us dhe distance between them increases, +The size of the positive nuclear charye ~ a more positive nucleus has ‘greater attraction for the outer electron, leading to a higher ionisation energy. + Tamer shale of electrons repel the outer electron, sroening or shielding it from the ‘mucleus ~ the more electron shells there are between the outer electron and the nucleus, the less firmly held is the outer electron and the lower will he the fonisation energy.Unit 1 The core principles of chemistry Ionia energy ineeass acta period —t becomes) RE harder to remove sa ckectron. This is the result of the te increasing positive nucicar change across the period na ‘without tne addition of any extra electron shells to screen the outer electrons. ‘The atomic radius gets smaller and the electrons are held more firmly, s0 it requires more energy to bring about ionisation. Figure = 1.3.33 (a) shows the fist ionisation energy of the Rist 55 dement. "The end of each peri fe marked by the high ionisation energy of «nab gus. As you have seen, this cistncivly high ionisation energy is @ result of the sabe electron structure of the noble gases 4 nus indcaive of ther unreactive nurs. 4 el As fg, 1.338 () shows fis onation energies do a (oa not incase smoothly ares a period, Ths s due —E to the presence of subshells within each shell. In the 4 i G period lithiam to neon, the first ionisation energy Fit inition energy (re) * of beryllium is larger than that of boron, The relationship is seen for magnesium and aluminium in the next period. Removing one electron feam an tom, of boron or aluminium removes the single electron in the p subshell. However, for beryllium or magnesium i an electron must be removed from a fall s subshell, Fall subshells are particularly stable, so this requires more energy than removing the single p el boron or aluminium. ron form ‘The unexpectedly high first ionisation energies of nitrogen and phosphorus can be explained by the fact that both these elements contain half-full outer pp subshells. Hal-full sutshells also appear wo be associated with greater stability. Removing an electron from an atom of oxygen or sulfur removes the fourch clectron in the p subshell, leaving a half-fll p subshell. On the other hand, removing one electron from a nitrogen oc phosphorus ator requires breaking into a half-full sabshell, a process that requires more energy. Successive ionisation energies like these provide clear evidence for the existence of energy shells and. subshells in the structure of the atom, Fis inisatian ener (i! ma") 4 eff a 0 Aba ks % TR Ionisation energy generally decreases doren a group ~ it Aconerumber becomes easier to lose an electron. You will be looking fig 1223 (a) The istioniaton energy ofthe First SS elements ofthe at this in more detail later, when you consider the pelotic tale Clear patterns are Immediately ebvicus.(b) closer look st pater within individual perade reveal mere subtle lctustions properties of group 2 elements,Patterns in physical properties Periodic mrends are not limited to the chemical properties of the elements ~ they are clearly seen in the physical properties as well. Periadicity is seen in the melting temperatures of the elements, their boiling temperatures, their densities and many other properties. “These physical properties are closely linked to the structure und bonding of the atoms in the element and the ways in which the atoms are packed together. ‘This in tum depends on the electronic structure of the atoms. You will be looking at bonding in more detail in chapter 1. ‘The melting temperature of given substance is the temperature at which the pure solid is in equilibrium ‘with the pure liquid, at atmospheric pressure, The melting temperature i affected by both the packing and the bonding of the atoms within # substance. This changes as you move aeross & period. Many seientise prefer not to analyse trends in moking temperatures of elements across periods because there is considerable debate about the validity of some of the explanations commonly given. However, itis possible to see patterns in some of the periods ~ fig. 1.3.34 shows the melting temperatures of the elements in periods 2 and 3 DaseTesONRHubieT te Aerie muenber fg. 13.24 The melting temperatures ofthe elements of periods 2 end 3 show clear perotlty. DOs Se ee cei ae ‘The relatively high melting temperatures of the metals such as lithium, magnesium and aluminium are due \o their metallic structure. ‘The atoms are held tightly together in a sea of electrons. It takes a lot of energy to separate them which gives thes high meking temperature, elements u relatively Moving across the periods you meet giant molecular structures like thove found in the metulloide silicon and carbon in the form af diamond. They have strong covalent bonds between the ators which holds them tightly within a crystal structure. As a result itis very difficult to remove individual atoms and these clements als have extremely high melting, temperatures In contrast, the simple molecular structures found jn most non-metals on the right of the periodic table mean they exist as small, individual molecules. Although the forces holding the atoms within the molecules together are strong covalent forces, the molecules themselves are only held iogether by weak intermolecular forces (you will leam more about these in chapter 1.4). This means the molecules ean be separated relatively easily and most non-metals have ow melting temperatures as a rel, At least partly hecause of these structural differences, dramatic changes are seen in melting temperaures across a period, mirroring the changes of structure and bonding in the clement aD 11 Why does ionisation energy increase across & period? 2 Why does ionisation energy decrease down a group? 3. Why are the first ionisation energies of sulfur and aluminium lower than those of phosphorus and magnesium respectively? 4 How do periodic trends in observations such as atomic radius, ionisation energy and melting temperature confirm the current model of the lectronic structure of atoms?® 4 Bonding Bonding in ionic compounds (Phe forces holding atoms together are called chemical bonds, and understanding them is a central part of chemistry, since changes in bonding underli all chemical ccactions. The physical and chemical propertics of both clements and compounds are affected by the type of chemical bonding between the atoms As you saw in chapter 1.3, the bonds between atome in elements determine physical properties such ae the clement’s melting temperature. The orientation of bonds is also crucial in determining the shape of a molecule, In chapter 1.3 you saw that it is the electrons in the ‘outer shells of aioms that are involved in dhe pro of bonding. Atoms can los when they react. 3; gain or share electrons, Sodium (3 soft matt witha lw melting teperatrs eats olny wih citrine (a greensn ges) to produce sodium crionce [a hit sli with a high melting tesperture) Tonic compounds are usually formed when metals bond with non-metal. Oppositely charged ions are formed, which are held cogether by aan extremely strong eleetrostatie force of attraction, This arractive force is called the ionie bond. an arrangement known as a giant lattice structure. he ions are held in Tonic bonding can be thought of as the net clectrostutic attraction between the ions. An ion attracts ions with the opposite charge and repels ions with the some charge. ‘The lattice structure of a particular ionic compound is simply the arrangement of ions in a way that maximises the attractive Forces between oppoxitely charged ions and minimises the repulsion between similarly charged fons, ‘The forces exe -d by the ions in a giant lattice act equally in all directions, holding the fons cogether tightly. Giant latices of jons form fonte erystals, ‘A model ofthe one ltice of sodium chloride, NaCL shows sodium metal reacting with chlorine gas, Uberating a substantial amount of enemy in the process, The reaction forms an ionic compound, sodium chloride, which has from its elements ay different properties Why docs sodium chloride smple) Nar and Ci? ions? The answer lies in the electronic mntsin, Na ancl CI ions and CI* ions, ar even han (for es Ni structure of the sodium and chlorine atoms:Tn chapter 1.3 you saw that full (and half-full) subshells of electrons are particularly stable, and the ionisation energies of the elements (sce fig. 1.3.32) suggest that the electronic configuration of the noble gases, with full outer shells, is particulatly stable, g the clectron in its 3s subshell to become an Nat ion. Sodium can achieve a full outer shell by losis This gives it the same electronic configuration as the aoble gas neon, and Nat and Ne ate said to be isoelectronic (they have the seme number and arrangement of electrons): Not 1522:22p6 Ne 152252296 Just as sodium schieves a full outer shell of electrons by losing an electron. chlorine can do so by gaining an extra electron in its 3p subshell. The CI ion so formed is isoelectronic with the argon avon: Ch 15229229 63s23p% Ar 1s72s?2p63s?5p% So sodium and chlorine can each achieve the elecwronic configuration of 2 noble gas by wansferring the clectron in soium’s 35 subshell to chloriae’s 3p subshell. We can represent this as shown in fig. 14.3, cium ‘which also shows the same process between a atom and two fluorine atoms, his complete transfer of electrons from one stom to another forms an ionic or electrovalent bond. In the process of tn ion which is isoelecwonie with the nearest noble sctron transfer, each atom becomes gas, and dhe substance formed is held together by. clectrostatie forces between the ions, ‘The tendency for the ions formed by elements to have 2 fall outer shell of electrons is expressed in the octet rule: + When elements react, they tend to da so in way that results in an outer shell containing eight electrons, Like most simple rules this one has exceptions, slthough itis useful in many situations, Accounting for electrons - dot and cross diagrams Counting electrons is helpful to show how atoms: may donate or receive electrons inv order to obtain a full outer shell. This is usually done using dot and cross diagrams, which show the electrons as dors, oF crosses. Figure 1.4.3 shows two examples of such ‘electronic book-keeping’. Only the electron in the ‘outer shell are shown, because these are the ones involved in chemical bonds Dot and cross diagrams distinguish between the cleesrons in different atoms using dots and crosses, but remember that all electrons are identical. When sodium atom loses an electron to a chlorine atom, itis impossible to tell which of the electrons surrounding the Cl- ion came from the sodium atom, ® Nae cls —» [Na]? tl ” (ig 14.3 The transfer of electrons inthe Ferration f(a) sodium chloride and () calcium flags Coch atom forms anion withan cuter Shell comtaning eg electrons. OED 1 fan jon s isoelectronic with another elernent, what does ths mean? Give an example, 2 Draw dot and cross diagrams to showr the bonds inthe simplest compounes formed betiveen: chlorine and potassium chlorine and calcium © oxygen end sedi: oxygen end calcium,CR eed Giant ionic lattices ‘When sodium and chlorine react to produce sodium chloride, a compound results with properties quite different from these of iis two elements, 2s table 1.4.1 highlights. od Chlorine rs Appearance and state Soft metal melting temperature | Greenish gs. boiling White cystaline sofd. meting 36°C temperature 35°C temperature 601°C feaction wth water Reacts vigorously with water soluble in water Soluble in water lectical conductivity | Goud conductor of eecticty in| Does nat conduct eecticty Good conductor of electikity ia solid and liquid states liquid state and in aguecus solution ‘able 14.1 The properties of sodium, eharne and sodium chloe, Redlusof postveon smaller ‘han store ras _.o« reds (or) 0191 @e reds (om) @.160 ‘The explanation for the different properties of sodium chloride and its cements les in dhe fact that sodium chloside is an ionic compound, made up ofa lattice of Ne* and Cr ions. In contrast sodium consists of a latice of metal atoms, und chlorine is « gus mide up of Cl; molecules. The structure cof substances has a major effect on their chemical and physical prepertis. Trends in ionic radii In chapter 1.3 you saw how stomie radii vary across and down the periodie table. The ionic radius is the radius of an ion in a crystal. The radius of positive ion is smaller than the elements atomic radius because the remaining electrons are more strongly attracted to the positive nucleus, In ‘the same way, negative fons are larger than the stom that formed them. because Ue additional negative charge means all dhe elecirons are bound kes Lightly tw the nucleus, Reds of negative enlarger odectoniclons ‘than otarvc ras 71 asa) redius(om) 174 oMo ass one ore ano ‘ig. 18. You can se cles trands in onic ad both across the periods and down the groups of the vio tableTypes of lattice structure I you pass X-rays through a crystal, they ere scattered or diffracted by the electrons in the atoms: or ions in the structure. This produces a diffraction pattern which can he used to tell you about the arrangement of the atoms or ions in the crystal “These patterns ure known as electron density maps. “You will soon be looking at this in more detail Electron density maps show that the exact arrangement of ions in an ionic latice varies depending on the relative sizes of the different ions present, For example, sedlium chloride has the face-centred cubic structure shown in fig. 14.5(a). Bach ion has six nearest neighbours, so we say that the coordination number is 6. As you can see from this diagram, the chloride ions are considerably anger than the sodium ions, and so che sodium ions fit into the spaces between the chloride ions. ‘The packing of ions in the NaCl lattice is commonly. found in ionic compounds, and is known as the rock salt structure 5g. 1.45 (a) Sodhum chore hax» face centred struct, Ech ation i surounded by CR occ Rea ‘The strcmre of caesium chloride, shown in fig. 1.4.5(b), is different because the cuesium ion is langer than the sodium ion, More chloride ions can therefore fit around the caesium fon ~ you can see here that each caesium ion has a coordination number of 8. This erystal structure is known as a body-centred cubie structure. onic compounds tend to have very high melting and boiling temperatures because of the large number of ionic bonds between the oppositely charged ions. These need to be broken or weakened! in order to melt an ionic solid. We can relate the crystal structure model to the formula Df CSCI. Figure 1.4.5(b) shows that each unit cell contains, bone caesium atom at iis cente. AC each corner of the cell is a chloride ion. Bach of these ions is shared between, seven other unit cells, 50 effectively one-cighth of each chloride ion *belongs’ to the unit cell, Therefore: 1x Gs* fon = 1x Cs joins with 8x WyCh ion = 1x CF ‘Therefore the formula is CsCl 1 Look at the radi ofthe isoelectronic ions shown in Fig 1.4.4. They all have the same rummber of electrons. Explain the differences in the radi, 2. Whateffect doss ionic radiut have or: a the reactivity of anion bb the arrangement of the ions Iman jonic lattice? ‘alors and vice Vesa he Unt cls Stown In two diferent ways. (0) Caeswum chore has _2body-cented ube stmcture with a coordination umber of 8CR eed es Its impossible to see ions, yet the models used to explain Tonic bonding and many other aspects of chemistry depend on thelr existence, What isthe evidence far the existence of ions? Physical properties ‘The physical properties of what we know as ienic compounds are explained by the existence oF charged ions In sore ways ionic compounds are similar to metas in that they have high melting and boling temperatures and are quite hard. These facts suggest thet the partcies that make up ionic substances are held tightly to cach other, an¢ the existence of positively and negatively caged ions would explain this property ‘As you have seen the model fora soli ionic compound consists of a lattice containing both positive and negative ions. The properties GF lon solids reflect the sion interactions that est between fons, with opposite charges inthis lattice, Suc a structure also accounts for the observation that ionic solids conduct electricity when molen but notin the solid stot. Ths Fits with the model ~ in the solid the ions willbe held immobie in the lattice, and wil be unable to move to conduct electricity. However, when the ionic substance melts, the attraction between the ions in the lattice is overcome and the ions bbecome motile. n this state they can cery an electric current in the same way as the moble electrons in a metalic sold Simial, when an ionic substance isin aqueous solution the ions are free to move and the solution conducts electric. (0) fon so Tons hed in positon ~ ‘amnct conduc leticy Mrstaircnnce 9 @ O @ ‘conducts eleticty e@@%,0 @ es 8 e @° a? (148 Thanablelnatnarcter eribnune ora aunt thon cnn acre nc bu eadtom eee (9 kenkestotonccin xqecus stein carduet elect lone substances differ from metals in one important way namely that they are britle = they break easly when bit. In contrast metals are generaly both malleable (they canbe hammered into sheets) and ductile (they can be drawn out into wires) This suggests thatthe particles in tonic substances e held na reguler structure and have no see of electons’ es do metal. Again this is exploined by a medel of charged ions held in 9 regular atice.A fore could cause the ions in one Layer in the lticn to shift relative to the other layers, puttirgions ofthe same charge next to each ther. The repulsive force that results would force ‘the two ayers apart so the ios substance simy shatters (see fg. 1.4.7). fig. 147 lone subrtarces shatter If thay are itor cuted = more evidence that they ae made wp of fons. Electrolysis ‘The behaviour of ioric substances during electrcysis is another clear piece of evidence for the existence of ions. For example, aqueous copper!) chromate(V), CuO is an olve green sclution If 2 Specially prepared solution undergoes elecroyss, 4 blue colour appears around the negative eectiode (Gethode) and a yellow colour appeers arourd the postive electrode (anode). These chenges con be explained by the existence of ions Positive blue copper) ons, Cu are attracted tothe cathode ‘and yellow chromate( V1) fors, C10," ave attracted to the anode. This and other similar demonstrations of electrolysis show the presence of ions in the solution,se ig 1.4.8 The colour changes seen atthe electredes dering ‘the elcrolyss of copper chromate¥) cermensrate tie presence of psitive and negative iors. Electron density maps Eater in this chapter you looked et some ionic crystal strectures reveled by electron density maps. ‘These electron dersity maps provide mere evidence for the existence of ions. When X-rays are pasted ‘through anionic crystal arto photographic fim, they are difacted by the elects and procuce bright spots onthe firm. The biger the ion (or ater) the more electrons thas and the brighter ‘he spot it produces By analysing che postions and Intersite of the spts experts can work out the charge density of the electron inthe crystal. This chorge dersity con be defined as the amount of clectic charge per unit volume and iti measured 5 electrons pe cube nanometre. Pints of equal density ere joined up to fer contour lines which reduce an election desity'map'-This direct of Krays na clear and repeatable pattern is futher evidence ofthe presence of onsin the crystal TOR eee ee Fig, 149 Phetos ke these ae not easy to Interpret unless you ae an ‘expert — but they provide evidence forte existence of ions in compounds suchas lysonyme. an ant-bacteral enzyme, shown bere. Measurements taken from electron density raps allow different Jons to be identified and their distance apart inthe lattice. All ths adds tothe evidence forthe exstence of ions ‘ig. 4.10 lecten density maps for sodium chloride OE 1. ons ate invisible What 2 Lock at the elactron density map in Fig 1.4.10, Which are sodium fons and which ‘evidence can you provide for ‘are chloride ions? What is the ionic radius of the sodium and chloride ions? their existence? ‘What is the ionic radius of the sodium and and chloride ions? How cid you ‘make your decision?CR eed Lattice energy In chapter 1.2 you looked at bond enthalpies and. the enthalpy changes involved in the formation of a compound. You saw how these can be used to predict, for example, whether a reaction wil be exothermic or endothermic, You have also seen in this chapter how the formation af ionic bonds involves the transfer af lectrans between atoms t0 form oppositely charged ions, and the coming together of these ions to form a lattice. ‘The formation of ionic substances in this ‘way is associated with energy changes. The formation of ions in the guscous state from elements in the standard state is endothermic, while the formation of the lattice involves a release of energy ~ the Jattiee energy (sometimes known as lattice enthslpy). You ean compare the lattice cnergy of an ienie compound with the bond enthalpy of « molecular compound, although lutice energies are negative becuue they relate to forming the | because they relate to breaking the bond. 1e, while bond enthalpies ure positive ‘The lattice energy of an ionic crystal can be defined! as: + The enthalpy of formation of one mole of an ionic compound from gaseous ions under standard conditions. ) HSW Practical measurements of lattice energy all “The laticeenerges of substances canbe calculated froma special type of erthalpy level diagram called a Born-Haber eye. ll the enthalpy changes inthis cele can be measured, which allons you to calculate the lattice energy. AHG, ofthe compound. Figure 7.4.11 shows the fom: Haber le room che, Nate cel saison | ua Nalgl + e+ MClo(a) qe, nyputslssoctiner! ENT Nalg) + %C(g) ‘ath INe(] = +107 8 mot MMI Na" CE (sll =? _|_ nals) + 4200) ine =—at 8 mt wow (ig 14.11 The Born-Haber eye forsediom chloe. ‘The tens in the Born-Haber cycle are as follows: + AMINaCI()} standard enthalpy chenge of formation cf sodium chiovide, measured using a borb calorimeter. + AMG[Na(s]]_stondard enthalpy charge of atomisation ‘of sodium, calculated ror erthalpy changes of fusion and vaporization and the specific hast capacty oF sodium. + AKG{Na(gi] fst fonlsaton energy of sodium, found by spectroscopic measurements + AWSICL@)] standard enthalpy change of atomisation of chlorine, found by spectroscopic measurements. + AHG{CI(g) ist electron affinity of chlorine, feund by methods similar to those used to measure iovisation energies. Given measured quantities forall these terms, the lattice energy of NaCl can be ealeuated: ‘HE [Nec] = 411-107 ~495 122 348) KJmot? = 787 Kmot* This value forthe lattice energy of sodium chore gives you some idea of the size of te attractive forces between the ions in socium chloide ~ notice that it sof the same order of magnituce asthe bond enthalpies given in chapter 1.2, comparing the strengs of ionic bonds and covalent bonds. However, in fonic latices each on ished by attractive forces toa number cf other ions within the lattice. As 2 result the overall energy nceded to separate them is mech higher than that needed to break an individual covalent bond This ‘explains the high melting and boling terperatures of ionic substances“Table 1.4.2 shows some lattice energies for ather compound, also calculated from Born-Haber cycles. Pee me Cn) of cation of anion ‘energy a) (om) Chea) acl ‘ane 0.180 -720 abe ame 0.195 -182 a one 021s -n5 acl ‘oz 160 ~7a0 va 0138 0.180 m 0072 0.133 257 ct, ‘0100 oa 2530 able 142 Late ener or «rage of compounds What affects lattice energies? Looking at table 1.4.2, you can sce that the lattice energy of a compound is affected by both the charge and the size of the ions. The effect of the ionie radius is shown by the trend in the sodium halides, in the chlorides of socium and potassium, andl in the fluorides of magnesium and calcium, The lattice energy becomes, less negative as the size of the fons increases. In smaller ions the atractive force of the positive nucleus holds the outer electrons more tightly because they are closer to the nucleus. You can alo sce that the lattice energy becomes, more negative with fons of grester charge (Ma?*, C22") because they attract other ions more strongly = compare the latice energy of sodium fluoride with those of magnesium fluoride and calium fluoride, ‘which have # much greater magnitude. Why is the lauice energy aflected by the ion size and charge in this way? To answer this question, you need to know that the size of the foree of attraction of one ruined by electrostatic theory and can be calculated using Coulomb's law: fon on another i Force of attraction, F whe: the © 4 and g, are the charges on the ions, and r is jstance between them. This relationship shows you CR acre ce Rea that increasing the charge q on either ion increases the atiractive force F between two oppesitely charged ions, in the lattice. Decreasing the size of ene or both ions decreases the distance r between them and so increases why ionic radius is such aan important factor in determining the strength of ionic bonds, the attractive force F. This Predicting stability ‘You can use stanclard enthalpies of formation and Born-Haber cycles to help you precict the relative stabilities of different compounds, and indeed why particular ionic compounds exist. Why is sodium chloride always NaCl, never NaCl? Why don’t you! come actoss MgCl or MgCl? ‘Theoretical lattice energies can be calculated for substances like these that do not exist or do not form ionic bonds. These can be used in a Born-Haber cyele 10 calculate the theoretical enthalpy of formation for these compounds ~ and this will usuuily show you esaedy why the compound does not form! [t usually reveals a very highly endothermic enthalpy of formation, because the ionisation energy for fone of the electrons is $0 high. In the case of relatively simple molecules like NaCl; or MgCly, you know that the arrangement of electrons in the outer shell is not favourable, Using theoretical lattice energies and Born— Haber eycles ea give you the » ne information ~ and allows you to make predictions about the compounds of less familior clement ‘The very high energies associated with substances such as MgCl, are because the third ionisation involves breaking into a noble gas configuration, and this takes 2 great deal of energy. So for example, in the case of sodium, the ionisation enengy of the second clevtzon is almost 10 times greater than that of the First, Figure 1.4.12 shows a theoretical Born Haber ceyele for Ni |». You can see that NaCI is much more stable — the energy budget to create NaCl, would be huge! Na(g) > Natig) = AH® = 496 J mol"! Nut@g) > Na2*(@) +o AHG = 4563 5 molt AHPINACI,()} = 107 + (2 122) + 496 + 4563 + (2 x 349) + AABINACI6)] It you estimate the lattice energy for NaCl, as being, the same a that for MyCly, namely =2526 Kf mo: AHPINUCI,G)] = 42186 KJ mot!CR eed Nafa) + 2c1) Na"(g 2g) + 26° —— Decal] H,{Nalg + ‘aH [Nal] AH INACLASI] OH, [Na 6)] 2 OHalCllel a Nala) +2445) ala) Nelo) + Cla) fig. 14.12 A Born-Haber cycle forthe theoretical compound NaCl, pnt@ezr@ 4 Nett) Accloser look at lattice energies By using Coulomb's law in conjunction with Inowledge of the structure of ionie lattices, chemists can calculate theoretical lattice energies for ionic compounds. Table 1.4.3 compares these theoretical values with the lattice energies obtained from Bom-Haber cycles. ne Born-Haber Theoret oF se si Necl 180 10 New raz 735 Nel 105 esr AF 958 so acl 905, 233 peor 891 a6 ne 889 77 ‘ble. 143 Latte emerges calculated from Born-Haber eyes ane {fom theratical models of attraction ahd rpution between rt Inenstallaticer Jn the case of the sodium halides, the lattice ‘energies obtained in these different ways are very’ similar, agreeing within 3% or better. But in the cate of the silver halides, agreement is much less ‘good — why is this? Polarisation in ionic bonds Tonic bonds can be distorted by the attraction of the positive cation for the outer electrons of the negative anion. The electron density maps in 1g 1.4.13 can help you mode! this effec. Figure 1.4.13(@) shows & wholly fone bond, with the electron clouds of the 1wo ions quite separate. Tn fig. 14.13(b) you ean see a situation where the lectron. cloud of the anion is attracted to the positive cation. Ifthe distortion is great, it may lead to/a charge cloud that begins to resemble that of a covalent bond (see fig. 1.4.13(¢)). You will be Tooking at the electron density maps of covalent ‘poms on the next few Fae.The polarising power of a cation depends on its charge density, and this in tum depends on both its ionic radius and its charge. Cations with a small ionie radius are much mor polarising than large cations charge density is higher ~ the effect of the positive nucleus is felt more strongly. Also cations because the with @ lange positive charge are mere polarising than cations with a smaller charge, because again they have 1 stronger attraction far the outer electrams. (On the other hand, how readily an snion is polarised depends solely on its ionic radius which affects how tighlly the electrons are held, The larger the anion, the more easily it is polarised. . @ © - 0@ » of (ig. 1.412 The dotorton of an ion bond Distortion is favoured ifthe (postive cations small witha large cxage, and the (negative) anon Islerge ‘You can see this effect demonstrated clearly in the silver halides. Table 1.4.3 shows that the theoretical lauice enengy of the silver halides is considerably less negative than the litice enengy calculated from Born-Haber cycles. This suggests that the silver halides tre more stable thon a purely ionic model indicates. In other words, they show 2 considerable degree of covalent character, This is the result of the effect of the different relative electronegativities on the nature of the bonds. When the difference in electronegativity enween the different ions in a crystal is high ~ one ion is much more electronegative than the other ~ dhe fonte model works well, and there is good agreement between the swo values of lattice energies. When the difference in electronegativity is smaller, the bonding in the crystal has a considerable degree of covalent character. ‘There is less attraction henteen the oppositely charged CR occ Rea particles and more electron sharing. ‘The melting Temperatures of the silver halides are about 20% lower than those of the sodium halides, agreeing with the idea that they have a greater covalent character. Why do these wends show up when you compare lattice energies calculated using a theoretical model with the values from a Born-Haber cycle using experimental valuer? The theoretical model assumes that all the ions are spherical snd separate, and that the electron charge is always evenly distributed across the ion, Polarisation of the bond, a distortion in the shape of the ion and inereasing covalent character in the bond all rectuce the lanice energy and show up in the experimental values, =D 1 How does the ionisation energy of en atom affect ‘the likelihood that i will undergo fone bonding? 2. How docs lattice energy differ from bond enthalpy? 3 How do the joni radiue and the ion charge affect the lattice energy of an ionic substance? 4. What trend can you see in the difference between the theoretical and Bom-Haher values forthe lattice ‘energy of the silver halides? How do you explain it? 5 Using the method for NaCl, above as a model, and ‘the data In figs. 14,11 and 1.4,12 and table 1.4.3, calculate the enthalpy of formation associated with the following reections: 2 Mal) + Clg) > Mgcl(e) (AH; negative) bMg(s) +CL(@) > Mec) (a4, more negative) © Mls) + THL(@) > MECLIS) (AH; positive) Valve si (nna nchaby of atomisaton of magnesiun 148 Fintienisation energy of magnesium 738 Second ionisetion energy of magnesiom 1451 Th ionisation energy af magnesium 7733 lattice energy of NaCl (we for MgCl) —780 lattice energy of MaCl, 2526 awe energy of A, (use for MgCl.) 4590, able 14 Oat for Any caedlations.CR eed Covalent compounds Sharing electrons ‘Many elements do not form ionic compounds ~ the energy released in the formation of the lattice of ions ‘would be insufficient to overcome the energy required 1 form the ions in the fist place. ‘These atoms use another methed of achieving a full ower shell of electrons ~ electron sharing. ‘This is especially true for clements in the middle of the periodic table, for which the loss or gain of three or four electrons would be required to firm stable ions, which would require a great deal of energy. Think about two hydrogen atoms approaching one another. Each atom consists of a single proton as its nucleus, with a single electron orbiting around it, AS the atoms get closer together, each electron experiences tn attraction towards the two nuclei, und the dectron density shifts so that the most probable place to find the two electrons is between the two muclei (see Fig. 1.4.14). Fffectively, each stom now hss a share of bath electrons. The electron density between the two nuclei exerts an attractive force on each nucleus, keeping them held dighdly together in « covalent bond. © ® © Fig: 14.14 A enalant bord fering between twe hydiogen atom (@)!weo hychogen atoms 2 large dtence apa (2) A the atoms ‘pproach the electron density betveen them increases (¢) Eventual ‘he electron derity becomes greater between the two etoms then rywhiee else inthe nelgnbourhood ‘The covalent bond represents a balance benween the attractive force pulling the nuclei together (due w the electron density between the auclei) and the repulsive force of the cwo positively charged nuclei pushing each other apart. For two hydrogen atoms, this balance of the attractive and repulsive forces occurs when the nuclei are separated by x distance of 0.074 um, ‘This distance is known as the bond length for the bond. As you have seen int dl energy released as the two atoms come together to form the bond is the bond enthalpy (bond energy) — Which is of course also the amount of enenzy rexquinad to break the band. In the case of the H molecule, the bond energy is 436 kJ mol! spter 1.3, the ‘Work has tobe dene to push che ruclet together, so energy of H; molecule rises Energy of ‘wo bola Wators ay E Separation 2 ET \ aa6kjmor? nergy released asthe atoms move together Attractive andrepttsive forces folance at thi separation 074 nm {ig 14.15 The energy oF two hydiogen ators at diferent separations A covalent bond arisos from a shared pair of clectrons. Covalent bonds form between atums of non-metal elements such as Cl, and Py, as well as in compounds such as HO and CH,. A covalent bond Js usually represented as a line, so that the hydrogen molecule is represented like th HOH his is called the structural formula of the hydrogen molecule, which zs you know has the molecular formula Hy. [As with ionic bonds, covalent bonds can be represented using dot and cross diagrams. Once again the octet rule can be applied in many cases, us fig. 1.4.16 shows, Nosice that it is possible for two atoms to share more than one pair of electrons ~ sharing ‘hwo pars results in. double bond (eg O=0), and sharing three pairs produces a triple bond (ez N-However, such diagrams are only used for ‘electronic book-keeping’ ~ they do not tell you anything about the shupes of molecules, and they do not represent the real positions of electrons. eclecl H2O:H cect —O-H N=N fig. 14.16 Dot and erse diagrams canbe used to show how th stom tna cvaleity borded moet share electrons in order to oan 2 full, cuter shel of electrons. Dative covalent bonds Sometimes both of the electrons that make up a covalent bond come from the same atom. ‘This type of covalent bond is called a dative covalent bond. An example of such a bond occurs when ammonia is dissolved in a solution containing hydsogen ions, for Which we cata write: NUH(aq) + H(aq) > NH," (aa) Figure 1.4.17 shows how a Got and cross diagram enables us «0 do the electronic baok-keeping for this reaction. Notice that the NH,* ion produced (called the ammonium ion) contains a nitrogen ators with « full outer shell of electrons, together with four hydrogen atoms, each of whieh also has fall ter shel «| HONGH Ho. {ig 14617 The fomatin of nt ermoni on Nie the the NOH bonds are equivalent so taf practice is impossible to tnglshbetonen ther Another example of a dative covalent bond isin aluminium chloride, which consists of molecules of AICI, in the vapour phase. AS the vapour is cooled, however, pairs of molecules come together to form imers, in which they are held gether by dative fig. 1.4.18) alt ONS ca cl cl 1418 The formato of AC re Ona sion tlectronie book-koping nd ols us nathing about the shape ofthe ‘gee molecte (Compounds that have unshared electron pairs readily form dative covalent bonds. It is imporant to realire that once they are formed, dative covalent bonds ate che same length and strength as any other covalent bora exactly Dative covalent bonding can be used to explain the existence of different oxides. For example, carbon dioxide is the result of normal covalent bonding between carbon and oxygen, but carbon monoxide has two normal eovslent bonds along with « dative covalent bond formed by electrons fram the axygen stor,CR eed ) HSW Evidence for the nature of the covalent bond Covalent bonds ate strong bonds which arse from the loctrostatic attraction between nuclei and the electrons between them. Many covalently bonded substances exist as discrete molecules. However, cthers form either atomic crystals or molecular crystals, and these ae very useful for providing evidence of the nature of the covalent bond. In the same way that ionic bonds may shaw some covalent ccherecter, covalent bonds may be polarised and show some onic character. You will be learning mare about ths in unit 2. Giant atomic structures ent atomic structures {sometimes known as giant molecular structures) form distinctive atomic crystals. ‘The lattice postions contain atoms held togather by covalent bonds The whole lattice can be thought of as @ siant molecule, One of the best known of these is damord, with carbon atoms held together by covalent bonds silicon('v) carbide, SIC and sticoniV) oxide, tO, ae also examples Atomic crystal ae very hard, wth high melting temperatures demorstrating the great strength of the exelent bonds o oS ig. 14.19 The structure of diarnond with al the coal bonds olding the ators in the latice poston. Electron density maps and the shapes of covalent molecules i you look at the electron density maps of simple covalent compounds, you wil see thet covalent bonds are highty Airectional The shared electrons ofa covalent bond, or 3 pair of unshared electrons (alone pai of electronegatvity Each ara ofelectronegatvity repes the others and ths gives covalent mclecules with more than two atoms a very definite shape in which the three OYE? © corn eZ mall ‘ eS ppm ote corn tet fanartng Zeon espn ic. 157 DDTisaveryetfective insecticide and ts use brings many benefits to people expecially in the control ofthe moscutces tht carry malari. However, it bulls up in fod chains so the rik tothe cerwronment is very high ard the cherical is now only used when there no aterative. 1. What isthe difference between hazard and isk? 2 Whyy are chemical and explosives laboratories relatively safe places 10 Work? 3. What ethical issues would you need to consider when deciding whether to se natural or synthetic pesticides on a large scale?Why does carbon form four covalent bonds? Carbon forms four covalent bonds by sharing electrons with other atoms, and the arrangement of the four bonds uround a carbon atom is tetruhedral or very neatly so, The clecironie stmactare of the eihon atom fn the ground state is 1s?2s22p%, which means that the weds to gain four electrons to achieve @ 18). Onoe the four carboa atom noble gas configuration (see fig. Donds are made, the outer shell electrons form 2 fully shared octet, the inner shell is complete and there ure no lone pairs or empty orbitals, so carbon atoms do not bond to more than four other atoms, H ° I 4 HicCeH C. ” rae H wy i H caben to methane bend ange 1095 4 ea) ‘eked same dearori arrangement 25 180n ‘ig. 1535 In methane carbon fs comblned with hydrogen to achieve stable octet of electrons the outer el. Carbon atoms are unique in their ability to form covalent bonds with other carbon atoms and with ouher non-metal at the same Une. Carbon forms very stung bonds with itself, whieh can be single, double or triple bonds (sce table 1.5.1). Carbon also forms very strong bonds with hydrogen and almost all organic molecules contain at lesst one carbon— hydrogen bond. Table 1.5.1 shows the average bond energies of cirhon atoms with other carbon with hydrogen and with oxygen. ‘The Si—Si and SiH bond energies are given for contrast ~ silicon is the most similar element carbon and yet the bond energies are very different, Bond anna) co 307 cc 4612 coc 88 ca vai co 4358 sinsi 4206 SiH 4318 ‘able 151 Carbon fos very strong bonds. The bonding of carbon and the strength of its bonds produce a great diversity of organic compounds. ‘They ccan lead to the formation of chains of carbon atoms which may be thousands of carbon atoms long, with many different groups of other clements attached Carbon ean also form complex ring structures. 1— I tot —coc—c—a fot ot butane Uni ci Lor cha fatty acid ‘ig, 159 Ae these few examples show rgaricmoleales come Ina vaviety of shapes end ie,Organic families Classifying organic compounds ‘The millions of ditferent organic molecules ean be clissifed in various ways, ‘The fst major division is based on the armingement of the carbon chain ite + Aliphatic molecules contain straight- or branched- chain carbon skeletons, eg propanol 2aredybutene + Allicyelie molecules consist of closed rings of carbon atoms which amy comain single of multiple ‘carbon-carbon bonds. + Arenes, which are covered in the A2 course, are all derived from the benzene molecu ind contain a benzene ring with six carbon atoms in their structure. ‘These different motecular aerangements have & marked effect on the reaccions of orgenic compounds, Another important facior is the presence of duubke and triple bonds in the structure. You will remember from your work on fats at GCSE level that on unsaturated facty acid containing a cazboa-carson double bond is much more reactive than a saturated fatty acid containing only carbon-carbon single bonds, Ag well as these tivo main divisions of aliphatic compounds and arenes, organic compounds fell into a range of families or homologous series. Families of orgunic chemicals can be identified by the possesion of a particuler fianetional group. A functional group is an atom or group of atoms that is typical of a particular organic family and which determines the chemical properties of the molecule. The functional group has the same distinctive effect on the properties of all the molecules in the family. However, the Concuonal group is ulsu influenced by Re Cay dts environment, eg as the hydrocarbon chain gets bigger it has an increasing effect on the chemistry of the molecule and the influence of the functional group gets less as a result, The different functional groups ‘The simplest organic molecule is a chain of carbon atoms joined by single bonds, with hydrogen being the only other atoms in the molecule. The homologous series with this structure is the alkanes (ee chapter 1 ) and an example of aa alkune is propane, Bach homologous sevies has @ general formula describes the number of carbon atoms and their relationships to the other atoms — eg the general formula of the alkanes is CJH,.2 methane ethane propane Another homologous series of organic compounds is ilar to the alkanes, but all the members have sn -OH functional group. 