te gal) (BM Pea) ee CHEMISTRY STUDENT BOOK 2 ats) JASON MURGATROYD PTO Se UEPDF COMPILED BY SAAD PEARSON EDEXCEL INTERNATIONAL A LEVEL CISL Student Book 2PPdsehod by Pamzon Edicion Lied, 0 Stand Londer, WO2R ORL. wa pasrscagceets com Copies ctl epacteasons al Etevcatquifcascre uy ba found cnn ‘cea Moa quale: pasar 2a Tat Pearson Eucation Lied 219 eae Yocnet im Garon UK ‘peter by toon Sette autres Ue [Ed by Coven Dvn, Saran devon ane Sar gh (grat racons G Proran Educate Linced 208 uted och Ga, Caterea UX (Cover design © Pera Estate ic 2098 ‘covrimages Fore Getty mages: ov Miner Foxton Irae rot ene: Suttrstes-comvemty Lance ‘Thang e# Ci Cre, Saas Ghul Dais Seom te mars a ‘ua rs wos baa asec by then nascodarce we th COoyeh, eis and Patera ct YEO, ‘Bh Leary Galalegung ie Pesto: ota ‘cota ecard Se took ie avait rom te Brees Lory Ween orev suze aaze 3 Copmtgh nation ‘rch reaoved. Not ofthis pleats may be epruced nao er by {ur mazes inauteg petocopeng or song In any mecuraby secre eS {be wher or rer mnseray cr itoertal ose er use of Oi pubeeel ‘tno ti ett peranin othe conyngh omnes excel oEcorance WE tRavaere eta Copyrent Oana ne Pairs at SOB or use Bare a deares nase ay the Cag Leaaig Agi), th Fleer Shacsletan Hause | Batierge Lana, London SEI ZAK fy aso ak) Applets the ‘copsegh enrartunlar pemiesan shui adaaned ote patna Perec Sowa by Neng Ackontasigaments ‘garcons fo perietlnta mpmaduce capa aor Protoprapins (Mey: troanens «-cnes; H pects os) £79 Shutestoot: warn barbero’Stuneracoc: 5 Science Photo Leary Lc ancien Larrcer ecranny ance Po Utrary Lidar Fohitadeieoe Moto Livy La ver cis Protogani’Soarce Prato Lire Lis 30 Gey agen in Vssarteaee etroGaty ges 1 Ghufterstoeke Varian hatantscked Pearson Easeation Lt i!) Dever, (cfr PeareanScucatn Lid OA) Anan Stak I2IRF, $4 Toyo Notee Sale: Coury of Y's Malo Saha U-BA. In 08-48 Sutera (tien \ahcuunersiox 7) amy Stock Photo: PCN Prezaaraxnary ‘Sek Phot; TS Gerry images: attra OrscerierPamarety Pape "ih Shutterstock testes 0 amy Sox Mote) Hato Inageahamy Stock Pete: (22) Thomas Morn Lowe: TM Lou 9 Selence Proto Library Lie rcs arta Petogrgry Seanes Pho Livery et 02 ‘Sftersiack Gana Shutterstock, 12 HARE: Fercaot! ESE, TOS 7 Shatterstoks USwtentock 116 V20AF: Chay 23FS, 128 Selence oto tirary Un Arce Laban Phetogepry ene Pt Lory {Uc on anew taroer Photogaeny/Slonce Prom Urey Ls. 120 Sune ‘oto Litrary Lie arch Larter [Hu esenon Pte rary Ue ne Lambert Psogrphyoanch ms Usa 128 RF eres /IESRE TA Getly loge lich Bourg rot! (ety ragas135 Alay Stock Phota: CHASSEHET/ESI Mary tock Prt 158 Goty images: BS/Unrera rages SroupGars rages 60 Alam ‘Stock Poe: A trupea/Aien Sock Pos: 11 HAP: esc TE 1 Shutters: Image Saures Tea Un'Shutraock 148 Seca POI Library Lic Mau Fereanaa’Scace Frat eary Li: 158-169 Shutartock. anaarSronemeeks 172 Gmey mages Tari/ceksGaty Ine! 174 ‘alenen et bry Li Aras Larner Psogspy eee Mote Ub i 178 28AF: Grisho Maren’ 297; 92-108 hatter Poot! Shunasaack 18 Bclence Phow Library it 1 Solonce Phot Lirary bat Arerew titer ProtoyrapyiSctoe Pha bry id: 19s Beence roto Urry Ld: Furion Andrade sceccimoe Pots Lira 186 ‘Suites’ Suan tinmunangoct, 1 Science Photo UB Ua Are Lat Presagaphclone Prat Livy La 200 Sele Phots Library Lee 1H Mary Cuno Sceres Pata Levan Ui oj Mary hitmaiSource Photo ery Li 201 WEAF hare SRF? Alam Back Photo: ahr, HebervSrocFend LeMay Siac Plot, 298 Selene Pro Lbray id Thee Clad Phtogracty Sica Pe by te, 708 Smee Pho Lay LU arch Larter hotogrct Soe Photo Lary Ut 282 Seance Pots LUbrary Ue: Dex CunsScheree Pho vay Lo 713 Selanca Photo Lary Lintted a hanna reader Werverscinos Poo Losey aa 213 Soence Da Liter Le: Martyn FC2onaccascs Praia iy Li, 118 Seine Proto Library Ld: itor Avior Sue Somer Photo Leary Li 220-281 ‘Shuflrstack Dyara Denncrashutlasick 222 12: Nia MowemsZ2F; 2721 Sclenee Pato Leary Lie: evar itcraPPotoaaneySoatee P20 Lipa 277 SAF: Gepost ZF 20) Alay Stock Phot 25) Irag® Sones Phony shes Pte: 232 123 Dey Sich FF: 208 2 Smuberstoeks Eras Steck 238 ARP: OuicaY2AR 28 ‘Suuteratck: ft Taneelenshutloract: Gelenge Pata Ubrry Ltd} Comal pelo Pt Liver Li 247 Baer Olga ican ters 251 Shutlerlon Surya yer tro PSI-250 Gat Imam Car ‘oanranCoty lage, Pas Alamy Steck Photo: hone aaryy Stncx Pas ‘Moths magus © Paar" Eicaton Loa 2018 1s a Le flew ls par wpe epg a eure Foverclvcage a tam tea tseer seta; resin, pyar edit shan Capormion A retarecanoa ere n page {ito Easerin Samard GCcowe sapwagntaors Age anagem ‘Coty agate stu Eausecn Fama (ey riges aly ‘oot gain nD ey fs joann tranny capo © Aaya Seca o Chery Fees ah pe {be nm Fat got tr tga bad. Easanw Charney Be ban Gary Mann 2990 hewmen crpec Calon etna tOMa ne Ses Cesar Rn dans epee Rel Sey! Char — Ji Reg Stier of Chair Enger Metatonnre Cathe rica at racton by Catia Mousa 3 Novem 9 20 Rapraduoed forssins To Reale of Charis. St Tota Meta Sls: {Ryan The se Sey of aya UN doa Gon toa ea roman aride'n Tra Gumaan Soariie sey Gnas Aneeten aan atenPotn by som Rrtacy, We Fey 2017s gar terveermarthna ceva pore ON TRet Wout ‘en deren o human eater colin 162 Mig Lwae Fr Te ay hae byl dans ren atc 28 8 ee 15s Royal Socety ce Chomaey: Eicang heer at etsy by samen ‘oman 8 Noreen 018 Raprecucacbyperstn tra hol S508) St chit, 78 hatha Ear agrees Fm er Bary Be by {amy lingrenas non soercgbacrornrsoanay poxerSCcoose. aya Mena Seen sue Sooctisbe cee ice ual Cou Terpeaan 10d 2293 atonal Sopra Socety Uses ‘en peonanuns 232 pl Sot of Chanday. a Tee neo ‘Excesnoy Sum Cones Fenian 200 Ressouces ty parssaoe oe Rov SSescy Coonan 21 Raya Society of Chamerty: ep ours ee Srey Saar ned | howaroe SEF ON, Repo veteran Endorsemartsatement Ieeder nara thal or acre ira hull support ar the moc Pearson quatiemion It has been tough are rocers by he aud boo. Ths process cota ut tg mouce at coer he asian leaning conereatie spectaton wnch Wa atod Wis come as © ‘Sears an appraisal thong taut ab, eowlecoe ar intarsencag, a adation tpmperaton or ssamnrer. Edersemant dos rot caver ary qudanoe on aecessmens acts preceus lee pracce quesians orien anhow to answer assess qestons| Fludagin me resources nar ast peste any paren eperachio Pe teasing ar calvary of amecccune \Whlothe publshars have race ovary ster io eraum that ace en he fuallcatan sedis seein accra te fla aecieain and issiatedaesorsrnet guidance mata are thom) aurertatve ee "aerator a Sposa sw e eae 3 debe gacance Payson weaminare Race nt cone rac ne asus axa ‘amon paper es ay nt eanenay ‘ssesamer at by Paarion Ender ta ream does ot maa that he Tecoura s mqubed a achave tis Poaan qualia forces foot Is wey austen wale i poet ne aalfeaban ora ay feeoues Ine pein by Mi mami fey ol esi i tharOey COURSE STRUCTURE ABOUT THIS BOOK 2 |'2 PRACTICAL SKILLS ASSESSMENT OVERVIEW TOPIC 11 TOPIC 12 TOPIC 13 TOPIC 14 TOPIC 15 TOPIC 16 TOPIC 17 TOPIC 18 BBB alalsinis|. TOPIC 19 TOPIC 20 MATHS SKILLS PREPARING FOR YOUR EXAMS COMMAND WORDS GLOSSARY PERIODIC TABLE INDEX B/ZB 8 S888UNIT 4: RATES, EQUILIBRIA AND FURTHER ORGANIC CHEMISTRY TOPIC 11 KINETICS 2 141A FURTHER KINETICS 1 TECHNIQUES FOR MEASURING THERATE OF REACTION = 4 2 RATE EQUATIONS, RATE CONSTANTS AND ORDERS OF REACTION ie 3 DETERMINING ORDERS OF REACTION 10 4 RATE EQUATIONS AND MECHANISMS: 15 5 ACTIVATION ENERGY AND CATALYSIS 6 EFFECT OF TEMPERATURE ON THE RATE CONSTANT = 22 THINKING BIGGER: CATALYST CRAFT 26 EXAM PRACTICE 28 ENERGETICS 30 172A ENTROPY 1 INTRODUCTION TO ENTROPY 2 2 TOTAL ENTROPY 36 3 UNDERSTANDING ENTROPY CHANGES 12B LATTICE ENERGY 1 LATTICE ENERGY, A, .H AND BORN-HABER CYCLES 44 2 EXPERIMENTAL ANO 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STRUCTURE a TOPIC 14 ACID-BASE EQUILIBRIA 78 14A STRONG AND WEAK ACIDS: 1 THE BRONSTED-LOWRY THEORY 2 HYDROGEN ION CONCENTRATION AND: THE pH SCALE 3 IONIC PRODUCT OF WATER, K, 4 ANALYSING DATA FROM pH MEASUREMENTS 88 8 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 106 150 CHIRALITY 1 CHIRALITY AND ENANTIOMERS. 