Cambridge ENDORSED BY International AS and A Level # CAMBRIDGEENDORSED BY [3 CAMBRIDGE International Examinations Cambridge International AS and A Level eta Peter Cann & Peter Hughes (> HODDER ? EDUCATION ‘ater UR Com‘Questions from Caunbrdge International AS und A Level Chemisty papers are reproduced by ‘Permission of Cambridge Inernational Examinations, ‘Cambeidge Intemational Examinations hears no responsiiay forthe example answers to ‘questions taken from is past question papers which are contained in hls beolCD. ‘Questions fom OCR past papers ate rependiced by permisslon of CCK. 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Apt fromm any use permited under UK copyright law, no pat ofthis pblcation may be repreuced or tansmited in any fon of by any means, electronic o¢ ‘mechanic, nehiding photocopying and recording, of hold within say sformaien storage ane renee system, without person in weting frm the publisher or under cence fom the Copyright Lcersing Agency Lime Frter datas ef sch Heences (or reprogaphlc reproduction) may be obtained from the Copyaght Licensing Agency Limite, Sfiron House, 6-10 Kuby Stoo, London CANT. Cover photo by © kurgaya ~ Poti. ‘Musrauons by Backing Dog An ‘Typeset in ITC Garamond Light 9/12 by Aptara In. Priced Dubal ‘tale recon fo dis eis vate fom the Bish tary ISBNOTS 1444 18133 3Contents Introduction AS Level CR us Topic 1 Chemical formulae and moles Topic 2 The structure of the atom Topic 3 Chemical bonding i Topic 4 Solids, liquids and gases simple molecules . Topic 5 Energy changes in chemistry Topic 6 Acids and bases Topic 7 Oxidation and reduction Topic 8 Rates of reaction Topic 9 Equilibria... reseed 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. rece) ee) Topic 19 Practical work 20 44 Cy 97 118 136 14 1m 186 202 209 24 251 267 281 294 305 316Contents rN ETA} DER eusi ‘Topic 20 Further energy changes. Topic 21 Quantitative kinetics Topic 22 Quantitative equilibria Topic 23 Electrochemistry Inorganic chemistry Topic 24 The 3d block. Cees 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 forthe help given by Judy Potter in selecting and writing topic-oriented questions, and forthe unstntingly professional support and cooperation given by the staf at Hodder Education: Nina Konrad, Emilie Kerton, Laurice Suess, Anne ‘Trevllion and Anne Wane ‘The Publishers would like to thank the following for permission to reproduce copyright material: Photo credits: p.1 © The Granger Collecion, NYC/TopFoto; p.2 © Jeff Blackler/Rex Features; Iv © Bicipici/Alamy; be © Niks Jorgenseny/Rex Features; br © Chis Lofty ~ Fotolia; pt © Eye OF Science/Sclence Photo Library; p14 © lowefoto/Alamy: p.21 © Rex Feauures; p.23 © RGB Ventures/Supersiock/Alamy; p.27 © Geoff Tompkinson/Science Photo Library; p.73 © Zygimancas Copaitis— Fotolia; p.81 he © De Jeremy Burgess/Sclence Photo Library; br ® Alired Pasicka/Scionce Photo Library; p.87 © David Hughes/Hemera Thinkstock; p.88 © Paul Fleer/Alamy; p.90 be © Charles D. 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Chilleaid P.6; p.9s P-12; p.16; PBL; P.8G; P.87; p.8B; p.L18; p.127: p.129, p.130, p.145: p-A4T, p.158; p.1GI: p.205; p.206; p.215; 216; p.224: p.225; p.255; P.255: p.256; p.269; p.283; p.300; p-301; P-519; p.320; P.321; P.375: PAT: PAT: PAST: P.ATT: ATS: p.529: p.530 Every effort has been made to trace all copyright holders, but if any have been inadvertently overlooked, the Publishers will be pleased to malce the ncceseary atrangements atthe Fst opportunityIntroduction Cambridge International AS and A Level Chemichy ses some of the content from Chemistry for Advanced Level, but thas been completely revised by the original authors to cater for those students and teachers involved with the Cambridge Invernational Examinations syllabus 9701 ‘The book has been fully endorsed by Cambridge Intemational Examinations, andl i listed as an endorsed textbook for scents studying ths syllabus. The syllabus ‘content has been covered comprehensively, and has been separated into AS material, which comprises Topies 1-19, ‘hilt the A Level material is dealt with in Topics 20-30 All the Learning ouitcomes specified in che syllabus are Included in the hook. Af the stat 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 answer, 10 illustrate the concepts recently introduced. These are followed by a few ‘Now try this’ questions, allowing suidents 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 ist of key reactions where relevant Finally, several past examination questions have been selected that ilustrite how the subject matter of the Topic thas been assessed in the past. Answers to these questions ‘will be Found on the Teachers! CD-ROM ‘To allow students andl teachers locate easily the various aspects of the subject, the onder of Topics is a logical one, ‘starting withthe essential basi principles of physical chemisry and then inirlucing the application of those principles fsaly to inorganic chemisty and then to organic chemistry. No teaching order is implied by this, however Tr has been found that axing principles and applications with facmial content ‘thionighout the course is often the best way to achieve a deeper and broader understanding of chemisty, Teachers are recommended to consul the schemes of work published by ‘Cambridge International Examinations on their website for some suggested methods of delivering the subject material, A feature of the new 2016 syllabus isthe intreuction of Key concepts. These are essential ideas, theories, principles ‘of mental tools that help learners o develop a deep Understanding of their subject and make links between the different topics, Although teachers are likely 1 have these in mind at all times when they ae teaching the syllabus, we have included in the text the following icons at points whece the Key concepts relate to the text. Atoms and forces ~ Matter is built from atoms intecacting and bonding through electrostatic forces. The structure of iter affects its physical and chemical propeaies, and inflvences how substances react chemically Experiments and evidence ~ Chemists use evidence sained from observations and experiments to build models ‘and theories of the structure and reactivity of materials e 8 Patierns in chemical behaviour and reactions ~ By Identifying pattems in chemical hehaviowr we can predict the propetios of substances and how they can be transformed into new substances by chemical reactions. This allows us to design new materials of use to society. (Chemical bonds — the understanding of how chemical bonds are made and broken by the movement of electrons allows us to predict patterns of reactivity. e. 8 Energy changes ~The energy changes that take place ducing chemical reactions can be used to predict both the lextent and the rate of such reactions “This hook has heen designed to he accessible to all AS and A Level students, but also attempts to go some way towards satisfying the curiosity of the able student, and to answering the questions of the inquistiv. although based firmly on the AS and A Level syllabus of Cambridge International Examinations, teachers and students will ind the subject matter and style of questions make i suitable {or several other syllabuses. The subject mater 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 ext in panels, and can be bypassed on first reading “The majonity of students starting an AS course in ‘chemistry come from 2 backgroud of IGCSE Chemisy ‘oF Combined Science, and the inkial chapters sat at a level and a pace that is sited to all such students, Some students come to AS chemistry with the belif that they wil find the mathematics dificult, although the mathematical concepts required for chemistry are simple in principle and Jew in number, We hope to demonstrate tha, 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 IGcse* students also sometimes consider that chemistry isa subject fll of dificult concepts. Ths is nt tae. Most of |‘chemistry is based on the very simplest idea of electrostatics = like charges repel, unlike charges atract. When the subsle ramifications of this generalisation are studied during the AS and A Level courses, students should constantly remind themselves of the inherent simplicity ofthis relationship, Chemisty is the central science, atthe crossroads of biology and its associated disciplines on the one hand, and phiysies on the other: Chemistry relies on physics for its Uunderstanding of the fundamental building blocks oF matte, and biology relies on chemisry for an understanding of the ‘enicnares of living organisms, and the processes that go oa inside thom that we call life, Standing at this crosscoads, the chemist is uniquely positioned 10 understand, and make significant contributions to, many interdiseiplinany areas of ‘cocrent and future importance. The chemisty-based sciences of biochemisty, genetic engineering, pharmacology, andl polymer and material science will all make increasing ‘contibutions to our physical and material well-being in the future. Chemists are also playing a key role in the fight against industrial society's pollution of our envionment ‘We hope you enjoy discovering the secrets of chemistry during your A8/4 Level course, Peter Cann Peter Hughes (® IGCSE is the registered trademark of Cambeidge International Examinations sow the Cantngeoxring cts cote bythe 30 Tes eee 1 [eis 16 [rat 2 [zras wp 3 [pa saas0 is | @ isiab ies @ fauaaasamas, [19 ]- a2 630.08 = [eae 529 20a Sh, Ha, 53541010) & [isa 7a | > [@e-m) 926,83 7 [asm,61.629 | 2 [720473 20) a ab, aaa, | 2 [62.63.68 aad ofa be |b), 122, 3 BA us 1 [aasasa |B [wa isave totae, 131,122 TW [tens 25 [7d 9H) 12 | 1.5b), 14.12),b), che), 27 | 20.1, 20.2, 203 tants B [si 15308 Ea REE ve [raa.ts2 va |i. 222,723,724 bs i [ia t62 30 [a3This page intentionally left blankAS Level Physical chemistry 1 Chemical formulae and moles inthe levels emia!) (eaming outcomes ere etten eMA | by end cftstone yous babe o valencies (or combining powers) of ‘atoms and ions. We also introduce the chemists’ fundamental counting unit, the mole, and show you how ‘1.4a) define and uso the terms relative atomic, isotopic, molecular and formula masses, bbasad on the "scale 4124) deline and use the term mole in terns ofthe Avogacio constant, {.a) define and use the terms empirical and molecular formula Uiconibe ales cer iree ier {Lb) calculate empircal and molecular formulae, using combustion data or composition ‘empirical formulae and the amounts yas SIRE ee) 15a) orite and construct balanced equations rari chloe) feiss ores 115b) perform calculators, including use ofthe mole concept, involving reacting open col ena eset mass (rom formulae and equations), volumes of gases (ein the burning of the worked examples, and then try hhysrocarbors), volumes and concentrations of solutions, and relate the number of the ‘Now try this’ questions that ‘igatficant figures in your answers to those given or asked for in the question follow them. 115¢) 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 matter, we mean the substances that we can see, feel, touch, taste and smell ~ the stuff that males up the ‘material world. Passive observation forms only a small part of a chemists interest fn the world, Chemisss are actively inquisitive scientists. We tr Co understand why matter has the properties it does, and how 10 modify these properties by changing ‘one substance into another through chemical reactions Chemistry as a modern science began a few hundred years ago, when chemists started to relate the observations they made about the substances they were investigating to theories of the structure 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: @ the atoms of different clements were different from each other the atoms of a particular clement were identical to each other 4 all atoms stayed the same over time and could be neither created nor destroyed all mater was made up From a relatively small number of elements (Dalton thought, bout 50) combined in vardous ways Figure 1.1 iohn Dalion, who fist suggested Although Dalton's theory bias had to be mocified slighty, is sil a useful starting tha madein Atomic Theory point for the sul of chemistryPHYSICAL CHEMISTRY Since that time chemists have uncovered and explained many of the world's mysteries, from working ont how elements are formed within stars to discovering. how our genes replicate, On the way they have discovered thousands of new methods of conveiting one substance into another, and have made millions of new substances, many of which are of great economic and medical benefit the human race (see Figure 1.2) Figure 1.2 some examples ofthe economic medical and agrcutural bereits of chemisty Classifying matter - elements, compounds and mixtures (Chemists classify matter into one of three categories. '¢ Elements contain just one sort of atom, Although the atoms of particular element may lifer slightly in mass (see Section 2.3), hey all have identical chemical seactions. Examples of elements include hydrogen gas, copper metal and diamond crystals (hich are eashon), {¢ Compounds are made up from the atoms of ro or more different elements, boncled together chemically. The ratio of elements within a particular compound is 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 it up. Examples of compounds inchude sodium chloride (containing sodium and chlorine ions), water (containing hydrogea and oxygen atoms) and penicillin (containing hydrogen, carbon, aiteogen, 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 proportion, and the proper ties ofa mixture are often the sum of, oF the average of, the propenies of the individval components, Examples of mistuces inchide aig, sea water and alloys such as brass, 1.2 Intensive and extensive properties ‘The propenies of matter may be divided ito two groups. f¢ The extensive properties depend on how much mater-we are studying. Common examples are mass and volume —a cupful of water has less mass, and less volume, than a swimming pool (¢ The osher group are the imensive properties, which do not depend on how much matter we have. Examples inchide temperature, colour and density. A copper Using the 4: values O= 16.0, Mg = 240, S= 3200, calculate the amount of substance {in moles) in each ofthe following samples. 1 2409 of caggen 2 2409 of sulfur 3 16.09 of magnesium 1 =6,022 « 10 mot! Now try ti Calculate the amount af substance (in moles) in 1a sample of uranium that contains 1.0 10% atoms 2 a sample of fluorine that contains 5x 10" atoms Chemical formulae and moles Ie follows from the above definition thar there is a clear relationship berween the ‘mass (mi of a sample of aa element and the number of moles (n) it contains arount(n makes) =« TS co) amp What i the amount (in moles of carbon in 30g of carbon? Use the value 4,carbon) = 12.0 to wrt its molar mass, and use equation (1) above: m=30g and M=120gr0l" ee ‘Togmort 25mol er As we saw on page 5, the actual masses of atoms are vory smal. We would therefore ‘expect the muimber of stoms in & mole of an clemeat to be wea lage. This is indeed the ease. One mole of an clement contains «staggering 6.022% 10" atoms (six duunded and two thoussnd two hundred milion milion mlion atoms), This value is called the Avogadro constant, symbot L “The approximate value of = 6.0 x 10 mols often adequate, and will be used fn calewlations i this book. ‘The relationship between the number of moles in a sample of an element and the amber of atoms & contains sa follows: number of atoms = Lx number of roles of N=Ln How many hydrogen atoms ae there in 1.51mol of hydrogen ators? Answer Uso equation (2), and the value of Lgivan abow: 1=60x 102mor? and n=1.5mol $2 N=60x 102mor x 1.8mol = 9.0% 102 1.6 Atomic symbols and formulae ach clement has a unique Symbol. Symbols consist of either one or two letters. The fictis always a capital letter and the second, if present, is always a lower-case letter, ‘This rule avoids confusions an ambiguities when the symbols are combined to make the formulae of compounds. For example: {the symbol for hydrogen is H {the symbol for helium is He (aot HE or 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 carbon and one of oxygen).PHYSICAL CHEMISTRY How many atoms in total are present in ‘one formula unit ofeach ofthe following compounds? NHN} 2 NoxCriO> 3 KCHSOd2 4 Calin06 5 NasFetC20.), Symbols are combined to make np the formulae of compotnds. f more than ane atom ‘of a panicilar clement is present, ts symbol & followed by a subscript giving the numer of atoms ofthat clement contained in one formula unit 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 («wo atoms of hydrogen combined with one atom of oxygen) {the formula of phosphori(V) acd is H,PO, (Uhree atoms of hydrogen combined ‘with one of phosphorus and four of oxygen). Sometimes, especially when the compound consists of ons rather than molecules Gee Tapie 4, groups of atoms ina formula ate kept together by the use of brackets, TF more than one of a particular group is presen, the closing bucket i followed hy a subscript giving the mimher of groups preseat. This practice males the connections berween similar compounds clearee. For example: 6 te formula of sodium nate is NaNO (one sodium on, a combined wil ene rate Jon, NO}, which consbis cf one mitogen atom combined wilh uee cxygen atoms) the formula of calcium nivate is