1 alcohols - an example is propan-L-ol, (The way chemists name organic molecules is discussed later in this chapter.) is series is known as the i it iit Hp mem emoh etn etert tat so If the -OF functional group of the alcohols is rephieed by COOH we get another organic family ~ the carboxylic acids, An example of this group is propanoic acid. O ,f oO wey rth on Lyf etwoe rope oH =TT Td Nd As you have seen, the properties of organic families are determined first and foremest by their functional group, with the shape and size of the carbon chain also affecting how the compound reacts. The number of double and tiple bonds between the carbon atoms in the carbon chain slso hus its effect. Alkanes and alcohols have a single bond between each Of their carbon atums, Other homologous series are distinguished by the double or tiple bonds beween their carbon atoms. The allkenes (see chapter 1.7) have at least one carbon-carbon douible bone and another family, the alkynes, have 2 carbon-carbon triple bond, As vou would expect, the alkenes and alkynes show grester reactivity than the alkanes. a mem |e Atkanes Hane HyCHs ethane) Alkenes CH CHC, ethers) Ales Hore CHCH (ethyre) Alcotos Han 20 HOH (ethan Halogenoattanes | GH>,_:X cH lagen x | Gertie) Aldehydes GHC fo | crycHo (ethan) J “ew ot Heo, (oroparone) Carbonic acids CH,CH,COOH (oropaoie x table 15.2 Some ofthe main functional groups and the organic horclogous series to which they belong, Fig 15:10 Dierent aumbes of erbon ater and ifferent functional groups make a range of onanic ‘compounds with diferent physical at wll 5 choral ‘properties Rhubarb cortains ethareeicic acid which ic eal at room temparstire. Dropare-1,2,3¢id ia ‘Wscous (hick qui, and trccromethane Is ane scous (unm) ligule The methane you use Ia 2 Bunsen burner Ia gas at room temperature. Describing organic compounds Representing organic compounds “To understand the chemistry of a compound you nced te know its chemical rmuke-up ~ the numbers of atoms of ifferent elements which are involved and the way in which they are arranged, ‘The structural formula of an organic compound is the first step to determining its functional groups and unravelling its chemistry Jn chapter 1.1 you met the tecms empirical formula and molecular formula or inorganic compounds the molecular formula is usually the most useful How relatively large and the types of boads ‘er, organic molecales are often benveen carbon atoms have a big effect con the chemical nature of the compounds.For organie molecules the structural formula is often used, as it shows not only the numbers of atoms present but also the way in which they are arranged relative 10 each other. However it doesn't tell you anything about the bonds between the different atoms. “The structural Jormula of propan-t1-ol can also be wriuen with some uf the bonds shown to give you more information abuut the molecule. This is the displayed formula. Here you can see that it shows both the relative placing of the atoms and the mmber of bonds between ther: propan-tt np forme ene creer forme eno srucuceltormula creHEH One cjAcHO Hono I isplayee Formula ‘Sometimes even the displayed formula is not detailed enough because you need wv know not only whst (ype of bonds are present but also how they are arranged in space, A more detailed version of the displayed formula ccun show the shape of a molecule more accurately by showing the orientation of the bonds: Mo wos ets ‘ [Sete | é ‘The type of formula that you use depends on the information you need. Fmpirical, molecular and structural formulae are commonly used, Space-filling models cin also be used to model a molecule in three dimensions. ‘These may be produced using computers (especially the case of complex molecules) or using modelling kits which conneet together weeden oF pls spheres Re Cay Computer-generated spat particularly useful to scientists for research tasks such as drug design. Often the shape of 4 molecule is crucial to the way it works in @ biological system, so the ability to create models like the one in fig. 1.5.11 can be vital, Tn sehuol laboratories space-filling models are usually mach simpler! ling models are tig. 15.0) Space-ting models ke ths, whether produced by a computer or simply by Fitingcaloured spheres tegethor, ce a hte to represent eccurtely the enent ofthe eet cloud in a molecule, Finally, there are times when you may use skeletal formulae. ‘These ure more difficult eo interpret ~ in a skeletal formula you do aot show any hydrogen or carbon atoms, All that is lef is ‘carbon skeleton, with the carbon atoms represented by the junetions between the bonds, and functional groups are shown, Skeletal formulae sre most frequently used for ring compounds =D ‘1 Boplan the wide range of organic compounds, with reference to the electronic stucture of the catbon atom, 2. foreach of the following compcunds state \hich homologcus series of organic compounds It belongs to an¢ give the empirical, molecular structural, displayed and skeletal formulae. 2 ethanol b_ propanoic acid 3. What are functional groups ard why are they so Important in organic chemistry?TR ed Naming organic molecules Naming inorganic compounds is usually quite straightforward because small numbers of ators ere involved, However, the naming of organic molecules i rather different. The name of an organic compound needs to show the homologous series to which it belongs, the number of carbon atoms in the molecule and whether the chain is straight, branched or in a ting, and to ako inchde any additional atoms that may be in the molecule, The IUPAC system A rigorons system of naming is used for both onzinie and inorganic compounds, according to rules drawn up by TUPAG (the International Union of Pure and Applied Chemistry). The system is very useful although complex organic compounds can end up ‘with names that are longer and more involved than the formula of the compound! However, this is rarely 2 problem because often thes very large molecules = such as carbohydrates, amino acids and fats ~ have standardised common names that are easier to remember, It is well worth taking the time to get to grips with the way systematic names are built up, becuse then the name of an organic compound will give you a considerable amount of information about ity structure and therefore the way in which itis likely to react. Naming aliphatic compounds You have scen that aliphatic orgenic compounds are mace up of straight and brenched chains. For an aliphatic compound, the first part of the name refers to the number of carbon atoms in the carbon chain or, if the molecule is branched, the number of carbon atoms in the longest carbon chain (see table 1.5.3) Prefix. Number of carbon ator in the maln carbon cha meth | 1 tn z pre 3 bu 4 pent 5 ee 6 hepte 7 ote 8 ec 0 dose. | 12 vic | 20 ‘ble 1.53 The pripes of naring carbon skeletons ‘The second part of the name, the suffix, refers to the functional group of the homologous series to which the molecule belongs (see table 1.5.4). For example, propane is an alleane with three chain, while propyne is an alkyne which also has three carbon atoms, Propanol is a three-carbon alcohol, and ropanal is @ three-carbon aldehyde, Equally, ethene has (wo carbon atoms, While pentene has five carbons and dodecsne bas 12, ull being members of the alkene homologous series. srbon atoms in the Pe Pe “me alare ene alkene “al alcohol “sci | catboxylic acid a alcetyde -one ketone ‘able 1504 The suffi tells you which Funcranal group the eompound belongs to.Re Cay ‘The organic families other than the alkanes contain double or triple bonds or other functional groups. Numbers are used to show where in the carbon chain the functional group 1s. For example, in an alkene the parent or main carbon chain is taken to be the longest one in which the double bond occurs, ICs numbered from the end that gives the frst carbon of the double bond the lowest possible number, ex: butane hepta-,35-triene ‘Many orgunic molecules ure not simple straight chains but hhave branches tat are offen alkyl groups. An alkyl group i an alkane molecule that has lost a hydrogen and joined w another carbon chain, so it has the general formula C,Hyqy ‘Typical ally! groupe include: methyl CH ethyl CAH, propyl C34. or CH,CH- or CH,CH;CH,- ‘The position of a side chain js again indicated by the lowest possible number, tw show tw which carbon aiom in the parent chain itis attached, ex: 2emethybutene S-thythevane If more than one side chain is attached then the name of the compound inchides the side groups in alphabetical order, regardless of the number of the carbon atom on which they are found. So the onder for referring to the smaller alkyl groups is: + butyl, ethyl, hexyl, methyl, pemyl and propyl If two side chains ore attached to the same carbon atom then the number of the carbon atom is repeated in the name (see below). IF there are ‘to methyl groups the compound is described as dimethyl, and if there are three methyl side chains it becomes trimethyl, etc. ch, o1-cH, lot Ch OCHO, oH, 3-ethyl2methylpertane cH, cH cH, 2, 5-dhmetnynept2-ere cH,-C—CH,-cH, cH, ca, 2.2-imethylpentane ‘You can see thut the systematic nsming of onganic compounds allows you to identify the functional group, as well as any side chains present and where they are found within the molecule. In most eases throughout this section and the work you will de in orgunic chemistry liter in this course, organic chemicals will be given their IUPAC names, although there will, be times, particularly for very large molecules, when common names will be used instead.TR ed The shapes of molecules Isomerism in organic molecules Another complication that contributes to the lunge number of exgunic compounds i that, the vast majority of organic compounds have 1890 or more dsomers, Inomerism occurs when two or mort compounds have the same molecular formula but the atoms are connocted together differently. All orgnie molecules containing four or more carbon atoms show isomerism, and many smaller molecules do too. There are several types of isomerism and organic chemicals exhibic all of the different types. In this chapter you will be looking at structural isomerism. In chapter 1.7 you will meet geometsic isomerism, 18 (one ofthese & major constituent of petro) 6 Cae 366319 Cotlag 625% 10"? (estimated) {ble 15.5 Some ofthe lager organic compounds have ‘ast numbers of isomers, contiting ta the anormoue umber and varty of organic cereals. Structural isomerism ‘Strucrural isomerism is probably the simplest form of isomerism to understand. For example, the molecular formula CyHyq gives two isomers, butane and 2-medhylpropane (see fig. 1.5.12). ‘These structural isomers remain part of the same homologous series although their boiling temperatures differ considerably. Butane is a straight-chain isomer, while 2-methylpropane isa branched-chain isomer. ‘The differences in boiling temperatures and other physical properties of structural isomers can be striking. ‘They are brought about by the different shapes of the molecules which affect the intermolecular Jorces bewween the molecules due w differences fn the way the molecules ean pack together. 1 HocoW HoH OH w H K rite I Hote ce cH oH © coc OH Pred rt butane 2-methypropane: boiling tempertare 24°C beng temperature 1.020 Fig, 1.5.12 The two isomers of C,H,» are members ofthe same homologous series but have diferent physical properties. Another example of structural isomerism is shown by compounds with the molecular formula C,H,O. In this case the ovo structural isomers are members of different organic families and have very different properties ~ ethanol is an alcohol and methosymethane belongs to a homologous series called the ethers (sce Mg. 1.5.13). ethanol imethonymethare: bong temperature 786°C —bolingtemperature 249°C Fig, 1.5.19 The two structural homers of CHD are members of different ‘organic faites and have very diferent physical ard cherical properties as reat oftheir free structures,Some pitfalls in drawing isomers IF you know the molecular formula of an organic compound, you can Work out the different strtura ssomers by drawing them out ~ and then you can name them! However, thee are some comma mivakes when drawing structural Somer, Isomers often involve branched chains. Many people make the mistake of drawing 90° beads in a carbon chain rather thaa beanches, thinking that chis forms a different isomer. Another easy mistake to make is to draw the same molecule in two different ways and think they are isomers when in fact, if vou look at them carefully, they are the same representation drawn in a different orieauaion (gee fig. 1.5.14). Making. models is the casiest way 10 get isomers tight! I I Lot Hoc c ¢ cee cH Pree I necdene i Hocow i Hoorn I I hee-2ene x ‘-methyipent-1ene h ‘ 2.3dimethyut-loene i I a i 2 methyoent-2ene fig. 15.14 Strctral cies of heme cme conn mista when drawing somes. Re Cy Stereoisomerism Another torm of isomerism is stereoisomerism. (isomerism in space). [earises when the three- dimensional arrangement of the bonds in a molecule alow different possible orientations in space, This results in vo different forms ~ they look similar but however hard you try you cannot superimpose the mirror image of one onto the other. The two isomers are called stereoisomers und you will be looking at these in more detail in chapter 17. OED 1. Name and viite cut the full structural formulae for the following compounds: a CHCH),C. —b_ CH,CICH,),CHICH,)CH, 2. What ie an izornar? Why are izomeric forme £0 common in ganic chemistry? Draw out the three structural isomers of pentane. 4 Decide whether the rrembers ofthe pairs of ‘molecules In fig 1.5.15 are identical compounes, are Iserners or ae chemically unrelated. Give all the pessible structural formulae for C,H, (CHgCHaCHyCH2CH . chs CHgCHZEHZC1Z0H ——_CHyCHacHOH ‘ Cr a « 4 Wo Nemec” W 7 « " / W fig. 15.15 temers or not? TgUnit 1 The core principles of chemistry 6 The alkanes — a family of saturated hydrocarbons What are hydrocarbons? ‘The hydrocarbons are a group of crgunie compounds containing several homologous series. The common feature of hydrocarbons is that their molecules contain only the elements carbon and hydrogen. They can be divided into the aliphatic hydrocarbons (Gtrsight- and branched-chain molec), the alicyelies (hydrocarbons with closed rings) anel the arenes (bised on benzene, with rings of carbon toms stabilised by delocalisalion of electrons). In this chapter you are going to concentrate on the aliphatic Inydrocarbons. However, all hese hydrocarbons have certain properties in common: + ‘They are insoluble in water. + ‘They all burn, and in sulfcient oxygen they give carbon dioxide and water as the anly combustion products ‘Virtually all of cur usable supplies of hydrocarbons come from finsil fucks = evel, petroleum and natura 45, which yield pure hydrocarbons after varying toiling temperature (2) 4 density (gem 3) oot belting temperatre (°C) 0 ensty (gen) 0579 degrees of processing. The hydrocarbons can be classified as belonging to one of three families ~ the alkanes, the alkenes and the alkynes. They have very wide variety of uses from fuels to the rw materials {or an enormous number of industrial processes, In this chapter you will be concentrating on the alkanes. General properties of the alkanes ‘The alkanes are a family of saturated hydrocarbons: = they have no double or triple bonds between the carbon atoms, so they contain the maximum amount of hydrogen possible. The general formula for the alkanes is C,Hyy4 and they ean occur as both straight and branched-chain molecules. Some alkanes form rings, but you will not be looking at these molecules here, Straight-chain alkanes form a classic homologous series with predictable physical properties. However, there is considerable structural isomerism in the alkanes, us you saw in chapter 1.5, and this makes predicting the properties of # particular chemical from its molecular formula harder than it might at first appear. How a) Lil Lit oct Koc cH rot Lo How HoH ow thane rrepane 88 42 sis 501Unit 1 The core principles of chemistry Where are alkanes obtained from? ‘The single most important source of the allsines is the fossil fuels. In prehistoric times a far greater proportion of the Harth’s surface was covered with water than is the case today, Minute animals and plants lived in these seas. As they died and sank to the bottom, deep layers of rich, decomposing. ‘material formed which became encapsulated in rock. Over great lengths of ‘time, exposed to immense heat and pressure deep in the Earth, this trapped ecaying mawer has formed what we know cxday as erude oil or petroleum Crock oil). Its fiequendy found with snother product of the same ccomposition process, natural gas, which is largely methane. ‘The fossilised remains of land plants form coal by 2 similar process. In a mysterious extinction not unlike the one that brought an end to the age of the inosimrs, giant prehistoric “fern forests’ were largely destroyed. ‘The remains of these plants, fossilised after millions of years buried underground, form coal. Occasionally a clear imprint of an ancient fern leat is seen on a piece of coal. ‘Over 100 milion years agp scetchin plankton, ‘ny animals ae plats dug layer of dead ‘aiimals and plans + secimentary basin Milions oF years later ‘fred from the selon ‘ot heat and pressure on the caved animals and pants ilig lad ys oe appedinan anteline Impormesble rock ee ‘ol formation dependson ‘Scombination of facters — ead orgasms heat, pressure and sultable ook foration| tig. 19.2 Foss ues ae used for heatng our horns, to generate electra and a5 rw materials for pasties, pharmaceuticals and courelss other chemieals.‘edern Ife depends on crude el which provides fuel for transport and for generating eleeticty. ks the sure of raw materi ft many ofthe major chemical industries curd the world. However, crude oil and natural gas are found in orly a limited umber of places cn the planet, ad very large depots ae relahely oe The meaty ofthe verso supplies ere found n paca serve trees the world The supply of ol and Is pce affect the whole ob economy. Until the 1970s oil was egaded a a chegp and plentfl resource Then the Midde Eastern countries that supply much of the crude ol to the UK decided to produce less ad also ta ress the prices Ever since then ol pron and prices ave Muciated (6c ig. 1.6 3f0).As you can see Fig. 1.6.3), ll prc vary from mont tomonth and even orm day to day, and predicting these changes can make fortes ~ and ose ter ~ nthe franca, markets The overall end In ll ples hasbeen an increase, feving knock-on effect onthe cst of reraport and ofthe rw rater for any indus Ad Inthe fac that fos ful a a ite resource and you can see rouhat dees the ltal economy is affected by te rice and aval of ol andthe power held by counties that hold rich al reserves. Bede eee terineett edna malas and probleme in some oF the major ol-suppng curtis. The long-term impact cof these changes on the world economy will become earin time cre PESSSSEECESESS fig. 1.5.3 Ol reserves andthe pices charged for ths vital resource hae a major effect en wold economies. These _gophs show how the pice Muctuates in both the long and sitter, Pres 1 Sauel Arabia z ened 1788 3 in 1325 4 ea 7150 5 Kuwait 101s 6 72, 7 737 8 Russa 00 9 lity = 10 Nigeria 359 " aa uw china 183 B Oster 382 rs Mexico cr 6 Algerie ma 16 Breet 12 7 Kavakistan 30 8 Norway 7 19 Aaorbaijen 70 Ey indie 38 Top 20 countries 12245 (95%) Rest of world 8. (536) World roral ve926 ‘able 16:1 These figures show the counties with the biggest eserves of cree cil (Fem the US Knergyinlonmation Adminstration, 2095) Proved reserves ar estrated to be worth extracting with present technology ard ances. “ World crude oil prices Cnt 2005 weld ae pce cnet we redhigiot 33828 bere OF Mayo, teamedoun 1054794 abarel On fine Zt Tbutheda neigh oF $58 abort. wulll ii ti wang Sperbaret Das 2 esUsing crude oil The crude oi extructed from the ground is of lithe use without processing. It is w miture of many different hydrocarbons, many of them alkanes along, with some alkenes and alkynes. The basic pracess by which petroleum (crude oil) is turned from a dark, thick, smelly but very valuable liquic! into useful chemicals with u whole variety of properties is known us primary distillation, an industrial version of the fractional distillation you can carry out in the Tabosatory. Petroleum is boiled and the vapours are cooled and liquefied at particular temperatures. The liqaid collected over each range of temperatures is known as fraction. This process provides five major fractions (see fig. 1.6.4). It can also be used in further, more precise, fractional distillation processes to give a ure yield of 2 particular alkane. fig. 56.4 Theol Industry locates oposite of ude cn the ground feciact it and procesesit 10 supoly fis and anyother organic source materials, )—> herosene Geses pass up the toner ‘tough bute caps. the epee coo naugh the pcos onthe cap = theliqud Colets on atray beneaty deseo ‘tha patoloumis mates ec pa fees be : TS Reena ‘The main fractions that result when crude oil is distilled are: + 1-2% refinery gas ~ the lightest fraction of crude oil with the lowest boiling point. Contains the gaseous alkanes (1-d carbon atoms in the chain, C.-C,) with a large proportion of methane. Used ‘mainly as 2 fuel or as a starting point for other organic syntheses, + 18-30% gasoline ~ a mixture of liquid hydrocarbons (C.-Cg) which is widely used as fuel for the internal combustion engines that power cars. This is a mixture of straight- and branched- chain alkanes, and the more branched molecules there are the mors useful che fuel. Some gasoline is also used in the production of other organic chemicals, although this usually invelver further processing such a catalytic racking, + 10-15% kerosene ~ mainly Cy, and C,> fractions, this is largely used as fuel for aircraft engines. It can also be ‘cracked! to provide other useful chemicals such as gasoline. % diesel olllgas oil ~ used bod in the diesel engincs suggested by the name and as a fuel for industrial boilers. Diesel cil can also be fiarther split up in a catalytic cracker to yield other useful 1s fractions + 40-50% residue ~ this complex mixture of hydrocarbons is very viscous and has a high boiling temperature. It can be used as fuel for the furnaces of power stations or large ships, or it can be further fractionated to yield Tubricating oils and ‘wanes and a solid material which we know as the bitumen used co surface roads. This final distillation hhas 10 be carried out in a vacuum 10 avoid the need for high temperatures which would ‘crack’ or break ‘open ruther than separate the components. Peon 1) What isan alkane? Which ofthe folowing belongs to the homologous sees of kanes? CqHe, Hye CicHay CaoHen 3 Why ave fossil fuels regarded asa finite resource? 4 Explain why the different fractions of crude cil are collected at different tomporstues. OO1 The core principles of chemistr Making the most of crude oil Different fractions in demand Crude oil from different sources contains slightly varying proportions of the different fractions. While the lighter fractions produced during the fractional distillation of erude oil ure ia great demand both as fuels and as the raw materials for the chemical industry, some of the heavier fractions are of less use ~ and they can maike up t0 50% of the products, depending on the type of crude oil (see Fig 1.6.5). ‘The demand for the li there is a constant pressure to find ways to make the heavier fractions more useful Jbter fractions i enormous, snd ee Y $ seta fe ee roo me —— ‘set ‘solvents, light 1-20 tee 1 bees = Pend = ~ 23 fuel oil, —— 350- reside 43] buen, wax ——- 99, Pecicted demand for cide oi rsctons inthe Uk lesa ot aotthe fig. 185 There isa mismatch between the demands cf the market ard ‘he factions cbtaned frm ene ol ‘To address this imbalance, sciendsts have developed a way of treating the heavier, long-chain fractions of crude oil and breaking them down (eraeking them) to produce more of the lighter compounds. Heating long-chain alkanes to high temperatures cases the molecules te split and form shorter-chain molecules Some of these are alkanes which can then be used, cz in gasoline. Others will be alkenes, particularly ethene, which is extremely useful. Apart from combustion, the alkanes are a very unreactive family af compounds and so they are of lim sd we as a starting point for the petrochemical industry. Ethene, on the other hand, coniains a double bond which makes it much more reactive and so very suitable as 9 starting point for synthotic reactions (see chapter 1.7), Producing the high temperatures needed to crack the heavy petroleum fractions would be very expensive, By using catalysts the process can be carried out at a much Tower temperature. Tt is known as eatalyde oo eat cracking and is curried out in a eat cracker. Crystalline aluminosilicates (zeolites) are commonly used as catalysts in the process i f I 1 a tt I I I occene 1 I Il a jl Il 1 HHH HOH AW Ow ethene Cs {ig 166 Thestfec of attic cracking on large alkane molecules,TSR on Ceca ne ga ) HSW ‘knocking’ and the need for catalytic reforming ‘The allanes in gasoline, the crude ol fraction used 2s petro, have carbon chains which are usually 5-10 carhon atoms lang, The power is produced in engine cylinders by the explosive combustion of gasoline in the cylincers. ‘The smooth running of a car engine depards on the explosion inthe cylinder occurring at just the right moment so that energy wastage as heat is minimal and the maximum amount of energy is trnsferree 1p the pistors. I the explosion occurs to9 early the pistons ae jrred and the engine not only makes dsconcerting hnocking nolses but also leses power. ‘This ‘knocking’ Is particularly common when fuels ith a large proportion of straight-chain alkanes se used, Heptane, octane and nonane in particular ignite very easly. Branchad-chain alkanes euch as 2.24-trimethylpentane are ignited less readily so their combustion is uch more cortralable. Gasoline mistures high In these branched-chain ‘alkanes meke much more efficient fues than situs high in steight-chein molecules. To indicate the proportion of branched to straight-chain molecules ciferent mixtures are ‘gen an octane rating, The octane rating of 224 ‘vimethylpenterte (old neme isooctane) is set at 100, whilst that of streignt-chain heptane is set at GLA fuel con be tested by compering it with known mixtures of heptare and 22.4-trimethylpentane in a test engine. The ratio of heptane to 2.2.4- ‘vimethylpentane is varied in the comparator ‘mixture until it has the same igrtion properties as ‘he sample of fuel being tested. The percentage of 22.4-timethypentane in the mixture Is ther taken as the octane rating of the fuel Other methods for measuring an octane number involve detailed crerieal analysis of fuels. Octane ratings are shown en petrol pumps by 2 Research Octane Number, 1 Compare the processes of cetalytic cracking and catalytic reforming. 2. What is meant by the term knocking? OF FON seb mnaing the prormancs ofthe fuel under set condition na serch engire-Crdiray unleaded pets 9 ON, white sper unleaded 88 20N Fee ee eee ten te eee eee dee ee rrthods of preening Knoctng Hstrcaly teortngled(V) PB(CH,), ws ded to gatclne to retard its ition Tis aed lead polio rom cx exhausts which can potenti cause heath problems #0 mos courtieshave irnated th use of leaded pel By 207 oly 17 cours in the word st sed leaded peel ache number algal he tne Te otter alma so produce ysctne tres that ee etal high Inbrorched chan ekaresThiscan be done aa rest of eatabyle eet ee eel See ete beeing up strat chal lace the hae il Faction eect sta ea ese ence platinum catalysts used, so he process sotines refered to as‘lattorming” nce the witaval leaded etl aay eres eo tee cetaceans eerie eae areal er cece ee fig. \67 High-performance cas tke this have alvays needed ig-otane ee eee eee ee ean asall cas become more sophisticated their engines need more branched chai alkares in ther uel 1 prevent unwanted Loss of power Cutline each methoe, explaining the advantages and disadvantages. Which methed is ead almost exclusively inthe UK and why?Unit 1. The core principles of chemistry ‘The old, non-systematic name For the alkanes as the paraffins. This came from the Latin partum affinis which means ‘ule affinity’ tnd it described the alkanes as a family very well, Apart from combustion, they are v unreactive, having few reactions with other clements or compounds. This makes the alkenes very useful. They are non-corrosive with metals, which makes them good lubricating oils. They are also harmless to your skin, yet protect it = which is why petroleum jelly is effective at preventing your skin from chafing, At room temperature the alkanes are unaffected by concentrated mineral acids such as sulfuric acid or concentrated alkalis such as sodium hydroxide sclution, ‘They are not affected, by oxidising agents such as potassium manganaie(VI) and they do not react with even the most reactive metals. The reason for this lack of reactivity is that both CC and ic clectrons, since the electronegativities of carbon HI bonds involve a very even sharing of and hydrogen are very close. This means that the bonds in the molecules of the alkanes are not polar to any extent, and so there are no charges to attract other polar or ionic species. Almost all of the reactions of the alkanes oveur due to the formation of free radicals, witich contain an unpaired electron. As a result chey have high activation energies, but once this barrier to reaction is overcome they proceed. 10 react very rapidly in the gos phase. Before you move on 10 look in further detail at the reactions of the alkanes you can find out mose about these free radicals. The chemical properties of the alkanes Breaking bonds As you have seen, chemical reactions involve the breaking and making of bonds between atoms. Breaking bonds is also known as bond fission, In organic chemistry we almost always tlk about the breaking and making of covalent bonds with varying degrees of polarity or ionic character. Within a covalent bond; two electrons are shared between two atoms. ‘When chat bond is broken curing a chemical reaction there are two ways in whieh the electrons may be shared out. Homolytic fission Homolytic fesion involves the equal sharing out of the electrons in the bond, so that exch of the participants in the bond receives one electron hen the bond spl To show exactly what's going on in chemical reactions, chemists use curly arrows. The most common use of curly arrows is 10 show the movement of pairs of electrons (sce Chapter 1,7). However, in homolyie fission, because just one electron is moving, # curly hall-arow is used (as seen in fig. 1.6.8) ~ note how the hed of this arrow only has a single line head rather than two lines. The unpaired cleetron gained bby cach atom is indicated by «1 dot H+ c-cl > Heals cr ‘The important point is chat although neither atom has an overall charge, those free radicals with their unpaired electrons are extremely reactive. This is becuse the unpaired electron has a very scromg tendency to pair up with an electron from another substance, ‘The reaction of one free radical with another substance usually results in the formation of a further free radical. ‘The equal sharing of the clectrons of hemolytic fission usually occurs in situations where there is lithe or ae ionic churacter in the covalent bond, Cr+ CH, 2 CHy +HICI @ aid —> a-+a- 2G: se + cs Fig, 168 Homoltie fasion guns each rew species one electron From the bord These free rca can be abovn (2) using dos to represent the unpaired slectrons anda cst halt arrow t> represent the movernent of the singe tlectrn,o (8) by the dot and eros agrars you are aeady familar withTS Reena & & Hcl ——> Het Heterolytic fi Heterolytic fission involves an unequal sharing of the electrons of the covalent bond, so that both electrons go co one wiom. This results in ovo charged particles ~ ue atom receiving the electrons gaining a negative change and the other atom gaining a positive pe charge. Fererolytic fission is usually seen when the covalent bond already has 9 degree of polarity. a + Bae Hrd: Hie tcly H-Cl> HY + cr = 3 Hocl —> We ce £5159 biforentepresentains of heterotic ison Ee ee Free radicals are an important element of cur model for A pleriful supply of fresh fruit and vegetables containing ‘many organic reactions. and they are obviously of great vitamins C and € in the diet helps the onaymo superoxide importance for that mason. But foe radical also make guest —_—_dlsrutate to deactivate free radials and so provert ary ‘appearances in the rredia on a regular basis. This is as a damage they may cause result of thelr role in several common human problerns. Cancers one ofthe major caures of death in the developed ‘world Cancer aceurs when the narmal growth-contrlling mechanisms ofa cel break down, so that rapid repraduction cof smal unspecialsee cols takes place. This results in the formation of a tumour or growth which may itself cause serous illness cr death by fling up and destroying a vital erg. More commonly svall pieces wil break off the ‘tumour, travel eround the body in the blcodstream and lodge in other places to grew again Many eifferent substances are thought to be resporsble for ‘te cellular charges that bring about the loss oF control over call gonth they are hnown as careinogente substances Free tadials in the body are now considered to be one of ‘the culprit The numberof free racials in the body can be reduced by cutting down on the intake of focd high in fee radicals ~ bumt toast and charred food from the barbecue fig, 16.10 The extreme recut of fee races which enables 30 many erpricreactons to actus also te eaton that they are £0 ron ese Ct ne Co Ms clever ieee potently damaging >the cells of your body when they czar enabiing the body t0 "moo Up' ree radicas which may frm. xcs. 1 Why are alkanes so unreactive? 2 What isthe difference between homolytic and heterolytic fission? Explain a benefit of eating frit and vegetables with reference to reactions ‘demonstrated in the alkanes. aryUSO CCR The reactions of the alkanes ‘The alkanes have just wo common types of reaction, occurring when they are heated or in the presence of halogens. These are both considered in mare detail below Heating alkanes Cracking ‘When alkanes are heated to high temperatures in the absence of air they split into smaller molecutes, ‘The thermal dcvompynition of methane yields finely powdered carhon, which is used in ear tyres and to make artificial diamond coatings, and hydrogen, which fs used as a raw material for the chemi CH,g) > CO) + 2H) al industry Cracking is thermal decomposition that involves the breaking of carbon-carbon bonds to form smaller molecules (see page 112). The cracking of ethane gives ethene, one of the most imporsant raw materials of the chemical industry, as well as hydrogen. This process involves the breaking of the C—C bond followed by dhe formation of ure C=C bund: Ciel) 9 CH,=CH,(2) + Ha@) Combus' When allsanes are heated in a plentiful supply of sir, combustion occurs. Allunes are energetically unstable with respect to their oxidation products, water and carbon dioxide, so once lit they will bum completely Alkanes only bur when they are in the gaseous state s0 solid and Tiguid alkanes wend 10 be less flammable than gascous ones ~ they must be vaporised before they will bburn, You can see this in the burning of « candle flame the solid wax mel as the wick bums. The ligule souks up through tiny channels in the wick, waporises, mixes with the surrounding air and then burns. This releases more heat to keep these provesses going. Convection currents are produced in the air sround the hho« flame and these carry the products of combustion away from the candle. This allows more air ve mix with the newly vaporised wax. ‘The combustion of the alkanes is of great importance of life ~ it is used to generate electricity. to fuel fires in the home, to provide central heating, {ig 16-11 The hes from the flame mate the wae, hich than apotses from the wick where ic burs for cooking and for transport. In all these examples the central process is the transfer of energy from the exothermic combustion reaction into heat and light energy as well as into the bonds in the combustion producis, cla) + Bl + 10010) 8388 = 24804 mor? 3Clg) +2(¢)+ S048) exangiono, . Saco a] ewtte—o) cexanstt! a] 28 TScacenhna! = 2 347 kj mc = 8542 lJ mo! BS] lanansitmar! " = 3538 | mor? Carsle) + 5048) A= 3936K mo” + 260K! ro! “asta mot? 0s mor TY 3CO ta) + 44.018) (ote that thie cot the standard enthalpy ofcombusto, since ‘he ete Formed ise the geseots Sate, rot alii) Corel + S09 300,69 + F009 fig 6:12 When propane burs in ar the erergy required to break part the propane ard enygen molecules crore than compensated for bythe energy relessed when che bonds in eatbon diode and water ae formedAs with all exothermic changes, the release of energy results from the fact that the energy needed to break the bonds in the chemical reaction of combustion is less than the enerzy relumed when the new bonds are made 2s the products of combustion form ~ see fig. 1.6.12, ‘Methane (natural gas), propane and butane are all commonly used as fuels. In many areas nanural gos is piped into homes, Where this i not the eae, canisters of propane can be supplied. The great advantage of propane over methane is that it can be liquefied readily under pressure and at low temperatures, so that a large quantity of gas can be stored in a very small space. The liquid alkane will not burn until itis retuned to the gaseous state ands it can be stored and transported relatively easily and safely. This liguid petroleum gas (LPG) is transported t© countries uch as Korea in enormous rel rated ships and is then stored under pressure in vast tanks underground. Te is translemed to ps and heating in the home. In contrast, in the UK the main use of propane is for Ieisure purposes ~ camping and BBQs! ssarised cylinders to be uted for cooking Although the combustion of the alkanes brings huge benefits to people around the world, itis also central to some major environmental problems which you will consider at the end of this chapter. fig. 16:13 Gyinders of wells on boats. In cold climates propane (balling temperature 42°C) used In preference to butane (toting temperature 04°C) because ona cad morning the nud butane would not vapors, ui butane ae a common sight en caravan holidays as TS Reena HSW Alkanes for heating - risk If an altane is burnt without plenty of oxygen, Incomplete combustion occurs The preducts cof an incomplete combustion reaction may Include caroon or the potentially fatal gas catbon monoxide. Mary people who use gas heaters end boilers may be unaware of the potential hazard of a inadequate supply of ‘cxygen to 2 heater, er inadequate venting of the waste gazes. Every year there are tragic ‘examples of deaths resting fram eathon rmenaxéde pcisorirg. This isk can be reduced sgeatly by the proper maintenance of gas ‘appliances. You can also buy carbon monoxide ‘monitors which ge a warning when te gas Is fprduced in the room. Landlords need a safety cenifcate which guarantees that their gas appliances have been checked, something all tenants should be aware of “1 What happens to alkanes when they are heated to high temperatures: a. in the absence of air in the presence of air? ive chemical equations for ecamples of these reactions. 2. Use the example of a gas fire in a student's room to produce a short report or poster ‘e CHy + HCI AH = -19 kJ mol e radical then reacts Phe methyt tr with gnother chlorine molecu to form chloromethane and a chlorine free raciica: CHy +c,9 CHC + cr chloromethane 103 Xf mot ‘The process is then repeated hundreds of times in these propagation reactions that produce another free radical. This rapid tnd repeated propagation results in a chain reaction, an explorive process Reactions of the alkanes with chlorine intistion py propagation eS { _ erorann | “@ Ba fig. 1.6.14 The reaction of methane with clvine se Fee-raial chain eetion. The propagating stepe of this reaction continue until there is @ termination step. This is a reaction herween tw free raclicals a highly exothermic process. A termination step happens every few thousand reactions! arscrsc, 243 4 mor cHy + cI'>-cH,CI 46 35 mot chiy = CHy > Catt, “347 WI mor ethane e e 8 & a a. as @ o— @-Nemnnon CHSC Hy CH, ea @ fig. 16.15 The termination ofa chain reactionIf the supply of chlorine is limited, the net result af this reaction is Joes of ehloromethane, CHCl and hydrogen chloride, and relatively litte ethane. However, if there is a plentiful supply of chlorine then further substivations of the methane will ake place Co give dis tr and tetrachloromethane as follows: CH, + Cl > CHSC) + HOS CHCl; + Cl > CHCl, + HCL CHCl + Cl > CHCl, + HC CHC! + Cl, > CCL, + HCL Some of these halogenated alkunes (hulogenoalkunes) ane well-known chemicals. Trichloromethane or chioroform, CHC1, wes one of the first anaesthetics to be used for surgical operations and to ease the pain of childbirth, whilst tetrachloromethane, CCl, was widely used 18 a solvent until its carcinogenic properties were recognised. TS Reena =p 1 Under what conditions do the alkanes react with chlorine? 2 Explain, using chemical equations, the mechanism of the reaction between hexane and chlorine, showing why the reaction conditions are so important. 