108 2 OPTICAL ACTIVITY 110 3 OPTICAL ACTIVITY AND REACTION MECHANISMS 112 15B CARBONYL ‘COMPOUNDS 1 CARBONYL COMPOUNDS AND THEIR PHYSICAL PROPERTIES 2 REDOX REACTIONS OF CARBONYL COMPOUNDS 117 3 NUCLEOPHILIC ADDITION REACTIONS: 19 15€ 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 © PRINCIPLES OF NMR ‘SPECTROSCOPY 142 6 SCNMR SPECTROSCOPY 144 7'HNMR SPECTROSCOPY 148 8 SPLITTING PATTERNS IN ‘HNMR SPECTRA 151 THINKING BIGGER: LIFE'S MIRROR IMAGES: 154 EXAM PRACTICE 156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 UGANDS AND COMPLEXES 187 3 THE ORIGIN OF COLOUR IN COMPLEXES 4 COMMON SHAPES OF COMPLEXES 192 5 SQUARE PLANAR COMPLEXES 194 6 MULTIDENTATE LIGANDS 198 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 MANGANESE COMPLEXES: 207 ‘5 THE CHEMISTRY OF VANADIUM 208 6 REACTIONS OF NICKEL AND ZING 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 ‘3 ELECTROPHILIC SUBSTITUTION: MECHANISMS 228 4 PHENOL 230 THINKING BIGGER: MOLECULES OF FRAGRANCE AND TASTE 232 EXAM PRACTICE 234TOPIC 19 ORGANIC NITROGEN COMPOUNDS: AMINES, AMIDES, AMINO ACIDS AND PROTEINS 236 sa A 1 AMINES AND THEIR PREPARATIONS 238 2 ACID-BASE REACTIONS OF AMINES 3 OTHER REACTIONS OF AMINES, 4 AMIDES AND POLYAMIDES 245 5 AMINO AGIOS 249 6 PEPTIDES AND PROTEINS 252 THINKING BIGGER: PROTEIN MOLECULES: LIFE'S HARDWARE 254 EXAM PRACTICE 256 TOPIC 20 ORGANIC SYNTHESIS 258 20A ORGANIC STRUCTURES 1 ORGANIC ANALYSIS 260 2 ORGANIC SYNTHESIS 264 3 HAZARDS, RISKS AND CONTROL MEASURES 269 4 PRACTICAL TECHNIQUES IN ORGANIC CHEMISTRY: PART 1 272 ‘5 PRACTICAL TECHNIQUES IN ORGANIC CHEMISTRY: 274 THINKING BIGGER: CHALLENGING ORGANIC SYNTHESES 278 EXAM PRACTICE 280 rsa 3 MATHS SKILLS PREPARING FOR YOUR EXAMS: SAMPLE EXAM ANSWERS COMMAND WORDS GLOSSARY PERIODIC TABLE INDEX 288ca ABOUT THIS BOOK ‘This book is written for students folowing the Pearson Edexcel international Advanced Lavel (AL) Chemisty specification. This book covers the full intemational Advanced Subsidiary (LAS) course and the first year of the International A Level (AL| course, The book contains full coverage of IAL units (ar 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 xi-xil for further information. Students can prepare for the written Practical Paper by using the IAL ‘Chemistry Lab Book (see pages x-1i 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 leaming and activities supported by the taatures explained balow, Leomning cbjeatives Specification reterence beaming ts Worked examples Eschetapter tarts witta stot | Treexact speczeaon ‘These help you toext yourleaming | Worked ekamples show yous objectives points coveres i th fare avaid common rare. Crowe | ho to werk Uieugh coer, ection ara provided reterenens to prewsave er olowirg | and sot eit cacalations Sludert Back contect help you to agate course conten Weactay ines) erste an inte Diayou know? ‘Cheskpait ‘Subject Vocabay Tp how eens ear Intoreetng Hts na you (Obertions at he end ofeach Kay tres aa highlighted siyfe questions and guldence reverb hs hey concopts secon cher uncersiersng ot | in Dein tha tet, Clear for exam preperation, noua ‘hey learing pais in each finan ere growed at recente chapiec Cerlar questions alw | theend of sac sachin for Darteatar command words Yuta oavitcp skills nae willbe | any refwrence, and are asa Saluale fer ather study ancin | colltedn's glossary a ht the womeplace ack of se box‘Yusheald be abo to put every stage at your earn corti, chapter by ehaneor * Li 9 lhe areas of Cherry Inds previnusanswdedgs that eb Frits top and Futura areas ot knawlackge ane “Nate kneicgs requires ‘detaled in hana eneciet.# you aed fo paces nerate you Falerecoa a-ha back ofthe beok = PEM en ee —— CATASTROPHE FOR CORAL? == Exam Practice Eran-stiequeetons at the and ofeach chapter are tlre to the Pesrton Edancel spectestion ta albu foreractice aid develooment of exam ‘erling tctriqe, Ty so ow prcice maa the exams ee the cornenaind ‘Exams {seedon a he back of the Book, ferseralsexarm nei i pom PACU g Thinking Blogoe tthe end oF each top thar Sar epperunity ts rad verity about scsovos. Tho actives ‘sepects of your larg tagethes Thace Thirkang Bigger acts Tega on ey vansterable sift,PRACTICAL SKILLS Practical werk is central to the study of chemistry. Tha secoad year of the Pearson Edexcel International Advanced Level JAL) Chemistry course includes aight Gare Practicals that link theoretical Knowledge and understanding to practical scenarios. Your knowledge and understaning of practical skis and activities will bo agsessed in all examination papers for tha UAL Chemistry qualification. ‘© Popers 4 and 6 wil include questions based on practical activities, including novel scanarlos. * Paper 6 willtest your ability to plan practical work, including risk management and selection of apparatus n onder to develop practical skils, you