CatNO,); (one calcium fon, Ca, combined wih two nite ions [Note that in caleium niteate, the formula unit consists of one calcium, wo nitrogens and shx oxygens, bur its not writen as CaN,Os. This Formula would not make cleat the connection berween Cx(NO.)s and NaNOs, Both compounds are nates, and both undergo similar reactions of the aitate ions ‘The formulae of many fonic compounds can be predicted if the valencies of the fons are known. (The valency of an ion is the electrical charge on the ion.) Similac, the formulae of several of the simpler covalent (molecular) compounds can be predicted if the covalencies of the constituent atoms ate kaown. (The covalency of fan atom 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 how to use them, are given on pages 49 and 79. How mary atoms of each element are presentin one formula unit of each of the folowing ‘compounds? a AKOH)s b (NHhS0, Answer 4 The subscript aftar the dosing bracket multiplies all the contans ofthe brackat by threo, ‘There are therefore three OH (hycrexide) oroups, each containing one oxygen and one lnydrogen atom, making a total of three oxygen atoms and three hyrogen ators, ‘togethor with one aluminium atom. Here there are two ammonium groups, each containing one nitrogen atom and four lnydrogen atoms, and one sulfate group, containing one sulfur atom and four oxygen atoms. In total, therefore, there are: two nitrogen ators * eight hydrogen atoms 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 eazbon (12.0), so we can weigh out a mole ‘of a compound such as ethanol (alcohol), We Fist ced to calculate its relative ‘molecular mass,Figure 1.6 one-tenth of amole of each ofthe compoures wate, potassium dichromate (kx en sullate--water (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, C3H;0, swe have: B= 24LO) + GAD + ALO) 2x 120+6% 10+ 160 = 460 Just as with relative atomic mass, values of relative molecular mass are ratios of ‘masses, and have no units. The molar mass of ethanol is 460gmoF". For ionic and giant covalent compounds (see Topic 4), we cannot, strictly, refer to thelr relative molecular masses, as they da nce consist of individual molecules, For these compounds, we add together the relative atomic masses of all the cclements present in the simplest (empirical) formula, The result is ealled the relative Formula mass, but is givea the same symbol as relative molecular mass, My Just as swith molecules, the mass of one forma unit is called the molar mass, symbol A For example, the relative formula mass of sodium chloride, NaCl, is calculated as follows: Bie= ANA) + ACD 204355 = 585 “The molar mass of sodhum chloride is $8 Sgmor We can apply equation (1) (page 7) to compounds as well as fo elements, Once the: ‘molar mass has been calculated, we can relate the mass of a sample of a compound! to the number af moles it contin, € Cusd,5H,0 2503 7m Calculate the relative molecular mass of glucose, CeH1z0e. Answer M,= 6A{C)+ 124,(H)+ 640) =6x 120+ 12x 1046x160 720+ 120+ 96.0 180.0 = urPHYSICAL CHEMISTRY 1 Coleulote the relative formula mass of ‘ch ofthe fllowing compounds. (Use thelist of Ayvaluesin the data section fon the CD) «Iron sulfate, FeSO b calcium hydregencartaonate, CaQCOnle « ethanoie acd, CoHs02 4 ammonium silat, (NH4) SOx «© the complex withthe formula NasfelCa0a)s 2 How many moles of substance are ‘therein each of the folowing samples? 4 209 of magnesium oxide, MgO bb 0g of methane, CH «609 of calaum carbonate, CacOs 1d 809 of cydopropene, CoH {© 1009 of sodium dichromate, NazCrO7 3 What isthe mass af aach of the following samples? 43 1'S males of magnesium sulfate, NigSO bb 0.333 mote of aluminium chloride, alc Calculate the empirical formula of each of the following compounes 1 asullide of copper containing 3.979 of copper and 1.00g of sulfur 2 ahydrocatbon containing 81.8% catbon and 182% hydrogen 3 a mixed oxide of on and calelum \which contains 51.9% iron and 18.59% calcium by mass (the rest being caygen) How mary moles are there in 609 of glucose? Answer CConert he relative molecular mass calculated in Worked example 1 to the moar mass, M, ‘and use the fomula in equation (1: 09 M= 180 gmol A mole of what? ‘When dealing with compounds, we aced to dafine clearly what the word ‘mole’ refers to. A mole of water contains 6 108 molecules of H,0. But because each ‘molecule contains two hydrogen stoms, a mole of 140 molecules will contain rwo moles of hydrogen atoms, that is 12 x 10 hydrogen atoms, Likewise, a mole of sulfuric acid, H,50,, will contain two moles of hydrogen atoms, one mole of sulfur atoms and four moles of oxygen atoms. A mole of calcium chloride, CaCh, contains twice the number of ehloride ions as does a mole of sodium chloride, NaCl. Sometimes this also applies to elements. The phrase ‘one mole of chlorine! s ambignous. One mole of chlorine molecules contains 6 10" Ch unis, but it contains 12 x 10® chlorine atoms (2mol of CD. 1.8 Empirical formulae and molecular formulae ‘The empirical formula is the smolest formula that shows the relative numberof atoms of ‘each element present in @ 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 ratios of atoms ‘The steps in the calculation are as follows, 1 Divide the percentage Cor mass) of each element by the elements relative atomic 2 Divide each of the figures obtained in step 1 by the smallest of those figuees 3 Ifthe results of the calcultions do nat approximate to whole numbers, auliply them all by 2 to obtain whole numbers (In rare cases we might have to muhiply by 3.06 410 obzain whole aumbers) rk CCaleuate the empirical formula of an oxide of ito that contains 70% Fa by mass. ample Answer ‘The axide contains ron and oxygen only, so the percentage of oxygen is 100~ 70. Following the stops above: 70 vrege=125 o:B1a75 128, 1875 2 Fe 128, L878, TB-100 0: 5B 1.50 23 Multiply both numnbors by 2: Fo=2, O= 3, Therefore the empirical formula is FeaOs 5Chemical formulae and moles ‘The molecular formula is either the same as, ora simple multiple of, the empirical formula. For example, the molecule of hydrogea peroxide contains ewo hydrogen atoms and two oxygen atoms Its molecular Formula is HO, but ts empicical Formula is HO. ‘The molecular formula tells us the actual number of atoms of each element 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 measirable change in mass atall. Many obvious events can often be seen taking place — the evolution of heat, flashes of light, chaages of colour, noise and evolution of gases, But despite these “sometimes dramatic signs that a reaction is happening, the sum of the masses of all, the various produets 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. I cin be illustrated simply bur effectively by the Following experiment. Figure 1.7 During the formation of lel The conservation of mass A small test tube has a length of cotton thread tied round its neck, an is half filled ‘with lead) nitrate solution. Ie is carefully lowered into a conical flask containing potassium iodide solution, taking care not to spl ts contents, A bung is placed In the neck of the conical flask, so that the cotton thread is trapped by is side, as, shown in Figure 1.7, The whole apparatus is then weighed “The conical flask is now shalcen vigorously to mix the contents, A action takes place, and the bright yellow solid lesa) iodide is formed. On re-weighing the conical Nask with its contents, the mass is found to be identical tothe inital aes lead riteate solution potasium yellow precipitate Todide Bf lend) ouide mmassbefore= 286.7469 *NNOP ass after = 246.746 3 Balanced equations ‘The reason why the mass does not change during a chemical reaction is because no atoms aze ever created or destroyed. The number of atoms of exch element is the same at the end as at the heginning, All that has happened is that they have changed WPHYSICAL CHEMISTRY their chemical eaviconment. In the example in the experiment above, the change can be represented in words as: lead) nitmte_, potessiam iodide _, solid lead) potassium oikate = - te = | \ 4 i x \ “x4 ( sy z 4 4 “There are several steps we must cany out to convert this Word equation into 2 balanced chemical equation, 1 Work out and write dowa the formula of each of the compounds in turn, and describe ts physical state using the correct one of the following four state symbols, @=ms M=liquid G)=s0lid Gq): For the above reaction: lead) nitrate solution is PhNO»)aq) ‘potassium iodide solution is KTGaq) solid lead) iodide is PIs) potassium nitrate solution is KNO,(aq) yueous solution (dissolved in wates) “The equation nowr becomes PHINO,),(aq) + Klleq) > PHI,G) + KNO(sq) 2 The next step fs 1 balance the equation, That is, We must ensene that we have the same number of atoms of each element an the right-hand side as on the lefhand side, Looking atthe equation ia stop 1 above, we notice that there are two iodine atoms of the right, in Pb, but only one on the lef, in KI Also, there are two nitrate groups on the left, in Pb(NO})>, but only one on the sight, in KNOs, We can balance the iodine atoms by having two formula units of KI oa the let, that is 2K1. (Note that we cannot change the formula to Kl ~ that would not ccorrecly represent potassium iodide, which always comtains equal numbers of potassium and iodide ions.) «We can balance the nates by having two formula units of KNO, on the sgh chat is 2KNO,, This also balances up the pocusiom atoms, which, although originally the same on both sides, became unbalanced when we changed KI 10 2KT in step b. ‘The fully balanced equation is now: PHINO, saa) + 2KIlaq) — PbI,) + 2KNO,(0a) leis clear that we have neither lost nor gained any atoms, but that they have swapped pattness ~ the iodine was criginally combined with potassium, but has cended up being combined with lead; the nitrate groups have changed their partner from lead to potassium, 121 Copy the following equations and balance them, 4 Halg) + 0x9) + 2010 b 1x5)+ Chia) Chas) © NaOH(aq) + AKOHIR) NaAlOaq) + H201) HeSlq) + SOxe) + Sis) + HOD © NHi4q) + Oalg) > Nala) + #200) 2 Write balanced symbol equations for the following reactions. ‘2: magnesium carbonate + magnesium oxide + catbon dioxide b lead +slvor nitrate solution —» load ritrata solution + svee « sodium oxide + water ~» sodium yori solution «4 iron(l) chide + chlorine (Cla) iron chloride « iron sulle + sodium hydroxide —+ iron hydeoxide-+ sodium sulfate Chemical formulae and moles White the balanced cherica equation forthe folowing rection: Zinc metal + hydrochloric aid -» zine chlo solution + hydrogen gas Answer Folowing the stops gven above: 1 Zincmatal is Zn. Hydrochloric aide Hctfag) Zinc chloride solution i rca. Hydrogen gasis Hi) hydrogen, lke many non-metalicelemen, eds in molecules mad up of two atom) The equation now becomes 2nis-+HCkaq) > Zag) + HG) 2 There aro two hydrogen atoms and two chlrin ators on the right, but only one of each ofthese onthe lf 'b We can balance both of them by just one change —having two formula units of HCLon thelett The fly balanced equation is now: Zn\s) +2HCKaq) > ZnCh(eq) + Halo) 1.10 Using the mole in mass calculations {We are now in a postion to loolk at how the masses of the indiicual substances in 2 chomical equation are related. As-an example, take the reaction berweon marble chips (calctum carbonate) and hydeochloric ace: (CaCO) + 2HCMag) + CaChGeq) + H,000 + CO) ‘When this reaction is caied 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 on page 1 the overall number of atoms does not change dusing a chemical reaction. Rather, it due to the fact thatthe gaseous Gabon dioxide produced escapes into the ait.) We can use the knowledge gained in this topic 1 calculate the answer tothe following question: '¢ By how much would the mass decrease if 50g of marble chips were completely reacted with an excess of hydrochloric acid? ‘We use the following steps! 1 We can use equation (1) (page 7) to calculate the number of moles of calcium carbonate in 50g of macble chips: = 0.50mol of CaCO, 2 From the balanced equation above, we see that one mole of calcium carbonate produces one mole of carbon dioxide, Therefore the number of moles of carbon dioxide produced isthe sime as the number of moles of calcium carbonate we started ovth, namely 0.50mol of carbon dioxide, 3 Lastly, we can use a rearranged form of equation (1) to caleulate what mass of cathon dionide this comresponds to, BPHYSICAL CHEMISTRY n= wo m=nxt — -MCO)= M : 2.042% 160-440 4.ogmor! 50mal also m= 050ml x 44.0 gmor" 0g ‘The loss in mass (due tothe cathon dioxide being evolved) Is 22.08. ‘The three steps can be summarised as shown in Figure 19. Figure 1.9 Finding the mass of 2 ps from the mass of reactant, of vice versa ‘ass of first reactant or product sk moles of fst reactant or product |___, [ati rem balanced eguation| i moles of second reactant or product| | [pan xm | ‘mass of second reactant or product ‘The highly exothermic thermit reaction (sae Figure 1.10) is used to weld together the steel rails of ralway tacks. lt involves the reduction of ron(l) oxide to ron by alia, 2s) +Fep03S) > Alz046)-+ 2Fls) Figure 1.10 weld together the Use the char in Figure 1.9 to calculate what mass of aluminium is needed to react completely with 10.09 of iron) oxide1 What mass of silver wal be precipitated \when 5.09 of copper are reacted with an excess of silver nitrate solution? CuG)-+2AgNO4aq) + CulNOs)e9) + 2Aa(s) 2. What mass of ammonia wil be formed when 50.09 of nitrogen are passed ‘through the Haber process? (Assume 100% comeson) xa) + 3Hy(Q) + 2NHYa) 1 What volume of carbon dioxde (measured at room temperature and pressure) wil be produced when 5.09 of calaum carbonate are decomposed by heating according to the folowing equation? acd; + €a0+ 0, 2 Sulfur dioxide and hydrogen sulnde 9280s react according to the equation: 2H,S + $0; 24,0 + 35 What volume of aufurdloide will be needed to react completely ‘with 10Dcm? of hydrogen sulfide (both volumes measured at room ‘temperature and pressure), end what ‘mass of sulfur will be formed? Chemical formulae and moles 11.6 +480 1596 5584316! 159.6amot" ‘number of moles of Koni) one (9) = 109. m6 627d 2 Fro tho blanca uation one mol of ron oxide eats with wo ok of alumina. therefore Tui of moles ein 7) = 0.06272 3 A(AI)=27.0 so M- 128mal 125melx27.0gmor 389 1.11 Moles of gases “The molar masses of most compouinds are different. The molar volumes of most solid and liquid compounds are also diferent. But the molar volumes of gases (when 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 less than a thousandth of its volume at normal temperatures (ase section 4.13). The volume of the molecules is negligible compared with the total volume, and so any variation in their indivial size will not affect the overall volume, AE oom temperature (25°C, 298K) and normal presse (Lata, 1.01 % 10°Pa 4.0m? mor the molar volume of any gas So-we ean say that volume Gin dr) molar volume av mo ‘oF volume of gas in din? = molar volume x moles of gas v=240x0 amount of gas (in moles) irked = \What volume of hydrogen (measured at room tamperature and pressure) wil be produced ‘when 7.0g of iron are reacted with an excess of sulfuric acid? Answer ‘Tho equation forthe raactions as follows: Fels) + ,50,(aq) + FeSO4(aq)+ Hale) 1 Alfe)=55.8 so M=55.89mor! amount Gn moles) of on = 700 Barer = 0.125 nol 2 From the balanced equation, one mole cf iron produces one mole of hysrogen molecules, ‘therefore: ‘number of moles of Hy= 0.125 mol 3 volume of Hy dn dm®)= molar volume x moles of Hy 4. Odir# mot" x 0.1250 Odin? CS 5PHYSICAL CHEMISTRY Figure 1.11 colours related to concentration, an intensive pron not depend on how much soltion thee & 1.12 Moles and concentrations ‘Many chemical reactions are carried out in solution, Often it convenient to dissolve a reactant in a solvent in advance, and 10 use portions as and when needed. A ‘common example of tis isthe dilute sulfuric aed you find on the shelves in a laboratory. Tis has been made up in bulk, ata cerain concentration, Sokutions are ‘most easily measured out by volume, using measuring cylinders, pipettes or buretts. Suppose we need a certain amount of sulfuric acid (thats, a ceraia number of moles) for a panicular experiment. If we know how many moles of sulfuric acid each ‘Lem? of solution contains, we can obtain the required aumber of moles by measuring cout the correct volume. For example, if our sulfuric acid contains 0.001 mal of 150, per Lem’, and we need 0.005 mol we would measure out Sem? of solution, ‘In chemistry, the concentations of solutions are normally sated in units of moles ‘per cubic decimetre (= moles per lire). The customary abbreviation is motday Cceastonaly the older, and even shorter, abbreviation Mis used. 1 Lam ofa solution coniains 1.0 mol of solute, the solution's concentration is ‘LO mold” (or 10M, verbally described as a one molar solution’). Ifmore moles ate dissolved in the same volume of solution, the solution is a more concentrated one. Likewise, if the same number of moles is cssolved ina smaller ‘volume of solution, the solution is also more concentrated. For example, we ean proche a 20moldar solution (20M, ‘wo mola’) by: 6 cither dissolving 2mol of solute in dm? of selution 6 or dissolving mol of solute in 0.5din®of solution, amount (in mols) concentration = amount (in moles)_ ‘olame oF solution Ga dav) et (or amount (in mols) = concentration x volume (in di?) na cx Unlike the mass ofa solid, or the volume of a gas, which are extensive properties of a substance (see page 3), the concentration ofa solution isan intensive propery. It ‘does not depend on how much of the solution we have, Properties that depend on the ‘concentration of 4 solution are also intensive. For example, the mice of rection between sulfure acl andl magnesium ribbon, the colour of aqueous porassium manganatetVID, the sowmess of vinegar and the density of a sugar solution do not depend on how -mich solution we have, but only on how much solic is dissolved ina given volume.1 Chemical formulae and moles 20cm? of a sugar solution contains 0.40mol of sugar. What the concentration of the solution? Answer Uso the fst equation inthe panel on page 16: Remember, 1000cm#= 1.0 dr? 50 200cm?