3 What type of experiments would ‘you like to see to help to confirm ’ growing body of experimental radicals exist in the human body where they ae responsible for many regative affects. As you saw earlirthey ae linked to the development of cancer They have also been linked to heart disease and very specifally tothe ageing recess. For example. your skin changes very noticeably as you age The smooth elastic appearence of yourg skins due in part to collagen a fexble protein. One theory of ageing tha: free radicals in te body attack the cross- links between collegen fires mekng them stifer and ess flexible, wich in tur affects the appearance ofthe skin. Free radicals aso seem to alect the biochemistry of cells and may eve attack the DNA in the nuclei of cells This could be how they cause cancers Totty to counteract these eects people are increasinaly {uring to antioxidants — compounds thas ‘mop up'tree radicals. Viamin € isa well-known exarnpe ofa natural free-radical inhibitor. Many people take antioxidants as ezary supplements and use them in cosmetics. Do they ‘work? Thre is evidence that peeple deficient in vitamin E show skin charges similar to those of ageing 0 maintaining healehy levels of such vitarins in the dit should have a protective effect. study published in 2000 showed that healthy centenarians (people of over 100, years cl) all hac high levels ofthe antoxidanes viarin A and vitamin . Studies on a number of mammalian species the effects of antiexidants such as vitamin Ein preventing ageing? ———<$<$<$<__/ also seem to show a link between the levels of antioxidant vitamins in the blood and life expeczancy (soe fig. 1.6.16). ating plenty offrlt and vegetabies increases the cletary Intake of articxidants and til is accepted by most scientists as sound edrice. However, the benefits of rubbing antioxidarts into your skin, r eating excessive arnounts in the diet, have stl to be proven scientifically. & a ama inet cumin gon") & erage life cxpezaney (yes) fig 16.16 This staph suggests a link betwen vitamin Eleven the blood pln andthe Uc cpecioney ofthe entree “hs suggests thatthe antoxdant efecto! the tain may help proleng lie by reducing damage by free radicals (Rhews and Capuchin ae types of monkey), orySmt? Cars and society ‘The combustion of alkanes in the form of fossil fuels ives most of the great econcries of the world. One of ‘the major uses oF fossi. fuels is in the internal combustion engine that powers road vehicles. Public atitudes to the car ‘are changing and more people are now questioning she use cf the car than at ary time since they were fist given the freedom of the roads at the turn of the twentieth century 110 mow 160] Mi certo! fs Ha sigh 140} pm ecu 971-1986 Lo 100 1066. ig. 15.17 Heed bythe power of advertising the caryou dive ea are eerie eee ‘roduced bythe UK Department for Trensport, shows How rand trafic has increased - ani predicted to contre increasing the fire, Cars are one of the majer pelluting agerts on planet Earth but using a car has beceene so converient and even necessery that its difficult for Ieivduals to see the collective damage that each joumey is doing. The advantages of restricting moter venicle use are to society as a whale; the dlsadvantages are all personal. This balance cf personal end public good hes to be adresed in all the arguments over how to make the cat more environmentaly accoptable. What's the problem? Ina car engine, Fydrocarbon combustion is not always ‘complete and so carbon monoxide is formee along with, cafoon dioxide. carbon monoxide not only a greenhouse 1 (see below] but f also highly toxic as it combines ith the haemoglcbin of the blood more effectively than ‘oxygen, preventing the blood from carrying oxygen around the body. Oxides of nitrogen and sulfur are also produced ‘om impurities inthe fuel, and these cause acid rain ard smog if they are not removed from the exhaust furs. Catalytic converters convert carbon monoxide end nitrogen ‘oxides into less harmful gases, but cannot remove the carbon éienide, ‘The quantity of pollution produced today is to0 great to be abscrbed by the atmosphere without an adresse effect on the environment. How is this effect felt? Increased levels of carbon dioxide n the atmesphere are ‘thought to be causing global warming, with resultant changes in weather pettems (see below). Ary process that adds tothe leve! of carbon dioxide or other greenhouse gases therefore a problems. The greenhouse effect Radiated energy from the Sun reaches the Earth, The Eart’s atmosphere reflects some of this ration back into space, but some of It passes through the atmosphere to te Earth's surface, The Earth absorbs this radiation and also radiates its own infrared radiation, which hes a diferent ‘wavelength from thet of the Sun. Some ofthis infered dogs not pass out through the atmesphere and back into space. It is re-adiated back down to the Earth sean by greenhouse gases in the atrmasphere so keeping the temperature of the Fath higher then it would otherwise be Greenhouse gases incluce water vapour, carbon divide and mathane amongst athers. This re-adiation as part of the natural balance inthe atmosphere is called the greenhouse effect. Increased acunts of greenhouse gases in the atmosphere lead to an increased greenhouse effec, and thisis widely belleved to be causing glozel warming. Twentieth-century ura 0 iviies have produced a massive increase in certain greenhouse gezes in the upper atmosphere, Including carbon cicxide from the buring of Foss fuels and mathane ‘rom rotting vegetation, from pady felés and the flatulence produced by cattle rssad for cheap beef At the same time people have removed vast areas of the world’s vegetation in the much-publicisec destruction of the rainforests This adés to the carbon dioxide loading because the trees are often burnt after feling and the toss of tees reduces the abiity ofthe biosphere to absorb catbon diexide. What & more, the trees are Frequently replaced by cattle which ad to the greenhouse gaces byTS Reena producing methane, The ability of trees to take Lp carbon dioxide also seems to be reduced as ‘temperatures increase. Carbon dioride mates ‘the largest single cortibution to the Incase geenhouse effec although methene is chemically a more potert ges. coz conerttion (om) SERRBRSERRAESS ‘The long-term effects of global warming remain 19 be seen, although increasingly violent and unpredictable weather patieins ere often blamed on global wer veo | tar! ee ‘ig. 1.6.18 The deta shown inthis raph were measured cr 2 mountaintop in Havel The oval tend shows a steady rein carvon dixie levels ‘Amount (gigatonnes pa) Carbon storage nl nunca ‘Annual erissior: 7-31 Atmosphere 750 Fossil fuels, 69-70 Fevests 600 Land use change (deforestation) 1-20, surface ocaan 1580 ‘other on Deep ocean 100 ‘Anna abrorption: ayo4 Forel fuels *| ‘5000 Femains in aurosphere 45 Coal 4000 ‘Absorbed by oceans 23 ol 500 ‘Absorbed by vegetation 19:23 Noturl gas 500 table 1.52 published data on soe ofthe soures of global carbon donde and whee i stored tn the Earth (Souce-Kesting 1956) This data varies widely deperding on when ie was cllected and who publshes i. Carbon is locked up in fs fuels andsreleased on buming. fig. 15.19 There have been many cases cf catastrophic flooding and other ‘tural drasters over the ast decade or mor Ae there the ru ofplabsl warming ~ cr us natural fuctuators in rate? Precicte¢ outcomes of global warming include the melting ofthe polar icecaps causing arise n sea levels and the loss of lov-lying region of many ‘countries. ti also suggested that relatively smell ‘changes in global temperature could bring about majer shifts in climate, destroying the present pattern of world food pracuction as many curently fertile countries become barren deserts. Whether ‘these predictions hold true remains to be seen. IS ‘easy to blame any unusual weather conditions on ‘global warming ~ yer ¢ look back in history often reveals sila events centuries ago. However, the ‘evidence of a real problem seerrs to be mounting, and there isa growing consensus among scientists ‘that the rising levels of greenhouse gases in the _atmasphera do pose a real treat to the future ‘well-being of the planet. Ar present. ll we can co is ‘act to reduce or avoid adding to the current levels ‘of greenhouse gases and then wait and see, OaUnit 1. The core principles of chemistry Developing new fuels Medern cars have catalytic converters which absorb most cof the pelluting gates from the exhaust emissions, They ‘are certainty cleaner than their predecessers. She modern cars proclice less pollution than one 1970s model. But the escalating nurrbers of vehicles outweigh the Improvernents ‘made. Over 100 000 cars are produced per day, with an estimated 600 milion vehicles on the road worldwide ‘To mahe @ real impressicn on pollution levels altemetive, sustainable energy sources must be developed. ‘There are 2 rumber of options Cars which run on methane, ‘ats powered by ethanol produced by the Fermentation of sugat cane, hydroger-buring vehicles and solar-powered cats are all possible alternatives to the traditional petrol cr diesel. powered vehicle. For avery alternative fuel, you ‘eed to concider the overall carbon ecaramy. What carbon emissions are released in the production of the alternative fuel? How rruch carbon dioxide is released as it is burnt? How easy it to refuel the vehicle? Is the process relly catbon neutral? For exemple, methane can be produced by ‘the fermentation of plant and animal waste, Catbon dioxide is ebsorbed during the growth of the plants Ethanol too is preduced by the fermentation of plants such as maize, so ‘the plants act as a earbon sink or reservoir. But the energy ‘needed for processing, and the amount of land needed to produce biofuels such as ethanol and biodiesel, mean they ‘may nat be the answer that was hoped for. People reed land to grow food before fuel Rattery-powered vehicles ‘The most prectical globally evellable alternative to petrol is the electrically powered cor. Electric vehicles are not new — eg electric milk floats have long been seen on our streets No echaust gates are produced because there vehicles ‘are powered by an electric battery — bu this has its own problems. The vehicle has a United range and cannot travel very fast once the bettery runs down. There are two man types of electric vehicles being designed by the major ‘moter companies ~ battery-powered and fuel-cell vices The technclegy forthe latter i till in its infancy, but battery-powered cars and cars that can switch between battery and electric power are abeady gaining in popularity. {ig 1620 Ths sone of the fst ‘ual fuel cars to become popula. “The cr avitchea between tier poner for whan diving ard petal poner or lenge journeys. However, batteries have a high energy density ~ Klogram {or blogram they provide far less energy than petrol. This ‘means that, wth conventional batteros at least, electric cats have to cary extremely heavy batteries to provide them witha reatonahle range of travel. Batteries need to be recherged ~ refuelling an electric car entails not 2 five ‘minute stop at the garage but around 12 hours plugged into the mains! And although the cars therrselves ae pollution-ree, the production of mains electrciy from the corrbustion of gas, ol and coal s far from e pollution= ‘ree process. Only when nuclear fuel is used to generate the electricity to charge the battery isthe environmental impact considerably less in toms of carbon emissions than {for 2 petrl-fuelled car. Real advances have been made in battery technology in recent years, and research s still continuing. The hydrogen call ‘One of the most exciting developments is the hydrogen- cell motorbike, The ENV (Emissions Neutrl Vehicle] wos designed in the UK. tis an almost silent motorbike, whieh can travel at around SO mph It tune en hydagen and £9 combustion produces only water and heat. it can travel 100 rriles on a single tank of compressed hydrogen costing around £2 The system Is based on a proton-exchange ‘membrane (PEM) fuel cell This works by using the energy produced during the axidation of hydrogen to generate clectrcity.The call cantains special membranes fer clecrclyss to take place. The electricity produced by the fuel cell ie stored in batteties and used to drive the motor,TS Reena ‘This isa promising way of powering vehicles. Hydrogen is relatively safe —it does nat explode readly when kept in pressurised botle away trom the air. However refueling Is not easy atthe moment, because garages are not set upto supply hydrogen. And a prese ‘eenhouse gases are produced inthe formetion and pressrisation ofthe hydrogen. I the future, bioluls mey be used a the source of the hydtogen which woud reduce carbon emissions further Ths techrology isatill developing, ‘ig. 1621 The hydrogen powered motorbikes quet and clea. Wl vehicles tke this redece _greerhous emissions enough to seve the planet? Your studies of the alkanes have given you an introduction to the chemistry of the hydrocarbons, und into some of the reaction mechanisms that are important in all the familics of organic chemicals. In the next chapter you Will look at the chemistry of the unsaturated hydrocarbons and sce how this differs trom thar of dhe saturated slkanes, 1. What are the main environmental Issues Unked to the use of Fossil fuels n car engines? 2 Using this book and other resources, investigate the evidence for the greenhouse effect and global warring. 3 Chooe a way to represent the data in table 1.6.2 to show clealy (in gigatonnes}: 2 annual carben emissions b- annual absorption ¢ the main carbon storage reservelrs. 4 From the data presented in table 1.6.2, 2 What are the maximum and minimum percentages of global emissions which come from fossil fuels? 1b What ate the maximum and minimum percentages of global absorptions whichis the result of piant activity? © How do these data support ot undermine your ideas about the role of deforestation in global warrirg? 5 Use ICT to bring the story ofthe hydrogen-cell motertike up to date, What impact have they made, are they selling well and what isthe current state of hydrogen cell technology In the car industry as a whole?ead 7 The alkenes — a family of unsaturated hydrocarbons 4 i fhe HCC he i 4 there oh x % fig 1721 Akenes contain two fewer hydrogen ators thn the ‘omesponding akene. a ‘ig. 172 The distribution ofthe electors in (a2 carbon aren singe bond and (b) a dose bend A doubie bond Consists ofboth bond and ax bond, This fle the shape ofthe mcevul, which in ture dictator the proprtes ofthe compound. ‘The alkenes, and cthene in particular, are of immense importance to the chemical industry. They occur naturally aly in very small quantities but are obtained from crude oil by the processes of cracking and catalytie reforming described in chapter 1.6. Ethene is the starting point for a great many synthetic processes ~ itis used for the production of polymers, detergents, solvents and many other chemicals. Like the alkanes, the alkenes are hydrocarbons (they contain carbon and hydrogen only), but they are unsaturated. Unsaturated compounds de not contain the maximum amount of hydrogen possible because they have one or more carbon-carbon double or triple bonds. All alkenes contain at least one carbon-carbon double bond, and for every carbon— carbon double bond in the molecule there will be two fewer hhydrogen atoms than in the corresponding saturated molecule. So the general formula for an alkene containing just one double boad is C,tT,,. The carbon-carbon double bond In a carbor-carton single bond (alo known as ao bond or sigma bond) the electron cloud is symmetrical about the contral axis of the molecule (see fig. 1.7.2). Because it Ties along the line joining the twa carbon atoms, the c bond ccm rotate about this axis, so the two ends of the ethane molecule are free to rotate relative to each other. In the carbon-carbon double bond the geometry is different. ‘The ethene molecule CH=CH, is flat. The double bond in ethene involves a o boad plus a sccond bond which has its clectron density concentrated in wo regions on either side of the axis of the bond, above and below the plane of the molecule, This second bond is known as a x bond (pi bbond). The = bond does not allow rotation around the axis, and this has a big effect on the structure, and therefore also the properties of compounds that have a 7 bond. ‘The electron density in the t bond is on average further from the nuclei of die uve carbon atoms concemed, so the double bond is less than twice as strong as aa band, As you will see in this chapter, this arrangement of cleetson density ako explains «wo other properties of molecules containing cearhon-carhon double hands:+ They are reactive, due to the attraction of positively polarised groups to the electron-rich x bond within the double bond, These electron-secking groups are known 8 electrophiles, The x bond provides an eleciron pair 1 form 2 new bond with the electron-seeking group. + Many unsaturated compounds show geometric isomerism, Rotation about the bond axis is not possitle without breaking the 2 bond. Naming the alkenes As you saw in chapter 1.5 the alkenes are named using the IUPAC system, based on both the number of carbon atoms in the chsin and the position of the Functional group, which in this case is the carbon-carbon double bond. For example, for an alkene with four carbon atoms, the double bond can occur in three different places, forming but-1-ene, but-2-ene and methylprapene. ‘The properties of the alkenes are physically very similar to the equivalent alkanes, although the melting and boiling temperatures are a little lower. Also, like the alkanes, the unbranched alkenes form a family with regular wends jn properties. pon er formula eee) {able 17.1 Theallenes show alse in belting terpertireas the nurber of can atoms inthe mole insreses, Teco es ee ed there [s the smallest akene. tis also a plant hormone, which has the effect of ripening fut. This property of ethene is used commercially to make sure Frit arrives in the supermarket in perfect condition. So, for example, banan are picked in the Caihbeon ar South America long before they are ripe They are chilled stored, transported, stored again and then, once te supermarket is ready for them, they are exposed to ethene to ripen them ready for sal. This means that bananas and many other exotic fruits that do not grow in the UK can be available in our shops al year round, ‘This great for consumer choice ~ but ist good for the planet? Transporting fruit thousands of miles, and keeping it in refigerated storage over periods of ‘weeks fellowed by exposure to ethene, all use huge amounts of energy whose generation releases vast amounts of carbon dicxide into the atmosphere. this tho right use of our resources? Another aspect ofthis issue is thatthe velinaods of many people fn the banana-growing countries are dependent on this method of futt production ~if we change our ‘eating habits to reduce our carbon footprint, what happens to ther? fig 173 tthe use of ethene to ‘manpuatensture Sd provide ur with bananas wherever ‘we wort them @ 200d thirg forthe planet? 1) Give the structural formula of the Following compounds: 2 but2-ene b 2-mathylbut-2-ene, 2 a How does a carbon-carbon double bond differ from e carbon-carbon single bond? b_ How does the presence of 2 double bond affect the physical ard chernical properties of the alkenes? 2 Outlire the pros and cons of using ethene as 2 Fuit- and ethical probleme ‘pening hormone, What zac might arise if. 2 the process continues b the process was banned?TRC Geometric isomerism But-Z-ene, C,H, can be separated by distillation into ovo components that have significantly different boiling temperatures and other physical properties but that show no significant differences in chemical reactivity. How de we ‘explain this? ‘The luck of free rotation around the double bond in but-2-ene results in molecules known as geometric isomers, Geometric isomers occur when components of the molecule are arranged on different sides of the molecule, ‘The traditional way of naming geometric isomers is known as efs-trans isomerism, The cis- and crans-isomers of ut-2-ene are shown in fig. 1.7.4, ou 4 e Voy cic fN ng cH, cetue2ene rans-buezane ‘ip. .74 Che and ran-but.2-ene.Ceometic isomers ofthe same molecule often have ciferent properties Jin the cis isomer both methyl groups are on one side of the bond snd both hydrogen atoms are on the ather. Tn fnane-but-2-ene the two methyl groups are on opposite sides of the doable bond (cis means ‘on the same side? ‘und frans means ‘on opposite sides’). Geometric isomers frequently show different physical propenies. Their meling and boiling temperatures as well ss the density of the compound are often affected. Sometimes the chemical fucnced 109, but often the chemical reactivity of the isomers is the same (eg the two isomers of but-2-enc). reactions of the isomers ai ror urea ae ety foo) (ec) cie-but-2-en8 139 4 rans-tut-2-ene ~108 1 ‘ble 172 Physical properties ofthe geometric omer of but-2-ene) SW cis-trans isomerism, cooking tomatoes and A a ene Biclogkcalsysterns are often very sensitive to different geomeric, isorners Far example, In recent yeas It has been clscevered that the centicxident lycopene is very elfective in helping to prevent a variety cof prablems, from heart disenze to prestate cancer. It may even help raclice the effects of ageing. Lycopene is found in many red-calaured fruits and particularly high levele are found in tomatoes. Sciantets have found that cocked tomatces seerred to be more biologically active than raw cnes, although their lycozene leve's are simi. Then it was shown that there are diferent isomers of lycopene. The dominant. \somer found in most red tomatoes is trans-lycopene,a straight-chain rmolecule, The biologjcally active form Found in the human body is cis lycopene, a tent molecule. Scientists are nat sure whether the body converts one isomer into anather using an enzyme or whether the cis isomeris absorbed into the body more cally. However, they have discovered that cooking tomatces can alter the ratio of transics isomers in the fruit from 19:1 t2 11:9 The mare ci isomers inthe food, the more readily the lycopene is absorbed and the more useful it sin the body. So cook your tomatoes thoroughly before you eat them for maximum beneft! Wha’ more, specially bred tangerine tomatoes have been produced which contain high levels ofcis-lycopene. In atrial in the US, 12 adults te two diferent test meals each, One had a spaghetti sauce made from tangerine tomatoes, whila inthe other the sauce was made From ‘ordinary tomatoes The tial participants were acked to avoid tamato- fich foocs for 13 days before the test meals. Blooé samples were taken at regular intervals ater the meals. ‘The averall level of lycopene absorpticn was 2.5 times higher in pecple \who had eaten sauce made from the tangerine tomataes, showing that the human bogy i very sensitive to the difference, Commercial varieties of these tangerine, cis‘ycopere rch, tomatoes are now in the pipeline. 0.1.7.5 Tangsrine and red tomatoes. future jst by choir food ‘containing te right lomer to eat, yourray beable to mprove your heath an reserve your looks alin oe delicious real! e principles of che E-Z isomerism ‘The cis trans system for naming geometric isomers has been used for many years However, i: has some limitations because the system does not work for all geometric isomers, The IUPAC system for naming ‘geometric isomers is now the sysiem of E-Z isomerism, Alhough you wil sill ‘come across civ-trans isomers, the E-Z system is better because it works for all geometric isomers. iched round 2 carbon-carbon double bond (or other rigid bond) are ranked based on their atomic number. ‘The atom with the ‘highest number has the highest priority carbon outanks hydiogen. So you look at che position of the higher-priority In the FZ system, groups group at one end of the carbon-carbon. double bond and compare it with the hhigher-priority group at the other end of the double bond. Tf the two higher-pricrity ‘groups are on the same side they are usammen (together) and this is the Z= isomer. If the higher-priority groups are ‘on opposite sides of the rigid bond then they are entgegen (opposite) and this is the E-isomer. Look at isomer (a) of but-2-ene in fig. 1.7.4, At the leftchand side of the double bond, the two atoms attached to the carbon atom are hydrogen on top, and carbon below, Carbon has the higher ‘atomic number so it has the higher priority, and the higher-priority group is ‘down’, At the other end of the double bond the same is true ~ again the atoms are hydrogen and carbon. Carbon has higher priority = and it ig in the ‘down" position. Roth hhigher-priority groups are on the same Side of the double bond (susammmen) so the isomer is Z- uul-2-ene, Now Jook at isomer (b). You can see that rere the higher-priority group is ‘down’ on the left-hand side of the double bond bat ‘up’ a the right-hand side, ‘The groups are on opposite sides of the double bond Centgegen) and so this is F-but-2-ene, rrPour zene Eur Zone Fig, 176 ln ths ease 7-but-2-ene the ct samer and Fbut-2-ne is the tant iomer However. end Zor tas and Fare nat elrye the sere. For but-2-ene. both the cisirans eystem und the E-Z system work. However. this At true in all cases, as the example in fig. 1.7.7 will show you, @ Ca Zicomer isomer ig. 17.7 Too diferent stuctres af 1 brome: 2 chlo ? Moret iadocthene. ‘These two chemicals are geometric isomers with different properties and different stroctares. ‘The cis-mrans system cannot name these isomers, but the E-Z system works well In isomer (a), on the left-hand side of the double bond, the stoms are bromine and iodine. Todine has the higher priority because iL has the higher stomic number. I isin the ‘down’ position, At the other end of the bond, chlorine has the higher atomic number and so has higher priority over fluorine, Tt too is in the ‘down’ position, So in this igemer the two pricrity groups are on the same side of the double bond sund this is the Zisomer. In isomer (b) iodine is in the ‘doven’ position but chlorine is in the ‘up’ pesition. ‘The priority groups are on opposite sides of the double bond so this is the #-isomer, Oa 1 Lookat the evidence forthe effect of the ci-isomer levels in tangerine tomatoes. How would you assess this research in terms of reliability and ‘validity? What further studies would you like to see done before the new tomatoes are used in the mass praduction of food? 2 Work out the main Isomers of pentene. Identify any geometric isomers, and _gve them thelr correct &-Z nomenclature.‘The double bond is the obvious main festure of the alkenes, and it is this that makes their reactions rather different from those af the alkanes. The double bond has two main effects on the chemistry of the alkenes: + Alkenes exhibit EZ geometr zo rotation around the double bond isomerism. There is + Alkenes unclergo addition reactions rather than the substitution reactions of the alkanes. An addition reaction is one in which two substances reuct to form a single product As you saw carlier, alkenes are more reactive than alkanes because the energy required to break the double bond is lees than ewice the energy required to break the single bond. Far example, the bond enthalpy for the C-C bond in ethene is 347 kJ mol, while the bond enthalpy for the C=C bond in ethene is 612 KJ mot, ‘This shows that the bond enthalpy for the w bond is only 265 XJ mol"!, The reactions, of the alkenes do not involve fice radicals. Instead, hetcrolstic fission of the double bond occurs, and this is what determines how the molecules behave, ‘The high electron density associated with the double bond means that the alkenes are attacked by bath electrophiles (negative-charge-loving species) and oxidising agents. Electrophiles An alkene’s carbon-carbon double bond is attacked When a species containing an atom with a whole or partial positive charge approaches the electron rich double bond. Such a spocicy is suid 19 be electrophilic, since it is ettructed to arcas of high cleciron density. An clectrophile is an electron deficient species that can form 2 new covalent bond, using an electron pair provided by the carbon compound. The most common electrophilic agent is the provon, H* Pee Rea Reactions of the alkenes Addition reactions of the alkenes Reaction of the alkenes with hydrogen ‘The alkenes do not react with hydrogen ander normal conditions of temperature and pressure. However, in the presence of # finely divided nickel catalyst and at moderately high temperature (around 200 °C), alkenes undergo an addition reaction with hydrogen to form, the corresponding alkane. The reaction of ethene with, hydrogen (see flg. 1.7.8) is a typical example, “ + op ‘ig, 1.78 The alton of tycagen across «double bond is called Irydeogeraton,« process widely used the menufactre of marge React ns of the alkenes with the halogens ‘The alkenes react with the halogens way from the alkanes. For example, when ethene is bubbled through bromine in the dark, the bromine is decolourised and a colourless liquid which is immiscible with water is firmed. ‘This reactian is sa typical of the alkenes that it is used in analysis to demonstrate the presence of a double bond. In it, the ethene undergoes an addition reaction with the bromine forming 1,2-dibromocthane, a colourless liquid which docs aut mis with water. This is a disubstituted halogenoalkane. (See p.133 for more details of the reaction mechanism). a very different +B . W " 1peibremaethare H 4 How ! a a I aa 12dichoroethane ‘ig, .79 Trereaction ofthe akanes withthe halogen produce: ston products such at those shown he,TRC All alkenes reset vigorously in addition reactions with fluorine. ‘The vigour of the addition reactions, with the halogens decreases down the halogen group: reactions with iodine are relatively slow. Ethene sand Muorine react explosively w form eww molecules of | (etrafluoromethane, while with iodine a much slower reaction takes place to form 1,2-diiodoethane. The reaction of ethene with chlorine thowa in fig. 17.9 is particularly important as part of the process in the manufacture of chloraethene (which has the non- systematic name of vinyl chloride). his in turn is used to make poly(chlorvethene) (also known as poly(vinyl chloride) or PVC), @ widely used polymer = you will be looking at polymers in more detail liter in this chapter, All the reactions of the alkenes with the halogens praceed at raom tempenture, which suggests that the addition reaction does not invelve free radicals. This is bore out by further studies, as you will see when you Jook ut the reaction mechanisms below. Testing for alkenes - bromine water and the carbon-carbon double bond Bromine wuter (an aqueous solution of bromine) is used as a test for the alkenes. If you shake an alkene with bromine water, or bubble a gaseous alkene through bromine water, you will see the solution become colourless. ‘This demonstrates the presence of the carbon-carbon double bond because an addition reaution takes place ueress the double bond, which is why the bromine water becomes colourless, The major product of the reaction is 2-bromoethancl, because OND ions from the water take part ia the reaction as ‘well as Br° ions. However, some 1,2-dibromoethane is formed as well. So there are two different reactions taking place (see fig. 1.7.10) but the end result is always that bromine water is decolorised, # 4 on Me i a 6 iy Hoe HCC He aa i bow I a vo i 1g 1710 The acoboation of rine wate - aes for dee ns of the alkenes with the halogen "The double bond in the alkenes reacts readily with the hydrogen halides, producing the corresponding, ‘monosubstituted halogenoalkane. For example, ethene reacts as follows: ‘This reaction proceeds rapidly at room temperature, ‘arming bromoethane. The addition of hydrogen halides to alkenes, such as propene, which are asymmetric can lead to two possible products, eg Hon ow Hoc-c—ck 2 bromopropane In this case, the major product formed is 2ebromopropane, with 2 smaller amount of the akerative 1-bromopropane (see p.132 for more details). The likely products of the addition of hydrogen halides to asymmetric alkenes can be predicted using Markovnikov's rule: When HX addy across ant asymmetric double bond, the major product formed is the molecule in which hydrogen adds to the carbon atom in the double bond with the greater number of hydrogen atoms already attached to it ‘This is almost always the most stable alternative. Like all simple rules in science, this one has its exceptions — however, Markoynikoy’s rule does provide a useful way of deciding the most likely product of this ype of reaction. There is more about this on dhe following pages.Teco Reaction of the alkenes with aci manganate(VIl) ‘The reaction of the ulkenes with acidified potassium manganate(VID) solution involves both addition across the Gouble bond and oxidation, The products of the reaction are alkanediols, and the manganate(VI1) solution is decolorised in the process, turning from purple to colourless. For example, when ethene is added to an acidified solution of potassium manganate( VID) the solution is decolorised and ethane-1,2-diol is formed: d potassium H oH on KMA04/ dll HzS0y | os ee) I " 4 how ethane-t2-diat ‘The manganate(VI1) ions are reduced to manganese(Il) ions in the reaction, ‘Although ethane-1,2-diol is an extremely useful chemical in a variety of induswial processes, this is not the way it is made commercially because potassium manganste(VID i a relatively expensive chemical. [tis cheaper ‘und more efficient to produce ethane-1,2-diol from epoxyethune, produced in the catalysed reaction of ethene with oxygen. ‘The resction of ethene with potassium manganateCVID can be used to istinguish the alkenes from the alkanes ~ the alkanes do nok react. a 11 Why are the alkenes more reactive than the alkanes? 2 How does the reaction of the alkenes with the halogens differ from the reaction of the alkanes with the halogens? |3. Give the chemical equation for the reaction when propene is rnixed with hydrogen in the presence ofa finely divided rickel catalyst at around £200 °C. Explain what happens inthe reaction,TRC You have seen haw the halogens and the hydrogen, halides react differently or don’t react with alkanes and alkenes. Observing a wide range ef reactions has given chemists information that helps build up a picture of how organic reuctions happen — described as reaction mechanisms. These mechanisms not only tell you more about how organic reactions occur, they also help you to predict the outcome of similar reactions that you have not met before. Using curly arrows As chemists have developed models of reaction mechanisms, they have also established a way of showing what is going on using eurly arrows. In chapter 1.6, you saw how a curly half-acrow represents the movement of u single lectron. A full curly arrow represents the movement of « pair of clecirons. In reactions invalving alkenes, scientists have hypothesised that the electron pair of the x bond forms a new bond with a positively polarised attacking, group (an clectrophile). Figure 1.7.11 shows the breaking and making of bonds in the first sige of the reaction of a hydiogen halide with ethene. ‘rs araw show the two ‘lector inthe xbond Forming bona withthe hyrogen stor H H— | a Cc Wa “This row show the Hr bond breeking andthe tra electors ‘he bond gongte the bromine atrn “ip. 17.17 nthe fest stage ofthe reaction of HB with an alkene, the bond breaks,9 CH bonds frmed, andthe HBr bond bresks, berating Brion. “The first stage of this reaction involves electrophilic attack on the electron-rich ot bond. As a result of this attack, one of the carbon atoms in the ethene molecule gains a positive charge, forming on ion called 2 carbocation or sometimes a carbonium ion. You will find out more about these fons later in the course How do organic reactions happen? ‘This positively charged carbon is then open to auick by nucleophiles (positive-charge-loving species). In this case the bromide ion formed in the frst stage af the reaction attacks the carbocation, forming a new CoBr bond (see fig. 1.7.12). “hi cy ton represents the formation of rew Ctr bode the romideion S atvacted rote positively chaiged carbon _atomin the carbocation H / H wton H t Br i ‘ip, 712 The nucleophilic attack of carbocation by the rere fon Ethene is a symmetrical alkene. Propene in contrast Js asymmetrical, with three carbon stom and only one double bond. If you react hydrogen bromice with propen, the electrophilic addition reaction has two possible end products. (ig, 171 The lech dition of hydrogen bromide to prepene. ‘The carbocation in fig. 1.7.13(3) is more stable chan its alternative in (b), because the nwo methyl groups: donate electron density and stabilise the positive charge. So carbocation (a) tends to be formed in. preference. This means that the major product of the reaction is CH,CHBrCH,, with less CH,CH,CH,Br formed. The reaction largely follows Markovnikoy's ruleTeco ‘The aeldition of bromine 10 ethene ie another example of an elecsraphilic sdlliton reaction. ‘The Br—Br molecule is purly polarised by the eectrun- rich :« bond. The mechanism involves a nuckeuphilic attack, followed by lectrophilic ausck on the resulting carbocation. ‘This is the mechanism of the reaction of all Ue halogens with ethene, Figure 1.7.14 shows the addition reaction of bromine with ethene. VY | | i & —C— 8 —c—8r | *8r—Br ——» es l re, + —t—e fo a fig. 17.14 The mechanism of attack bromine ana carbon-carbon double bend involves slectophc stark by te rleeala with an irtartancews dipole Pace ad Chemists have developed models of reaction ‘reaction ef bromine with ethene which you eansidered above. ‘mechaniems hy devising hypotheses based on ‘evidence comet trem the observation tha ‘observations and then looking for further evidence to ‘nucleophiles are present in the reaction support ther ideas For example, scientists hypothesised CI” sons ate present when ethene reacts with bromine), a ‘at organic reactions often involve the formation of mixture of products is formed as you can see In fig. 1.7.15. several different incermeiat species as ators are exided or removed. Unfortunately there often isn't direct evidence for these cifferent intermediates. Much ‘ ‘ alone ofthe evidence that alow sie to develop 2 weil, Irypothetes about reaction mechanisms into models of a % 1 | how they work is indirect. Experiments tend to be " ee esigned to confirm that the proposed mechanism is ON wine presen logical. Sometimes a theoretical intermediate can be Shon to ext during the proces. In some cases reaction rates play av important part in determing " the mechani, scents cn show thatthe comersion of one compound to anather follows the athnay they preci, his els to conf their meds. Sctortts have some concrete evidence forthe PN ae rere ceed een eee ete eee ee rescton of hydrogen bromide with propene and the cobain o __lla- 1 What are curly arrows used to represent in reaction mechanisms? 2. Propene is bubbled through bromine in the dark. Describe, using chemical equations, the reaction you would expect to take place. 13. What is the mechanism for the reaction described in question 2? EdRC Polymerisation — A polymer is a very large molecule made up of Jong chains of smaller units joined together. ‘These smaller units are knows as monomers, Molccules arc generally regarded as polymers, rather than jst very lunge molecules, when there ure around 50 or more monomer units in the chain. The alkenes snd their derivatives, with their reactive doulle bonds, are some of the main sources of monomers in the production of many commercial polymers. Artificial polvmers include ‘what we commonly call plastics, and these polymers. play an important role in modern life, The synthesis of polymers (One widely used method of forming polymers by addition reactions. Two monomer units, which tre usually identical, react together und an addition reaction occurs across a double or tiple bond, The polymer is the enly product. monomer + monomer + monomer + ... > polymer Ethene, the simplest of the alkenes, tandergoes polymerisation to form poly(ethene), more commonly referred to as polythene. ‘The double bonds bresk and the carbon atoms of the repeating units Tink together to form a long chain (see fig. 1.7.16). 4 to 1 4 I eee I How ow ig, 17.16 The formation of poy(ethene) ramits ethene monomers How Polythene was first discovered in 1933 by the British chemical company ICI The first polythene, made by the polymerisation of ethene with races of oxygen at 200 °C and 1200 atm pressure, had highly branched chains which made it relatively soft and malleable with 2 fairly low melting point. This material is useful for packaging and forming utensils and it is still the main form of polythene made today. Recuuse of its he most important reaction of the alkenes branching molecules it is known as low-density polythene (LDPE). Karl Ziegler, the German chemist who won a Nobel prize in 1963 for his work on polymers and plastics, developed a different way of producing polythene which uses catalysts and ss result needs only low emperatures (around 60 °C) and aimospheric pressure. The polythene produced by the Ziegler process is called high-density polythene (IIDPE) - it has few branched chains which make it more rigid and deascr than low-density polythene. It also melts at 4 higher temperature (135 °C as opposed to 105 °C). Polythene of both types softens as it is warmed, but each type has a dietinet melting temperature. made from the alkenes inciude Other plasti poly(propene), which is also made using the Ziegler process. Poly(preperte) has closely and regularly packed chains. It can be moulded, used in fms or turned into fibres to make, for example, ropes that do not rot. Chlorocthene polymerises to form poly(chloreethene) which is better known as PVC from its non-systematic name poly(vinyl chloride) ‘There are many intermolecular forces in PVC 2s a result of the polar nature of the CCI bonds, and so the basic polymer is rather rigid. The addition of other compounds known as plasticisers makes the plastic much softer, and increases its range of uses ccunnsiderably. ne po'y(oropere) ‘ip, LZ The tomavon of poypropene rom is monomer, a wa Hoa 4 4 How Hon 4 proper ae ahaaZi LHE Sel ae as ove {ig 17-10 The phys properties of @ polymere greatly infivenced bythe structure ofthe pelymer chains andthe forces between them. Teco The properties of polymers ‘The properties of polymen depend on the chains of monomers fem which they are made, They can vary greatly, from very soft and flexible with very low melting temperatures to hard, brittle materials with very high melting temperatures. What features of the polymer chain have most effect on the properties of the polymer? +The average length of the poivmer chain ~ tensile strength and melting, temperature increase with the length of the chain until there are sbout 500 units in the chain, Increase in chain length beyond this has relatively liede elfect on the properties of a polymer. + Branching of tho chain ~ branched chains cannot pack together as regularly as straight chains, so polymers with highly branched chains tend to have low rensile strengths, low melting temperatures and low dens + The presence of intermolecular forces between chains ~ these are of immense importance in natural polymers and abo affect synthetics. If there are strong Intermolecular forces between the chains che polymer will be strong and tend to have a high melting temperature. The strength of the intermolecular forces is largely determined by the side groups on a polymer chain. + Crss-links hetseen chains ~ these chemical bonds holding the chains together make a polymer very rigid, hard and brittle, usually with a very high meling temperature. Synthetic polymers made from the reactions of the alkenes, their derivatives and other organic molecules are an excellent example ef the way in which chemists can take chemicals from naturally occurring materials such as oil ‘and coal and create novel materials of great usefulness to the human race, The double bonds of the alkenes ancl their tendency to undergo addition reactions ‘means that they and their derivatives sre frequently used in polymerisation reactions, Hundreds of alkene monomers react with each other to form long- chain polymers which have become a fundamental part of our everyday life. Polymer chemists can now develop “designer polymers’ with exactly the Properties required for a particular ask. Where would we be without plastics? aD 1 Wy do alkenes often form the basis of the monomer uri in polymers and plastics? 