should carry out a range ef practical experiments related to the topics eavered in your course. Further suagestions in addition to the Core Practicals are included in the specification, whien is available ning. Baia et a IAL CORE PRACTICALS: ‘TOPIC AT CP9a Following the rate of the iodine-propanone reaction by a titrimetric: KINETICS: method CPOb investigating a ‘clock maction’ (Marcourt-Esson, iodine clock) PIO. Finding tne activation energy of arsaction ror 4 CPI Finding the, value fora weak ae AcID-BESEEQULIBTIA orc 16 GPI2 _tnveligatng some electrochemical coils REDOX EQUMLIBRIA CPI31 eden tations wnt ron ons and potassiom manganate\i CP130 Redox titrations with sodium thiosulfate and iodine ‘Topi 17 CP14 — Proparation of a transition motal complex TRANSITION METALS AND THEIR CHEMISTRY: ‘TOPIC 1 CPI5 Analysis of same inorganic and organic unknowns. ORGANIC NITROGEN COMPOUNDS: AMINES, AMIDES, AMINO ACIOS AND PROTEINS ‘TOPIC 20 CPIB Preparation of aspirin ORGANIC SYNTHESISPRA inthe Stocent Book. te Core Practeal spsciteatons ‘ra supple w theroewsrt Practica! Sais Practlea sil boxes expla tachniques used inte Gore Precikeda. ane also deta! uneful ‘lsd knoweage gained in ‘her lated irvertgatons The Student Back ie ccomparieaty a Lab aot, whien mnlutan renructione and wring Names forthe Core Practeal or you to record your reauls and veieet an fotr siork Practical nk rover a sl pretsee ‘The Lab Book records can bo vee a8 prepara Far the Practica! Sila Paper PToy Cea) ASSESSMENT OVERVIEW The following tables give an overviow of tha assessment for Pearson Edexcel International Advanced Level course in Chemistry, You should study this information closely to help ensure that yau are fully prepared fer 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 far your exams on page 266 of this book. Geiss Dregne) SN iy co aid ee RATES, EQUILIBRIA AND FURTHER = 40% 20% 90 Iheur January, Jone and Oerober ORGANIC CHEMISTRY ‘Written exam paper Paper code WCH4/01 Externally set and marked by Pearson Edexcel 45 minares parc assessment January 2020) Single tier of entry earns nes coat are jae | ld ooo ‘TRANSITION METALS AND ORGANIC 40°: 20% 30 howe January, Janeand October NITROGEN CHEMISTRY APMED, Sepa aeacietsce ryeacaaon Writ exam paper Paper cote }CHSIM1 ermal sec and marked by Pearson Edsel Single ie of entry eas | Cea ares Jor ia Ca ea PRACTICAL SKILLS IN CHEMISTRY IL 2% 10% 30 ibour January, Joneand Getnber Written exam paper 10 minutes Figs assesses Juve 2020 Paper Unit cade WOETLAOL Escernally et and marked by Pearson Edexcel Single tier of entryPoses as] xi ASSESSMENT OBJECTIVES AND WEIGHTINGS eee a aoa) pa 1A2:| 6 INLIAL ‘At iemansirate knowledlse and understanding of science. 336 31 (3) Anpbiation of kenge nd wasting of ne a Mah 3G 32K ie janiiar aed Unfamiliar contexts [b} Analysis and evaluation of ssentifc information to make oot fudgemente and reach conchutions Esperimental sill ia sccoce inching analrsis an evalaaion a of daa and method 0 20 20 RELATIONSHIP OF ASSESSMENT OBJECTIVES TO UNITS Cy UNIT a8 pas 45-85 on unit 2 1k ine 45-35 on Nir 3 on 0 a0 » TOTAL FOR INTERNATIONAL ADVANCED SUBSIDIARY 36 3-98 on a UNIT NUMBER 028) ‘0a UNIT. 22-245 on uni 2 R90) 2b24 oo unr on 00 a 10 UNIT 4 7298 8a 340 on UNIT 5 7378 sa89 36-40 oo UNIT 6 oo oo a0 0 ‘TOTAL FOR INTERNATIONAL ADVANCED LEVEL HM 3368‘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 tics, 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 kinatics to: understand the bady/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 bend 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? ithas 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 contral the rates of chemical reactions within the bad, In this topic we will study the rates of chemical reactians and the mechanisms by which they take place. Recognise and make use of appropriate unitsin caleulation Recognise and use expressions in decimal and ordinary form Use calculators toind 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 linear relationship Draw and use the slope of a tangent to a curve as a measure of the rate of changeWieden ek ce aetna SE aT Mitel a cteLed et atvar than metas @THE RATE OF REACTION eae B el sy IM Understand the term ‘rate of reaction’. IM Select and justify a suitable experimental tecllique to obtain rate data for a given reaction, ineluding: (titration (ii) colorimetry (li) mass change (hv) volume of gas evolved (¥). other suitable tecUlique(s) fora given reaction, RATE OF REACTION ‘The Fate of a reaetion can be expressed! in two ways) {1} How the congentvation of a product increases with tise (2) How the concentration of a meactant eee we tine cn of reactant time “The negate sign inthe second expression ahows thatthe ‘concentration of the reactant is decreasing and therefore gives a positive value forthe rate Rateis messured ‘most common un units of concentration ger unit me, and the are mal der? st ‘The expressionsiin calculus notation are ‘This rate of reaction is sometimes called the ‘overall cate of teaction ‘TECHNIQUES FOR MEASURING THE RATE OF REACTION isfore investigating the vate of a particular reaction, it is necessary to lew the everall equstion, Including state ayeSbls {or the reaction so thet we can decide what technique 12 wwe te felleny the resetion, “There are various techniques available to use, such as: 1 measuring the volune of a gasevolved 2 meusuring the change in mass of a reaetion mixture 3. monitoring the change in intensity of colour of areaction mixture (colorimetry) 4. measuring the change in concentration of a reactant or product using titration Eat aa Wee ete USS Trae) cies Te 11.3(¥) 5) measuring the change in pH of 2 solution 5 measuring the change in electrical conductivity of 2 reaction miauee, The technique chosen to fallow the reaction will depend on the nature of the reactants and products, 2s well as the conditions under which the reaction is carried aut For example, the teaction between calciuin carvoniste and dilute hydrochloric acid, (CalO,fs| +2HChiag CaCizlaq)+ H.O()) + COLlg) could conveniently be followed by measuring the volume of gas (technique 1) given aot regular time intervals r by measuring the change in mass of the reaction mixture with time fechrique 2) Hever the reaction between propanone and jadinc in aqueous CH.COCH, fa) + Lae) + CH.COCH, (aq) + HY (aq) + Mae) ‘ould not be followed by rmeasunng the change in mass because all preducts of the reaction remain in solution, It would be possible, however to follow the reaction by monitaring the Hecrease in intensity of colour af the reactien. mixture, snc 1,(aq) is the only colcured species present {technique 3) TECHNIQUE 1: MEASURING THE VOLUME OF & GAS EVOLVED The tie mest common techniques lor cellecing and measuring the volume of gas evolved during a reaction are: 1 collection ovor weterinio a meanuring cylinder (fig A). and 2 collection using a gas syrnge fg B) ‘The technique chosen will depend partly onthe level of precision roquired. The gas syringe has greeter degree of precision, but if a large volume of a5 being measured, the difference in the degtee of measurement uncertainty becomes so small that either instrument is suffisienty precise is roacicn iste & figA Colketng a producing yases that are very sobuble inwvater. such as ‘hte cmon the pan oa cgar ‘6 ngs a or A fig conecing 2g nge TECHNIQUE 2: MEASURING THE CHANGE IN MASS OF A REACTION MIXTURE This is another techmique applicable to reactions in which a gas is evolved. The reaction ack and contents ave placed on a digital balance and the decrease in mass is meaeured as the reaction proceeds (fig C) This technique is mest precise when the gas given off has a relatively high density, such as with carbon dioxide, With a low-density (.e. low relative molecular mass) gas such as hydrogen, the mass changes are so small thas the meesurernent uncertainties become significa TECHNIQUE 3: MONITORING A COLOUR CHANGE (GOLORIMETAT) Colour change can sometimes be monitored using observation only. However. using a colorimeter gives more precise results (fig D). A calorimeter can detect far more subtle changes than the human eye can observe, and provides a quenitative (rather than a subjective) measurement TECHNIQUE 4: ANALYSIS BY TITRATION This technique involves u jernaie eal earnplex (aliquots) fron at regu can either’be stepped by adding another twit or slowed down to almost 2010 by is it in an ice bath. The aliquot is then