=020dm? in the folowing solutions? 2-2Omolof ethanol in 75cm" oF How many gras of sat, NaCl, need to be clssolved in 0.50dm? of solution to make a (0.20 moldi~ solution? rolaton 539 dium catonate,NaxCOa, | Answer in 2.0dm’ of solution ‘Use the second equation in the panel on 16; «¢ 0g of ethanoic acid, C2Ha02, in ae P ae mala ‘800cm? of solution mY 2 2 How many molesofsolte areinthe | 7 0Z0meldny <0 Sd following soktions? 2 0SDdm’ of 15moldnr? solution | Now use equation (1) (page 7) to convert moles into mass: of sulfuric acid n= = © m=nxM b 22cm! of a 20moldn solution of a sods hydroxide m=0.10molx58Sqmol" « Soar fa ohn contig 205 9 of salt, NaCl assum hyCrogencarbOnte, |S KHCOs, por dr? ‘We shall come across the concentrations of solutions again in Topic 6, where we look at the technique of tation 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 to give the prochcts and the nitios {n which the products are formed. This is called the stoichiometry of the reaction ‘Most calculations involving reactions can he broken down into a set of three eps (ee Figure 1.12), similar to those described for mass calculations on page 14 Figure 1.12 Calculations inohing the pure tae Gpiilfns inass of solid A, orvolume of gas A, orvolume (or cancentration af slution containing A | ‘moles of reactant or product A Ceeeeete=| “oles of reactant or product + ‘ass of solid Bor volume of ga cor volume for concontration) of rlution containing B 7PHYSICAL CHEMISTRY Use Figure 1.12 and the A velues in the data section on the CD to answer the following questions. 11 What volume of hydrogen ges wil be given off when 2.39 of sodium metal react with water? 2Na(S)+ 2HOX > 2NeOHag) + Hola) ‘The equation forthe complete combustion of methane, CH n oxygen i: (CH4(Q) + 20316) + COxo)+2H,0(a) Calculate the volume of oxygen needed to bum 4.0g of methane. What volume of 0.50 mold? sulfuric ack, H;S0,, is needed to react exactly with 5.0g of magnesium, and what volume of hydrogen wl bo ovolad? Magis) + H»S0ylaq) » MgSO,ea) + Hla) \What mass of sulfur will be precipitated when an excess of hydrochloric acid fs addad 0 100m? of 0.20moldm? sodium thiosulfate solution? 'NazS,0xaq) + 2HCKag) + 2NaC\aa) + SO2{g) + HOt) + Sia \what would be the concentration of the hydrochloric acid produced i all the hydrogen chloride gas from the reaction between 50g of pute sulfuric acd and an ‘excess of sodium chloride wes collcted in water, and the soltion made up toa volume of 200m? with water? NaCl] + :SO))—+ NaHSOU6) + HCKa) © Chemical equations reflect this when balanced, they contain ‘the same numbers of atoms of each element on thar left-hand 'e Atoms and molecules are smal and light - about 1 x 10min se, and about 1 10°g in mass Relative atomic mass and relative molecular mass are defined in tarms ofthe mass of an atom of carbor-12. ‘One mole is the ammount of substance that has the sarne tnunber of particles (atoms, molecules, et) as there ae atoms in 12.0009 of carbor-12 The relative molecular mass, M, of @ compound is found ‘by summing the aatve atomic masses, A, ofall the atoms present. The empirical formula of a compounds the simplest formula ‘that shows the relate number of atoms of each element presen inthe compound, The molecular formula tels us the actual number of atoms of ‘each element present in a molecule ofthe compound, ‘Chemical reactions take place with no change in mass, and no change inthe total number of ators presen. and right-hand sides. ‘The following equations alow us 1 cakulate the number of ‘moles prsant in a sample: ‘© amount Gn roles) = ron M volume of gas dh dm!) 7a0 er Tmolarmass ‘© amount in moles) concantraton of solution in mal) cx concantraton of solution Gn mold ar volume inden?) © amount inrmoles) ¢ amount Gnmoles)Chemical formulae and moles Examination practice questions Please see the data section of 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 twa simple compounds of zinc that ‘could each react with lute sulfuric aid to produce zine sulfate 2) bb A simple experiment to determine the value of xin the formula ZnSO,.14,0 is to heat it carefully to drive off the water 2750 ,.44, 01s) -+ 2nS04(9)+ x#4,0%0) ‘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 to fi and ili to calculate the value of x in 2nS0, 4,0. m For mary people, an intake of approximately 15 ma per dy of zinc wil be sufficient to prevent deficiencies Zinc ethanoate crystals, (CHjCOqZ7.2H,0, may be used in this way. i What mass of pure cystaline zinc ethanoate (M,= 2194) will need to be taken to obtain a dose ‘of 15 mg of zinc? ii this dose is taken in solution as § em? 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 8701, Paper 21 Q1 November 2012) 2 Washing soda is hydrated sodium carbonate, 1NajCO,xH,0. student wished to determine the value of x 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 flask, 25.0cm! of this solution reacted exactly with 35.8cm® of 10.100moldnr? hydrochloric acid and carbon dioxide was produced. ‘a1, Write a balanced equation for the reaction between Na,CO, and HC. ii Calculate the amount, in motes, of HCI in the 35.8¢m™ of solution used in the titration. Use your answers toi and ito calculate the amount, in moles, of Na.COs in the 25.0cm’ of solution used inthe tration, fy 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 5.139 cof washing soda crystals je bb Use your calculations in a to determine the value of xin NaCO4.1H,0. ai [Cambridge International AS & A Level Chemistry 9701, Paper 23 Q2 June 2012) 3a Acompound containing magnesium, slicon and oxygen is present in rock types inlay. A sample ofthis compound ‘weighing 5.27q was found to have the folowing ‘composition by mass: Mg, 1.829; Si, 1.0549; 0, 2.409. 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 Mo(OHys) + 2HCKaq) + MgCl faq) + 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 me, of HCI used. m1 ii Determine the amount, in mal, of Mg[OH) present in the table. a il Determine the percentage by mass of Ma(OH)s present inthe tablet, e) OCR Chemistry A Unit F321 Q2 (part) May 2011) 19AS Level Physical chemistry 2 The structure of the atom oa eeEes Learning outcomes the proton and the neutron. We By the end ofthis top you should be abe to: Poca aed Pepper eae, 1.3) analyse mass spectra in terms of isotopic abundances (pat, see also Topic 29), they ace arranged inside the stom. Calculate tho relative atomic mass of an elemont given the rolatwo abundances ee ee 1.3) calculate the relative ato Fan elemant given the 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) deiuca the behaviour of boars of protons, nautzons and alectrons in olctic ils ‘sotopo, and describe how thor relative ‘abundances can be measured using the mass spectrometer, We outline the types of energy associated 2.1¢) describe the distribution of mass and charge within an atom withthe particles in chemistry 214) deduce the numbers of protons, neutrans and elactonspresantln bath atoms and ‘Against this background, we look ions gen proton and nucleon numbers and charge at how the electrons are arranged | > 23) qexribe the conttaion of protons and neutons to atomic nul n terms of around the nucleus and how this proton number and nucleon number arrangement explains the positions | 2.24) dinguis between topes on th bass of cferertrumbers of neutrons resent cof elements within the Periodic 2.20 ecogrise and use the symbol JA fr sotopes, where" the nickeon number Table, their ionisation energies and ithe proton number and the sizes oftheir atoms. ’ 2.3a) descibe the number and relative enargias ofthe , p and d orbitals for the principal quantum numbers 1,2 and 3 and also the 4s and ap orbitals, 2.36) describe and sketch the shapes of s and p orbitals 2.30 state the olectronic configuration of atomrs and ions given the proton number and charge, using the convention 15232298 etc 2.34) oxplein and usa the term ‘onksation eneray, explain the facters influencing the Tonisation energies of elements, and explain the trends in ionisation energles ‘across a Period and down a Group of the Periodic Tele (see aso Topic 10) 2.3e) deduce the electronic configurations of elements from successive ionisation energy data 2.38) intorprot successive ionisation energy deta of an element 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 tem ‘atom! (hich fs derived from the Greek word meaning ‘cannot be cut, in around 40%, his idea of matter being compasex! of small particles was dismissed by Arise, ‘Because Aristotle's reputation was so great, Democritus’ atomic idea was ignored for ceaturies. Ir was nct wasil 1808, when Joba Dakon published his Atomic Theory, that the idea cf atoms as being indivisible constituents of matter was revived. Dalton suggested that all the atoms of a given element were identical © each osher, but differed from the atoms of every other element. His atoms were the smallest parts of an cloment that could exist. They could not be broken down or destroyed, and wore themselves without sictice 20Figure 2.1 Emest aut ans the in atom: Figure 22 1 mth picture century for ight oe int The structure of the atom. For most of the nineteenth centiry the idea of atoms being indivisible ted in well ‘with chemists ideas of chemical reactions, and was readily accepted. Even today it is believed that atoms are never destroyed during a chemical reaction, but merely ‘change their partners. However, in 1897 the physicist JJ. Thomson discovered the frst sub-atomic particle, that is, 2 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 electical charge. What is more, he found that under the conclions of his expetiment, atoms of different elements produced identical elecyon particles. 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 celecrons they rust also contain particles witha postive charge. An smportant ‘experiment cartied out in 1911 by Emest Rutherford (a New Zealander), Hans Geiger (4 Germ) and Ernest Marsden (an Eaglishesan) showed thatthe pos atom is concenteated into an incredibly small nucleus sight in the middle of it. They estimated that che diameter ofthe nucleus could aoe he greater than 0.00001 times that cof the atom itself. Eventually, Rutherford was able ta chip away from this nucleus small positively charged particles. He showed that these were also identical to each ether, no matter which element they came from. This postive particle i called the proton. I is smuch heavier than the electron, having nearly the mass of the hyerogen atom, charge in the se-was ancther 20 years before the lst of the three sub-atomic particles, the neutron, ‘was discovered. Although its existence was fist suspected in 1919, it was not until 1952 that James Chadwick eventually pinned it down. As its name suggests, the neutron is electrically neutral, but tis relavely heavy, having about the sime mass as a proton, Scientists had therefore to change the earlier pisure of the atom, In a sense the pcture had hecome more complicates and were mace up of other, smaller partices. But looked at in another way i had become simpler ~ the 99 oF so diferent types of atoms that are nceded to make up the various elements had heen replaced by jst thice sub-atomic particles. It tarns ‘out that these, indifferent amounts, make up the atoms of all the different elements showing that atoms had an internal structure, most of the volume ff the atom Ie occupled by the electrons tho mucous is very smal ‘contain te protons find the neutrons aPHYSICAL CHEMISTRY Table 2:1 The rerio the sub-atomic arte Nea that ho mass the st roe Seger late to the ras an atm of carbon 12 These haces ate often led Ile fo the mass of the potion instead when the relative mass of the electron & —L., andthe elathe asses ofthe proton an neuton see beam of particles Figure 2.3 Tho behavour of protons, neutrons and electrons in an electric Held Table 2.2 The relate abundance of some botopes Tho isotopes ofan clement diffor in thor ‘composton in only one respect - although they all contain the same numbers of clecrons and protons, they have different rhumbers of neutrons. 2 2.2 The properties of the three sub-atomic particles ‘Table 2. lists some of the properties of the three sub-atomic particles. electrical chargefcoulombs =loxio" — faicxio™ [0 charge (elatve to that of te proton) [1 # a mass iret [rex i [ers rmassam (ee section 1.8) Saasxiot [1007 11008 ‘Because oftheir relative masses and charges, the three particles behave diferently in aan electric field, as shown in Figure 2.3. Neutrons are undeflected, being electrically neutral. Protons are attracted towards the negative pole, and electrons towards the ‘positive pole, If their initial velocities are the same, electrons are deflected to 2 greater extent than protons because they are much fighter “The pictare of the stom assembled from these chservations is as fllons 4 som are smal, spherical stcrues with diameter ringing fom 1 10"!m to 3x10 m. The particles that comabute to the tom's mass (protons and neutoas) are contained within a vory stall cental avcleus hat has a ameter of about 1 10m 4 The clectoas osaupy the segion around the cleus. They are tobe fod in the space Jnsie the ato but ouside the nucleus, whch is alos dhe whole of the am, 4 Allthe atoms of a particular clement contain the sume auinber of protons. This ako equals the numnber of electrons within thove atoms. The atoms ofall elements except hydrogen also contain neuons. These are in the rueleus along with the protons, Almost the only effect they have on the properties ofthe atom isto increase is ras 2.3 Isotopes Atthe same time as Rutheiford and his team were finding out about the structure of the aucleus, it was discovered that some clements contained atoms that have different ‘masses, but identical chemical propetties, ‘These atoms were given the name isotopes, since they occupy the same (io) place (epos) in the Periodic Table. The fit isotopes to be discovered were those 6f the unstable radioactive element thorium, CThosium is element number 90 in the Periodic Table.) In 1913, however, Thomson was able fo show thata sample of neon ‘obtained from liquid air contained atoms with a relative atomic mass of 22 a8 well as those with the ustal relative atomic mass of 20, These heavier neon atoms were sable, unlike the thorium isosopes, Many other elements contain isotopes, some of ‘which are listed in Table 22 ‘boron-10 100 20% ‘oron-11 no 0% neon-20 200 31% neon-22 20 2% magnesiu-28| 200 Be rmagnesiu-25 250 10% magnesium-26 260 11% ‘Most of the narurally occurring isotopes are stable, but some, like those of ursaium ad also many artificially made ones, are unstable and emit radiation. These are called radioactive isotopes.2 The structure of the atom. 2.4 Extending atomic symbols to include isotopes ‘For most chemical purposes, the alomic symbols intsoduced in Topic 1 are adequate. If, however, we wish o refer to a particular isotope of an element, we need to speciy {ts mays number, which # the number of protons and neutrons in the nueleus. We “utite this as a superscript before the atomic symbol. We often add the proxon umber a a subscript before the symbol. So for carbon 19 AC isthe symbol for earbon-12, whieh is the most common isotope, containing 6 protons and 6 neutrons, with a mass number oF 12 ‘© '2C is the symbol for earbor-14, whieh contains 6 proxons and 8 neutrons, with a mass number of 14. ‘The proton number (atomic number) ofan atom isthe number of protons ints rucleus. The mass number of an atom isthe sum af the numbers of protons and rae TEES How mary protons and neutrons are erin each of the following ators? » "By How many protons eecrons and Answer eta aae Tho subscript geste protan number thts the number of protons, S for oe lou carer number of preonse 6 endfor nly, rumba of potns= 32 Subsracting the proton number fram the mass number gies the numberof neutrons So for enygen, number of neutrons.= 188 = 10, ad for uranium, number of 2 neutrons = 235 ~ 92 = 143, ee 1 PN 2.5 The mass spectrometer The ae eal i Nt er RRL a a amy EL a many epeciecneter, Has mochine in wach soma tat hae boca aloe by the los of elecuons are aceclerated toa high veloc, and thei tnjectorcs (path) smelt deneeca tea ea Me Gy pong a Mec Cnc, uct eld has snlar bendog eect on moving charged pues the elect field in igure 23 (ex pape 22), Figure 24 Schama aa OFS 4 pe Some "Sahel Ny lonisation chamber pe etree 2 electron gun Figure 2.5 4 modern mass spectrometer 4 magnetic field heavier particles particles of intermediate mass | ighter particles recorder I amplifier ‘to vacullm pump 2BPHYSICAL CHEMISTRY Figure 2.6 Mass specttum of krypton Py Five procestes occur in a mass spectrometer 1 I itis not already 4 gas, the element is vaporises in an oven, 2 Blectrons are fired at the gaseous atoms, These knock off other electrons from the atoms Mig) +e 5 Mg) + 2 3 The gaseous ions are accelerated by passing them through an electric field (at a voltage of S-10kV). 