Cambridge ENDORSED BY International AS and A Level 3 CAMBRIDGE ChemistryENDORSED BY <3 CAMBRIDGE 9) International Examinations Cambridge International AS and A Level eta Peter Cann & Peter Hughes (> HODDER ? EDUCATION ZatBACHETE UK COME‘Questions fom: Card International AS und A Level Chemisty papers are reproduced by ‘Permission of Cambridge Inernstional Examinations, Cameidge intemational Examinations hears no responsiay forthe example answers to ‘quastiony taken frm ts past question papers which ae contained in this book. ‘Questions fom OCR past papers ats rependiced hy permisslon of OCR. 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Apt fmm any use permited under UK copyright law, no pat ofthis fblcation may be repreluced oe transoited in any form of by any means, electronic o¢ ‘mechanical, chiding phosocopying and recorting, of hok! wehin any information storage and reteeal system, without pennkson in weting from the publisher or under cence fom the Copytighr Lcersing Agency Lime Ferter dtl f such Hcences Ger reprogphic eproducion) may be obtained from the Copynght Licensing Agency Limi, Safiton House, 10 Kirby Stee, London CAN gr cover photo by @ kmiragaya ~ Poet ‘Musrauons by Backing Dog An ‘Typeset in ITC Garamond Light 9/12 by Aptara Ine. Prize Dual -s ental secon fo ds he save fom the Bich tray ISRNOTS 1444 18133 3Contents Introduction AS Level CR eis) Topic 1 Chemical formulae and moles Topic 2 The structure of the atom Topic 3 Chemical bonding Topic 4 Solids, liquids and gases mple molecules... Topic 5 Energy changes in chemistry Topic 6 Acids and bases, ‘Topic 7 Oxidation and rediiction Topic & Rates of reaction Topic 9 Equilibria . Inorganic chemistry Topic 10 Periodicity Topic 11 Group 17 Topic 12 Introduction to organic chemistry Topic 13 Alkanes Topic 14 Alkenes, Topic 15 Halogenoalkanes Topic 16 Alcohols Topic 17 Aldehydes and ketones. Topic 18 Carboxylic acids and esters Topic 19 Practical work 20 oT] Cy 97 118 136 154 1m 186 202 209 2a 251 267 281 298 305 316 iiContents ONT} CR usiy ‘Topic 20 Further energy changes Topic 21 Quantitative kinetics ‘Topic 22 Quantitative equilibria Topic 23 Electrochemistry, eed Topic 24 The 3d block. Organic chemistry Topic 25 Arenes and phenols Topic 26 Carboxylic acids ~ derivatives and further reactions Topic 27 Amines, amides and amino acids Topic 28 Addition and condensation polymers Topic 29 Techniques of analysis ‘Topic 30 Organic synthesis and analysis. Student's CD contents Answers to ‘Now try this’ questions Additional work Interactive tests Topic summaries Revision checklists Examination structure Planning your revision Examination technique Glossary of command words Mathematical background Chemical data Glossaries iv 329 349 367 381 397Acknowledgements ‘We are grateful for the help given by Judy Potter in selecting and writing topic-oriented questions, and for the unstnsingly professional support and cooperation given by the staff at Hodder Education: Nina Konrad, Emilie Ketton, Laurie Suess, Anne ‘Tevilion and Anne Wane, ‘The Publishers would like fo thank the following for permission to reproduce copyright material: Photo credits: p.1 © The Granger Collection, NYC/TopFoto; p.2 © Jelf Blackler/Rex Features; fr 8 Bicipicl/Alamy; be © Nis Jorgensen/Rex Features; br © Chvs Lofty ~ Fotolia: pa © Bye Of Seience/Science Photo Library: p14 © lowefoto/Alamy: p21 © Rex Feanures; p.23 © RGB VentureySupessiock/Alamy: 9.27 © Geoff Tompkinson Science Photo Library p.73 © Zygimantas Cepaitis~ Fotolia; p81 he © Di. 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The slabs ‘content has been covered comprehensively, and has been separated into AS materia, which comprises Topies 1-19, ‘hilt the A Level material is dealt wih in Topics 20-30. All the Learning outcomes specified in che syllabus are Included in the hook. AE the sta of each Topic the specific Learning outcomes relevant to that Topic are cleadly stated, sing the same wording as in the syllabus, so that students ‘can cleuly see the syllabus areas covered by the Topic. ‘The chatt on the following page summarises the syllabus ‘coverage in each Topic. “Throughout each Topie there are worked examples, with answers, 10 illustrate the concepts recently introduced, These are followed by a few ‘Now try this’ questions, allowing siuidents ta test themselves, Answers to these questions are ‘on the accompanying Students! CD-ROM, Each Topie ends with a simmary of the key points covered, together with a list of key reactions where relevant Finally, several past examination questions have beea selected that ilustrite how the subject mstter of the Topic has been assessed in the past, Answers to these questions ‘will be Found on the Teachers! CD-ROM ‘Toallow stulents ancl teachers locate easily the various aspects of the subject, the onler of Topics isa logical one, starting withthe essential basic principles of physical chemisiry And then iniroxiucing the application oF those principles fsaly to dnorganic chemisty and then to organic chemistry. No teaching order is implied by tis, however chs been found thar axing principles and applications with facmal cootent thionighout the course is often the best way to achieve a deeper and broader understanding of chemisny, Tenchers are recommended to consul the schemes of work published by (Cambridge Intentional Examinations on their website for some suggested methods of delivering the subject material, A feature ofthe new 2016 syllabus isthe intweuction of Key concepts. These are essential ideas, theories, principles ‘or mental tools that help learners to develop a deep Understanding of their subject and make inks between the diferent topics, Although teachers are ikely to have these in mind at all times when thoy are teaching the syllabus, we have incliced in the text the following icons at points where the Key concepts relate to the text. _ Brion and forces — Nats bat om tons tenting and bonding through electrostatic forces, The structure of matter affects its physical and chemical propenies, and inflwences how substances seact chemically @ Prperiments and evidence — chemists we evidence gained from observations and experiments to build models tnd theories of he stricture and reactivity of materials, @ Pavers in chemical behaviour and reactions —By idemifying patterns in chemical behaviour we can pret the properties of substances and how they ean be transformed into new substances by chemical reactions. This alloys us to design new materials of use to soci. (Chemical bonds — The understanding of how chemical bonds are mide und broken by the movement of electrons allows us to predict patterns of reactivity. 8 Energy changes ~ The energy changes that take place ducing chemical reactions can be used to predict both the extent and the rats of such reactions “This hoo has heen designed to he accessible to all AS aad A Level students, but also attempts to go some way towards satisfying the curiasity of the able student, and to answering the questions of the inquisive. alchowgh based firmly on the AS and & Level syllabus of Cambridge International Examinations, teachers and swidents will lad the subject matter and style of questions make i suitable Jor several other syllabuses. The subject matter has been ‘extended in some areas where an application, oF a more Jundamental explanation, is deemed to be appropriate ‘These extensions are clearly delimited from the main text in panels, and can be bypassed on first reading “The majonity of suidents stating an AS cots in chemistry come from 2 background of IGCSE Chemistry ‘oF Combined Science, and the inkial chapters st ata level and a pace that is suited to all such students, Some students come to AS chemistry with the belif that they wil find the mathematics dificult, hough the mathematical concepts required for chemistry are simple in principle anc Jew fn number, We hope to demonstrate thi, as long as the processes are understood, rather than learned by roe, the mathematics in both the AS and A Level Topics is well within the grasp of those who have gained a grade C at Tacse, Stents alse sometimes consider that chemistry isa ssubjec fll of dificult concepts. This is not tae, Most of |‘chemistry is based on the very simplest idea of electrostatics = like charges repel, unlike charges attract. When the subtle samafications of chs generalisation are studied during the AS and A Level courses, students should constantly remind ‘themselves ofthe inherent simplicity of this relationship, Chemisty isthe central science, atthe crossroads of biology and its associated disciplines on the one hand, and phiysies om the othet: Chemistry relies on