2. Show how addition polymerisation takes place using tetraluoroethene as an example.TRC Polymer problems and solutions a ed Se nae ee eee el ‘The development of synthetic palymers has led to a great change in the workd, with many natural materials having been replaced by their synthetic equivalents. One possible consequence ofthis is that the development of plastics has saved much natural material fern destruction ‘The ecological effects are not as streightforward as this, however. When looking at the energy balance of these useful products, s numberof different factors have to be considered The benefits, the problems and the possible solutions of the use of synthetic polymer products depend (on science — and aso the will of socety! ‘The energy costs ~ polymers are produced from chomicals ‘obtained from fessi fuels, These hidden energy costs cf polymer products are very high, because large amounts of ‘energy are used both in the production of the polymers ‘and the manufacture of goods made from them. At the ‘morment around 4% of world production of fos fuels s used each year to generate the electricity used to rake polymer products. That is @ lot of energy! The resources used — because many pelymer products are made from alkenes from fossil fuels, they use up valuable resources. The limited supply end ever-rising costs of fossil fuels give e strong incentive to develop different polymers based on monomer units from eifferent sources, Disposal problems ~ syrthetic polymers are not eesy 10 cispose of.They are causing a substantial weste problem. ‘When they bum a variety of toxic gases may be produced which con include hydrogen chloride (fram hslogen containing polymers lize PVC) and hyéragen cyanide, which ‘xe damaging both to human health and to other living, “organisms, Plastics themselves can also darmage animals in the wild. {ig-17.19 Simply buring plastics often produces poisonous sroke, ‘50 CIs not the taightionward solution to the elspasal posters. The carbon footprint of plastics carbon footprint is defined es a messure ofthe impact that a particular human activity has on the envionment in terms of the amount of greenhouse gases produced. Your carbon footprint is measured in units of carbon dioxide ~ and the objective is that we should al try to make our carbon footprint as small as possible. The use of fossil fuels, in the production of plastics, boch ta generate energy and as raw material releases carbon, Burning waste plastics releases carbon dioxide and toxins into the atmosphere, So using plastics adds to your carbon foctprint in « number of ways, particulay if you throw away plastic items rather ‘than rocycling or reusing them, ‘The boom in the development of synthetic polymers in the lat 50 years has improved our quality of life in many ways making products lighter, cheaper and often more durable, Plastics are an integral part of our everyday Ue, ‘rom sandwich wrappings to artificial valves weeking in someone's heart and they have brought mary benefits However, the disadvantages highlighted above need 10 be addressed The quantities of nan-biodegradabie polymers around the Earth is growing all the time. But as the problerrs of plastic production, use and dispose have Decorne more apparent, so some possible solutions are emerging, Solutions to polymer problems Renewable energy sources Making polymer products uses fossil fuels ané energy, Usirg renewable energy sources in their manufacture i therefore a good option If electricity generated from nuclear, Solar or wind power is used instead of fossi fuels, the environmental effet is greatly reduced, Another option 's to generate heat by burning methane from biodigesters, and also to combine energy recovery (see p.140) with power generation. Reducing use of polymer products There is a mave to avoid using too many polymer preducts 8 10 use fabric or paper hags instead of plastic ones in supermarkets, This is 8 ood idea although resources are used In the production of all bags.Reusing polymer products isan effective way of recucing their energy costs. For yeats many plastic products have been disposable, single-use only items, By developing polymer products designed to be used for ¢ much longer time, the energy costs, catbon factprint and resources used can be greatly racliced. Supermariet bage and packing crates that con be reused for years are just two obvious ‘examples. Reusing polymer products also reduces, the amount of waste going into laefil sites. On ‘ar individual level people can also reuse plastic bags anc bottles, and reduce their use o single-use material such as plastic food wrepping. t) ig. 1.7.20 Mulpied bythe milons of people who shop at supermarkets around the word, change fom single-use to lee eet ete ete et ace ‘emacs and the resburces needed 19 cary Shopping home. Recycling, Many plastics are very dificult to dispose of in ‘2 way that does not damage the environment. Plastc articles can be dumped on rubbish tips along with other household waste, but many synthetic polymers are not broken dawn by living organisms in the way that natural compounds are — they are not biodegradable, Recycling net only recuces the need for plastics disposal ~ it also reduces the demand for the production of new plastics. Recycling thermoplastics ofr only thermoplastics tha soften on heating) cen be recycled Tis includes mich ofthe waste plastic produced in manufacturing indurries ~ thie wastes clesn and often doesnot need to be transported fr fr processing The resulting recycled polymers can often be used 3 if they were new and so the proessis often relered to a8 reprocessing rater than recycling About 250.00 tones cf plastics reprocesse Uke this each yearn the UK Teco However, to most people recycling means the processing of used domestic plastic items. In many couneries there are now ccllection points for mil botties and other drinks bottles made ofa plastic called PET [poly(ettyleneterephthalate). When recycled this plastic can be used to make Fibres in the manulacture of carpets and textiles end new uses as a waterprocfing material are being, developed. In the US almost 2 quarter of all lastic bottles are row recycled ~ that means almost a quarter of a milion tonnes of plastic reused each year! In the UK and across Europe similar recycling of plastic bottes is tating piace (see fig. 1.7.21).What is more, many car manufactures now label plastic cormponents in thelr vehicles to meke reclamation ard recycling easler when the cars eventually scrapped. g eins pecent tees (iu rae epee ae PGES ee VAR, arepean county a @ 8 anf plate pckaglng person es yea (hg) 8 Fig. 7.21 Levels recycling of paste packaging vary considerably rom country to ccurtry. Improving this across Europe would greatly rede the Steel eeeeret treet tes How effective is recycling? I the plastic that is recovered after recycling sas good as che original, then effectively all the hidden energy from its original production hos been saved apart from the energy used in recycling, If the quality ofthe recycled plastic i less good than the oxginal it cannot be used in the same way the second time ercund so some of the hidden energy is lest ‘When considering the benefits of recycling you need to take into account al te environmental and energy costs. The transport cost of individuals taking the waste plastic to be racyclad is reduced when there are kerbside callections of callecting points at supermatkets. Transporting the plastics to the processing plants the electricity used to break up or melt the plastic and the Urarsport costs of the new goods all have Lo be taken Into account.Tce ud ‘A report on the production of carrier bags ‘made from recyeled rather than virgin polythene concluded that the use of recycled plastic gave the following environmental benefits: ‘+ reduction of energy consamption by ‘two-thirds ‘+ production of only a third of the sulfur dioxide and half ofthe dinitrogen oxide + reduction of water usage by acarly 907% + reduction of carbon dioxide generation by two-and-a-half times, ‘Adifferent study on the same subject ‘conclusded that 18 tonnes of ol are saved for ‘every tonne of reeycled polythene prodaced. ig. 17.22 How oftective ie reeyeting? How are plastics recycled? There are cwo main ways in which the recycling of | plastics can be carried out. Mechanical recycling involves physical changes to the plastics ~ they may be melted, shredded or med into granules before reuse, The plasties have to be sorted carefully before processing. ‘This is usually done by hand, an expensive process in the UK. In fact muck plastic waste is shipped to countries such 2s China where the costs are much cheaper for sorting and. processing, The energy costs and environmental impact of the transport have to be taken inte account. People are working hard to develop technologies 10 allow plastics ro be sorted efficiently, cheaply ancl automatically. At the moment nothing has emerged that 4s both effective and cheap - and of course technology usually has an energy and environmental cost. (Chemical recycling is also known as feedstock recycling, Tt involves the breakdown of the waste plastic into monomer units which can then be used ‘gain in the formation of new polymers or in other reactions in the chemical industry. Scientists ae working on & number of ways of doing this which include burning the plastics, thermal cracking and ausification (see p.140 under Energy recovery). The plastics do not need to be so carefully separated as or mechanical recycling processes, andi there is more tolerance of impurities. Chemical recycling is expensive and can require a significant input of energy. It has been estimated that 4 minimum of $0 000 tonnes of waste plastic a year needs to be processed to be economically viable ~ but itcan be done. ig 1728 UIMPAC sa gobal company which produces packaging and iso specases in recycling a variety of polymers. They produce recycled polymers which ae comparable in culty torial used (vg) polymers Tis benefits UNPAC, ther castermer and the environment Biodegradable polymers Another growing solution to the plastics dilemma js the development of renewable resources known as biopolymers, bioplastics or ‘green plastics’ ‘These are polymers which ane made by modifying, natural polymers such as starch or eeshulose, Most biopolymers are derived from plants such as maize oor sugar cane. This is a sustainable, renewable source which uses carbon dioxide from the stumosphere during its growing time, reducing the carbon fowtpcint of the subsequent plastic. Bacterial fermentation offen plays an impertant part in breaking down the plant ‘material to produce the monomer units, snother low energy, low carbon-emissian aspect of the process What is more, most polymers mace from renewable sourees can ako be uttucked and broken down by microbes ~ they are biodegradable. The degradation may (ake 20-30 years, but eventually the product will be destroyed. The production of biopolymers has many positive points. However plants 10 make polymers is not being used to grow food. When people are still dying of starvation in the world, should we he using land to grow plastios? land used to geowfig 17.24 plastic ubbsh urns up everywhere. But the biodegradable pastes we can mae from slants sso rie ethical sie Oe ed ‘Two important factors will determine how successful renewable biodegradable plastics become. Ce is cost —a5 lithe technologies are stil very new, they tend to be more ‘expensive than convertional plastics. However, as demand {ows the price should fall The ether factors the performance of the biopolymers, However keen people are to.use materials that have a minimal impact an the ervironment, they will not want lower standards of pestormance, ‘Tabler 1.7.2 ard 1.7.4 compare some data for the biocagradable plastic pely(lactie acid) with the traditional non-biodegradables poty(styrene) anc PVC. Pee ere ere Seed (polystyrene) Thickness (um) 230 250 250 Tensie strength (MPs) 59 4 50 Elastic modulus (G¥a) 25 8 18 longation (96) 6 4 1 Tear stength (gf) 110 90 850 Folding encurance 560 10 1000 ssrenigh (times) ‘ble 173 Characteristics of hard poly(lactic ai) shoet (PLAS) compared with pey(styrene) and PVC. ea ey ea) eer eas (polystyrene) eve) Thickness (um) 5 5 35 Tense strength (MPa) 3 7 14 Haste radu (Gra) 13 10 oz Elengaton (8) 480 430 340 Tear tena (a) 2 20 400 ‘ble 174 Characteristics ot set polyactic ald) I (PLP) compares with ptystyere) and PYTRC Energy recovery Another rlaively new approach to reducing the energy ent carbon footprint of polymer protucs is the concept of energy recovery of the energy that was pur into producing the polymer. One example is buring waste polymer products, eg municipal waste which contains very high levels of plastics and other polymers, and asing the energy released to generate electricity. This reduces the use of fossil fuels to generate electricity. In the process of energy recovery; incinerators sre used which operate at very high temperatures to prevent toxin production. These incinerators have special pollution-control systems which make sure that aay pollutants such as dioxins are no: released into the atmosphere. Energy recovery incinerators are used in the United Srates, where it has been calculated that one family burning waste in their back garden will produce as much dioxin in @ year a8. local waste plant burning the rubbish fom 50000 homes! Polymers contain « great deal of stored energy 30 they are a high-energy fuel source. The heat produced in the incinerators can be used 10 drive the generation of electricity and to produce hot water for heating in combined heat and power systems, 4 materials processing fig. 12.25 A heey analyse lake all hess facets ot he te ofa poymer product to quay les impact an the erwlonment There are a number of ther ways in which the energy from polymer products can be recovered and reused. These include pyrolysis and gasifieation. oth of these processes convert polymer wastes into energy-tich fuels which can be used for clecuicity generation and gs feedstock for the chemictl industry. Ts pyrolysis, the polymers are broken down by heat in the absence of oxygen. The formation of charcoal from wood is an example which has been used for centuries — now more modern procestes are being developed to deal with polymers. Gasification involves che breakdown of solid Inydrocarbons in a limited oxygen stinosphere to make syngas. ‘This is mainly = mixture of hydrogen and carbon monoxide, which can be used as feedstock in « wide range of diferent chemical processes. So far, work on gasification has been based en low-density poly(ethens) film and a mixture of different rigid plastics which are very common in domestic wuste, [Mang of these new processes are not very efficient at the ‘moment, and they are also often seen as relatively expensive. There are about 100 sites worldwide and they process sound 4 million tonnes of waste per year. However, asthe need for energy recovery and more sustainable use of resources increases, tand the demand! to lower the cusbon footprint of our lifestyles increases, processes such as these will become more and more important in the way we manage our waste polymer products. Life cycle analysis Sa - oe manufacture destitution mo <— [¢ raters | . eco of materia fr other productsIncreasingly industry is using 2 life eycle analysis of polymer products to quantify the effect they have on the environment. “The product’ life cycie is exemined from the extraction of the raw materials used in its mamusactare to the costs of recycling, reusing oF disposing oF it at the end of its useful life. An inventory is made of the enengy and materials used and any missions. This type of analysis makes it possible ta identify where improvements can be made in a proces to reduce the environmental impact, and ako to compare two different polymer products and decide which to use on the hesis af its life cycle impact on the environment. For example, table 1.7.5 shows some life cycle analyses carried cout in the Netherlands on different materials for making, gas pipes. The researchers themselves were surprised at the results! As a result of this study, the Dutch govemment recommends that PVC ie used in gas supply pipes. Analyees like these will play an ever-inereating role in our choice of materiale and how they are mantfenared and disposed of Environmental Material con: ey pas cont) ova (polythene) Photochemical ‘oxidant creation (0C?) 216 26 25 Aquatic ecotoxeity (ECA) | 26 54 39 Global warning potential (GW?) | 31 2 a Aeidfication potential (AP) B 2s 1 Abiotic depletion potential (ADP) | 97 1 04s Human tonicry cu) “ 19 076 ‘Nutification potential (NP) 25 ost 033 Odour threshold mit (onL) n 03s 08 ‘omane depietion potential (ODF) | 125 par 007 {nergy content (ecinc) 78 303 19 {able 17.5 Comparison of dierent materials usedin gs supply pes Teco OD 1. What are the main environmental problems wich result from our increasing use of polymer products? 2 What isthe diffrence between reusing ‘2nd reeyaing polymer products? 3, How do biopolymers fer trom ‘compounds such as poly(ethene) ard Pvc? 4- Use tables 1.7.3 and 1.7.4 to compare ‘the hard and soft types of poly(lactic ‘s forming two bonds a ight anges to the plane. The bond angles here are 90°. The shape is @ pentagonal bipyramid (se fig. 2.13). “he ig. 201.3 The shape ofthe iF molecale canbe preted from céectron pair repulsion theory. eee eres Fy ny Baampie Boron chord, ACL, Methane, CH, Phosphoru(V] chloride, 2Cl, Sulfur) fluoide, Fe Dot and cass diagram Cc H Shape and bond eagle tond ange tondange= 1095" | tondange= 90" and 720" bond angle= 90° Naar of shape “Wigalpaner Tetrahechal ~ Tigonalbipyramidl—two Octal ~ two triangular based tetrahedrons with bases _square-bated pyramids pyramid jeinee wth bases joined ‘able 2.1.1 The shapes of molecules can be pretcied rom Wee numberof electrons around the cena b) atom They se based on minimisig the rpution between the electron isTe Ser eee ea od How do lone pairs affect the shapes of molecules? Not all molecules contain a central stom with electron pairs in bonds around it. For example, ammonia can be represented as shown in fig.2.1.4{a), The central nitrogen atom has four electron pairs around it, only three of which make up the NH bonds ~ the fourth is a nor-bonding pair or Ione pair. As a result, the electron pairs take up a shape which is wetrahedral (see fig. 2.1.4(b)), and the shape of the molecule (that is, the nitrogen atom and the three hydlrogen atoms) is pyramidal (see fig. 2.1.4(c)) G in ammonia shows that they are 107°. This is 2.5” less than the predicted 109.57 if the electron pairs were arranged around the nitrogen atom in a tetrahedral shape, all repelling cach other equally (as they do in methane). ‘The retson for this difference is dhat the sefal measurements of the HN—H bond angles clectron pair in a bond is further from the nucleus of the central atom than the electron pair in a lone pair. ‘This means that the repulsion between a lone pair and 8 bending pair is greater than the repulsion berween ‘nwo bonding pairs. This extra repulsion ‘squeezes’ the bonding pairs in ammonia closer together, accounting for the smaller than expected bond angle. @ 9 " a 0 re BS, HA wis H & ) @ {ig.2.14 The electonicarangement and shape ofthe ammonia mole [As you saw in chapter 1.4, in a water molecule there are two bonding pairs and two lone pairs of electrons around the central oxygen atom. ‘The four pairs of electrons are approximately tetrahedral (see fig. 2.1.5) ‘The result is 2 bent linear molecule. ‘The HOH bond angle is 104.5°, compared. approximately 109.5° in methane or 107° in ammonia As before, the two non-bonding pairs of clectrons give extra repulsion, AY H H fig. 2.15 Theelectronic arrangement ant shape of the water motecule. Cooke ‘AS You saw in chapter 13, chemists orginally accepted the Kea that noble gas elements do not form compounds. The completed eleczron shell in a noble 2 etomn gives the etom stebilty. In 1933 however, Linus Pauling, about whom you wil Find out mere later inthis unit, precfcted that heavier noble gases might beable to fern cemmpounds. In 1952 Nell Bartlett prockiced 3 complex xeron compound which ed other chemists to try to make compounds. Later in 1962 Howard Clazssen found that xenon would combine \with fluorine at high temperatures to form xenon tetreflucride, Hef, This molecule i not tetrohecl in shape like methane, but planar. How can electron pair repulsion theory explain this? ‘The central xencn atom ferms four cavalent bones and ‘also has two lone pairs of electrons. The four covalent bonds le et the four comers of a squere with the xenon atom in the centre. One pair of non: bonding electrons Ig above the plane at ight angles, and one below (see fig. 21.6) All bord angles are SO" ‘ig. 21.6 Xenon tetraftuorde sa planar molec, ‘Other nobie gas compound have since been made, eg Irypton((V) fluoride, KrF, and xenor(l) fluoride, XeF,. No compounds have been made with helium or neon. Multiple bonds For molecules containing double or tiple bonds, the lectron pairs making up the bond all exist tozether between the (wo atoms they join. A multiple bond ean therefore be ueated in exactly the same way 28 a single jre2.1.7 shows hhow this leads to a linear shape for carbon dioxide, CO), but u bent linear shape for sulfur diewide, SO,. bond when predicting molecule shapes.° £0. o-c-o ° oo) of So fig. 2°17 The electronic rangement ané shape of (3) the carbon rie molecle,(b the slfr dioxide molecule, The shapes of ions A molecule that gains or loses one oF more electrons forms an ion, and the shape of the ion can also be predicted by electron-pair repulsion theory. For example, an ammonium ion is formed when an ammonia molecule and a hydrogen jon combine, Figure 2.1.8(2) shows a dot and cross diagram for the reaction. The ammonium ion contsins a central nitrogen atom with four bonding pairs of electrons around it, This is similar to the structure of methane ~ the ammonium ion is tetrahedral with bond angles of 109.5, ay ne NH a 2 Ht > ca o ° ° | - | N 5. 5. || o/s | of tethe trigonal plane emi fig.2°18 (a) The tetera ammonium ion, (8) The nitrate(V) onthe sullate(V1 lon and the sulate(V) ion Figure 21.8(b) shows the structure of the nitrate(V) ion, the suifate(VI) ion (sulfate) and the sulfated) ion (sulfite). These are trigonal planar, tetrahedral and pyramidal respectively Tee na oy Precorie For each of the following shapes give the Formula of ‘a molecule that has the shape: a linear b trigonal planar c tetrahedral d octshedral, Note that the question asks for ¢ molecule, not an fon The linear molecule must have rrore than two atoms: — HCL would not be acceptable. ‘There are many examples that could be chosen, ¢g aBecl, b EC, eCH, 4 Sfp Aluminium forms an anionic complex with hydrogen ‘with the formula Hj. Use electron-pair repulsion ‘theory to prediet the shape of this ion. Explain your answer. What is the approximate H—AI-—-H bond angle? Figure 2.1.9 shows the structure ofthe AIHz ion. ‘There are four bonding psirs and ne nen-bonding pais, For minimum repulsian between electron pairs ‘the chape is tetrahedral with bond angle 109.5". fig. 219 A det and cots agra shows the electron pair sreurd te cential atom, allowing you to work our the shape ofthe All fon, QED 1 What shape would you expect 2 tetrachloromethane molecule, Cl, ta have? Explain your answer 2 Hew many pairs of electrons are there eround the central Sater in 2 molecule of hydrogen sulfide, HS? What shape would you expect this mclecule tohave? 3. Sulfur tionde, $0, ise planer molecule. Explain how clectron pair repulsion theory predicts this shape, 4 suggest a shape for a molecule of oxygen difluoride, OF Explain your choice, 5 eplain why ICL; isnot tetrahedral rrAlkanes ‘You have seen that the simplest alkane molecule, methane, has a tetrahedral structure. In an alkane, all the carbon atoms have a tetrahedtral arrangement around them, Figure 2.1.10(a) shows space-filing models of the frst three alkunes ~ methane, ethane and propane, You can see that in cach molecule the arrangement around each blue carbon atom is tetrahedral. When drawing molecules to show their three.cimensionsl shape, the convention shown in fig. 2.1.10(b) is used, — ethane ween fig.21.10 (a) Spacetting models cf methane, ethane ane propane. (0) Instructural formule in thee dimensions straight ines shew bonds In te plan ofthe paper. Dashed Ines are bonds bend ths plane, ac wedges show bonds coming out ofthe plane towards you Alkenes ‘The simplest alkene is ethene, G3Ey. The wo carbon atoms arc joined by a carbos-earbon double bond Around each carbon stom there are three bonds alin the vame pling, at an angle of wbout 120° (se fig. 2.1.11) Ho ae H Nem ghne H” H £21.11 The ethane mele lin one plane Shapes of simple organic molecules Alcohols ‘The simplest alcohol is methanol, Figure 2.1.12(a) shows its structure ~ there are four bonds aryund the carbon atom and so the HCH bond angle is 109.5° (tetrahedral). Around the oxygen atom there are ‘wo pairs of bonding electrons snd vo non-bonding pairs, so the C—O—H bond angk: is sbour 104°, similar to the angle in the water molecule, @ {ig 2112 [a} Ammethanel molecule. (2) alcoho. Figure 2.1.12{b) shows ball and stick modkls of ‘methano}, ethanol, propan-I-ol and propan-2-ol. You can see that the arrangement around the carbon stoms is tetrahedeal but the C—O—H atoms are in the same plane in exch case. Carboxylic acids Methanoic acid is the only carboxylic acid which is planar (see fig. .1.13(a)). Figure 2.1.13(b) shows a computer-generated model of ethanoic acid, In all carboxylic acids the COOH (carbaxyl group) is plana, with dhe rest UF the molecule being based on) tetrahedral carbon atoms,Tee na oy Aldehydes and ketones Aldchydes and ketones are two homologous series that both contain x cacbonyl group, as you saw in chapter 1.5. Propanal is « typical aldehyde, and propanone the simplest ketone, In both molecules the central carbon, atom has three groups bonded to it and this part of the molecule is therefore planar with bond angles of about 120° (see fig, 2.1.15). 1%6.2:103 (2)Adiagam of metnancl ac. (b)A computer generated red ofethaace acd. Carbon shonin white, hydagae i green and agen inblie ) HSW Using molecular models CChemints frequently use enodels of molecules to help peopl tetera propanone ‘they react. On these pages you will see three common a aa aa oar (ig, 21.15 Propana ard proparone hove a planar central carbon ator have advantages and disadvantages, + Space-filing models show the shape of the molecule and which atoms are combined, but they do not give a clear indication of the bonding 1 tee ee a i an structure of propene, CH fre Isa clagram of the alkane octane: + Ball-end-stick models are eany to construct end 2 Here se agra of the alkane oct erly show which atoms are which, the bords between the atoms and an ind cation ofthe relative 20s of the ators. © Corpatergercteted reves ae yt proce el teeta erated Se ee ee erate ate Peter oneal eee eter ee ee information abot the shape cf an cctane molecule What does it sages thats incorect?” Halogenoalkanes 3 Wits dot te rr of hres ccarfron ong Bromomethane, CH,B¥ is a simple halogeroalkane. ee eer a an Like methane it has 2 central carbon atom with four Re methane i teal carbon torn wid 4 Methane, HCHO isthe simplest aldehyde. Drew the displayed formula of methanal, Describe the shape cof mathanal and bond angle: in the molecule. bonding psits of electrons, The shape of the melecule is tecrahedral (see fig. 2.1.14). ig.2.1.14 sloganosltanes have similar shapes te allone molecuCarbon The allotropes of carbon Allotropes are different forms of the same element that exist in the same physical state. The differences in the allotropes are down to different ‘ways of bonding between the atoms. and so different molecular shapes. For example, pure carbon hus several allotropes that have different crystal forms. ‘Two of these allotropes arc diamond and graphite Diamond Pure diamond is componed entirely of interlocking tetrahedral carbon atoms, cach of which is covulently bonded to ity four nearest neighbours (see fig. 2.1.15). ? ‘steve rangenient of aeereei aN ge fig, 20.16 The combined svength ofthe mary carbon-carbon bonds In the structure of diamond give it bath great haréness ane alack | chara rene, As you saw in chapter 1.4, ciamond is uniformly bonded tiroughout and may be thought of as a giant molecule. The exceptional strength of the carbon— carbon bond und che covalendy interlocked crystal structure accounts for the physical propertics of smend. I ig the hardest substance known and most of its user in drilling, cutting and grinding and os bearings are based on this exceptional hardness Although pure diamond is colourless and transparent, when contaminated with other minerals it may appear in varivus colours ranging frum pastels 1 opaque black, The dismond crystal iy chemically inert but ‘may be induced to burn in air at high temperatures. Te is a poor conductor of heat and an electrical insulator. Until 1955 the only sensce of diamond was aatarsl deponits of volcanic origin. Since then diamonds have been made sriilically from graphite subjected to high pressures and temperatures. Before the 1970s only diamonds of industrial quality could be made in this way ~ they had the hardness of diamond but dil not have the attractive appearance and were not large enough t be used as gemstones. Diamonds of gem quality have now been produced antificially but they are so expensive to create that they are nat made in this way for jewellery Graphite Graphite is a black or grey, Iustrous substance that easily crumbles or flakes. Tt has a slippery feel because of its tendency to cleave from the crystal in thin layers. Itis chemically inert, slthough somewhat less so than diamond, and in contrast to diamond is an excellent conductor of both heat and electivity, Ie occurs as a mineral in natare, usually in a somewhat impure form, and can be produced artificially from amorphous carbon (see below) Graphite is composed entirely of planes of trigonal carbon atoms joined in a honeycomb pattern. Each carbon atom is boncled to three others at 120°, ‘These planes are arranged in sheets 10 form three- dimensional erystals. The layers are too far spart for covalent bonds to form betweea them. Instead weak forces (called London (van der Waals) forces, sce chapter 2.3) maintain the arrangement of the layers, which are therefore easily maved relati dther. Because each atom is formally bonded 10 only: three neighbouring atoms, the remaining outer shell cleciron (one in each atom) is tree to Greulate within each phine of atoms, cuntibuting (0 graphite’ ability tw conduct elecuticty (see fig. 2.1.17). to eachfig. 2.197 The structure of yophite Whi the bonds between the ‘aben atoms are strong those ber wen the layers are not ard so they tlie ovr cach other eat. (One of the main uses for graphite ~ us a lubricant esulty from the characteristic sliding of one layer over enother within the crystal, The ‘lead? in pencils is actually graphite and the mark it leaves on the page is the result of layers of graphite being scraped off the crystal. Graphite is also used as an electrical conductor and electrode material (in dry cells, for instence), and in nuclear reactors in order to absorb some of the energy of the neutrons, increasing their ability tw cause fission. Other forms of carbon Amorphous carbon is less well defined than diamond or graphite, Its physical and chemical properties may vary depending on its method of manufacture and the conditions to which itis later subj in nature as a component of coal, and is also seen frequently as soot. It may be obtained artificially from almost any organic substance by heating the substance 1 very high temperatures in the absence of air. This ted. It is 2 deep black powder that 0 is how coke is produced from coal, and charcoal from wood. Burning organic vapours with insufficient oxygen also produces amorphous forms such as soot Amorphous carbon is the most reactive form of thereby serving as a fuel, and is attacked by strong oxidising agents. Amorphous carbon is not finely divided graphite but appears to have some of its structural features, such as local regions Of sheets and layers. Its atomic carbon. Tt burns relatively easily in ai structure, however, is much more irregular. ‘The most important uses for carbon black are as a stabilising filler for rubber and plastics and as a black pigment in Teor ay inks and paints, Charcoal and coke are used as clesn- burning fuels. Certain types of ‘activated charcoal” are useful as absorbents of gases and of impurities from solutions, Fullerenes For some years scientists predicted the existence of further allomropes of carbon. A football-shaped molecule was discovered in 1985 by Harry Krow, Robert Curl and Richard Smalley. In this allotrope 60 cacboa atoms are linked to form a more oF less spherical molecule. A whole family of spherical allotropes, with differing numbers of atoms, is now now to exist. The first one had 60 carbon atoms and 32 sides (20 hexagons andl 12 pentagons), [t was nicknamed ‘buckyball’ and was then formally named buckminsterfullerene because it resembles the geodesic domes developed by an American inventor called Robert Buckminster Fuller. The spherical carbon molecules are called fullerenes, group of fig. 2.1.18 Harry Hrot, Robert Cur ard Richard Salley were sword the Nobel rine for chemistry in 195 fr discovering buckminsterfulerene an working out it structure Buckminsterfullerene is a black solid that dissolves in petrol to form a deep red sclution. Like graphite, it has electrons that are free to move and so it ean conduct electricityTe Ser eee ea od Nanochemistry Tn 1991 the Japanese scien: while he was making fullerenes he had discovered clongated eage-like structures, Other scientists replicated his work and this led co the development 1 Sumio Iijima reported that in the soot produced of nanotubes and nanotube technology. These closed-cage carbon structures membered rings and almost any number of six-membered rings. They make highlv complex shapes - doughnut shapes, corkscrews and ccones have been produced. Figure 2.1.19 shows a single-walled. corkscrew- shaped curbon nanotube. all contain 12 ig. 2.1.19 Ths Just one ofthe rarotube molecaes that ee expected to ply an Frportan oe the fitureo techology eed Chemists have produced single-walled nanotubes [SWNTS) ‘and muiti-walled nanotubes (MWINTS). Reacting MWWNTs with metal oxdes produces carbon manorods, some cf ich are superconducting (they have zero resistence to the pessage of electric curents). Studies of nenatubes show that they are stifle: than other known materials. ‘embedded in polymer resins they could produce comparite materials which would have good electrical conductivity ‘long with enormous strength and great lightness. They ‘ould find uses in the aircraft, space and car industries. (One ides ie to develop nanoprobes which could circulate ‘sound the human blood systern and identi cancerous call Then surgeons could use laters to heat up these cals and destroy them. It might sound like science fiction today {iy 2.120 Nenorebots attaching cancer. This computer generated but some scientists believe itis possbe. ‘mage shows nancrobots (rey) attacking 2 carcercus tuaur red).Tee na oy ‘ou are probably swore that mixtures of coal dust and sir can explode, although Lumps of coal do not expla in ae Thi because cost duct hae a much ager srtace area forthe combustion reaction to take place than a lump of coal Fatiles celled nanoparticles are much smal then the particles in coal dust, just fev nanometres across. One nanometre (rm) is one billonth of @ metre (10-9m). For eorpatison, pial carbon-carbon bond lengths or the spacing between these stoms in a molecule are in the range 0.12-0.15 mm, The sralet cellular lieforrs, the bacteria of the genus Mycoplarma, are scund 200 ora in length Meterals reduced to the nanoscale can show very ferent properties compared with ‘what they exhibit one macroscale This offers new opportunites for exiting applications, such as + cpaque substances become transparent eg coppet) + inert materials became catalysts (eg platirum) + stable materials turn combustisle (eg alurirum) + sols tum int liquids at room temperature (god) + insulators become conductors (eg sco, Nanoparticles are now being used in cosmetic preperation. The skin provides a natural tarer to chemicals beirg absorbed through it. Howevet, ifthe patces in cosmetics are scaled down tothe size of nanoparticle, tney becorne small enough to penetiaie the skin. Such particles ae smaller than the wavelergth of ight and therefere too sal 10 see, Very sal particles of ttarluiIV) oxde are already being use in sunscreens, becouse they csappear completely into the sin, providing en irvsble protective layer Medications called serums are sld which deliver vitamin E into the stn via ranepartcies. However, some toxicologists are alarmed by this tend to deliver cosmetics through the skin. The skin forms a barrier with the function of keeping harmful substances out ofthe boll. If nancparticies can penetrate the skin might they end up in the bloodstream and the brain? Wnat damage might they do? Will other, less welzorne, substances piggy-back fon those tiny particles? And what will happen if a number of different ranoparticles, @g from hand cream, sunscreen and foundation, join together? Majer cosmetics companies state that nanoparticles will nat penetrate the skin to reach the bloodstream or circulate arourd the body. They claim that their chemical compounds “ill not go further than the frst layer, the stratum comeurn. The realty is that we do not know what the effects ofthese preparations ate and further research is necessary. 11 Both diamond and graphite have giant structures of carbon atoms, Why do these two «allotropes have such diferent physical properties? Suggest why fullerenes clsclve in petrol but élarnond and grephite do not. Explain why we cannot he sure whether using nanoparticles in easmeties is totaly safe.Poe eae Ceca 2 Intermediate bonding and bond polarity Electronegativity lonic to covalent: a continuum You have already met ionic and covalent bonding in chapter 1.4. These represent extremes in terms of classifying bonds, and compouncis frequently have bonding which is partially ionic and partislly covalent The position of the electrons ina covalent bond Ina hydrogen molecule, one pair of electrons is shared enween the two atoms. The positive attraction from each hydrogen nucleus is the same because both nuclei are the same, The pair of electrons in the bond is shared equally. The seme is true in a molecule of chlorine (see fig. 22.7). HiH ls Cle hrygragen ctlorre fig.22. Inthese distor molecules both atoms are the same, so the bonding electrons experiance the some attraction from each uct ‘end are dstibute evenly between ther. However, when the to atoms at cach end of covalent bond are different, the attraction by the muclei may be different and the pair of electrons is no longer equally shared. For example, in hydrogen chloride the chlosine muclens is better at attracting the electrons in the covalent bond than the hydrogen nucleus. Hid: hydrogen chlerre fig. 2.22 this hydrogen ehoride molecule the atoms are dierent, ‘and the bondirg electrons experence a greater atracton fom the corine nace thon from the bydragen nucleus. ‘We can predict the relative attracting powers of the nuclei of atoms of different elements by using the concept of electromegati the attraction of an atom in a molecule for a pair of electrons in a covalent band, ‘This is a measure of The Pauling scale ‘There ure various scales used 1 mesure dectrunegutivty ‘The one most commonly used was devised by Linus Pauling, and is the called the Pauling seale of clectronegativity. It i a relative seale and so has no units It runs from 0 to 4. The higher the number, the higher the covalent bond are attracted to the nucleus of the stom. cetromegativity and the more the electrons in the ‘ig, 22.3 Pauling i scemboldng « model of weter melecules. In 1954 Pauling wor the Nobel Pie for chemistry fr bis work on molecular ‘There are trends in the clecrronegativity of the elements which can be clearly seen in the periodic table. ‘The Pauling electronegativity values make these trends very lear (see fl. 2.2.4.) You can see that: + Non-meuls have higher clectronegatvities than metals. + Blectronegativity increases across 2 period of the periodic table. + Down a group int the main block ef the periodic table, the dectroncgativity decreases ‘The most electronegative clement is fluorine, F with a value of 4.0 sind the least electronegative element is caesium, Cs with a value of 0.7.Urol uae er ary iD 21 of Be B]C|N)O|F 1.0/1.5 2.0| 2.5|3.0 3.5/4.0 na | Ma avs|rio ssa 0.9] 1.2 1.5/1.8| 2.1 2.5/3.0 Kfalx|T|V]@]™|e]@)N]a]ina@lala se] 0.8 | 1.0|1.3|1.5]1.6|16|1.5]1.8 | 1.8/18/19]16 1.6| 18/20 24/28 wm] s |v] a) N| Mole ]m] ah Pa] mela im [a | el 0.8 }1.0 18 19|1.7 18/19 2.1/2.5 almlelw|m)wlela) > rk |alme[ || m rola 0.7/0.9 2.4/1.9 1.8/1.9 {ig 22.6 Theelectronegativty of some ofthe elements, measured n te Paling scale Notice there are no electronegativity values given for the source to source. ‘They were originally calculated by noble gases. Atoms of these elements very rarely form Pauling, who chose hytirogen as a standard which was covalent bonds and so they have no alfinity for electrons. given an arbitrary value of 2.1. Hydrogen was chosen it forms a large aumber of cov 1pounds ‘Values for Pauling’s electronegativities may vary from La Te eae ee You have used several types of model io depict Ina chlorine molecule, the electron distibution Is the same smclecules, including ball and stick, space-filling, around both etorrs. The election density s greeter when itis cr computer generated models, However, none of shaded red or yellow and less when shaded blue and groen. The these medals takes accourt ofthe effects of the slectron charge is evenly distrbuted between the twe stems. clectronegativity ofthe atoms irvolved.A stick na However in an iodine flucride molecule F, the model shows that ball and stick model eoresents 2 pai of electrons in the electron density is greater around the smaller fluorine atom. ‘a covalent bond, but it does nat shaw how the pair of ocere mame electrons is cistrbuted. In chapter 1.3 yeu came across electron density maps showing the positions of electrons in orbital. In chapter “LA you saw such 2 mp for sodium chleride inthe context of the structure of ionic lattices. These electron density maps can also be used to show the distrbution mn I T ; cf electrors in two covalent molecules (see fig. 22.5). ‘The maps are drawn on 2 computer using knovvledge of the electronegativities of the combining stams. Oe Vie 225 Becton dersity maps fr (a) chorne and (b) fadine frie 1 Fluorine is the most electronegative element. Find the 3 Inthe electron density map for methane, the electrons thee elements with the next highest electronegativites, «are distributed fay evenly with just a sighaly greater ter fluccine in the Date booklet. density around the ceibon eter then the hyckogen Pee ea eee eerie rece ator. Explain what this illustrates about the banding in electronegativities between scandium and zinc? aigUNIT 2 Application of core principles of chemistry Intermediate bonding lonic and covalent bonds In chapter 1.4 you saw how atoms bond by ionic or covalent bonding. Jn @ covalent bond one electron fram each atom is made available and is shared, between the two atoms. + Iman ionic bond there is a loss of one of more clecuoas by the metal atom and a gain of one of more electrons by the normetal atom. The resulting ions are held together by electrostatic charges. ‘These are ewo extremes and in practice ll degrees of intermediate bonding occur. Bond character You can calculate to what degree a bond ie ionic and to what degree it ie covalent by comparing the dilference in electronegativity bewveen the two stoms in the bond, For example, the clectronegativities of carbon and hydrogen are 2.5 and 2.1 respectively. ‘The difference in clectronegativity is 0.4, If you read off the percentage of ionic and covalent character from table 2.2.1 you will see this bond is 967% covalent and. 4% fonic. CEE Ean a ae i a ee character character 04 os 995 a 51 2 02 1 99 18 55 “6 03 2 98 19 38 a 04 4 96 20 3 7 05 € 34 24 7 3 05 . 