a tr PEARSON EDEXCEL INTERNATIONAL A LEVEL CISL Student Book 2Publishes by Peston Eaueston Limited, 60 Stand, London, WOR OAL, se peasonglobascluns.cort Copies ofoa specication or at Edexcel quot teations maybe founsonthe ‘eo hipe/qustetonspeerson com “ext © Pearson Eoin Lintad 2019, Designed by Tech Set Lid, Gated, UK “yore! by Teh Sat Lid, Gateshead, UK bed by Gerad Daan, Sharn Jordan en Sarah ihe ‘rigral tuations © Pearson Education Lad 2018 ‘Musvatd by © Teeh-Sot Lis, Gateshead UK (Cove desig © Pearson Eaton Led 2019 Cou mages: Front Getty mages: Dawid MaivScience Faction ‘ese front cove Shutterstock convDrity Lobanov “Tho ight of Cit Curtis, Jsaon Murgatroyd and Davis Scot tobe ened a6 autor fis werk have been asserted by hem accordance With tba Copy (estan an Patents Ac 1088. 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Aran eceve.Fiwes 09 page 273 tem Esucaton Scatand © Crown capyight 2012; Figures on page 4 fom “Cataysts era green ndsty’ Education n Cram (lery Heese) ky 2008, Mp /hewsrse cgfeducatlon fase 7000. eat generis ressareh-inausty.as, coppght © Royal Scity of Chen: igus or pape 208 tom ‘ue tras good, our rigs bd, Eaucaton Chemisty (Or Son (ott, March 2070, tputwew sc.rpleducaton/sicTssvs/2010MaF¥e Rings (Good Four Rings Bad ssp, conyrit © Royal Soi of Chemie. Tent Crete: 25 Royal Society of Chemist Engnered Mealowryine Cataysus Frida Cats Feacton by Dabae Houten, 3 Hoven 2014, Reproduced by permission of The Royal Social of Chemisty 5 Toyota Motor Sales: From “ojeta The Ofical 8g of Toyota UK by Joe Grd blog toyetaco how coe iojoas-futcl-rile wars 74 Guardian Nows and Meda Lind: From ar ace in The Guardian, Soentsts Study Ocean Absorzon of Human (Carbon Palio by dot Arana, 1 Fetruary 2017, pew eauaedan amlenvtoemetimae-corsenais-57-per e201 T6scerts-ty- ‘oean-abeerton of huran career poli: 102 Miguel anos: Fem The Daly Cesta by Mua anes tu aalyemate oy 2508789581 Mn, 184 Royal Society of Chemistry: Enviching tho origin offen by Joanne Thomson, 26 November © 2010, Rescued by permission of The Royal Society of Chamsr: 17 Anthony Edward Hargreaves: For Aer Battery Power by Tony Horgresves psec rscog'sectonTeatueater-power 2020096, arco; 216 Natlonal Geographic Socket: Bus Eced Habe Octopis SuNve ‘Brutally Cold Temperate, 1. © 2013, National Geogapie Sociely, Unb tn permission: 22 Royal Society of hemity Fron THe Swoot Scot of ‘Stes by Emma Davie, February 2008; Reproduced by permasan af The Rays ‘Secity of Chom 278 Royal Society of Chemistry: Sto chang or oranie syne by Flas Van Norden November 2007, ©2007, Reprocuces By Parmisin of The Royal Society of Chemisty. Inover to ensure that ths resource ofr hah uaty suport forthe associated Pearson qufcaton thas tan trough arvow process oy te awacing ‘boo Thi grocess contre tat th sures ty covers the teaching ars Ieuing contrt of te spctiton at which tis med also cone tat t emanstates an aporopate batnce between the deveormen of at Sl romeo ara unceretanding,m ation o preparation for asosemen. Enorsement as nt cover any gudanoe 0 asessmentactvteso rocesea (ea. pracice questions or avn n hw lo anewerassessren queron) inouded mth resource, rar doe # prescribe any parbouar approach tthe toachirg o daar of aroatos course. le the pubiaars nave made every tert to ensue that aaice onthe ‘aalfcattn and te aecemert accra, the fea speciation an sicoised assessment guidance materals we the any autora suse o! ‘oration and stout aay be retro oor dente gudanes Pearson examiners have not contributed to ay sections in this recut leant 0 ‘ramiraton paar for whies toy fave oopansbuny. Eamier wi et use endorsed resources a Sout atl oy ‘resource i require to achieve ths Pearson qualiteation, nr does mean that Fe teoneultee mata walle to suppor the qualcaton and ay resource lists produced bythe awarsng body shal eld this and ether appropriate resources.(UST COURSE STRUCTURE iv ABOUT THIS BOOK viii PRACTICAL SKILLS x ASSESSMENT OVERVIEW xii TOPIC 11 2 TOPIC 12 30 TOPIC 13 58 TOPIC 14 78 TOPIC 15 106 TOPIC 16 158 TOPIC 17 182 TOPIC 18 220 TOPIC 19 236 TOPIC 20 258 MATHS SKILLS 282 PREPARING FOR YOUR EXAMS 286 COMMAND WORDS 293 GLOSSARY 295 PERIODIC TABLE 298 INDEX 299Dead 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Ceara 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: APROBLEM 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.Peat 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 MANGENESE 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 FHAGRANCE AND TASTE EXAM PRACTICE onsMase 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 PARTY em 5 PRACTICAL TECHNIQUES a oe IN ORGANIC CHEMISTRY: 4 AMIDES AND PART 2 274 