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

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