4 The fast-moving ions are deflected by an electromagnet. The larger the chaege fon the ion, the larger isthe deflection. On the other hand, te heavier the ion, the smaller isthe deflection. Overall, the deflections are proportional to the ions’ chagge-fo-mass ratios. If ll ons have a +1 charge (which is usually the ease, the extents of deflection will be inversely proportional to their masses, 55 The deflected ions pass through a narrow slit and are collected on a metalic plate connected to an amplifier. Fora given strength of magnetic field, only ions of a certain mass passthrough the sht and hit the collector plate, As the (pastive) ions hic the plat, they cause a cursent to flow through the amplifier, The more tons there are, the larger the curren ‘The fons may travel a metre or so theowgh the spectrometer. In order for them to-do this without hitting too many alr molecules (which would deflect them from their course), the iaside of the spectrometer is evacuated to a very low pressure, When the situation is such that a steady stream of ions is being produced, the current through the electromagnet is changed ata steady rate, This causes the magnetic field to change in strength, and hence allows ions of diferent masses to pass successively through the slit, A mass spectrum is produced, ‘which plots ion current against electromagnetic current. This is equivalent (© relative abundance against mass number, Figure 26 shows the mass spectrum (f krypton, [A mass spectrum enables us to analyse the proportions of the various isotopes in aan element. However, by far the main use of the mass spectromecer nowadays isin analysing the formulae and stauctures of organic and inorganic molecules. We shall ‘return to this application ia Topic 29. percentage abundance 2 % 0 abo) atomic mass units1 Chromium has four stable isotopes, ‘with mass numbers 50, 52, 53 ard 54, and relative abundances 4 3%, 83.8%, 9.5% and 2.4% respectively. Calculate the average rlatve atomic mass of chromium. Usa the figures in Table 2.2 (nage 22) {calculate the average relative atomic masses of baron, néon and magnesium to 1 decimal place, (Harder lium has tw isotopes, with ‘mass numbers 197 and 193, and ks average relative atomic massis 192.23, Colculate the relative abundances of the two fsotopes. Figure 27 The two ators in adi molecule, such a5 rtrogen, behave as tho thay ae ined by a spring, which ks tern brat in and out. The two atoms can aso rotate about the conve of the bond ‘The structure of the atom Glorine consats of two isotopes, with mass numbers 35 and 37, and with relative abundances "76% and 24% respactivay. Calculate the average relative atomic mass of chlorine. Answer ‘The percentages tellus that ifwe took 100 chlorine atoms at random, 76 of them would have a mass of 35 units, and 24 of them would have a mass of 37 units, ‘total mass of the 100 random atoms = (35 x 76)+ (7 x 24), Calculate the average relative atomic mass af krypton from the table in Figure 2.6. ieee Be ced rien (78 x 0.3) + (80 x 2.3) + (82 x 11.6) + (83 x 11.5) + (84 x 569) + (85x 17.4) 70 9 5 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 made up of two components ~ Kinetic energy, which is a ‘measure of the motion of atoms, molecules and ions i a chemical subsiance, and potential energy, which is measure of how strongly these particles attract one another, Kinetic energy Kinetic energy increases as the temperature increases, Chemists use a scale of teimperature called the absolute temperature scale, and on this scale the kinetic ‘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 ‘eanslation, 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 energy. For moleciles containing two or more atoms, however, there is the pessibility of vibration. and rotation as well (sce Figure 2.7). Both these forms of energy involve the movement of stoms, even though the molecule as a whole may stay sl. In atomic gases, the principal fonm of kinetic energy is uanslation, but in more complex molecules, such as ethane, vibration and rotation become the mare important factors . BPHYSICAL CHEMISTRY “2 distance ¢ e= Figure 2.8 T septate opposte'y charg lens through a distance a force Fis required Figure 2.9 fneray is needed to lit 2 book from the floor and pat ont In solids, the panicles are fixed in position, and the only form of kinetic energy is vvbmtion. In lil, the pamicles ean move fiom place to place, thotigh moe sly than in giees, and so liquid particles have tranalational, rotational and vibational kinctic energy. Potential energy Jn studying chemical energy, we are usually more interested in the potential energy ‘ofthe system than in its kinetic enengy. This is because the potential energy gives us {mporant quanttaive information about the stengths of chemical bonds, At normal Aemperatures, potential eneray is much larger than kinetic energy’. Potential energy arses because atoms, fons and molecules atruct and epel fone another. These atraetions and repulsions follow from the basic principle of electrostatics, that unlike charges attract and like charges repel. tonic compounds contin panticles with clear positive and negative charges on them. Two positively charged ions repel each other, as do two negatively charged ions. A postive fon and 4 negative fon atract exch other. Atoms and molecules, which have no ovecll charge fon them, also atract one another (sce section 3.17) Ie requires energy to pull apart a sodium ion, Na’, from a chloride ion, CI the potential encrgy of the system increases beeause we need to apply a 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), —_c stance d force F I Tn contrat, if we start with sodium ion and 2 chloride ion separated from each ‘ther and then bring them together, the potential energy decreases, We also deczease the potential energy of 3 book if we allow i to fall from the desk to the floor. [As we shall sce in Topic 5, chemists are usually interested i the change in chemical energy that occurs during a reaction, This change is represented by the symbols AZ the Greek letier dela, A, being used to mean ‘change’. IF we look at energy changes that occur at constant pressure, which is normally the case in the laboritory, we use the symbol AH, which represents the enthalpy change of 4 reaction, The most commonly used unit of enemgy in chemistry i the kJ mor (kilojoule per mote), whese 1k} = 1000), 2.7 The arrangement of the electrons — energy levels and orbitals (On page 21 we concluded thatthe atom is made up ofa very dense, very small nucleus containing the provons and neutrons, and a much Luger region of space around the rmucleus that contains the electrons. We now turn our attention to these clecroas. We shall see that they are not elstibuted randomly inthis region of space. They occupy specific volume regions, called orbitals, which have specific energies associated with them2 The structure of the atom Energy levels and emission spectra When gaseous atoms are given enengy, ether by heating them up 10 several hundred deggees, oc by passing an electric current through them, the electrons become excited and move from lower energy levels to higher levels. Blectons in gaseous atoms can also ‘move from lower to higher energy levels by absorbing specific frequencies of light. Tis Jeaves dark absorpsion Hines in the spectrum of fight transite through the gas. It was these absorption lines that provided the fist evidence fora new element discovered in the otter regions of the Sun. Ir vas named hall, after the Geoele word forthe Sun, Ibolios. The technique of atomic absorption spectroscopy is widely tsed tol to meas accurately, for example, the conceatrtions of calcium and sodium in a blood sinaple, or the elements contained in a sample ofa ste alloy (see Figure 210) Eventually, the excited electrons lose enetgy again by falling down to lower encegy levels. During this process they radiate visible or ultraviolet light in specific ameunts as “packets called photons. We can analyse the radiated ight with a device called a spectroscope, shown in Figure 2.1. The emission spectrum shows that only a very few speciic frequencies are emited, ond these are unique to an individual element. All the atoms of a particular ‘element radiate atthe same set of frequencies, which are usually different from) those of Figure 2.10 An stom: pectomete colous of the clamonts of Gi all her elements (see Figure 2.12). Tis the process that responsible forthe fame wp 1 and 2 (see Topics 10 and 19). The observation of line specer, implying that photons of only specific energies are emited or absorbed by atoms, ‘constintes song evidence forthe existence cf discete electronic energy levels within toms, Figure 2.11 Outine dlagram showing haw roscoe work spectrum Figure 2.12 a White ight spectrom a white ight b Sodium amscon spectrum 4 Ce ene Lae equeneyO™ He 420 500 600 as wavelengehvnm 70 sto sto ‘400 be sodium vapour (yellow) frequency" Hz 4.29 500 690 28 wacclengtivnm — 700 600 500 & € cadmium vapour (turquoise green) frequency" He 429 500 600 as & warelengthvnm 700 eo 500 uPHYSICAL CHEMISTRY Figure 2.13 A ph botwaon st Figure 2.14 Part 2B sin energy & ‘The energy F of a photon of light is related to its frequency, f by Planck's equation: aig swhere tis the Planck constant, I photons of a particular frequency are being emitted by an atom, this means that the atom is losing a particular amount of energy. This energy represents the difference Dewwreen two sates of the arom, one more energetic than the other (ee Figure 2.13). S55 "= photon emitted, with energy f= $ SSS "The spectrum of the simplest atom, hydrogen, shows a series of lines at different frequencies (See Figure 2.14). This suggests that the hydrogen atom can Jose diferent amounts of energy, which in turn suggests that K-can exis in a range of energy states. “Transitions herween the various energy states cause photons to he emitted at various frequencies. These energy sates can be identified with stations where the single hylmgen clectron isin cemain oabitals, at specifi distances from the nucleus, a8 we shall sce. (ionisation) % fe & excted electron fallston=2, 5 mh. 2 photon is released 6 Arequency, 110!Figure 2.15 Energy against electon-proton {stance forthe hydrogen atom. the red ‘curve represents how the potential energy ‘ofthe hydrogen atom would vary with ‘lectron-proton distance i he energy could take on any value, 35 preted by simple ectrosiatc theory. Bu as we hava sean ove, the potential energy fs quantised, and ‘an oly take on certain values, shown in blue ‘Therefare the eecton can only be at certain (exerage) distances fom the nucleus. These are the electronic oral, and ate glen te Symbok 1,25 etc. Mote that the energy of the proton-election systom is usualy defined 2 baing 20 when the two particles are an infin cistance apart As soon as they start {getting Coser together, thy atract each ther and ths causes the potential energy ofthe system to decease, This is why the energy values onthe ys ae all negative ‘able 2.3 The numberof exits in each shall 1 2 36 ‘The structure of the atom Quantum theory “The fact that only cenain frequencies fight are emitted rather than a continuous spectrum, is compelling evidence thatthe enengy of the hydrogen atom can take only ceftin wikis, nota continuous riage of alice Tiss the basic notion of the UHM. “theory. We say thatthe energy ofthe hyelrgen atom quantised Gather thin continous), 1 can lose (or gain) energy only by les Cor gaining) a quanam cf coer ‘A good analogy is 4 staircase. When you climb a staircase, you increase your height boy certain fixed values (he height of each sep). You can be four steps from the bettors, for five steps but not fourand. half steps up. By contrast, if you were walking p 2 ‘amp, you coukt choose to be at any height you liked from the bottom. Iecurns out that the encray of al objects dsrured in staiteases ater tha in ramps, but the oboe Js large encugh, the height of each step i vanishingly small. The energy values then seem to be almost continuo, ther than stopped. [eis only when we look at very somal, objects like atoms and molecules tha the height of each sep hecomes agian. ‘The size of an encngy quantum (the height of cach step) is not fixed, however, 1 depends on the type of energy we ae considering. We shall etm to this point in Topic 29 when we study spectroscopy, We can use the methods of quantum mechanics to calculate not only the energies but also the probability distributions of ombitals Gee Figures 2.16 and 2.18, page 30). Energy levels in the atom Hydrogen is a very small spherical atom with only two paticles ~a proton and an electron. Apart from energy of movement (translational kinetic energy), the only energy it can have is that associated! with the electrostatic attraction between is (80 panicles see page 26). The different energy levels are therefore due to different clectrostatke potential energy states, where the electron is at different distances from, the proton (see Figuee 2.15). 05 08 energy kB ‘These enemy levels, associated with cifferent distances of the electron from the nucleus, are called orbitals, by analogy with the orbits of the planets at diferent ‘distances from the Sun ‘The orbitals are arranged in shells, Each shell contains orbitals of roughly the same energy. The shell with the lowest energy (the one closest to the nucleus) contains only one orbital, Shells with higher enorgies, further out from the ‘nucleus, contain increasingly large aumbers of orbitals, according to the forma umber of orbitals in nth shell = nt ‘Table 23 shows the number of erbitals ip each shell, according to this equation. 29PHYSICAL CHEMISTRY 200 2.8 Subshells and the shapes of orbitals Wa, Electron probability and distance from the nucleus 50) Unlike a planet in a ciculae orbit, whose distance from the Sua does not change, 3 aa electoon in aa orbital does not remain at a fixed distance fom the nucleus 3 Although we can calculate, and in some cases measure, the average electron s nucleus distance, if'we were to take an instintancous snapsbot of the atom, we 2 ‘would be quite likely t find the electron ether futher away From or closer tothe : nucleus than this average distance. The graph of probability of finding the electron 2 iS against its distance from the nucleus for typical orbital is shown in Figure 2.16, 2 and by contrast a similar one forthe Eanth-Sun distance is shown in Figure 2.17. q Notice that, because of the gradual falling-off of the electron probability, there i a £ 10 o finite (but very small) chance of Finding an electron a very long way from the centre & | of the atom, * os. Fen 15 108k 10. } ° 0 02 ko adnan Figure 2.16 The elecron probability dlstbutlon fra 2s obital Figure 2.17 The proba the Earth-Sun dso radiate The first shell —s orbital “The single orbital in the first shell is spherically symmetrical. This means that the probably of finding the electron ata given distance from the micleus fs the same no ‘matter what direction from the nueleus is chosen. This exbital i called the 1s orbital The second shell - s and p orbitals (Of the four oxbitals in the second shell, one is spherically symmetscal, like the orbital in the frst shell, This is called the 2s Oebital. Its probability curve is shown in Figuee 2.16. The other three second-shell orbitals point along the three mutually perpendicular x, and zaxes, These are the 2p orbitals. They are called, respectively, the Zp 2py and 2p, orbitals. They do not overlap with one another. Yor example, an electron in the 2p, orbital has a high probability of being Found fon oF near to the axis, but a ze%0 probability of being Found on either the jaxis or the 2axis, These two different ypes of orbitals ~ the 25 and the 2p — are of slightly different energies, They make up the two subshells in the second shell of orbitals ‘When an electron is located in an s oxbital, there is afar eiance of finding it ight athe cente of the atom, atthe nucleus. But the issibution curve for the 2p oxbital fn Figuce 218 shows that there isa zet0 prchability of Finding a p electron in the centre of the atom, This s general forall p octal. Elections in these orbitals tod to ‘ccupy the otter reaches of atoms In three dimensions, an s orbital can be likened to a soft sponge ball, whereas a p cxbital is ike a long spongy solid cylinder, constricted around its centre to form two Jobes, as shown in Figure 2.18, lectron probability (forthe 2p orbitay Figure 2.18 the stb ution2 the 2s orbital Figure 2.19 The shapes ofa the 2s orbital an b the three 2p orbitals Figure 2.20 The shapes ofthe fve 24 ‘ttl, Four of them have the same shape, but diferent orentstons the fifth has 3 ciferent shape, 2s shown ine, Figure 2.21 The shape of one 4 ebital. ‘There are eight lobes pointing out fom the centre ‘Table 2.4 The number and type of eis in each shel The structure of the atom. b the three dporbhal g . y 2, %, 2, The third shell - s, p and d orbitals ‘rom the formula on page 29 we can predict that there wil be nine obits in the third shell One ofthese, the 3s orbital i spherically symmetrical, just like the 1s and 2s orbials. Three 3p orbitals, the 3p 3p, and 3p, orbitals, each have two lobes, pointing along, the axes in a similar fashion wo the 2p oxbitals. The other five have a diferent shape. The most common interpretation of the mathematical equations that serine their shape auggest that four ofthese orbitals each conalst of Foe lnbes ia the same plane as one another, and pointing mutially at right angles, whoreas the fith is best represented asa rwovlobed orbital asctinded by a ‘doughnut of electron density around its middle They are clled the 5d orbitals, iusrated i Figure 2.0. So the third shell coasts of thee subshell~the 3, the 4p and the 3d subshells. Mp oz 23, b3te Z , y y y eMep 7 oa ! y y The fourth shell —s, p, d and f orbitals ‘The process can be continued. Inthe fourth shell, we predict that there will be 4? = 16 orbitals. One of these will be the 4s orbital, three will be the 4p orbitals, ive will be the fc onbital, leaving seven orbs of a new type. They are called the f orbitals. Each consists of many lobes pointing away from one another, as shown in Figze 2.21 Shells and orbitals in summary “The number and type of omits within the elifernt shells are summarised in Table 24 1 7 1 2 4 T 3 3 9 T 2 5 a 6 T 3 5 7 31PHYSICAL CHEMISTRY How many orbitals wl be in: 2 the Sp subshell b the Sf subshel? 