sooeule> 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POC d 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-xii 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. Learning objectives Each chapter stats with a Ist of key leaning objectives. Sowa sea ou a aNme diy ton reference The exact specification points covered inthe Section are provided Learning tps | and avoid commen errs. Grose Student Book content Help you to navigate course content. ‘These help you focus your learning Feterences to previous or folowing Worked examples irked examples show you how to work through questions, and set out caletions Exam hints Tips on how to anewer exam- syle questions and guiaance for exam preparation incucing rexjiements inccated by paniclar command words. Did you know? Intersting facts help you remember the Key concepts, Checkpoint {Questions atthe end of each section check understanding of the key learning points in each chapter. Certain questions alow you to dovelop skills that wil bo ‘raluable for fer study and in the workplace Subject Vocabulary Key forms are highlighted Inve the text, Clear fintions ae 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 yourlearing In carte, chapter by chapter: + Lins to other areas of Chemistry include previous know/ed ‘thats ult on fn the topo, and future areas of knowledge and appeation that you wil cover lator in your course, + Maths knowledge required is Getalled in ahandy checks. you need to practise the maths you reed, you can use the Maths Skis, feterence atthe back ofthe Book a8 Astatng point DEMON ai) CATASTROPHE FOR CORAL? > == Exam Practice Examsyle questions at the end ofeach chapter are tailored tothe Pearson Edexcel ‘spectication to allow for practice {ahd development ct exam ‘tg technique. They algo allow fr practea responding {othe command worse Used in the exams (so the command ‘words glossary at the back of this book. You can aso reer tothe Preparing for Your Exams: ‘section atthe back of the book, for sample exam answers with ‘commentary. Cec ails Ev Thinking Bigger [Attha end of each topic there Is an opportuni to read ana work ith rea esearch anc vting about science. The activites nalp you to read real-lle material that's relevant to your coureo, analyse now scientists write, ink crdealy fad consider how eterent Aspects of your leaming piace together “These Thinking Bigger activ focus on key wansterabl sls, inion are an important basis for key academic gual.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 act Chemistry qualification, * Papers 4 and 5 will include questions based on practical activities, including novel scenaris. * Paper 6 will test your ability to plan practical work, including risk management and selection of apparatus. jes will be assessed in all examination papers for the IAL 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 Gore Practicals are included in the specification, which is available online Baa IAL CORE PRACTICALS 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 energy of a reaction TOPIC 14 P11 Finding the K, value for a weak acid ‘ACIO-BASE EQUILIBRIA ToPIC 16 P12 Investigating some electrochemical cells (ene CP13a_ Redox titrations with ron(l ons and potassium manganate(V) 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SRN t Ca ae In the Student Book, the Core Practical speetications are supplied inthe relevant Sections Practical Skile Practical skills boxes explain techniques used in the Gore Practical, and also detal useful sills ane knowledge gained in ‘other related investigations. This Student Book is accompanied by a Lab Book, which includes Instructions and wring frames for the Core Practical fr you to record Your eaults and refect on Sour work Practical skis Bractice questions and answers are also provided ‘The Lab Book records can ‘be used as preparation for the Practica! Shile Paper.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 Cad ie asin we Leh 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 OF AL Sm AVAILABILITY TRANSITION METALS AND ORGANIC 40% 20% Thour January, June and October NITROGEN CHEMISTRY 45 minutes Written exam paper Paper code WCH1S/01 Externally set and marked by Pearson Edexcel Single tier of entry PERCENTAGE | PERCENTAGE CHS Ct SiS PRACTICAL SKILLS IN CHEMISTRY II 20% 10% Thour January, June and October Written exam paper 20 minutes First assessment: June 2020 Paper / Unit code WCHIG/01 Externally set and marked by Pearson Edexcel Single tier of entry First assessment: January 2020 First assessment: June 2020PTs ay cu ASSESSMENT OBJECTIVES AND WEIGHTINGS Ss a aan) CATT [seman | ea | Demonstrate knowledge and understanding of science. 