PEARSON EDEXCEL INTERNATIONAL A LEVEL CITA Student Book 2Publishes by Pesta Eoueston Limited, 60 Stand, London, WO2R OAL, sn pearsonglobascluns. cont Copies ooo specications ot Edexcel quoteations maybe founs onthe ‘tebe hipe/qustestonapeeraon oom “ext © Pearson Eoin Lita 2019, Designed by Toc Set Lid, Gated, UK “yore! by Tet Set Lid, Gateshead, UK ed by Gerad Oaaney, Sharon Jordan end arch ihe rica tusrtons © Pearson EoveahonLiiad 2079 usvatd by © Teeh-Sot is, Gateshead UK (Cove desig © Pearson Eaation Led 2019 Cou ages: Front Getty mages: Davis MaivScience Faction ‘ese front cover Shutterstock comDmitvy Lobanov “Tho ights of Cit Cur, Jaan Murgatroyd and Davi Soot tobe ened a6 autor fis werk have been asserted by hem naccorance Wt tba Copy Design an Patents Ac 1088. 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Tent Crete: 25 Royal Socal of Chemisty Engnered Metalowrayine Cataysus Frida Cats eacton by Dabs Houghan, 3 November, 2014, Reproduced by permission of The Royal Sci of Christy; Toyota Motor Sales: From “ojta The Ocal Bog of Toyota UK by Joe Cord bg tyotacouihow- coe iojoartut clio wor 74 Guardian Nows and Meda Limited: From ar ace in The Guardian, Soentsts Study Ocean Absorzon of Human Carbon Plc by dot raha, 1 Fetruary 2017, ps wwe egusedan omlenvtoomeimate-consenais-57-perel201 et T6scerssty- ‘oean-abeerton of human career poli: 102 Miguel anos: Fem The Daly Gesateby igual Lames ts. aalycimate oy 2506729581 Ml, 184 Royal Society of Chemistry: Envichig tho origin oF fe aon by Joanne ‘Thomson, 26 November © 2010, Repcucad by permison of The Raye Society of Charan; 17 Anthony Edward Hargreaves: For Aer Battery Power by Tony Horgresves hse rscog'sectonetuebater-power 2020096, arco: 216 Natlonal Geographic Sootety: Bus Hced Hage Octopus Suva ‘rualy Cold Temperatires, 1. © 2013, National Geosape Soil. Unit tn parison: 22 Royal Society of Chemisty Fron THe Swoot Scot of ‘Sccces by Emma Davie, Februny 2008, Reprdced by permason of The Rays ‘Secity of Chom 278 Ral Society of Chemistry: Sto chang or rane syne’ by Picard Van Noorden 1 November 2007, © 2067, Repco By Parmissin of The Royal Society of Chemisty. Inover to ensure that hs resource ofrs hah uay suport forthe associated Pearson quafcaton thas tan trough arvaw process oy te awacing body Thi grocess cafes tat ha esures ty covers the teaching ars leuring corto te spctiton al which tis med also conte tat t emanates an aporopate alice between the developmen of abet Sl kroofedge ard incereandng, mation oprpsraton for acest. Enorsement os nt cover any gusance 0 asessmentacttaso process (ea. pracice questions or accu on ow lo anewerassessren quero) Inouded the resource, rar does prescribe anyparbouar approach tthe ‘washing o daar of aroatos course. Wl the puiaars nave made every tert to ensue that aaice onthe ‘qalfcaton and te anecemart accra thecal speciation an ‘sicotsed assessment guidance materals we the ony autora souce of Irtomaton and stout aay be retro tor dente gudanes Pearson examiers have rt convicted to any sections in tis resource io ‘ramiraton papar for whies toy have oopanstuty. amie wi et use endorsed esouoes a Sout atl oy Tesource i requis to achove this Pearson qualiteation, nor does mean tht Ie tecny cutee mata walle to suppor te quateaton and ay resource lists produced bythe awarsng bod shal Pld this ad ether appropriate resources.(UTLEY COURSE STRUCTURE iv ABOUT THIS BOOK viii PRACTICAL SKILLS x ASSESSMENT OVERVIEW xii TOPIC 11 TOPIC 12 TOPIC 13 TOPIC 14 TOPIC 15 1 TOPIC 16 1 TOPIC 17 1 TOPIC 18 TOPIC 19 TOPIC 20 MATHS SKILLS PREPARING FOR YOUR EXAMS COMMAND WORDS GLOSSARY PERIODIC TABLE INDEX BlSl8lalSisin BIBI SSSR Bil8TCU UNIT 4: RATES, EQUILIBRIA AND FURTHER ORGANIC CHEMISTRY TOPIC 11 KINETICS 2 11A FURTHER KINETICS 1 TECHNIQUES FOR MEASURING THE RATE OF REACTION 4 2 RATE EQUATIONS, RATE CONSTANTS AND ORDERS OF REACTION 7 3 DETERMINING ORDERS OF REACTION 4 RATE EQUATIONS AND MECHANISMS 15 5 ACTIVATION ENERGY AND CATALYSIS: 19 6 EFFECT OF TEMPERATURE ON THE RATE CONSTANT = 22 THINKING BIGGER: CATALYST CRAFT 26 EXAM PRACTICE 28 TOPIC 12 ENTROPY AND ENERGETICS 30 12A ENTROPY 1 INTRODUCTION TO. ENTROPY 32 2 TOTAL ENTROPY 36 3 UNDERSTANDING ENTROPY CHANGES: 12B LATTICE ENERGY 1 LATTICE ENERGY, A,.H AND BORN-HABER CYCLES 44 2 EXPERIMENTAL AND THEORETICAL LATTICE ENERGIES 48 3 ENTHALPY CHANGES OF SOLUTION AND HYDRATION 51 THINKING BIGGER: HYDROGEN REVOLUTION 54 EXAM PRACTICE 56 TOPIC 13 CHEMICAL EQUILIBRIA 58 13A CHEMICAL EQUILIBRIA 1 EQUILIBRIUM CONSTANT, K. 60 2 EQUILIBRIUM CONSTANT, K, 63 3 FACTORS AFFECTING EQUILIBRIUM CONSTANTS 1 65 4 FACTORS AFFECTING EQUILIBRIUM CONSTANTS 2 67 5 RELATING ENTROPY TO EQUILIBRIUM CONSTANTS = 71 THINKING BIGGER: CATASTROPHE FOR CORAL = 74 EXAM PRACTICE 76eset n TOPIC 14 ACID-BASE EQUILIBRIA 78 14A STRONG AND WEAK ACIDS 1 THE BRONSTED-LOWRY THEORY 80 2 HYDROGEN ION CONCENTRATION AND THE pH SCALE 83 3 IONIC PRODUCT OF WATER, K, 86 4 ANALYSING DATA FROM pH MEASUREMENTS 88 14B ACID-BASE TITRATIONS 1 ACID-BASE TITRATIONS, pH CURVES AND INDICATORS 91 2 BUFFER SOLUTIONS 96 3 BUFFER SOLUTIONS AND pH CURVES: 100 THINKING BIGGER: A PROBLEM GROWS 102 EXAM PRACTICE 104 TOPIC 15 ORGANIC CHEMISTRY: CARBONYLS, CARBOXYLIC ACIDS AND CHIRALITY 106 15A CHIRALITY 1 CHIRALITY AND ENANTIOMERS 108 2 OPTICAL ACTIVITY 110 3 OPTICAL ACTIVITY AND REACTION MECHANISMS 12 15B CARBONYL COMPOUNDS 1 CARBONYL COMPOUNDS AND THEIR PHYSICAL PROPERTIES 114 2 REDOX REACTIONS OF CARBONYL COMPOUNDS 117 3 NUCLEOPHILIC ADDITION REACTIONS 15C CARBOXYLIC ACIDS 1 CARBOXYLIC ACIDS AND THEIR PHYSICAL PROPERTIES 122 2 PREPARATIONS AND REACTIONS OF CARBOXYLIC ACIDS 124 15D CARBOXYLIC ACID DERIVATIVES 1 CARBOXYLIC ACID DERIVATIVES: ACYL CHLORIDES 126 2 CARBOXYLIC ACID DERIVATIVES: ESTERS 129 3 CARBOXYLIC ACID DERIVATIVES: POLYESTERS 132 15E SPECTROSCOPY AND CHROMATOGRAPHY 1 SIMPLE CHROMATOGRAPHY 134 2 DETERMINING STRUCTURES USING MASS SPECTRA 136 3 CHROMATOGRAPHY: HPLC AND GC 138 4 CHROMATOGRAPHY AND MASS SPECTROMETRY 140 5 PRINCIPLES OF NMR SPECTROSCOPY 142 6 "C.NMR SPECTROSCOPY 144 7 ‘HNMR SPECTROSCOPY 148 8 SPLITTING PATTERNS IN ‘HNMR SPECTRA 151 THINKING BIGGER: LIFE’S MIRROR IMAGES 154 EXAM PRACTICE 156Mcussoieatiig UNIT 5: TRANSITION METALS AND ORGANIC NITROGEN CHEMISTRY TOPIC 16 REDOX EQUILIBRIA 158 16A STANDARD ELECTRODE POTENTIAL 1 STANDARD ELECTRODE (REDOX) POTENTIALS 160 2 ELECTROCHEMICAL CELLS 166 3 STANDARD ELECTRODE POTENTIALS AND THERMODYNAMIC FEASIBILITY 168 16B REDOX IN ACTION 1 FUEL CELLS 172 2 REDOX TITRATIONS 174 THINKING BIGGER: ELECTROLYTE EVOLUTION 178 EXAM PRACTICE 180 TOPIC 17 TRANSITION METALS AND THEIR CHEMISTRY 182 17A PRINCIPLES OF TRANSITION METAL CHEMISTRY 1 TRANSITION METAL ELECTRONIC CONFIGURATIONS 184 2 LIGANDS AND COMPLEXES 187 3 THE ORIGIN OF COLOUR IN COMPLEXES 189 4 COMMON SHAPES OF COMPLEXES 192 5 SQUARE PLANAR COMPLEXES 194 6 MULTIDENTATE LIGANDS 196 17B TRANSITION METAL REACTIONS 1 DIFFERENT TYPES OF REACTIONS 199 2 REACTIONS OF COBALT AND IRON COMPLEXES 201 3 THE CHEMISTRY OF CHROMIUM 203 4 REACTIONS OF saiiaiane? COMPLEXES 207 5 THE CHEMISTRY OF VANADIUM 208 6 REACTIONS OF NICKEL AND ZINC COMPLEXES: 210 17€ TRANSITION METALS AS CATALYSTS 1 HETEROGENEOUS CATALYSIS 212 2 HOMOGENEOUS CATALYSIS 214 THINKING BIGGER: POWERFUL PIGMENTS 216 EXAM PRACTICE 218 TOPIC 18 ORGANIC CHEMISTRY: ARENES 220 18A ARENES: BENZENE 1 BENZENE: A MOLECULE WITH TWO MODELS, 222 2 SOME REACTIONS OF BENZENE 226 3 ELECTROPHILIC SUBSTITUTION MECHANISMS 228 4 PHENOL 230 THINKING BIGGER: MOLECULES OF FRAGRANCE ‘AND TASTE 232 EXAM PRACTICE 234Mss eg oT TOPIC 19 TOPIC 20 MATHS SKILLS 282 ORGANIC NITROGEN ORGANIC PREPARING FOR YOUR COMPOUNDS: AMINES, = SYNTHESIS 258 | EXAMS 286 AMIDES, AMINO ACIDS SAMPLE EXAM ANSWERS 288 AND PROTEINS 236 | 200 ORGANIC COMMAND WORDS 293 STRUCTURES GLOSSARY 295 19A AMINES, AMIDES, 1 ORGANIC ANALYSIS 260 PERIODIC TABLE 298 AMINO ACIDS AND PROTEINS 2 ORGANIC SYNTHESIS 264 | INDEX 299 1 AMINES AND THEIR 3 HAZARDS, RISKS AND PREPARATIONS. 238 CONTROL MEASURES 269 4 PRACTICAL TECHNIQUES 2 AGID BASE REACTIONS OF” INORGANIC CHEMISTRY: 3 OTHER REACTIONS OF Pant t ere 5 PRACTICAL TECHNIQUES ‘AMINES ane IN ORGANIC CHEMISTRY: 4 AMIDES AND PART 2 274 BOTA 245 THINKING BIGGER: 5 AMINO ACIDS 249 | CHALLENGING ORGANIC 6 PEPTIDES AND PROTEINS 252 | SYNTHESES 278 THINKING BIGGER: EXAM PRACTICE 280 PROTEIN MOLECULES: LIFE'S HARDWARE 254 EXAM PRACTICE 256rf ABOUT THIS BOOK This book is written for students following the Pearson Edexcel International Advanced Level (VAL) Chemistry specification, This book covers the full International Advanced Subsidiary (IAS) course and the first year of the International A Level (IAL) course. ‘The book contains full coverage of IAL units (or exam papers) 4 and 5. Each unit has five Topic areas that ‘match the titles and order of those in the specification. You can refer to the Assessment Overview on. pages xii-xil for further information. Students can prepare for the written Practical Paper by using the IAL Chemistry Lab Book (see pages x-xi of this book) Each Topic is divided into chapters and sections to break the content down into manageable chunks. Each section features a mix of learning and activities supported by the features explained below. ‘Leaming objectives Each chapter tats witha Ist of ‘key leaming objectives. ion reference. The exact specification points covered inthe Section are provided SOWA sau ana Nme say Learning tips ‘These help you focus your learning and avoid commen arors. Grose Feterences to previous or folowing Student Book content help you to navigate course content. Worked examples irked examples show you how to work through questions, and set out calculations Exam hints Tips on haw te anwer exam- syle questions and guiaance for exam preparation, incucing rexjurements inccatod by Denicul” command words. Did you know? Intersting facts holp you remember the Key concepts, ‘Checkpoint {Quests atthe end of each section check understanding of the key laaring points in each ‘chapter Certan questions alow you to develop skills that wil bo Aaluable for further study and in the workplace Subject Vocabulary Key forms are highlighted inpiue nthe text, Clear efintions are provided at the end of each section for fasy relerence, and are also Colated na glossary atthe bck ofthe book,‘You shoul be able to put every stage of yourlearning i context, chapter by chapter * Lins to other areas of Chemistry include previous knowed ‘thats bul on fn the topo, and future areas of knowledge an appieation that you wil cover lator in your course, + Maths knowledge required is Getalled in ahandy check. f you need to practise the maths you ed, you can use the Maths Skis feterence atthe back ofthe Book a8 ‘staring point PRMD LOE) CATASTROPHE FOR CORAL? > === Exam Practice Examsyle questions at the-end ofeach chapter are tailored tothe Pearson Edoxcel ‘specication to allow for practice {ahd development of exam ‘writing technique. They algo allow fr practeo responding {othe command worse Used in the exams (se the command ‘words glossary at the back of this book. You can aiso reer to the Preparing for Your Exams ‘section atthe back of the book, for sample exam answers with ‘commentary. Eva Thinking Bigger . — = [Attha end of each topic there — Is an opportuni to read ana work ith rea-He reseazch and vting about science a The activites nalp you to read real-le material that's relevant to your coureo, analyse now scintits write, ink cridealy land consider how cterent aspects of your leaming piace together “These Thinking Bigger activ, focus on key wansterable sks, hich are an important basis f+ key academic quale. Ete Cee aePRACTICAL SKILLS Practical work is central to the study of chemistry. The second year of the Pearson Edexcel International Advanced Level (VAL) Chemistry course includes eight Core Practicals that link theoretical knowledge and understanding to practical scenarios. Your knowledge and understanding of practical skills and activities will be assessed in all examination papers for the IAL Chemistry qualification. * Papers 4 and 5 will include questions based on practical activities, including novel scenarios. * Paper 6 will test your ability to plan practical work, including risk management and selection of apparatus. In order to develop practical skills, you should carry out a range of practical experiments related to the topics covered in your course. Further suggestions in addition to the Core Practicals are included in the specification, which is available online Sea Pea) Toric 11 (CP9a_ Following the rate of the iodine-propanone reaction by a titrimetric KINETICS method (CP9b Investigating a ‘clook reaction’ (Harcourt-Esson, iodine clock) (P10 Finding the activation eneray of a reaction TOPIC 14 P11 Finding the K, value for a weak acid ‘ACIO-BASE EQUILIBRIA TOPIC 16 P12 Investigating some electrochemical cells aa CP13a_ Redox titrations with ron(l) ons and potassium manganate(VI) CP13b Redox titrations with sodium thiosulfate and iodine TOPIC 17 P14 Preparation of a transition metal complex ‘TRANSITION METALS AND THEIR CHEMISTRY TorIC 19 P15 Analysis of some inorganic and organic unknowns ORGANIC NITROGEN COMPOUNDS: AMINES, AMIDES, AMINO ACIDS AND PROTEINS. ToPIC 20 (P16 Preparation of aspirin ORGANIC SYNTHESISSR aay In the Student Book, the Core Practical speetiations fare supplied inthe relevant Sections, Practical Skile Practical skills boxes explain techniques used in the Gore Practical, and also detal useful sills ara krnowiedge gained in ‘other related investigations. This Student Book is accompanied by a Lab Book, whic includes Instructions and wring frames forthe Core Practical fr you to record Your reaults and refcct on Sour work. Practical skis Bractice questions and answers are also provided ‘The Lab Book records can ‘be used as preparation for the Practica Skile Paper. eyASSESSMENT OVERVIEW ‘The following tables give an overview of the assessment for Pearson Edexcel International Advanced Level course in Chemistry. You should study this information closely to help ensure that you are fully prepared for this course and know exactly what to expect in each part of the examinations. More information about this qualification, and about the question types in the different papers, can be found in Preparing for your exams on page 286 of this book. PERCENTAGE | PERCENTAGE ud ie aati sr cea RATES, EQUILIBRIA AND FURTHER 40% 20% Thour January, June and October ORGANIC CHEMISTRY 45 minutes Written exam paper Paper code WCH14/01 Externally set and marked by Pearson Edexcel Single tier of entry PERCENTAGE | PERCENTAGE Ca) are Cant cm AVAILABILITY TRANSITION METALS AND ORGANIC 40% 20% Thour January, June and October NITROGEN CHEMISTRY 4S cuinutes Fig assessment: Jane 2020 ‘Written exam paper Paper code WCHISI01 Externally set and marked by Pearson Edexcel First assessment: January 2020 Single tier of entry PERCENTAGE | PERCENTAGE GAS Gas Ss PRACTICAL SKILLS IN CHEMISTRY II 20% 10% Thour January, June and October ‘Written exam paper 2O-minutes Fist assessment: June 2020 Paper / Unit code WCHIG/O1 Externally set and marked by Pearson Edexcel Single tier of entryPsa) cc ASSESSMENT OBJECTIVES AND WEIGHTINGS Se sa aa) ES ‘Demonstrate knowledge and understanding of science. 34360-2931 324 {a) Application of knowledge and understanding of scienee in 3436 33536 33.36 familiar and unfamiliar contexts. A02 (b) Analysis and evaluation of scientific information to make oa 416 td judgements and reach conclusions. 