31 22 10 0 or % ry 23 74 ~ os 6 as 24 16 Ey 03 9 8 25 79 a 10 2 w 26 8 6 4 = 7 27 ro 6 12 3” 7 28 6 4 13 2” 6 29 8 14 2 6 30 9 " 15 a s7 Fa 7 ° 15 ar 33 32 [@ 8 ‘able 22 Uslngelectronegtites to determine the percentage ionic and covalent character of bond.er ae ee cet Calculate the percentage of fonic and covalent bonding ire 2 lithium fluoride, LF & ammoria, NH 18 The electronegatvities of lithium and fluorine are 1.0 and 4.0 respectively. The rpuline fore ‘ig. 23.2 Permanent ipole-permaner dipole interactions between molecies. Attractive forces between oppositely charged portions af molecules re general srenge thon the repulsive forces between similarly charged portions of rolecins andthe rolacues experience a net stractve forceasaresut. It is quite easy to see how interactions of this sort account for the forces between polar molecules, but what about non-polar molecules? Tt is possible to liquefy non-polar substances, s0 there must be forces between their molecules. How do these forces arise?London forces ‘The forces of attraction that exist between two non-polar molecules are also explained in terms of charge distribution, Ina neutral atom, at any instant in time the electron distribution around the mucieus may result in the centres of positive and negative charge failing to coincide, producing an instantaneous dipole. Over time these instantancous dipoles average out, producing a net dipole of zero. Any other atom next to aa atom with an instantaneous dipole “will experience an electric field duc to the dipole, and 50 ‘will self develop an induced dipole (sce fig. 2.3.3(2)). ‘The instantaneous dipole_induced dipole interactions benveen neighbouring molecules provide the farce 10 bring non-polar molecules together to form a liquid when. the temperature is sufficiently low. “The forces are small however, since the attraction between two molecules lasts only a very short ime as the Instantaneous dipole is curnedt on and off as the electron density Auctuates (fig. 2.3.3(b)), ‘These interactions are given the name London forces (van der Waals forces). after the German-American physicist, Fritz London, Cos poe ‘pote {ig 233 (@)Anieatenteneoun dipole in oe storm gives tive 1. indeed lpoten a nearby ator, thus causing a net attractive force bebven the two stems. (B) The itantancous eipele varies oer tims, sometimes heving a value of rr0.As a result the atractne force between the atoms Mucuates, ands sometimes tra In addition to instantaneous dipole—induced dipole interactions, London forces also inclide instantaneous dipole-instantaneous dipole forces, sometimes called London dispersion forces. For example, the Cl,-Cl, interaction in a sample of chlorine gas is an example of a London dispersion force (Gee fig. 2.3.4). Application of core principles of chemistry Vig 234 London forces between chine melecues London dispersion forces exist between all atoms. London forces are the only forces between noble gas atoms when the gases condense at low temperatures. ‘The size of the Londoa forces in a substance Ucpends on the size of the electron clouds of the particles that are interscting, Moms “with large electron clouds tend not to hold on to their outer clectroms #0 tightly, so lange electron elovds tend t0 be easily deformed. ‘This favours the existence of an instantaneous dipole (and also favours the creation of an induced, dipole), so London forces tend to increase With the size of the electron cloud. This can be clearly seen in the boiling temperatures of the noble gases (sce table 2.3.1). London forces becwoen molecules are affected by the size of the molecules for the same ccason ~ so ethane (CoH) is a gas at room temperature, while hexane (CH) isa liauid. Nobie gas Coa cling 427 | a7 | 121 166) 201 temperature ) table 23.1 The baling temperatures ofthe note gases.The boing temperature rises with atomic sa, because the Londan forces get correspondingly ageUNIT Application of core principles of chemistry Hydrogen bonds ‘The boiling temperutures of the able guses increase down the group due to the increasing size of the cleciran cloud. Haw does the behaviour af other groups compare? 100 Inguamperawerc fig 235 Thearatinin bong temperature ofthe dies eroups 450end7 Figure 2.3.5 shows the boiling temperatures of the hiyelrides formed by the elements in groups 4, 5, 6 and 7 of the periodic table. While the hydrides of group 4 behave in a very similar way to the noble gases. the hyulrides of the other groups do not ~ at least not as far as the lightest element in each group is concerned. ‘This suggests that the hydrides of the lightest elements are much stronger ntermolceula forces in the than expected on the basis of the behaviour of the other elements in exch group, The strength of thexe intermolecalar forces cin be illustrated by comparing the molar enthalpies of vaporisation of the hydricies of the elements of group 6, as shown in table 23.2. ‘The molar enthalpy of vaporisation of 4 liguicl is the enthalpy change when one mole of the liguidl changes into one mole of its gas at the boiling temperature ~ this is a direct measure of the intermolecular forces in the liquid. Notice how energy required to turn one mole of Tiquid water at 100 "C into steam at 100 %C is more than twice the energy needed t tum one mole of liguid hydrogen sulfide into gaseous hydrogen sulfide at its boiling temperature. Pe re ee oe ed Standard mclorenthalyy 41.1 187189738 of veprseton (@ mot) ‘able 23.2 The molrentalges of vaporistion ofthe hycies of wou. ‘To explain these particularly strong interactions, a different type of intermolecular force comes into play. ‘This interaction is called a hydrogen bond, and it exists beuveen a molecule that contains a hydrogen atom attached to an electronegative element und another molecule eataining a lone pair of dectrons on an clectronegative element, You have seen that a big difference in electronegativity js a good indicator of a polar bond. There is a big difference hetween the electronegativigy of hydrogen (2.1) and the two elements oxygen (3.5) and fluorine (4.0). This results in the HO and H—F bonds being very polar, with a substantial amount af the clectron density in each bond being drawn away from the hydrogen atom, leaving it with a 6+ charge. This polar boad causes the exceptionally strong interactions that leod to the higher than expected boiling temperatures of hyclrogen fluoride and water, Hydrogen bonds form because of the special nature of the hydrogen atom, which bas no inner shells of electrons. As a result, the nucleus of the hydrogen, atom in dese molecules is eft unusually exposed by hin the bond, making ‘t easily accessible for strong permanent the shift in electron density ale permanent dipele interactions to occur. This happens when the lone puir of elzetroas of an atom (oa oxygen in the of hydrogen fluoride) in another molecule is attracted 10 the positive ‘rump’ of the hycrogen, leading to the formation of a hydrogen bond. This is shown in ig.2.35. we of water, on fluorine in the case Ammonia is another common example of a compound that shows hydrogen bonding. Nitrogen is more electronegative than hydrogen, and there is a lone pair available for hydrogen bonding on the nitrogen atom,Tee i ey Relative strengths of intermolecular forces Covalent bond strengths are typically between 200 and 500 kf mot, although they can be outside this range. Hydrogen bonds are weak in comparigon ~ about $40 kJ mol! London forces are weaker stil. Hydrogen bonds and London forces are not strong enough to influence the chemical behaviour of most substances, although both can affect the physical Propertics of substances. } HSW Models of bonding and physical properties Ethanol, CH.CH,CH and the ether methoxymethane, CH,CH, have the same hydrogen fluoride ‘molecular formula and therefore the same molecular mass. They have very we ferent boiling temperatures however. The boiling temperature of ethanol = . 78°C and that of methoxymethare is -25°C. In Both compounds there are trong covalent bonds within the melecules ard the differences rust be cue to intermolecular forces. Our model of intermolecular forces relies on the possiblity of hydrogen bonding between a hydrogen atom attached to an electronegative element (oxygen in this case) and a lone pair on an electronegative element in ‘an adjacent molecule. Both ofthese are present in ethanol. in methoxymethane armoria HL ‘there s alone pair on the oxygen but there's no hydrogen attached 10 itso 4 HOON tydragen bonding isnot posible, Our boring de explains the cference in uM bolting temperature. 1 ral F fig. 235 Hyerogen bonding water hyhege aoe ond amrria "Predict the type of intermolecular forces between molecules of 2 chioromethane, CHL hydrogen methanol. CH,0H, 2. Arrange the following in order of increasing strength: 2 covalent bonds bb ydrogen bonds «€ London (van der Woab) forces 4 ipole-dipote interactions. 3 Why ist posible to have hydrogen bonding in water or hyckogen fluoride ‘i 25,7 Wihowt water eon Earth PeeferreenteeteerieneZ ‘would not be possible. itis hydrogen but ror th ending which ves weer ts igh toting temperate, and So makes Sire the satace ofthe plete water hich door rot simply bot ny nea the atmosphere!Trends in physical properties UNIT Z Application of core principles of chemistry Introduction The ideas about intermolecular forces that yon have just met are very useful for explaining diflerences in the physical properties of different substances. These intermolecular forces in tum depend on the detailed molecular structure und polarity of tae substances. Trends in alkanes In chapter 1.6 you studied the alkanes, a family of saturated hydrocarbons, Table 23.3 compares the meling snd boiling temperatures of the first 10 straight-chain alka. ere en Melting oo oon ee eet i) i) Methane | CH, 4 182. 164 I Hoc I 4 ethane | Ce ~188 8 Propane | C3Hy -190 4 Butane | C,Hip 138 05 Pentane | CyHyp 130 6 Hane | GHag CH,CH,CH,CH,CH,CH, -95 cy Hopeane | CHa, CH,CH,CH,CH,CH,CH CH, ° Octane | Gag CCH CH,CH,CH,CH,CHCH CH, 7 a5 Nonane | CyHay CH{CH,CH,CH,CHCHCH,CH CH, | 51 151 Decane | Cightyp | CHACH,CH,CH,CH,CH,CH,CHCH CH 4 be 23.3 Some physical properties ofthe st 10straigt-chaln alone.Tee i ey oe ‘The melting and boiling temperatures of the alkanes increase as chain length increases (see fig.2.3.9(a)). The 07 intermolecular forces in the alkanes are weak ~ they are Density em induced dipole-induced dipole forces. However, despite being weak they are important because they hold together the particles in organic liquids and solids. These forces become larger as the length of the molecules increases * because there are more places where these forces can os ~ operate. Figure 2.3.9(b) shows ro long allane molecules and the weak intermolecular forces between incicel a clipoles, which are partially o¥ercome when the alkane ores ecb or 89 Ww Number af earben ators inthe alkare chan ‘ig. 2555 The dente oF the ist 1 straight-chain kanes plored sgslewt number of carbon ators Inthe chin ‘melts and completely broken when it boils. (Remember that the strong covalent bonds within the molecules ane not broken during melting or builing.) ‘weak intermolecular forces betwee induced dples CH CH Ha “CHy CHa’ “CH CH han “CH” ™CHy’ SCH,” CH” CH,” ‘in.239 al Te boing termpertresof the alles incense with cnn length Methane isa as 1 fe Landon fr a ater ang bean mall melas Hwee th onde oer between ectane mole opt mea hats lane a Fi at om temperate. (TH lenge te ell, the more part tre ave whore wea nero fre an orm rong cole tons CH, ‘ CH, cus CHa” CH ‘Volatility is 2 measure of how easily molecules excape from # Hauid. A. ‘volatile Liquid loses molecules from the surface very easily so it will have a ow boiling temperature, Pew is s volatile liquid, Tn very general terms, branching of the molecule lowers the boiling temperature, because the side chains interfere with the packing together of molectiles and reduce the formation of weak intermolecular forces between induced dipoles, However, variations in the parent chain and the side chains male it difficult to predict the extent of intermolecular forces that will form.UNIT Application of core principles of chemistry Jn table 23.4 the metting and boiling temperanares of theee alkanes are shown ‘They all have the same relative formula mass and the same number of carbon. and hydrogen atoms. You can sce thar the alkanes become more volatile (the hi boiling temperature decreases) a8 the amount of branching increases Se nd ake ‘ig. 23.10 The clkanes are easily used 1 fuels but to get ethane tumng ‘on your Chstmas pudding yeu nene eee ee veting | 130 =160 “6 Zondtcadaeiscem | Seve end: between the moles of tre alco toting | 6 2 10 tempesstite eo) ‘able 234 Melting and boling temperatures of straight and branched-chain alkanes. Comparing alkanes and alcohols ‘Table 2.3.5 companss the boiling temperutures of some alkanes and alcohoks, Organic compound coe Relative formula mace 60 a sa Boling temperature (°c) 97 2 -08 {able23.5 Boling temperetres ofan alcchol and se allares, Propan-1-ol and propane beth contain three carbon atoms in the chain, However, the biling temperature of propan-t-ol is much higher than that of propane. Also, propan-1-ol and butane have very Similar relative formula masses. Again, the boiling temper propan-1-ol is much higher than the boiling temperature of butane, ‘What causes these differences? ure of ae haw In propane and butate the intermolecular forces are weak forces Ae . between induced dipoles. These are also present in propan-I-o we —C—| t —H However, propan-1-ol can also form hydrogen bonds between its A relecules, These Form because an electronegative oxygen atom is 19.23.17 nydrogenbordingbetween molecues —-ondedd to a hycrogen atom, andl this positively poluriseel hydmogen br ethanal attracts an oxygen stor in another molecule (see fig. 2.3.11)Trends in boiling temperatures of the hydrogen halides 1 Figure 2.3.12 shows a graph of the boiling temperatures of the hydrogen halides against the period in which the halogen is placed fig. 23.12 Graph of th haies against period ling tempers of the hychogen You might expect © gradual increase in boiling temperature from hydrogen fluoride to hydrogen iodide because of the incressing size and mass of the molecules leading to increased Londor forces. This is the case from hydrogen bromide to hydrogen iodide bur the boiling temperature of hydrogen chloride is higher dian you might gxpect, and that of hydrogen fluoride is very much higher. {able 23.5 The lectrenegtivties ofthe talogrs and hydrogen Table 2.3.5 shows the electronegativities of hydrogen, fuorine, chlorine, bromine and iodine. ‘You can see that the HC] bond will be muck more polar than the HBr or H—I bond so ai this will explain the higher boiling temperature. jole-dipole interactions will be greater anc In hydrogen fuaride, because of the very high clectronezativity of fluorine, there will be considerable hydrogen bonding 2s well. This, accounts for its much higher boiling temperat Tee i ey OED Plot a graph of beiling tomperature against number ‘of carbon atoms for the first five members of the straight-chain alkanes. What i the effect on beiling ‘temperature of increasing the length of the carbon chain? Explain why this i so. 2 Figure 2.3.13 shows the beiling temperatures of the hydrides of elements in group 4 and group 5 of the periodic table. ead ig. 2.313 Gallng temperatures of the group 4 and hyde, Describe the tre in boing temperatures from CCH to ShHy Explain this trend in terms of, Intermolecular forees. Describe the tend in boiling temperatures from NH, to StH,, Explain this trend in terms of intermolecular forces and electronegativties. TdCrane Roo ung Solubility Introduction You are familiar with the idea of solubility — a sohuble substance will disselve in a solveat to form a solution, You will also know that water is a Very good solvent because it dissolves a wide range of substances, However, it doesn’t dissolve some substances ~ eg chlorophyll the green pigment in grass, is not soluble in water. Other solvents, sometimes called non-aqueous solvents, will dissolve many of the substances that water does nor dissolve, Examples of non-aqueous solvents include hexane and paraflin, ‘The word solubility striclly means the mass of a solute that dissolves in. 100 g of selvent at a particular temperature. Here however, the word will be used qualitatively rather than quantitatively. ZNaC\) ° ° a ‘The small number undemeath the symbol for exch clement represents its oxidation number. IBy convention, the oxidation number of an uncombined element is 0. The loss of an electron from sodium is shown by its oxidation number increasing from 0 to +1. In contrast, chlorine gains an electron, which is showa by its oxidation number changing from ( to -1. Notice how the sum of the oxication numbers on each side of the equation is the same (in this case it is 0) ~ this shows that we have not lost or gained any electrons, and our electron book-keeping is correct “The equation below shows the reaction of lithium with oxygen. On first sight the sum of the oxidation numbers on each side Goes noc appear to be the same, However, they can be belanced if you also take into account the numbers of atoms on each side of the equation: 2LiG) + 40, (8) > Li,O%s) ° ° v2 ‘There are two lithium ions on the right-hand side of the equation, so the oral oxidation mumber associated with lithium is (2 x +1) = +2. Now the book-keeping is correct! ‘You willbe Familiar with jonie equations fiom chapter 1.1. These ean be broken down into half-equations, which have the advantage of showing how electrons are transferred. For example, for the reaction of soditim with chlorine above: Na(s) > Na* (aq) + y@ + 2e > 2Cre@) Note that for ionic hali-couations, the exidation numbers con cach side of the equation do not balance: Nai) > Na fag) + ‘Once more, the increase in oxidation namber of sodium by 1 shows that it has lost one electron. However, combining both ionic half-equations for @ reaction will produce oxidation numbers that balance Oxidation numbers in covalent compounds ‘The examples above show ionic compoures, but chemists also find it useful to extend the oxidation number concept to reactions which involve covalent compounds. For example, think: ahour the reaction of hydrogen and oxygen 2H (x) + O,(g) > 211,00) ‘This reaction looks very different from the reaction of potessium with oxygen, since one involves the formation of K* ions and O2 ions while the other produces a molecule held together by shared electrons. But there is a similarity between the two reactions. In chapter 2.2 you saw that the electrons in the O—H_ bond are not equally shared, because oxygen is more clecaromegative than hydrogen (it has a greater tendency to attract electrons than hydrogen in a chemical bond) During the reaction above, the electron density around the atoms changes — a hydnogen atom sturts with zens charge in H, and finishes with a partial positive charge in HO, while an oxygen atom starts with zero charge in O3 and finishes with a partial negative charge in HO. The reaction therefore involves a shift in electron dunsity ~ whieh is not so very different from the change that happens in the reaction of potassium anel oxygen,Ural uae er ay Oxidation numbers and electron density Osidation number provice a way of following shifts in electron density. We first need to ustign oxidation numbers to the clements in the molecules involved, In doing this, we continue to assign an oxidation number of 0 to uncombined elements. Furthermore + we assign oxidation numbers to elements in covalent compounds so that the oxidation number of aa atom is che age it would have if the lectromns in each of its bonds helonged to the more electronegative clement. In this way, in water the hydrogen atoms are treated as though they had Jost an electron and the oxygen atom is treated as though it had gained two electrons. The oxidation number of hydrogen in water is therefore +1, while that of oxygen is =2, and the reaction of hydrugen with oxygen can be waiter, with its osidation numbers included: 2Hig(g) + O3(g) > 2H,010 Once again, notice how the oxidation sumbers balance once you take ins account the number of atoms involved on each side of the equation. To summarise, here are some simple rules for assigning and using oxidation numbers which will help you Keep track of what is happening in reactions. 1. The oxidation number of any uncarbined element is 0, 2. The oxditin number of an uncombined fon Is the some ar Bs chage 3 The sum ofall the ondeton numbers ia molecule ts pestine) zero fr i @ complicated fn sequal to the charge on the part). 4 Fluorine alvays hasan oxidation number of 1. Hydrogen alays has an onidation number of +4, except in metal hycrices (when its oxidation nurbers 1) Using these we can assign oxidation numbers 1 the elemens in compourds es shown, NH, —Tieatas(N*UH"), 50 3 oxidation number of N in NH, Ammonia ‘and oxidation number of H in NH = +1 PC, Treat as (P*(Ct), «9 _ovidation number of Pin PC, ~ +5 Phosphorus(y) chloride and oxidation number of Cin PC = =1 MnOj Treats [IMn"*)(O > 20 Manganate(Vl) ions OF, Teas (OF, 0 Ovygen dituoice HO, Teatas (0, 0 Hydrogen peroxide oxidation number af Mn in MnO; = +7 ‘and oxidation number of O in MnO; = oxidation number of © In OF, = +2 ‘and oxkdetion number of Fin OF oxidation number of H in HO, = +1 ‘and oxidation number of O in H,O; (ig. 2.41 Fel cels use «redox process — ‘the reaction of hydrogen gas and oxygen = toproduce eleciiity. Tas isa vel cll from apacecraft As well electricity, the fuel cel produces water. 6 Onygen always has an oxidation number of -7, except in peroxides (when it hasan oxidation rumber of 1), and when it combines with flucrine (wen ts Chlorine always has an oxidation number of -1, except with oxygen anc fluorine when it is positive. 8 Croup 1 elements always have oxidation number +1, group 2 always have 42 and group 3 always have +3. ) HSW Does oxidation preened Many students nave cificuity with oxidation number because itis an abstract idea. Chemists Use this tool becouse its cconveniont and gives the right answer. We know, for example, that in ammonia there cen never bbe N>- or H* fons but treating itas if they exist gives the rightCea cera ed Reduction and oxidation — a shift in electron density ‘The concept of oxidation number is usefial in studying the many chemical reactions that involve 1 shift in electron density = redox reactions. The ‘many important redox processes include burning. respiration and rusting, as well as generating electricity in bateries. Driginally the definition of reduction and oxidation was very narrow, being used by chemists 10 deseribe zeactions that involve hydrogen and oxygen, ‘Nowadays the term is applied to any process involving 1 transfer of electrons, in which the oxidation number of an element changes. Osidation can be defined as any process in which electrons are lost, and reduction is any process in ‘which electrons are gained. It might help you to. remember this using the mnemonic OIL RIG, which stands for oxidation is less of electrons, and reduction is gain of clectrons. IF you think shou the reaction that takes place when chlorine is bubbled through potassium iodide solution: Chy{¥) + 2KIGas) > 2KCKau) + Ifauy) you would not call his a redox reaction if you used the simple definition of oxidation in terms of loes or guin of onrygen or hydrogen. However, the ionic equation for this reaction is: C1,(@) + 2-(aa) > 2CrGa) + L(aa) Each chlorine atom has gained an electron and each indide ion has lost an electron. ‘The iodide is therefore oxidised and the chlorine is reduced. In this reaction iodide ions act as the reducing agent = they reduce another substance but are themselves oxidised. Chlorine acs as the oxidising agent ~ it oxidises another substance but is itself reduced, ‘You can write this equation as so ionie hal-equations. Wea FL + 2° Cl) + 26° 2Cr faa) Adding these half-oquations together in such a way that the cectroms on each side are cancelled out from the equation gives the overall equation Redox: loss and gain of electrons Redox reactions: metals with oxygen Probably one of the first types of redox reaction that most of us come across is the reaction of metals with the oxygen in the si ANa(S) + 0,(@) > 2Na,06) For sodium: In this reaction electrons are removed frem sodium and transferred to oxygen — we say that sodium is oxidised and oxygen is reduced. ‘These processes can bbe shown more clearly by writing (wo half-cquations {or the reaction: ANa(s) 9 ANat(e) + de 04(g) + de > 207%8) Notice how this way of writing the reaction emphasises the fact that the four clectrons required by the ‘wo oxygen atoms in order to achieve 2 nable gas configuration are supplied by the four sodium atoms. In the process, the sodium atoms achieve # noible gas configuration r00. "This makes it clear that Na loses electrons and is oxidised to Na*, while O. gains electrons and is reduced to O%. Sodium acts as a reducing agent, while oxygen behaves as an oxidising agent. Redox reactions: metals with water ‘The reactions of metals with water will be familiar you. Figure 2.4.2 shows sodium reacting with water. You may never have thought of this reaction as a redox reaction, ‘but if you split it into halt-equations you can see that itis. fig. 242 Sod reacting with water Anindictor hasbeen added to the water bath which shows the production of the aka odie Inyo bythe reaction |The symbol equation 2Na(s) + 2H,00) > 2NsOH(aa) + Hye) The ionic equation i: 2Na(s) + 2H,0() > 2Na" (aa) + 2OHMaq) + Hy(e) This can be written 95 two ionic halfcquations: Nats) > Na"fag) + & 2H) + 26° > 20H-(oq) + H(e) Before adcling these together you need to multiply the first equation by 2 so that there are the same number of electrons in each half-equation and they cance! out. You can see that sodium loses electrons und so is oxidised, and water gains electrons and so is recluced Redox reactions: metals with a ‘Again the reactions of metals with acids are familiar reactions that you have probably never thought of ws redex reactions, Figure 2.4.3 shows magnesium eucting with hydrochloric acid. ‘ig. 24.5 Magnesium and ite hydrocMorc aid ‘The symbol equation is Mg(s) + 2HCI(@@) > MeCLaa) + H(e) “This equation can be written as the sum of two ionic half equations, Mats) > Mg?" (aq) + 2e~ 21g) + 2° > Tye) ‘Magnesium loses ebetroas and so is exidised, and hydrogen ions gain electrons and so are reduced. Ural uae er ay Redox reactions: displacement Iron reacts with copper(ID sulfate solution to form copper und iron(II) sulfate. You will be familiar with this as a displacement reaction ‘The symbol equation for the reaction is: CuSO,(aq) + Fels) > Cuis) + FeSO4(aa) Writing so ionic half equations: Cu?* (ag) + 26° > Cuts) Fe(s) > Fe?"aq) + 2e- Iron loses electrons s0 is oxidised, and copper gains clecirons so is reduced. Disphicement reactions involve 4 shift of electron density and so sre redox reactions. Poms) 1 What i the oxidation number of hydrogen in Hp and nitrogen in No? 2 Outline why the concept of oxidation numiver {5 useful even though its not en accurate representation ofthe charges in e covalent molecule 3 Work out the ondation nurnber of each elernent tn these compounds a PH, b FeCl, © Ne,S0, d MnO, 4 Inthe reaction of sodium with water, which substance is oxidised and whichis reduced? Which substance is the exilsing agent and which fs the reducing ogert? 5 Copper reacts with siver nitrate solution to form silver. Write @ symbol equation and then tw ionic hatf-equations. plain what is happening in terms of oxidation and reduction 6 Lincreacts with cllte sulfuric acid solution to foim zinc sulfate and hydrogen. ite a symbot equation and then two onic half equations. Explain what i happening in terms of oxdation and reduction Does the equation below representa redox reaction? Explain your answer NaCiH{an) + HCl(aq) —+ NaCifaq) + H,0%0)Using oxidation number in naming compounds Oxidation numbers are a very useful tol for naming compounds. Some elements can exist with more dhan one oxidation number, so there might be some confusion if we don't use their oxidation number in their names. For compounds of just two elements this is not usually a problem, so we have: + PCI, phosphorus(IID chloride or phosphorus trichloride + PCI, phosphoras(V) chloride or phosphorus pentachloride + CO carbon monoxide + CO, carbon divide + OF; oxygen difluoride + O3F, dioxygen diftuoride In more complex compounds, the same of the clement which has a varisble oxidation number is written, ‘with its oxidation number in Roman smumerals after it: + KMaO, potassiuas manganate(VI) + K,CrO, powssium chromate(V1) As you saw in chapter 1.5, the systematic names of chemical compounds are agreed by IUPAC (the International Union of Pare and Applied Chemistry). Generally speaking you should use the systematic names of compounds, although you will ofien find the common names used too. ‘Some chemicals when named using the IUPAC rules are cumbersome and people often use the wad Uwivial names for these chemicals. Some 1 mal or of examples are given in table UNIT 2 Application of core principles of chemistry Changes in oxidation number Substance eed HNO, Nive) acd Nitrous acid ND, iti) acid Nite acid Noy Nivate() Nitrite NO Nivate(¥) Nate 150, SultictV) a6 Sulfurous cid HS0, SulfrctV) ac Sulfuric acid a sullate(¥) suite $0, Sullate(“) Sulfate ble 24.1 Systematle names use xstion numbers tobe urambigucus, Sometimes the tretianal names av til see. Redox in terms of changes in oxidation number You have seen that if'a species gains or loses an electron, then reduction or oxidation has tekken place. It fellows that a change in oxidation number also indicates a redox reaction, since changes in ‘oxidation numbers represent shifis in electron density. An increase in oxidation number corresponcis to oxidation and a decrease in ‘oxidation number corresponds to reduction For example, in the reaction of chlorine with hydrogen sulfide: Cly(g) + H,S(@) > 2HCI@) + S@) the exidlation namber of chlorine changes from 0 (in the element) to -1 in HCl, Chlorine is therefore reduced because its oxidation number is reduced from 0 10-1 ‘The oxidation number of sulfur c mnges from 2 in HS to 0 in S Sulfur is oxidised because its oxidation number has increased. ‘As another example, think about reaction of lead(ID oxide with hydrogen. The equation is PoO(s) + Fi,(g) > Pois) + 1,00) The oxidation number of lead changes from +2 in PLO 10 0 in Pb, so lead is reduced, ‘The oxidation number of hydrogen changes from 0 in Hig to +1 in HO, s0 oxygen is oxidised. ‘The thermite reaction is a useful process invelving the reaction of iron(II) oxide and aluminium (sce fig. 244),fig. 204.4 The there rection has many Inds applications Iisa exthermic reaction thal produces rolten or useful inweling ) HSW Using cobalt unter i’ (Oxidation number is useful to work out changes that take place during a reaction at an atomic level Ural uae er ay ‘The equation for the reaction is: Fe,0,@) + 2Al(6) > 2Fe) + A156) In this reaction the oxidation umber of iron changes from +3 19 0, s0 iron. ig reeluced. The oxidation number of aluminium changes from 0 to +3, so aluminium is oxidised Disproportionation A disproportionation reaction takes place when a substinc® is herh cxicised and reduced in the same reaction, An example i the breakown of hydrogen peroxide into water and oxy 21,0,(49) > 217,00) + 0,48) Writing this as two ionic halftequations, you can see how the reactant is both oxidised and reduced: HO, (ag) > 02(g) + 2H"(ag) + 26° oxidised Hy 0 4 H,Oyfaq) + 21*(aq) + 2° 2HjOA) reduced +a 4 +2 ‘The hydrogen peroxide disproportionates Another example of dispropartionation is the reaction of eapper(]) oxide with dilate sulfuric acid to form copper(0) anc! copper(II) sulfate Cu,019) + HySO,laq) > Cas) + CaS Oy(ag) + H,00) Copper is both oxidised from +1 to +2 and recluced from +1 to 0 in the same reaction. Other examples of disproportionation that you will mect include the reaction of chlorine with water, and the reaction of chlorine with hot sodium hydroxide solution, Lowen 1 Ine chemical reaction, MnO,2> is changed frst to MnO,” td ther to MnO, Are these changes oxdation or reduction? Explain your arswer in ‘erie of changes in oxidation number 2 Woite the cherical formula of ron(t) suvate(V) 3 Inthe folowing reactions, work out the oxidation numbers ofeach element in told. hen decide whether this element is oxidised, reduced or neither oxidised nor reduced. 2 Ki(eq) + ARNO:(eq) > Aal(s) + KNO,oq) uS0,(eq) + Zn(s) > Cu(s) + ZnS0,(20) Sncl,feq) + HeCiploq) > Hal + SrCiyloq) 2CuSD (aq) + KCN{oq) > 2CuCNI:) + CN fg) + 24,50 (09) 10FeS0, aq) + 2kMinO,(a5) + 8H,$0,(2q) > SFe{50,);(00) + XK 50,(q) + 2MnSO,(aq) + 84,040}UNIT 2 Application of core principles of chemistry ‘Some clements show a whole range of oxidation states A colourful reaction you might see is the reduction of vanadium(V) through successive oxidation numbers to vanadium(II) (see fig-2.4.5). Zine and dilute hydrochloric acid ure added to a solution of ) (yellow). The zine and hydrochloric acid produce hydrogen, which reduces vanadium(V) frst to vanadium(IV) (blue) then ammonium vanadate( vanadium (II) (green) and finally vanadium(I}) (purple) fie. 245 Vanadium shows a range of oxidation stats Common oxidising agents Below is list of ionic halt-equations for some common oxidising agents. Oxidising agents react by oxidising something else, and are themselves reduced. So the clecurns are always on the lefi-hand side of the coation, Oxygen Ox(@) + de> > 2076) Chlorine Chlg) + 2 > 20r@) Bromine Br,(g) + Je 3 2B) lodine 1g) + Je" > 206) Manganate(Vi!) in acid solution MnOj(aq) + SH" (aq) + Se" > Mn?*ag) + 411,00) Dichromate(Vi) in acid solution Cr,0F Ga) + 14H (aa) + 6 9 20H aa) + 7H,0(), Some useful ionic half-equations Iron(it) salts Be*(ag) + > Fag) Hydrogen ions 2H" (aq) + 26° > Hye) Hydrogen peroxide in absence of another oxi agent H,0,(aq) + 2H"(aq) + 2° 2 2H,00) Concentrated sulfuric acid +26" 9 SOF (aq) + 2H,0 Common reducing agents Below isa list of fonic half-equations for common reducing agents. Reducing agents react by reducing something else, and are themselves oxidised. So the clectrons are elvays om the right-hand side Metals M@) > M"*(eq) + ne Por example: Za(s) > Zn2*(ag) + 2 Iron({l) salts Fe?" (aq) > Fe?"(aq) + Acidified potassium iodide 2P(ug) > Tytay) + 2 Thiosulfate D3 (ag) > S,Of(aq) + 26° Ethanedioic acid and ethanedioates C,OF (aq) 3 2CO,(g) + 2° Sulfuric(IV) acid SOF (a) + HO) > SO} (a) + 2H" (aa) + 2e Hydrogen peroxide in the presence of an acid and absence of a strong oxidising agent H1,0,(aq) > Op{e) + 2H Mag) + 2° Hydrogen H,(g) + O26) > H,O() + 26° Iron({t) satts Fe? (ag) > Fe™(ag) + =Ural uae er ay Seca ‘Write a balanced equation for the following reactions 3 by combining the relevant halfequations. 1. Reaction of mangarate( Vil) in acd solution with iron(t) ions. ‘Mn0j(aq) + BH"(eq) + Se" > Mn#*(aq) + 4H,0(), Fe2¥(aq) > Fe¥(aq) + Now you need te edd these helFequations together 0 thot the electrons cancel out To do this multiply the axcord equation threugh by S: ‘MnO; (aq) + 8H"(eq) + Se” > Mi?*(eq) + 44,00) Siet(aq) > SFeP*(eq) + Se ‘Adding these together gives the balanced ionic equation: 19 j(aq) + 8H (aq) + SFe?*(aq) > Mn?*(aq) + 44,0()) + 5Fe(aq) 2. Reaction of mangarate(Vl) in acid solution with acidified potassium iodide, MnO ;{aq) + BH*(aq) + Se" > Mn2#(aq) + 4400), 29) > ble) 26° For the electrons to cance out on action the fst ‘equation must be multiplied through by 2 and the second by 5: ‘2MnO an) + TH" (aq) + 10e" > 2Mné*laq) + 84,01 104 (eq) > Siloq) + Te ‘Adding these together gives the balanced loric equation. 2Mn0;(aq) + 16H*(aq) + 10 (aq) > 2Mn#*(aq) + 8H,0(0 + 5I,(a0) Producing a balanced ionic equa’ To write a balanced ionic equation from ionic hal equations, first choose the corect ionic half-eqqations, If you have an ionic equation, itis easy to turn itinto a molecular equation if you need to. For example, for the reaction of pouassium manganatecVI) solution with iron(ID) sulfate solution in une preseace of dilute sulfurieaciel you ald in the spectator ions 2KMn0 (29) + 84,0, (a9) + 10FeSO,(80) > 2MnSO,4(aty) + SHO) + &,80 ua) + 5Fe,(80,) (4) Reaction of acidified dichromate(Vl) with hydrogen peroxide tolution. Fig. 2.4.6 shows the change of colour as dichromate(V/) reects ta preduce chromium(! In selecting the ionic haf-equations, make sure you ‘odse the correct equation for hyceogen peroxide acting as @ reducing agent. a {ig 24 Petes divomte() elton acts an ving agar duced form evar 04180. cr OF-{aq) + 14H*(aq) + Ge- > 2cr°*aq) + 7,00) H,0,foq) > Off) + 2H*(aq) + 26° Multiply the second equation by 3 and add them together: ,0F (eq) + 144" (ac) + 3H,0, (00) > 20° "(aq) + TH,O() + 30,(2)+ 64"(eq) ‘You can simplify the equation by subtracting 6HY(aq) fre each side: (Cr,0F (aq) + BH*(eq) + 3H,0,(2q) > 2CF>"(eq) + TH,O(l) + 30,(8} Oram 11 Write an ionic equation for the resction of thiosulfate ons and iedine. 2. Write om ionic equation forthe reaction of bromine and iron() fens. 3 Write anionic equation for the reaction of copper and concentrated sulfuric acid 4 Tum the ionic equation forthe reaction of potassium manganare(Vil) with potassium Iodide solution inthe presence of dilute sulfuric acd into a molecular equation.UNIT 2 Application of core principles of chemistry 5 The periodic table - groups 2 and 7 Group 2: the alkaline earth metals ‘You have probably studied the properties of the alkali metal elements in group, 1 of the periodic table st GCSE, You will have seen clear patterns in the physical and chemical propertics of these elements. In this chapter you are going to study two further groups ~ group 2, a family of metals, and group 7, a family of non-metal. fig 25.1 Group 2 metas From the et Sepiten maprakm aki tomtom Ignition energy ‘As you saw in chapter 1.3, the fonisation energy depends on the electronic structure of sn clement, and it has 2 marked effect on its physical andl chemical properties. The first ionisation energy is the enemy change when one mole of atoms of an clement in the gascous state loses one electron cach to form one mole of positively charged ions: Mg) > Mtg te “The second ionisation energy is the energy change when a second electron is removed from the io: MA@ > M® +o Remember that the value of the frst ionisation energy depends on: + the distance berween the outer electron and the nucleus (the atomic racius) + the effective muciear charge + the shielding prociuced by inner electron shells. Shielding is cused by the repulsion between the inner, filled shells and the electron being removed in the outer shell, lonisation energies of group 2 elements “The elements in group 2 of the periodic tuble are called the alkaline earth metals. ‘They are named after their oxides, culled the alkaline earths. ‘Their cld-fashioned names were bervllia, magnesia, lime, strontia and baryia, “Earthy is an old term used by early chemists for non-metallic substances that are insoluble in water and do not split up by heating, Antoine Lavoisier was the first person, in 1789, to realise that these substances were not cements and ‘suggested that they might be metal oxides. Humphry Davy became the first ‘to obtain samples of the metals by electrolysis of their molten earths at the beginning of the nineteenth century. Figure 2.5.1 shows samples of the group 2 metals.‘Table 2.5.1 shows the first, second and third ionisation energies and atomic rudii of the elements in group 2. en Fist Second Third teyliom —amt2 900 | 757 | 14809 Megpetiom ono 73a | asi | 7733 Corum | ars7 580 | 145 | ote stontum zis 550, | 1064 | az sanum zee. 503 | 9655390 ‘able 25.1 The oisation energies ofthe group 2 elements, These dements For M2 fo ready ‘You can see that for all the group 2 elements there is a big increase between the second and the third ionisation energies. These elements readily lose ‘two electrons to form a 2+ ion, but the large third ionisation energies make it impossible for them to lose three electrons snd form # 3+ ion, ‘Table 2.5.2 shows the electronic configurations of the clements in group 2. These elements in the s block have two clectrone in the outer shell, so losing, two electrons gives them a noble gas configuration, ‘This is consistent with their tendency to form M2* ions readily. Cee Magnesium Calc ca 282 2882 Strontium = Sr 28,1882 sanum es 28181882 fable 25.2 Here electronic configurations are show iy simple for, with 15725 berg shown simply as 22 and soon. ‘You will notice from table 2.5.1 that the ionisation energy decremes down the group ~ it becomes progressively easier to remove an electron 2s you move dawn the group. Why i this? Creole sou er a ‘There is an increasing effective nuclear change as yon move down the group. This might suggest that it should become more difficult to remove an electron down the group. However, you can sec in table 2.5.1 that there is an increase in atomic radius down the group so that the cutermest electrons are farther from the mucleus and so they experience the change less strongly. Also, there is more shielding from inner subshells as yous go denen the group — beryllium has just one full inner shell, magnesium has two, and so on up to barium with five. These two factors together are more significant that the increasing effective nuclear charge, and so the ionisation energy decreases down the group. You will notice a similar tend if you consider the sum. of the first and second ionisation energies. You will see later how this links with the reactivity of alkaline earth metals omer eee _ 7 atomto explain trends The explanation for trerdin ionisation enegy giver above is based on a simple model of the atom devised by Niel Bohr in 1913.In his atom the nucleus of protons (ravtrons were nat discovered urtil 1932) ‘were sutrcunded by electrons in ceary defined shells Each shell could hold @ maximum number of electro. ‘We know today that this sa simplified model of the atom but itis sufficient ro explain te reactions ofthe _g70up 2 metab. ——__Y =D 1. Wiite an equation for a metal M which represents, ‘the third ionisation energy. 