titrated to determine the concentration of a reactant-ae preduct species ‘The process of stopping or slowing: down the reaction in an liquot is krown as "quenching! For example, ifthe reaction invalves an acid, the aliquot, alter quenching could be trated against a scandard solution af acid This technique is used to investigate th iodine and propanane, which is catalysed by acid. Sodium hydrogen carbonate is added to the aliquat to remove the acid catalyst and, as a rel, eflectively ‘ope the reaction. The remaining iodine Is then tireted against a standard anlutiow of sedium thiasulfne (8 E), CHCOCH, {ag} + leq) Teg) + 25,03 (ag 21 the concentration of COCH aq) + H*4aq) + (aq) a) + SOF (aq) cae a A ge Twens asians at ACR IC therotal number ar lype.ef fons in solution changes during & resetion. it might be pessible 10 folaw the action by measuring changes in the eieetnical conductivity of the salulion using & conductivity metar For example. it could be used ta follaw this reaction: SBe-(eq) + BrO5taql + GH "faq) — 2Be,fag} + SHON) 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 guid (diaiometsy’,chiralty and refractive index. 1 Statesutable teeiques to collect rate data for earn of the following reactions. fa) Magnesium with ate sulfuric acid Mes) +24 (aq) — Mg (an) + Hila) Ib}Ethyothanonte with saesum hydroude CHCOOCH.CHitN + OF faq) — CHi€80 fag} + CHACH,OHlag) {ep Hyarogen gas with tose gas: Helga) 248) Be Why would the teclJique of measuring the change in mass of areaction vessel and:contents not ‘work Wallin the reaction between magnesium and dilatesutturcacig? IB: The reaction betmeen calcium carbonate and dite hydrachlodc acid canbe fllawed by eclecting and measuring the volume of gas produced. The gas could be elected ever vate in a measuring fynder or ina gassyringe. Which tecUique would be the move suitable fortis reaction? Explain your ansret Tau Agveralll rat of reaction the charge in concentration ofa soecies divided by the tim it takes forthe ‘change to occur All reaction rates are positive ‘chemical species an ator, a motecule or an te that stakeng patina chemical resctionSOU UE eS) aud Seni) ESV) ccna Understand the: terms: (i) rate equation, rate = AjA}"[B)", where m and.n are 0, 1 or 2 (G))_order with respect to a substance in a rate equation overall erder of a reaction (iy) rate constant (W) fate-determining step RATE EQUATION WHAT IS A RATE EQUATION? The usual relationship between the mite of réactioc’ and the concentration of @ reactant isthat the Fate of reacton is directly proportional to the concentration. In other words, as the concentration is doubles, the rate af reaction doubles Unfortunately this is not always the case. Sometimes the rate will double, but sarnetines it will increase by a factor of four In some cases, the rate af wesction dees not increase at all,or it increases ln an unexpected way, Let ws consider the simple relationship where the rate is directly ptopartional ta the concentration of areactant say A. We cam represent this by the expression: rte > [A] rate = HA where Kis the proportionality constant. This is called the fist onder rate equation. The constant # i called the me corsont + Brery reaction has ts own particular rate equation and its own ate consiant + Rate constants will only change their value with a change in ternpereture: Osher common rate equations with respect to an individual weactant are ay {AD orate = & Zero order resctions do not occur very often, and it night be dificult at this stage for you to imagine wy they sheuld oceur atall However, you wil find out shortly why they can occur secone! order rateequasion rate zero onder ate equation. rate 1 two.of mare reactants are involved, then its possible to have a thind order rate equation: third onderrateegeation: rate = K\AFIB) THE UNITS OF RATE CONSTANTS Table A shows the unis forrate constants, wing mol dm” as the unit of conbertraiion and senonds atthe unirof rime, You fied the unite by weaeranging the rate equation The val eam reaction in rate equations vail om mah? only everbe 0.1 or 2at International ALevel, on marsThe unis are obtained by rearranging the rite equation. For ‘example, for a second odor reaction: ‘mol der? * mol dre? Tals