7 Experimental skills in science, including analysis and evaluation, ii p a of data and methods. RELATIONSHIP OF ASSESSMENT OBJECTIVES TO UNITS ASSESSMENT OBJECTIVE (%) aot 02(A) n02(8) ‘803 TOTAL FOR INTERNATIONAL ADVANCED SUBSIDIARY 33-36 4-36 on 20 AOI ‘02 (A) ‘02 (8) ‘03 ‘TOTAL FOR INTERNATIONAL ADVANCED LEVEL, 24 33-38 44 2Your health depends on a complex interplay of a large number of chemical reactions taking place in the cells of your body. In a healthy body, these reactions will take place at the correct rate, in the right place and at the right time. These reactions are controlled by enzymes. The branch of chemistry concerned with the rates of chemical reactions is called chemical kinetics. The term ‘kinetics’ implies motion and comes from the ancient Greek word for movement, kinesis. We can use the information obtained from the study of chemical kinetics to: understand the body's metabolism (the chemical processes in the body) model the effects of pollutants in the Earth’s atmosphere develop new catalysts, which is of great importance to the chemical industry. In Topic 9 (Book 1: IAS), we used a qualitative approach to the understanding of reaction rates. In this topic we will develop this further by adopting a quantitative approach. This will enable us to begin to understand what is happening during chemical reactions: We know how atoms can bond together to form molecules, but why do the atoms change partners during, chemical reactions? What exactly happens when a hydrogen molecule meets an iodine molecule and they subsequently react to produce hydrogen iodide? It has been reported by scientists that the herb ginseng may be just as effective as Prozac at treating depression. Herbs and plant extracts have been used for centuries to cure diseases and to relieve pain. In 7 many cases they are effective because they control the rates of chemical reactions within the body. In this topic we will study the rates of chemical reactions and the mechanisms by which they take place. Recognise and make use of appropriate units in calculation Recognise and use expressions in decimal and ordinary form Use calculators to find and use power functions Use an appropriate number of significant figures Change the subject of an equation Substitute numerical values into algebraic expressions using appropriate units for physical quantities Solve algebraic expressions Translate information between graphical, numerical and algebraic forms Plot two variables from experimental or other data Determine the slope and intercept of a linear graph Calculate the rate of change for a graph showing a linear relationship Draw and use the slope of a tangent to a curve as a measure of the rate of changeWiracc e nce ey eer) nes allo atures andOU aaa Ce) Dee TR Sas I Understand the term ‘rate of reaction’ I Select and justify a suitable experimental tecUlique to obtain rate data for a given reaction, including (titration (ii) colorimetry (i) mass change (iv) volume of gas evolved (¥) other suitable tecUlique(s) for a given reaction. RATE OF REACTION ‘The rate of a reaction can be expressed in two ways: (1) How the concentration of a product increases with time. change in concentration of product time (2) How the concentration of a reactant decreases with time. ‘change in concentration of reactant time ‘The negative sign in the second expression shows that the concentration of the reactant is decreasing and therefore gives a positive value for the rate, rate = rate = Rate is measured in units of concentration per unit time, and the ‘most common units are mol dmv! 5“! ‘The expressions in calculus notation are: _ product] dt reactant] dt This rate of reaction is sometimes called the ‘overall rate of, reaction’ TECHNIQUES FOR MEASURING THE RATE OF REACTION Before investigating the rate of a particular reaction, itis necessary to know the overall equation, including state symbols, for the reaction so that we can decide what technique to use to follow the reaction, rate rate = ‘There are various techniques available to use, such as: 1 measuring the volume of a gas evolved 2 measuring the change in mass of a reaction mixture 3. monitoring the change in intensity of colour of a reaction mixture (colorimetry) 4 measuring the change in concentration of a reactant or product using titration Se OPP Wee OU ee AUT Cece ca 11.361) EO) TERE) 5 measuring the change in pH of a solution 6 measuring the change in electrical conductivity of a reaction mixture. ‘The technique chosen to follow the reaction will depend on the nature of the reactants and products, as well as the conditions, under which the reaction Is carried out. FFor example, the reaction between calcium carbonate and dilute hydrochloric acid, CaCOy(s) + 2HCHaq) —+ CaCl{aq) + HOt) + COs(g) could conveniently be followed by measuring the volume of gas (technique 1) given off at regular time intervals, or by measuring the change in mass of the reaction mixture with time (technique 2) However, the reaction between propanone and iodine in aqueous solution, (CH,COCH (aq) + I:(aq) CH,COCH, (aq) + H"(aq) + (aq) could not be followed by measuring the change in mass because all products of the reaction remain in solution. It would be possible, however, to follaw the reaction by monitoring the decrease in intensity of colour of the reaction mixture, since 1,(aq) is the only coloured species present (technique 3). TECHNIQUE 1: MEASURING THE VOLUME OF A GAS EVOLVED ‘The two most common techniques for collecting and measuring the volume of a gas evolved during a reaction are: 1 collection over water into a measuring cylinder (8g A), and 2 collection using a gas syringe (fig B). ‘The technique chosen will depend partly on the level of precision, required. The gas syringe has a greater degree of precision, but if large volume of gas isbeing measured, the difference in the degree of measurement uncertainty becomes so small that either instrument is sufficiently precise. ator A figA Collecting a gis over water. ExUnIE Reactions producing gases that are very soluble in water, suchas, sulfur dioxide, cannot use the gas collection over water tetiqueae gas evoved 9° 0 conical ask A figs Collecting a gasina gas syringe TECHNIQUE 2: MEASURING THE CHANGE IN MASS OF A REACTION MIXTURE ‘This is another technique applicable to reactions in which a gas is evolved. measured ‘The reaction flask and contents are placed on a digital balance and the decrease in mass i as the reaction proceeds (fig C). A fig Coton woos placed in the neck ofthe fast prevent ‘This technique is most precise when the gas given off has a relatively high density, such as with the oss of liquid spray carbon dioxide. With a low-density (Le. low relative molecular mass) gas such as hydrogen, the mass ‘changes are so small that the measurement uncertainties become significant. TECHNIQUE 3: MONITORING A COLOUR CHANGE (COLORIMETRY) Colour change can sometimes be monitored using observation only. However, using a colorimeter gives more precise results (fig D), A colorimeter can detect far more subtle changes than the human eye can observe, and provides quantitative (rather than a subjective) measurement, A figD colorimeter TECHNIQUE 4: ANALYSIS BY TITRATION ‘This technique involves using a pipette to remove small samples (aliquots) from a reaction mixture at regular intervals. The reaction in the aliquot can either be stopped by adding another substance to tor slowed down to almost zero by immersing it in an ice bath. The aliquot is then titrated to determine the concentration of a reactant or product species, The process of stopping or slowing down the reaction in an aliquot is known as “quenching For example, ifthe reaction involves an acid, the aliquot, after quenching, could be titrated against a standard solution of sodium hydroxide to determine the concentration of the acid. This technique is used to investigate the reaction between iodine and propanone, which Is catalysed by ackd, Sodium hydrogen carbonate is added to the aliquot to remove the acid catalyst and, as a result, effectively stops the reaction. The remaining iodine is then titrated against a standard solution of sodium thiosulfate (fig E) CH COCHs(2q) + 1x(aq) 1:(aq) + 28,0¥ (aq) + 2-(aq) + 8,07 (aq) A AigE Tirating ine against sodium thiolate CH,COCH, (aq) + H"(aq) + I-(aq)MSR nus aca) aC aay sus TECHNIQUE 5: MEASURING THE ELECTRICAL CONDUCTIVITY If the total number, or type, of ions in solution changes during a reaction, it might be possible to follow the reaction by measuring changes in the electrical conductivity of the solution using a ‘conductivity meter For example, it could be used to follow this reaction: SBr-(aq) + BrO5(aq) + 6H*(aq) —> 3Bn{aq) + 3H,O(}) TECHNIQUE 6: MEASURING ANY OTHER PHYSICAL PROPERTY THAT SHOWS A SIGNIFICANT CHANGE Possible physical properties that have not already been mentioned include changes in the volume of liquid (lilatometry), chirality and refractive index eas 1. State suitable tecUiques to collet rate data foreach ofthe following reactions. (a) Magnesium with dilute sulfuric acid: Ma(s) + 24-09) — Mag) + 6) (b) thy ethanoate with sodium hydroxides (CH;COOCH;CH,(!) + OH (aq) + CHsCOO (aq) + CHCH-OH(aq) (©) Hydrogen gas with iodine gas Hale) + Le) 2418) 1B Why would the tecUique of measuring the change in mass of a reaction vessel and contents not ‘workywellin the reaction between magnesium and dilate sulfuric ack? 3.0) The reaction between calcium carbonate and dilute hydrachloric acid can be followed by collecting and measuring the volume of gas produced, The gas could be collected aver water mn a measuring cylinder or in a gas syringe. Which tecLique would be the more sultable for this reaction? Explain. your answer Berea (veal) rate of reaction the change in concentration of a species divided by the time it takes forthe change to occur ll reaction rates are postive (Chemica) species an atom, a molecule or an ion thats aking part ina chemical reactionEr SRA Uae UU Oa EOS Reon EDN sssK 00:1 24110) Understand the terms: rate equation, rate = k{A]"[B]", where m and n are 0, 1 or 2 ‘order with respect to a substance in a rate equation ‘overall order of a reaction rate constant rate-determining step. RATE EQUATION WHAT IS A RATE EQUATION? ‘The usual relationship between the rate of reaction and the concentration of a reactant is that the rate of reaction is directly proportional to the concentration. In other words, as the concentration is doubled, the rate of reaction doubles. Unfortunately this is not always the case. Sometimes the rate will double, but sometimes it wl Increase by a factor of four In some cases, the rate of reaction does not increase at al or itincreases in an unexpected way Let us consider the simple relationship where the rate is directly proportional to the concentration of reactant, say A. We can represent this by the expression: rate x [A] rate = HA] ‘where is the proportionality constant. ‘Thisis called the frst order rate equation. The constant ks called the rate constant + Every reaction has its own particular rate equation and its own rate constant + Rate constants will only change their value with a change in temperature. Other common rate equations with respect to an individual reactant are second order raie equation: rate = HAI? zero order rate equation: rate = KAJ? or rate = k Zero order reactions do not occur very often, and it might be difficult at this stage for you to imagine ‘why they should occur at all. However, you will ind out shortly why they can occur If two or more reactants are involved then its possible to have a third order rate equation: third order rate equation: rate = HAJ"B) THE UNITS OF RATE CONSTANTS Table A shows the units for rate constants, using mol dm” as the unit of concentration and seconds as the unit of time. You find the units by rearranging the rate equation, ORD ze EXAM HINT as oS The values for orders of Second dm? mot" s ‘reaction in rate equations will Third dni mols only ever be 0, or 2at table A International A Level.ane \TE EQUATIONS, The units are obtained by rearranging the rate equation. For example, fora second order reaction: rate (ar Inserting the units we obtain: molds" mol dn x mol dm This cancels down to: moldar® ‘which equates to dm? mol? s~ “The majority of reactions involve two or more reactants. If we call the reactants A, B and C, then the reaction may be first order with respect to A, first order with respect to B and second orcer with respect to C. The overaf rate equation will be: rate = MAYBICP and the overall order of the reaction is four (1 + 1 + 2), Note that you are adding the powers, For a general reaction in which the orders are m,n and p, we have rate = KAPTBYICY The overall order of the reaction is m+ n+ p. REACTION MECHANISMS Many reactions can be represented by a stoichiometric equation containing many reactant particles. For example, the reaction, between manganate(VIl) ions and iron(tl) ions in acidic solution can be represented by: MnQ"(aq) + BH"(aq) + 5Fe*(aq) — Mn?*(aq) + 4H,0() + 5Fe™(aq) If this reaction actualy proceeded in a single step, then the reaction would be very slow indeed, The probability of 14 particles simultaneously colliding. all with the correct orientation and energy, is so small that we can say itis effectively zero. The reaction is, however, very fast indeed even at room temperature. It must therefore, proceed via a series of steps. all of which follow on quickly from one another. It is important to recognise that a reaction involving simultaneous collision of more than two particles is very rare. The orders of reaction of the individual reactants can help us to suggest a possible mechanism for a reaction. The mechanism cannot be inferred from the stoichiometric equation, because the ‘mathematical relationship between the rate of reaction and the concentration of reactants (ie. the orders of reaction) can only be determined through experiments. Consider the reaction: A+B4+C9D+E for which the experimentally determined rate equation is: rate = AJB] This could mean that C was present in such a large excess that changes in its concentration were negligible and therefore had no ‘measurable effect on the rate of reaction. aC aay however this is not the case, and changes in [C] really do not have any elfect on the overall rate of reaction, then a cifferent explanation ust be sought for why (C]does not appear inthe rete equation. In this case, there must be a step involving a reaction between A ‘and B that has an effect on the rate of reaction. There must also be another step in which C reacts, but this reaction has no effect on the overall rate of reaction. This could be explained by assuming that the reaction between A and B takes place before Chas a chance to react, and that the reaction between A and B is significantly sioner than the reaction involving C. If this were the case, then the ‘mechanism for the reaction could be Step 1: SLOW Step 2: FAST Since only Step 1 is rate-determining, then only changes in [A] and [B] will affect the overall rate of reaction. Changes inthe rate at which Step 2 occurs, owing to changes in [C], will be negligible. A+BOZ Z+C3D4E Important points to remember are that +The slowest step in a reacion determines the overat rate of the + The slowest step is known as the rate-determining step of the reaction ‘We will return to the concept of reaction mechanisms, and consider them in much more detail, in Section 114.4. Wesel ‘useful way of visualiing the idea of rate-determining step iso imagine that three students are aranging some sheets of note into set (ig A). Step 1: the notes are arranged into ten ples and the ist student callects a sheet rom each of te piles Step 2: the second student takes the set often papers and shuffles them so that they are tidy and reagy for stapling Step 3: the third stude staples the set of notes together The overall ate ofthis process (ie. the ate at which the final sts of notes are prepared) depends onthe rate of Step 1. the calecting of the sheets of notes, since thi is by far the slowest sep. itdoes not mater within feason, hove quick the tidying up for staplngis done. For most ofthe time the second and third students wal be doing nothing while they wait forthe fist student to colet the sheets The mechanism ofthe process therfore Step: Student Tcolects sheets SLOW Step 2: Sudent2tdies set ofsheets FAST Step 3: Sudent 3 staples set ofsheets FAST A fig. Analogy for ate determining se.ae EI All reactant species involved ether in, or before, ‘reaction and will appear inthe rate equation. Ceol 1. Therate equation forthe reaction beeen peroxydisulate ions and iodide ions is rate = 45,081] {a) What is the order of reaction with respect to (i) peroxydisulfate ions and (ii) iodide ions? (b] What's the overall order of reaction? 2. The ate equation forthe eacion between Pand Qi sate ~ HPIQF ‘What wl be the increase in at (0 [Ps doubled, while [Q] is kept constant? {b) [Q] is doubled, while [P} is kept constant? (©) [P] and [Q] are both doubled? 3. Inthereaction between R,S andT: + when the concentration of Ris doubled, the rate increases by fur times + when the concentration of is doubled, the rate does not change + when the concentration of s doubled, therate doubles. Dy (0) Deduce the orders of reaction with respect to R, Sand. ELIE rronen-soume (b) Write the rate equation for the reaction. (©) Whatis the overall order of reaction? 1 rate-determining step have an effect on the rate ofthe Baar ‘ate equation an equation expressing the mathematical relationship between the rate of reaction and the concentrations ofthe reactants ‘order (ofa reactant species) the power to which the concentration ofthe species israised in the rate equation ‘overall order (ofa reaction) the sum of al the individual orders rate-determining step (oF a reaction) the slowest step in the mechanism for the reaction11A 3 DETERMINING ORDERS Oa eae) Dee TR Sas Concentration of 120) IE Understand the terms: (i) rate equation, rate = KIA}"(B}’, where m and are 0, 1 or 2 (il) halite. Be able to cakculate the half-life of a reaction, using data from a suitable graph, and identify a reaction with a constant halflife as being first order. I Understand experiments that can be used to investigate reaction rates by: ()_ an initial-rate method (ii) continuous monitoring method. Be able to deduce the order (0, 1 or 2) with respect toa substance in a rate equation, using data from: ()_ a concentration-time graph (i) @ rate-concentration graph (i) an intial-rate method HOW CAN WE DETERMINE THE RATE EQUATION? This question can equally be phrased ‘How can we determine the order of reaction with respect to each reactant?” ‘There are two methods for determining orders of reaction. They are both experimental. Indeed, orders of reaction can only be determined by experiment, The first is sometimes called the ‘continuous method’ The second is sometimes called the ‘Initial-rate method! ‘THE CONTINUOUS METHOD In this method, one reaction mixture is made up and samples of the reaction mixture are withdravm at regular time intervals. The reaction in the sample is stopped, if necessary, by quenching, ‘The concentration of the reactant is then determined by an appropriate experimental technique, such as titration. + The frst step isto draw a ‘concentration-time’ graph, + The second step isto find out the half-life for the reaction at different concentrations, If the half-life has a constant value, then the reaction is first order with respect to the reactant. ‘The Isthal.if, fr the change in concentration from 120 to 60 units is 1005 (fig A) Se Poa 11.40) Te CTT RBI) 11.500) Tr 115¢i) 11.40) reactanvarbtary uns Tana aa ratte hale atte Ak fig. A graph of concentration of reactant against tine for afistordet ‘The 2nd halFlife, for the change in concentration ftom 60 to 30, Units, is 100s. “The ard halflife for the change in concentration fram 30 to 15 units, is 100s. Since all three half-lives are the same, the reaction is first order with respect to the concentration of the reactant plotted, If the halflife doubles as the reaction proceeds, then the reaction is second order Ifthe graph isa straight line with a negative gradient, then the rate of reaction is constant no matter what the concentration of the reactant (fg B). In other words, the reaction is zero order with respect tothe reactant. Concentration of reactant Tne Ab fig A graph of concentration against time fora zero order reacion. A typical set of results is shown in table A for the reaction 2N,Os(g) — 4NOx(g) + Ole)ae Se ares Deseo eC 80 216 90 185 cca o | 0 | 2 | 3% | 4 | so | 60 | 70 ose 22.90 1627 | 1229| 9.35 | 689 | 4a8 | 368 | 274 table A If you plot a graph of [N,O,] against time using the above data, you will ind that the line is curved and the halflife is constant; as a result, the reaction is frst order with tespect to N;Os, CALCULATING RATE FROM A CONCENTRATION-TIME GRAPH ‘The rate of reaction at any given time can be determined from a concentration-time or volume-time sgraph by craving a tangent to the curve at the given time and calculating the gradient of the tangent Fig C shows the change in concentration of a reactant with time, Concentation 2.00 ofreactersimot m= 2 1.60" 140 120: 1.00. 