2 An Mg? ion has a radius of 0.072 nm compared ‘with 0.160 rm, the radius of the magnesium ator, Explain why the magnesium ion is smaller than the ‘magnesium ator, (Locking back to chapter 1.3 may help you) 3. Explain the trends in successive ionisation energies of the group 2 elements, refering to their electronic structures,3 of core principles of chemistry Chemists often want to do # quick and simple test 1 identify the metal ions (cations) in a sample. A flame test is usciul for this purpose, particularly for identifying metals from the s block ~ groups 1 and 2. Carrying out a flame test A few drops of concentrated hydrochloric acid are added 10 the sample on a watch glass. A clean platinum oF nichrome wire is dipped into the mixure snd then the wire is held in a hot Bunsen burner flame. ‘The colour of the flame allows you to identify the cation in the mixture (see fig. 2.5.2). 9¢.252 The deincivecojoure of te group 1 and 2 metas a fle ‘est is a tefl too inthe analysis a leon compounds in the laboratory This shows the red lame produce by ium compounds Table 2.5.3 summarises the colour of the flame produced with different group 1 and 2 cations, res uihium | Reo sodium — | Yellow Potastim | Uae Mognesiom | Nocolour 4 Calcium — | (Yetow-) red Strontium | Red saium | (Pale) geen fig. 253 Flame tests tor table 25.3 Flame text colour, secur and bara. Flame tests and characteristic reactions of the group 2 metals Flame texts can only be a guide ~ many cations have no effect on the fame and sodium, which has an intense yellow flame, can mask the presence of other cations What causes coloured flames in flame tests? Ina flame test, the sample is converted to a chloride because chlorides are more volatile than other salts, ‘You know from chapter 1.3 that electrons occupy certain discrete energy levels in an atom or un ion. When an electron is promoted from its usual energy level to a higher energy level, the atom becomes excited, When the electron drops back to its ground state, the atom emits phoroa of light in the visible range (wavelength range dbout 400-700 am, see fig. 2.5.4) ke econ Spon connm T0nm Uv voit red ‘ig 254 The waveengts ofthe spectrum of isble Ugh Each element has its own characteristic energy levels. Vou can sce that red light has an approximate wavelength of $00 nm, and this is the wavelength of the energy given out when a lithium ion returns to its ground state from the excited state. Similarly, a sodium ion gives out energy of wavelength $87 nm, in the vellow range, Atoms or ions that give out energy in regions of the spectrum outside the visible region do not show a characteristic colour in a flame west For some the difference benween the mnergy levels is too large for the ion to become excited in a Bunsen burner flame. A more accurate test — the flame photometer A flame photometer ic an instrument that can be used to measure quantitatively the wavelengths of light given out by ions such as sodium, potassium and barium in a sample by analysing the flame produced (se fig. 2.5.5).Creole sou er a A flame phoromerer is used routinely to find the levels of Sodium and pouassium ions in blood. samples. Millions of blood samples are analysed every day and without this technique the analysis would be extremely slow and very expensive. The technique is also used to ‘monitor the concentrations of sodium, potassium und calcium daring the (ig. 255 lame photometer manufacture of wines. Reactions of the group 2 metals AAs well as flame tests, there are other characteristic chemical properties of the group 2 metals and here you will look at their reactions with oxygen, with chlorine and with water. Once again trends in their reactivity dowa the group are obvious. With oxygen ‘The group 2 metals burn in air or oxygen to form solid metal oxides. They usually burn brightly in oxygen (see fig. 2.5. o o — — 15.255 ( Buming rages nat. (0) Burning car oxygen “The general equation shows the reaction: 2MG) + O,{g) > 2MOI) For example: 2Mg(@) + 0,(g) > 2MgO(s) als) + O(g) > 2Cr0%s) ‘The reactivity of group 2 mesals with oxygen increases down the group. Barium, being the most reactive, is often stored under oil ike the alkali metals With chlorine The group 2 metals bum in chlorine ges to form solic ‘metal chlorides: M@ + CG > MCI,{s) For example: Magis) § Cl(s) > MeCl,() Ca) + Chie) > CuCl) Again the reacti iy increases down the group, although this is not as cleanly seen as in the reaction with oxygen. With water ‘The group 2 metals react with water to form oxides or hydroxides. ‘The reactivity inereases down the group, as you can soe in table 2.5.4, No reaction due toa thick exide layer on the surface ofthe meta Magnesium | Very, very slow reaction with cold water = rapid reaction with steam calcum Reection with cold weter to produce hychegert Strontium | — reactivity increases down the group Barium ‘able 25.4 The reaction ofthe group 2 metas with water Magnesium reacts with steam to form magnesium oxide and hydrogen: Mais) + H,0(g) > MeOG) + H,(@) Calcium, strontum and barium react to form the hydroxide and hydrogen, for example: Cas) + 21,0(g) > CalOH) (ae + H®) In cach case the hydecside forms an alkaline sohution. =D 1. Suggest wity calcium compounds produce a coloured flame but magnesium compounds donot. 2 Hew do you clean a wire fora flame test? Explain ‘why this is important, 3 Describe and explain the trends in reactivity af the ‘group 2 metals with water. 4. Barium is the most difficult group 2 metal to extract by electrolysis, Suggest way this b.UNIT 2 Application of core principles of chemistry Group 2 oxides and hydroxides are not found naturally but the elements are usually found as carbonates which decompose on heating to form the oxide. This reacts \with water to form the hydroxide. For example, calcium carbonate occurs in different forms, including limestone, chalk and marble, Hesting these strongly decomposes them to form calcium oxide (sometimes called quicklime). Adding water to ealeium axide produces calcium hydroxide (sometimes called slaked Time). You will be familiar with 2 solution of calcium hydroxide in water in the laboratory limewater. Reactions of the group 2 oxides With water Beryllium oxide docs not react with water, while magnesium oxide reacts only slightly. When cole water is added to calcium oxide, the mixture swells, 4 fizing sound is heard and a considerable amount of energy and water vapour are released, CaO) + HO > Ca(OH), (aa) ‘This process is sometimes called slaking lime and the product is calcium hydroxide. (The word ‘sake’ is Angio-Saxon and means to satisly a thirst for water. In this reaction it is clear that calcium oxide has a liking for water, Calcium hydroxide has many uses including in water treatment, neutralising acidic soils and making whitewash, mortar and plaster ig 25,7 Tradiona balling tetris une alee oflime ntime ‘washes, time patty ard ther raters here ie ill srarkot for ‘these products todsy =thisman is mating line putty. Stroatium oxide and barium oxide reset in similar ‘way to calcium oxide. Reactions of the group 2 oxides and hydroxides With dilute hydrochloric acid and nitric acids Group 2 metal oxides react with dilate hydrochloric acid to form a chloride salt and water oniy, eg: MgO(s) + 2HCIfag) > MgCl, (ae) + H,0@) Simila nitrate salt and water only, eg C206) + ZHNOs(aa) > CaCNO;)9(0a) + HOM y they react with dilute nitric acid wo form a Reactions of the group 2 hydroxides With dilute hydrochloric acid and nitric acids Group 2 metal hydroxides react in a similar way to oxides, eg Mg(OH),(6) + 2HCI(aq) > MgC1,(q) + 2H,0 Ca(OH) A() + 2TINO,(ag) CalNO.) Cae) + 21,00) Solubility of group 2 compounds Chemists often need to be aware of the relative solubilities of different compounds, For example, sometimes doctors need to see inside the gut in detail = hut sof tisenes dv not shaw up well on Kerays However, barium compounds show up really well. [fa patient swallows a ‘barium meal’ containing a barium compound, or is given 2 barium enema, the shape of that region of the gat will show up clearly on any Xomys taken. However, soluble burium compounds are poisonous to people. Fertunutely burium sulphate is insoluble in water, 0 it ir ideal for the job. It shovrs up well on Xerays but doesn't poison the patient! fig. 253 An ray taken ater» baum real showing the gastrointestinal ractThis is just one example where knowing the solubility of different compounds & vital in the way they can be used, ‘There ure a few general trends in solubility in the compounds of the group 2 mews, All the group 2 metal nitrates are soluble, and so are the chloride. Group 2 salts in which the anion has a charge of -2, such as the sulfates, are largely insoluble with the exception of a few magnesium and calcium salts In addition to these trends, there is a tendeney for the solubility of the salts to decrease down the group as the atomic numer and ionic size of the metals increase, shows the solubilities of group 2 metal sulfites and hydroxides. The solubility of the sulfates decreases down the group while the selubility of hydroxides increases, Magnesium — | 3500 10 ozx 104 Caleum tix 16x10 Strontium | O62 104 mI Bavitmn 0009104 | 240 104 Trends nthe slubltles ofthe group 2 metal sulfates and hye ‘The insolubiity of barium sulfate is used in dhe labocatory test for sulfate ions, To test an unknown sample to see if itis a sulfate, dilute hydrochloric acid is added to the sample to destroy any carbonate. ‘Thea barium chloride or barium nitrate solution is added, A white precipitace of barium sulfate conficms thet the sult is a walfate The eal ofa (j= . postive slat test. Ba?*(aq) + SO,?-(aq) > B1SO,() The relative insolubility of calcium hydroxide can be demonstrated by adding sodium hydroxide solution to calcium nitrate solution. A white precipitate of caleinum, hydroxide is formed (soe ) ‘recptatng aio tyrone stowsitisrore sole than ers yo cannes or od ata. By comparison, the group 1 metals produce hyccoxides, sulfates, chlorides, nitrates and carbonates that are soluble in Water. Because group 2 compounds are more Tikely to contain 2+ and 2-i ikely to have higher lace energies (ee NaCl ~780 KJ mot! compared with MgCl, -2526 KJ mot. Although the hydration enthalpies of group 2 ions are generally lager, this does por compensate for the ns, they are higher lattice energies (see chapter 2.3). 1. White symbol equations for: ‘a the reaction of barium with water the reaction of barium oxide with dilute hydrochloric acid the reaction of barium hydroxide with nitric ac 2 In ‘the units used are moles/100 g of water. Suggest why this is better than using 2/100 g of water, 3 With barium axide and barium hydroxide, the usual reactions of a metal oxide and hydroxide with dlute sulfuric acid do not occur in practice. Relering to Suggest hry this is.UNIT 2 Application of core principles of chemistry Volumetric analysis In chapter 1.1 you sew that there are different ways of expressing the concentration of a solution, and you looked at how solutions ean be made up w an accurate concentration. But haw ean you find the concentration of un unknown solution? The most usual way in the lab is by carrying ou! volumetric analysis, snd this is explsined here. ‘The concentration of calcium ions in a solution can bbe measured quantitatively using a flame photometer. However magnesium, which docs not colour the flame, cannot be measured in this way. A solution of EDTA (cthylenceliaminetetraacetic acid) can be used to measure the concentration of calcium and magnesium in water samples (testing for hardness of water) or in rock samples. Principles of volumetric analysis In volumetric analysis you can find the accurate volumes and concentrations of reacting solutions. The common method of volumetric analysis is called titration. In this method, the concentration of an unkown solution can be found by reacting it with a standard solutioa, A standard solution is onc whose concentration is known and does not change with If the volumes of two solutions whieh exuetly rexet \with cach other are measured, ep sn acid and an alkali, the concentration of one can be calculated if the concentration of the other is known. As you saw in chapter 1.1, the volume of 2 solution is measured in cubic decimetres, dm? and the concentration of a solution ia moles per cubic decimetre, mol dm-3 Dee ore ne ‘You can carry out an acid-base titration to find the molar mass of an organic acid By dissolving a known, mass of the acid In water, you can trate this against a known solution of an alkali An incicator tells you when ‘the reaction is complete, and the volume of alkali can be used fo cakulate the rumber of moles that have reacted. Precision, accuracy and reliability gure 2.5.11 shows the apparatus commonly used for volumetric analysis * | fig.25.17 A buretie onda pipetie,cmmony used for volumetric nays ‘The pipette delivers a fixed volume of solution, usually 25.0 oF 10 em3. Ie a precision instrament capable of Aotivering an exact volume to within 0.05 em? Similarly the buret isa precision instrument that can Aaliver any volume measured to the nearest 0.05 om? However, a pipette might be wrongly calibrated and it amighnt scully deliver 25.05 em cach time. [tis then precise but not accurate. It delivers the same volume cach time, but not the volume it claims to have delivered, ‘To check the aecuracy of a pipette you can transfer its contents fo @ weighed heaker and find the mass of the beaker and contents. From this and the density of the contents, you can work out the exact volume delivered. ‘The reliability of the method depends upon errors particular to the experiment and the skill of the experimenter, For example, if you do not line up your eye with the top of the liguid (the meniscus) and. with the graduation on the apparatus, you will read the wrong result. Repeating: an experiment does not increase the reliability of the experiment or the accuracy of the result. It will, however, give you in the result if readings are the same when jent is repeated. confidenc: In an experiment 3.02 g of a monobasic organic acid (an acid that will donate jast one hydrogen ion (proton) when reacting with an alkali) was dissolved in water and the solution made up to 280 emThis solution was placed in a burette 25.0 cm? of sodium hydroxide solution (0.10 mol dm) solution were pipetted. into a conical Mask and a couple of drops of phienoiphidhalein indicator added. Acid solution was ran in from the indicator showed neutralisation. The procedure was repeated three times more, warctte until and the results are shown in table 2.5.6 Final volume onburette 250 2535 25.55 | 2545, fem) Ina volume onburette 000 | 010 025 | 020 os) Volume of acdatded 2550 2525 2530| 2525 fem) ‘ble 256 Sample results forthe tration af an unkown RCOONAlan) + H20() 25.0cm? of 0. 10mol dm sodium hydroxide solution reected with 25.25em of acid solution. ‘Amount of NaOH = 0.025 4m? x 0.1moldm-3 = 0.0025 mal From the equation, 1 mol of NaCH reacts with 1 mol of the acid s0 2525cm of the acid solution contains 0.0025 mol cf the acid, So the concentration af the acids ooo2§mel - ¢.989moldm? 002825 dm? 250cm? of the acid solution centains 202g ofthe aci, so 1d} contains 12084, and this is .099mel.So 1 mel oft is 12.08, 0099) So its relative molecuiar mass is 122.s-block elements ‘The s-block elements in groups 1 and 2 show some similarities in their properties and reactions, but also some differences. Thermal stability of the salts of the s-block elements es [-) Heating the s-block metal Cpe ‘You can investigate the action of heat on a vatiety of carbonates and nitrates. Lock for changes in state or olor and test any gat evolved. ‘When the s-block elements react they form sales which all contain positive metal ions ~ either Mb or M?. There are several Key factors in predicting the stability of an ionic compound, not the Teast of which is its lattice energy. This is closely determined by the charge and size of the ions in the lattice (see chapter 1.4). Because of this, in general, the stability of ionic vompounds increases as: + cationic radius decreases + the charge on the ions increases. Tn thinking about the stability of the satis of the block elements you need ty think not just in terms of theie stability in relation to their clements but also rdative t other substances that may be formed. In particular, the carbonate, COZ anion may decompose to procluce carbon diavide and the oxide, 07 anion, whik: the nitrate, NO3 anion may also decompose to give tbe oxide, O? anion, or the larger nitrite, NOy anion. The thermal statility of the carbonates and nitrates ef the group 1 and 2 dlements is greally dependent on these changes in size and charge. ‘Table 2.5.7 shows the radius and the charge on the cations in groups 1 and 2, cn Group2 ood Ca co od Ec) a) uthum | oo7s | +1 feyllum gz? 42 Sedum | o1oe | +1 Mognesium 07242 Potaniuen 0.138 | 41 Cakium 010042 Rubidium | 0.149 | 41 Strontium 011342 caesium | 0.170 | +1 Baum = 13642 ble 257 the stably of one compounds depends an the fae ras and the charge on the cation. ‘The latice energies of both the oxides andl carbonates become less negative as you go deswn group 2. They do not, however. fall ac the sume mite — the oxide lattice energy falls fuster than the carbonate value. The value of the overall enthalpy change of the decomposition reaction gradually becomes more positive as you go down the group, abn, = Abe, [XCO,\s)] ~ AM, [XOG)] i “x Thisisa postive numer ‘The size of the lattice energy’ is governed by several factors, one of which is the distance between the centres of the positive and negative ions in the lattice. Forces of attraction are greatest if the distances between the ions are small. If the aatructions are lange, then a lot of energy will be given out when the lattice is formed from the ions and so the lattice energy will have a large negative value. ‘The lattice energies of both carbonates and oxides fill 2s you go down groups 1 andl 2 because the pasitive ions are getting bigger (see table 2.5.7). The distances between ions are increasing andl so the attractions become weaker. ‘The lawtice energies fall at different rates because of the different sizes of the wo negative ions ~ oxide and carbonate. The oxide fon is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is mach larger.Tn the oxides, when you go from magnesium oxide to calcium oxide for example, the distance beeen ions increases from 0.212 nm (@.140 + 0.072 nm) to 0.240 om (0.140 + 0.100 nmi) ~ an increase of about 13%. Tn the carbonates, the distance between ions is dominated by the much larger carbonate jon, Although the carbonate ion increases this distance by the same smount for both magnesium carbonate and calcium carbonate, as a percentage of the total distance the increase will be much less for calcium carbonate, Fig. 2.5.12 shows how marble (@ form of calcium carbonate) can be decomposed only by strong heating. fig. 25.12 Callum carbonate has high theta stably, When heated to the temperature of an ordinary Bunsen burner flame, the group 1 metal carbonates are stable, with the exception of lithium carbonate, LiCO; which decompores to give lithium oxide and carbon dioxide: Li,COX9) > Li,06) + C03) ‘The group 2 metal carbonates decompose to form stable oxides, with the formation of carbon dioxide gas, ep: CaCO4(s) > C10%8) + CO}(g) ‘The temperature at which the group 2 carbonates start to decompose increases down the group (Gee table 2.5.8). Beryllium carbonate i so unstable that it does mot exist at roam temperature Creole sou er a ere eas) carbonate starts Magnesium carbonate Calcium carbonate Strentiumcabonate | 1280 Barium carborate 1360 table 2.8 The group Z metal carbonates become mere sale to thera 2NaNO4(s) + On(e) In contrast, lithium nitrate and all the group 2 metal nitrates 1s oxide, the larger eations needing the much smaller Q ion to give them stability ALINO,(s) > 21:06) + 4NO,(@) + Op(@) 2Mg(NO})2(8) ZMgO(S) + 4NO,(4) + O2(8) Thermal stability of s-block hydroxides ‘The hydrowides of the s-block elements follow the same pattern a the carbonates and niuates. All group 1 metal hydroxides are stable up 9 quite high cemperstures, with lithium hydroxide dhe first to decompose at around 650 °C, All of the group 2 metal decompose on heating to form their correspont hydroxides decompose so form the corresponding oxide and 2LIOHG) > Li,0) + 1,0) sa(QH)3(5) > CaO(s) + H,0(@) aD “1 Describe the trends in ease of thermal decomposition of the nitrates and carbonates down group 2. 2. White symbol equations for the decompesitian of potassium nitrate, calcium nitrate and strentium carbonate,‘The elements of group 7 of the periodic table are betier known as the halogens. ‘The name dates back to the carly years of the nineteenth century when Jéns Jacob Bervelius used it to show that chlorine, bromine and salts. ‘The term ‘halogen’ is derived from the Greek and means ‘salt producing’. It remains appropriate ~ the halogens are very reactive and readily form salts, all occur in the sex as Physical properties of the halogens ‘The halogens are a family of non-metallic elements which exist as diatomic molecules. ‘They are all very reactive and are strong oxidising agents. Chlorine and bromine are poisonous. ‘The chemicsl behaviour of the halogens is governed by the seven electrons in their outer shell ~ the addition of only one further electron by either ionic or covalent bonding will give dhe halogen atom a noble gas configuration, ‘The mast common oxidation stare for the group 7 elements is therefore 1, although other oxidation states do exist (except for fluorine) As the atomic number increases down the group not only do the group 7 elements ‘become less reactive, they also become less volatile and darker in colour. Chlorine is f greenish yellow ges. Bromine (which takes its name from the Greck word Bromos meaning stench) is a dark red liquid giving off 3 dense reddish brown vapour, while indine is a shiny, greyish-black crystalline solid. ‘The physical properties of the elements of group 7 are summarised in table 2.59, in hich the trends discussed earlier in this section can be clearly seen. UNIT 2 Application of core principles of chemistry Group 7: the halogens € Chlern = ome ruber ” % 3 tecroniceontiatin | 287 = 281872818187 tectronegatty 30 28 2s Devs (0779) 1st ane 493 Metingterpentire( | 01 4 Boling temperate (C) | 35 9 84 ‘Atomic radius (rem) O14 0.133 Electron attnity (kj mot 325 295, Enthapy ofatambacion | 122 12 ‘7 (mot) pation energy “35288 BE) > Xe] H mot) Lattice energy of NaX(s) 742 -705 (mw) “a za8k table 2.59 Physical propartins of the group 7 alarents. “The solubility of the halogens in water decreases down the group, Chiorine reacts in water forming a solution that is sometimes called Chlorine water ~ @ mixture of hyutrovilorie seid and ehlorie) ai. Cg) + HO@ > HCltaq) + HCIOGq) Aye) + HOM > 2H" (ag) + Cr-(ag) +CIO“(aq) CChiorio(D) soid isthe substance thar gives a solution of chlorine its bleaching properties, Bromine dissolves and reacts with water in a similar way, but to 2 lesser extent. Todine is almost insoluble in water but is soluble in potassium iodide solution because of the formation of P ions: 1,66) + Fiag) > P @a) Halogens are non-polar so they are more soluble in hydrocarbon solvents than in water (See chapter 2.3), as shown in fig. 2.5.13. In cach tube there is water (lower layer) and cyclohexane upper layer). Chlorine is addled to the first tube, bromine to the second and iodine to the third. You will notice. especially with bromine and iodine, that most of the halogen bas dissolved in the cexelohexane lager.fig. 25:13 Malogens are more sluble inorganic solvents such 95 ‘eyconecane than water ) HSW Properties of fluorine and astatine ‘The trend in elecronaffnity Is inked toa gradation of physical ard chemical properties fom flucrne (atthe tap of group 7) to astatine (at the bottom. Fruotine isa pale yellow gas consisting of diatomic molecules. I reacts explosively with hycrogen under al Condon reacts with metals and non-metal I mere reactive than chlorine. ‘Astatine is intensely radioactive. The most stable 'sot0pe has & halite of ony 8.3 hours. tis found nly very rarely in certain ura deposits and has n9 Izrown significance ouside the reseerch laboratory —————___ n reactions of the halogens Halogens are strong owidising, agents, and this is shown in the reactions with metals, with non-metals ‘and with iron(T) ions in solution. With metals ‘The halogens react strongly with all of the more eleciropositive elements. This means that when they react with metals they remove some or al of the outer electrons and become reduced 10 negative halide ions themselves. This is scen particularly clearly in the reactions of the halogens with the group 1 and 2 metals. ‘The vigour of the reaction between Creole sou er a 2 particular halogen and metal is @ function of the reactivity of the particular metal and the particular hhalogen (chlorine always reacts more vigorously than ‘bromine, for example). ‘The reactions with sodium (group 1) ad magnesium (group 2) are shown here: INu(s) + Chg) > ZNECIG) Mais) + CL(@) > MsCl) Iron reacts with halogens to form iron(II] halides, ex: 2Fe(6) + 3C1z{g) > 2FeCI3(s) With non-metals In resection with the non-metals, the halogens usually’ achieve @ noble gas configuration through covalent bonding. This may be a single covalent bond such as thot formed in the hydrogen halides, HX. Table 2.5.10 summarises the reactions of hydrogen with halogens, ¢@: Hy(a) + Cly(g) > 2HCIce) ee hydrogen: CORA baru} Chlorine Explodes indirect sunlight, proceeds slowly inte dank "Bromine 300 °Cand platinum catalyst lodine 300 °C and platinum catalyst = proceeds slowly ane only partielly {ble 25:10 the rsctvtes ofthe halogens are demenststed in their reaction wth hyorogen.Chlcrnerescts ready in sui, we bromine and iodine aque catalyst to bring about thereactlon ‘The halogens react with other non-metals, including phosphorus. Chlorine reaets with phosphorus to form) hosphorus(HiI) chloride: 2PG) + 3CL,@ > 2PCI,0) ‘With excess chlorine, phosohorus(V) chloride is formed: 2PG) + SCly@) > IPCs) With iron(Il) chloride solution When @ halogen is added to pale green iron(II) chioride solution, the halogen exidises the green iron(II) ions to brown iron(II) ions, ep: 2FeCly(aq) + Cly(g) > 2FeCl;(aq)ox You can imvestigate the amount of iodine liberated by an oxidising agent (og brydrogen peroxide solution) sing titration with sodium ‘thiosulfate solution, UNIT 2 Application of core principles of chemistry lodine/thiosulfate titrations Earlier in this chapyer uation is a redox strat a redox reaction, A common example is the reaction of iodine and thiosulfate ions, which is curried out in a similar way to acid-base titrations. 1 studied acid-base Girations. Another (ype of which the reaction is not a neutralisation but lodine/thiosulfate titrations In chapter 2.4 you saw how ionic half-equations can be written for oxidising and reducing agents, One common oxidising agent is iodine Iy(aq) + 26° > 2r(aq) “The reducing agents you met incinded! thiosalfate: 28,07 (aq) > S,Og? (aq) + 2° ‘Combining these (wo, the overall onic equation for the reaction of iodine ‘with isu i: Ty(aa) + 28,0,2taa) > 8,0,2-aa) + 2F faa) “This reaction isthe batis of the iodinethiowulfate titration ding the purity of potassium iodate(V) Todate(¥), 10%, reacts as an oxidising agent: 105 (aq) + 5T- (aq) + 6H" (aq) > 31,(aq) + 3H,00) If iodate(V) ions are added to excess potassium iodide solution, iodine is liberated. ‘The mixture can be titrated with standard sodium thiosulfate solusion using starch as indicator. A weighed sample of impure potassium iadate(V) solid (0.80 g) is dissolved fn water and made up co 250 em? of solution in a volumetric ask 25.0 cm? of this solution are adced to excess potassium iodide solution, to berate iodine, In the titration 20.00 em? of 0.1 mol dar? sodium thiosulfate were needed to reuct with dhe liberated iodine, 20.00 x G.1mol sodium thiosulfate = 0.002 mol of thiosulfate 1000 From the equation (or the reaction of iodine with thiosulfate above, you can see that 0.002 mol of thiosulfate will react with 0.001 mol of Ty, So 0.001 ‘mol is the quantity of iodine that was liberated by 25.0 em? of impure potassium iodute(¥) solution, From the equation for the reaction of icelate(V) with iodide above, you can see that the number of moles of iodate(V) required to liberate 0.001 mol of indine is given by: umber of moles 105 = 0.001mel = 0.000333 mol 3Creole sou er a M(KTO,) = 214, so: ‘Mass of potassium iodate(V) in 0.000333 mol = 0,000333 x 214 = 0.0713 @ ‘The mass of potassium iodate(V) in the sample weighed out is 10 times this, since 25 em? of the 250 cm? solution was used in the reaction: mass KIO, = 0.0713 g x 10 = Percentage purity of potassium, mass calculated : x 100% mass weighed out % 0.718 « 100, 2 = 99.1 0.80 "% ED ‘There must be some doubt in the certainty of the result above. For example, Ifthe umber of moles of potassium ladate(V) were adjusted from 0.000333 10 0.00035, the final percentage would be 9.69%, 4 calculation lke tis involving several steps can lead to diferent results depending upcn the use of significent figures. ——$ ding the percentage of copper ‘An application of this redex tation is in the analysis of brass, Brass is an alloy of copper and zine (see fIg.2.5.14). brass ‘A weighed sample of brass is reacted with concentrated nitric acid to produce a mixture of copper(I) nitrate and zinc) nitrate. The sotution is then neutralised. and excess potassium iodide solution is added to liberate iodine 2Cu(NO,),(aa) + 4KIau) > 2Culs) + 4KNO; (au) + IyGae) ‘The liberated iodine & titrated with standard sodium thiosulfate solution, ‘This gives a measure of how much copper was in the original sample. ce 11 White an ionic equation for the reaction of capper(l)ritrate with potazstum ledide solution. Explain the changes that have happened in terms of oxidation fg. 25.14 Wang to red the pecerage and edction, of copperinbs 2 Suggest wiyit is necessary to neutrals the solution inthe brass experiment before tating 3) What assumption about inc nitrate 's made in te titration forthe brass ‘experiment? esDisproportionation With chlorine, bromine and iodine, the products of the reaction with sodium hyetroxide solution depend on the temperature at which it takes place. In cold (15 °C) dilue alkali, « mixture of halide, X~ and hhalate), XO" ions is formed: X2 + 2OH"(ag) > X°(ag) + XO“ag) + H,00) CLY@ + 2NaOH (ag) NeCl(ag) + NaCIO(ae) +H,00) (These halate(D ions may then decompose to give more halide and halatecV), XO* ions. The decomposition takes place at different rates depencling on both the halogen involved and the temperuuire: 3XO"(aa) > IXtaad + XO5-faa) 2NaClO(ag) 2NaClaq) + NeCIO, (aa) Sodium chiorate(1) > sodium chloride + sodium chloraie(v) 3NalO(aq) > 2Nal(aq) + NalO(aq) Sodium iodawe() > sodium iodide + sodium. iedate(V) In the case of chlorine, the decomposition accurs only very slowly at 15°C, but at 70° it is very rapid. “This provides a way of obtaining the «wo different produce, simply by varying the temperature at which the reactions take place. "The same is true for the reactions of bromine with alkalis, although in this case both reactions occur rapidly at 15 °C and the temperature needs to be lowered to 0°C to prevent decomposition of the BrO- ion. Both reactions occur rapidly even at 0.°C in the case of iodine, and so separating the differeat products is considerably less easy. All dese reactions of chlorine, bromine and iodine With alkali are examples of dispropertionation (see chapter 2.4). When chlocine reacts with all Cr ions snd CIO~ ions are formed. This involves a change in oxidation number from 0 (in Cl) to =1 (in Cr) ant +1 Gn CIO). Similarly, the decomposition of CIO” also results in a simultaneous increase and decrease in the oxidation number of chlorine: 2C1O“Gaa) > 2Cr aa) + CIO* (aa) Reactions of the halogens and halides Reactions of the hydrogen halides ‘The hycirogen halides result from the reaction of the halogens with hydrogen, as you saw cari in the chapter. ‘The hydrogen halides react with ammonia, 48 1 form ammonium halides, ex hydrogen ehleride and ammonia gases react to form ammonium chloride fumes (fig. 2.5.15): NHy(@) + HCI) > NH\Cis) Hydrogen chloride dissolves in water to form hydrochloric acid fig 2595 Formation af sanmmoniun chore, Redox reactions of the halogens with potassium halides Potassium halides will react with another halogen in a displacement (redox) reaction, For example, chlorine reacts with porassium iodide solution to form potassium chloride and iodine. ‘The equation for the reaction is: 2KI(eq) + Cly(e) > 2KCi(aq) + (eq) Figure 2.5.18 shows the reaction when chlorine is bubbled through potassium iedide solution, This occurs because chlorine is ¢ stranger oxidising agent than iodine. fig. 25.16 The rscton of chloe wh potessum odie ‘olution ca eden reactionfig. 25.17 Te Fst test tube contains ‘a precptae cf sve chloride, whieh ‘dssoles in dite arroria solution The thin tent tube contain aver bromide precisitae, which dissolves in concentrated ‘rvmori solution (test tube 4). The fifth ‘es abe contain slr och, which ‘doesnot desi In concentrated “ron sluon (test tbe 6). =p 1A student testing for halides ocidifies wth elute hydrochloric acié rather than lute nitric acid. Why does ‘this cause a problem? 2. How could sodium bromide and sodium chloride be distinguished vith, concentrated sulfur acid? Creole sou er a Reactions with concentrated sulfuric acid Concentrated sulfitic acid reacts with a halide to form a hydrogen halide, og NaCI) + H,S0,() > NaHSO,(s) + HCI) ‘With soxtium bromide and sodium iodide, however, the concentrated acid acts as an oxidising agent, oxidising the product to bromine or joetine respectively: 2HBr(g) > Br,(g) + 2H (aq) + 2e 2H" (aq) + H,SO,(aq) + 2° > 24,00) + $068) overall: 2HBr(g) + H,$O,(ae) > Bry(e) + 21,00) + $0,(8) Hydrogen iodide is oxidised even mors thoroughly by concentrated sulfuric n this case, partly to hydrogen sulfide, because hydrogen indide is an even stronger reducing agent than hydrogen bromide: H,S0,() + SH'(aq) + Se" 3 H,S(g) + 47,00) SI(ag) > 4I(ag) + Se overall: H,80,() + 8H"Gq) + 8PGq) > HS(@) + 4H,0() + 4lp(aa) The sulfuric ne is edu the silver halides Testing for hal TF you have an unknown halide salt and want to see what sort of halide it is, you can use silver nitrate solution to do a standard test.‘ ‘the halide ions is bused on the different solubilities of the silver halides (see fig. 2.5.17). Dilue nitric acid is added to the unknown halide solution wo prevent the precipitation of any other silver salts, Silver nitrate solution is then added. If the unknown halide is a chloride, CI a white precipitate of silver chloride results which ia turn is soluble in dilute ammonia solution: is analysis of Ag*tag) + CM(oq) > AKC) white AgClG) + 2NHy(aq) > [Ag(NH,),)"(ea) + Cr(as) TF left in sunlight, partial decomposition of the silver chloride into silver and chlorine makes the precipitate tum greyish in colour A bromide, Br gives a cream precipitate of silver bromide which in turn issolves in concentrated ammonia solution in the same way s the chloride: Agtlag) + Re(eq) > Agheis) AgBe() + 2NH,(aq) > [Ag@SH,),]"(eq) + Beas) Tdi, > gives a yellow precipitate of silver iodide which is insoluble in concentrated ammonia solution Aatian) + Mea) > Ast‘The halogens are a group of very reactive elements, which form very stable compounds Yet. the halogens ae a group cf great mportance, both in bilogical systems and in industrial epplications Scientists have found a variety of ways of using these pcisonous elements to improve the human condition ~althcugh sore ethical issues have raised thelr heads asa result Chlorine ‘4s you have seen eater in this chapter, chlorine Is a very effective oxidising agent. This property Is wally emportant hen it comes to providing us with clean drinking water In counties like the Uk, all of our drinking water is Chlorinated, Weter from reservoits and rivers is filtered +> remove selid particlos and then treated with chine 19 kil any bactovia in it, Small amounts of chlorine remain in the treated weter and this prevents possible recontarination by bacteria. When chiorine dissolves, ‘In water, an equllbrlum reaction Is et up in which hydrochloric acié and chiosk(!) acids ae produced It 1s ‘the lates which 's responsible forthe oxidsing power of ‘aqueous chlorine. Most people don't even think about the importance of chlcrine in the water ~ encept pethape in ‘swiermnirg pools when its use is mare abvious, However in the developing world eround 1.5 milion people, mainly children, die every year as @ resu: of crinking dirty, contamineted water The United Nations has set a target to halve the number ef people without access to dean crinking water by 2015, Chlorine and chlorine cormpounds wil play a big pat in this process. In some places big water tarks can be built to supaly ‘a whole vitage. Caiclum hypochlorite — involving both youp 2 and group 7 elements! ~ is used to sterlise the water which cen then be supplied to the vilagers ‘through pipes. ut in some stuations it isn’t even postible to provide tanks. Millon of people worldwide simply collect the drinking water ftom rivers and lakes — often the same rivers and lakes wich are sad 25 tilets and for washing both people and clothes. Even well water is often contaminated by cirty water from nearby. So an ‘alternative strategy #10 supply people with calcium cr sodium Iypochlorite which they can add to their water 19 make it safe to drink. Chlorive eready saves milion of lives around the world through clean crinking water future it may well save many more fig. 2518 When natural dsstrs tke anywhere inthe word chionne-basee chemicals can stenise any dirking water avalatle and prevent the spread of diseases sich as cholera, Fluorine CCHrine was First added to drinking water in 1897. No- fone questions it, and iti intemationally agead to be the best way to provide clean drinking water. However, when it comes to adding another tyze of halogen salt to the drinking water, cpinions are more divided. Fluoride ions have been shown to help fy the development of healthy tooth enamel. Enamel isthe hard, shiny white covering of the teeth that protects them from attack by acids formed in the mouth by the action of bacteria on. food, Ic isthe hardest substance formed by the bed. The ‘normal structure ofthe tooth enarrel involves en open lattice of » compound known as hydronyapatite. Ths is ‘made up of calcium along with phorphorus, ocygen and hydrogen (see fig 2.5.19). However scientific studies have shown that trace concentrations of fluoride ions present at the time cf tooth formation in the gurrs enable the body {0 produce even harder enamel. When fluoride ions are present, flucroapatite|s formed. The fluoride lons effecvely block up vive hols in the enarne structure, a5 Hlustiated by fig 2.5.19, making the teeth much less vulnerable to ecey. Only races of fluoride are needed - a good thing as fluoride ions are toxic at higher concentrators.Unit ce of hydroxyapatite Structure of ucrapaite ao Pet Oyen baygen ryerogen fuarne fig 2519 fata fluoride ions laa toa denser enamel hich it ey tel ped ete meter ereey et brceria ‘The apperent benefit of fluoride ions to the teeth came from observatiors that children who grew up with naturally igh levels of fuorie ions in ther dtinking water appeared +t» have less tooth decay and fewer filings and extractions than children who lived in areas with las natural uote, ‘There is also evidence that older people are loss likely 19 lose ther tenth if they lve in areas with naturally igh fluoride levels. A team at York Uriversity looked at evidence from a numberof studies and reached a number cf conclusions about the value of adding Muoride fos to ‘Une water supply in erees where the levels are naturally low: Children from poorer famities, who ere peshaps most Uicely to eat cheep processed focds high In Hidden sugar, {and who may not be able to afford, or be aware of, the benefits of flicride toothpaste sermed to henefit most. Creole sou er a 2, low fuwise as i). a Be igh tore 2 is “nM lew i av cic (ecayeemisirg leeet (et| by s00a das nhigh ndio funnde seas for daen age Sas) ‘ig 2520 Based on evidence sucha this te cast for ading (Rive fv to the dking vater spy aces very eee. Fluoridation of the water supply could even aut some of these inequalities. There isa large body of evidence hich suggests that fluoridation of drinking water, so that everyone gers about ppm, would have many benefits \hroughout the comunity and could save a great deal of ‘money in the long term on dental care for both the young and the old However, not all of the evidence for fkuoration Is so positive, Australia, New Zealand and the US are some of the counties which already have fluoride ions added to their water supply. Some scientists there feel thatthe possible toxic effects of flucride, from dscolouring the teeth to possible effects on the skeleton, causing arthits- like symptoms, have not been investigated suificently and that any negative evidence 's ignored in the face of vested interests. Sore peopl feel that adding fluoride to water removes a1 element ct personal choice and responsibly ~ although interestingly that argument is not put forward {or edding chlorine to water. The debate continues! ©) 11 Vihy do you think no one queries the addition of chlotine to the water supply, when fluoridation can cause heated debate? 