343602931324 (a) Application of knowledge and understanding of science in 343633363336 familiar and unfamiliar contexts A02 (b) Analysis and evaluation of scientific information to make oul 446 td judgements and reach conclusions. _ Experimental skills in science, including analysis and evaluation a Pa ‘of data and methods. RELATIONSHIP OF ASSESSMENT OBJECTIVES TO UNITS ‘AO ‘02 (A) ‘A02(B) 03. TOTAL FOR INTERNATIONAL ADVANCED SUBSIDIARY 33-36 4-36 on 20 ‘AOI ‘02 (A) ‘A02(B) ‘AOS ‘TOTAL FOR INTERNATIONAL ADVANCED LEVEL, 24 33-38 144 Ey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 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 7Wintncnuee ence Topic9 (Book 1145) res Hcy eee so eet ee ionsto than other catalysts eee!OU aaa ae) Dee R/S I Understand the term ‘rate of reaction’ I Select and justify a suitable experimental tecUique to obtain rate data for a given reaction, including (titration (ii) colorimetry (il) 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 mal dmv! s+ ‘The expressions in calculus notation are: _ product] et 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, tis necessary 10 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 Re OPP Wee ee AUT Cero Coacad 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. For example, the reaction between calcium carbonate and dilute hydrochloric acia, CaCOy(s) + 2HCHaq) —+ CaCl{aq) + HOt) + COs(g) could conveniently be followed by measuring the volume of gas (echnique 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 ,(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 a large volume of gas is being measured, the difference in the degree of measurement uncertainty becomes so small that either instrument is sufficiently precise. A fig Colecting a gas over water ExUnIe Reactions producing gases that are very soluble in water, such a5 sulfur dioxide, cannot use the gas collection over water teUiquea ny DNR ara a / 788 Syringe 08 eotved 25 Pat conical ask A fig Col TECHNIQUE 2: MEASURING THE CHANGE IN MASS OF A REACTION MIXTURE ‘This is another tect ing a gasin a gas singe igue 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 is as the reaction proceeds (fig C). A fige Coton wool placed in the neck ofthe Rast prevent This technique is most precise when the gas given off has a relatively high density, such as with thelos of iu spay. carbon dioride, With a low-density (Le, low relate molecular mass) gas such as hydrogen, the mass changes are so small thatthe 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 A- 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 inthe aliquot can either be stopped by adding another substance to itor slowed down to almost zero by immersing itin 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, if the 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 acid, 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) CHCOCHLaq) + (aq) + CHSCOCH,I(aq) + H"(aq) + Mag) eS sonia (aq) + 28,0% (aq) + 21-(aq) + 8,07 (aq)CRRA ua as) aC Dah) eo ‘oneartiry 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 conductivity meter For example, it could be used to follow this reaction: SB (aq) + BrO3(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 (llatometry), chirality and refractive index eas 1. State suitable tecUiques to collect rate data foreach of the following reaction. (@) Magnesium with dilute sulfuric aia Mgfs)+ 24(aq) — Mg(ag) + Hla) (b) Ethyl ethanoste with sodium hydroxide: ‘CH,COOCH, CH) + OH fa) + CHJCOO (aq) + CH,CH.OH(ag) (6) Hydogen gas with iodine gas: Hug) 14@) 24) JB Why would thetecUique of measuring the change in mass of a reaction vessel and contents not ‘work well inthe reaction between magnesium and dle sulfuric ack? J) The reaction between calcium carbonate and dite hydrochloric acid can be followed by collecting and measuring the volume of gas produced. The gas could be collected over ater in a measurng cylinder orn a ga syringe. Which tecUique would be the more suitable for this reaction? Explain your answer BEG a (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 (chemical) species an atom, a molecule or an ion thats aking part ina chemical eactionSy rae Sate eee DN sssX tat.) 24110) 1 Understand the term: (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 (ii) overall order of a reaction (iv) 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 tothe 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 will increase by a factor of four In some cases, the rate of reaction does not increase at all o it increases, in an unexpected way. Let us consider the simple relationship where the rate is directly proportional tothe concentration of a reactant, say A. We can represent this by the expression: rate x [A] rate = HA] ‘where isthe proportionality constant. ‘This called the fost order rate equation, The constant kis called the ate 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 rave equation: rate = HAP zero order rate equation: rate = HAJ? 