080: 60 == 040 020 SS SPSSESSEERS Time's A. fig Determining an instantaneous at of reaction om a graph of cancentation of reactant aginst time. ‘A tangent to the curve has been drawn at time = 400s. “To find the rate at this time point, draw as large a tangle as possible and then measure x and y, x= 1470s and y= —1.60mol dm. Shange in concentration of react time rate 1.60 mold? 14708. CALCULATING RATE FROM A VOLUME-TIME GRAPH ‘The procedure is exactly the same for a volume-time graph for a gas evolved (Section 114.1), = 1.09 x 10-*moldmrs* This time the curve wll slope upwards not downwards (fig D) Yel ot gas evoved gradient at time = 1 Tine A. fig Determining an instantaneous rate of eaction from a graph of volume of gs evo ‘The rate of reaction obtained in this way is sometimes called the instantaneous reaction rate. TTSED aU esa a aC aay ‘THE INITIAL-RATE METHOD FOR DETERMINING THE RATE EQUATION In this method, severa reaction mixtures are made up and the intial rate (ie. the time taken for a fixed amount of reactant to be used up or fora fixed amount of product to be formed) is measured, From these times, its then possible to calculate the mathematical relationship between the rate of the reaction and the concentration of the reactant. A typical set of results is shown in table B for the reaction A+B—oC CE 1 ai ai 002 2 a 02 004 3 az a O04 Ee i tables If we now look at experiments 1 and 3, we can see that (AJ has doubled while (B] has remained constant. The rate of reaction has also doubled. This indicates that the reaction is first order with Tespect to A and, as a result. we can write: rate o [A] If we now look at experiments 1 and 2, or experiments 3 and 4, we can see that [B] has doubled ‘while [A] has remained constant. The initial rate of reaction has also doubled. This indicates that the rate of reaction is directly proportional to [B]. That is. the reaction i first order with respect to B. Asa result, we can write rate x [B] ‘The overall order of the reaction is two, and the complete rate law (rate equation) is: KAJB) Note that the numbers in table B were deliberately kept simple to illustrate a point. Real ‘experimental results rarely ft such an exact pattern, and you may have to look for the nearest whole ‘numbers to obtain orders. rat DETERMINING ORDER FROM A RATE-CONCENTRATION GRAPH “The method described above to determine intial rates, with changing concentrations, results in ‘only approximate values for the initial rates. However, since most orders of reaction with respect to individual reactants have integer values, this approximation is usually acceptable, In an inital rates experiment, the time measured is that fora fixed amount of product to be formed, ‘or that for a fixed amount of reactant to be used up. Since the amount of product formed, or reactant used up, is kept constant, the intial rate of reaction is proportional to the reciprocal of the time, ¢ ‘measured. That is: sax! ‘This assumes that the rate is constant for the whole time period, z However this is not true because as soon as the reaction stars the rate begins to decrease. The rate calculated from the expression is, therefore, the mean (average) rate over time, z, and not the sae initial rate of reaction, The approximation becomes poorer with larger values of «However, the approximation is good enough to determine integer order Itmight be possible to determine orders of reaction from just a few measurements. However, itis usual toecora ang of eu an ota gph apt concen of recat ‘The shape of the graph in table C indicates the order of reaction,ae ears Deas Ca 13 Se en On ed eed CCL Peer ae o en Oy eer Be careful to check the units on the axes of graphs. Graphs wth thesame shape wl have diferent meaning there are diferent units on the axes ti i iy table Itisimposibeto determine diel by sight fom arate-concentration graph thatthe reaction is second order Ifthe graph is a curve a shown, then its necessary to then plot + against (AP. I this produces a straight ne passing through the origin, then the reaction is second order with respect to A i hi fei gph of eaten et hconcron ola manera econ elerclon, 1. compound P decomposes when heated. The graph shown the change in concentration when a SKILLS Sa sampe of is heated 6 Concentration of Pin ati jo 060 800 1000 1200 1400 1600 1800 Timals (a) Stare what is meant by the term half-life of reaction (b) Use the graph to show that the decomposition of Pi a fist order reaction. (0) Beplain the effect on the half-life of doubling the inital concentration of (d) Calculate the rate constant, for this reaction using the following expression: 0 half-life Include units in your answer. (6) Write the rate equation fr this reaction (8. ()_ Use the graph to determine the concentration of Pat 800, (i)_ Use the rate equation from (e) and your answers to (a) and (f() to calculate the rate of reaction at 800s, Include units in your answer (g) Describe how could you determine the reaction rate at 800s directly from the graph.MRED ae sea ao aC aay ESLER wvreneneranon .B The equation forthe reaction between bromide ions and bromate(V) ons in acidified aqueous solutions: 5Br (aq) + 8-O3(aq) + 6H"(aq) —- 38raq) + 34,01) The table shows the results of four experiments caried out using different concentrations ofthe three reactants. Soo aaa roy Try Cy pati tie ota ota 4 0.10 020 020 96*10 (a) Deduce the order of reaction with respect to: (ar (i B05 (iH (b) Write the rate equation for the reaction. (6) Using the results from experiment 1, calculate the rate constant, k; for the reaction Include units in your answer, Bere eng hal life ofa reaction) the time taken fo the concentration of the reactant to fal one-half ofits inital valve instantaneous reaction rat the gradient ofa tangent drawn to the lin ofthe graph of concentration agaist ime. The instantaneous rate varies asthe rection proceeds (except fora zero order reaction)Er Rae ee LD oer HE CHAIGGE ce I Deduce the rate-determining step from a rate equation and vice versa. | Deduce a reaction mechanism, using knowledge of the rate equation and the stoichiometric equation for a reaction. HI Understand that knowledge of the rate equations for the hydrolysis of halogenoalkanes can be used to provide evidence for Sy1 or Sy2 mechanisms for tertiary and primary halogencalkane hydrolysis. Understand how to: ) obtain data to calculate the order with respect to the reactants (and the hydrogen ion) in the acid-catalysed iodination of propanone Use these data to make predictions about species involved in the rate-determining step deduce a possible mechanism for the reaction, @ REACTION MECHANISMS You will remember from Book 1 that the baste view as to how a reaction takes place at a particulate Jevel is that particles (atoms, molecules, ions or radicals) frst have to collide in the correct orientation and with sufficient energy for products to be formed. For the following reaction: P+ Q-— products we expect the rate law to be: rate = HPIQ] In other words, we might expect the reaction to be first order with respect to each reactant and second order overall ELEMENTARY REACTIONS A reaction taking place inthis manner (a single collision between the two reactant particles) is described as being elementary. If we know that a reaction is elementary, then we can deduce the rate law directly from the stoichiometric equation. For example, the following reaction is known to be elementary: NO(s) + Osa) —+ NOXa) + 0.) 40 the rate equation is: rate = NOYO3) ‘The reaction takes place when a molecule of NO collides with a molecule of Os. If the reaction is not elementary, it is nor possible to deduce the rate equation by simply looking at the stoichiometric equation for the reaction For example, the decomposition of dinitrogen pentaxide into nitrogen dioxide and axygen is first ‘order with respect to dinitrogen pentoxide, not second, 2N,Os(g) — 4NO,(g) + O,(2) ‘The experimentally determined rate equation is rate = KN,O4] ‘A reaction that isnot elementary takes place via a series of interconnected elementary reactions that ate collectively called the meckanism fr the reaction. You will have already come across a number of, such mechanisms in your study of organic chemistry. For example, the radical substitution reaction between methane and chlorine to form chloromethane (CHCl) is thought to have the flloeng mechanism:nr) aU Se NOMS) Step 1: Cl, 2Cl* Step2 Cle + CH, > HCL+ «CH, Step 3: Cly + +CHs > Cle + CHC] ‘The overall stoichiometric equation for the reaction is CH, + Ch + CH,Cl + HCL ‘The species Cl+ and *CH, are called intermediates. They do not appear in the overall equation for the reaction, but are involved in reactions that ultimately result in the reactants being converted Into the products. If the experimentally determined rate equation does not match the overall stoichiometry, then its almost certain that the reaction isnot elementary. For example, the rate equation forthe following reaction: NOxg) + CO(g) > NO{g) + COs) rate = HNO} This suggests that only molecules of NO, are involved in the rate-determining step, and that to molecules of NO, are involved inthis step. ‘The order indicates the number fof molecules involved in the rate-determining step rate = KNO,I? S._ Indicates hat only molecules ‘of NO» are involved in the rate determining step. ‘A. fig. Noleculesinobed inthe ate-detemining step. Using our knowledge of molecules that do exist two possible rate-determining steps are: 1 NO, +NO,— NO, or 2 NO, +NO, —2NO +0, Both of these reactions are equally Vaid, and we have no way of knowing, without carrying out further investigations, which is the more likely to be taking place. We also have no way of knowing what is involved in the remaining steps, but we do know thatthe sum of all the steps must add up to the overall stoichiometric equation. Using the second of the two possible rate-determining steps, the following mechanism is consistent with the data NO; +NO,+2NO+0, SLOW CO +0;,+C0, +0 FAST NO+0—NO, FAST This shows how the particles in the proposed mechanism cancel to produce the overall equation: NO, + Ber + Ber + NO + ot core + +e BOHM per NO, + CO = NO + ©, aC aay AAs it happens, further investigations into this reaction have identified the mechanism as: NO; +NO;—-NO,+NO SLOW NO,+CO-—NO;+CO, FAST This is not what we would immediately suspect as the mechanism because the existence of NO, is not something with which we would be familiar Even if the experimentally determined rate equation is simple, it does not necessarily follow that the reaction proceeds in a single elementary step. For example, the rate expression for the following gas-phase reaction: 2N,0,(8) > 4NO,(z) + Ox(g) rate = KN,O4] Yet, the reaction is thought to involve several steps and a number of intermediates, ALKALINE HYDROLYSIS OF HALOGENOALKANES ‘The hydrolysis of halogenoalkanes by hydroxide ions is a reaction ‘we introduced in Topie 10 (Book 1: IAS). The hydroxide ion acts as a mucleophile and replaces the halogen in the halogenoalkanes. ‘The reaction, therefore, can also be described as nucleophilic substitution HYDROLYSIS OF A TERTIARY HALOGENOALKANE. ‘The equation for the alkaline hydrolysis of 2-chloromethylpropane is (CH,)CCl + OH” = (CH;),COH + Cr ‘The experimentally determined rate equation for this reaction is: rate = H(CH,),CCI] ‘The reaction is first order with respect to 2-chloromethylpropane, but zero order with respect to the hydroxide ion. “The sensible conclusion to reach is that the 2-chloromethyipropane undergoes slow ionisation as the rate-determining step. This is then followed by a very fast step involving attack by the hydroxide ion on the carbocation formed in Step 1. Step: (CH),CCI-+(CH),C*+ Cr SLOW Step 2: (CH)),C*+ OH” —(CH,),COH FAST ‘This type of mechanism is named Sy, ie. Substitution Nucleophilic unimolecular “The rate-determining step is said to be unimolecular because there is only one reactant particle present, (CH,),CCl ‘The carbocation, (CH,),C*. formed in Step 1 is an intermediate (see Section 114.6) HYDROLYSIS OF A PRIMARY HALOGENOALKANE “The equation forthe alkaline hydrolysis of 1-chlorobutane is: CH,CH,CH,CH,Cl + OH — CH,CH,CH,CH,OH + Cr ‘The experimentally determined rate equation for this reaction is rate = K{CH,CH,CH,CH,CIOH]ae DCCs UC ee nay 7 ‘This time the reaction is frst order with respect to each reactant, so its reasonable to suggest that ‘one patticle of each reactant is present in the rate-determining step of the mechanism, ‘The accepted mechanism for the reaction is: cHcrten, enone cHoHcH, So—a + or ——+] Hob. | —+ Hoc’ +01 Hd 4\ hy 4 ah H treration sto (A. fig 5,2 mechanism ofthe alkaline hycolsis of I-chlorobutane ‘This type of mechanism is named $2, ie. Substitution Nucleophilic bimolecular ‘The rate-determining step is bimolecular because there are two reactant particles present Its a continuous single one-step reaction. The complex shown in square brackets is not an intermediate {lke the carbocation formed in the Sy mechanism), but is a mansion state (see Section 114.6). Gee Ca ‘A study of the acid-catalysed iodination of propanone ‘The reaction between propanone and iodine in aqueous solution may be acid catalysed: Lag) + CH;COCH faq) + H'faq) —+ CH,COCH,I(aq) + 24*(aq) + Maa) ‘The influence of the iodine on the reaction rate may be studied if the concentrations of propanone and hydrogen ions effectively remain constant during the reaction This is achieved by using a large excess of both propanone and acid in the orginal reaction mixture. You will investigate this in CP9A Following the rate of iodine-propanone reaction by a titrimetric method, Procedure 1. Mix25 em? of 1 mol dr aqueous propanone with 25 cm? of T mol dr? sulfuric acid 2. Start the stop clock the moment you add SOc of 002 mol dm iadine salution hake wel 3 Using pete withers 1Denamoleand pace tin acon Stop teveacionbyaéiogs FST TT ‘spatula-measure’ of sodium hydrogen carbonate. Note the exact time at which the sodium hydrogen GLE carbonate added Examiners may ask you to 4. Ttate the remaining iodine present inthe sample with 0.01 mol dm sodium thiosulfate) olution, value diferent methods for Peete pi cation ‘snark te eee ee 5 Witaw hither 10cm simplest stable tana porn Sto rit andtet tem det ete ne lay say lays notte cate atic ne soon hyorogen rbot Waste shols beeen thang escon be contained in a fume cupboard. ‘sample by pipette and suerching Roth codn Trexmentof sits ogee ‘The Lab Book can give additional guidance in the treatment and analysis of results + Plota graph of tre against time. (The tte is proportional to the concentration of iodine) ‘+ Deduce from the graph the order of reaction with respect to iodine. Analysis of results ‘The graph produced shows that the reaction is zera order with respect to iodine. Similar experiments show that the reaction is fst order with respect to both propanane and hydrogen ions. This gives us the folowing rate equation: rate = KCH.COCH JH] This would suggest the following reaction asthe first step of the reaction cH, —O—CH, + HY + CH—o—cH, OH Similar reactions in other mechanisms are very fast, so this reaction is unlikely to be the rate-determining step of this reaction,ccm} aU Se NOMS) The second step probably controls the rate of the reaction and produces H" that, being a catalyst fs not used up in the reaction siow This rearrangement sikly to be very slow and hence is probably the rate-determining step of the reaction lodine can now react in a faststepas follows: Testing the mechanism We have a proposed mechanism forthe reaction thats consistent, withthe kinetic data obtained from experiment. This snot the same as saying thatthe mechanism is the correct one, or indeed the most likely one, We now need to carry out further experiments to confirm, or deny, ‘our proposed mechanism. Here are thee tecLiques that can be ‘employed inthis case. + Usea wider range of concentrations The experimentally determined rate equation may hold over only a limited range of concentrations. For example, the mechanism We have proposed for the iodination af prapanone predicts that, at very low concentrations of iodine, the order of reaction with respect to iodine wil change from zero to first. This is because the rate ofthe final step in the mechanism s given by the expression Rate = KLICH,C(OH)=CH] and so the rate ofthe step will decrease as] decreases. This has been shown to be the case, so supparts the proposed mechanism. + Use instrumental analysis This may be able to detect the presence of intermediates that have been proposed, Nuclear magnetic resonance can be used to show that acidified propanone contains about one molecule ina milion in the form CH.C(OH)=CH. Thisis an intermediate stated inthe proposed mechanism + Cany out the reaction with deuterated propanone, CD,COCD, Deuterium iH (or simply D} behaves slightly differently to hydrogen H (or simply H). ‘AC-D bond is slightly stronger, and therefore harder to break than a C-H bond. If this the bond that breaks in the rate-determining step, as suggested by our proposed mechanism, then the iodination of CD;COCD, will be slower than that of CH,COCH,, This is found to be the cas. aC aay 1 ‘The equation forthe reaction between ethanal, CH,CHO, and hydrogen cyanide, HCN, is: ‘CH{CHO + HCN + CH,CH(OHJEN ‘Two mechanisms that have been proposed for this reaction are: ‘Mechanism 1 Step 1: CH,CHO + HY —[CH,CHOH) Step 2; [CH,CHOH}: + CN" —- CH,CH(OHJCN ‘Mechanism 2 Step 1: CH,CHO + CN" — [CH CHOCN Step 2: [CH.CHOCN) + H’ — CHCH(OHICN ‘The rate equation forthe reaction is rate = KCH,CHOICN JH" (a) Explain which of the tio mechanisms is consistent with the rate equation (b] Which step in this mechanism i the rate-determining step? ‘The equation forthe reaction between hydrogen and nitrogen monoxide is 2H,(g) + 2NO(g) — 24-0) + Nola) ‘The rate equation forthe reaction is: rate= KHJINOP ‘Aproposed mechanism for this reaction i: Step 1: 2NO(@) —+N,0,() ast Step 2: N,O,() + Hi) H.0(g) +N,0(@) SLOW Step 3: N,Olg)+ H.