phiysies for ies ‘understanding of the furamental building blocks oF matter, and biology relies on chemisry for an understanding of the ‘encnares of living omganisms, and the processes that ga ca, inside them that we call life, Standing a this crossroads, the chemist is uniquely postioned t0 understand, and make sigaificant contributions to, many interdisiplinary areas of ‘cocrent anc furute importance, The chemisty-based sciences of biochemisty, genetic engineering, pharmacology, and polymer and material science will all make increasing ‘contributions to our physical and material well-being in the future, Chemists are also playing a key role in the flit against industrial society's pollution of our environment ‘We hope you enjoy discovering the secret of chemistry uring your AS/4 Level course, Peter Cann Peter Hughes (® IGCSE ts the rogistoned trademark of Cambie International Examinations. Howth Cantncgelosnng ones cote by th 30 Tec ee + [hts 16 [van z [znas ra 3 [pz saas0 is | @ [isiab. ies @ ansassaman | 19 |- a2,e3008 5 psiaa,s23 3 a Sh, a, a, £35410 0) = [isa 7a | 3 [@0-m) 29,839 7 [4261629 | 2 [7204.73 8 | 5.2b), 8.12)b),82a)b, | 23 | 62,63,64 aad a fa be |b), 122, BS, BA as [aaasasa | B pwaisave tow, 131,132 Wiens 26 [Wid HI) 1 [150) 12 BG, | 27 [205,202,203 tants B [si 15300) ma [Paes TIA ve [aa.ts2 va |i. 222, 723,72 as is [eit 30 [aa 232 [*]This page intentionally left blankAS Level Physical chemistry 1 Chemical formulae and moles inthe leveled eal) (Leaming outcomes Fe REEMA | by end cFtstoseyouspodd beste Cease 11.48) detine and use tho terms relative atomic, sotopi, molecular and foxnula masses, boasad on the "°C scale 112) deline and use the term mole in terns ofthe Avogadio constant define and use the tems empirical and molecular formula ‘atoms and ions. We also introduce the chemists’ fundamental counting tunit, tho mole, and show you how Ses ae eabeinse do 4b) calculate empircal and molecular formule, using combustion data or composition ‘empirical formulae and the amounts rae een ere 4USa) wite and construct balanced equations BEGG SCRE Nata Ti stiels 1156) perform calculations ncuging use of the mole concept involving reacting ‘As you read through the topic. study ‘masses (rom formulae and equations), volumes of gases e.. inthe burning of the worked examples, and then ty hycrocarbors), volumes and concentrations of solutions, ane lat the numbor of ‘the ‘Now ty this questions that significant fguresin your answers to those given or asked for inthe question follow them. 1150) deduce stoichiometric relationships from calculations such a those in 1.5b) 1.1 Introduction What is chemistry? ‘Chemistry is the study of the properties of matter. By mater, we mean the substances that we can see, fel, touch, taste and smell ~ the stuf that makes up the ‘material world. Passive observation forms only a small part of a chemists interest fn the world, Chemisss ate actively inquisitive scientists, We ty co understand why matter has the properties it does, andl how 10 modify these properties by changing ‘one substance into ancthér through chemical eenctions Chemistry as a modern science began a few hundred years ago, when chemists stared to relate the observations they made about the substances they were investigating to theories of the structuse of matter, One of the most important of these theories was the Atomic Theory. It is just over 200 years since John Dakton put forward his ides that all matter was composed of atoms, ‘is theory stated that: 6 the atoms of different elements were different from exch other the atoms of a particular clement were identical to each other @ all atoms stayed the sime over time and could be neither created nor destroyed @ all mater was made up From & relatively small numer of elements (Dalton though, about 50) combined in vartous ways Figure 1.1 John Baton, who fist suggested Although Dalton's theory bas had to be mocified slightly, its sil a useful starting themaaein atomic Teoty point for the suid of chemistryPHYSICAL CHEMISTRY Figure 1.2 some examples of medical and agrcutural benoit 0 Since that time chemists have uncovered and explained many of the worlds mysteries, from working ont how elements are formed within stars to discovering. hhowr our genes replicate, On the way they have discovered thousands of new inethods of converting one substance into another, and have made mallions of new substances, many of which are of great esonomic and medical benefit the human race (see Figure 1.2) Classifying matter - elements, compounds and mixtures Chemists classify matter into one of three categories, 1 Elements contain jast one sort of stom. Although the atoms of @ particular clement nay clifer slighty in mass (see section 2.3), hey all have identical cheeical seactions. Examples of elements include hydrogen gas, copper metal and diamond cexyatals hich are eashon), ‘¢ Compounds are made up trom the atoms of ro or more different elements, boncled together chemically. The ratio of elements within a particular compound fs fixed, and is given by its chemical Formula (see page 7). The physical and chemical properties of a compound are akvays different from those of the elements that ‘make ic up. Examples of compounds include sodium chloride (containing sodium and chlorine ions), water (containing hydrogea and oxygen atoms) and penicillin (containing hydrogen, carbon, nitrogen, oxygen and sulfur atoms).‘Chemical formulae and moles (¢ Mixtures consist of more than one compound or eloment, mixed but not chemi- cally combined. The components can he mixed in any peapostion, and the proper ties ofa mixture are often the sum of, oF the average of, the propenies of the individual components. Examples of mixtures include aig, sea water and alloys such as brass, 1.2 Intensive and extensive properties ‘The propenies of matter may be divided ito Wo soups. The extensive properties depend on hen muich manter-we are studying. Common examples are mass and volume a cupfal of water has less mass, and less volume, than a swimming pool. (¢ The other group ave the imensive properties, which do not depend on how ‘much matter we have. Examples inchide temperature, colour andl density. A copper coin and a copper jug can both have te same intensive propemies, although the jug will be many time's heavier ane! karger) than the coin. ‘The chemical propeties ofa subsunce ae ako tensive. A smal o a lange han of ead will reac in the same way with either 3 epi a joa of water. Fo each ease wil Fiz, give of steam and hydsogen gas, and preduce am alaine solution in the water dean water sovered with powder Figure 1.3 The ol'drop expatment The oil-drop experiment Ate fle wth leas water and some ie pode, mich a pellen giao Alou piled ove te unc, Awl op os placed onthe suace fi ede Ur The peng, A Hs ek the poner bik sot eee an prolate cer area cero powder, Pa eC EHC RY Saag ag a teste Alla miso meaning ince owt deny, a caer teatiod woUk! be find hess of sy, 2 op) We can cate the ae fh a lob tom Sa ABeatng So woe tet change when the drop peas eu we cathe id che he ln Ths cnn be bal inte length one mele ugh oy be bles ef sven mole tk =e no way eng. Me flowing ae et 1.0% 104en* diame tl fn = 30cm 3.14 x 15tem" ToTom® cea X thickness volume 10x19%cm* 70T ea 14x 107 em.4 x UPD Distances this small are usually expressed in units of nanometes: A nanometre (am) = 1% 10 metres (im) So the film is 1-4nm thick. Oil molecules cannot be larger than thisPHYSICAL CHEMI Figure 1.4 Colowed slecton micrograph spre of rolled ral acorns re eure f the tbs ISTRY Table 1.1 standard form ‘Standard form | Fully wetien-out equivalent xe 600 Bax 10?_| 71420000 2x1" ooo 002 3521 x10" 000038521 1.3 The sizes of atoms and molecules Just as we believe that elements are composed of identical atams, so we also believe that compounds ate made up of many identical units, These units are the siallest ents dat sill retain the chemical properties ofthe compound. They are calle _molecules or fons, depending on how the substance is bonded gether (see Topics 3 and 4). Molecules contain so oe mone stoms houtnd together The atoms may he of the same element (e.g. ozone, Oy, which contains three atoms of oxygen) or ditforent clements (e- water, H;0, which contains two atoms cf hydrogen and one atom of ‘exygen). Ions are atoms, of groups of atoms, tha cary an elecrical charge Molecules are extremely emall ~ but how small? Sometimes, « simple experiment, a short caleulation and a little thought can lead to quite an amazing conclusion. The well-known oildrop experiment is an example. I¢ allows us 10 obiain an onder-of magnitude estimate of the size ofa molecule using everyday apparas (cee the experiment on page 3). Because molecules are made up of atoms, dhis means that atoms must be even smaller than the oil molecule. We can measore the sizes of atoms by various techniques, including Xay crystallography. A carbon atom ss Found fo have a diameter oF 0.15: That means it takes 6 million easbon atoms touching one aneeher to reach a length of only tram! Standard form ‘The numbers that chemists deal with can ten be very large, or very somal. To make these more manageable, and ta avoid having to waite long lines of zeros (with the accompanying danger of miscounting them), we often express numbers in standard form. ‘A number in standard form consists of ewo pats, the first of which is « number between 1 and 10, and the second isthe number 10 mised to-9 positive oF negative power, Some examples, with their Fully written-our equivalents, ave given in Table 1.