2 Investigate some of the evidence for and agairst the fluoridation of ‘water. Evaluate the research on both sides and draw your ov personal conclusions, based on the evidence you have found. You are now ready to try the fist Exaraone test for Unit 2 (Examzone Unit 2 Test 1) on page 252. This will test you on what you have leamt in Unit 2 chapters 1 to 5.Tee ea uae ieee 6 Kinetics Rate of reaction Reaction rates ure of fundamental importance to the esearch chemist, in the chemical industry and in the living world. The rate of reaction describes the speed swith which reactants disappear and products form for 2 particular reaction. Information sbout what affects reaction rates gives chemists the opportanity to speed up or slow down a particular reaction in the lab. In industry st allows operating conditions to be chosen that ‘make the process take place with maximum efficiency and economy. Studying the rates of reactions also gives us information sbout how reactions actually wake place. What factors affect the rate of a chemical reaction? A variety of factors ean influence the rates of cher reactions, speeding them up or slowing them down, ‘There are five main factors that affect hew fast a chemical reaction takes place: + concentration + + pressure : ‘We shall look at each in tam. temperature = surface area catalysts Concentration and pressure Figure 2.6.1 shows two containers of gascous mixtures of hydrogen and bromine, You can see that there is a higher concentration of particles in (b) tha (a) tb} @& &$ % (ig. 26.1 Two contalers wth ixturee of hydrogen (ed aed bromine (row, the gases havea ngherconcertracin in () than in). In both containers the particles are moving randomly in all directions, If a particle of hydrogen and a particle of bromine collide with sulicient energy, & reaction will take place ta form hydrogen bromide You can sce that in container (b) there are more particles in a given volume, and so there will be more collisions, The rate of reaction will be faster in container (b). Ina mixture of gases, such as a mixture of hydrogen and bromine, increasing the pressure has the same effect as increasing the concentration in a solution. Teincreases the number of particles per unit volume, leading to an increased ceaction rate. === ‘Chemists find it useful to use a collision theory model 10 explain wht is happening during a chemical reaction at the molecular level Locking st a static diagram like fig. 2.6.1 itis easy to forget that the particles shown are moving randomly in all dictions and in three dimensions, The number of colisions that involve sufcient energy t0 lead to 3 reaction is related to the umber of colisions overall. Increasing the number of ‘collisions by getting the particles to be closer togeties, ‘or mating them move faster, will not only result more cellisons but also, in consequence, more ‘successful collisions. But this is not the whole story ‘When particles collide they rest have more than just sufficient energy. They must colide with the correct orientation. That means one part of a molecule rust calide with a certain part of another motecsle with sufclent energy before the reaction will tate place. You ‘wll see the importance of this later when you study reaction mechanisers, Temperature Collision theory says that particles have to collide ‘with a certain energy for « reaction to take place. IP the temperature ie raised, the number of particles unchanged but the average energy of exch particle is greater ~ they are moving faster on average. ‘This ‘means that more colisions will bave sufficient energy 1 result in a reaction, and so the reaction will be faster at a higher temperature.ee eee Surface area For any reaction to happen. the particles of the reactants, ‘must be brought into contact with each other. If the reactants are in the same phase (either liquids or guses) their reacting particles can intermingle freely, giving them the maximum opportunity to react together. This is why the majority of chemical reuctions are carried out in aqueous or organic solution, or in the gaseous state, A. reaction with reactants in the same phase is known as a homogeneous reaction. However, if one of the reactants is a solid then the reacting particles can only meet at the surface of the solid, Ifthe surface area of the solid can be increavcd, then the rate at which the reaction can take place will be increased too (see fig. 2.6.2). Reactions between ‘wo substances in different phases are known as heterogeneous reactions (sce fig. 2.6.3). Heterozencous reactions can be pretty explosive = there have been a number of occasions where the tiny size of particles of grain dust have allowed the combustion reaction betvicen the solid carbohydrate and the gaseous oxygen present in a flour or grain silo to progress so rapidly that it has been completely destioyed! tem Volare = 1 ? ae Surface area = 6x Ten’ =6en® : ‘ivideirto 190 cubes each o Olemxdtemxd1em a Volume = yom? > 1000 Surtace area = 6 x (0) em)? = 0.06er? OO ‘Totatvolume = Ten? “Tolalsutace aes = 60cn” fig. 262 Ifyou divide at emcabe ito 0:1 em eubes yo incense the surface aes fom 6 cm 10 60 on, . es fig. 263 Inthe heteogencous reaction between wood in the std state and oxygen in the gaseous state the surface area ofthe nicod exposed t2 ‘the air makes allthe ference tothe rate ofthe combustion reaction Catalysts A catalyst is u substance that changes the rate of « chemical reaction (usually speeding it up) without, being used up or undergoing any permanent chemical change. Catalysts can enable reactions to ‘oceur that woul! simply be too slow to be recognised without them. Almost every major industrial chemical process depends on catalysts t0 enable a profitable reaction rate to he maintsined! ‘without resorting to excessive andl expensive ‘conditions of temperature and pressure, The enzymes that control the biochemistry of every ving cell are also specialised catalysts, made of protein, You will return to how catalysts work later inthis chapter. 4 S Nal 1g 204 emymes-obgel aay wey wen de Ts ees ae CD ‘1A student is studying the reaction between calcium carbonate and hydrochloric acid. He ants to find out whether increasing the concentration ofthe acid has more effect on the rate of reaction than raising the ‘temperature, What advice would you give him when plarning his experiment? 2 Food decays by a series of chemical reactions. Why is It that food car be stored much longer Ina refrigerstor than at room temperature? 3 Flour dustin @ flour rill can explode in air. ‘Suggest why this may happen, when a bag of flour Inthe kitchen wil not explode. | —<—<$<$<$_$_$_—_—— rrUNIT 2 Application of core principles of chemistry Measuring reaction rates You have scen that five main factors affect the rate of a reaction, How can you measure their effect? To Follow the progress of a chemical reaction quantitatively, chemists take measurements and calewlate the reuction rate, ‘There are various methods but they all depend on measuring how quickly the reactanis are used up, or how quickly the products are formed, This amounts to measuring the change in concentration of either one of the reactants or one of the products with time. The mate of a chesnical reaction ean be expressed a rate of reaction = change in concentration change in time So, fur example, If the concentration of @ product of a reaction increases by 0.25 mol dm’? each second, then ‘we can say that the rate of formation of this product fs 0.25 mol dem is increasing (ie you are monitoring a product), the rate is expressed as a positive number. If the measured concentration is decreasing Gie you are monitoring 3 reactant), the rate is expressed 28 a negative number. So, for example, if 0.5 mot dm of a reactant is used up every second then the rate of reaction is 0.5 mol da sl If the measured concentration ‘These values are average rates of reaction for the period of time over which the measurements were takea, Measuring the volume of a gas In some renctions it is easy to soe how the rate changes cin a reaction that produces bubbles of ga Mg() + 2HCK(ag) > MeClx(oq) + 1168) you can vary the reaction conditions ~ eg the ‘concentration of the acid, the temperature or the surface area of the magnesium ~ and see what effect this has on the rate by simply counting the umber of bubbles at regular time intervals, eg every 15 s, For ‘more accurate results you can messure the volume oF gas given off at regular time intervals throughout the reaction, using the apparatus shown in fig. 2.6.5(a).. ‘You can then plot a gruph of the toul volume of gas praduced against time (see fig.2.6.5(b)) reosuring ‘tnd xin =| sassy resction finshed fig, 265 (6) Two practical methods of messiting the volume of 25 occnd every 15 secon (b) Graph of wolameo! gas callectee est tie, In fig. 2.6.5(b) you can see that the graph is steepest at the start of the reaction and the steepness (cute) reduces throughout the reaction. If you draw a tangent to the curve at the siart of the reaction (as shown by the dotted line) you can work out the gradient of the line. This is the initial rate of reaction, The reaction rate changes throughout the reaction, as does the concentration of reactants and products, s0 it is most accurate for comparing the initial rates of different reactions, You could study the decomposition of hydrogen peroxide using the same apparatusMeasuring the change in mass of the reaction mixture Another way of monitoring the change in concentration of « gaseous product is to measure the mass of the total reaction mixture as the reaction progresses, and see how quickly it decreases. For example, the rate of the reaction between calcium carbonate and dilute hydrochloric acid: CaCOJ) + 2HCI(ag) > CaCl,(2q) + HOW) + CO,68) can be monitored by measuring the mass of the apparatus every 15 seconds. ‘The mass decreases as carbon dioxide escapes from the solution. This method can be used to investigate the effect of changing the cemperature, dhe concentration of the acid or the particle size of the calcium carbonate, Monitoring a colour change Colour changes provide unother way of measuring the rate of a reaction. In the ‘iodine cock? reaction, you can ccmpare the effect of altering the concentration of one of the reactants, hydrogen peroxide. A solution of hydrogen peroxide and sulfuric acid is added to 2 solution of iodide ions, thiosulfate ions and starch. A slew reaction forms iodine, Which reacts rapidly with thiosulfate util the chiosulae is used up. ‘The excess iodine then reacts with the starch 10 form a blue-black complex. Hlere are the equations for the reactions: 2H*(aq) + H,0,(ag) + 2F (au) > 1,68) + 211,00) Tag) + 28,0529) > 8,0,2-(aa) + 21-Ca9) “The ime is messured from the mixing of the solutions unt the solution turns blue-black. UNIT 2 Application of core principles of chemistry Other methods of finding the rate of reaction Some ether commenly used methods of monitoring the rate ofa reaction while investigating the effects of different factors are summarised below. + Titrimetric analysis involees removing small portions (aliquots) of dhe reaction iixture ot regular intervals. These aliquoss are usually added to another reagent which immediately stops or quenches the reaction so that there are no farther changes to the concentrations in the reaction mixture until further analysis can be carried out. ‘The quenched aliquots are then titrated to find the concentrations of known compounds in them. + Colorimetric analysis is particularly ‘valuable where one of the reactants or products of the reaction is coloured. The coloar changes throughout the reaction ccan be detected! using apparatus called a photoelectric colorimeter. The colour changes measured in this way can thea be used to calculate changes in concentration, + Conductimetric analysis involves ‘measuring the conductivity changes in & reaction mixture over time, These reflect the changes in the ions present in the solution and so can be used to measure the changes in concentration of the various components of the mixture. Fd 1. a Which method in fig. 2.6.5(a) do you think is Ukaly tt give the more accurate results? Suggest why. 1b Ifthe gas produced were soluble, which method ‘would be better and why? 2. Why would the method involving measuring the mars ‘of the reaction nat work well in the reaction of magnesium and dilute hydrochloric acl? Think about the density of Fydrogen.Dn nay Activation energy Collisions between reacting particles ‘You have seen how collision theory says that for a reaction between Ovo partices to occur, those particles must collide in the correct orientation and wich sulficient energy. ‘The reaction rate iy a measure of how frequently effective collisions occur ~ an effective collision being one that results in the formation of product particles, ‘The factors you have met that inerewse the rate of collisions will slso increase the rate of a reaction Activation energy Few collisions between particles actually lead a chemical change. Why is this? As you have seen, in order to react they must collide with a certain minimum Kinetic enezgy. This is known as the activation energy. Ey. I! wo slow-moving particles collide, even if dey are in the ight orientation, they will simply bounce spart as a renult of the repulsion of their negutive cleciron cloud. An increase in temperature will increase the kinetic energy of the particles andl so increase the rate of reaction, because a greater proportion of particles will have sufficient energy to overcame the activation energy and react (see fig. 2.6.6) vere Fraction of molecules having given Kineticenengy inet energy fig. 26:5 These curves show the linetic energy dstitutions of the patties for reaction mature at two diferent terperetires. The sheded areas ae proportional to the total eatin ef particles that ave the minimum activation energy. YoU can see that a the higher ternporsture, Ty more patces have enough energy £0 react What happens during a reaction? When particles collide with the correct orientation, they slow down, stop and then fly apart again. In an ‘unsuecessful collision the particles separate unchanged, whereas in # successful collision the activation energy barrier is crovseu and ube particles that separate are chemically ifferent from the original ones, As the particles slow down and stop they posress Jess and less kinetie energy and their potential energy The relationship between thi energy and the total potential energy of the colliding reactants is shown in fig. 2.6.7. This is a reaction profile, which follows the path of a reaction as reactant particles come together, collide and produce product sctivarion particles which then separate. Inthe te upward slpes, the ‘eactare moleciles are coming topether and breaking par. Separating ators the reactant roles vegies bonds be Broken, so this part of tre eaction absorbs every i fenhaley \ Inthe two downward topes the prodict mleces are frre and moving apart. Protucing Ppoic meleries invoke Fring bono that of the reaction relesses ser crergve, on 5 (ennai B | cuangeot Saget reaction) resto) (3) Reactonccornate ” —(p) Reaction ccornate ‘ig. 26,7 Reaction prot lags fo (a) an exctherme reaction and (b]an endothermic reaction The progress of the reaction fs shown on se reaction coerdinate As 1wo particles collide, they slow down and their kinetic energy is converted to potential energy ~ they begin w climb the activation energy hill. If uheie combined initial kinetic energies are less than the activation energy, H, then they cunaot reach the top their Kinetic energy agzin. On the ather hand if the of the hill so they fall back as reactants, gain origins combined energies are equal to or greater than F, and the particles are correcily orientated, then they can overcome the activation energy barrier und form product particles,Ee ens ‘The activation energy model can be used to explain how 2 catalyst increases the rate of a resction. One simple explanation is that a catalyst lower: the activation energy. so more calsions have encugh energy to result in a eaction.A more sophisticated model suggests that ifthe particles cole with sufcient energy and in the correct cxlentation they form an activeted complex. The cectivated complex is nota chemical substance that cen be isolated but consists ofan assocation of the reacting particles in which bones are inthe process of being, broken an formed Figure 2.6.8 shows the acivated ‘complex in the decomposition reaction of hysragen iocide into hycrogen and iodine. 1—1bona ~ fermi + ons trea ‘ig, 26 The activated carey in the deesrpasition of hydrgen| perone, Fig. 2.6.9 shows « more sophisticated model for the reaction profile of an exothermic reaction involving 4 catalys. *._profiefor neatalysed rection i \ x seteted comploe products activation energy of uncatalysed reaction bextinetion energy of estalyaedvection fig.269 A catalyst lowers the scthation energy ofa reaction by forming an acated complex, a levrenergy ntsrmedate stage. ) HSW The Max Sn ‘The partces in a rection mixture do not al. have ‘the same binetic energy. There is a spread, with some particles moving very slowly, some very quickly and the majority being somewhere in the middle. Figure 2.6.10 shows the Maxwell-Baltzmann model, 2 mathematical picture ofthis Gstribution of velocities, ‘This made! war created independently in the mid- nineteenth century by Ludwig Boltzmann (in Vienna) ‘and james Clerk Maxwell (in Carnbridge. Number of particles have Dncessng velocity ‘ig. 26:10 The Maxwel-Boltemann dstibution shows the range ot ‘eoctos of the paris in» reaction mistre ‘The vertical dotted line shows the velocity the particles must have if collision isto bring about a reaction ~ it represents the activation energy. This model can help explain why an increase in temperature speeds up a reaction rate. Figure 2.6.11 shows the Maxwell-Boltzmann distribution fora reaction mixture at three different temperatures. You ean sce thar as the temperature rises the graph becomes ‘Tater and « much grester proportion of particles are moving fast enough fo overcome the sectivation energy (dotted line), This leads (0 more collisions and a faster reaction. 200 Asthetempesture ofa gas acres, {he agvbbon of moles spe within Itcharges At higher temperatures the sverag spond ofthe molees nose (the mera emegy ofthe gos geet, [though he proportion ot motecler wah the mest probate sped eecesss 3500 Proportion at motauls with given velocity _— Weocity (ig. 26.11 Seventy yours etter Boltemarn published bis thereticl ‘model it was shown practcaly that the dtributon of velocities ina 8 apred with hie predictions. So the Maxwell Boltzmann distribution is an example of a mathemstical model that allows you 10 understand and predict the effect of changing conditions on the rate of reaction, —_— tna particular exothermic reaction, the activation energy i high, What does this suggest about the likely rate of reaction? 2 What two factors determine whether two colliding particles wil react? 3 Suggest problems that Boltrmann and Maxwell might have had in collabor ee)Pee ane Ceca 7 Chemical equilibria brium Dynamic equi Equilibrium - a balance In chapter 2,6 you thought about the rates of chemical reactions, and factors that affect how quickly reactions £0, Tere you will be looking at not how fast, but how far ~ the extent to which x reaction goes ~ or how much of che reactants is converted to products, Many reactions are equilibria ~ their reactanss and products exist together, rather than going 1o completion with all the reactants tuming readily to produets. You will alsa be looking at the fetors that affect the position of equilibrium — how far 2 reaction goes cowards completion, In understanding a chemical equilibrium, you can picture a liquid put in an empty box which is chen scaled, The particles of the liquid evaporate andl collect in the empty space above it, These particles fly around and collide with each other, with the walls of the container and with the surface af the guid. When a gaseous particle collides with the liquid surface it tends to rejoin the liquid. Its kinetic energy is transferred to the particles in the liquid so that it rng longer pessesses enough energy w escape feo the liquid again, ‘her energy tote other particles inthe cul. At first, far more particles leave the liquid than enter it, because there are very few particles in the vapour phase. As the number of particles in the vapour phase increases, the rate at which particles rejoin the liquid increases, beceuse there are more particles in the vapour phase colliding with the liquid surface, Eventually a point is reached where the rate at which particles are leaving the liquid is the same as the rate at which particles are joining it ‘When this happens we have reached a point where ‘nwo opposing effects, evaporation and condensation, are gecurring at equal rates so that they cancel out, Clearly we have an equilibriam ~ but more importantly, this is an example of a dynamic equilibrium. A dynamic equilibrium involves ‘two opposing processes that occur at equal rates. An equilibrium of this type is often established in chemical processes t00. Another way of describing a dynamic equilibrium is vo say that it has constant macroscople properties (those properties that an external observer ean see and measure) while at the same time microscopic processes (processes on 2 molecular scale) continue to ‘oceur, For our example of the liquid in the box, the oral amounts of liquid and vapour are constant (he macroscopic observation), while at a microscopic level individust particles are continually moving between, the phases, Nitrogen dioxide and dinitrogen tetroxide — a steady state In heavily polluted air, x brown haze may sometimes be seen, The gas responsible for this is nitrogen dioxide, NO, formed by oxidation of the nitrogen monoxide, NO emitted by ear engines. Nitrogen dioxide is in equilibrium with dinitrogen tetroxide, N,O, which is colourless: 2NOx(g) = N,O,(e)Coy Tn an investigation, 0.0800 mol of nitrogen diewide are sealed in a container and kept at a constant 25 °C. Eventually the amount of nitrogen dioxide rops to a stexdy 0.0132 mol while the amount of dinitrogen tetroxide rises to a steady 0.0334 mol, The left-hand side of fig. 2.7.2 shows this. Suppose that now we tke a container of the same size and pat 0.0400 mol of dinitrogen tetoxide in it, (This is exactly the amount of dinitrogen tetroxide that 0.0800 mol of nitrogen dioxide would produce if it reacted completely to form dinitrogen tetroxide.) If we keep this container at 25 °C, ve find that once agsin we end up with 0.0132 mal of NO, snd 0.0334 mol of NzO, when a steady state has been reached ~ the right-hand side of fig 2.7.2 represents this situation. ‘You can see that the same final sitastion comes about whether we start ith pure nitrogen dioxide oF pure dinitrogen tetroxide. In both eases the amount of reactant (NO, or N,O,) fills and the amount of product (N30, oF NO>) rises until equilibrium ip attained. At this point the amount of nitrogen Gioxide reacting to form dinitrogen tetroxide is exactly equalled by the amount of dinitrogen tetraxide reacting to form nitrogen ciewiee, ‘00800 mel NO 0.0132 mSINO; + 00534 mal NO, (O40 maIN;O, {e.2172 The fialequiltriar state is the same no matter which gas we start with ‘This example shows how a dynamic equilibrium is established in a chemivel process. As the reaction proveeds, « plot of the concentrations of the reactants and products looks like the one shown in fig. 2.7.3. These concentrations change fairly rapidly at fist, and then reach steady values. At this point the mate of conversion of reactants into produces exactly equals the rate of conversion of products into reactants, and we have a steady state, Another ‘way of saying this iso say that at equilibrium the rate of the forward reaetion sand the rate of the buckwurd reaction are equal. ‘corcenetion concerti reach stay values §|\ creates “equtscur i estabisnee tps ° o ine 1ig.2.73.ASequllbrum is reached the concentrations of reactants and products na cherncat rocers reach steady values,UNIT 2 Application of core prin: Croc The reaction of nitrogen and hydrogen to produce ammonia You may have studied the Haber process at GCSE. Ie is a good example of an industrial process where itis important to control an equilibrium reaction in order 10 get a good yield of product. Ny(e) + 3H,@) = 2NHA® ‘The forward reaction is exothermic. 9.27 Armmoni-based ferlisers have been sed for over 100 years 22 Increase rop yee and help feed the everaxpandirg weld poptation What affects a dynamic equilibrium? he position of equilibrium is not fixed for a reaction, but changes as vou change the reaction concitions. When a system in dynamic equilibrium is upset, it reyponds in such a way ay Go rotura it to equilibrium again, The tendency of systems to behave in this way ‘was noted by the French chemist Henri Le Chatelier. who in 1888 proposed thst + Whenever a system which is in dynamic cquilibrium is disturbed, it tends to respond in. such 4 Way as to oppose the disturbance and so restore equilibrium. This is known as Le Chatelier’s principle ‘Three main factors affect the position of equilibriam, or the ratio of reactants:produets in the equilibrium mixture: + temperature + pressure + concentration ‘You will look at each in tum, Temperature In the Haber process example, the forward process is exothermic. If you inerease the temperature, the qui oppose the rise in temperature, the reaction moves to te left (the endothermie direction), resulting in less product and more reactants in the equilibrium mixture um responds to oppose the change ~ 50 19 For an endothermic reaction, the opposite is true. Increasing the temperature drives the reaction further to the right, resaking in more products and less reactants in the mixtare. Pressure For a gsiseous reaction, the pressure affects the concentration of particles (the number of particles per unit volume). ‘The effect varies depending on whether the number of moles of product is the same as the number of moles of reactant or not. In the ammenia reaction, there are more moles of reactants (4 mol) than product (2 mol). One mole af any gas occupies the sume volume, so at constant pressure the reactants luke up twice the volume of the product. Inereasing, the pressure has more effect on the reactants than on. the products, effectively increasing their concentration (see below), 60 an increased pressure drives the reaction t0 the right, forming more product. Concentration For a reaction in aqueous solution, increasing the concentration of the reactants will drive the reaction to the right - once agsin the system is responding {0 oppose the change. Conversely, increasing the concentration of the products drives the reaction 10 the lent,Cee ne lodine(I) chloride and iodine(IIl) chloride If chlorine ges is passed through a U-tube containing solid indine, « brewn liquid, iodine()) chloride, ICI is formed with a brown vapour above it. The bottom of the Utube geis hot ~ the reaction is exothermic. If more chlorine ss s passed though the U-tube a yellow solid, iodine(IM) ehloice, 1Cly i forme: 1,6) + Chi) > 2c) TCI + Chie) = IA) If the chlorine supply is removed, and the U-tube is tipped horizontal, the yellow crystals disappear and a brown gas is seen. The equilibrium is moving, back to the left to reform the iodine(1) chloride and chlorine, These were separated from the reaction mixmre when the U-tabe wss tipped. If the chlorine supply is attached again the yellow solid forms ss the equilibrium ‘moves 10 the right, opposing the increase in chlorine concentration and producing iodine(IT1) chloride again. 0 o o @ an ven FB Be a a & a Iodine erie eu ck eh, In (clove reacts withotre fist to proce ine code () ard then indie) hiosds() Who the Utube tied, sho ein) crice ‘ceorposes to reform ide chloride The elibium moves tothe le 1g.2.75 ivestigatirg the equlloium between lone!) chord lene) chionde and clone aD 1 The equation shows the reversible reaction between nitrogen cioxide and dinitrogen tetroxide: N-O4g) * 2NO,(8) yellow brown a sealed bulb containing an equlibrium mixture of NO, and NO, is heated, the mixture goes darker in colour. ‘a_ Is the equilibrium moving left or right as the temperature rses? 1b Suggest 2 reascn why the equilibrium might move inthis direction. ‘¢ Ithe pressure acting on the equilibrium mixture increased, how would you expect the mixture to change colour? Explain your ansiver. 2 Explain the results of the iocine() chloride experiment in terms of Le ‘Chatellers principle ——— hheyotasUNIT 2 Application of core principles of chemistry Pe ‘The Hater process —a compromise CControling equilbrium reactions in industrial processes [s vital if a chemical manufacturer is to maximise profits, Returning to the Haber process, to get the maximum yield cof emmonia, high pressure would push the equilbrium ‘to the ‘ight to make more ammonia, Because the forward reaction is exothermic, running the resction at a low ‘temperature would tend to produce mare ammonia (2s ‘the equilbrium responds by trying to oppose the low ‘temperature). However, if the temperature Is too low the reaction i slow to come to equilibrium. A compromise Is, siruck at 450 °C — traditionally an iron catalyst is used to speed up the reaction, The catalyst does not produce a higher yield of ammonia by moving the pesition of ‘equilibrium but it makes the reaction reach equilibrium faster Because the ammonia is removed as it is produced, the low concentration af armania also pushes the action in the forward direction, The role of a catalyst {As you have seen in the Haber process the usual catalyst is ‘ron, However, esearch has shown thet ruthenium catalyst hhas a 40%6 better efficiency. A more expensive catalysts justified because it snot used up in the process. Honeves, ruthenium does not enable the process to take place ata lower temperature and chemists are working constantly to find a better catalyst that will work ata lower temperature ‘Although theory suggests that a greater yield is obtained athigher pressures, increasing the pressures an expensive process 20a compromise prossure is used, The preduct is continually removed to push the equiibrium to the right. ‘Also. in the Haber process all ofthe nitrogen and hydrogen are not combined when the mixture of gases goes through the catalyst chamber the fst time, but they are recycled through to incease the yield. ‘The atom economy for this process is 100%, because all ofthe reactant are turned into products and there are no waste products. pup octclate gases. expanding pemco Greeacted NeewH Mig outer vo store tank posted eed grees” ("30-300 ate) ‘ie 2.06 The Maver process suse to make ammenla ty controling an equllrum ea=ton,Stored methane in equilibrium ‘There are huge amounts of methane trapped ss solel methane hydrate in ice structres deep in the oceans (see ‘ig. 2.7.7(a)). Methane lyarate is in equilibrium with gaseous methane and water: ‘methane hycrate(s) = methane(s) + water() ‘The forward reaction is endothermic. According ty Le Chatelicr’s principle, if the Barth’s temperature rises, the equilibrium will move to the right ‘© ‘oppose this change, releasing, more methane into the atmosphere. Iv there is an increase in pressure, since methane is a gas, the equilibrium will more 10 the left. Moving to the left suru the methane gas back into solid methane hydrate, which does not exert a pressure, so this change in the equilibrium reduces the pressure, I has been suggested that the sudden release of large amounts of methane gas from methane hydrate deposits could be a cause of past and future climate change. ig 277 (a) Mode of methane hycrate Coy Or ed ‘This equation summarises the conversion of chromate{VI) ion to dichromate(V/) ions: 20103 (aq) + 2H*(eq) = Cr,07 (0g) + H,0() ‘chromate(VI) dichromate(VI) orange a excess acid b excess alkali, Predict the colour changes you would expect in each case 2 The selution turns orange. ‘According to Le Chatelier’s principle, the equilibrium moves to the right to oppoce this change (an increase in concentration of 2 resctant) and use up the excess acid. b The solution turns yellow. ‘The alkali will neutralise the acid, s0 reducing the concentration of Ht on the left-hand side of the equation. According to Le Chatelie?= Principle, the equilibrium will move to the left to oppose this change ‘and produce more ace OD 11 The equation fr thereecton ofetharoie acd and ethancl i: CH,COOH() + C,HeOH() = CH,COOC,H4() + H,00) 1a Pradict whether the equilibrium position will move the prossure isincreased Suggest a reason for your prediction b Predict the eect on the postion ofthe equlixium of edding (excess CH,COOH(Y) (11) ational water (i) excess C,H,O4() (i) catalyse. in. 277 (A) A vidous cycle? Asgrenhovse gros such as methane cause a se inthe temperatre atthe rfc of he arth, the 32 temperature ses 25. wal thee Ice structures melt a a result then huge reservors of mathane could be released tro the etmospere to act a greerhoute ges and tnake the tution evenTEC er oe eo 8 Organic chemistry — alcohols and halogenoalkanes The alcohols - a ‘Alcohol Bepiaped ene eee homologous series Methanol Wn impr 15 you met he man grep of F organic eompeurt ad ern how eran oe , compound are nard. The fil tw i chapter in uit {needed vo orgie fumes, the aikane an llones. Here ou wil sudo mere herons sent =the Sls nt Flopenalanes on Ethanol Alcohols are extremely important organic compounds in industry. This is because they are good solvents and also make suitable raw materials for converting to other compounds. The alcohol functional group Propan-1- As you saw int chapter 1.5, alcohols have an alky! group, which can be represented by Ry slong with an -O1T or hydroxyl fanesional group: ROOK butan--al ‘The naming of alechols is relatively simple = the name of the ally] group containing the largest number of carbon atoms is used \with the suffix -ol. A rmmber may be used {in front of the -ol to indicate which carbon atom it is attached (0, Side chains are named in the usual way, Table 28.1 and fig.2.8.1 Butan-2-ol show some examples of alcohols HOW HOw I I He cercec ence i i oH HOH On 2.methylbutan 4 “ol I i: It Hoc thy Pio HOH OH fig. 21.1 Ball ard stick models of ethan, etharo, propan-2-L and popan--al (elockwice Fom the to). tbe 2227 Some examples from the homologous sees of alcohols,Ue ee Types of alcohols Alechols have one of three types of structure ~ they may be primary, secondary or tertiary. The definition of these three fypes of alcohol depends on the number of alkyl groups present on the carbon atom attached to the functional group (see fig.2.8.2). These differences in structure affect the way in which the alcohols react. (2) some primary eohots WoW i —c—c—on II How ftrarol (b) seme seconcaryslahols HOOK N HOH OF Ww It Lot I Wee ew Hee ee ew rot rt Hon ow Hon oH How roper-2-0l pentan-3-c (€) sere tertiary alcohols HOW HH HoH A © I H 2emetiybstan2- 2methyipopan-2-cl fig. 28.2 Pimary,cacandary and tartar alechae show dtnet chemical properties. + Primary aleohols have the general structure RCH,OH. This means there are two hydrogen atoms attached to the carbon joined to the -OH group. + Secondary alcohols have 60 alkyl groups and fone hydrogen atom attached! to the carbon that is joined to the OH group, giving them the general seracture RR, CHOHL. + Tertiary alcohols have three ally] groups and no hydrogen atoms attached to the carbon that is joined to the -OH group, so they have the general seracture RR, R,COH, Combustion of alcohols Aechols burn in a plentiful supply of air or axygen to produce carbon dioxide and water vapour and release enengy, e&: CH,CH,OH() + 30,(6) > 2C0,(g) = 31,00) Bioethanol is being produced by fermentation of plant ‘material in large quantities to be used as a motor fuel, usually mixed with petrol. ‘This reduces reliance on crude oil products and cuts air pollution. However, producing more and more biocthanol reduces the land available for growing food crops. Reaci When a small piece of soxtiur is put in water it rushes about on the surface, because sodium is marginally less dense than water (water has a density of 1,0 g enr compared with 0.97 g em for sodium). The vigorous reaction results in the formation of hyelrogen gas and a solution of sodium hydroxide with the evolution of heat, The water is sting as an acid and losing a proton, H'. When a similar piece of sodium is put in ethanol it sinks ~ sodium is more dense than ethanol (density 0.79 g em"). A steady stream of hydrogen is then produced. A sclution of sodium cthoxide is formed with the evohation of heat. n with sodi These wo reactions are obviously very similar with ethanol, ike water, acting as an acid. Because the reaction between sodium and ethanol is less vigorous than that between sodium and water it is reasonable to assume that ethanol is a weaker acid than water. 2Na(s) + ICH,CH,OH) 3 2CH,CH,O-NsGk) + 1,16) sodium etherside {cissolved in ethanod Figure 2.8.3 shows this reaction of sodium with ethanol. "This reaction is often used in the laboratory to remove unwanted pieces of sodium from reaction mixtures. {ig 283 Therescton of edum with ethanol.Cece ad Testing for alcohols ‘You may carry out reactions of alcohols, eg metharol, cethancl, propan-1-01 end ‘methods. This could include reactions with phesphorus(¥) chloride to show the presence of the -OH group. Substitution reactions to form halogenoalkanes Alcohols react with phosphorus(V) chloride, PCI, to produce a ehloroallcone and hycrogen chloride gs, ox CH,CH,OHQ) + PCLgs) > CH,CH,CId) + POC) + HCI) chlrvethane Corresponding reactions occur with other phosphorus halides “hic reaction is used at a qualitative test for the presence of the ~OH group = if you acd phosphorus(V) chlocide to an unknown liquid, the evolution of hydrogen chloride gas is evidence for the presence of the ~OH group. Oxidation of alcohols Ovsidation reactions of alcohols invalve the interaction of both the carbon skeleton and the —OH functional group. These are very useful for finding ‘our whether an alcohol is primary, secondary or tertiary because these all sive different reactions with common oxidising agents such as acidified poussium dichromate(VD), + Primary alcohols are casly oxidised to form aldehycies, and these aldehydes are themselves rapidly oxicised to earboxylic acids (cce fig 284). This means that the most common product of the oxidation of a primary alcohol isa carboxslic acid unless the aldehyrle is separated uring the reaction outed secondary and Sond ———————_ You may distinguish primery, secondary and tertiary sleohols using potassium dichromate(V/I using imierascale techniques. etanal butarois ait fig.2.84 The oxietion ofa pximary alcohol ves an aldehyde followed by acarboxyle acid. + Secondary alcohols are also readily oxidised to form ketones, but these ketones do not in general undergo any farther oxidation and so they are retrieved as the final product of oxidation (see fig.28.5) i H i H HOC cco HO ri i Pri HOW on HHO W buton 201 butanare ‘ig. 2.8.5 The onidtionofasecendayalcahal gies baton + ‘Tertiary alcohols are not readily oxidised by any of the common oxidising: agents Figure 2.8.6 shows the results of oxidising primary, secondary and tertiary alcohols with sciifed potassium dichromate(VD). With the primary and secondary alcohols, the orange dichromate(VD is reduced co dark green, chromium(II})Te ea u ‘ig. 28. Testing primary, steondary and tertiary aleto's with potas eicromata( Extracting the products of oxidation of alcohols thermometer —| miture \ on ey ed \ 1 FS snare ‘ig.28,7 This apperatus use fer preparinga ketone fom 3 secondary aeshol. rest he apparatus in fig.2.87 can be used to prepare 2 ketone from a secondary alcohol. If butan-2-ol, is heated with acidified potassium dichromate(V1) soluiion, Dutanone is produced and this distils of and is collected us the distillate in the receiver, ‘The boiling temperatures of butun-2-0l and butsnone are 99.5 °C and $0 °C respectively. Providing the temperature on the thermometer is kept below about 95 °C, only butanone will distil off “The same apparatus can be used for the oxidation of 48 primary alcohol, eg ethanol, Table 2.8.2 shows the boiling points of ethanol and the products of oxidati ee) Ethanol Ta fthanal 2 ethanaic acid ne {sble 22 The boling temperatures af ethane and is eddtion prods PL) cme Using this apparatus in fig.2.7, the ethanol is oxidived to ethanal, and providing the temperature om the thermometer is above 21 °C and below about 70 °C the distillate is ethanal. It is removed from the mixture before it has the chance to be oxidised further. In order to convert ethanol into ethanoie acid, the apparatus in fig. 2.8.8 can be used. The flask contains ethanol and excess acidified potassitam dichromate(V1). The vertical reflux condenser prevents ethanol, ethanal and ethanoie acid vapours from leaving the flask. After the flask has been heated for some time, all of the ethanol will be converted into ethanoic acid. The apparatus in fig.2.8.7 can then be used to distil off the ethanoic acid + waterout - | AK ea if mitre ig. 298 Refhac epperates for prepeings carbonyl eld (rm 9 primary alcohol 1 Draw the alsplayed formulae of four alcohols with «2 formula C,HOH and write the name of each ‘alcohol. Classify each aleohel as primery, secondary or tertiary. 2 Write an equation forthe reaction of methanol ‘with oxygen, Suggest what might be formed if there isa limited supply of oxygen 3 Ibdomethane can be produced when methanol heated with phosphorus and iocine. Phaschorus and Iodine react to form phosphorus) ledide. Write equetions for these reactions, 4) Write equations for the two stages inthe oxi of ethanol 5A liquid produces hydrogen chloride furnes with phosphorus(V)chlevide but is nat oxida hy ‘cified potassium dichromate(V). What does this suggest about the identity of the liquid? oTCee Halogenoalkanes Halogenoalkanes are a family of chemicals that are found relatively rarely in the natural world. Most of them are synthesised in the chemical laboratory or on 2 larger scale in chemical plants. Talogenoalkanes play a wide variety Of roles in the world, man or example, they are important in medicine, agriculture and the production of plastics. However, they are also implicated in much environmental damage, both on the surface of the planet snd in the atmosphere around it of tem 10 the benefit of die human race, A halogenoalkane has a hydrocarbon skeleton with a halogen functional group. It is formed when # halogen atom replaces a hydrogen atom in a hydrocarbon molecule, The halogen may be fluorine, chlorine, bromine or jocine. The properties of an organic halogen compound ace therefore affected by thrve things: + the twpe of hydrocarbon skeleton + the halogen or halogens attached + the position of the halogen in the molecule. It is also possible to have hslogenoulkanes containing, more than one halogen ator, eg 1,2-dibromocthane, CH Pre halogen atoms within the same molecule. Figure 289) shows some examples of halogenoalkanes. Br and even for there to be different an a H Hoc & Hoe co cu Nl I h how romomethare cchlorumethane __1.3cNeropropane ys dl ‘ig. 2189 (a) Displayed frmula of bromemetnane,eichlorrethane snd 12:deHoropropane. (1) Spacefiling model of bromosthane The halogenoalkanes — another homologous series ‘Structural isomers are a very coramon feature of halogenoakanes, and so both the drawing and the naming of the compounds need particular care a 4 halogencalkane makes a great difference to the iging the position of a halogen atom within properties of the molecule. Like the alcohols, the halogenoalkanes may be classified as primary, secondary or tertiary compounds, + Primary halogenoalkanes, eg -ciloropentane ave two hydrogen atoms bonded w the carbon atom carrying the halogen (see fig. 2.8.10(a)), ce) @aprinary . I ‘nalogenoatkane © ‘ coc ee HoH oH How ‘Horopentane (0) esecondary balogenoaane (ntertary talogeroatkane 1 Hoc 2.choro-2-methylbutsne ‘ig, 28:10 {0} Pimary,(b) secondbry and c) tertiary halogenoallanes + Secondary halogenoalkanes, eg 2-chloropentane have one hydrogen atom bonded to the carbon atom carrying the halogen (sce fig. 2.8.10(b)). The hnalogen-carrying carbon is bonded to two other carbon atoms. + Tertiary halogenoalkanes, cz 2-chloro-2-methylbatane, have no hydrogen atoms bonded to the carbon currying the hulogen. This cachon atom is bonded to three other carbon atoms (soe fig. 2.8.10(6)).People have been developing surgery —atterrpting to remove ‘dseased parts of the body of mend damaged internal regons = for centuries. However, developing fine surgical sls fs _drmost impossible when working on ¢ conscious patient encesthetised only by elcahol end held down by straps and ‘ether helper! Ie wee only with the develepment of naesthaties that surgery could move from the glorfiee butchery ofthe berber-surgeons to the sophisticated techriques increesinly used today. These range From cpettions carred out through minute openings made in the body wal (keyhole surgery) to massive transplant operations involving many hours in the operating theatre ‘The history of moder anaesthesia can be said to have begun in 1861 when the American Charles Jackson discovered that ethonyethane (ether) acts as an anaesthetic, Cranford Long used it to perform surgery in 1842, but because he did not publish his work immedietely the credit goes to Wiliam Mereton, who used ethoxyethane for dental surgery in 1846, Ethoxyethane is an effective anaesthetic but i highly flammable. Mearile in 1844 Horace Wells used nitrous oxide dinitrogen oxide or laughing gas) 23 @ dental anaesthetic for the fis time. Nitrous exe is not Rammable or tonic but it produces only 2 very light anaesthetia, The final discovery of this extraordinary decade inthe history of anaesthesia wes when the Scot Sir James Simpson showed thatthe halogenaalkane ‘tichloromethane (chloroform was a superior anaesthetic to both ethoxyethane and nitrous oxide Tichioromethane received the royal stamp of appreval when used by Queen Victorie herself during the deliveries of several of her children. Te ea ‘rchiorcrmethane procuces a ceep level of anaesthesia but it «an also cause liver éamage 50 I 15 no Longer Used. The risks ‘unvreigh the benefits and better compounds have been developed, Interestingly, although wrichiorometiane is no longer used for pain relief during childbirth asi is too toxic, ritrcus oxide i til very euch present as part ofthe gas and aif’ micture used by rany women during labour. Ie was not unt the mle ofthe twentieth cerry that. further strides were made in the development of anaesthetics Demend grew for compounds thet could be inhaled easily and that produced deep sleep yet were non- toxie and non-flammable. By this time oxganic chemists recogrised two Important features of organic compounds \which helped them in thelr seerch: + Tho substitution of achlorine atom into a molecule of the alkane farily sls ina compound with anaesthetic properties —trichlercrethane was a cleer example. Increasing the numberof chlorine atoms in the ‘compound increased the depth cf anaesthesia given, but unfortunately ic also made the compound more tox + Carbon-fluorine bonds ate very stable ard se their presence in 8 compound leads to non-flarmable.ron- ‘oxic and unreactive properties Using this information, chemists came up with Halothare! (flucthane or 2-bromo-2-chloro-1.1,1-flucroatnane) With this effective compound giving deep yet safe anaesthesia, ‘along with similar compounds which followed, modern surgery really 100k off fig. 28.12 Halothane (lsthone) ia deceptively simple molecule which ha allowed surgery to progress so that operations are very tafe for the patirt end an enormous ronge of suglesl procedures have become posse. EE 1. Draw two displayed structures of GjH ty. Name these compounds. 