(@) Nag) + H.0lg) FAST Isthis mechanism consistent withthe rate equation? Explain your answer. ‘Assume the following proposed reaction mechanism is correct Ch 2ch stow Ho + Ch HCL He Fast He ch Hel FAST (a) Wate the overall equation forthe reaction, (b] Wate arate equation for the reaction that is consistent with the mechanism. (0) What would be the effect on the rate of reaction of doubling the concentration of C:? (4) What would be the effect on the rate of reaction of doubling the concentration of Hi? 4. The nucleophilic substitution reaction between equimolar {quantities of CHCl and OH" is second order overall However, if the reaction is carried out using a large excess of OH the reaction becomes frst order overall. Suggest an explanation for these observations Bromine can be formed by the oxidation of hydrogen bromide with oxygen. [A proposed mechanism for this reaction is: Step 1: HBr + 0; —HBrO; Step2: HBrO; + HBr — 2H8r0 Step 3: HBrO + HBr — Br, + HO. Step 4: HBFO + HBr — Br, + H,0 (a repeat of Step 3) ‘The rate equation for ths reaction is rate = KHBIO,] {a) Explain which of the above four steps i the rate-determing step for ths reaction (b} Write the overall equation forthe reaction,Er 11A 5 ACTIVATION ENERGY AND Preven CATALYSIS orc oT Understand the terms: (activation energy )_ heterogeneous and homogeneous catalyst i) autocatalysis. | Understand the use of a solid (heterogeneous) catalyst for industrial reactions, in the gas phase, in terms of providing a surface for the reaction. ACTIVATION ENERGY, E, In Topic 9 (Book 1: IAS), we defined activation energy: F,, as the minimum energy that colliding particles must possess for a reaction to occur ‘The activation energy represents the energy thatthe colliding particles must obtain in order to reach the energy level of the eansiton state (see Section 11A.6 for more details). Once the energy level of the transition state has been reached, the particles can react to form the products and release energy as they do so. The energy profile diagram for an exothermic reaction is shown in fig A. Energy Progress otreaction A. MEA. A reaction profi for an elementary exothermic reaction. CATALYSTS In Topic 9 (Book 1: IAS), we defined a catalyst asa substance that increases the rate of a chemical reaction but is chemically unchanged atthe end of the reaction. ‘We then went on to explain that a catalyst works by providing an alternative route for the reaction, and that this alternative route has a lower activation energy than the original roure. Although the original route is stil available for the reactants, most colisions resulting in reaction will occur by the alternative route, since the fraction of particles possessing this lover activation energy will be greater Catalysts can be divided into two groups: + homogeneous catalysts + heterogeneous catalysts. HOMOGENEOUS CATALYSTS ‘A homogeneous cataiys isin the same phase (solid, liquid, solution or gas) as the reactants,EP UUs ae MURR) Many reactions in aqueous solution are catalysed by the hydrogen ion, H’(@q), An example isthe iodination of propanone, a reaction we discussed in detail in Section 118.4 (CH,COCH aq) + 1{aq) -> CH.COCH,I(aq) + H"(aq) + Haq) “The production of chlorine radicals from chlorafluarocarbons, (CFCs) is responsible for the destruction of czone in the upper atmosphere. Ultraviolet radiation from the Sun produces chlorine radicals, Cl, rom CFCs such as dichlorodifluoromethane, CLF: role ecaton corp ig) + cg) cory) “The chlorine radicals then take partin a chain reaction wth ozone: ‘Cle(g) + O(a) + ClO*{g) + O.f8) ‘ClO+(g) + fg) — 20,(g) + Cle(g) “The chirine radical is regenerated and so is acting asa catalyst. Since the catalyst isin the same phase, Le. the gas phase, asthe reacting species, it is classified as a homogeneous catalyst. ‘The overall reaction is 20s(g) + 30,8) Another reaction involving a homogeneous catalysts the one betucen perenycisulfate ions and iodide ions in aqueous soon S,0F (aq) + 21 (aq) —- 280% (aq) + laa) ‘This reaction is catalysed by either Fe**(aq) or Fe’*(aq). ‘With Fe®*(aq), the reaction mechanism is: ‘Step 1: S,0} (aq) + 2Fe**(aq) + 2SO¥ (aq) + 2Fe™*(aq) Step 2 2Fe*(aq) + 21 (aq) > 2Fe(aq) + La) With Fe*(aq) as the catalyst, Steps 1 and 2 occur in the reverse order Ea The action of Fe(aq) of Fe(aq) as catalyst inthe rection between S,OF (aq) and (a) sometimes explained in terms of standard electrode potentials (E° values). However itisimportant to note that standard electrode potentials «an predict only the thermodynamic feasibility ofa reaction, and not the Kinetics The reason why the eactions are faster in the presence of ether Fe” or Fes that the activation energies for both Step 1 and 2 are lower than the activation energy forthe overall reaction, HETEROGENEOUS CATALYSTS A heterogeneous catalyst i in a different phase to that of the reactants, ‘Two important uses of heterogeneous catalysts in industry are in the Haber process and the Contact process. The use of solid vanadium(V) oxide (V,Os), in which the vanadium changes its oxidation number in the Contact process is described in the section on transition elements (Topie 17) We will now describe the action of solid iron as a catalyst in the reaction between nitrogen gas and hydrogen gas to form ammonia gas in the Haber process. aC aay ‘The equation for the formation of ammonia in the Haber process is Na(g) + 3H,{e) = 2NHe) Iron is able to act as a catalyst because it can form an interstitial aydride with hydrogen molecules. In this hydride, hydrogen atoms are held in spaces between the metal ions in the lattice. The atoms are then able to react with nitrogen molecules that are adsorbed onto the metal surface nearby. There are three stages in catalysis involving surface adsorption. These are: 1. Adsorption — the reactants ate first adsorbed onto the surface of the catalyst 2. Reaction — the reactant molecules are held in positions that tenable them to react together 3. Desorption ~ the product molecules leave the surface ‘The rate of reaction is controled by how fast the reactants are adsorbed and how fast the products are desorbed. As mentioned in Topic 9 (Book 1: IAS), once the surface of the irom is covered with molecules, there is no further increase in reaction rate even if the pressure of the reactants is increased. DID You KNOW? The efficiency ofa heterogeneous catalyst depends on the surface ofthe catalyst. In particular, the efficiency ofthe catalyst can be affected significantly by poisoning and by the use of promoters. POISONING ‘Many catalysts are made ineffective by trace impurities. For ‘example, catalysts used in hydrogenation reactions are poisoned by sulfur impurities. This is one reason why nickel is preferred to platinum as a catalyst in the hydrogenation of alkenes. Nickel is ‘relatively inexpensive, so a large quantity can be used. If some of itis deactivated by poisoning, enough will remain for it stil to be effective. On the other hand, platinum is expensive, and so small ‘Quantities would have to be used. In this case, its possible forall of the catalyst to become poisoned. PROMOTERS: The spacing on the surface of the catalyst is important. For ‘example, only some surfaces of the iron crystals act as effective catalysts in the Haber process. The addition of traces of potassium ‘oxide and aluminium oxide act as promoters by producing active sites where the reaction takes place most readily. DID You KNOW? {An interstitial hydride, sometimes called a metallic hydride, is ‘ot strictly 2 compound. Its more like an alloy than a compound, ‘The hydrogen absorbs into the metal and can exist inthe form of elther atoms or diatomic molecules. For example, palladium ‘absorbs up to 900 times its awn volume of hydrogen at room temperature, and forms palladium hydride. This material has been Considered as a method to carry hydrogen in fuel cells for use in, vehicles (see Section 14.2.1), A heterogeneous catalyst is used in a three-way catalytic converter, which is employed in the exhaust of cars. This converts unburned hydrocarbons into water and carbon dioxide, and ccarbon and carbon monaxide into carbon dioxide. It also convertsae ‘oxides of nitrogen into oxygen and nitrogen. The reactions involved are discussed in more detail in Topic 17. ECP an UE oe Uke UR Fa] You can show this effect by plotting the concentration of one of the reactants against time. The graph obtained is unlike the normal rate curve for a reaction, ‘DID YOU KNOW? The electrophilic adton reaction between ethene and bromine vapour (Topic 6 (Book 1: IAS) was once thought tobe enticly homogeneous process in which the molecules colded inthe gas phase and reacted. itis now known thatthe reaction tkes place almost entrely on the surface ofthe walls ofthe reaction vessel, The reaction takes place very quickly on a glass surface and even more quickly when the surface ofthe vessels covered with apolar substance such a3 cetyl alcohol (hexadecan-1-l, HCH) 0H takes place ‘ven more quickly stil on asuraceof stearic acid octadecanoic acid, CH,(CH,);eCOOH), presumably because stearic acid ‘molecules are more polar than molecules of cet! zoho However, ithe walls ofthe reaction vessel are coated with a non-polar substance such as paafin wax, vey litle reaction, i any, occurs. So, a process once thought tobe a homogeneous gas phase reaction is now known to be heterogeneously catalysed. itis sometimes stated that a catalyst does nt change the products of a reaction, but only increases the rate al which the reaction takes place. This is not entirely true, as demonstrated by the different products obtained when hot ethanol vapour is passed over different solid catalysts. With copper or nickel as the catalyst, at 400°C, a dehydrogenation reaction takes place in which the products are etanal and ‘hydrogen: CH,CH,OH(g) —+ CH,CHO(g) + Hag) Ha the same temperature, aluminium oxide is used asthe catalyst, the more familiar dehydration reaction into ethene and ‘water takes place: CH,CHOH(g) —» CH=CH) + H,0(0) {tis interesting to note that the dehydrogenation catalysts, copper and nickel, adsorb hydrogen very strongly, whereas the dehydration catalyst, aluminium onde, adsorbs weer in preference, These two examples illustrate that thee is a lat more to heterogeneous ctaysis than is mentioned at iterational ALevel. Tis might encourage you to do your own research into the topic and learn even more about it. (7 Pe ecton srs of sooty ve Concentaton at reactant be reaction then speode up the reacton then ‘104s down before J oe sc65 Time A. fig 4 aph of conce ation aginst time for an autocaalysed reaction. In fig B you can see the slow (uncatalysed) reaction atthe beginning, As catalyst begins to be formed in the mixture, the reaction speeds up ~ it gels fster and faster as more and more catalyst is formed. Eventually the rate decreases in the normal way as the concentrations of the reactants decrease EIT Do not assume that arate curve similar to the curve in fig B always ‘shows an example of autocatalyss. There are other effects that might produce a similar graph. For example ifthe reaction involves a solid reacting with aliquid, liquid might have to penetrate a substance on the surface of the solid before the expected reaction can happen. ‘Another possibility is thatthe reaction is strongly exothermic and the ‘temperature isnot being controlled The heat evolved during the teaction speeds up the reaction, Explain why only a small quantity of a homogeneous catalyst is required in order fort to be effective Cars in some parts ofthe world stil rn on leaded petral. Leaded petrol contains a compound called tetraethyl lead, (CH,CH,),Pb. OXIDATION OF ETHANEDIOIC ACID BY MANGANATE{VII) IONS In autocatalysis, the reaction is catalysed by one of its products. One of the simplest examples ofthis is the oxidation of ethanedioic acid by acidified potassium manganate(V), The ‘equation forthe reaction is: 5({COOH),{aq) + 2MnO;(aq) + 6H"(aq) > 10COx(g) + 2Mné*(aq) + 8H,O() ‘The reaction is very slow at room temperature, but Is catalysed by ‘manganese() ions, Mn**. The Mn* jons are not present intially, so the reaction starts off extremely slowly at room temperature, However, Mn? is a product of the reaction, As sacn as itis produced in a catalytic amount, the reaction rate increases, ‘Tetraethy/ lead reacts inthe engine with oxygen and forms lead and lead(l) oxide. These substances remove radical intermediates inthe combustion reactions, thus increasing the ‘octane rating ofthe petrol. Excess lead and lead) oxide fs removed by adding 1,2-dibromoethane, This forms volatile lead) bromide that escapes through the exhaust. Suggest why a catalytic converter could not be used in a car ‘unning on leaded petrol. oan ‘adsorption the adhesion of atoms, molecules or ions to the surface saved autocatalysis when a reaction product act a a catalyst for the reactionSe eH a Ue ac THE RATE CONSTANT IM Use the Arrhenius equation to explain the effect of temperature on the rate constant of a reaction, Use calculations and graphical methods to find the activation energy for a reaction from experimental data. RELATIONSHIP BETWEEN TEMPERATURE AND RATE OF REACTION In Book 1 we discussed qualitatively why an increase in temperature increased the rate of a reaction, ‘There are two reasons for this + an increase in the fraction of molecules with energy equal to or greater than the activation energy forthe reaction + an overall increase in the frequency of collisions between the reacting molecules. ‘The second effect is considerably less significant than the frst and means that we can effectively ignore the overall increase in the frequency of collisions. ‘THE ARRHENIUS EQUATION STG In 1889, Svante Arrhenius, a Swedish chemist, proposed a quantitative relationship between. temperature and the rate constant, &; for a reaction. This is described by the Arrhenlus equation and is, usually expressed in the form: ‘You will abvays be given the ‘Arrhenius equation ifs, needed in an exam question, keAel where + Aisa constant known a the pre-exponential factor, which is @ measure ofthe rate at which cllsions ‘occur irrespective of their energy I aso inches other Factors, the mast important of wich shat reactions can only occur when the molecules are correctly orientated a he time of callision + Bis the activation energy of the reaction + isthe gas constant + Tis the absolute temperature (i.e. the temperature in kelvin). If we take natural lgarthns (Le logarithms tothe base e) of the Archenius equation we obtain At RT L # IF. graph of inks potted ageinst 4, a strsight lines obtained witha gradient of “This provides an experimental method for determining the activation energy of a reaction. Ink +InA ‘The intercept with the vertical axis gives Ind, Ween Table A shows some data related to the reaction between peroxydislfate and iodide ions in aqueous solution: S,0¢"faq) + 2+faq) -+ 250,"(aq) + I faq) oy Img rr cua 300) 0.00513 0.00333, 310 0.00833 0.00323, 320 00728 0.00313 330 (00201 0.00303 340) (00301 0.00294 table Aae Sues ORCC e Fig Astor i plated gina creo 9m core one ome) oom Be Se SIRS SESE me v0} 4.00. - Ik ~450: A FIEA. A graph of in against 1/7 The gacientof the line, ~ (-350--527) (0.00333 - 000294) =-4538 (R=831)mot* K'] “4538 831)» 37700] mol! =+37.7K mot" (03s) DID You KNOW? i When we state that the relationship between Ink and — is linear, we have assumed that both E,and A remain constant over a range of temperatures. Tis isnot Strictly true, However, the change in the values of ,and A with temperature are insignificant compared withthe effect of temperature on the rate constant, and so can be ignored. DID You KNOW? The significance of the factor e” ‘The factor 6% represents the fraction of colisions that have energy equal to or greater than the activation energy, €,.For example, a reaction with an £, of 60 ks mol gives a fraction, at 298 K, of: efO000031 20) = 9 107 ‘80, only one collision in 3 x 10" has sufficient energy to react Itis often assumed thatthe fraction of collisions with energy equal to or greater than F, isthe same as the fraction of molecules with this energy. This isnot strictly true, but the difference is insignificant at high energies, where the fraction is very small. Itis, therefore, reasonable to draw the molecular energy distribution curve, instead ofthe collision ‘frequency curve, when demonstrating the effect of temperature on collision frequency. (See Topic 9 (Book 1: IAS). aS ete aes pes ea le de ec or oth eee ae ane Fe)PRC aru URLs Vatu aC aay ip You Know? Reaction profiles ‘When drawing reaction profile diagrams for multi-step reactions, is important to lstinguish between an intermediate anda transition state. + an Intermediate has an energy minimum + transition state occurs atte top of the energy curve and therefore has an energy maximum, ‘Anintermediate is a definite chemical species that exists for a inte length of ime. By comparison, a transition state has no significant permanent ietime ofits own: it exists for a period ofthe order of +10 seconds, when the molecules are in contact with one another. Even a very reactive intermediate, with lifetime of only 10 seconds has along lifetime in comparison with the period that colliding molecules are in contact with one another. ‘simple one-step reaction, such asthe Sy2 hydrolysis ofa primary halogenoalkane, hs a single maximum energy. The reaction profil forthe hydrolysis of primary halogenoalkane, represented as Ral, is therefore: Ent, (anton stat) HOB Fela OH ron Progress a eacton A. fig The eacton rte dagam forthe hydichés oa primary alogenotane, ‘The reaction profile for the Sy1 hydrolysis of a tertiary halogenoalkane, R,CHal, which is a two-step reaction involving the intermediate R,C*, is: ental. (itermecto) Roa on OOH Fa Pragres lescion A Fige The eaten profile diagram er the hycrolsis oa tet halogencalane (ETI In the 5,1 hydrolysis ofa tertiary halogenoalkane, the fist step ofthe mechanism isthe rate-determining step ofthe reaction, and it therefore has the higher activation energy. Thats E,() > E2). If the second step in a reaction mechanism is rate-determining. EI) < £2)ae Sues ORCC e Fe) ‘DID You KNOW? ‘The relative rates of Sy1 and §,2 reactions depend on structure You learned in Book 1 that alkyl groups donate electrons by the inductive effect. This means that the stability of carbocations increases in the order 1° < 2° < 3°, as the number of alkyl groups donating electrons towards the positive carbon atom increases. 