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 itis 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, 7 m0 a EV Second dim mals The values for orders of reaction in rate equations will Third dm® mal conly ever be 0,1 or 2at “em International A Levelares \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” moldm-? x mol dry This cancels down to: mold swhigh equates to den? mol “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 order 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 = KAYTBYICY ‘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({l) ions in acidic solution ccan be represented by: MnQ,"(aq) + BH"(eq) + 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+C9DHE 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 neglighble and therefore had no measurable effect on the rate of reaction. aC Dah) I however this is not the case, and changes in [C] really do not have any effect on the overall rate of reaction, then a different explanation "ust be sought for why (C]does not appear in the rate 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 C has 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+C4D4+E Important points to remember ate that +The slowest step in a reaction 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. Wredecuad ‘useful way of visualiing the idea of rate-determining sep iso imagine that three students ae arranging some sheets of note into sat ig A). Step 1: the notes are arranged into ten piles and the ist student collects a sheet rom each of te ples Step 2: the second student takes the set of ten papers and shuffles them so that they re tidy and reagy for stapling Step 3: the third studee staples the set of notes together The overall ate ofthis process (the ate a which the final sts of notes are prepared) depends onthe rte of Step 1 the calectng of the sheets of notes, since this 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 therefore Step: Student Tcolects sheets SLOW Step 2: Student 2tdies set ofsheets FAST Step 3: Student 3 staples set of sheets FAST A. fig. Analogy for ate determining se.a A a1 PE ‘All reactant species involved either in, or before, the rate-determining step have an effect onthe rate of the reaction and will appear inthe rate equation. Creal 1. Therate equation forthe reaction beeen perorydisulate ions and iodide ions is rate = 45,07 [1] (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 eaction between Pand Qi rate = HPIQF ‘What wl be the increase in at (0 [is doubled, while [Q] is kept constant? {b) [Q] is doubled, while [P} is kept constant? (€) [P] and [Q] are both doubled? 3. Inthereaction beween R, andT: + when the concentration af Ris doubled, the rate increases by four times + when the concentration of is doubled, the ate doesnot change roy + when the concentration of Ts doubled, the rate doubles. D(e) Deduce the orders of reaction wit respect to R, Sand T ELIE rron.en- sows {b] Write the rate equation forthe reaction (€) Whats the overall order of reaction? Baar ia ‘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 is raised in the rate equation overall order (ofa reaction) the sum of al the individual orders rate-determining step (oF reaction) the slowest step in the mechanism far the reaction11A 3 DETERMINING ORDERS Oe) Dee R/S Concentration of 120) IE Understand the terms: (i) rate equation, rate = K{A}"(B}", where m and 1 are 0, 1 or 2 (ii) halite. I Be able to cakclate 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: (i) an initial-rate method (ii)_@ continuous monitoring method. I 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 initial-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 first 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 Ist half, forthe change in concentration from 120 to 60 units. is 1005 (fg A) Re Poa ne} TE 11.16) 11.4) 11.1(vi) 11.500) Tr 0) reacanvarbitay units 0 70200 —~—«0 Tina gta tae alte hale atte Ak fig A graph of concentration of reactant against tine for afistordet ‘The 2nd halPlife, 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 frst 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 graphis a svaight line witha negative gradient, then the rate of reaction is constant no matter what the concentration of the reactant (fig B). In other words, the reaction is zero order with respect tothe reactant. Concentration of reactant Te Ab fg A graph of concentration agains time fora zero order reaction. A typical set of results is shown in table A for the reaction: 2N,Os(g) — 4NO,(g) + Og)a ear Det (a) Ea o | 1 | 2 | 2% | 4 | so | 60 | 70 ay table A 80 GERM 2290 | 1627 /12.29| 935 | 689 | 48a | 368 | 274 216 If you plot a graph of [N,O,] against time using the above data, you will ind thatthe 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 raph 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, Concentzatin 299, ofreactersimoi m= 2 1.60" 140 120: 1.00. 