‘Chemical formulae and moles If the 10 is raised to a postive power, the superscript tells us how many digits to the tight the decimal point maves. Asin the examples in Table 1.1, we often need ext zeros fo allow this fo take place, Ifthe 10 is raised to a negative ‘power, the supersesipr number tell us how many digits ro the left che decimal point ‘moves. Hore again, we often aced to write extra 2er05, but this timo to the left of the ‘original number Significant figures In mathematics, numbers are exact quantities, In contrast, the numbers used in chemistry usually represent physical quantities which a chemist measures. The aceuracy of the measurement i shown by the number of significant igure to which the quanty i quoted. If we weigh a smal coin on a digital then scale, the machine may tellus that it basa mass of ig. A onedecimal-placehalance wil show its mass a5 3.5, whereas con 4 two-decinal-place balance ts mass will be shown as 3.50. We should interpre the cading on the Iitchen scale as messing that the mass ofthe coin lies between 35g and 45g. it were asa litle lighter than 3.5, the scale would ave told as {at ite mass was 3g. It were a litle hemver than 4:54, the read-out would have been 5x. The one decimal place balance narrows the range, teling ws dhe miss of the coin is between 35g and 3.554, The two.decimal-place alae narrows sill funher, to between 84954 and 3.5054. In this way the mumber of significant gures (1, 2 or in the above examples) tells ‘ws the accuracy with which the quantiy has heen messed ‘The same istic of waloeres Usa a 100em® measuring cylinder, we can moaaize 2 volume of 25cm? to an acenicy of 40 Sem, so we wold pote the volume as 25cm Using s pipette oe bucete, however, we cin measute vohimes to 3a accurscy of 40.05em and s0-we would quote the stone volun as 25.0 (that is, somewhere between 2495c0 and 25.05em°). ‘Mos chemical balances and yolumetic equipment will measre quantities to 3.0 4 significant figures. Allowing for the accumulation of erors when values ace calculated using several measured quanties, we tend to quote Valles © 2.08 3 Sgpiican igs, In the examples in Table L.1, the number 6% 108 has 1 significant figure, and the suumber 7.142% 107 has 4 significant fires, 1.4 The masses of atoms and molecules ‘Being so smull, atoms are abo very light. Their masses range from 1 x 10g to 1 107% g. 1s impossible to weigh them out individually, but we can aecurately measure thie relative masses, that is, how heavy one atom is compared with another. "The most accurate way of doing this is by using a mass spectrometer (see sesion 25) Originally, the atomic masses cal the elements were compared with the mass of an atom of hydrogen: seltive atomic mass of element ses niicnemeine imass of onestomof hydrogen ‘This Is because hydrogen isthe lightest clement, so the relative atomic masses ofall ‘other clements are geester than 1, which is convenient, Because of the existence of isotopes (see section 2.5), and the central importance ‘of carbon in the masses of onganic compounds, the modern definition wes the isotope carbon-12, as the standard of reference: average mass of one atorn of & relative atomic mas of elmer =PHYSICAL CHEMISTRY Figure 15 on and lead ih of a mole a each (ofthe elements aluminum, suf, bromine “The difference between the two definitions is small, since a cachon-12 atom has almost exactly 12 times the average mass of a hydrogen atom (the actual ratio is 11.9121). Relative atomic mass is given the symbol 4, Since it is the satio of two masses, it sa dimensionless quantity ~ it has no units, We shall be looking at Isotopes, and relative isotopic mass, in more detail in Topic 2, where we investigate the structure of atoms, ‘The masses of atoms and sub-atomic particles (vee Topic 2) are offen expressed in atomic mass unis. An atomic mass Unit (amu) is defined as 1/12 the mass of one ftom oF carboa-12. It his the value of 1.6606 % 107%, Although we cannot use a lahoratory balance to weigh out individal atoms, we ‘can use i weigh oat known sitios oF atoms oF various elements, as long as We know their reitive atomic mnasses. For example, if we know that dhe relative atomic ‘masses of carbon and magnesium are 12.0 and 24.0 respectively, we can he sure that 120g of carbon will contaia the same number of stoms as 24.09 of magnesivon. What {is more, 24.08 (12.0 x 2) af eathoa wll contain rice the number of atoms as 24.08 of magnesium. Indeed, we can be cenain that any mass of caybon will contain twice the aumber of atoms as the same mass of magnesium, since the mass of each carbon. atom is only half the mass of 1 magnesium ators Sumulaly, if we know that the relative atomic mass of helium is 4.0 Gwhich is ‘one third the relative atomic mass of carbon), we can deduce that identical masses (of helium and carbon wall always contain three times as many helio aromas as ‘carbon atoms, 1.5 The mole ‘Chemists deal with real, measured quantities of substances, Rather than counting atoms individually. we prefer to cow them in nits that aze easily measteable, The [gram is a conveniently sized unit of mass to use for weighing out matter (a texspoon, fof sugar for example, weighs about 5g). The chemist’ unit of amount, the mole (symbol moD, is defined in terms of grams ‘One mole of an element isthe amount that contalns the same number of ators as there aren 12.000g of carbon 12. © 87800 ymolbx) @ #62079 "The mass of one mole of an element i called its molar mass (syimbol MD. Ibis numerically equal to its relative atom mass, Ay DUC is given én grams per moles relative atomic mass of carbon = 12.0 ‘molus mass of eathon = 120gmor* telative atomic mass of magnasinim = 24.0 solar mass of magnesium = 24.0gmol>Using the A: values O= 16.0, Mg = 240, S= 3200, calculate the amount of substance ‘in moles) in each ofthe following samples. 1 2809 of ciggen 2 2409 of sulfur 3 16.09 of magnesium 1 =6.022 « 10 mot! Caleulata the amount of substance in moles) in +1 a sample of uranium that contains 10x 10% atoms 2 asample of fluorine thet contains 5x 10" atoms | ‘Chemical formulae and moles Ie follows from the abave definition thar there is a clear relationship berween the ‘mass (mi) of a sample of an element and the number of moles (n) it contains avout (r makes) TS 0 xcample What i the amount (in moles) of carbon in 30g of carbon? Use the value A,carbon) = 12.0 to write its molar mass, and use equation (1) above: m=30g and M=12Z0gr0l" pe. ‘Togmor 2.5mol ja Aswe saw on page 5, the actual masses of atoms are very small We would therefore ‘expect the number of atoms in a:mole of an element to be very large. This is indeed the ease, One mole of an element contains «staggering 6022 % 10" atoms (six hundred and two thousand two hundred! million million million atoms), This value i called the Avogadro constant, symbol L ‘The approximate valle of £= 6:0 x 10? mor is often adequate, and will be used {in calculations in this book, ‘The telaionship berween the number of moles in a sample of an element and the ‘umber of atoms it contains is as follows: number of atoms = Lx number of roles ot ela a (ie How many hydrogen atoms ae there in 1.S1mol of hydrogen atoras? Answer Uso equetion (2), and the value of {given abow: 1=60x (02mor! and n= 1.5mol $2 N=6.0x 102 mors 1.5mol = 9.0% 10 en 1.6 Atomic symbols and formulae Hach clement has a unique symbol. Symbols consist of either one or two letters: The fict is always a capital eter and the second, if present, is always a lower-case letter, ‘This rule avoids confusions and ambiguities when the symbols are combined to make the formulae of compounds. For example: {the symmbol for hydrogen is {she symbol for helium is He (oe HE of bE} the symbol for cobalt is Co (not CO — this is the formula of carbon monoxide ‘which contains two atoms in its molecule, one of cashon and ane of oxygen).PHYSICAL CHEMISTRY How many atoms in total are present in ‘one formula unit ofeach ofthe following compounds? Symbols are combined to make up the formulae of competinds f mors than ane atoan ‘of a paricalar clement is present is symbol is followed by a subscript giving the number of atoms of that clement contained in one Formula uni of the compound, For example 1 the formula of copper oxide is CuO (one atom of copper combined with one atom of oxygen) the formula of water is HO (two atoms of hydrogen combined with one atom of oxygen) «© the formula of phosphoric(¥) acid is HPO, three atoms of hydrogen combined \with one of phosphorus and four of oxygen), Sometimes, especially when the compound consists of fons rather than molecules Gee Topie 4, groups of atoms in formula ate kept together by the use of bauckets If mote than one of a panicular group i present, the closing bracket i followed by a subscript giving the number of groups preseat. This practice makes the conaections berween similar compounds clearee. For example: 6 te formula of sodium tate is NaNO (one sodium on, a combine wih ene ate Jon, NO}, which consbis cf one nitogen atom coubined wilh thee eaygen ans) 6 he formu of calcium nivate is CatNO, (one clean fom, Ga, combi wih two nivte ions [Note that in caleium nitate, the formula unit consists of one calcium, (wo nitrogen ‘and six oxygens, but its not writen a8 CaN,Og This Formula would not make clear the connection between ©x(NO,)y and NaNOs, Both compounds are nates, and both undergo similar reactions of the aiteate ions ‘The formulae of many fonic compounds can be predicted if the valencios of the Jons are known. (The valency of an ion is the electrical charge on the ion.) Similac, the formulae of several ofthe simpler covalent (molecular) compounds can be predicted i the covalencies of the constituent atoms ate kacwn. (The covalency of fan stom is the number of covalent boads that the atom can form with adjacent atoms in a molecule.) Lists of covalencies and fonic valencies, and examples of iow to use them, ate given on pages 49 and 79. Work How mary atoms of each element are prasentin one formula unit of each of the folowing ‘compounds? a AKOH)s b (NHhS0, Answer 4 The subscript aftor the dosing bracket muliples all the contans ofthe bracket by three, There are therefore three OH (hye) oroups, each containing one oxygen and one hnydrogen atom, making a total of three oxygen atoms and three hyeogen ators, ‘togethor with one aluminium atom. » Here there are two ammonium groups, each containing one nitrogen atom and four hhydrogen atoms, and one sulfate group, containing one sufur atom and four oxygen atoms. In total, therefore, there ere: two nitragen store laa ie wert © one afar atom = four oxygen atoms, 1.7 Moles and compounds Relative molecular mass and relative formula mass Just as we can weigh out a mole of eatbon (12.03), so we can weigh out « mole ‘of a compound such as ethanol (alcohol), We Fist ced to calculate its relative ‘molecular mass,Figure 1.6 One-tenth of amoleof each ofthe compoures water potassium omater (kxcr,0;) and en ullate Swale (CUS0y 5420) ‘Chemical formulae and moles To calculate the relative molecular mass (4) of a compound, we add together the relative atomic masses (4,) of all the elements present in one molecule of the compouind (remembering to snultiply the -, values by the correct mumber if ‘more than one atom of a particular element Is present). So for ethanol, C3H0, swe have: B= 24fO) + GAD + 4f0) 2x 120+ 6x 104160 = 460 Jost as with relative atomic mas, wlies of relative molecular mass are ratios of masses, and have no units. The molar mass of ethanol is 46.0¢m0"* For ionic and gant covalent companinds (see Tape 4), we cannes, sicty, refer tothelr relative molecular masses, as they do noe consist of indfidual molecules For these compounds, we add together the relative atomic masses ofall the clements present in the simplest (empicca) formula. The results called the relative formula mass, bu is given the same symbol as clative molecular mas, Me Jus as ‘with molecules the mass of one formnula nits called the molte mass, symbol A For example, the relative formuls mass of sodium chloride, NaC, is calculated as follows: 2he= Aine) +A,CD. 2304355 =585 ‘The molue mass of sodium chlosde 58 5gmor" ‘We can apply equation (> (page 7) ta compounds as well st elements. Once the molar mass bas been calculated, we can relate the mass ofa sample of a compound {0 the numberof meles t contains 2 0 1.86 b Ksc10, 2949 © uso, $4,025.09 Calculate the relative molecular mass of glucose, CHiz06. Answer M,= 6A{C)+ 124,(H)+ 64/0) =6x 120+ 12x 1046x160 720+ 12.0+ 960 80.0 esPHYSICAL CHEMISTRY How mary moles ate there in 609 of glucose? 1 Calculate the relative formula massof) Angwor {ch ofthe fllowing compounds (Us | Conert the relative molecular mass calculated in Worked examnplo 140 the molar mass, the Ist of A,valesin the data section | Sites ihe fonda equation ( fon the CD) 4 ron) sulfate, FaSOx a b calcium hysregancartonate, CaQHCOnls « sthanoie acd, CoHa0z 4 ammonium sulfate, (NH4) SOx «© the complex withthe formula NasFelC0a)s 2 How mary moles of substance are there enc ofthe folowing ses? | 20g of magnesium oxide, MgO A mole of what? 9 = 180 9mol" i 40g of methane, Cre When dealing with compounds, we need to define clearly what the word ‘mole! 60g ofcalium carbonate, CacOs | refers to. A mole of wiater contains 6 10 molecules of H,0. But because each 44 809 of cycorropene, CoH ‘molecule contains two hyeogen atoms, a mole of 140 molecules will contain rwo {© 1009 of sodium dichromate, moles of hydrogen atoms, that is, 12 x 10" hydrogen atoms, Likewise, a mole of NaxCn0r sulfuric acid, ,50,, will contain two moles of hydrogen atoms, one mole of sulfur 2 What isthe mass af aach of the following samples? 49 1/S males of magnesium sulfate, iSO hagindadtambimsies | caging capes onsen Shasw EEF SAGER ‘oniains 12 x 10% chlorine atoms mol of Cb. atoms and four moles of oxygen atoms, A miole of calcium chloride, CaCl, contains twice the number of chloride ions as does a mole of vodium chloride, NaCl Sometimes this also applies to elements. The phrase “one mole of chlorine! is 1.8 Empirical formulae and molecular formulae ‘The empirical formula is the smolost formula that shows the relative numberof atoms of each element present in a compound If we know the percentage compasition by mass of a compound, or the masses of the various elements thar make itp, we can work out the into of atoms ‘The steps in the caleulation are as follows 1 Divide the percentage (or sass) of eae element by the elements relative atomic 2 Divide each of the figutes obvained in step 1 by the smallest of those figutes 3 Ifthe results ofthe calculations do not approximate to whole numbers, multiply them all by 2 to obtain whole numbers (In-rare cases we might have to muhiply by 3.08 410 obtain whole numbers) CCaleuate the empirical formula of an oxide of iron that contains 70% Fe by mass. (em Calulate the empirical formula of each of tho following compounds 1 asullide of copper containing 3.979 of Answer ‘The axide contains ion and oxygen only, so the parcentage of oxygen is 100~ 70: Following the stops above: copper nd 1.005 slur rreglar2s 0 Zere7s 2 Shydocnbon containg 81.8% 5s. e Caton and 182% Syogen elo 08. srbon and 18.2% hydroge Bhs 100 OSE = 1.50 3 amixed oxide of ton and calcium ‘which contains 51.9% iron and 18.59% calcium by mass (the rest being caygen) 3 Multiply both numbers by 2: Fe= 2, O= 3 Therefore the empirical formula is FeaOs 2Figure 1.7 D joe ‘Chemical formulae and moles ‘The molecular formula is either the same as, ora simple muliple of, the empirical formula, Por example, the molecule of hydrogen peroxice contains two hydrogen atoms and two oxygen atoms, Its molecular Foranula is HyO,, but ts empicical Forma is HO. ‘The molecular formula tels us the actual number of atoms of each elernent present in a molecule ofthe compound, 1.9 Equations Mass is conserved ‘A chemical equation represents what happens dusing a chemical eeaction, A key feature of chemical reactions is that they proceed with no measiable change in mass atall. Many obvious events can often be seea taking place ~ the evolution of heat, flashes of light chaages of colour, noise and evolution of gases, But despite these “sometimes deamatic signs that a reaction is happening, the stm of the masses of all the various products i always found to be equal tothe sum of the masses of the ‘This was one of the Fist quantitative laws of chemistiy, and is known as the Law of ‘Conservation of Mass. Ic cin be illustrated simply but effectively by the folowing experiment The conservation of mass ‘A small test tube has length of cotton thread ted round its neck, and is bal filled ‘with leac) sitraze solution. Ie is carefully lowered into a conical flask containing potassium iodide solution, taking care not to spill ts contents, A bung is placed In the neck of the conical flask, s0 that the cotton thread is tripped by is side, as, shown in Figure 17, The whole appanitis is then weighed. ‘The conical flask is now ahakea vigotously to mix the canteats, A seaction takes place, and the bright yellow solid lesa) iodide is formed. On re-weighing the conical Nasi with its contents, the mass is found to be identical tothe inital suas lead ritcate solution potasium yellow precipitate Todide Bf lend) ouide massbefore= 286.7469 "MNP mass ater = 246.746 3 Balanced equations ‘The reason why the mass does not change during a chemical reaction is because no atoms azo ever created or destroyed. The number of atoms of each element isthe same atthe end as 2t the beginning. All that has happencd is thar they have changedPHYSICAL CHEMISTRY their chemical eaviconment. In the example in the experiment above, the change can be reprosented in words as lead) iste, potas ioe _, solid lead), potassiam mitate solution solution ‘edide soltion ;- yf =a = SF ’ ‘ Figure 1.8 The formation of leat oitide “There ate several stops we must cany out to covert this Word equation into 2 balanced chemical equation, 1 Work out snl write dewa the formula of eich of the compouncls in turn, describe ts physical state using the correct one of the following four state symbols, @=ms Meliqud G=s0lid Gq): Forthe above reaction: 1queons solution (dissolved ia wates) ead nitrate solution is PIN») aq) ‘potassium iodide solution is KTfaq) solid lead) iodide is Pht 5) potassium nitrate solution ts KNO,(aq) “Te equation now becca PINO)),(4q) + Klag) > PoIyG) + KNOYq) 2-Mhe next step sto lance’ the equation. Thats, we mus ens hat we have te same nunber of atoms of each element on the righ side as on the lef-hand se, 2 Looking tthe equation instep 1 above, we notice that there are two iodine atoms on the igh, in Phi, but only one on the Ie, in KI. Als, there are 5:0 atsate groups on the let, in Pb(ND4), but only one on he sight, in KNOy b We can balance the iodine atoms by having two formula uns of Kl.on the let that is 2K1. (Note that we cannot change the formato Kl,—thit would not correaly represent potassium fodide, which always contains equal numbers of potassium and fodide ions) «¢ We can bakine the nirstes by having two Foils unis oF KNO, on the sgh, that { 2KNO,, This also balances up the portssm atoms, which, although originally the same on both ses, became unbalanced when we changed KI to 2K1 i step b. ‘The fly balanced equation is now: PUNOs)aq) +2Raq) — PBI) + 2RNOS(ag) itis cear that we have nether lst nor gained any atoms, but that they have swapped partnets—the iodine was orginally combined with potassum, but hes tended up being comabined with lead; the nate groups have changed their parmet fiom lead to potassium, 24 Copy the following equations and balance ther, 4 Halg) + 0xg) + 201) b 1x5) Chia) ich) © NaOH(aq) + AKOHR) NaalOaen) + 200) dd HeSlq) + SOxq) + Sia) + HOD {© NHs{q) + Oalg) > Nata) + #200) 2 Write balanced symbol equations for the following reactions ‘4 magnesium carbonate + magnesium tide + cateon dioxide b lead +slvor nitrate solution —» load ritrata solution +svee « sodium oxide 4 water —» sad hycrosie solution 4 ron() chiovida+ chlorine (Cla) iron chloride « iron) sulle + sodium hydroxide —+ iront) hydeoxide-+ sodium sulfate ‘Chemical formulae and moles am \Wite the balanced chemical equation forthe folowing reaction zinc metal + hydrochloric acd ~» zinc chloride solution + hydrogen gas Answer Following the steps given above 1 Zincrnetal is Zn) Hydrocnlone acid is HCIlag Zinc chloride solution's ZnCl. Hydrogen gas is Hyla)(nydrogen, ke many non-metalic elements, exits in molecules nade up of two atoms) The equation now becomes: Zr\s} + HCKaq) > ZnClelag) + HG) 2. There.’ro two hydrogen atorns and two chlorine ators on the right, but only one of teach ofthese on the lf 'b Wo can balance both of them by just one change —having two formula units of HCl on theleft The fly balanced equation is now: Zn\s) +2HCKaq) — ZnCh(ea) + Halo) a 1.10 Using the mole in mass calculations {We are now in & postion to loole at how the masses of the indivienal mibstances ia 4 chomical equation are relisted. As-an eximpla, take the reaction berweon marble chips (calctum carbonate) and hydrochloric acd: (CaCOs) + 2HCMag) + CaChGeq) +H,00+ CO.@) ‘When this reaction is cxmied out in an open conical Mask on a top-pan balance, the mass is observed to decrease, (Note that this is not due to the destruction of matter ~ as was mentioned oa page 11 the overall number of atoms does not change dusing a chemical reaction. Rather it 5 due 10 the fact thatthe gaseous Gabon dioxide produced escapes into the air.) We can use the knowledge gained in this topic 10 calculate the answer tothe following question: 1¢ By how much would the mass decrease i 50g of marble chips were completely reacted with an excess of hydmehloric acid? ‘We use the following steps: 1 We can use equation (1) (page 7) te calculate the number of moles of calcium carbonate in 50g of macble chips: a M{CaCO,) = 49.1 + 12.0-+ 3x 16.0= 100.1 10 = 100.1gm0r! 50 "Too gmat = 0.50mol of CaCO, 2 From the balanced equation above, we see that one mole of ealcivas carbonate produces one mole of carbon dioxide, Therefore the number of moles of carbon dlionide produced isthe sime as the number of moles of calcium) carbonate we started sth, namely 0.50mol of carbon dioxide, 3 Lastly, we can use a seareanged form of equation (1) to caleulae what mass of cathon diode this comresponds to, 1BPHYSICAL CHEMISTRY so m=nXM ——-M(CO)=12042%160= 440 Hogmor! Smal also m= 050mol x 44.0 gm0I" 2208 ‘The loss in mass (due tothe cathon dioxide being evolved) Is 22.04. ‘The three steps can be summarised as shown in Figure 19. Figure 1.9 Finding the mass ofa from the mass oF reactant, of vice versa ‘ats of first reactant or product sk moles of fst reactant or product |_ eeSeeE t— moles of second reactant or product| i [pan xn | mass of second reactant or product wc ‘The highly exothermic thermit reaction (sae Figure 1.10) is used to weld together the steel ‘als of ralway tracks. I involves the reduction of ion) oxide to ton by aluminium. Als) + Fey) -> AlgDy)-+ 2Fls) Figure 1.10 veld together ho Use the chart in Figure 1.9 to calculate what mass of aluminium is needed to react completely with 10.09 of iron) oxide11 What mass of silver wal be preciitated \when 5.09 of copper are reacted with an excess of sver nitrate solution? CuG)-+2AgNOaq) + CuNOs)e0) + 2Aq(s) 2. What mass of ammonia will be formed when 50.09 of nitrogen are passed ‘through the Haber process? (Assure 100% conversion.) xa) + 3Hy(Q) + 2NHQ) Now try thi 1 What volume of carbon dioxde (measured at room temperature and pressure) willbe produced when 5.09 of caloum carbonate are decomposed by heating according o the folowing equation? acd; +€a0 +0, 2 Sulfur dioxide and hydregen sulfide 9280s react according to the equation: 2H,S + $0; 24,0 + 38 What volume of aufurdlida will be needed to react completely ‘with 100cm? of hydrogen sulfide (both volumes measured at room ‘temperature and pressure), and what ‘mass of sulfur will be formed? ‘Chemical formulae and moles 55843 160= 1116 + 480= 1595 159.6amo" ‘umber of males of kant) oxide (0) = 100 i506 (0627 mal 2 From the balanced equation, one mole of irondl) onde reacts with two moles of aluminium, therfore: ‘number af moles of alurinium (9) = 0.0827 2 2 AMAD=21.0 50M 125mol 125melx27.0gmor 389 1.11 Moles of gases “The molar masses of most compounds are different. The molae volumes of most solid and liquid compounds are also diferent. But the mola volumes of gases (whe measured at the same temperature and pressure) are all the same. This strange coincidence results from the fact that most of a gas is in fact empty space — the molecules take up les than a thousandth ofits volume at normal temperstures (see section 4.13). The volume ofthe molecules is negligible compared with the total volume, ‘and s0 any variation in their inlivihal size will not affect the overall volume, AE room temperature (25°C, 298K) and normal presse (Lata, 1.01 % 10°Pas 14.0? mor" ‘the molar volume of any gas Sowe can say that volume tin dr) Tolar volume vO mo ‘oF volume of gas in din? = molar volume x moles of gas v=240%0 amount of gas (in moles) \What