4 R R | y i mee eee | | t 1 4 t ‘A the stably of the carbocation increases, the activation energy fr the reaction leading to its formation also decreases. Energy Pragoss of reaction A. fig Reaction profiles for he 5,1 hyrohss of primary and tentary halogencalkanes. We therefore expect the rate of the S1 reaction to increase inthe order 1° < 2° < 3°. ‘No carbocations are formed during the $2 reaction. in an $2 reaction, the transition state has five ‘groups arranged around the central carbon tom. Iti therefore more crowded than either the starting hhalogenoakkane or the alcohol product, each of which have only four groups around the central carbon atom. Alkyl groups are much larger than hydrogen atoms. Therefore, the more alkyl groups around the central carbon atom, the more crowded willbe the transition state, and the higher the activation energy for its formation. We therefore expect the rate ofthe S,2 reaction to increase inthe order 3° < 2° < 1% ‘The two effects reinforce one another. The Sy reaction is fastest with tertiary halides and slowest with primary halides, while the S,2 reaction is fastest with primary halides and slowest wit tertiary halides. Overall, primary halides react predominantly via the $2 mochanism and tertiary halides react predominantly via the S,1 mechanism. Secondary halides tend to react via a mixture ofthe two mechanisms. esate rate AL AIRE 5.1 and S.2 hytralysis eactions for primary, secondary and tertiary halogenoalanes, EXD cx Use the Arthenius ‘equation to explain why temperature results in an increase inthe rate of reaction. 2. Therate constant, fora reaction increases from 1005" to 100.05" when the temperature is increased from 300 K t0 400 K Calculate the activation ‘eneepy, for this reaction. [R=831] mol K")11 THINKING BIGGER CATALYST CRAFT EXD cen In this article you will look at an example of how an engineered metalloenzyme can improve both the kinetics and specificity of a reaction, The extract is from Chemistry World, the print and online magazine of the Royal Society of Chemistry ENGINEERED METALLOENZYME CATALYSES FRIEDEL-CRAFTS REACTION Reprogramming the genetic eode of bacteria to include an unnatural amino acid has allowed scientists in the Netherlands to create a new metalloenzyme capable of catalysing an enantioselective reaction, “Nature is extremely good at eatalysing reactions with very high rate accelerations and very high selectivity. But it does so, from our perspective, with a relatively limited set of reactions,’ explains Gerard Roelies from the University of Groningen in the Netherlands, who led the study. His ‘group is looking at existing reactions that use traditional catalysts, but fil to achieve the same rate acceleration and selectivity as enzyme catalysed rea A. figA. The ariical metaloenaymes were applied in a catalytic asymmetric Fredel-Crats allylation Metalloenzymes combine the flexibility of metal catalysts wih the high activity and selectivity of enzymes. Artificial retalfoenzymies are produced by inserting 4 catalytically active transition metal complex into a biomolecular scaifold, like a protein. Roelfes' team engineered Escherichia colt cells to include a copper-binding amino acid into one of its proteins. This method requires no further chemical modification or purification steps, giving it an advantage over existing methods. The resulting metalloenzyme was tested ona catalytic asymmetric Friedel-Crafts alkylation reaction, achieving an enantiomeric excess of up 10 83%. ‘Takafui Ueno, who researches the ‘mechanisms of chemical reactions in living cells atthe Tokyo Insitute of Technology in Japan, is impressed by the work. “Treould be applied not only for rapid screening of artificial metalloenzymes but also for in vivo use of them to govern cell fate in future” The group are now looking to develop new aif metalloenzymes with the capability to perform chemistry that traditional transition metal eatalysts cannot Ultimately, they hope to integrate these enzymes into biosynthetic pathways ‘Adapted (with permission) from ‘Engineered Metalloenzyme Catalyses Friedal-Crafts Reaction’ by Debbie Houghton, Chemistry Word, 3 November 2014ae a ey ee Pa Bee eo 11 (a) After reading the article for the first time, write a one-paragraph summary of what you think You may find that itis easier the ance s about. than you think to get an (6) Now write down alist of any words rom the article of which you do notknow the meaning. overall understanding of Do some research into what they mean. Is there anything about your summary from a)that_ What a detailed scientific you would change? article is about. You do not need to understand every single word to learn something new and interesting GrEvnnao a 2 Assuming the reaction is exothermic, sketch an energy profile forthe catalysed reaction showing: | When you are asked to draw something, make sure you usea sharp HB pencil so that your drawing is clear, (a) the overall reaction enthalpy change (b) the activation energy for the formation of the enzyme—substrate complex 3 Under certain conditions the rate equation for an enzyme-catalysed reaction takes the form: and usea ruler ifyou are Rate = KE), where [Eis the enzyme concentration and kand n are experimentally determined drawing straight lines, constants. What does this rate equation suggest about the reaction mechanism under these conditions? 4 Name the type of bond that is formed between the copper ion and the unusual amino acid in the metalloenzyme shown in fig. 5 Suggest why the use ofa metalloenzyme of this type might be a better alterative than the traditional Friedel-Crafts methods for alkylation. 6 Suggest why this method might be expected to increase the enantioselectivty of this reaction, 7 Suggest why the Zn® ion may not be a suitable replacement for the Cue fon inthis enzyme, vei ‘Although the metalloenzyme detailed above is genetically engineered, there are many naturally ‘occurring metalloenzymes that carry out a range of reactions in organisms. Most of these can be found in a freely accessible online database called the PDB (alternatively, the PDBe) Choose one of the follawing metals: Fe, Zn, Cu, Mo, Co. + Finda protein that contains the metal «+ Find our whas the protein does. + Find out how much ofthe metal is present in atypical healthy adult. Give a five-minute presentation on your chosen metal featuring na more than five sides. You will have the opportunity to display your chosen molecules using some of the freely avaliable software packages such as Jmol. ‘DID You KNOW? Although a typical adult has only about 1.6 mg of copper per kg of body mass, an inability to regutate copper has disastrous effects. For example, the inability to excrete excess copper from the body (Wilson's disease) can be fatal if let untreated. Menkes’ syndrome manifests itself if the body is ‘unable to retain (hold on to) copper. Although not fatal, it can lead to developmental delay and neurological problems.11 EXAM PRACTICE 1. An experiment is set up to measure the rate of hydrolysis of methyl ethanoate, CH;COOCH,, CH,COOCH, + H;0 = CH,COOH + CH,OH ‘The hydrolysis is very slow in neutral aqueous solution. When dilute hydrochloric acid is added, the reaction is faster What is the function of the hydrochloric acie? A to increase the reaction rate by acting as a catalyst B tomake sure thatthe reaction reaches equilibrium tomaintain a constant pH during the reaction D to dissolve the methyl ethanoate uy (Total for Question 1 = 1 mark) 2. Forthe gaseous reaction 2X(g) + Y() —+ Z(g). the rate equation is rate = & [XPV If the pressure in the reaction vessel is doubled but the ‘temperature remains constant, by what factor does the rate of, reaction increase? A2 B3 C4 De 1 (Total for Question 2= 1 mark) 3. The alkaline hydrolysis of RB, where RBr = (CH), Br takes place in two steps: RBr RY + Br SLOW R'+ OH — ROH FAST ‘Which of the following rate equations is consistent with this scheme? A rate = [OH] B rate = k(RBr} C rate = k(REY|OH] D rate = k(R*JOH] ut) (Total for Question 3 = 1 mark) 4 The table gives data for the reaction between X and ¥ at constant temperature, Experiment | [x1/ 1/ | initial rate / mol dor? | moldm? | mol dm?st 1 03 02 40 10 2 06 04 16% 102 3 08 08 64% 107 ‘What is the rate equation for the reaction? Avrate = k(XIY) B rate = k(XFIY] rate = kXP D rate = k(VP a (Total for Question 4= 1 mark) 5 The reaction of acidified aqueous potassium iodide with aqueous hydrogen peroxide 2iaq) + H.0ag) + 2H"(aq) + Lag) + 24,00) is thought to involve three steps: HO, +r +H,0+0r — sLow Or + Ht — HOI FAST HOI + HY +P +1, +H,O FAST Which of the following conclusions eamnot be deduced from this information? ‘A The acid isa catalyst B The reaction is frst order with respect to the iodide ion. The rate determining step is H,0, + - + H,0 + OF D The rate equation forthe reaction is: rate = k[H:O,]l1] [1] (Total for Question 5 = 1 mark) 6 Propanone and iodine react in aqueous acidic solution according tothe following overall equation: CHsCOCH, + ly +H” + CHyCOCHsI + 2H" + I> ‘The experimentally determined rate equation fortis reaction is: rate = HCH,COCH,|[H*) (@) With initial concentrations as shove, the initial rate of reaction was 1.43 x 10-¢mol das Tnitial concentration/molam™ (CHACOCH, 0.400 To (0.200 L 00 «10 Calculate a value forthe rate constant, & for the reaction. [3] (0) Explain the effect on the rate of reaction of doubling the ‘concentration of fone, but keeping the concentrations of propanone and hyrogen ions constant. i) (©) The proposed mechanism forthe overall reaction is Step? CHCOCH, + He Step 2 steps sep 4aT Explain which of the four steps could be the rate-determing step. fe (Total for Question 6 = 8 marks) 7 Most chemical reactions involve two or more steps. The experimentally determined rate equation indicates which species are invalved either before or in the rate-determining step, (@) State what is meant by the term rate-determining step. [1] (©) Hydrogen reacts with fodine monochloride in a two-step mechanism according to the following overall equation: Hy(g) + 21CK{g) + 2HCKg) + La) ‘The experimentally determined rate equation for this, reaction is: rate = k[H,(@)01C\g)] ‘The rate-determining step is the first step in the mechanism for the reaction, () Write an equation for the rate-determining step. [1] (i) Write an equation for the second step. a (©) A series of experiments were carried out on the reaction A+B + C— products. The results are shown in the table. Experiment | Initial concentrations/ | Initial rate/ ‘moldm”? ‘moldm?5-* a | | tc 1 ‘100 | 0100 | 0100 | 620% 10~ z ‘0100 | 0200 | 010 | 620% 10% 3 400 | 0100 | 0200 | 248x107 4 0200 | 0.100 | 0100 | 124% 10 () Determine the order of reaction with respect 10 A, B and C. Show how you obtain your answers. (3) (3) Write the rate equation for the reaction, fe (i) Which reactants unlikely tobe in the rate determining step? tt] (Total for Question 7 = 8 marks) 8. Nitrogen pentoxide decomposes on heating to form nitrogen tetroxide and oxygen. The equation for the reaction is: N,Os(a) —+ NiOulg) + 70x(8) “The progress of the reaction can be followed by measuring the concentration of NO; present. The graph shows the results cbtained in an experiment conducted at constant temperature. 20. * a 10 20 40 40 “Time/minutes — 3 60 70 8 90 100 DCW aad Fz) (@) (Use the graph to predict the rate of reaction after 20 minutes and after 90 minutes. 8) (i) Deduce the rate of production of oxygen after 20 minutes? uy) (6) (i) Plot on the graph two successive halves for this reaction. [2] (i) Deduce the order of reaction with respect to N.O Justify your answer i (Gi) Wiite arate equation fr the reaction. a (©) (Calculate a value forthe rate constant, k for his reaction, e) (i) Deduce the intial rate of reaction wien the initial concentration of N,O; is .50moldm, Assume the reaction is carried out under the same concitions of temperature and pressure ri (Total for Question 8 = 14 marks) 9 Nitrogen dioxide, NO,, is decomposed on heating into nitrogen ‘monoxide, NO, and oxygen. The proposed mechanism for this, reaction is NO, +NO,—+ NO, +NO SLOW NO, NO +0, FAST (2) (i) Write an overall equation for the decomposition of nitrogen dioxide. tu) (i) Write a rate equation for the reaction, i) (b) The rate constant, k, for the decomposition was determined at several cfferent temperatures. The results obtained were ‘used to plot the graph shawn below. 8 Se: nk wo 1m 12 18 14 15 WTO" (i) Use the graph and the expression E, Ay RT ine. to calculate the activation energy E,, for the thermal decomposition of nitrogen dioxide. Give your answer ‘oan appropriate number of significant figures. [4] (i) A vessel of volume 2.00 dm is filled with 4.00 mol of ntitrogen dioxide ata temperature of 650 K. The initial rate of reaction was found to be 12.64moldm”?5"! Ink Calculate a value for the rate constant, kat this temperature 2] (Total for Question 9 = 9 marks)ENTROPY AND Sate alts People lived very simply in the Stone Age. Their energy needs were supplied by the Sun, and by burning plants and trees. Because the plants and trees were continuously renewed, and populations were small, energy supplies during the Stone Age period were plentiful. However, this simple lifestyle has almost completely vanished, and people today cannot survive without abundant fuel. Today, most of the world's energy is supplied from fossil fuels, which consist of natural gas, coal and products from crude oil, such as gasoline, diesel and kerosene. Fossil fuels are not renewable and will one day run out. To manage these energy resources and develop new fuels we need to understand how energy is released or used in chemical reactions, including the reactions in plants, animals and our own bodies. Energy is an essential part of chemistry as well as of civilisation as we know it. In chemistry, energy determines which reactions can occur and which compounds can exist. You have already studied a large number of chemical reactions. All of these reactions either absorb or release energy. In this topic we will develop an understanding of how to measure and report these energy changes. Have you ever wondered why water evaporates? Why hot objects cool? Why hydrogen combines with ‘oxygen? Why green leaves turn red in the autumn? Why anything happens? Part of the answer is related to energy. We need energy to think, to move and to live. Every chemical reaction makes use of energy to rearrange the bonding between elements in compounds. Thermodynamics deals with questions like these. In the first half of this topic we will deal with the second law of thermodynamics, which governs the direction of natural change. The second law enables us to predict whether or not a reaction has.a tendency to occur, and to what extent it will occur. The second law is of fundamental importance in chemistry because it provides a basis for discussing, explaining and predicting equilibria, the subject of Topics 13 and 14 in this book. The second law is also the foundation of the whole field of electrochemistry, the subject of Topic 16. MATHS SKILLS FOR THIS TOPIC + Recognise and make use of appropriate units in calculations + Recognise and use expressions in decimal and ordinary form + Use calculators to find and use power, exponential and logarithmic functions + Use an appropriate number of significant figures + Change the subject of an equation + Substitute numerical values into algebraic equations using appropriate units for physical quantities + Solve algebraic equations + Use logarithms in rel ion to qual ities that range over several orders of magnitude 2 a Sad+ Lattice energies and Born-Haber cycles Enthalpy changes of atomisation, solution and hydration + Standard conditions of temperature and pressure ferret etree ean caer ey eee See eC and . Polarisation of anions by cations to explain the een en ecm aati Sen Ce ua ay coe +The relationship between total entropy change eee)12A 1 INTRODUCTION TO ENTROPY Rae Caco xm eed i rz] Dee Raa) Understand that, since endothermic reactions can occur spontaneously at room temperature, enthalpy changes alone do not control whether reactions occur. Understand entropy as 2 measute of disorder of a system in terms of the random dispersal of molecules and of energy quanta between molecules. Understand that the entropy ofa substance increases with temperature, that entropy increases as solid — liquid — gas and that perfect crystals at zero kelvin have zero entropy. _Beable to interpret the natural direction of change as being in the direction of increasing total entropy (positive entropy change), including gases spread spontaneously through a room, WHAT MAKES A REACTION OCCUR? Perhaps one of the most important questions to ask in chemistry is ‘Willa reaction occur? We know that, once started, some chemical reactions simply ‘go with no further, continuous help from us. For example, ammonia gas and hydrogen chloride gas react together at oor temperature to form the white solid, ammonium chloride: NH) + HCI) > NH,Cl(s) Magnesium, once ignited, will burn in oxygen to form magnesiurn oxide: Magis) + 303{2) > MzO(s) In other reactions, rather than the reactants changing completely into the products, a position of equilibrium is reached, with the final mixture containing a measurable amount of both reactants and products. For example, ethanoic acid dissociates in water In a 0.1 mol dm? solution of ethanoic acid only about 1% of the ethanoic acid molecules are present as ions CH,COOH|aq) = CH,COO"(eq) + Haq) Another example i the dimerisation of nitrogen diode in the gas phase: 2NOulg) = N.OK8) ‘At atemperature of 298 K and a pressure of 100 kPa, the equilibrium mixture contains about 70% N;O. ‘There are other types of reactions that simply do not occur at al at least not without some help For example + ammonium choice does not spontaneously decompose into ammonia and hydrogen chloride + magnesium oxide does not break apart to form magnesium and ‘axygen without some continuous intervention from us in the form of heating If we consider all of these types of reaction together. we see that the rel difference between them is the positon of equilibrium that is established. For some reactions the position of equilibrium is, so far over to the products side tha, to all intents andl purposes, the reaction has gone to completion. For some other reactions, significant amounts of both reactants and products are present at cecuilibrium. For other reactions, the equilibrium lies so far to the left that they appear not to take place at all, So, pethaps the better question to ask is nor ‘Will a chemical reaction occur?’ but ‘What will be the position of equilibrium?” ‘This is the question we hope to answer in this topic. ‘DID You KNOW? ‘A campfire is an example of increases in entropy. The solid wood ‘burns and becomes ash, smoke and gases, all of which spread ‘energy outwards more easly than the solid fuel. EXOTHERMIC AND ENDOTHERMIC REACTIONS ‘The reaction between magnesium and oxygen is exothermic and can be represented by the enthalpy level diagram shown in fig A. Ena 71 ats) + $0.6) Reaction pabnay AA fig Enthalpy evel cgram forte ection between magnesium and onyeen, As the products have less energy than the reactants, we often say that the products are more energetically stable than the reactants Itis very tempting to conclude that this reaction occurs because the magnesium oxide is energetically more stable than its clements, magnesium and axygen. However tempting this argument may be, we must discard it, because experience tells us that many endothermic reactions occur at room temperature, Let us consider the dimerisation of NO,(g) at 298 K 2NOrfg) = N:0ule)aad ‘The enthalpy level diagram for this reaction is shown in fig B. Enthalpy 2NOLe) heat ney heat energy | |sivenout taken in Nia Reaction pay ‘A. fig Emhalpy level ciagram forthe cimersaton of NO; ‘This reaction is readily reversible and reaches a position of ‘equilibrium at 298 K. The forward reaction leading to the formation of N,O,(g)is exothermic, However, the backward reaction is endothermic. As we discovered in Topic 9 (Book 1: IAS), the position of ‘equilibrium can be reached from ether direction. This means that if we place some N,O,g) ina sealed container at room temperature, some of it wll decompose to form NOx) So, an enciothermic reaction staking lace at room temperature without us doing anything toi, We say thatthe reaction is spontaneous {see later in this section). Clearly itis not only exothermic reactions that can take place spontaneously The driving force for spontaneous endothermic reactions cannot be the formation of more energetically favourable, ie. lower-energy products but must involve another factor we have yet to consider. ‘That factor is a quantity known as entropy, which is governed by the Second Law of Thermodynamics. But first, we need to appreciate what is meant by the term spontaneous process, SPONTANEOUS PROCESSES A spontaneous process is one that takes place without continuous intervention by us. ‘A good example of a spontaneous process isthe freezing of water to form ice. If water is placed in an environment at ~20°C it will turn into ice. However. the reverse will never happen: at ~20°C ice will never melt to form water Another example of a spontaneous process is the mixing of {ases. If two unreactive gases are present in a container, they will ‘mix completely ina process known as diffusion \We can bring about the reverse of spontaneous pracesses by intervening For example, we can melt ice by heating it, and ‘we can separate a mixture of gases by liquetying followed by distillation ‘The key point, however, is thatthe reverse of a spontaneous process never happens on its own. A mixture of gases will never separate on their own, At the beginning of this section we stated that, in chemistry, we are concerned with whether or not chemical reactions will occur, and we suggested that perhaps the most important question to ask in chemistry is ‘Why does a reaction occur” PMOL ad Ex] From the point of view of thermodynamics, all reactions are reversible, so we suggested that an even better question to askis When a reaction reaches a point of equilibrium, what determines whether the equilibrium will favour the reactants ‘or the products, and to what extent? ‘This question is answered using the Second Law of ‘Thermodynamics, in which the concept af entropy is introduced. ENTROPY ‘The Second Law of Thermodynamics allows us to predict ‘whether a process is likely to occur Its, therefore, the key to understanding what drives chemical reactions and what determines the position of equilibrium. ‘The Second Law of Thermodynamics introduces a term called entropy, which isa property of matter just like density or energy. ‘The simplest way to describe entropy is to say that itis a quantity associated with randomness or disorder ‘This definition is rather basic and has to be used with care Entropy refers not only to the distribution of molecules but also to the ways of distributing the energy of the system in all of the energy levels available. ‘To help you to understand entropy, it helps to think about what happens during the diffusion of gases. DISTRIBUTION OF MOLECULES Fig C shows two gas jars. The bottom one contains bromine gas and the top one contains ai A fig Gas ars containing ar and bromine When the cover slip between the two gas jars is removed, the bromine and air diffuse so that the molecules of each gas are spread out evenly throughout both gas jars ‘To understand wy this happens we can look at a much simpler example where there are only five molecules. Fig D shows two gas jars. The left-hand jer contains five molecules of bromine and the right-hand jar contains no molecules.RaW MLO ROL ag CTR ‘As soon as the cover dips moved, the molecules ar ree to move between the jas 4A. fig Diffusion in agas one ofthe ways the molecules might rearrange Remeber that ar molecules ae also Each molecule has two possible arrangements. It can be in either the left-hand jar or the right-hand jar We can write the number of possible arrangements for molecule 1 as W,, and the number of possible arrangements for molecule 2 as W., and so on, As there are two possible arrangements for molecule 1, W; = 2. For molecule 2, W,= 2, and so on. ‘The equation for the ¢otal number of ways, W, that the five molecules can be arranged is given by: We W, x Wx Wa x We * Ws 2x2x2K2x2 2 = Most of the 32 possible arrangements have molecules in both jars. Only one has all five molecules in the left-hand jar. [t would be surprising if this arrangement happened very often, If we increase the number of molecules to 100, W becomes 2". The left-hand gas jar would contain all 100 molecules oniy once in every 3.2 x 10% years! We would have to wait for a very long time indeed to see all 100 molecules in the left-hand jar! You can see that as the number of molecules increases, the number of possible arrangements also increases very rapidly. To make the numbers easier to work with we need to use an equation to help us, You do not need to remember the equation, but it helps us to see how the spreading out of the ‘molecules is related to an increase in entropy. Entropy, Sis linked to Wby the equation En S= knw Ikissatisfyingtomakelinks where Wis the number of ways of arranging the molecules, kis constant called the Boltzmann between topics in chemistry. constant, with a value 1.38 x 10K"! and In is the natural logarithm (i.e. the logarithm to the base ¢). you multiply the Boltzmann Constant (138 x 10-23} by the Entropy is measured in units of JK*mot ‘vogatr consantL(602* _Enropy measures the degree ofrandormess, so you woul expecta gas to havea large entropy than its liquid form, and a liquid to have a larger entropy than its solid form. The figures in table A show that this is the case for water vapour, water and ice, {you wil get 8.31, This is also known as the gas constant, wihich you should remember from PV = nRTin Topic 1 (Book 1: 14S) ‘water vapour 189) water 70 ice 48 {able A Eniropies of water vapour water andice DISTRIBUTION OF ENERGY ‘The spreading out of molecules in diffusion is an increase in entropy, because the molecules become ‘more randomly dispersed. In the same way, the spreading out of heat energy also represents an Increase in entropy. Energy exists in ‘packets’ called quanta. You can have a whole number of quanta, but not halves or fractions of quanta,Ate PSE RO ag 35 The distribution of the quanta between molecules is random. The more quanta there are, the more ways there are of arranging them between the molecules. Also, the more molecules there are, the more ways there are of sharing the quanta, ‘As an example, table B shows that there are five possible arrangements of four quanta between two molecules. Table C shows that there are six possible arrangements of five quanta between two molecules. Table D shows that there are 10 possible arrangements of three quanta between three molecules, table B table C table D 4 0 5 o 3 0 0 3 1 4 1 a 3 o 2 2 3 2 a 0 3 1 3 2 3 2 1 a 0 4 4 2 0 1 ° 5 1 1 1 1 z a 1 0 2 table les 4 quant, Savrangements a 1 2 table ¢ 2 molecuies§ quanta, 6 arangements 7 y ; table D3 molecules, 3 quanta, 10 atangements The higher the temperature, the more energy a substance has. The more energy a substance has, the more ways there are to distribute the energy. The more ways there are to distribute the energy, the higher the entropy. So, increasing the temperature will Increase the entropy. PERFECT CRYSTALS ‘A ‘perfect’ crystal is one in which the internal lattice structure is the same at all times. In other words, the particles (atoms, molecules or ions) are fixed and are not moving in any way, rotating or vibrating, The Third Law of Thermodynamics states that the entropy of a perfect crystal at the temperature of absolute 2ero (i.e. 0 K) is zero. THE SECOND LAW OF THERMODYNAMICS ‘The Second Law of Thermodynamics is sometimes misquoted, You may have come across the statement that in a spontaneous change, entropy always increases, This cannot be true: if it were, water could never freeze because this change involves a decrease in entropy. Another example is the reaction between ammonia gas and hydrogen chloride gas: NH,(g) + HClg) ~ NH,C\(s) Clearly, there is a reduction in the entropy of the system, since two gases are forming a solid, yet this reaction occurs spontaneously at room temperature, The statement entropy always increases is almost correct. It needs to be expressed more carefully to give the Second Law of Thermodynamics: Baan Ina spontaneous process, the tia! entropy increases. entropy a property of mater In Section 12A.2, we explain whats meant by the term total entropy’. that fe asoclated withthe degree of disorder oF degree Geni Seo roniee ie a For each of the following predict whether the changeis accompanied by an increase ora deceasein__a60.with the dstibution of the total entropy Suara erry betwen (@) H.0(@)— 1.00) (b) 149) 1g) (€) Naf) — Nas) Oe 2. Arrange te following inorder of entropy, with the lowest ist Leesan steam at 110 °C; ice at-10 °C; water at 30°C ‘continuous intervention by usRae Caco 12A 2 TOTAL ENTROPY Por 12.9(i)| 12.10 | 12.11 Dee Raa) Understand that the total entropy change of any reaction is the sum of the entropy change of the system and the entropy change of the surroundings, summarised by the expression: AScui = ASyatem + ASuuncundings Be able to calculate the entropy change of the system for a reaction, AS, Biven the entropies of the reactants and products. Be able to calculate the entropy change of the surroundings, and hence AS,.., using the expression aH Surnandng = Understand thatthe feasibility ofa reaction depends on: (i) the balance between ASjiay aNd AS.s,oupdingy $0 that even endothermic reactions can occur spontaneously at room temperature (i) temperature, as higher temperatures decrease the magnitude OFS, rasan Sits contribution to AS nai es. Understand that reactions can occuras long as SS. i positive even ifone of the other entropy changes is negative. Understand and distinguish between the concepts of thermodynamic stability and kinetic stability TOTAL ENTROPY CHANGE, AS ‘The total entropy change of a process comprises two components: + the entropy change of the system, AS.jage aNd + the entropy change of the surroundings, ASwrnter Ina chemical action, the system is the species that are aking part inthe reaction ‘The surroundings is everything else. In practice, this usually means the reaction vessel, eg test nude or beaker and the ar inthe laboratory ‘The total entropy change is defined as the sum of the entropy change of the system and the entropy change of the surroundings. That is: AS ou = ASytee + ASwcrndtnas For a reaction to be spontaneous, AS,,,i must be positive. This is another way of expressing the Second Law of Thermadynamics. DID You KNOW? ‘The offical definition of the Second Law of Thermodynamics does not use the term ‘total entropy ‘change: Instead, it refers tothe ‘entropy change of the universe: These two terms have the same meaning, We will use the term ‘total entropy change" throughout this book. ENTROPY CHANGE OF THE SYSTEM Spar calculated using the expression AS yuun = 3S (products) ~ © (reactants) ‘where S represents entropy and © represents ‘the sum of” ‘The standard entropy values of some substances are shown in table A. ‘Standand refers to conditions of 100 kPa and 298 K.aad PP WAM ag rr) SOLD #01) H.065) CH.OH (diamond) 3. 2050 CH.CH.OH Clgraphite) No ford GH 20 cl 1650 aco, 929 0; 2136 NH 1923 tableA ree Use the values in table A to calculate ASS, forthe following reaction CaCO) + CaO) + COE) ASSpam * {CAO + $ACOLe) - S*ICACOYS)] = 38) + 2136-929 = #1604)" mol? Weer Use the values in table A to calculate ASS, fr the following reaction Nolg) + 3H.(e) > 2NHAg) 2 x SNF(@) - S*INde}| - 3x STH) =(21923) - 1916-3 * 1306) #71988) K mot? ASS cen ENTROPY CHANGE OF THE SURROUNDINGS ‘The entropy change of the surroundings, AS.,,unieo i Telated to the enthalpy change of the reaction, AA, by the expression: Aq Soran a where Tis the temperature in kelvin. For an exothermic reaction, where AH is negative, AS,.q.2sns Wil always be positive, so the entropy of the surroundings increases Conversely, for an endothermic reaction, MS, a.sins Wil always be negative, 90 the entropy of the surroundings decreases, (reece) Calcul AS.ransng: a¢ 298 K when one mole of hydrogen gasis bumed in oxygen. Hi@)+309— 4,00) 4H = -2861 mot” =286 238 = +0.960W) K mol or +960) K"! mot AS, arat ‘CALCULATING THE TOTAL ENTROPY CHANGE, Suu [Now that we know how to calculate both AS,., 8d ASyemzsnge WE ate in a position to calculate the total entropy change, AS. fora reaction 37 EXAM HINT ‘An examiner may ak you to ‘suggest why the standard entropy vale of diamond is lower than that of graphite Diamond is ordered in three dimensions (a 3D lattice), whereas graphite is ordered in ‘two dimensions and has greater degrees of freedom between the layers, Pea "Note that entropy values are usually quoted in JK"! mol", whereas enthalpy changes are usually quoted ink) mol. So, in any equation linking AS and AH, one ofthe energy terms will need a conversion of units.WORKED EXAMPLE 4 Using the information intable A calculate thettal entropy change a 298 K for the folowing reaction: Hufg) +1046) = H.0() AH «2864 mot = SH.00)]- SH] - 3» SOxe) ECM W MOM ag aC aad 99-1306 (1 205) = -1632) K' mol 1632) K? mol +960) K" mot! 796.8)" mol” SUMMARY AS Will be positive i + Doth ASwaronings ANG ASynan are Positive + ASwrcundnos is positive and ASyuom is negative, but the magnitude of ASjrrundng: > the magnitude Of MSc © MSwecundng iS negative and AS.j.n is positive, but the magnitude of AS,nounangs < the magnitude Of ASyon THERMODYNAMIC AND KINETIC STABILITY ‘The reaction between methane and oxygen is exothermic, and the total entropy change has a positive value CH(g) + 20:{e) > COx(e) + 2H,00) AK Sout 890.3 kJ mol"? #295 le} mol! Since AS... is postive, he reaction is thermodynamically feasible at 298K. However, the reaction does not take place until the reaction mixture is ignited, usually with a flame, ‘The added heat energy is required to overcome the high activation energy of the reaction, A reaction mixture with a high activation energy, where a teaction will not take place spontaneously ‘at room temperature, is said to be kinetically stable. ‘You can see here that a reaction mixture (such as methane and oxygen) can be thermodynamically unstable but kinetically stable, s0 a reaction does not take place under standard conditions. THE ROLE OF TEMPERATURE ‘The increase in entropy obtained by supplying a certain amount of heat energy to an object depends con the temperature of the system. If an objects very cold, the molecules are not moving around very much, Supplying some heat ‘energy to the object will make the molecules meve around more, so the entrapy increases. If we supply the same amount of heat energy to a much hotter object, the entropy will stil increase, but not by as much as with the cold object. This is because in the hot object the molecules are already moving around vigorously and the increased degree of movement is less for the hot object. WHY DOES WATER FREEZE? ‘We will now apply these principles to explain why, under certain conditions, water will freeze Ice has lower entropy than liquid water so AS.jaomis negative. ‘The process is exothermic, $0 ASynansng 8 Past If the magnitude of ASzerunang > the magnitude of ASyaem then Sa Is pastive and the water A fig Why cossvaterfresze? il freeze.Ate PPA ead ‘We will now calculate AS,,.. for the change of water into ice at +5°C and ~5 °C using the following data, HO) +H,0() AH=~6010J mol* + Se(water) = 69.9) K"' mol” hase ASyyoiem = (47.9 — 69.9) = —22.0 J K-' molt ‘The total entropy change is negative, meaning thatthe change is not thermodynamically spontaneous. ‘The water will not freeze. |At-5 °C (268 K) Sguen = (279 ~ 699) = ~220) K! mol : 6010 Svein: =~ “36g = 1214) mol" Sig = +045 KO molt “The total entropy change is positive, meaning thatthe change i thermodiynamically spontaneous ‘The water wil freeze Irisinteresting to note that what has changed between +5 °C and ~5°C isthe entropy of the surroundings. The reason that AS, emaning, has Changed in magnitude is simply because of the temperature change. The same amount of heat energy has been transferred tothe surroundings but, because the entropy of the surroundings has a higher temperature when at +5°C than when at =5°C, the change in entropy is smaller as explained eater. So, the reason we put water into a freezer when we want to make ice is because the entropy change of the surroundings (ie. essentially the air inside the freezer is large enough to compensate for the decrease in entropy when the water freezes Crea ULus 1. Hydrated cobalt) chloride dehydrateson heating according tothe following equation: CoCl; 6H,O(5) = COCI{S)+ 6HLO{) SH" = + 88.11) mol D (0) Calculate the standard entropy change ofthe system, AS ue S5{CoC6H,0(s)]= 343.0) K mot! S{CoCIds]] = 109.2) K" mol S{H,0(0]= 689) "1 mot {b} Calculate the standard entropy change of the surroundings, AS Zann t 298 K {€) Calculate the standard total entropy change, AS‘, at 298 K for this reaction. {6 Explain whether hydrated cobalt) chloride can be stored at 298 K without it dehydrating? 