080 60: ——— 040 020 SB PSPSPS OES RS Time's A. fig Determining an instantaneous at of reaction fom a graph of cancertation ef 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 triangle as possible and then measure x and y, x= 1470s and y= —1.60mol dm, ‘hange in concentration of reactant time 1.60 mold? 1470s. 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-* molds ‘This time the curve will slope upwards not downwards (ig D). Yous ot ges evoned radon at time = 1 Tine A. figD Determining an instantaneous rate of action fom a graph of volume of gas evoled aginst time ‘The rate of reaction obtained in this way is sometimes called the instantaneous reaction rate. 1"SED aU ese ot aC Dah) ‘THE INITIAL-RATE METHOD FOR DETERMINING THE RATE EQUATION In this method, severa reaction mixtures are made up and the intial rate i.e. 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 Sm dav? | INTIALRATE OF FORMATION OF Cio do? =" 1 a a 002 2 a4 02 004 3 02 a 204 2 = 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 « [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 is 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 ilustrate 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 initial 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, f ‘measured. That is: L rate x + ‘This assumes that the rate is constant for the whole time period, & However this is not true because 4s soon as the reaction starts the rate begins to decrease. The rate calculated from the expression is, therefore, the mean (average) rate over time, z, and not the zrue 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 usu toecorarange of eu an ota gph aginst cencenraion of reecant ‘The shape of the graph in table C indicates the order of reaction,a ear Det (a) 13 ZERO ORDER WITH RESPECT TOA | FIRST ORDER WITH RESPECT TOA | SECOND ORDER WITH RESPECTTOA [ll EXAM HINT: een Ou eer OU peu oer Be careful to check the units on the axes of graphs. Graphs wth the same shape wll have diferent meanings there are aifeentunits onthe axe! ty i iy tablec Itisimposibeto determine dey by sight fom a rate-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 stuaght ne passing through the origin, then the reaction is second order with respect to A i Bi ea paph of Vegeta suse hn cononetien cle manele a rcdevte eaten {LA compound Pdecompotes when heed. The graph shows the change in concentration when a ELITE) wcesrnernon sample of is heated 6 Concentration of Pin ati oo = 280 abo @60 850 1000 1300 +400 1600 1400 Timals (a) Stare what is meant by the term half-life of reaction (©) Use the graph to show that the decomposition of Pi a fist order reaction. (©) Beplain the effect on the half-life of doubling the inital concentration of ® (¢) Calculate the rate constant, for this reaction using the folowing expression: 04 half-life Include units in your answer. (6) Write the rate equation fr this reaction (8 (9 _ 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 aU ska so aC Dah) ESLER wrreneneranon 2.0) The equation forthe reaction between bromide ions and bromate(V) ions in acified aqueous solution is: 5Br (aq) + 8rO3(aq) + 6H"(aq) — 38raq) + 34,0() The table shows the results of four experiments caried out using different concentrations ofthe three reactants. Ero aaa ry [x Cy patti tie pots ota 4 010 020 020 96% 10° (a) Deduce the order of reaction with respect to: (ar (i810; (iH (b) Write the rate equation for the reaction. (6) Using the results from experiment 1, calculate the rate constant, k; forthe reaction Include units in your answer, Bere eing halflife ofa reaction) the time taken for the concentration of the reactant ofall one-half ofits inital valve instantaneous reaction rate the gradient ofa tangent drawn to the line ofthe graph of concentration against ime. The instantaneous rate varies asthe reaction proceeds (except fora zero order reaction)Sy ee LD Tore MECHANISMS Tee wi ining step from a rate equation and vice versa. I Deduce a reaction mechanism, using knowledge of the rate equation and the stoichiometric equation for a reaction. MI 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) first 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(g) + Oa) NO{G) + 0,8) 0 the rate equation i: 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 not possible to deduce the rate equation by simply looking at the stoichiometric equation for the reaction For example, the decomposition of dinitrogen pentoxide into nitrogen dioxide and oxygen is first ‘order with respect to dinitrogen pentoxide, not second, 2N,Os(g) — 4NO.