2 What isthe total rumber of orbitals in the fifth shel? How many of these are d orbitals? Answer Total numberof oral every shel above the third shell) a 25. OF these, 5 are d orbitals, (There are five d orbitals in 2.9 Putting electrons into the orbitals ‘The atoms of different elements contain elferent numbers of electrons. A hydrogen atom contains just one electron. Aa atom of traniim contains 92 electrons. How these electrons are atranged ia the various orbitals is called the atoms electronic ‘configuration. This a key feature in determining the chemical reactions of an element “The electoas around the nucleus of an atom are most likely t be found in the situation ‘of lowest possible energy. that i, they will occupy orbitals as close to the nucleus as posible, The single elecuon in hydiogen wil therefore be in dhe ts orbital. The electronic configuration of hydrogen is writen as 1s! (and spoken as ‘one ess one’, The next clement, helium, has two electrons, so is electronic configuration is 1s® Cone e350) For reasons that we shall look at later, we find that each exbial, no matter what sell or subshell i in, cannot accommodate more than two electons. The third electon in lithium, therefore, has to occupy the orbial of next lowest energy, the 2s, The electronic configuration of lithium is 1522s. Beeytiom (1382s?) and boron (4262p follow predictably ‘Whea we come to carbon (1s"2s"2p, we need to clfferentate herween the three 2p orbitals, Because clectrons are all negatively charged, they repel one another clectrostically. The thrce 2p orbitals are all ofthe same energy. Therefore we ‘would expect the two p electrons in earbon to occupy different 2p orbitals (For example, 2p, and 2p,), as far away from one another as possible. This isi fact what happens. Likewise, the seven electrons in the nitrogen atom arrange themsclves 1s?2s?2p4! 2p,!2pz,Itis only when we arrive at oxygen (1s?2s?2,?2p,!2pe!) that the 2p orbitals start ro become doubly occupied. For many purposes, however, there is no need to distinguish between the three 2p orbitals, and we can abbreviate the electtonie configuration of oxygen to 18122 apt "This process continues uni element number 18, agon. With axgon, dhe 3p subsets filled, and we woukl expect that the nest eletzon sboukl sat 10 occupy the 34 sushell ‘But here the expectation is noe what happens, Instead, the nineteenth electron in the next clement, potassium, occupies the 4s subshel. We shall now explain why this isthe cae 2.10 Shielding by inner shells In a single electron atom like hydrogen, the potential energy is due entirely to the single electrostatic attraction between the electron and the proton, When we move t0 the tworelecteon atom helium, two changes have occurred 1The nucleus now contains (Wo protons, ane! has a charge of +2. I wil therefore trict the electrons more, and reduce the potential energy of the system, chat i make it more sable, 2 However, the second electron in the atom will repel the first (and vioe versa). This sakes the decrease in potential energy cescribed in 1 above less tan it woul sosherwise have been ‘This has a clear effect on the ionisation energies ofthe two elements, ‘The fonisation energy of an atom (or fon) is defined as the energy raquired to remove completely a mole of electrons from a mole of gaseous atoms (or ions). Thats, the Tonisstion energy is tho anergy change forthe following process Xi) Xo) +Figure 2.22 The energy an electron from a hyetoge stom and Figure 2.23 Variation ofthe energy ofthe 1s oil with pro rumba ‘The structure of the atom FFor hyelmgen and helium the ionisation energies at: HOST) +e AH= 13124) mot Hels) $He'() += AH= 2372} mol [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 out at constant pressure (see Topic 5). takes more energy to remove an electron from a helium atom than from a hydrogen atom, This shows that, compared with the energy when the electron iat infinity, the energy of the 1s orbital has become more negative in holitim (see Figure 2.22) than in hydrogen (sce Figure 2: ee 29) ws he ° E 1000 2 ahaa! P & 2000 “This decrease in enesgy for the 1s orbital continues as the proton number increases (Gee Figure 2.23). The decrease in energy is also tre for other orbitals. The reason is that as the number of protons in the nucleus increases, the electrons in a particular orbital are attracted to it more. The decree in energy is aot regular, however, and is not the same for all orbitals, This is due to two Factors proton number re ee 3BPHYSICAL CHEMISTRY f¢ The average dieance of a p orbital from the aucleus is leger than that ofthe comesponding s orbital in the same shell (see Figures 2.16 and 2.18, page 30). Elecons ia p ofbitals therefore experieace less ofthe stabilising effec of incressing nuclear chaige than electrons ins onbitals, Fora similar reason, electrons ind orbitals experience even less of the increasing nuclear charge than electrons in p orbital, «All electrons in outer shells are to some extent shielded from the nuclear charge by the electrons in inner shells. This shielding has the effect of decreasing the effective fauclear charge. In the ease of luhium, for example, the outermost electzom in the 2s orbital does not experience the full nuclear charge of +3 (ee Figure 2.20. The two, electrons inthe filled 1s orbital mask a good deal of this charge. Overall, the Figure 2.24 The itium nucleus and inner effective nuctear charge experienced by the 2s electron in iin is calculated shal tobe +13, which is consicerably less chan the actual nuclear charge of +3. A plot of orbital energy against proton number for several esbitals is shorvn ia Figure 2.25. Figure 2.25 Graph of oral energy agaist proton number for shell numbers 1-5 28 Table 24, page 30) 00-4 aso] energykd mol" 4d Se ~itee-| 12007 os Sp ag He Ge CO NeMg SiS Ar Ca Ti Cr Fe Ni 2n Ge Se Kr S& Or VUE Ted FS EL Vince cde wy ap 4Figure 2.26 Mnemoni orbitals the cdr of ling ‘The structure of the atom Ie can be seen that, for each shel, the electrons ia the s orbital decrease thei energy faster than elects i the p osbitals Electrons ia the p orbitals ia tam decrease their ‘cacray faster than electrons in the d erbitals, and so on. In particular, electrons in the 4s and 4p orbitals decrease their enemgy faster than electrons in the 3 exbitals. So much so, that by the time 18 electrons have been addled (it so happens), the next ‘most sable orbital is the 4s rather than the 3c. The orbital filling continues ater potassium in the order 4s-3-4p-5s-4d-Sp-6s-4F-5d-6p-, reflecting the Tagging behind’ of the d and f orbitals, This is due to the effective shielding, by filed inner clectron shells, ofthese orbitals from the increasing nuclear charge. “The simple mnemonic diagram in Figure 2.26 will help you to remember the order Is are fille fn which the o 2.11 Electron spin and the Pauli principle bBlections are all identical. The only way of distinguishing them is by describing hhow their energies and spatial distributions difer. Thus an elecon in a 1s osbital is different from an electron in a 2s orbital because it occupies a diferent region of space closer to the nucleus, citsing it to have less potential energy. An electron in 4 2p, orbital differs From an electson in a 2p, orbital because although they have ‘exactly the sime potential energy, they occupy diflerent regions of space. ‘Two electrons with the same energy and occupying the same orbital must be distingvishable in some way, or else they would, infact, he one and the same particle Experiments by Otto Steen and Walther Geslach, ia Germany in the 1920, showed that an clectron has @ magnetic dipole moment. A spinning electrically charged sphere is predicted to produce a magnetic dipole —it acts like a tiny magnet, with a north and a south pole, Therefore the most common explanation for the results of the ‘Stera-Gerlach experiment is thatthe electron is spinning on its axis, and the direction of spin can be either clockwise (let us say) or anticlockwise. These two directions of spin produce magnetie moments in opposite ditections, often described as “up! (given the symbol 1) sacl “down’ (given the symbol 1, We could therefore distinguish between two electrons in exactly the sume exbital if they had slifferent directions of spin, All electrons spin at the stme rte, andl there are only exo possible spin directions. Therefore there ate only two possible ways of describing electrons in the same osbital (for example, 1st and sb). So there can only ectrons in each orbital, and they must have apposite directions of spin. A third eleciton wotld need te have the same spin direction as ane of the rw already there, which would make it indistingtishable from the similarly spinning one ‘The situation is neatly summasised by dhe Paull exclusion principle, which states that [No more than two electrons can eccupy the same orbital, and iFtwo electrons are in the same orbital, they must have opposite spins. 2.12 Filling the orbitals \We are now in a positon to Formulate the rules to use in order to predict the electronic configuration ofthe atoms of the elements, and also the ions derived from them, Collecting together the conclusions of rections 2.7-2.11, we aurve atthe following. 1 Work out, from the element's proton number (and the charge, iF an ion s being considered), the total number of electrons to be accommodated in the orbitals, 2 Taking the orbitals in onder oftheir energjes (sce Figure 226), fill them from the lowase energy (18) upwards, making se that no exbital contains more than to electrons 3 For subshells that contain more than one orbital with the same energy (the p, dl and f subsholls), place the electrons into diferent ovbitals, until all are singly occupied (Only thea should further electrons in that sabshell staat donbly occupying orbitals. For example, place one electroa into each of 2px. 2py and 2p. before putting two clectsons into any p orbital 4 Two electrons sharing the same orbital must have opposite spins ‘This procedure fs known as the Aufbau or builing-up' 1 35PHYSICAL CHEMISTRY Figure 2.27 Elecronsin-boxos diagram showing the electronic configuration of sulfur Note that the bores can als be, ard usally are, aranged in one rw, with no step’ to incicte energy levels a in Figure 228 below) Figure 228 ‘Write out the long linear form of the electronic configuration of each of the following atoirs or ions. IN 2Ca 3 AP “The electoonie configurations of atoms and ions ean he represented in a vatiery of ‘ways. These are illustrated here by using sulfur (proton number 16) as an example (One way is as an ‘electonsin-boxes' diagram, as showa ia Figure 2.27 fii 27 [i] 1 2 fla afm” * sii energy 2 As akan nig Kner fen pty dvd porta 12512p.2p,32p.36 3p 3p) SP Below isthe shortened linear form, whic is the most wsal repreventation stastaph3et3o% ‘As even sorts form i INel3s"3p* were INE] represents the file shell inthe neon atom, 1=#262p6 Sometimes, if we are only concemed with which shells ae fled, her than which sub-shells the clecon configunation ofthe sulfur atom can be described as 2365 ‘meaning 2 electrons in the fist shell 8 electrons in the second shell: and 6 electwons in dhe third shel Wire out 4 the ‘electronsin-boxes' representation ofthe slicon ator b the shortaned linear form of the electtoni configuration of the magnesium atom « the long linear form of the electronic contiguration ofthe fluoride ion Answer « Siicon has proton number 14, so there are 14 electrons to accommodate, as shown in Figure 2.28. Note that the last two electrons go into the 3p, and 3p, crbitas, with unpaired spins. sit] si] ea) »| ye H » Gl ~y bb Magnesium has proton number 12. The 12 electrons doubly occupy the six orbitals lowest in energy: 182522963 «Fluorine has proton numba 9. The Fon wil therefore have (8+ 1)= 10 electors 122s22p22p,22p? 2.13 Experimental evidence for the electronic configurations of atoms — ionisation energies A major citforence between electrons in different types of orbital is their encegy. We can lavesigate the electronic configueations of atoms by measuring experimentally the enetgies of the eleczons within them. This can be dane by measuring ionisation, ‘energies (see page 32)Figure 2.2 Graph af the twelve ional energes of magnesium against actron rumbe, ie cenfigura magnesium i s82s! 20° ast ‘The structure of the atom Tonisation eneegies are used to probe clectonic configurations in two ways ‘successive ionisation energies forthe same atom «first ionisation energies for different atoms We shall look at each in tun, Successive ionisation energies ‘We can look at an atom of a particular element, and measure the energy required 10 remove each of ts electrons, one by one: XQ IK OE AH=1B, XO OKO +E AH=IE, QO OIE AH=IB, a “Those suecessive tonisation energies show clearly the arangement of electrons fn shells around the nucleus. If we take the magnesium atom as an example, and measure the enetgy required to remove successively the first electron, the second, the third, and so on, we obtain the plot shown in Figure 2.29, 10203 4 5 6 7 8 9 HH BR ‘number of electrons removed ‘Succetsive ionisation enetgies are bouned to increase because the remaining electrons are closer 10, and less shielded from, the nucleus. Buta huger increase occurs when the third electson is removed. This is because once the wo electzons in the outer (hird) shell have been semoved, the nest has to be stripped from a shell that is very ‘much nearer to the nucleus (the second shell) A similar, but much more enormous, jump in ionisation energy occurs when the eleventh electron is removed. Tis as to come from the fis, innermost shell sight next (othe nucleus, These two large jumps in the series of successive fonisation energies are very good evidence that the clectrons in the magaesivm atom exis in three diferent shells, 37PHYSICAL CHEMISTRY Figure 2.30 Graph oflogarthms ofthe ‘weNe foisation energies of magnestum agaist clacton number Decide which group elomant ¥is in, based on the following successive iomsation energies: 599, 1145, 4012, 6474, 8144ismol* “The jumps in successive ionisation energies are more apparent if we plot the logarithm of the ionisation energy against proton number, as in Figure 230. (Taking the logarithm is a scaling device that has the effect of decreasing the differences Derween adjacent values for the larger ionisation energies, so the jumps between the shells become more obvious) 4s tog te) as. 25: 19203 4 8 6 7 8 § wn umber of electrons removed ‘The first five succassve ionisation enorgias of cloment X are 631, 1235, 2389, 7089 ard aBdakImot" How many electrons are inthe outer shell of element x? Answer ‘The difforences between the successive ionisation energies ae as folows: 2-1: 1235-631 = 604idmol 3-2 2389- 1235=1 154k) mob* 4—3: 7089 2389 = 47001) mot? 5-4: 84d 7089 = 175K mob* ‘The largest ump comes between the third and the fourth ionisation energies, therafore X thas thee electrons ints cuter shel ee First ionisation energies “The second way tht ionisation energies show us the details of electonic configurition fs to look at how the fn ionisation energies of elements vary with proton number. Figure 231 isa plot for he fist 40 elements, “This graph shows us the following 1 All ionisation energies are strongly endothermic it takes energy to separate an electron fron an atom. 2.As we go down a pasticula group, for example from helium to neon to asgon, oF from Ithium to sodium to potassium, ionisation energies decrease, The larger the atom, the easier it sto separate an electron from it2 ‘The structure of the atom Figure 2.31 Fist ionisation energies forthe fist 49 eemants proton number 5 The ionisation eacegies gencrally increase on going actoss a period. The Group 1 clemeats (the alkali metals) have the lowest ionisation energy within each period, and the noble gises have the highest 4 This general increase across a period has two exceptions. For the fist two periods, these occur