2. Use the data provided to calculate the total standard entropy change, AS ay, t 298 K, for the following reaction 2Fels) + 11048) — Fe, 046) AH? =-8221) mol! FFs = 27.2)" mot 5°104g)]= 2050)? moh” Sffe,O.(s]}= 90.0) K" mot! ED = wry Et)12A 3 UNDERSTANDING ENTROPY rN eles) Rae banca 125(i) rac} 12.5() 0) Dee Raa) Understand why entropy changes occur during: (changes of state dissolving of a solid ionic lattice i) reactions in which there is a change in the number of moles from reactants to products Be able to use entropy and enthalpy changes of solution values to predict the solubility of ionic compounds and discuss trends in the solubility of ionic compounds covered in Unit 2 REACTIONS INVOLVING A CHANGE OF STATE We have already mentioned that in general, entropy increases in the order: solid < liquid < gas So, we would expect an increase inthe entropy of the system if @ gas is produced from a reaction involving a solid and/or a liquid. EXAMPLE 1 When solid ammonium carbonate is added to pure ethanoic acid, bubbles of gas are rapidly produced. Despite its violent appearance, this is an endothermic reaction, as can be shown by placing a thermometer in the acid before the ammonium carbonate is added. The temperature falls considerably as the reaction takes place. 2CH,COOH() + (NH):CO,(s) = 2CH,COONH,(eq) + H,0() + CO,(e) Since the reaction is endothermic, SS snunsny Will be negative However, there is a large increase in the entropy of the system, Sq. because a gas is produced from a liquid and a solid, The magnitude of AS, .9,i8 greater than that of ASyrcunings 290 this makes AS... positive, so the reaction is thermodynamically spontaneous EXAMPLE 2 Hydrated barium hydroxide reacts with solid ammonium chloride in a rapid endothermic reaction at room temperature: Ba(OH), 8H,0(9) + 2NH.CIfo) — BaCl,(s) + 10H,0() + 2NH,fa) Asin the previous example, the driving force of the reaction iS ASiyuay which overcomes the negative value of ASyrunéns caused by the endothermic nature of the reaction. The reactants, are solids and the products are a solid aliquid and a gas EXAMPLE 3 Magnesium burns in oxygen to form solid magnesium oxide Ma(s) + 30:(@) > MgO%s) The reaction Is highly exothermic, $0 AS;,nardngs Wil Be positive, ‘ASowum 18 negative since a solid and a gas are changing into a solid, However the magnitude of the value of ASwrousins is greater than that of AS,crs taking AS. positive. So, the reaction is thermadynamically spontaneous, DISSOLVING IONIC SOLIDS IN WATER ‘When an ionic solid dissolves in water two changes take place: + the lattice structure is broken down, and + the ions become hydrated “The breaking down of the lattice structure is an endothermic process, equivalent tothe reverse of the lattice energy. It also results in an increased number of moles of particles present, so increases the entropy of the sat. ‘The hydration of the ions is an exothermic process, but results in the water molecules becoming more ordered as they arrange themselves in an orderly manner around the positive and negative ions. The increase in ordering of the water molecules produces a decrease in entropy of the water This ordering of the water ‘molecules is particularly significant when dissolving anhydrous solids in water. ‘To explain why some ionic solids are soluble in water, while others are insoluble, we need to look at both the enthalpy and the entropy changes involved, ‘The solubility of an ionic solid is determined by the total entropy change for the solid. + MS crus since this expression becomes: MS t= ASyoen ~ a = AS tn ‘The value of AS... and hence the solubility of the sold, depends con the values of three factors: + the entropy change of the system, AS. cn + the enthalpy change of solution, A,uéf + the temperature, in kelvin, of the water, 7 Letus have a close look at the dissolving of ammonium nitrate crystals in water at a ternperature of 298 K.aad 4 NH.NOs(s) “2s NH.t(aq) +N AwH = +258KI mol Suan = SINH¢ (ag) + SINO,-(aq)]~ SINH.NOS()] = +1184 + 146.4 ~ 191.1 mor faq) = +1087 K mol = SM #29800 _ Spot MScsrandnp =~ get = PBB 96.6) "1 mol MSs Since AS... is postive, the dissolving of ammonium nitrate in water at 298 K is thermodynamically spontaneous. Since the activation energy for this process is very low, ammonium chloride is soluble Jn water at 298 K, (108.7 ~ 86.6) = +22.1.J K“' mol” ‘We are now ina position to think about the solubility in water of some other ion solids, ‘Table A shows the relevant thermodynamic data for some solids at @ temperature of 298 K. ‘The values have been quoted to the nearest whole number ces a r te NaCl +4 =13 +43 +56 | soluble NH.CI “15 50 67 +117__[ soluble Agcl 766 -221 +B 7188 | insoluble MgSO. -31 +305 “213 792 | soluble Cu80, 3 1245 182 "53__| soluble CaSO, -18 +60 =145 -85—_|linsoluble table® REACTIONS INVOLVING A CHANGE IN NUMBER OF MOLES FROM REACTANTS TO PRODUCTS If you increase the number of moles that you have, you automaticaly increase the number of particles (ie. atoms, molecules or ions) present. This will result in an increase in the number af ways that the particles can be arranged, and this increases the entropy of the system, making AS,.om positive We will now look again at the reactions shown above, bu hist we will consider the change inthe number of moles from reactants to products. ‘EXAMPLE 1 2CH,COOHI) + (NE),CO4s) — 2CH,COONH{s) + H;O{1) + CO{g) Number of mes of reactants = 3 Number of moles of products = 4 $0, AS yoni psive EXAMPLE 2 Ba(OH),8H,0(6) + 2NH,Cls) — BaCl{s) + 10H,O()) + 2NHA(e) Number of moles of reactants Number of moles of products = 13 $0, AS, juanis positive.CREMONA) ID You KNOW? ‘When we state thatthe solids AgGl and CaSO, are insoluble in water, this is a ‘simpliication. Both solids have a measurable solubility in water, bt the solubility is very small, What we are really saying is that the Position of the equilibrium in both cases is very far over to the solid side ofthe equation, ‘We will come back to this Point in Topic 13, when we discuss the relationship between the total entropy ‘change for a reaction and the ‘equilibrium constant, K, for the reaction. CTR EXAMPLE 3 Mg(s) + 30. + MgO(s) Number of moles of reactants 5 Number of moles of products = 1 $0, Sion is Negative, ‘SOLUBILITY TRENDS IN GROUP 2 In Topic 8 (Book 1: 1AS), we mentioned that for Group 2 the solubility of the metal hydroxides increases down the group and the solubility of the metal sulfates decreases down the graup We can now explain the reason for these trends in solubiliy. As we have mentioned eatlier. the two factors that affect the solubility of ionic compounds are the standard enthalpy change of solution of the compound, &,,/°, and the standard entropy change of the system, ASjzem Itis dificult to work out AS%jyeq accurately for many ionic compounds. We can use the standard ‘entropy values of the ions as @ guide, ‘SOLUBILITY OF GROUP 2 METAL HYDROXIDES. ‘Table B shows the standard enthalpy and standard entropy changes involved in dissolving the Group 2 metal hydroxides. The values are given here to the nearest whole number METAL c rad bc pointe MglOH) 33 Mer (aq) CalOH)> 16 454 | Ca®aq) 53 SiOHle =a | 154 |Se*aq) “33 Ba(OH)2 52 +174 Ba*(aq) +10 table B ‘The values forthe standard entropy of the hydroxide fon have been left out here, because the fon is ‘common to all ofthe metal hydroxides. The trend in the standard entropies ofthe cations mirrors the trend in the standard entropy change ofthe system, AS us ‘The standard enthalpy change of solution becomes more negative down the group. This favours solubility, a8 ASS, manany, Becomes moe postive. ‘The values of the entropies ofthe hydrated cations become less negative (Le. more positive) and this also favours solubly ‘As both factors favour an increase in solubility, the metal hydroxides become more soluble as you go own the group. ‘SOLUBILITY OF GROUP 2 METAL SULFATES ‘Table C shows the standard enthalpy and standard entropy changes involved in dissolving the Group 2 metal sulfates. The values are given here to the nearest whole number. Proc a cn ag nny ene Poa Me (aq) Ca(aq) sag) Ba(aq) table Caad Again, the values forthe standard entropy of the sulfate ion have been left out here, because the ion is common to all of the metal sulfates, The trend in the standard entropies of the cations mirrors the ‘rend in the standard entropy change of the system, AS, ‘The standard enthalpy change of solution becomes less negative down the group This favours insohubilty, a8 AS cundngs B2COMeS less postive. "The values of the entropy of the hydrated cation become less negative (ie. more positive), and this also favours solubility, ‘The overall decrease in ASzeranaae: down the group is 368 JK-! mol-' (+ 305 to ~63) ‘The overall increase in the standard entropy change of the hydrated cations is 148 JK-* mol (-138 to +10). ‘As the decrease in the standard entropy of the hydrated cations is much less than the increase in the entropy of the surroundings, the Group 2 metal sulfates become less soluble as you go down, the group, PE [A this level, itis assumed that AS, ., does not change with temperature, since the entropies of both the ‘wactants and the products change by similar amounts, The magnitude of AScring wil always decrease with increasing temperature. f AS, randing is negative it will become less negative If AS.rinanx is positive it will become les positive, Evidence from thermodynamics does not indicate the rate at which a reaction will occur. A reaction that Is thermodynamically spontaneous at a given temperature may have a high activation energy. This could result in the reaction not taking place at all Predict whether there is likely to be an increase, decrease or no change in the entropy ofthe system in each of the fllowing reactions. ln each case, give your reacons. Da) CuS0.5H,019 -» Cus04s) + 5H.040 ED eT ne {b) Hag) + NH) — NHC) (©) SOx{g) + 30.18) ~ SOslg) (6) Co(H,O} aq) + EDTA*(aq) — ColEDTA}iag) + 64,04) JD This question is about the following reaction: 5) ie) — 2g) {a) State why you might predict that the entropy change in the system for this reaction is zero, DP ()) The actual AS, for this reaction is +22" mol, Explain why the total entropy change for this reaction is not zero,12B 1 LATTICE ENERGY, A,-H ETO alam de a Rae Caco 12.12(i) | 12.1244) 1213 | 1218 PART 12.12() Dee Rate) i Beable to define the terms: (i) standard enthalpy change of atomisation, AH (i) electron affinity (i atice energy (asthe exothermic process forthe formation of one mole ofan jonic solid from its gaseous ions). Understand that lattice energy provides a measure ofthe strength of ionic bonding. 1H Construct Born-Haber cycles and carry out related calculations. 1H Understand the effect of ionic charge and ionic radius on the value of the lattice energy of an ionic compound LATTICE ENERGY In Boole 1, we saw that bond enthalpies can be used as a measure of the strength of the covalent bonding in molecules. The equivalent energy change for ionic bonding in ionic compounds is lattice energy, Aci (or lattice enthalpy), ‘The latice energy of a compound isthe eneray change when one mole of the ionic slid is formed from its gaseous ions. If standard conditions of 100KPa and a stated temperature (usualy 298 K) are applied (es shown by *). then the energy change is called the standard lattice energy. The equation that represents the standard lattice energy of sodium chloride is, Na*(g) + Cig) + Nace) For magnesium chloride i is: Mgi{g) + 2CI(@) + MgCl{s) A, 2#¥* = -2526kJ mol"! PETIT “The terms lattice energy’ and atice enthalpy’ are commonly used as if they mean exactly the same thing, You will often find both terms, sed within the same textbook article or website, including some university websites, In fact, there sa difference between ther. Itreates to the conditions ‘under which they are calculated. However, the difference is negligible hen compared with the different values for lattice energies that you vill find in diferent sources. Unless you go on to study chemistry at degree level, you do not need ‘toworry about the difference between the two terms. AigH*= ~T80KI molt DID You KNOW? ‘There are two ways of defining lattice energy. The one mentioned in the specification is the one we have already defined, This is ‘sometimes called lattice energy of formation, since the compound Js being formed from its ions. Using this definition, the energy ‘change will always be negative, However, some books define it as lattice energy of dissociation, in ‘which itis the energy change when one mole of the compound is broken down (or dissociated) into its ions. In this case, the energy ‘change will be postive. FACTORS AFFECTING THE MAGNITUDE OF LATTICE ENERGY ‘The lattice energy of magnesium chloride, Mg!