(g) + O.(g) ‘The experimentally determined rate equation is: rate = KN,O.) A reaction that is not elementary takes place via a series of interconnected elementary reactions that, are collectively called the mechanism for 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 following ‘mechanistn:cCuIT Wy Va WOOO ee WISLy Step 1: Cl, 2Cl* Step2 Cle + CH, > HCI + «CH, Step 3: Cl, + +CH; + Cle + CHC] The overall stoichiometric equation for the reaction is Chi, + Ch + CHC + 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) + COx(e) rate = HNO} This suggests that only molecules of NO, are involved in the rate-determining step, and that avo molecules af NO; are involved in this step. The order indicates the number of molecules involved in the 4 rate-determining step rate = HNO S_Indcstes hat onty molecules (of NO are involved in the rate- determining step (A. fig Noeclesinvled inthe ate-detemining ep. Using our knowledge of molecules that do exit, two possible rate-determining steps are: 1 NO;+NO,—N,O,,or 2 NO, +NO;—2NO+0, Both of these reactions are equally valid, 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 that the 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 C0 +0;+C0, +0 FAST NO+0—No, FAST This shows how the particles in the proposed mechanism cancel to produce the overall equation: No, + Bey + Ber + NO + gf cO+e + C+ er Dore yer No, + co = NO > ©, aC Dah) AAs it appens, 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) + Oslg) rate = N,O5] Yet, the reaction is thought to involve several steps and a number of intermediates, ALKALINE HYDROLYSIS OF HALOGENOALKANES: ‘The hydrolysis of halogenoalkanes by hydraxide ions is a reaction ‘we introduced in Topie 10 (Book 1: IAS). The hydroxide ion acts as @ nucleophile 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 (CHCl + OH" + (CH,},COH + Cr ‘The experimentally determined rate equation for this reaction is rate = A(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-chloremethylpropane 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. (CHy,Cel (CH),C* + Cr SLOW (CHy)C* + OH” — (CHy,COH FAST ‘This type of mechanism is named Sy, ie. Substitution Nucleophilic unimolecular Step 1: Step 2: ‘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 isan 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]a CL a1) IONS AND MECHANISMS 7 ‘This time the reaction is frst order with respect to each reactant, so its reasonable to suggest that ‘one particle of each reactant is present in the rate-determining step of the mechanism, ‘The accepted mechanism for the reaction is: cHcrten, emi oHotoH, So—a + or ——+] Hob. | —+ Hoc’ +01 wil A iy 4 ah Hi tortion ste (A. fig 5,2 mechanism ofthe allie hycroyss of I-chlorobutane. ‘This type of mechanism is named $2, ie. Substitution Nucleophilic bimolecular ‘The rate-determining step is bimolecular because there are vo 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 Sy1 mechanism), but is a ransition state (see Section 114.6). Eee Ca ‘A study of the acid-catalysed iodination of propanone ‘The reaction between propanone and iodine in aqueous solution may be acid catalysed: aq) + CH,COCH (aq) + H'faq) —+ CH,COCH,I(aq) + 2H"(ag) + M(aq) ‘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 1 mol dir? sulfuric acid 2. Start the stop clock the moment you add SOc of 002 mol dm idine salution hake wel 3 Using pipe withdraw TDen’sample and place tina coal ask top thereon byadéings 7 TTFTT ‘spatula-measure' of sodium hydrogen carbonate. Note the exact time at which the sodium hydrogen BULL carbonates added Examiners may ask you to 4 irate the remaining iodine presentin the sample with 001 mel dm sodium thiosulfate) solution, aluate diferent methods for investigating ates of reaction. using starch indicator. acetone Cen 5. Withdraw further 10cm samples at suitable ime intervals approx. 