between Groups 2 and 13 and between Groups 15 and 16 ‘We shall comment on each of these features in tum, 1 The endothermic nature of ionisation energies “This ls due tothe electrostatic straction betwen each electron in an stom (even the atermost ane, whichis always the eases to remove) and the postive nucleus {es won remembering that this applies even to alll metals like sod, which -ve usually thin of as wanting’ to form tons, We must hearin mind, however, that fonization energes as plotted in Figure 2.3 apply to the ionisation of nolsed atoms In the gas phase. tons ae much more stable when in solid latices or in solution, We shal be looking at this in detail in 2 The group trend “The nuclear charge experienced by an outer election i the effective nuclear chiarye, Zp. can roughly be equated to the numer of protons in the micleus, , minus the number of electrons inthe Inner shells, As we explained when considering the fonisation enesgy of Iinhlim on page 34, inner shells shield the cifea of the increasing nuclear charge on the outer electrons. Because ofthis the outer electrons of elements within the same group experience roughly the same effective nuclear change no mater what period the clement isn. What does change as we go down a group, however, is the atomic radius (eee Figure 2:32) ‘The larger the radius ofthe atom, the lagor is the distance between the outer electron and the nucleus, s0 the electrostatic atction between them s sale. 39Figure 2.32 The effective nuclear chara, Zu and sizes ofthe cores of thee alta metas. The core, reresented by the blue eles, comprises the nucleus pus al ths Inner shall of elecrons. Despite the increase in eq, the ionisabon energies decrease fom itium to potasium, owing to the increased electron-nadeus distance Table 2.5 Comparing the values of (0-8) and the effetve nuclear charge, Za, 1 Petiod 2.2 f not exactly equal to PF) for wo reasons 1 Electtonsin s otbtals panetrate the inner ctbitas to a certain extent, and are therefore les shlelded by them than one might have Predicted, 2 Electrons Inthe same shall do, to 3 certain ‘extent, shel one another for the nucleus. This oftect becomes largor as the outer shel ‘becomes moe fll of electrons, and so the dscrepancy between Zand (P—6 increases 8 we cosa period or 02 102 o2em sletronic Configuration tig sediim potaiom ofcore * weap re drape ae 36 2a, 13 as 3s atomic radhs/nm 018 o23 028 ieisation onrgy/ ima 196 a0 3 The periodic trend ‘As we go acress a period, we are, foreach element, adding a proton to the nucleus, and an election tothe outermost shell, The esta proton wil, of course, cause the nucleus to atuact all the clectons moze strongly. Electrons in the same shell are at (roughly) the same distance from the nucleus as one another. They are therefore not particulary good at shielding one anolher from the nuclear charge. As a result ofthis, the effective nuclear charge increases. Ths causes the electostaicatriction between the ionising electron and the nucleus © increase 100. Table 2.5 ilustates this for the second period, u 3 2 o 13 te 4 2 2 19 8 5 2 3 2a c § 2 4 Bt N 7 2 5 3a ° 8 2 6 as a 9 2 7 By Ne 70 2 ® 38 4 The exceptions ‘The two exceptions to the general increase in loaisation energy acrass a period (see Figure 2.31) asise from different causes. {In boron (1s*2s42p!), the outermost electron isin a 2p oxbital. The average distance from the nucleus of a 2p oxbital is slightly lager than that of a 2s orbital (see Figures 2:16 and 2.19). We would therefore expect the outermost electron in boron 10 experience less electrostatic attraction than the outermost 2s electron in beryliam. So the fonisation enesgy of boron is less. “The other exception is the decrease in foniation energy From nitrogen fo oxygen. This occurs when the fourth 2p electron is added, and is related the fact that thene are just three 2p oxbitals. As we have seca hofore, because they are of the same clectical charge, elactrons repel one ancther. The three successive electrons added to the series of atoms horan — carbon = aiteogen are therefore most likely to go into the thece orbitals 2p. 2p, aad 2p These orbitals are of equal energy aad at right angles to one another, so allowing the electrons to be as far apart as passible. They will Uherefore experience the least electrostatic repulsion from one another, and so, overall, the atomic sytem will be the most stable, In oxygen, however, the foutth 2p electron thas to be accommodated ian orbital that already contains an electron, These (0 electrons will be sharing the same region of space (by the Pauli principle, of course, their spins will have to be in opposite directions) and they will therefore repel each, ‘other quite strongly. This repulsion is larger thaa the extra atracton experienced! by the new electton from the adlitional proton in oxygen's nucleus. So the energy2 ‘The structure of the atom Figure 2.33 Fist ionisation ener against proton number for Patio 2 200 ‘xpd eration eneegy—— ‘Fro imerdatronreplion fiat mer needed to remove the election from the oxygen atom is less than the ionisation energy ‘of the nitrogen atom. Similar repulsions ate experienced by the additional electeoms in the fluorine and neon atoms, 3 the Sonisation energy of each of these clements is, lke ‘oxygen's, about 430k}mol™ less than one might have expected (see Figure 2:33). (Once the second shell has been filled, at neon, the next additional electron (in sodium) has to occupy the 3s orbital, and starts to fil the third shell. This is further ‘out from the nucleus than the 2p electron in neoa (remember, electrostatic attraction decreases with distance), It is also more shielded from the mucleus — by two inner shells rather than the one in neon — hence Zag for sium is only 2.5, On both accounts, we woul! expecta large decrease in ionisation energy from neon 10 sodium, which we indeed observe (sce Figure 231), 2.14 The effect of electronic configuration on atomic radius AL first sight, the radius of an atom might scem an easy quantity to visualise. But, as swe saw in Figures 2.16 and 2.18 (page 30), the outer reaches of atoms have an ever- decreasing electron probability, which is stil greater than zero even at large distances, A filled orbital is prety clusive affair that can easly be squashed or polatised. We ‘must therefore be prepared to accept that the value ofthe atone radius will oe be a fixed quantity, but will depend on the atoms environment. Keeping this ia mind, however, we can use the theories developed above to predict Ihowy the atomic rads might change with proton number. We have seen that we might expect 8 major influences on the size of an atom. One of these will he the number Of shells— the more shells, the bigger the atom should he. We should see this effect as we go down a group. The other influence will he the effective nuclear charge ~ the lager the charge, the more the orbitals are pulled in towards the nucleus, and so the smaller the atom should be. We should see this effect as we go across a period. These two factors combine to produce a predictable pattem in the ploc of atomic radius against proton number, which is borne out by experimental observations (see Figure 2.34), We shall return tothe trends in atomic rads in section 10.3. 4“PHYSICAL CHEMISTRY detesing rots 4 uke 8 co Nn oO F @ ®eoeee ee) a os Pos oa 70 0 @eee0 2 se hon @e Figure 2.34 Atoms get lager down 2 group, 3: the number of shal creates. They get smaller across period, 2 the efectve nucesr charge pls the clecuons dosor to the nucleus. {All atoms are made ofthe seme three sub-atomic particles — the electron, the proton and the neutron. Their relative electrical charges ae, respectively, 1, +1 and 0. ‘Their masses (lative to that ofthe proton) ae, respecthely, wage Vand 1. The proton number Gtomic number) is the number of protons contained inthe nudlaus of an elament’s atoms. tll us The ‘order of the element in the Periodic Table, Isotopes are atoms ofthe se element (and therfore withthe same proton number) but with diferent numbers of neuirons ‘The mass number ofan atom isthe sum of the numbers of protons and neutrons it contains, “The full symbol for an atom shows its mass number as 2 superscript and its atomic (proton) number asa subscript For example,'§C shows a cerbon atom with mass number 12, {and proton number 6. Massas and relative abundances of isotopes an be moasurod using the mass spectrometer. '@ Chemical energy has two components the kinetic energy cof moving parle, and the potential energy due to electrostatic attractions, f¢ The electons are artanged around the nucleus ofan atom in energy levels, or orbitals '@ When an electton moves froma higher to alower eneray level (orbit), a quantum of energy & released asa photon of light (Gometimes visible, but often ukzavolt light. ‘The numberof possible orbitals in the th shell sn? Each ital can hold a maximum of two electrons. The first shell contains only one orbital, which san s orbital, “The sacond shell cata one s and trea poitas, the third shel one s three p and fe d orbitals, and soon. ‘The elecronsin an atom occupy the lowast energy orbitals fst, Otbitals of equal eneray are occupied sinaly whenever possible, Successive lonsation energies ofa single atom, and the trends inthe fist ionisation energies ofthe element across periods ‘and down groups, give us information about the electronic configurations of atoms.‘The structure of the atom Examination practice questions Please see the data section of the CD for any 4, values you may need, 4 Although the actual size of an atom cannot be measured exactly itis possible to measure the distance between the ‘nucle of two atoms. For example, the ‘covalent radius’ of the Cl atom is assumed to be hatf of the distance between the nude’ in a Clz molecule. Similarly, the ‘metallic radius’ is half of the distance between two metal atoms in the crystal lattice of a metal. These two types of radius are generally known as ‘atomic rai The table below contains the resulting atomic radi forthe clements of Period 3 of the Periodic Table, Na to Cl. Na [Moa [s\_[P__[s [cl os [0.160 0.43 f0.117 0.190 [avo | 0089 1 Biplain qualitatively this variation in atomic radius ii Suagest why itis not possible to use the same type of measurement for argon, Ar. (a bi Use the data section on the CD to complete the following table of radi ofthe cations and anions formed by sore of the period three elements, nar [oe [ar [Pe cr li Explain the ferences in size between the cations and the coresponding atoms. Explain the differences in size between the ariors and the corresponding atoms. 5) [Cambridge international AS & A Level Chemistry $701, Paper 23 Q1 a & b June 2012) 2 This question is about a model of the structure ofthe atom. 1a A model used by chemists includes the relative charges, ‘the relative masses and the distribution ofthe sub-atomic Particles making up the atom, Copy and complete the table below: m proton Teuton ‘ectron ‘va000 | salt bb Early studies of ionisation energies helped scientists to develop 2 model forthe electron structure of the ator. Define the term first ionisation energy. By © Amodern madel ofthe atom arranges electrons into ‘orbitals, sub-shells and shel, Copy and complete the following table showing the maximum number of electrons which can be found within each region, a 2p orbital The 3 subshal the Ath hel dd The modem Periodic Table arranges the element in ‘order of their atomic number. Explain what is meant by the term periodicity. i} «In this part, you need to refer tothe Periodic Table of the ‘Element in the data section on the CD. From the frst 18 elements only, choose an element ‘hich fits the following descriptions. 1 Anelement with an icotope that can be represented. as "6X. for ‘The element which forms a2- ion with the same election structure as Ne a ‘The element which has the smalest third icnisation energy a iv The element with the fist si successive ionisation energies shown below, in kim! a 738 1451-7733 10541 13628. 17995 TOCR Chemistry A Unit F321 QT May 2011] Tin mining was common practice on Dartmoor (UK) in [pre-Roman times. Most of the tn extracted was mined \with copper to produce bronze. ‘The table below shows the sub-atomic particles of an isotope of tin. i Copy and complete the table. a In terms of sub-atomic particles, how would atoms of "sn lifer from atoms of "85n7 a bb The relative atomic mass of tin is 118.7. Define the term relative atomic mass. Bl ‘© Abronze-age shield found on Dartmoor contained 2,08kg of tin. Calculate the number of tin atoms in this bronze shield. Give your answer to three significant figures a d Tin ore, known as cassiterte, contains an oxide of tin, This oxide contains 78.8% tin by mass Calculate the empirical formula of this oxide. You must show your working, ay OCR Chemistry A Unit F221 Q1 May 2010}AS Level Physical chemistry Chemical bonding in simple molecules This topic isthe first of two in which we look at how atoms bond together | Learning outcomes to form molecules and compounds, By the end ofthis topic you should be abe to: at fea ase parte aver, crib, including the use of ‘dot-anccross’dagrams, covalent bonding (os ee a 3.2a) describe, incluting the use of ‘dot-and-cross diagrams, covalent bonding ( In hydrogen, oxygen, chiovine, hydrogen chloride, carbon dloxde, methane, ethene) and co-ordinate (dative covalent) bonding (asin the formation of the ammonium jon and in the Al molecule) describe covalent bonding in terms of orbital overlap, giving g and x bonds, including the concept of hybridisation to form sp, sp* and sp orbitals (see aso ‘Topic 14) explain the shapes of, and bond angles in, molecules by using the qualitative ‘model of eleczon-pair repulsion (induding lone pairs), using as simple examples: BF, (rigonal, CO, (linea, CH, (tetrahedral, NH; (pyramidad, HO (nor-lines, Sf (octahedral), Ps (rigonal bipyramidal) predict the shapes f, and bond angles in, molecules and los analogous to ‘those spoaffd in 3.2b) (so also Topic 14) describe hycrogan bonding, using ammonia and water as simple examples of ‘molecules containing NH ard O—H groups Understand, in simple tes, the concapt of electronegatity and apply it to.explain the properties of molecules such as bond polarity ard the dipole ‘moments of molecules (part, se also Topic 10) explain the terms bond eneray, bond length and bond polarity and use ther to compare the reactivities of covelent bonds (soe also Topic 15) describe intermolecular forces (van der Weals' forces, based on permanent and induced dipoles, asin HCL, ra() and the liquid Group 18 elements show understanding of chemical reactions in terms of energy transfers associated ‘with the breaking and making of chemical bonds (sae also Topic 14) form all the matter we see around us. ‘Horo vre describo the various types ‘of covalent bond, and explain some Cf the propertios of simple covalent ‘molecules. 3.1 Introduction (OF the total number of individual, chemically-pure substances known to exist, several million are compounds, formed when two or more elements are ‘chemically bonded together. Less than 100 substances are elements, Only six oF these elements consist of ree, unbonided atoms at room temperature, These are the noble gases in Group 18. All other elements exist as individual molecules, or sant molecules, or metallic latices. Tp all three eases, the atoms of the element are chemically bonded to one another. ‘his shows that the natural state of atoms (that Is, the state where they have the lowest energy) isthe bonded sate. Atoms prefer to he bonded to one another, ‘ther than to be Hoating free through space. They give out energy when they form bonds. Oa the other hand, it always requices an input of energy to break a chemical bond — bond-beeaking is an endothermic process (see Figure 3.1)Figure 3.1 Bond breskingis endothermic Figure 3.2 Potential energy aginst hydrogen e Chemical bonding in simple molecules separate atoms aH postive bonded atoms AB ‘The bond strength i related to the value of AAT in Figuee 3.1, that is, the enthalpy ‘huange that occurs when one mole of bonds ina gaseous compound is broken, forming gas-phase atoms (see section 5.5). The largor AF is, the stronger isthe bond ‘We saw in Topic 2 that the negatively charged electrons in aa ateun are attracted to the positively charged nucleus: an electron in an atom has less potential energy than an electron on its own outside an atom. It therefore requires energy to remove fan election from an atom. In this topic we discover a similar reason why atoms bond together to form compounds. This is because the electrons on one atom are attracted to the nucleus of another, causing the bonded system to have less potential energy than in its unbonded state, (The three major types of bonding ~ covalent ionic ard ‘metallic ~ differ from one another only in how far this atraction to another nucleus ‘overcomes the atiraction ofthe electron toi own nucleus) 3.2 Covalent bonding - the hydrogen molecule “We shal look fist a the simplest possible hond, that hetween the two bydrogea atoms in the hyerogen molecule. Imagine two hydrogen atoms, initially a large distance putt, approaching each other. As they get closer together, the Bist effect will be that the electron of one atom will experience a repulsion from the electron om the other atom, but this will be compensated by the atiraction it will experience towards the ‘rhe atoms utcleus Gn ado to the attrition i always experiences from is own nucleus). Remember that the elacton in an atom spends some of is time at quite a large dlistance frm the nucleus (see Figure 2:16, page 30) As the hydrogen atoms get closer alll, the ro electrons will encounter an even greater atsaction tothe opposite nucks but wil also continue to repel each other. Eventually, when the ro nuclei hecome very close together they in nica will start to repel each other, since they beth have the ‘same (postive) charge. The most stable sitaation will be when the ateactions of the thre electrons to the two nuclei are just balanced by the clectron-clectron and nucle ‘nucleus epulsons, A covalent bond has formed. The decrease in potential energy at this point from the nhonded sate is called the bond energy, and the micleusauicleus dlstance at which this occur is now as the bond Jength (sce Figure 3.2. HH internuclear distance ox 02 02 oa energy mot! 5PHYSICAL CHEMISTRY ‘maximum electron density Figure 3.3 A molecular orbital 2 region eon twa bonded atoms where the electron density sconcentiated Figure 3.4 Dotarx-cros diagrams showing ‘balium hyde, Bek, and boron hye, EHS qk worh rinerberng that al electors 2 identkal, ro mata which atom they came rom Our representing them as cots and ose is matey for our own benef, to make daat tous Which atom ty Ware erga aeccated wth ‘eing attacted to beth the hysrogen aucle, the two elections spend most of theie time in the region half-way herorsen then, and on the axis that joins them. This is ‘where the highest clectron density (or election probability) occuss in 2 single covalent bond (see Figure 3.3). “The two electrons ate therefore shared between the two adjacent atoms, As we mentioned in section 27, we use the word (atomic) Orbital to describe the region of space around the nucleus of an atom that is occupied by @ particular electron. In a simular way, we can use the term molecular orbital to describe the region of space ‘within a molecule where a particular electron is to be found. 