(CI’)s, is much larger (ie. more negative) than that of sodium chloride, Na*C ‘A number of factors are responsible fr this difference + The first thing to realise is that a magnesium ion carries twice the charge of a sodium ion. + Second, there are more cation-to-anion interactions in magnesium chloride because there are twice as many chloride ions per cation than in sodium chloride. +A third factor isthe distance between the centres of the cations ‘and their neighbouring anions, which is equal tothe sum of their ionic radi This distance is determined in part by the relative sizes of the ions involve (the Mg" ion is smaller than Na’, so reducing the sum of the ionic radi) and also by the type of lattice structure the compound has. In fact the retative ion sizes determine the type of lattice structure ‘Table A shows the effects that both the inter-ionic distance and. the charges on the ions have on the lattice energy. CT Pct RS cir uF 0207 +1 7031 NaF [0235 a | “318 Gr 0233 42-1 2630 u,0 0214 2814 MgO 0212 3791 ALO; 193 82 =15504 table A Comparison of LiF and NaF, where the charges on the ions are the same, shows that a decrease in the distance between the centres of the two ions (the inter-ionic distance) results in a more negative value forthe lattice energy. Comparison of NaF and CaF;, where the interionic distances are almost the same. shows that an increase in charge of even one of the ions (Ca as opposed to Na’) results in a more negative ‘value forthe ionisation energy. Similar comparisons can be made between Li,0 and MgO and also between Li,O and ALLO,aad Finally as we will se later inthis topic, there are also cavalent interactions between the ions, and these affect the magnitude ofthe latice energy. The values quoted in table A take these interactions into consideration since they are calculated values using a Born-Haber cycle (see later in this section). Ee ee eee ae eee z ievene ea atc pes ee types of lattice structures. In addition, the extent of the covalent un ase be ee eae ee aie ae ee ‘STANDARD ENTHALPY CHANGE OF ATOMISATION, 4,4” ‘The enthalpy change measured at a stated temperature (usually 298 K) and 100kPs when one mole of gaseous atoms is formed. from an element in its standard state is called the standard enthalpy change of atomisation of the element (see Topic 6 (Book 1: IAS)) [tis given the symbol Aa? Equations representing some standard enthalpy changes of atomisation at 298 K are given below. Cis) Clg) ght = 4717 mot! ‘Na(s) — Naja) AH? = +107kI mol 4Hi(g) + Hig) gH? = 4218s mol"! Chg) + Clig)—AyHe = 4122 mot! PE Note thatthe standard enthalpy change of atomisation isthe enthalpy change when one mole of gaseous atoms formed. Inthe ‘ase of elements that exist as polyatomic molecules, enthalpy change when one mole of gaseous molecu ELECTRON AFFINITY ‘The first electron affinity of an element, 1* BA, isthe energy ‘change when each atom in one mole of atoms in the gaseous state gains an electron to form a —1 ion, ‘The equations below represent the first electron affinities of some elements Cig) +e > Chg) 18 BA = ~349kI mot! Bile) + Bre) 1° BA = ~325 1 mot Og) +e = 0%@) 1 £A=—141kd mol"! ‘The first electron affinity has a negative value for many elements, including the alkali metals. Examples include: Lilg)+ & = Li-(g) 1 EA = -60kI mol” and Nalg) + e+ Nar(g) 1% BA = ~53 kI mol! PRPs ae 0) Nera (ans ‘There is a notable exception with the noble gases. For these repulsion caused by the electrons already present in the valence shell results in & positive value forthe first electron affinity asthe additional electron would have to occupy a new valence shell In contrast, second electron affinities, 2"! EA, tend to be positive, as energy is required to overcome the repulsion between the negative ion and the electron being added. For example: Ow+e 0%) 2 EA= +4798 mol! ‘Therefore, the formation ofthe oxide ion, O*, in the gaseous state from its atom in the gaseous state i an endothermic process overall Og) +26 0%) I A+ 2" BA = +657 kI molt his raises an interesting question: why does oxygen form O*- ions in its binary fonie compounds rather than O- ions, as the O- ion would appear tobe the more energetically favourable state? We will attempt to answer this question later inthis topic BORN-HABER CYCLES We are now ina position to consider the overall energy changes that take place when an ionic compound is made from its elements. These energy changes are summarised in an energy level diagram called the Bora-Haber cycle. Fig A shows the Born-Haber cycle for sodium chloride. Navig) +e" + Cle) Natig) +e" + cule) | +? -a0 Naviel+ Cre) Energy Nala) 3C1,8) Naloy+ Schie) A fig Boun-Haber cycle for sodium chit EXAM HINT Examiners may ask you to label enthalpy change of atomisation, ‘enthalpy change of ionisation, electron affinity and enthalpy change ‘of formation on Born-Haber cycle diagrams lke fig A. Make sure that ‘you can recognise each process and label it correctlyPRM Ued aoe UCU aka re ny The cycle includes the following energy changes all of which ean be determined experimentally + The enthalpy change of formation of NaC AWHINaCI(s)] = ~411 kd mol! + A,H{Na(s)] = +107kJ molt + the fist ionisation energy, 1* ZE[No(g] = +4961 mol! + AyH{Chig))= +122 mol" + EA[C\(g)] = -349kJ mol Applying Hess's Law to the cycle gives us: +107 + 496+ 122 + (-349) + Augf?= —411 Hence: AjgHINaCl(s)) = —411 - 107 ~ 496 ~ 122 + 349k malt 787 kJ mol-* PET Note: see Topic 2 (Book I: 1AS) forthe definition of ionisation energy and Topic 6 (Book 1:1AS) for an explanation of Hess's Law. WHY IS CALCIUM OXIDE CaO AND NOT Ca*O-? ‘You may think thatthe answer to this question i obvious, You might say that calcium oxide is Ca**O because both ions would then have a stable noble gas electronic configuration IF that is what you believe, then the following may come as a surprise. Acquiring a noble gas electronic configuration is not «reason for electronic changes to take place when atoms and molecules react together Afterall, many ions exist in stable compounds, in particular cations of the transition metals, in which they do not have the electronic configuration of a noble gas. In fat, compounds in Which the ions do have a noble gas electronic configuration are in the minority. So, why does calcium oxide form as Ca?*O- and not as Ca*O~ and why are we asking the question? You may remember that we have mentioned that the formation of 0°4@) from Ofg) is exothermic: Og) + 07g) 188A However the formation of O*(g) from O(g) is endothermic: Og) + 22° O%(g) IEA + 1" BA = +657K) mot! Since more energy is required, why is the formation of the O fon preferred over the formation of O°? 141 kd mot A similar pattern is observed with the formation of Ca(g) and Ca**(g from Calg) Calg) + Car(g) +e Calg) + Ca¥*(g) + 26° Similarly. since more energy is required, why isthe formation of the Ca** ion preferred over the formation of the Ca ion? 1 JE = +590kJ mol VE + 28 1B= +1735 KI mol ‘To angwer this question itis necessary to consider alf of the energy changes involved in the formation of an ionic compound from its elements ~ not just those involved in the formation of the CTR fascous ions from the gaseous atoms. In other words, we need to look at the information supplied by the Born-Haber cycle for each compound (se fig B and fig C). A Caria) + O19) as cai +O Ca’igl + 30.4 Energy Cais + 40,0) A fig. om-Haber oe for CeO) AR crag ow Energy Calg) + 30.0) Gal) + 50,9 A fige. Boin-Haber gle for CPO) Using the equation: AiH{Ca*O"()] = AyF{Cals)] + 1 TE{Ca(g)] + AuFit}Ox()) +1 EA[O(g)] + AipICa"O-(5)} we can calculate a value for AyH[Ca"O(s)] using a theoretical value for A, LY> MZ, BIX>MZ>LY © MZ>JX>LY D Mz>LY> Ix 0 (Total for Question 1 = 1 mark) we pe [Ye 045 | 014 [ 010 | 015 2. The table shows the lattice energies of rubidium fluoride, RE and caesium chloride, CsCl ‘COMPOUND “LATTICE ENERGY / ks mot! rubidium fluoride, RDF 783 ‘caesium chloride, CsCT 661 ‘Which is most likely tobe the latice energy of caesium fluoride? A ~647 kJnol* B -747 kImol* -847 kimol* D -947 kImol* 0) (Total for Question 2 = 1 mark) 3. Why do calcium and chlorine react together to form CaCl4s) rather than CaCl(s)? [A Less energy is required to remove one electron from the calcium atom than to remove two electrons. B More energy is released in forming chloride ions from chlorine molecules in the formation of CaCl,(s) than in the formation of CaCl(s) The latice energy of CaCl(s) is less exothermic than the lattice energy of CaCl,s). D When CaCl(s) is formed from its elements, more energy is released than when CaCl,(s) is formed from its elements. [1] (Total for Question 3 = 1 mark) 4 How does the entropy of the system change when ammonium nitrate crystals dissolve in water? A Itremains the same, B It decreases, because the hytirated ions are more ordered in the solution than they are in the crystal. € increases, because the ions in the crystal become hydrated in the solution D It increases, because the ions are arranged more randomly in the solution than they are inthe crystal 1) (Total for Question 4 = 1 mark) 5. Which statement is true for the exothermic reaction Zn(s) + 2HCl{aq) + ZnCl(aq) + Hg) A Ais positive B Saat 3 positive © AS 8 negative D AS,,, isnegative a (Total for Question 5 = 1 mark) 6 Calcium carbonate decomposes in an endothermic reaction ‘when heated to 1113 K CaCO 4s) + Ca0fs) + COg) ‘What are the signs of the entropy changes at 1113 K? Sven Swann: + - ~ ~ O (Total for Question 6 = 1 mark) voee 7 The Born-Haber cycle shown below can be used to calculate the latice energy for magnesium oxide BAO] + 2 EAU) (657 KI mol" Mag) + 2e- + O48) AO) 248 mol" A erg +26 +4010 2 deIMalo = +1450 mal! HIME Mais) +" + 20,0) Ais, = $786k mol! Mag) + 40,8) AH, = +1493 mor Mals) + 20,8) AH, = eon kd mot" Mg O19) (@) Give the name of each of the enthalpy changes labelled ‘AH, AF, and AF i} (©) Write the missing formulae ftom the tap of the Born-Haber cyele. Include state symbols 2)aR () The equations forthe first and second electron affinities of cnygen are Of) +e 1° BA>-141 Jmol O@) +e =O") 2° EA= +7981 mot Suggest wy the second electron affinity of oxygen is endothermic. pI) (@) Use the data in the Born-Haber cycle to calculate the lattice energy of magnesium oxide. fe (Total for Question 7 = 9 marks) £8 Latice energies canbe found eter via experimentally determined energy changes, using the Born-Haber cycle, or by theoretical caleulation using the ionic model fr the crystaline compound, (@) State the energy changes that need to be determined in order to find the ltice energy of sodium fluoride, using the Born-Haber cycle. al (©) The table lists the experimentally determined and theoretically calculated lattice energies for some compounds Compound ‘NaF | Nal | AgF | Agi Experimental value/i mol |=918 |~705 | -958|-8a9 ‘Theoretical value/kImol™” _ |-912|=687|-920|=778 Comment on the discrepancies between the experimental and theoretical values of the lattice energies (4) (c) The enthalpy changes of hydration, in kJ mol-', of the ions inthe compounds listed in the table in part (b) are Na*-406 Agt-464 F-58061 ~203 (Using the experimental lattice energy values, show by calculation which of the four compounds is the most soluble 2 (i) Explain what other information is necessary in order to make a valid comparison of the solubilities of the four compounds, RB) (Total for Question 8 = 12 marks) 9 Entropy changes are important in determining the feasibility of a proces, (@) For each of the four processes below, predict the Hikely sign of the entropy change of the system, AS,.ceq. In each, case, justify your answer (4) (Nig) + 3H.(@)— 2NH) (i) H,06) — H.00) (8) 2Nals) + 034g) > Na,Oys) (i) S(o] + Og) -» 280, (b) Magnesium oxide is used as a refractory Tining for furnaces Iecan be made by heating magnesium carbonate MgCOss) > MgO[s) + COs) AH? = +117 mol ‘The table shows the standard entropies at 208 K of MgCO,(s), MgO{s) and CO,(a). DCW aad Ey Substance °K" mol MgCO;s) 657 MgOVs) 270) COsB) 2140 () Use the data to show that magnesium carbonate is stable at 298K, 4] (i) Calculate the minimum temperature at which ‘magnesium carbonate will decompose py (Total for Question 9 = 10 marks) 10 (a) ‘The equation for the combustion of hydrogen is: Ha(g) + 20,2) > H,00) AH = - 285.5kJ mol" ‘The table gives the standard entropies at 298 K for Hg), (Og) and H,0(), ‘Substance Hig) Of) | H,O(!) Se/ik*mor | 1310 | 2050 | 639 () Calculate the standard entropy change of the system at 298 K, AS... for the combustion of hydrogen, py (ii) Calculate the standard entropy change of the surroundings at 298K, AS"yaning for the combustion of hydrogen. py (ii) Calculate the total standard entropy change at 298K, AS*,,. for the combustion of one mole Of hydrogen. Give your answer to an appropriate umber of significant figures. B (©) Explain why hydrogen does not react with oxygen unless the mixture is ignited. tu) (Total for Question 10 = 8 marks) 11 Ammonia can be made by reacting together nitrogen and hydrogen. The reaction is reversible. Nig) + 3Hy(g) = 2NH(g),H* (700K) AS tua (700K) = ~78.7 JK" mol"! 110.2kJ mol (a) ‘The * symbol represents standard conditions of a specified temperature and standard pressure. In this, instance, the temperature specified is 700K. State the standard pressure for thermodynamic measurements. [1] (b) Calculate AS snsnsng (700K) 2] (6) Caloulate AS (700K). ray (d) Ifthe reaction mixture is left for long enough, in contact witha suitable catalyst, iis possible to establish an equilibrium between the nitrogen, hydrogen and the ammonia Comment on what the value of AS fi (700K) indicates about the relative proportions of nitrogen, hydrogen and ammonia in the equilibrium mixture at 700K. ul (Total for Question 11 = 6 marks)ST EQUILIBRIA eee ele eT Tr Whenever chemical engineers design a chemical plant to manufacture a new chemical they must overcome a problem. They want the best possible yield from the reactants, but they find that most chemical reactions do not go to completion because they are reversible and can reach a state of dynamic equilibrium. All reactions have a tendency to approach equilibrium, whether they seem to go to completion or whether they seem to form no products at all. In many cases, such as the combustion of a fuel, the equilibrium composition corresponds to the complete conversion of reactants into products. Reactions that don't seem to take place at all, like the corrosion of gold in air, also tend to approach equilibrium, but in these cases the equilibrium composition corresponds to virtually unchanged reactants. Many reactions approach an equilibrium in which there are significant amounts of both reactants and products present. Finding and controlling the position of equilibrium in such reactions is the focus of this topic. MATHS SKILLS FOR THIS TOPIC Recognise and make use of appropriate units in calculations Recognise and use expressions in decimal and ordinary form Use ratios, fractions and percentages Use an appropriate number of significant figures ‘Change the subject of an equation ‘Substitute numerical values into algebraic equations using appropriate units for physical quantities Solve algebraic expressions Use logarithms in relation to quantities that range over several orders of magnitudeWan miko ones + How to deduce an expression for K, for eee eneerntnnty nee een 5 Howe deducean expression for the equilibrium Wire tired are ck Mad cee arene poets met red The quantitative effect of change in concentration homogeneous and heterogeneous systems How to predict the effect of change in temperature Topic (Book 1: 14S) erie ees See eee ee ee ce Bieri eee eearere ners tany +The qualitative effect of change in concentration, enna oa Parnes errs er eee re pare Beene ene STE aT cee aCe eet ees) pre tein eae) |The relationship between the equilibrium Penarth SecaSa 13A 1 EQUILIBRIUM CONSTANT, K, errs eT et RS aes) Ml Beable to deduce an expression for K. for homogeneous and heterogeneous systems, in terms of equilibrium concentrations. I Beable to calculate a value, with units where appropriate, for the equilibrium constant K- for homogeneous and heterogeneous reactions, from experimental data, HOMOGENEOUS REACTIONS Ahomogeneous reaction is one in which all reactants and products are in the same phase, For ‘example, all are gases or all are in aqueous solution. In Topie 9 (Book 1: IAS) we sa how the position of equillbrium of a reversible reaction can change ‘when the conditions are altered. In this section, we will study quanttately how changes in concentration affect the equilibrium positon, For the reversible reaction: N08) = 2NOxG) it can be shovm experimentally that at equilibrium and at a given temperature: (NOE es NOD, ‘This value Is called the equilibrium constant and is given the symbol K. ‘The subscript ‘c’ indicates that this equilibrium constant is calculated using concentrations. This is to cistinguish it from another equilbrium constant, K,, which uses partial pressures, Te subscript ‘eq’ indicates that the concentrations are those at equilibrium Ata given temperature, the value of the equilibrium constant does not change with concentration, unlike the equilioium position. The only factor that affects the value of the equilibrium constant is temperature. There are two ways of obtaining a value for the equilibrium constant + the first is by experimentation, and this is the method we will lok atin this section + the seconds by calculation using thermodynamic equations, and this will be cevered in Section 134.5. = a constant For a general reaction WA+ xB = C420 [Pel DFag

107, therefore Q. > Ke For equilibrium to be re-established, Q. must decrease. This can only happen by the equiibrium shifting 1 the lef, to increase the denominator in the equation. ‘The addition of more nitrogen, at constant pressure, results in a shift ofthe equilibrium position to the left (Qur prediction told us thatthe equilibrium would shifto the right, away from the nitrogen added. ‘The problem with making predictions is that two conflicting changes are accurring here: 1 the increase i the number of moles of nitrogen should result in a shift of equilibrium to the right 2 the inerease in volume should result in a shift to the let Wehaverna way of knowing which effec is greater unless we perform the calculations shown above,AUR) PRP aU iu es MSU) EFFECT OF PRESSURE ‘As with concentration, a change in pressure, at constant temperature, on an equilibrium system containing gases has no effect on the value of either K- or K ‘Once again, any change in the equilibrium position occurs in order to maintain the equilibrium ‘constant at @ constant value. If the partial pressure of only one of the component gases is changed, then the overall ellect on K,, can be predicted in the same way the effects of changes in concentration on K. were described in the previous section. However if the cota! pressure of a gaseous system is suddenly increased or decreased, then the partial pressures of aifthe gases will ether increase or decrease. The effect on the position of equilibrium can be explained using the equilibrium law. This is shown in the following worked example. Wiese Consider the reaction Nu + 3H.) = 2H) Wag “Bul on) Suppose the equilibrium partial presures of ittagen,hycrogen anc ammonia area band eat respectively Then iFthe total pressure i suddenly doubled, the pantal pressures of nitrogen, hydrogen and ammonia willbe doubled to 2a, 2b and 2c respectively. OF, 2a (2b ” Téab’ The value of Qs now one-quarter of the value of K, In order to re-establish equilibrium the numerator hasto increase wth a subsequent decrease in the denominator, until Q, =K,, This achieved by some nitrogen and hycrogen reacting 1o form more ammonia Hence, an increase in pressure increases the equilbrium yield of ammonia by shiking the equilibrium to he right EFFECT OF ADDING A CATALYST ‘The expression for an equilibrium constant of a given reaction contains only those substances included in the overall stoichiometric equation for the reaction. A catalyst does not appear in the ‘overall equation, and so cannot influence the value of the equilibrium constant, and hence the ‘equilibrium position \We can think about this in another way. In Tapie 9 (Book 1: LAS) you learned that a catalyst increases the rate of both the forward reaction and the backward reaction to the same extent. The catalyst therefore increases the rate at which equilibrium is established, but has no effect on the final concentrations of reactants and products at equilbrium. Therefore, a catalyst has no effect on the value (of the equilibrium constant fora reaction.