5 to 7 minutes) and teat them described here is the time delay similarly, always noting the exact time at which the sodium hydrogen carbonate isadded. Waste should between withdrawing a reaction be contained ina fume cupboard sample by pipette and {quenching it with sodium Treatment of results hydrogen carbonate ‘The Lab Book can give additional guidance inthe treatment and analysis of results + Plota graph of ttre 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 zero order with respect to iodine. Similar experiments show that the reaction is fist order with respect to both propanane and hydrogen ions, This gives us the folowing rate equation: rate = CH.COCH JH] This would suggest the following reaction asthe first step ofthe 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,cCmIL Wy Va WOOO ee WISLy 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 rearrangements ikly to_be very slow and hence is probably the rate-determining step ofthe reaction lodine can now react in a fast step as 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 that the mechanism i 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. + Use a wider range of concentrations The experimentally determined rate equation may hold over only a limited range of concentrations. For example, the mechanism Wwe 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 of the final step in the mechanism s given by the expression Rate = ML ICH,C(OH)=CH,] and so the rate ofthe step will decrease asl] 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-0 bond is slightly stronger than a C-H bond, Ifthis i the bond that breaks inthe 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 case. aC Dah) 1 2 ‘The equation forthe reaction between ethanal,CHCHO, and hydrogen cyanide. HCN, CCH,CHO + HEN — CH,CHIOHJCN ‘Two mechanisms that have been proposed for his reaction are: Mechanism 3 Step 1: CH,CHO +H" —[CH,CHOH) ‘Step 2: [CH,CHOH} + CN" > CH,CH(OH)CN Mechanism 2 Step 1: CH\CHO + CN — [CHCHOCNY ‘Step 2: [CH:CHOCN] + H’ — CH;CH(OH)CN ‘Te rate equation forthe reaction is rate = KCH;CHOJCNTH'? (a) Explain which of the two mechanisms is consistent with the rate equation. {b) hich tp in this mechanism isthe rate-deternining tep? The equation forthe reaction between hydrogen and nitrogen monoxide ts 2H;{g) + 2NO(g) — 2H-0(g) + Nag) The rate equation forthe reaction is rate = KHJ[NO} ‘proposed mechani for this reaction ‘Step 1: 2NO(g) > N,O;(a) Fast ‘Step 2: N,O,{g) + Hg) > HO{g) +N.O(g) SLOW Step 3: N,O(@)+ H.l@) +N) + H,0l@) FAST Isthis mechanism consistent with the rate equation? Explain your answer. ‘Assume the following proposed reaction mechanism i correct: Ch. 2Ch stow Ho + Ch HCL He FAST He ch Hel FAST (2) 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? ‘The nucleophilic substitution reaction between equimolar {quantities of CHCl and OH" is second order overall However, if the reaction is carried out using a larg 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 + Q;—HBrO; Step 2: HBrO; + HBr — 2H8r0 Step 3 HBrO + Hr — Br, + HO. Step 4: HBFO + HBr — Br, +H,0 (a repeat of Step 3) ‘The rate equation for ths reaction is: rate = KHBIIO,] {a) Explain which of the above four steps i the rate-determing step for ths reaction (b) Write the overall equation forthe reaction,Sy 11A 5 ACTIVATION ENERGY AND TEE) VAS at cet Understand the terms: (activation energy )_ heterogeneous and homogeneous catalyst i) autocatalysis. I 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 Topie 9 (Book 1: IAS}, we defined activation energy, £,, as the minimum energy that colliding particles must possess for a reaction to occur ‘The activation energy represents the energy that the colliding particles must obtain in order to reach the energy level of the vansition 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 Ab figA. A reaction roi 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 route. Although the original route is still available for the reactants, most colisions resulting in reaction will occur by the alternative route, since the fraction of particles possessing this lower activation energy will be greater Catalysts can be divided into two groups: + homogeneous catalysts + heterogeneous catalysts. HOMOGENEOUS CATALYSTS ‘A homogeneous catays isin the same phase (solid, liquid, solution or gas) as the reactants,Many reactions in aqueous solution are catalysed bythe hydrogen ion, H'(aq)-An example s the iodination of propanone, a reaction we discussed in detail in Section 118.4 (CH,COCH,(aq) + 1{aq) > CH.COCH,|faq) + Haq) + Haq) ‘The production of chlorine radicals from chloraftuarocarbons (CECS)is responsible forthe destruction of ozone in the upper atmosphere. Ultraviolet radiation from the Sun produces chlorine radicals, Cr, fom CFCs such as dichlorodifluoromethane, CC! coupge, MEMO UaMatOn . sccrpyg) + cig) “The chlorine radicals then take part in a chain reaction with ozone! Cle(g) + Ox(g) + Clg) + Oe) ClO*(g) + Og) + 20,(8) + Cleig) The