3.3 Representing covalent bonds Depending on the information we want to convey, we ean use various ways (0 ‘eptesent a covalent bond, as listed below 4 The dot-and-cross diageam: He oH HSH (The dotand-cross diagram including Venn diagram bounclaies ~ this is prefered for more complicated molecules, as it allows an easy check to be made of exactly ‘which bonds the electrons are in: ® @- o The te saz (i ns fr bd = i yao ral Simple molecules, but s often less confusing than deawing out inlvidual electrons for larger, more complex molecules, He+ HHH 3.4 Covalent bonding with second-row elements Bonding and valence-shell electrons ‘When an atom bonds with others, itis normally only the electrons in the outermeast shell of the atom that take part in bonding. The outermost shell is called the valence shell, All electrons in the valence shell cin he considered together asa group, Whea ‘ve look in simple tezms atthe bonding, we can ignore the distinction herween the ‘vatious types of orbitals (s,p, dct.) in a shell. The numberof electrons in the valence shell isthe same as the group number ofthe clement inthe Periodic Table Gee Topic 10), fan atom has more than one electron in its valence shell, it an form more than fone covalent bond to other atoms, For example, the beryl atom has & pair of 2s electons, When forming a compound such as beryium hydride, BeHy, these ‘an unpaic themselves and! form to bonds with two ether atoms, The boron atom (2322p! can form three bonds. The bonding ia beryllium hydride and boron hychide fs shown in Figure 34 4 Ha (Be) 2H Hee )ou ‘The carbon atom in methane has four electrons in its valence shell (2s#2p, and so forms four bonds.3 Figure 3.5 Dot-and-oss diagram for methane, CHa (Often, for darn, bonding zara show only the electonsin the outer Shall iting the Inar shel. For comparison, both dlagrars for methane are shown here) 4 weoc @ 4 H) Figure 3.6 Det-and.cross diagram for athe, Coe Figure 3.7 Dot andcross diagram Figure 3.8 Dot-and.cros dlagras for wate 1.0, and hydrogen faosde, He Oxygen ca form avo bonds (a ~ 6= 2) and fluorine jus one (8-7-0. Figure 3.9 Draw diagrams showing the bonding in the following molecules. 1BF, 2 Ny 3CHOH 4 CHF Chemical bonding in simple molecules 4 4 HB(c) Qu (ah oc gu “The general nile is that: laments with one to four electrons in thar valence shlls form the same number of covalent bonds asthe number of valence-sll electrons. Importantly, casbon atoms form strong bonds to ather carbon atoms (as do a few cother clements) This allows the millions of organic compounds to be stable. The simplest molecule with a carbon-carbon bond is ethane (see Figure 3.6) More than four valence-shell electrons ‘When the number of valence-shell electrons is greater than Four, the maximum possible ‘number of bonds is nox always formed. This is because atoms ofthe elements of the second ron of the Periodic Table have omy four orbitals in their valence shells 2s, 2p 2p, 2p) and so cannot aecomamosate more than Four pats of electrons. The numaber OF bonds they form is resticte! by this overall maximum of eight electrons, because every ‘new hood brings another election iat the valence shell. or eximple, nitrogen has five valence-shell elecons. Inthe molecule of ammonia (NH) there are three N—H bonds “These involve the sharing of three nitrogen electrons with theee from the hydeogen atoms, These three additional electrons bring the valence shell ttl to eight, The outer shells therefore filed, with a full octet of elections. No futher bonds can Form. The remining 160 of the five electrons in nitrogen’s valence sbell remain unbonded, asa Jone pair, occupying an orbital associated with only the nitrogen atom (see Figure 3. ‘The general rule is that laments ofthe second period with more than four electrons in thair outer shals Form (@— n)covalent bonds, where n = the numberof valence shel electrons. Simulaly, oxygen @s?2p, with six electrons in is valence shell, can form only two) covalent bontl, with two lone pairs of electrons remaining, Fluorine (25?2p"), with seven valence-shell electrons, can form only one bond, leaving three lone pairs around the fluorine atom (see Figure 38), ° Draw diagrams showing the bonding nitrogen trifuoride, NF, and hydrogen peroxide, H:O> Answer \ \ H er Bw @ F aA 1S fa fo fo} er} we # Ny 40, aPHYSICAL CHEMISTRY Figure 3.10 Dot-and- (LP-BP angle) > (BP-BP angle) 4 Although they are very important in determining the shape of a molecule, the Jone pairs are not included when the molecule’s shape is described. For example, the molecules CH,, NHy and H,O all have four pair of the central atom (see Figure 3.18). These four pairs anrange themselves in a (roughly) teaabedral fashion. But only the methane molecule is desertbed as having ‘tetrahedral shape, Ammonia is pyrumidal (it has only three bonds), and water x descebed asa bent molecule (it has only two bonds) ‘of electrons in the valence shell ‘Work out the shapes ofthe following molaculs. ach Answer a Figurest9 gq ber Ps ‘The valonce shal of the carbon atom in CCly contains ight elecvons, arrangod in four bonded pais, c therefore takes up a regular ‘wtrahodra shape, just lke methane (see Faure 319) b Figure 320 f ‘Thevalence shal of the boron atom in BF contains 9x electrons, arranged in tee bonded pairs (no lone pats - soe page 47) Tethus takes up a regular angular planar shape. with all bond angles being equa at 120° (s0e Figure 3.20) The valence shel ofthe phosphorus atom in PFs contains ten dlactrons: five fom phosphorus, ‘and one each from the five fluorine ator eee page 48). The shape wil be a regular trigonal z bipyrami, with bond angles of 120° and S0° (sce Figure 3.21), Double bonds and VSEPR ‘When a molecule contains a double bond, the four electrons inthis bond count as fone group of clectoas, as far asthe VSEPR theory is concerned. For example, the po region of overlap a ae region of overlap “The reashing atea of election density i in the region hetween the honded stoms, ‘with the largest demsity on the axis joining the atom centres. Looked at ‘end on’, these orbjals have a circular symmetry (see Figure 335), end view 1By analogy with the spherically symmetric s orbitals of atoms, these are termed! 6 (sigma) orbitals, ¢ being the Greek letter comesponding to s. The resulting bond is called ag bond, 57PHYSICAL CHEMISTRY Figure 3.36 The sp and spoils Hybridisation of orbitals ‘We saw on page 51 that the election paits which surround a central atom arrange themselves in such a way as 10 minimise the repulsion berween them, Irthere are three elecon pairs, they arrange themselves in a triangular planar arangement, and if tere are four electon pats they arrange themselves cetahexraly. What molecular ‘orbitals can be used by the electrons to point in these directions? In Topic 2 we saw that, for seconcl-row elements, the orbitals avaiable for bon are the spherical 2s o*itals and the three dumhbell-shaped 2p oxbitals Figure 3.4 shows how two 2p orbitals can overlap to produce a ¢ molecular ‘orbital. But, as can be seen ia Figure 3.34, this molecular orbital points inthe same dlrection as the original p atomic orbitals, So molecular orbitals Formed from the 2px 2Py and 2p, orbitals would be pointing along the x, j= and z-axes, that is, at right angles to one another. But forthe angular planar geomety of three electron pairs, there need tobe three omits tha are pointing at 120° from one another and in the tetrahedral case of four elecron pairs, there need to be four otbitals pointing at 109.5" from one anosher. Suitable orbitals that point in the ight directions can be formed by mixing, or hybridising, the s andl p atoniic orbitals the 25, 2p~and 2p, orbitals are hybridised togethes, the resul is three ideraical ‘osbitals pointing 3t 120" from one another ~ which is exactly what we want! This type ‘of hybridisation is called sp? (pronounced ‘ess pee two"), and the three hybrid atomic coxbitals are called sp# orbitals, Similay, if the 2s oebital is hybridised with ll unre of the 2p orbitals, four sp* (Coss pee three’) hybrid orbitals are formed, which point at 109.5° From one ancthet. Figure 5.36 shows what sp? and sp? orbitals look ike. eos fp fone and two p orbitals three sp? hybrid orbitals (trigonal planar) 2, four sp? hybrid ombital(otrahedra) 3.15 Localised x orbitals - the formation of m bonds ‘We now look atthe orbitals that are used to form double bonds. We shall soe thatthe sway double honds are formed can explain their shape and many of their properties. In Figure 3.34 we have shown two p orbitals overlapping ‘end-on' to form a bond. But its also possible for wo p orbitals to overlap sideways, to produce a ‘molecular orbital which has two areas of electron density, one above and one below the axis oining the two atom centres (see Figure 3.37)Figure 3.37 Sieways ovtiap of two Potbtals to form a orbital Figure 3.38 the x bond between two cabon ators Figure 3.39 A carbon-caroon double bone Figure 3.40 The bonding n ethene Chemical bonding in simple molecules S333B5 ‘The end-on' view ofthis orbital looks very lke an atom p cv tis called a (pi) oxbial, stbeing the Geek letter comespending top, and the resuking band is called a x bond. = endview ‘This sideways overlap of two p orbitals is always accompanied by the end-on ovedlap of ‘evo other orbitals on the same atoms. So, ahough ti possible to join wo atemns with ‘only @ 6 bond, its not possible to join two atoms with only ax bond, A double bond ‘consists of a ¢ bond and a x bond between the sime 1wo atoms (see Figure 339), eS DMa tone chain chain ‘thymine ‘adenine often cuanine3 Chemical bonding in simple molecules acolo and mane 18 “8 156 rth 1 6 pepene _[CHscHy Cry 2 =a Ta ethanol _[CHy-chy-On 26 FZ Twlane [CHRO 3H @ a propen-iol_[CH=CHy=cHy=O4 4 7 “Water shows several unusial properties cmving to the large dogece of hydrogen bonding withia it. These are described in soction 4.4 Deserbo al the intermolecular forces that can occur betwaen the molecules in each ofthe following liquids, and hence presict which vl have the lowest boing point, and which will have the highest ACHSCH:CHsCHs B CHCICHOH C CHsCHCly Answer Molecule of A will exporienco only van der Waals’ (induced dipole) forces. Molecules of B ill experience dipole-dipole forces (due to the C—Cl and C—O polar bonds), and hnydrogen bonding (due to the -O—H groups), as wel as van dor Waals’ frees. Molaculas (of C wil experiance digole-dipate forces (due the dipoles ofthe CCI bonds nat cancallng each other out in adction to van der Waals forces. Thetefore A wil have the least intermolecular attraction, and hence the lowest boiling point, and 8 wil have the highest. 1 Describe the intermolecular forces in the fllowing compounds, and place therm in ‘order of increasing boting points: CHLOH—CHOH— CHyBr—CHBrCHCI-CHc 2 Suggest a reason why the differences between the boling points ofthe alkanes and alcohols in Table 3.5 bacome smaller asthe chain length increases. (Hint: think of how the intermolecular forces other than hydrogen bonding are changing 2s chan leat increases) MUTE Chemical bonding results from the attraction af one atom’s electrons by the nucleus of another atom. ‘Atoms are more stable when they are bonded together than when thay are free, A covalent bond is due to two atoms sharing @ pat of elecrons ‘An atom can ofton form as many bonds to other atoms as it has electrons in its valence shell, withthe excention that, ifthe element isin Period 2, itcannot have more than aight, electrons in its valence shal Yalence-shell elections not involved in banding arrange ‘themselves into lone pairs around the atom. Dative bonding (co-ordinate bonding) occurs when one of the bonded atoms contributes both the bonding electrons. Double and tisle bonds can occur if tivo ators share two or ‘three electron pairs between them. ‘The shape of a covalent molacule is determined by the number ‘of electron pairs there ae in the valence shell ofthe central atom, according to VSEPR theory. two bonded atom cifer in electronagativity the shared clecron pairs doser tothe more elacronegatve atom. Tas results in the bond having a dipole. Complete molecules can have dipole moments if their bord dipoles do not cancel each other out Isoalectronic molecules and ions usually have the same shape as one ancther. ‘The overlap of atomic orbitals on adjacent atoms resultsin g oF molecular orbitals, There are three types of intermolecular forces: permanent dipole, induced dipole and hydrogen bonding. Their strengths increase inthis order ‘The strengths of intermolecular forces determine the physical properties of a substance, such ast baling point aPHYSICAL CHEMISTRY Examination practice questions Please cee the data section of the CO for any A, values you may need 1 This question is about different models of bonding and molecular shapes {8 Magnesium suifide shows ionic bonding. i. What is meant by the term ionic bonding? Draw a ‘dotend-cross” diagram to show the bonding Jn magnesium sulfide. Show outer electron shells only bb ‘Dotandt- Uw AHO = 131K) mol Catice energy) So the overall energy change, fom gas-phase atoms 0 solid compound, ig) + Fig) 9 LF) AH? = 185— 1031 =-s46 mot" “The complete process is seen to he highly exothermic, and therefore favourable. 4.7 lonic bonding — compound ions ‘The ions that make up ionic compounds are not always monatomic (that is, they do not always contain ony one atom), Several common fons contain groups of atoms ‘which are covalently bonded together, and which have an overall positive or negative change. Here ate a few examples, some of which we came across in Topie 3. The ammonium ion, NH,* “We first mentioned the ammonium ion in Topic 3 (pages 50 and 55). Ii formed from fone nitrogen atom and four hydrogen atoms, minus one electron (see Figure 4.15). Hy electron lost ‘ H) # mS eh __ pao ny — (16 s Ga) —|(aB w Gu WY He = = = ~ He An alternative way of looking at its creation is by forming a dative bond from an ammonia molecule 10 a proton (see page 50). Figure 4.16 shows this approach. 