volume of hydrogen (measured at room temperature and pressure) wil be produced when 70g of ron are reacted with an excess of sulfuric acid? Answer ‘The equation forthe actions as follows: Fels) + H,50,(aq) + FeSO,(aq]+ Hale) VAFe)=558 so M=55.8qmor! amount Gn moles) of on = 709 EBaner = 0.125 nol 2 From the balancod equation, one mole of ron produces one mole of hycragen molecules, therefor! ‘number of moles of Hy= 0.125 mol 3 volume of Hy dndin®) = molar volume x moles of Hy 4. Odir? mot" x 0.1250) Odi? 5PHYSICAL CHEMISTRY Figure 1.11 coer ited sok aepend ot Row mucho ty that dows 1.12 Moles and concentrations ‘Many chemical reactions are caried out in solution, Often itis convenient to dlssolve a reactant ina solvent in advance, and © use postions as and when needed. A ‘common example of this isthe dilute sulfuric acid you find on the shelves in a laboratory. This has been made up in bulk, ata ceriain concentration, Soh ‘most easly measired cut Suppose wwe neod & certain amount of sulfuric acid Gat is, a ceria umber of y volume, using measuring cylinders, pipettes or bueetes. ‘moles fora panicular experiment, f we knew how many moles of sulfuric acid each ‘Lem? of solution contains, we can obtala the required aumber of moles by measuring cout the correct volume, For example, if our ulfuic acid contains 0.001 mal of HSO, pet Lem’, and we need 0.005mol, we would measure out Seu? of solution. ‘In chemistry, the concentations of solutions ate normally stated in units of moles ‘per cubic decimetre (= moles per lie). The customary abbreviation is motda’ ‘©ceasionaly the olde, and even shorter, abbreviation M is used. 1F Lam ofa solution coniains 1.0m0l of solute, the soluson’s concentration is ‘LOmoldi” (or L.0M, verbally described as a one molar solution’). more moles ate dsolved in the same volume of solution, the solution is: more concentrated one. Likewise, if the same number of moles is dssolved ina smaller ‘yolume of solution, the solution is also more concentrated. For example, we ean produce a 20molday? solution (20M, ‘wo molae’) hy 6 cither dissolving 2mol of solute in dm? of selution © or dissolving 1mol of solute in 0.5dim of solstion. amount (in moles) concervaton -—_ aun oes) Mon rao slaton Gm GT et ‘oF amount (in moles) = concentrations wolume (in din?) na cx Unlike the mass of a solid, or the volume of a gts, which are extensive properties of a substance (see page 3), the concentration ofa solution isan intensive propery. It ‘does not depend! on how mich of the solution we have, Properties thar depend on the concenimtion of 4 solution are also intensive, For example, the mice of rection between sulfusle acd and magnesium ribbon, she colour of aqueous porassiom manganatetVID, the sowmess of vinegar and the density of « aigar soliton do not depend on how ‘much solution we have, but only on how much sole is dissolved ina given volume.1 Chemical formulae and moles 200cm* of a sugar solution contairs 0.40mol of sugar. What & the concentration of the solution? Answer Uso the fst equation inthe panel on page 16: Remember, 1000cm?= 1.0 dir? 50 200cm?=020dm? in the folowing solutions? 2. L0mel of ethanol in 75en¥ oF How many grams of sat, NaCl, need to be dissolved in 0.50dm? of solution to make a (0.20 moldin~ solution? solution b Sagot sodium caonate, Narco, | Answer in Z.0dm’ of solution ‘Use the second equation in the panel on 16: © 40g of athanaic acid, C2HaOz, in nsexl " p soak 800cm' of solution _ =) 2 2 Howmnary molesofsolteaeinthe | 97 020moldn* 05d folowing soktions? 2 -0.50dm? of a 15 moldm? solution | Nw use equation (1) (page 7) to convert mola into mass: of sulfuric acid a= 2 x m=nxM bb 22cm? of a .0moldnr® solution of ” sodium hydrcnide «50cm? of solution containing 209 of potassium hydrogencarbonate, KHCOs, por dn? m= 0.10101 58.5qmol" 9 of salt, NaCl “We shall come across tho concenttatons of solutions again in Topic 6, where we look at the technique of tiation 1.13 Calculations using a combination of methods Atthe heart of most chemistry calculations is the balanced chemical equation, This shows us the ratios in which the reactants react t give the prochcts nd the ritios ‘n which the products are formed. This is called the stoichiometry of the reuction ‘Most calelations involving reactions can he broken down into set of three steps Gee ‘Figure 1.12), similar 1 those deserbed for mass calculations on page 14 Figure 1.12 Cau fos Inohving the ‘mass of solid A orvolume of gas, orvoluma (or concentration af slution containing A | ‘moles of reactant or product A ‘noles of reactant or product + ‘nase of sold B, or volume of 9858, cor volume (or concontration) ef rlution containing B 7PHYSICAL CHEMISTRY Use Figure 1.12 and the A vluas in the data section on the CD to answer the following questions. 11 What volume of hydrogen gas wil be given off when 2.39 of sodium metal react with water? 2Na(S)+ 2HOX > 2NeOHag) + Hala) The equation for the complete combustion of methane, CHy, in oxygen is (HQ) + 20340) + COxe) +2401) Calculate the volume of oxygen needed to bum 4.0 of mathane. What volume of 0.50 mold’? sulfuric ack, H;$0,, Isneeded to react exactly wth 5.09 of magnesium, and what volume of hydrogen wil bo ovolac? Mais) +H»50yaq) » MgSO,ea) + Hla) What mass of sulfur will be precipitated wher an excess of hydrochloric acid fs added 10 100cm? of 0.20moldm? sodium thiosulfate solution? 'NajS,0xaq) + 2HCKag) + 2NaC\aa) + SO,(@) + HOt) + Sta \What would be the concentration of the hydrochloric aid produced i all the hydrogen cherie gas ftom the reaction between S0g of pute sulfuric acd and an ‘excess of sodium chloride wes collcted in water, and the soltion made up toa value of 200cm? with water? NaClls] + H,SO)—+ NaHSOU6) + HCKa) 'e Atoms and molecules are smal and light - about 1 x 10min size, and about 1 x 10-g in mass Relative atomic mass and relative molecular mass are defined in terms ofthe mass ofan atom of carbor-12. ‘Ono mole isthe amount of substance that has the sarne inunberof particles (atoms, molecules, et) as there ae atoms in 12.0009 of carbor-12, The relative molecular mass, M, of @ compound's found bysumening the rlatne atomic masses, A, of al the atoms present. The empirical formula of a compound s the simplest formula ‘that shows the rele number of atoms of each element present in the comoound. The molecular formula tels us the actual number of atoms of ‘each element present in a molecuie ofthe compound. ‘Chemical reactions take place with no change in mass, and no change inthe totl number of ators presen. ‘© Chemical equations reflect this - when balanced, they contain ‘the same numbers of atoms of each element on thesr left-hand and right-hand sides. ‘The following equations allow us to calculate the number of moles prasent in a sample: (© amount Gn moles)= TE or n= volume of gas dn dm?) 740 o concontraton of solution (in moldm’=) xv concentration of solution (in moldm) jo00 we a0 ‘© amount in moles) volume inden?) © amount neo ‘¢ amount Gnmoles) volume nan?) 71000‘Chemical formulae and moles Examination practice questions Please see the data section af the CD for any A, values you may need, 1 ine isan essential trace element which is necessary for the healthy growth of animals and plants. Zinc deficiency in humans can be easily treated by using zinc salts as dietary supplements. ‘a One salt which is used as a dietary supplements a hydrated zinc sulfate, 2nS0,.xH,0, which isa colourless ‘crystalline solid. Crystals of zinc sulfate may be prepared ina school or college laboratory by reacting dilute sulfuric acid with a suitable compound of zinc. Give the formulae of two simple compounds of zinc that ‘could each react with dilute sulfuric acid to produce zine sulfate 2) bb A simple experiment to determine the vaiue of xin the formula Zn$0,.%440 fs to heat it careful to drive off the water 2150,.41, 05) -+ 2n50,(9)+ 1,010) ‘A student placed a sample of the hydrated zine sulfate in 2 weighed boiling tube and reweighed it. He then heated the tube fora short time, cooled it and reweighed it ‘when cool, This process was repeated four times. The final results are shown below. i. Why was the boiling tube heated, cooled and reweighed four times? li Calculate the amount, in moles, of the anhydrous sat produced. Calculate the amount, in moles, of water driven off by heating iv Use your results toi and ii to calculate the value of x in 2nS0,,0. m © For mary people, an intake of approximately 15 ma per day of zinc wil be sufficient to prevent deficiencies, Zinc ethanoate crystals, (CHjCO,qZ7.2H,0, may be used in tis way, i What mass of pure cystaline zinc ethanoate (u,= 219.4) will need to be taken to obtain a dose ‘of 15 mg of zinc? ii this dose is taken in solution as § cm? of aqueous zinc ethanoste, what would be the concentration of the solution used? Give your answer in mol dm [4] [Cambridge International AS & A Level Chemistry 9701, Paper 21 QF November 2012} 2 Washing soda is hydrated sodium carbonate, NajCO, 0,0. student wished to determine the value of» by carrying ‘outa titration, with the following results 5.139 of washing soda crystals were dissolved in water and the solution was made up to 250cm* in a standard volumetric lak, 25.0cm! of this solution reacted exactly with 35.8cm° of 10.100moldnr? hydrochloric acid and carbon dioxide was produced. 