cancels down ta ‘which equates to din® mat = “The majonty nf reactions involve two or more reactants If we call the reactants A, 8 ane! C, then the reaction may be frst order wit respect to A, fist ener yrith respect to B and second erder with respect toC. The oveval rate equation will be: rate = HAIBICE and the overall order of the reaction is four (1 + 1 +2} Note that you are auiding the powers For general reaction in which the orders are m1 and p. re have: rate= AAMBNICP “The overall ore of the reaction ism-+ n+ p REACTION MECHANISMS ‘Many reactions can be represented by a stoichiometric equation ‘eontaining mary reactant particles. or example, the reaction between manganate(¥il) ions and irent!) ions in acc scion tim be represeniedity- MnO, (aq) + SE (eq) + SFE faq) — Mln(aq) + 41,00) + SFE aq) 1 this action actually proceeded ina single step then the reaction would be very slow indeed. The probability of 14 pert simultaneously collcing, all withthe comreet crientrion ‘and energy, is so small that we can say itis effectively zera TRE: reaction i, however, very fast indeed even at room temperature litmus, therefore. proceed via e seies of steps all of wich follow an quickly from one another I is important to recognise that a reactioa involving simultaneous colin of more than two porticles is very rare ‘The onders of reaction of the individual reactants can help us to suggest a possible mechanism for a reaction. The mechanism cannot be inferred from the stoichiometsic equation, because the Mathematical relationship between the rate of reaction and the ‘concentration of reactants (Le. che orders cf reaction) can only be Hetermined through experiments ‘Consider the reaction A+B+C4D+E for which the experimentally determined rate equation is rate= ANB) “This could mean that C-was present in such a lange excess that ‘changes in its cencentration were negligible and therefore had no measurable effect cn the rate of reaction. eae aCe ‘however thistsmat the case, and changes in [C] really do not have any effect onthe cvorll ate of reaction, then eiffoers explanation murs be sought tr why [C]eoes not appear in the rate equation. Inthe cate, thare must bea ate involving a reaction between A and B dut has an effect on the rate.ofregetion. There rust also be anther step in which C rasct, but this reacsismhas mo eet on the cveral rae of reaction, This could be expained’by assuming that the reaction between A and B takes place fore hasa chance sareact, and thatthe resction between A and B is significantly slower than ihe veaction involving C. If kis were the case, then dhe mechanism for he ceaction could be: A+B OZ ZtCaD4E SLOW Fast Step £ Step 2 Since only Step 1 is rate-determining, then only changes m [A and (E] will afc the eral rte of reaction, Changes in the Tate at which Step 2 occurs, awing ta changes in [C}, will bo negligible. Important points to serneeber are that © The doest spe reaction determin the overall of the rection The slowest step is known as the eudeteraining sp uf the reaction, \We will return to the concept of reactian mectanisins, and consider them in much more detail, in Section 118.4. Tees A setinay of ysuaiang te wes ota aiedeernng ep 0 ifagive tha tice students ie arangeg soft sets nots ie 2 nga} Step the nots ar avnged inte ten pies andthe st stud tallest raettrom sech cf the plz Suep 2: the secoad sent tikes the set ten gape and sulle ‘them so that they are ticly and ready For stapling. Scop 3: te shed stent apo the at one peer Tre ove ae oft procze(e the rae a hich he fies of poke prepare) pends on Beutel Sep 1, se easing oF the shecis of notes, sce ta by far the sone ep. eloes nat rater, within asin, how quichy the tidying up for Stapling 6 cone, For mart ofthe cme the second and Dad sudents ‘vik be doing oshingwile they walt for the fs studemt ra colect ihe sheets The mechanism af the process therefore: Step |: Student Lcollectsshews SLOW Step 2: Student 2diee set ofsheets FAST Step & Student staples cet ofsheece FAST FGA. Analogy lr sate determining epaC 11. Therate equation for the reaction between peroxyesullate ions and ladide tons i rate = S:02 11] la) What isthe order of reaction with respect io (} peronydisufate sans and (i) iodide ions? (6) What isthe overall crcler of reaction? 