2 _Perchioroethylene (or tetrachioroethene) cleaning uid Suggest the molecular formula and displayed formula of this. the most widely used dryDe Segoe Uses of halogenoalkanes Refrigerants Refrigerants are liquids which circulate inside a refrigerator. They change phase from a gas to a liquid and back, transferring heat from the inside of the refrigerator to the outside in the process. A good refrigerant shouldl be at liquid sat: + changes state from gus to liquid) and back at 1a temperature below the temperature of the refrigerator + has a high enthalpy of waporisation + fats a moderate density in liquid form and a relatively high density in vapour form + is not toxic, flammable or corrosive. Early refrigerators used ammonia or sulfur dioxide gas as the refrigerant. Fut these are toxic and were soon replaced, The compounds developed for this purpose ‘were often halogenoalkanes. Compounds containing both CCl and C—F bonds are called chlorofluorocarbons or CFCs. Within the CFCs, a set of molecules known by the trade name "Freon’ are widely used These are based around, methane and ethane, in which some oF all of the hydrogen atoms are replaced by chlorine or fluorine atoms So many halogenoallane refrigerants have been developed that a naming system has been devisedl by DuPont. The meaning of the codes is 2s follows + rightmost digit: number of fluorine atoms per molecule + tens digit: one plus the number of hydrogen atoms per molecule + hundreds digit: the number of carbon atoms minus fone (missed out for halogenamethsnes which have conly one carbon atom) + thousands digit: number of double bonds in the ‘molecule (this is omitted when zero) + any remaining bonds not accounted for are cccupied by chlorine atoms + asullix of a lower ease eter a, b oF € indicates unbalanced isomers (eee example below). For example, R1S4a has 4 fluorine atoms, 2 hydrogen atoms and 2 carbon atoms. The ‘a’ suflix indicates. that the isomer is unbalanced by 1 atom, giving Ly1s1.2etetralluorocthane, R134 without the ‘a? suilix would be 1,1,2,2-tetmafluorocthane (see fig.28.13) {ig 20:19 The melecuorsrctures ofthe halogencalkanes R1240 and t134 The problem with CFCs ‘Surrounding the Earth, in the upper atmosphere, fs a layer of ozone gus (Oy). ‘This absorbs short wavelength uluaviolet light very strongly, protecting, life at the surface from its harmful effects. Without this layer there would be more cases of skin cancer and eye catarsers. Because of their unreactivity, chlorofluorocarbons released into the atmosphere do not decay, znd find their way eventually into the upper atmosphere. When they reach the ozone layer, two reactions happen. ‘The first of these involves homolytic breakdown of the CFC molecules under the influence of ultraviolet light: COLE, > *CCIF, + Clr This reaction procluces the highly reactive chlorine free radical. ‘The atom may simply recombine with its original molecule, or it may attack a melecule of, Cr+ 0, > ClO+ 0, C10 +0, Ce + 20, Net reaction) 205 9 30,Notice that the chlorine atom is net used up in this reaction, so one CFC molecule can destroy literally thousands of ozone molecules, Decreases in yzone @meenteations in dhe ozone layer were first detected by Sherwood Rowland and Mario Molina in the late 1970s, and these have since keen confirmed. The most massive decreases happen over Antarctica, where ozone concentrations temporarily fall each spring, resulting in an ozone *hole’ (see fig.2.8.14). ‘The size of this hole appears to be increasing, and a similar hole now appears to have developed aver the Arctic as well fig. 28.14 The cxene hoe ver the Antarctic in 2001 In 1987 Montreal Protocol set out plans for a 1 international treaty called the reduction in the use of CFCs. Today about 190 nations have agreed to phase out their production and use of CFCs. However, high levek of CFCs in the atmosphere are likely to persist for some time. Scientists are not sure how quickly a reduction in the level of ozone depletion will be seen. There is some evidence it may be sooner than at first thought, It is important that all countries tackle this because it is a global phenomenon. What happens in one country affects everybody ‘The Montreal Protoco) appreciates that ‘meeting the targets of not using harmful (CFCs and replacing them with safer altematives is easier for developed countries. For example, the Protocol recommended stopping the use of CFCs in developed countries by 1995 but in developing countries by 2010, For more about CFCs, see p.238, Te ea C= Thomas Midgley (born in 1888) was very good indus chemizt who seed some of the most presng problems of his day. Unfortunately the solution he found eft mare problems for everyone who felloved ater im, dificult he cculd never have foreseen The eal rigeratrs uted unplaeant chemial which could be fatal when they lnaed, Midgely was commrssiened to ind better eegerant He vented bth tetflucrmethane ard dichlorfluoromethane the frst of the CFCs, In a demenstration to fellow scientists, Midgley recthed inthe gas ard then exhed itgemtly over a candle flame, wrich wen ou, showing hisnew compound was bath non-ioxic nd nov-lammable. The new cfflective ond sale reigrants became widely used or many years What Thomas Midgley could ot have known was thatthe CFCS he developed were also capable of damaging te protective ayer of cxone around the earth Twenty-first century sclentts realise that CFCs react with end destiay azane and there is international cooperation to reduce the use of these chemicals, Unfortunately it will take along time before atmospheric ozone ie restored to pre- Midgley level! Midgley alo developed tatrasthyllead, the poisonous antickncckirg agent which used to be adced to petrol Scientist can enswer questions ~ but they lio rele new isaues. How many of our new scientific developments will turn out to have done: ‘more harm than good? In spite ofall cur moder safeguards some almast certainly will What are the safe alternatives to CFCs? Hydrochlorofluorocarbons, commonly known as HCFCs, are a group of synthetic compounds containing hydrogen, chlorine, fuorine and carbon. They are not found anywhere in nature, Hi production increased afier couniries greed 10 Unlike the CFCs however, most TICPCs are broken down in the lowest part of the aimesphers, phuse gut the use of CFCs ‘and pose a amuich smaller risk to the ozone layer. Unfortunately HCFCs are also very potent greenhouse gases, despite their very low stmospheric concentrations, measured in parts per trillion (million million) ‘An csample of an HCPC is HPC134a, which is CF,CHF, You will notice this contains no C—Cl bonds but hus the even stronger C—F bones. Butane is also an sltemative to CFCs, but of course it is flammable, Hydrochlorofluorocarbons and bucane are ako used as propellants in aerosol containers. PorDe Segoe Halogenealkenes used to be used os fire retardants in scere types of fire ‘ectinguisher. For example, fire extinguishers to be used around electical equipment should net contain water-based chemicas. The halagenaallane extinguishers were green in colour and contained liquid bromachlorod fico methane (ECF or Halon 1211) under pressure. Ths liquid vapcrses when sprayed ‘onto the flames as it has a boling temperature of 4 °C, forming a heavy gas which does not bum, so it formed 3 layer over the flames, excluding air or oxygen, “The two prablems associated with ths type of fie extinguisher were: It contributed to the depletion of the czone layer end so had to be replaced fellowing the Montreal Protocel + Because of the narcoic effects of the gas people sometimes stole the fire extinguishers to inhale the gas. There were 16 deaths caused by ths ges in 1990, “These Halon-type fire extinguishers have now been replaced by extinguishers Containing liquid carbon dioxide. Carbon dioxide fre extinguishers are heavier anc more expensive than the Halon extinguishers. eee en eee Printed circuit boards, by their nature, cn ignite in use. Because of tis it has been standard practice to indude fre retardants within the resin system used for the circuit board (see fig. 2.8.15). “TBEPA isthe primary flame retardent used in polymers for printed circuit beard production. TBBPA is an organic molecule that ineludes approximately 5995 bromine ard therefore is ‘halogenated fire retardant’ There has bean a move towards halogen free’ printed circuit boards. Epeny polymers always contain ‘a small amount of halogen because they are formed as 2 by-product of the Ccherrical processes of manufactureTe ea ‘Synthetic fibres and fabrics are used in a growing variety of applications ranging from Clothing to carpets blankets and many industrial uses. The flaramablity ofthese fabrics is important not ory in everyday clothing but also for specialised apolcations such as those enccuntered in the space industry, Flarrabilty Is 2 measure of the bly of the fabric ta burn and propagate a flame cr fre. Mast fabrics decompose hen they are exposed to fire, Hawever, many of ther do not actually bur. The aim of using flame retardants isto prevent the propagation ofa Fir. ‘There are usually five methods for making a fabric flame retardant: + finishing the Fabris with flame-retardant chernicals + adding a flame retardant to the polymer the febrc is mede of, before tis made into converted fibres + copolymerisation ~ polymerising aflarne-retardent polymer with the polymer used to make the fabric + using a polymer that contains chicrine, bromine and fluorine, which give inherent flame retardancy to the polymer and wihich are also the bass for flame-retardant _adcltives added to the polymer to mate the fal fabric lame retercant + cherrically modifying the polymer, eg chlorinating polyester For exarrple, suppose you have a polyester fibre that is going to go into making a shirt that has to be flame retardant ~the polyester is chlorinated by chemical methods and this Increases the fe resistance of the fabre. In general, combustibility increases with increase in hydrogen content. A decrease in hydrogen content wil also decrease the height of the flame. As you have seen. the presence of elerrents lke nitrogen, chlorine, romine and fluorine tend to mate the polymer flame retardant. ‘The use of flame-retardant materials has chviouc benefits, eg making children's rightclothes less likely to catch fire where there are naked flames, bt these flame retardants can affect the environment, Other uses of halogenalkanes As well as being imporcant as anaesthetics halogenoakznes are used as insectcices ‘As you saw in chapter 15, DDT (dchlerodphenyltchoroethane) was widely used as an insecticie, However, DDT doesnot break down inthe environment but buds Lup in higner mernbers of a food chain The eggshels o birds of prey containing lage amounts of DOT ave fragile. OED ‘1 Draw the displayed formula and write the chemical name for R12,R22 and R152. 2. ive two rearone why chlorinated hydrocarbons are nat used todzy in fre extinguishers, 3 Suggest why chlorine-based insecticides last along time In the sol.De Segoe Reactions of the halogenoalkanes Substitution reactions “The chemistry of the halogenoalkanes is langely based on two factors: * which halogen atom is present ~ organic fluorine compounds are very stable so here yon will concentrate fon the chlero-, bromo- und iodo compounds + the position oF the earbon-halogen bond within che molecule, Organic halogen compounds uncego substitution reactions, and also to a lesser extent under different conditions elimination reactions. ‘These substicution reactions are nucleophilic. You will find out more about the mechanisms of these reactions of halogenoalkanes in chapter 2.9. With the hydroxide group tn these reactions of halogenoakanes (represented RX) the -O1T group sutsttutes forthe halogens ving an alcool and o hydrogen halide a reaction that is sometimes called hydrolyate (pling with water) The reaction with water is slow at room temperate - a more rapid rection occurs ‘wih OF one RX +110 > ROH +1 RX + OF 9 RON + X- For e: imple CHCl + H,0 > CH,OH + Hel chloremethane methanol CH,CH,CH,Br + H,0 3 CH,CH,CH,OH + HBr 1-bromopropane + water propan-1-ol + hydrogen bromide Phe C—Cl bund is more polarised than C—Br and CI bonds 2s a result of the greater electronegativity of the chlorine atom (see chapter 2.2), so it seems reasonable to expect the chloroalkanes to be hydrolysed faster than the bromo- or iodoslkancs. In fact, the opporite is the ease. ‘This is because of the greater strength of the C—Cl bond. compared with the C—Br and C—I bonds (see table 2.8.3) ‘This makes the chloroalkanes less reactive than bromaalkanes or iodoalkanes, This order of reactivity holds good for most of the other reactions of the group, and shows that itis the bond strength that is dhe decermining factor in Uwe rate of reaction of the halogenoalkanes rather than the ‘bond polarity ‘This also shows that Nuerocarbons are very unreactive due to the strength of the C—F bond. We will see the significance of this later. ee enna) coal | 346 ctr | 20 ll ca | ze Potussium hydroxide dissolves in ethanol ae ‘well as in water, With aqueous solutions of potassium hydroxide, halogenoalkanes undergo substitution reactions to form an alcohol. With alcoholic potassium hydroxide, elimination CH,CHRCCH, + OF 3CH,CH=CH,+ 10+ Be 2-bromopropane + hydroxide ions > propene + water + bromide fons Tn this reaction a molecule of hydrogen blige climinated from the halogenoalkane, forming an alkene as a product. When species such es OH or ROM are present, these may act as a base by necepting @ proton rather than as « nucleaphile, erry rr an ee eee inthe botox, As we have seen the progres of these reactions is often judged by the formation cf asiver hale. Te halogen stor bonded toa tere apr kes alopecia eee ener eee useful intermediates in crganic synthesis,Te ea ‘The reaction of potassium hydroxide with halogenoalisnes depends greatly con the reaction conditions (see table 28.4) Pn Substitution Alcohol | Refluveat with an aqueous solution of potassium hydroxide imination Alkene Refluceat with an alcohol solution of potassium hydroxide table 24 Conditions for substhition and elimination reactons ofthe halogencallanes With alcoholic ammonia Ammonia aets as a nucleophile because ofthe lone pair of electrons on its nitrogen atom, This means that it can easily coplace halogen stor in & Dalogenoslkane: CH,CHgl + NHy > CH,CHNH, + HI fodoetnane ethylamine “This is nor the end of the story, however. Fthylamine possesses a Tone pair of eleettons, just like ammonia, It reacts farther with iodoethane: CH,CHNH, + CH,CH,I> (CH,CH,,NH + HI ethylimine — jodoethane ——diethylsmine Ta turn, there are wo further stages: (CH,CH),NH + CH,CH, > (CH,CH),N + HI Giethvlamine —jodoethane triethylamine (CH,CH),N + CH,CH, > (CH,CH),N" triethylamine fodoethane —_te¢racthylammoniam iodice ‘To carry out this reaction, iodoethane is heated with a concentrated solution of ammonia in ethanol, The resction is carried! cut in a sealed tabe rathor than under reffus = the ammonia would simply escape up the condenser as gas because it does not condense. QED 1 Describe and explain the reactions that can occur when sodium hydroxide reacts with 1-chloropropane. Describe the conditions and write symbol ‘equations. 2. Write equations forthe reactions of iedomethane with an alcoholic ‘ammonia solution. 3 Why ist possible to get a substitution reaction with iodemethane and potassium hydroxide, but not an elimination reaction? “4. Suggest why ethylarnine is never prepared by reaction of lodoethane and ‘ammonia, If there wes no alternative, what could you do to maximise the yield of ethylamine? Por)How do different halogenoalkanes react? When halogenoalkanes react with water to form an alcohol, one colourless liquid reacts to form another colourless liquid. To follow the reaction you necel 10 detect cither the formation of ane of the products or the disappearance of une of the reactants, A useful indicator hore is silver nitrate, which lets you sce the sppesrance of the halide ions formed in the reaction, and also gives some idea of the reaction rate, Silver nitrate isan ionic salt that dissolves in water to form Ag* and NO; ions. Neither of these ions reacts with halogenoalkanes. However, the Ag’ ion does react with halide ions to form insoluble products Which appear as precipitates. Bach silver bi own characteristic colour (see fig. 2.8.16). So the reaction of u halogenoalkane with water ean be followed by spotting the formation of a silver halide precipitate ~ if the time taken for the precipi appear is measured, then some idea of the rate of the reaction can be obtained. re to ‘ig.28.16 The atterence rade by the dterent halogens cn the rate of reaction ofthe Falogenoalkanes can bestow clearly usngsiver nitrate In fig. 28.16, | em? of silver nitrate solution was paced in each of test tubes A, B and C, together with 1 em? of ethanol (as a solvent for both the silver nitrate ant the halogenoulkane). All three tubes were placed in a water bath at $0 °C, After 10 minutes, $ drops of I-chlorobutane, § drops of 1-bromobutane and $ drops of 1-iodobutane were added to tubes A, B and respectively, and the tubes were replaced in the water bath. The precipitate formed most rapidly in tube G, more slowly in B and Je «slowly in wibe A. ‘The result of the investigation confirms that the rate of hydrolysis of the halogenobutanes increases in the order: I-chlorobuuae < I-bromobutane < L-iodobutane (slowest) The effect of the carbon skeleton ‘You can carry out a similar experiment to compare the fleets of altering the Garbo skeleton of a hulogenoalkane. Figure 2.8.17 shows three hhalogenoalksnes that have the same number of carbon, hydrogen and bromine atoms 4 cH I aij, —e z-bromabutare 2-bromo-2-methybutane (ig. 28.17 omc halogenoaltanes. L-bromobutane is a primary hologenoulkane, 2-bromabutane is a secondary halogencalkane and 2-broma-2-methylpropane is a tertiary halogencallsne ‘Three test tubes labelled A, B and C are set up as before containing the three bromobutanes plus | em? of ethanol which is the solvent, This time it is not necessary warm the solutions, Just add 1 em’ of silver nitrate solution and shake the tubes, Leave them to stand and time how long it hes for them to go cloudy. ‘You have seen that when testing for 2 bromide the formation of the cream precipitate is instantaneous, “This is because itis an jonic reaction in solution: Agt(ua)+ Br(aq) > AgBr(s) With these rezetions, 2 covalent C—Rr has to be: broken each time and so this will be slower than the formation of the silver bromide.‘The results of this experiment show that the -methytpropane (tertiary hhalogenoalkane) is faster than with 2-bromobutane (secondary balogenoulkane) whici is in tum fester than With J-bromobutzne (primary halogenoalkane). reaction with 2-bromo In general halogencalkanes react faster in substiuuion reactions where the halogen is attached to a branched, chain, Preparing a halogenoalkane from an alcohol I-bromobutane can be prepared in the laboratory using butan-1-o! with sodium bromide, water andl concentrated suifrc acid, ‘The sodium bromide snd concentrated sulfuric acid react to produce hydrogen bromide. Hydrogen bromide Feacts with butan-I-ol to form 1-bromobutane Nakr(s) + H,SO,() > NaHSO,() + HBr(e) (CH,CH,CH,CH,OH() + HBe(g) > CH,CH,CH,CH,BrQ) + 1,00) Soclium bromide, batan-1-ol and water are placed in the flask (see fig. 28.18). topping unmet concenteted ‘Spmure sed cae stun bronide . ET a ane tee fig. 28.18 Apparatus for proparing = haloganalkane frm an sleshal. ‘The flask is put into a beaker of cold water and concentrated sulfuric acid is added slowly from the flask. The Mask is cooled because the reaction at this stage is exothermic. Te ea ‘The dropping funnel is removed snd the apparatus refluxed on a water bath for 30 minutes ‘The apparatus in fig. 2.8.19 is set up, the mixture is distiled and the distilate is collected. The distillate will be collected a8 Wo layers ~ a lower organic layer and an upper aqueous layer. | aqueous yer heat organic layer {ig 28.19 Apparatus for dsAingahalogencakane fromthe reaction L-bromobutane distils into the organic layer. Table 28.5 shows the impurities that may be in the distillate, and which layer they are likely w be i, Cee LUnreacted tan. tcl Bromine Oris of star aurtane Hyogen bromide water ‘able 285 lemputies that may be I T-bromobutane prepared fiom an sleshot ‘The squeous layer is discarded, The organic layer can be purified and finally redistilled to produce pure L-bromobutane (boiling temperature 102 °C) QD 11 In the investigation ofthe reactions of ‘-chiorobutane, 1-bromobutane and 1-iodobutane, ‘what was done to ensure a fair test? 2. What type of reaction is taking place when but-1-ene is formed as an impurity in the preparation of 1-bromobutane?Teas ne a 9 Mechanisms Classifying reactions Whether they are studying organic or inorganic reactions, in order to find out hhow a reaction takes place chemists first identify the products of the reaction. They then start thinking about the steps chat tuke place for the reaction tw gceur ~ the reaction mechanism. ean mechanisms It i impossible to stucy reaction mechanisms drectty because the particles are too small to observe. The mest common approach is to Look for evidence, then propose ¢ mechanism that supperts this evidence, ‘Chemists can generlly oniy disprove a mechanism, rather than proving that & particlar mechenism i correct. What sort of evidence do they collect? In the reaction between methane and chilorine, as you saw in chapter 1.6, some ethane is produced, The mechanism rrust explsin how this molecule with two catbon atorrs is formed from a molecule With one earben atom. The mechanism {or the reaction of methane and chlorine imolves CH*,a methyl fre radical. Two of these radicals can collide and form ethane, CH,CH,, So the existence of ethane in the products supports the free radical mechanism, but cannot prove i Chemists also use kinetic (rate ot reaction) studies You will see later that two very similar reactions can have diferent kinetic. These data help chemists to work out what is happening st a particle level ‘Throughout units 1 and 2 you have met 2 number of organic reactions. To help organise all the different reactions, and also 10 hholp predict the outcome of an unknown reaction, chemists classify these reactions into different types, including: + addition + oxidation + climinstion + reduction + condensation (addition followed + hydrolysis by elimination) + polymerisation. + substiration Here you can look at each of these reaction types in tum, Addition reactions Tn an addiden renetion two or morc substances couct to form a single product only: reactant 1 + reactant 2 > product, For example, bromine undergoes an addition reaction with ethene: CH=CH, +Br-Br — CH;BrCH.Br ethene 1,2-dibromocthane ‘You can see from this example that the organic reactant fas a double bond, which becomes a single bond after the addition, Addition may also occur across a triple bond to produce a double bond or a single bond. Elimination reactions {An elimination reaction is the opporite of an adcltion reaction One substance reacts to form two products. A small species such as water or a hydrogen balide is eliminated from the kanger molecule as one of the products reactant > product 1+ praduct 2 For example, the dehydration of ethanol is an elimination reaction: CH,CIT,O1 > CH,=CT, + 11,0 Condensation reactions A condensation reacdon involves an addition reaction [allowed bby an climination reaction, As a result, wvo reactants combine to form a larger melecule with the elimination of a small molecule such as water or hydrogen chloride.UNIT 2 Application of core principles of chemistry [An example is the formation of an ester from a carboxvlic acid and an alcohol, which is an equilibrium reaction: CHCOOH + CH,CH,OH = CH,COOCH,CH, + 1,0 ethanoic acid + ethanol = ethyl ethanoate + water Substitution reactions Ina substitution reaction ane stom or group of atoms is replaced by another atom or group of atoms. reactant | + reactant 2 > product 1 + product 2 For example, in chapter 1.6 you studied the reaction of ethane and chlorine, in which a hydrogen atom in thane is replaced by « chlorine atom: cl + Hct Another example is the reaction of bromoethane with sodium hydroxide solution, in which 2 bromine aiom is replaced by an -OFT group: HOH HOF I Hoe c oe t ar > He on + It How How Oxidation and reduction reactions ‘You studied the tpie of exidation and reduetion in, chapter 2.4. An example of an organic redox reaction is the conversion of a secondary alcohol to a ketone: eit, , bt... tbh Aa wo Ce ‘The alcohol is oxidised by an oxidising agent such a8 acidified potassium dichromate(VD. The orange dichromste(V1) ion, Ce,0,7> is reduced 10 dark green, chromium(IID, C+ Hydrolysis reactions A hydrolysis recction is the spliting up of « molecule by reaction with water, Onganie compounds are often refluxed with water to bring about the reaction, This js normally a slow process but is faster if a dilute aciel or alkali solution is used, for example the hydrolysis of bromoethane: CH,CH,Br + H,0 > CH,CH,OH + HBr Sodium hydroxide solution also helns the reaction go more quickly: CH,CH,Br + NaOH 3 CH,CHOH + Nakr + H,0 You saw sbove that 3 condensation reaction betwe «a carboxylic acid sand an aleohol forms an ester. The reverse reaction, the breaking down of the ester 19 reform the carboxylic acid and alcohol, is a hydrolysis CH,COOCH,CH, + H,0 = CH/COOH + CH.CH,OH ethyl ethanoute + water = ethanoie ucid + ethanol Polymerisation reactions A polymerisation reaction involves the joining of small molecules (monomers) together into 4 long chain. Sometimes 4 single monomer is involved: other polymers are made up of more than one monomer. If M represents the monomer, the polymer cauld be represented by: {—M—M—M—M—M— or = [MI,~ here are two types of polymerisation, depending. ‘on the reaction that joins the monomers ~ addition polymerisation and condensation polymerisation. OED ‘What type of reaction s shown inthe following equation? CH + NH, > CHAN, + Hl 2 Naturally occurring asters ae split up by baling with zacium hydrode zlution What type of reaction i taking place?Draenei aad Bond breaking As you saw in chapter 1.6, chemical reactions involve bond fission followed by the formation of new bonds. In a covalent bend two electrons are shared between ‘sv0 atoms, When that bond is broken during a chemical reuction there are two ways in which the clecirans may be shared out leading to homolytic and heterolytic fission, Homolytic bond breaking Figure 29.1 shows two atoms X and Y honed by 2 single covalent bond. > My ‘ig 29.1. Infometytic bond son each new species has one ofthe tlectons from te covalent bor In homolvtie fission this bond is broken so that both X. and Y wke a single unpaired electron. The prefix ‘homo" means ‘the same’. X> and Y- are referred to as free radicals (or just radicals) and 4 dot represents an unpaired electron. If X and Y contain more than one stom, the dot is placed close to the atom with the unpaired electron, ea clas ch+ cl chlorine CH,CH, > -CH, + CH, ethane Free radicals are extremely reactive and ae a result are short lived. They tend to react to gain an electron from another species so that they no longer have an unpaired electron, and this produces another free radical trom the other species, Heterolytic fission Figure 2.9.2 shows the heterolytic fission of a covalently bonded species X—Y. In this case both electrons go to X and none tw Y, xEY xt Y* ‘ig. 292 In heterotic ben fssion ions ar formed. with one on tai both of the electrons rom the cole bond Phe prefix ‘heters? means different. In this case, X hus a negative charge. An organic ion Tike this is called a carbanion and 2 positive organic ion such as Y is called 8 carbocation. ‘The curly arrow notation shown here is useful when depicting reaction mechanisms, The full-headed arrow shows the movement of a pair of electrons, while hulf-arrow heuds show single electrons moving in homolytic jon. It is important to draw these arrows accurately to show where these electrons start and where they finish during the reaction. Classifying reagent: electrophiles, nucleophiles and free radicals ‘When thinking about how organic reuctions tke place, chemists devise a reaction mechanism. A reaction mechanism often occurs a stages and involves species classified as electrophiles, nucleophiles or free racicals. An electrophile is an atom (or group of atoms) that js attracted to an electron-rich centre, or an atom. where it accepts a pair of el valent bond. lectrophiles either have a positive charge (carbocations) or are electron deficient (See fig.2.93) rons to form a newHoH i a Ts oT HoH oO fig. 293 Examples of electophiles— these species ave attracted to form covalent bonds with electronic cere A nucleophile is un atom (or group of stoms) that is attracted to an cketran-deficient centre, o an atom where it donates a pzir of electrons to form a new covalent bond. Nucleophiles either have a negative charge (carbanions) or are electron rich, having a lone pair of electrons (see fig 2.9.4). & an H—N—I H ‘ig. 29:4 examples otruciephles- these species are atvacted to form covalent bonds wth electon-ceficent centres. Whether a centre in a molecule is likely to be electron rich oF clectron deficient will depend on the polarity in bonds within the molecule Reaction of alkanes with halogens You will know from chapter 1.6 that the reaction of an alkane with « halogen is a free-radical substitation In the presence of ultraviolet light, halogen molecules are split into halogen stoms (free-radicals) sand these react with the alkane molecule, This reaction involves homolytic bond fission so does not require an cleciron-rich or electron-dticient centre, UNIT 2 Application of core principles of chemistry h bromine Reaction of alkenes wi and hydrogen bromide Electrophilic addition Chapter 1.7 covered these reactions of alkenes, which are electrophilic addition reactions. The double bond consists of four electrons (ewo in a x bond and vo in a 6 bond) and this provides an clectron-rich centre for the attack of an clectraphile. ‘The reaction of propene with hydrogen bromide can form two different bromopropanes (sec fig. 2.9.5) 2 bromopropane oromepropane (ig. 29.5 These two products ere posible fom the letrophile Aan of hydrogen bromide to propene. ‘The carbocation leading w the formation of 2-bromopropane is more stable than its altemative because the two methyl groups donate electron density and stubilise the positive charge. So the major product of the reaction is 2-bromopropane, in line with Markavnikeo’s rule OED 1 Suggest conditions under which free-radical reactions ae Ukely to take place. 2 Whet neme's given to an atom of group of atoms with a lone pair of electrons? 3A carbocation s attacked by a molecule. fs the molecule an electrophile ora nucleophile?Dra tas nee aad Nucleophilic substitution of halogenoalkanes In chupler 2.8 you seav how halogenoallkanes undergo substitution reactions, cg the reaction of I-iodepropane with aqueous potassium hydroxide solution: (CH,CH,CH,] + OH" > CH,CH,CH,OH + caked ‘What is the mechanism of this rection? Figure 2.9.6 shows the reaction in more deal. H H onc + H \ OH” 315d ect grep so “The hydroxide ion isa nucleophile, and it ettacks the electren-defcient carbon ‘atom attached to the more electronegative iodine. The two electrons from the Fyétoxide fon form a covalent bond with the cental carbon atom, The carbon Jodine bond breaks a: the two shated electrons in the C—I bond move towards the iodine atom. This atom leaves asthe lodide lon. The breaking of this bord Is Comparing the reaction of two bromoalkanes with hydroxide ions ‘Table 2.9.1 shows data from an experiment to messure the rate of the hydrolysis of bromoaliane A, Concentration of ka rots rey Serica (Coir) Cet ae) (mol dm) o4 04 1a e105 02 24 2201107 08 oy 333x105 01 02 wie oF a 03 ate 05 ‘able 29:1 Rests fom an experiment to measure the iil ate ef she hydrolysis of bremostkane ‘at iferert concentrations of ramoalane ana hydronic.‘You will notice that the initial rate of reaction depends upon only the concentration of A. ‘he initial rate is independent of the concentration of hydroxide ions, aut hud ed Knowing the exact way in which a ‘rug works can be of help to chemists syrthesi Table 29.2 shows similar data for the lyydrolysis of bromoatkane B. Here the initial rate of reaction depends on both the concentration of B and the concentration of OH ions. Jing new compounds, Understanding the reaction mechanism Concentration of Concentration of initial rate haar sania eared bromoalkene 8 hydroxide ions (onto a) cherrical groupings which could be eat) introduced into another molecule to cl ca Soc improve the pharmaceutical action and — - setin motion the evelopment of anew 02 aa 300% 10 aeiene hos 1 oz 7 Determining the reaction mechanism of 0 az 300x107 ‘arumber of drugs has enabled sletists a Fe 7sxi05 10 develop computer programmes which can madel new molecules and table 29.2 Rests oman expermert 19 measure the na rat ofthe hyray ot predic how they wil ocerac: wih bremoalane Bat diferent concentrations of brmcakane and hyde Compounds in the hurnan body o inthe So the results of kinetics exneriments Which shows, a8 you have structure of cisesse-causing microbes So seen, the colision rates of particles can give information we can understanding reaction mechanisms is use 10 suggest a mechanism for a reaction. Obviously these wa hoping us to develop better drugs. bromoalkanes react by different mechanisms. Hydrolysis or elimination Oz ‘There are a number of factors which affect whether a errr ‘And B with sodum hycroxide, in ‘one reaction hydroxide fons attack the electron deficient centre in the hralogenoalkane molecule. Which halogenoalkene undergoes addition or climination in the reaction with OH™, One important factor is the solvent in which the reaction takes place, Thus, when 2-bromopropane is refluxed with aqneons sodium hydroxide, the product i propan—2-cl (CH,GHI:CH, + OH > CH,CHOHGH, + Br Iervellone reacts inthis wn? In contrast, refluxing with ethanolic sodium hydroxide produces Sungest why. propene: HGH (CH,CHB:CH, + OH > CH. 1,0 + Br PetaDraenei aad ‘The ozone layer is a term widely used in the media — bbut what is ozone? It is a gas which is naturally found fn very small amounts in the stratosphere er upper atmosphere, between 10-S0km above the surfer of the earth. It is made up of three oxygen stoms. Phe ozane in the upper atmosphere is produced by the action of UV radiation from the Sun acting on oxygen molecules. This splits exygen molecules into oxygen free radicals which combine with ocher oxygen molecules to form ozone. 020 + iy > Q++ 0+ 0; + 0 > 0, ‘Ozone is also found in the lower atmosphere, fut here ic is produced as a result of air pollution. However the highest concenuation of the ezone in dhe aunosphere is in the upper atmosphere and it is this that is known as the ozone layer ~ although os you can see in fig.2.9.7 it only contains very low levels of ozone! As you have seen on p215, the ozone layer helps to protect the surface of the Earth from harmful UV radiation, There is a natural balance beaween the Formation of new azone and the breakdown of ezme molecules. Anything which alters this balance alfects the ability of the ozone layer to absorb UV light. If che rate of breakdown speeds up, the ability of the ozone layer to protect us from the damage caused by UV light from the Sun will he compromised " Chemistry in the ozone layer Antarctic winter and the ozone hole If you look back to p215, you can see that CFCs. catalyse the breakdown of ezome into oxygen molecules, However, the destruction of dhe ezome layer doesn’t happen all the year rounel. Why is it that the levels ef ozone drop so dramatically in the spring? ‘The reactions which bring about ozone depletion need light to take place. During the Antaretic wi the Sun never rises. The whole area is in constant darkness, At the same time, in the dark and cold, 2 \hicling vortex of stratospheric winds allow the air to get So cold that polar stratospheric clouds build up, ‘The cloud particles may be water, ice or nitric acid, depending on the conditions. These cloud particles provide a huge surface area for the reactions which Jead to the breakdown of zene. Then when spring comes, s0 does the sunlight, providing the final Tink in the chain. It triggers the homolytic breakdown of the CECs, producing tree radicals which do all the damage 1 the ozone layer, cutalysing the breakdown ult, the ezone hele is at its largest in October, when the full effects of the spring and early summer reactions can be observed. of the mokeules. As a a oA ‘ozone (parts per milion) fig. 29,7 Levels of orone peak about 20-38km above the surface of the earth ~ this ic the'enene layer”‘The role of the ozone layer iz 2 Vital one, yet ozone makes up only 0.00006% of the atmosphere. The levels of ozone in the atmosphere are measured both using satellite censors ssuch a the ozone monitoring instrument carried on the Aura satelite, and by ground-based measurements, Czone may be measured in parts per milion, but rrore often itis measured using Dobson units. A Dobscn unit isthe number of molecules cof onane that would be needed to create a layer of pure ezone (01mm thick ate temperature of O°C and a pressure of ‘atm. The thickness of the ezone layer is around 300 Dateon units. In other word, if all the oxone in the stratosphere was ‘compressed it would form a layer just 3mm thick around the Earth! In the area above the Anterctic an‘ceone hele’ has developed. ‘The ozone hole ien't actually @ hala stall —just an srea where the ozone levels are much lewer than narmal.In these regions the amount of azone is down to an average of about 100, Dobson uri. Growing or shrinking? Dara on o7one levels has heen collected since the ISS0s. tis known that no Dobson scores of lower than 220 units were measured over the antarctic before 1979, Since then the area of the ozone layer which has fever than 220 Debson units is regarded asthe area of the ozone hole. The ozone hole currently has an aree of about 27 milion km, and Dobson scores of well below 100 heve been recorded over recent years. ‘Since people became aware of the role of FCs in ozone depletion, workiwide efforts to contol te use of these chemicals heve had some success, to the extent tha: mary scientists now predict that the azane hele should statilse and then gradually start to diminish aver the next 20-30 years. At the moment it appears as ifthe peak we reached in arouné 2003, However it srt always easy to cellect and interpret data con contentious science lke ths. Figure 2.9.8 gives a variety of evidence for you to consider ~ what conclusions vould you draw? fig, 298 Data onthe ozone whole. You can 200m in en these on the Active Book. EE 11 How Is the change in sizeof the 2 Lock at the data provided in fig. 2.9.8, what it tells you about the ‘ozone hale in the stratosphere. ‘czone hole ever the yee linked to the Sure ‘mechanism ef the rection which causes ‘czone depletion in the stmosphere? 3 ow vad and reliable Is this evidence? 4 What further data would you want to see to decide what is happening to the ozone levels inthe stratosphere?UNIT 2 Application of core principles of chemistry 10 Mass spectra and IR absorption Using mass spectra with organic compounds The mass spectrometer You studied the use of a mass spectrometer in chapter 1,3, You will remember that inside the mass spectrometer the sample is first vaporised, then jonised, accelerated and finaly deflected by a varying magnetic field. A detector then detects the ions and pruduces a display which identifies vertain peaks, ‘These peaks occur at different masscharge ratios (7/3). ‘The mass spectrometer can be usedl to identify different isotopes in an clement, and to find the relative atomic mass of an clement snd the relative molecular mass of a compound. ‘The mass spectrometer has many applications in chemistry, from pharmaceutical research to space research and from radioactive dating 1 catching drug cheats in sport. Using a mass spectrometer to analyse organic compounds ‘There is u huge number of oganie compounds. Identifying an unknowa compound by qualitative and quantitati is slow and laborious. e process Using 2 mass spectrometer, along with infrared spectroscopy, can make this process much easier. We can represent an organic compound as RH. ‘When this is put into a mass spectrometer and bombarded with elecurons, one product will be ROH, which componds to the molecule losing, & single electron. ‘This peek will be shown on the sass spectrum as the peak with highest m/z vakie ‘This gives the relative molecular mass of the compound, and this peas is called the molecular jon peak (sometimes known as the pareat ion). Other peaks on the trace are produced by fragmentation of the organic molecule (see fig. 2.10.1). Only ction fragments arc detected by the instrument ~ unions end nidicals ure not detected, 9 cat get i~e=9@ Sgn