12.1, Wiite a balanced equation forthe reaction between Na,CO, and HC. ii Calculate the amount, in motes, of HC! in the 35.8em™ of solution used in the titration. Use your answers toi and ito calculate the amount, in moles, of NaxCOs in the 25.0cm’ of solution used inthe tration, iv Use your answer toi to calculate the amount, in moles, of Na,COs in the 250cm? of solution in the standard volumetric flask \v Hence calculate the mass of Na,CO, present in 5.13.9 cof washing soda crystals ja bb Use your calculations in a to determine the value of xin Na:CO, +440. Bi [Cambridge International AS & A Level Chemisty 9701, Paper 23 Q2 June 2012) 3a compound containing magnestum, slicon and oxygen is present in rock types inlay. A sample ofthis compound ‘weighing 5.27q was found tohave the folowing ‘composition by mass: Mg, 1.829; Si, 1.059; 0, 2.400. Calculate the empirical formula of the compound. Show your working. 2 'b Pharmacists sell tablets containing magnesium hydroxide, Mg(OH), to combat indigestion. A student carried ‘out an investigation to find the percentage by mass of Mg(OH) in an indigestion tablet. The student reacted the tablet with dilute hydrochloric acid Mg(OHy) + 2HClaq) + Mec xag) + 24,00) ‘The student found that 32.00em? of 0.500mol dr? HCl was needed to react with the Mg(OH), in a 500mg tablet. [1 9= 100mg} i. Calculate the amount, in mo, of HCI used. a ii Determine the amount, in mal, af Mg(QH), present in the table. ny i Determine the percentage by mass of Ma(OH): present inthe tablet el OCR Chemistry A Unit F321 Q2 (part) May 2011) 192 The structure of the atom {In this topic we introduce the three sub-atomic particles ~ the electron, the proton and the neutron. We look at their properties, and how they ara arranged insido the atom. We explain that some elements form ‘isotopes, and describe how thor ralative abundances can be measured using the mass spectrometer. We outline ‘the typos of energy associated ‘with the particles in chemistry. Against this background, we look ‘af how the electrons are arranged ‘round the nucleus and how this arrangement explains the positions ‘of elements within the Periodic Table, their ionisation energies and the sizes of their atoms. 20 Learning outcomes By the end ofthis took you should beable 13a) analyse mass spectra in terms of isotopic abundances (pat, see also Topic 29), 11.3) calculate the relative atomic mass of an element given tho relative abundances of Its sotopes, or is mess spectrum 2.1a) identify and describe protors, novirons and electrons in terms oftheir relative charges and relative masses 2.1b) deduca the bohaviour of boars of protons, nautzons and alectrons in lect ies 2.10) describe the istbution ef mass and charge within an atom 2.4d) deduce the numbers of protons, neutrons and electrons present in both atoms and ons given proton and nucleon numbers and charge 2.2a) describe the contritution af protons and neutrons to atomic nude in terms of proton number and nucleon number 2.2b) distinguish between isotopes on the basis of diferent numbars of neutons present 2.2€) recognise and use the symbolism JA for isotopes, where *'s the nuceon number and jis the proton number 2.3a) descbe the number and relative energias ofthe , pnd d orbitals for the principal quantum numbers 1,2 and 3 and also the 4s aed dp orbitals, 2.36) describe and sketch the shapes of s and p orbitals 2.30) state the olecronic configuration of atoms and ions given the proton number and charge, using the convention 15232208 etc 2.34) explain and uso the term fonsation enorgy, axplan the factors influencing the ionisation energies of elements, end exalain the trends in ionisation energies ‘across 2 Period and down a Group of the Periodic Table (see abo Topic 10) 2.3e) deduce the electronic configurations of elamonts from successive ionisation energy data 2.38) interpret successive ionisation enoray deta of an clement in torms of the position ofthat element within the Pariodic Table. 2.1 The discovery of the sub-atomic particles (Our understanding of atoms is very much a nineteenth and twentietl-century story Although the Greek philosopher Democritus was the firs to coin the tenn ‘atom! (hich fs derived from the Greek word meaning ‘canot be cut, in around 4003, his idea of matter being. composed of small particles was dismissed by Arison ‘Because Aristle's reputation was so great, Democritus” atomic idea was fgnored for cearuries. Iwas act unsil 1808, when Joba Dakon published his Atomic Theory, that the idea cf atoms as being indivisible constitiente of matter was revived. Dalton suggested that all the atoms of a given element were flentical to each oer, but differed fom the atoms of every other element His atoms were the smallest parts of 1a cloment that could exist. They could not be broken down or destroyed, and were themselves without sictaceFigure 2.1 Emest uthertord ight Mi Figure 2.2 The fic abot 1998. Thay meth cantury The structure of the atom. For most of the aineteenth conniry the idea of atoms being indivisible ited in well ‘with chemists ideas of chemical reactions, and was weadily accepted. Even today it is believed that atoms are never destroyed during a chemical reaction, but merely change their partners, However, in 1597 the physicist JJ, Thomson discovered the frst subatomic particle, that is, 1 particle smaller than an atom It was the electron. ‘Thomson found that the electron was much lighter than the lightest atom, and bad a negative elecrical charge. What is more, he found that under the concitons oF his expetiment, atoms of uifferent elements produced identical electron patticles. This ‘suggested that all atoms contain at least one sub-atomic component in common. Since atoms are electrically neutral objects if they contain negatively charged celecons they raust also contain particles with a positive charge. An Jmponant ‘experiment casied out in 1911 by Emest Rusherford (a New Zealander), Hans Geiger (4 Germ) and Ernest Massden (an Eaglishinan) shossed thatthe postive charge in the atom is concenteited into an incredibly small nucleus sight in the middle of it. They cstimated that che diameter ofthe nucleus could aoe he greater tha '0.00001 times that cof the atom itself. Eventually, Rutherford was able ta chip away from this nucleus small postvely charged particles. He showed that these were also identical to each ether, ao rater which element they une from, This positive particle is called the Peoton, It is| smuch heavier than the electron, having nearly the mass of the hyerogen atom, se was ancther 20 years before the lst ofthe three sub-atomic panicles, the neutron, was discovered. Although its existence was fist suspected in 1919, it was not until 1952 that James Chachwick eventually pinned it down. As its name suggests, the newtron is celecrically neutral, but 4s relaively heavy, having about the same mass as a proton, Scientists ad therefore to change the earlier pcsure of the atom, In a sense the picture had hecome more complicated, showing that toms had an iotemal secure, and wete made up of other, smaller partices. But looked at in another way i had become simpler — the 99 oF 50 diferent types of atoms that are aceded to make up the various clements had been replaced by jus three sub-atomic particles. Ie turns ‘out that these, indifferent amounts, make up the atoms ofall the different clements most of the volume ff the atom Ieoccuped by the electrons tho mucous is very sal ‘contain te protons find the neutrons 2PHYSICAL CHEMISTRY 2.2 The properties of the three sub-atomic particles ‘Table 21 lists some of the properties of the three sub-atomic particles. Table 2. Te properties ct thy subatomic res Note that he maser the astro ‘ate Given relative to the mass ofan atom electrical chargercoulombs a6xio" — fatgeio® [0 Siest12 Thselaseate fe unis) [age ovebe te Hatot ep) _[=1 a a Whenite cate mot thesecon cf, [a aire [rean™ [velsnio™ ans eth res fh ton a eT Saeki [07 a haut | beam of particles Figure 