4 4 noe o(H) —— [Cab on Ow 7PHYSICAL CHEMISTRY Figure 4.17 the ca Figure 4.18 The sulfate ion delecaled, and the bonds real equivalent, Figure 4.20 B Either description can be used ~the first method emphasises tha all four bonds are ‘exially the sume, while the second fsa better sepresentation of how the amamoniuim fon is ustally formed, by reacting ammonia with an acid NH® + HCI) > NHYCTO) The carbonate ion, CO; “To understand the bonding in polyatomic anions, it is offen easier to look fist at their corresponding acids, Chemically, carbonate ions are formed by reacting carbonic acid ‘with a base, that is, by removing hydrogen ions from the acid. If this is done, we can see that the two hydrogen atoms leave their electrons on the carbonate ion, giving a=2 charge (see Figure 4.17). ‘The delocalistion that occurs inthis ion was discussed in section 3.16 carbonic ace The sulfate ion, SO, “To say the ult fn, es look fist at the comesponding ai. The bonding in ‘ent cd het dead ay flow The puerto he a con mound ‘hell cam th four ofthese wo form ro doe bonds two oxygen om ft 2 ‘fur done, SO sce section 39). Thc ther we cecnons inthe ute hell Fst ii frm Ho ih bas ho bro snap cr Tse egy eel capac Stems then in tam form single bod oto ycogen atoms (xe Figute 415). Chis bonding anangement isn with the especie Covalencies given In abl 3.1, page $09 sulfuric acs {We can form sulfite fons by removing two hydrogen fons from sulfuric acid. Just as in the carbonate ion, delocalisation occurs, making all four SO bonds equivalent. The shape of the SO," ion is a regular tetrahedron (see Figure 4.19), am 1 Deduce the formula of the ion formed by the loss of the H* ions from boric acid, H.203- bb What wil be the overal charge on ths fon and hance the charge on each caygon ator in? «Suggest a shape forthe ion Answer 2 If all tae hydrogen ators are lst as H* ions, the resulting lon wil be BOS b The overall charge will therefore be~3, and each oxygen will havea charge of 1. «Boron uses all its electrons in bonding with the oxygen atoms, so the shape willbe ‘angular planar (se Figure 4.20)Table 4.4 The ionic valences of some common substances Solids, liquids and gases Pract the shape of the Ions derived fram the folowing acids, and work aut the fractional charge on each oxygen atom in each lon. | phosphonic acid, H,PO 2 chloriet) acd, HCI, 3. chloveti) acd, HCIO, 48 The ionic valency table “The ionic valency of a single atom from Groups 1, 2and 13-17 can easly be worked: ‘out from its group number. However, itis not so easy to predict the ionic valency of 4 wancition metal, or ofa compound ion. Table 4.4 includes all the valencies you will need 10 know Name Formula Name Formula Teo i yatta © intium ty uorde & sedium Ne chloride $F potassium Ke bromide Br slver ag" Toaide r copper) cu oie a magnesia ma sulfide = calcium oe ibid a ‘avium at hydroxide oF copper cue nite or nizateon) [NO "ane a nivateornitatet) | NO rent re Tydtogencatbonate | HCOe lead = Iydrogensufate [HOF ‘alurinion| ap carbonate CO iron) re sulie or sufatayy [505% hvomium cf sulfate or sua) | SO. ‘rnmonum NMA hosphate PO Ionic inorganic compounds ate names! according tothe following general niles 1 The name of te compound is usually made up of wo words, the fst of whic is the name ofthe cation (he postive ion), and the second isthe name ofthe anion Ade negative ion). 2 The oxidation state (oxidation number) isthe formal change on paricular clement ia compound or ion. Where elements can exist in different oxidaion tes (sce section 7.2), the patcular Oxidation sate it shows in the compound fn question is represented by a Roman numeral. Therefore soni) represents ‘con wit the oxidation number +3 (Fe), and so iron) chloride is FeCl Thi ‘a panicularly useful when referring to compound ions ~ the nitrogen atom inthe leatet) fon, NO, has an enidation sumer of +3, whereas the nitrogen in the aluateCV) i, NOs" hasan oxidation number of 15 5 Anions containing [usa single atom have names ending in “ide. Anioas containing conygen as well as another clement have names ending in ate. IF thece is ore than one anion containing a particular element combined with oxygens the coridation number ofthat clement is indicated asia nule 2PHYSICAL CHEMISTRY 1 Use Table 44 to write the correct formula for: 2 iron) fluoride bb magnesium nitride copper) axide irondt) hydroxide « caldum phosphate ammonium sulfate 9 copper nivate 2 Write the names ofthe folowing ionic compounds, FeSO, b as © MglHCOsh, dl KNOy 3 Which ofthe following formulae are Incorrect? For each incorrect formula, write the correct one, 3 Ago bb Bolo « PoltlOa), dA, 2 Fey50.)y 44 For some anions, the ending “it’ is used in the traditional name to indicate thar the particular clement is combined with some oxygen, but not ts maximus amount of oxygen. The recommended name uses the oxidation aurnber instead, For example NOP is ether nlite oF nitrate(IM) NOP is nitrate or nitate(V) $056 either sulhe or sult) S04" sale o sulle KAM Uso the fone valency table (seo Table 4.4) to predict the formula of 2 anc nitrate b aluminium sulfate, Answer 4 Zine ons are Zn*, and nitrate ions are NO; To obtain a compound that i electrically ‘neuiral overall we need two nitrate fons to every one zinc in En?* + 2NOS > ZnlNODh, bs Aluminium ions are AP*, and sulfate ions are S04, so we need two AP (total charge= +6) for every tree SO, (total charge =~6): 2AP + 3507 + ALASO. 4.9 lonic lattices Co-ordination number “The sections above have described how individual ions form; we now consider how they collect together in a latice, Cleasly, oppositely charged ions will attract ech other; also, ions ofthe same charge will repel each other. Each cation in an ionic lattice wil therefore he surrounded by a numberof anions as its closest neighbours, and each anion will be surrounded by a numberof caions, We never find to cations adjacent ro each ether, nor ean £0 anions be adjacent to each ‘other. The number of tons that suround ancther of the opposite charge in an ionic lasice is called the ¢o-ordination umber ofthat cea ion, The co-ordination number depends on two things ~ the relative sizes ofthe ions, and thei elative charges ‘The relative sizes of the ions If one of the ions is very small, there will not be room for many oppositely charged fons around it, With Zn", For example, he maximum co-ordination number is usually 4 1F the cations and unions are neatly equal in size, one jon can be surrounded by ight others. The intermediate ease of six neighbours occurs, as might be expected, shen one ion is bigger than the other, but not by very much. The relative charges of the ions “To gain electra! neutral, a cation with a charge of 42 needs twice as many —1 ons 28 does a cation of charge +. We therefore fin thatthe Ca" ion in ealeium chloride, (Cac, ts sured! by tice as many CT fons as isthe Li ton a hm chlrde, UCL “These two factors are detaled in Table 45, Two of the ionic latices from the table —thoee of sodium chlosde, NaCl, and caesium chloride, CxCl— are shown in Figure 4.21, which dearly ilustiates the difering co-ordination numbers of the sons in the structuresTable 4.5 The co-ordination Hee a tnnume Toe [eeipound [ation Anion | Anion radius | Co-ordination | co-ordination = aa === [as ace [ois [2a [a a [naci a0 a 18 le 6 [wgo oor ors] Te 6 eal 7 [ore 1 3 8 a ; ; Figure 4.21 Mode of the late Figure 4.22 a crystal of soda chon Solids, liquids and gases iar cub ain fucide ton 3.11 that many con Involve a slight separition of change, luc to the diferent elecronegativities of the two atoms involved in the bond. This alent bon: confers 2 small degrce of ionic characte 81PHYSICAL CHEMISTRY Figure 4.23 ton polarisation between a small highly charged caton and a lage anion Table 4.6 smal highly charged ions bond strongly leading ia bigh ating pois 82 Starting from the other extreme, we find that a small degrce of covalent character {is appareat in some ionic bonds. This is due to polarisation of the (negative) anion by the (positive) cation, Ir occurs to the greatest exteat when a small or highly. charged cation is bonded to a large anion. The outer electrons around the large anion are not very firmly held by ats nucleus, and can be attracted by the stioag clectric field around the smal, highly charged cation. This causes an increase fn electron density between the two ions, tha is, a degree of localised covalent bonding (soe Figure 4.23) 70 °€ ‘The idea of ion polarisation fs important ia explaining the thermal decomposition of ‘metal carbonates and nitrates (sce section 1044, “The strong electc fled around small, highly charged cations atracts not only the futershell electrons in anions, but alo the lone pairs on polar molecules such as ‘water, We shall see in Topic 20 that the enthalpy changes of hydration of small ions are much more exothermic than those of larger ions. “The concept of charge density isa useful one for explaining the influcace that an {on (usually & cation) has on the eleetons in adjacent ions or molecules. Imagine two +1 ions, one with «radius of O1nm and one with @ rau of 21m, For each ion, the +1 charge is spread over the surface ofa sphere, for which the fist ton has a surface area of 025mm? CAer?, with r= 6.1), The surface area of the second ion is 0.50nm, which i four times as lange asthe fist (area e 7) ‘The charge density (sometimes called surtace charge density) isthe amount ‘of charge per unit area of surface. This is —L— = § electron units per nm in the fst cise, and SL = 2 electron units per ami the second. The extent of poaristion (God hence the atriction) of the eleewons ia adjacent anions, lone pairs and bonds depends on the charge density of the cation. Small, highly charged ions (such as al" have a greater charge density than large, singly charged ions (such as Cs". If wo ions have similar charge densities, this often eval in their having similar properties. 4.10 Properties of ionic compounds Melting and boiling points In an ionic latice, there are many strong electrostatic attractions between oppositely ‘charged ions, We therefore expect that ionic solids will have high melting point, (On melting, although the regular lattice is broken down, there will stil be significant attactions between the ions in the liquid. This should result in high boiling points also, As we shall see in Topic 20, the ionic atractions are larger when the ions are smaller, or possess a larger charge. This is apparent from Table 4.6. NaCl 0.10 one “ i 80 Na 0.10 on a a 33 Ma 007 Or) 2 Ei U5 Mao oor ona 2 za 852Figure 4.24 A shearing force wil shatter an tone cyst Table 4.7 Metalic bonding s much stronger the instantaneous aiple forces in argon, ut not as strong as boncing in the gant covalent late of cabo argon 185 sive 362, copper ic) ren 1535) carton 3550 Solids, liquids and gases Strength and brittleness Ian ionic lattice is subjected toa shear or bending force, chat is, a force that attempts to break up the regular array of fons, this will inevitably force ions of the same change closer to each other (see Figure 4.24). The lattice resists this strongly. Ionic latices are therefore quite hard and strong, If, however, the shearing force is svong enough, the Taice does not ‘give’, but breaks down catastrophically ~ the crystal shatters into tiny pieces, The strength of an ionie lice isan all-or nothing? stvength, Electrical conductivity “The condaction of electricity is the movement of electwical charge. The individual ions that make up ionic compounds have 4 net overall electrical change. If they ae able to move, a8 they can when the compound is either molten or dissolved in water, then an electric curent can flow. When in a solid latice, however, the ions are fixed. Solid fonic compounds do not conduct electricity. “The electrical conductivity of a solution ofan ionic compound increases as its concentration ineeases, because there are mone ions to carry the curent. Silay, ‘Gay 1 mol dar), asa solution that contains highly charged ions sch as aluminium chloride, conducts beter thse 3 sl soliton with ions of a smal charge, sch as sodium chloride. “The conduction of electricity thcagh metals and other sald conductors is de to the movement of clecuons (sce below). When ioas that are moving in a solution give ‘up their charge toa solid conductor placed in the solution (an electrode) interesting chemical reactions take place This process, called electrolysis, described in Topic 23. 4.11 Metallic lattices All metals conduct electicity, They are also malleable (exsly beaten or rolled into shoots), ductile (easily drawn into rods, wites and nies) and shiny. These peopesies are due to how the atoms ofthe metal interact with their neighlsous in the latice. In a pure metallic clement, all the atoms are identical. IF we look closely at mast ‘metallic latices we find that the atoms are arranged in a very similar way to the argon atoms in solid argon, with each atom being surrounded by 12 others (see Figure 4.4, page 72). But clealy there are greater attrictions between them, forthe typical smeking point of a metal is at least 1000°C higher than that of argon (see Table 42. (On the other hand, an clement whose atoms are stongly bonded in» macromolecular covalent lice sich as carbon, has @ melting point 2000°C higher than the rypical ‘meta, So metalic bonding s strong, but not as srong.as some covalent boning, A clue to the nature of metallic bonding comes from looking at the atomic [peopeies of metalic elements — they all have only one, re of thice electrons in their cuter shells, and have low ionisation energies, The hull property that & most chamctesisic of metals ~ their electrical conductivity ~ often increases as the number of ionisable outer-shell electrons increases, Electical conductivity itself depends on the presence of mobile cariets of electric charge. We can therefore build up a picture of a metal structure consisting of an array of atoms, with at least some oftheir outershell clecrons removed and fiee to move throughout the latice (see Figure 4.250), These delocalised electrons (see section 3.16) are responsible for the various charactesistc physical properties of metas as detailed below. for the same concent BPHYSICAL CHEMISTRY Figure 4.25 a Thestructure of a metalic lace When a sharing fore applied, anjacent layers af callons can sk aver one ‘another, arid the metal atce can be deformed without shattering Allotropes are two (or more) forms of ‘the same element, in which the atoms or molecules ae arranged in efferent ways. Table 4.8 The properties of dlamond and orephite ude and elocaleed Iiershell cuter shal slecrone, elecvone Tee eatons . = '¢ After some electrons have been removed from the mata atoms, the atoms are loft as positive ons. The attraction berwcen the delacalised electrons and these positive {ons is responsible forthe strengths of the metalic lattices, and for their fey high cing points (© Hlectrons are very small, and move fast. When a potential difference is applied across the ends of a metallic conductor, the delocalised electrons will be attracted to, and move towards, the postive end. This movement of electical charge is what ‘we know as an electric current ‘© The paiallyjonised atoms in a metal lace are all positively charged. But they are shielded from each other's repulsion by the ‘sea’ of delocalised electrons in Doreen them, This shielding is still present nc matter how the lattice is dstomed. [As a sean of this, andl unlike fonic latices, metal latices can be deformed by beading and shearing forces without shattering (see Figuee 4.25b). Metals are therefore malleable and ductile. {9 ‘The shininess and high reflectivity of the surfaces of metas is also a property as sociated with the delocalised electrons they contain, As a photon of light hits the surface of a metal, its oscillating electric field causes the electrons on the metal's surface to oscillate to0, This allows the photon to bounce off the surface without any loss of momentum, 4.12. Graphite and the allotropy of carbon (On page 74 we looked at the macromolecular covalent stricture of diamond. Carboa's ‘ther common allotrope, graphite, is very diferent in its propertos (seo Table 4.8) colour colourlass and wansparent black and opaque Tahun, Very hard —the hardest raturally | vary soft and slppery — over 500 ‘ccurtng sod times softer than diamond 7 ‘ety poor—agaod insulator | very good along the layers tactical conduct | Gesstty = 1 10" acm) (resistivity ~ $x 10-0) density 351 gar? 227900"Figure 4.26 The stuctue of aaph Solids, liquids and gases “These differences in properties are due to a major difference in the bonding. between the carbon atoms in the two allottopes. In diamond, each carbon atom is tetrahedrally bonded to four others by single, localised covalent bonds. A tHree-dimensional network results, In graphite, on the other hand, each carbon atom is bonded to only three others (using planar sp? orbitals, see section 3.14) ‘A two-dimensional sheet of carbon atoms is formed. Each carbon atom has a spare 2p orbital, containing one eleciton, These can overlap with one another Gust a8 in benzene, see section 3.16) to form a two-dlimensional delocalised 1 ofbital spreading throughout the whole sheet of atoms, A graphite crystal is composed of many sheets or layers of atoms, stacked one on top of another (see Figure 4.26). Each sheet should be thought of as a single molecule, There is no boneling herween one sheet and the next, but the instantaneous dipole 12 substandal, because of the large susface aves attraction between them is qu involved delocalved orbital formed by overlap of 2p erbtals on ‘adjacent carbon stows, leading te: layers of delocalived ‘lactone bereen the layer. ‘Owing to its layered natace, graphite is an anisotropie material, which means that its properties are not the same in all directions. These properties of graphite ccaa he cleasly related to as steuctuse, and sesult in a variety of uses, outlined below. ‘© The use of graphite as an electrical conductor ~ whether as electrodes for electroly delocalised electrons, graphite is « good conductor along the layers, But because electrons keep to their own layer, and cannot jump from one layer to the next, _graphite is 2 poor conductor inthe direction at right angles to the layers. The same is tue for the conduetion of heat, Graphice therefore finds a use in large cruetbles, where the conduction of heat along the walls needs to be encouraged, but the transference of heat directly theotgh the hottom is not wanted (see Figure 4.27) ‘or as brushes in electric motors — is well known, Owing, 10 its 85