chlorine radical is regenerated and so is acting as a catalyst. Since the catalyst isin the same phase. Le. the gas phase, as the reacting species itis classified as a homogeneous catalyst The overall reaction is 20s(g) + 30,2) Another reaction involving a homogeneous catalysts the one between perenycislfate ions and iodide ions in aqueous soon S,0$ (aq) + 21 (29) — 280% (ag) + Ifa) ‘This reaction is catalysed by either Fe**(aq) or Fe’*(aq). ‘With Fe®*(aq), the reaction mechanism is: ‘Step 1: S,0j (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 PET ‘The action of Fe(aq) or Fe(aq) as a catalyst in the reaction between ‘5,0 (aq) and I (aq) is sometimes explained in terms of standard electrode potentials (E* values). However, itisimportant to note that standard electrode potentials ‘can predict only the thermodynamic feasibility ofa reaction, and not ‘the kinetics. The reason wity the reactions are faster inthe presence ‘of either Fe or Fe is that the activation energies for both Steps 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 inthe Haber process and the Contact process. The use of solid vanadium(V) oxide (V,0s), 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. POEUN ee Ue a aC Dah) ‘The equation for the formation of ammonia in the Haber process is Nola) + 3H,(g) = 2NH,(g) 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 conto 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 desotbed. As mentioned in Topic 9 (Book 1: IAS), once the surface of the iron 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 ‘lative 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 ‘not strictly 2 compound. Its more ike 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 (sce 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 ‘carbon and carbon monaxide into carbon dioxide. It also convertsa ‘oxides of nitrogen into oxygen and nitrogen. The reactions involved are discussed in more detail in Topic 17. Een UE oe 0) UN 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 adlton reaction between ethene and bromine ‘vapour (Topic § (Book 1: 1AS)) was once thought to be entirely a homogeneous process in which the molecules colided inthe gas phase and reacted. itis now known thatthe reaction takes 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 ‘as cetyl alcohol (hexadecan-1-ol, CH,(CH,),,0H). It takes place ‘ven more quickly stil on a surface of stearic acid octadocanoic acid, CH,(CH,);eCOOH), presumably because stearic acid ‘molecules are more polar than molecules of cet! eat However, if he walls ofthe reaction vessel are coated witha 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 tha a catalyst does nt change the oducts of a reaction, but only increases the rate at 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 ae etianal and hydrogen: ‘CH,CH,OH(g) — CH,CHO(g) + H{g) Ha the same temperature, aluminium oxide is used asthe catalyst, the more familiar dehydration reaction into ethene and water takes place: CH,CH,OH\g) —> CH=CH) + (0) tis interesting to note that the dehydrogenation catalysts, copper and nickel, adsorb hydrogen very strongly, whereas the dehydration catalyst, aluminium oxide, adsorbs water in preference, These two examples illustrate that thee is lat more to heterogeneous catalysis than is mentioned at international ALevel his might encourage you todo your own research into the topic and learn even more about it. 7 ection srs of stout Z Concentration ‘of reectant ne reaction then speode up the reacton then sio4s down before eventual stopping Time A. fig A 22aph of concentaton aginst time for an autecatalysed reaction. In fig B you can see the slow (uncatalysed) reaction at the beginning, As catalyst begins to be formed in the mixture, the reaction speeds up ~ it ges faster 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 producea similar graph, For example ifthe reaction involves a solid reacting with aliquid, liquid might have to penetrate a substance on the surface ofthe 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 reaction speeds up the reaction, Explain why only a small quantity of a homogeneous catalyst is required in order for it 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) > 10CO,ig) + 2Mn#*(aq) + 8H;0() ‘The reaction is very slow at room temperature, but Is catalysed by manganese(II) ions, Min#*, The Mn* ions are not present initially 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, ‘etraethy/ 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. BYEM Eee ead ‘adsorption the adhesion of atoms, molecules or ions to the surface of asolid utocatalysis when a reaction product act a a catalyst for the reaction