2.3 Tho behaviour of protons, naurons and olecrons in an electric Held Table 2.2 The eate abundance of some botopes ‘Tho isotopes ofan clement diffor in thor ‘composition in only one respect - although ‘they all contain the same numbers of 700 2.6 Chemical energy ‘The concept of energy is central to our understanding of how changes come ‘about in the physical world. Our study of chemical reactions depends on energy concepts. Chemical energy is suade up of two components ~ Kinetic energy, which is a ‘measure of the motion of atoms, molecules and ions i a chemical subseance, and potential energy, which is measure of how strongly these particles antact one anoiher, Kinetic energy ‘Kinetic energy increases as the temperature increases, Chemists use a scale of temperature called the absolute temperature scale, and on this scale the kinet ‘energy is direaly proportional to the temperature (See section 4.13), Kinetic energy can be of three different types. The simplest is energy due to ‘wanslation, that is, movement from place to place. For monatomic gases (gases made tp of single atoms, for example helium and the other noble gases), all the kinetic energy isin the form of translational kinetic encagy. For molecules containing two or more atoms, however, there is the pessibility of vibration, and rotation as well (see Figure 27). Both these forms of energy involve the movement of stoms, even though the molecule as a whole may stay sll. In diatomic gases, the principal fon of kinetic energy is tanslation, but in more complex molecules, such as ethane, vibration and rotation become the mare jmportant factorsPHYSICAL CHEMISTRY x distance d @o= Figure 28 Te lens through a dster 1 oppositely char 1, afrce Fs raxqated Figure 2.9 Energy is needed to fit a book from the fioor and put an the desk 1p solids, the panicles are fixed in positon, and the only form of kinetic encrgy Is ‘vbtstion. In lil, the pamicles ean moe fiom place to place, thosigh me sem than Jn gies and so liquid particles have tranalational, rotational and vibeational kintic energy, Potential energy Jn studying chemical eneigy, we are usually more interested in the potential energy ‘ofthe system than in its kineric enengy, This is because the potential energy gives us imporant quantitative information about the stengths of chemical bonds. At normal temperatures, potential eneruy is much larger than kinetic energy. Porential enengy arises because atoms, ions and molecules atact an! repel fone another. These atraetions and repulsions follow from the basic psnciple of lectosttis, that unlike charges annact and like charges repel, Tonic compounds contain panicles with clear postive ad negative charges on thet. Two positively charged ions repel each other as do two negatively charged ions. A postive ion and 2 negative fon atract eich other, Atoons and molecules which have no ovecll change fon them, also attract one another (sce section 3.17) Ie requires energy to pull apart a sodium foo, Na‘, from a chloride ion, Cr. the potential energy of the system increases beezuse we need to apply 4 force F (equal to the force of attraction between the two fons) for a distance d (see Figure 2.5). In a similar way, we increase the potential energy ofa book if we pick the book up off the floor and put ion a desk (see Figure 2.9), a stance d force F I Tn contrat, if We start with 2 sodium ion and a chloside ion separated from each ‘ther and then bring them together, the potential energy decreases, We also deczease the potential energy of a book if we allow i to fall from the desk to the floor, [As we shall see in Topic 5, chemists are usually interested ia the change in chemical energy that occurs during a reaction, This change is represented by the symbols AB the Greck letter dels, 4, being used to mesa “change’, IE we look at energy changes that occur at constant pressure, which is normally the case in the laboratory, we use the symbol AH, which represents the enthalpy change of 4 reaction, The most commonly used unit of enemgy in chemisry i the kj mor (kilojoule per mote), whese 1k) = 1000), 2.7 The arrangement of the electrons — energy levels and orbitals (Gn page 21 we concluded thatthe atom is made up ofa very dense, very mall nucleus coatining the prosans and neutrons, and! a much Luger region of space around the rmucleus tht contains the electrons. We now turn our attention te these electrons. We shall sce tht they are not clstibuted randomly inthis region of space. They occupy specific volume segions, called orbitals, which have specific energies associated wth them2 The structure of the atom Energy levels and emission spectra When gaseous atoms are given enemy, ether by heating them up to several hundred degrees, oc by passing an electric current dhiough them, the electrons become exeited and move from lower enemy levels to higher levels. Blectrns in gaseous atoms ean also ‘ave from lower to higher energy levels by absorbing specific frequencies of ght. This eaves dark absonpion fines in the spectrum of fight transaited throtgh the gas. twas these absorption lines thar provided the fist evidence fora news element discovered in the otter regions of the Sun. Iras panied hallo, after the Geoele wed forthe Sia Jbolios. The tachnique of atomic absorption specrroscopyia widely Used toy to measure accurately, for example, the concentrations of calcium and sodium in a blood saraple, oe the elements contined in a sample ofa ste alloy (see Figure 2.10) Eventually, the excited electrons lose enetgy again by falling down to lower encagy levels. During this process they radiate visible or ultraviolet light in specific amounts as packets called photons. We can analyse the radiated ight witha device called a spectroscope, shown in Figure 2.1. The emission spectrum shows tht only a very Few speciic frequencies ase emited, ond these aye unique to an individual element. AI the atoms of a particular ‘element racore atthe same se of frequencies, which are ususly different fron) those of Figure 2.10 An all other elements (see Figur Xt) +Figure 2.22 The energy an elecron from a hyetogen. Figure 2.23 Variation oft 1s orbital with proton rumba to remove com anda gy ot the The structure of the atom For hyelmgen and helhim the ionisation energies 2: HQ SH +e a Helg) $He') +e AH 1312i)mot 2372Kjmol + [Note that Al is the symbol chemists use for enthalpy change, The enthalpy change of a process isthe energy change that occurs when the process is catied our at constant pressure (see Topic 5). Tttakes more energy fo remove an electton from a hetium atom than from a Ibydrogea atom, This shorws that, compared with the energy when the election i at infinity, the enorgy of the Is orbital has boceme more negative in holitim (see Figure 2.22) than in hydrogen (see Finite 2.15, page 25) aH = 13121 mer energy mat" ‘This decrease in energy for the 1s orbital continues as the proton aumber increases Gee Figure 2.23). The decrease in eneegy is also true for other orbitals. The reason is that as the number of protons in the nucleus increases, the electrons in a particular corbital are attracted to it more. The decrease in energy is not segular, however, and is not the same for all orbitals, This is due to two Factors proton number er 2 a sg He 10 00" 15 00 energy 20.000" Be -25 000" 30 0001 35 001 3BPHYSICAL CHEMISTRY Figure 2.24 The lium nucleus and inner shal Figure 2.25 Graph ef ofl energy against ‘roton number fr shell numbts 1-5 8 Table 24, page 31) 4 f¢ The average dieance of a p oshital from the auicleus is leger than that ofthe comesponding 5 orbital in the same shell (see Figures 2.16 and 2.18, page 30). Elecons ia p orbitals therefore experieace less ofthe stabilising effec of incressing ngclear chaige than electrons ins ombitals, Fora sitalar reason, electrons in d orbitals experience even less of the increasing nuclear charge than electrons in p orbital, ¢@ All clectrons in outer shells are to some extent shielded from the nuclear charge by the electrons in inner shell: This shielding asthe effect of decreasing the effective nuclear charge. In the ease of luhium, for example, the outermost electzom in the 2s orbital does not experience the full nuclear charge of +3 (see Figure 2.20. The two clectrons inthe filled 1s orbital mask a good deal of this charge. Overall, the effective nuclear charge experienced by the 2s electron in Fidium is calculated {© be +13, which is consicerably less than the actual nuclear charge of +3. A plot of orbital energy against proton number for several ena is showvn ia Figure 2.25, 4d Se site| 3p ag de He Ge € © NeMg SiS Ar Ca Ti Cr Fe Ni Zn Ge Se Ke S Op VEE M Ta PSE. Vie cae eT