2. Therate equation fo the reaction between P anc'Q rate = HPTQE ‘What willbe the increase in rate: 6) [Fis doubled, white [Q] is kept constant? {P1101 doubled while] is haps constant? (¢) [Fl and Ql areboth doubled? 3. Inthe reaction betwen f,5 and T: + when me concentration of R i dauibieg, the tate inerencat by tour wanes + when the concentration of is doubled the rate does nat change + then the concentration ofT fs doubled the rate doubles, Be (2) Deckice the orders of maction with respmet io R, Sand T (0) rte the rate equation forthe reaction (6) What is the overall order al reacuon EES ‘rate equation an equation expressing the mathematica relationship between the rate of reaction and the Concentations af the reactants ‘aeder (fa reactant species) the pomer to which the concentration ofthe specie raised in the rate equation ‘averall onda (oF a reaction) the sum of all the individual orders rate-detesmining step {ofa weacticn} the slowest step in the mechanism far theeaction11A 3 DETERMINING ORDERS OF REACTION LEARNING OBJECTIVES Concentration ot — 120% I Understand the terms: i). rate equation, rate = k[A}"[B), where m and are 0, tore (fl) halt, If Be able to calculate the hall-life of a reaction, using data from a suitable graph, and identify a reaction with a constant haltlife as being first order: WM Understand experiments that can be used to investigate reaction rates by: (an initial-rate method (il) @ continuous monitering method, IM Be able to deduce the order (0, 1 or 2) with respect to.a substance in.a rate equation, using data from: ()) aconcentration-time graph (i) a rate-concentration graph (ii) an initial-rate method. HOW CAN WE DETERMINE THE RATE EQUATION? “Tais question can equally be phrased "How ean we determine the ‘order of reaction with respect to each reactant? ‘These are tio methods for determining orders al reaction. They are both experimental. Indeed, owers af reaction can only be determined by experiment “The first is sometimes called the ‘continuaus metho, The second is semmetimes called the “intialerete method’ ‘THE CONTINUOUS METHOD 1 thik mathod, eaeeeactioa miature's wade up end samples of the reaction mburure are withdraws at regular eve intervals. The feaeiion in the sumple is stopped, if necessary, by quenching. “The concentration of the réactant is then dtermmined by an appropulate expetimenraltechrique. euch as tixaion + The int steps to craw a ‘eencentration-time’ graph. + Thesecond sep ist find out the halflife forthe reaction at different concentrations 1 the halflife has a constant value, then the yeacton is fist order ‘with respect 1 the reactant “The Ist half-life, forthe change in concentratian from 120 12.60 unis, is 100 s (fig Et cies ne Tec) crea POM ESO} 12 5G) maclertrbtrary unig we ite MGA. A raph of concentiaten a acta agate fora fst ier ‘Ths 2nd halflife, for the ehange in cemcentrstion from 60 to 30 nits. 6 1005 The 3rd halh-of, far the change in cancentrarian fom 31 ta 13 units, 100. Since allthree hall-lves are the same. the reaction i fist onder respect to the concenzration of the reactant plotted If the helllife doubles as the reaction proceeds, then the reaction is second order If the graph is a straight line with a negative gredient, then the rate of reaction is constant no matter what the concentration of the reactant (fig B), In ther words, the reaction is zero order with respect to the reactant, Doncantation of eacart Tire Fig A graph oi cancersaticn agaist tine fara zen order action Atypical set of results s shownin table A forthe reaction: 2N,Orlg) + ANOYal + O40)TOPIC x] 40 || 0 | wm | ao | 90 gas | 699 | 498 | a6a | 274 [216 | Las table A Hf you plata graph of [N,Q] againattime using the wbave data, you vil find that the line is curved land the halle is constant; ai a result, the reaction is frst order with respect to NyQe CALCULATING RATE FROM A CONCENTRATION-TIME GRAPH ‘The rate of reaction at any given ime can be determined ftom a concertration-ame oF volume-tine raph by drawing a tangent to the curve at the ven time arc calculating the gradient of the tangent Fig C.shows the change in concentration of ¢ resctany with tne ‘Consertrater SP PSPSPS SPORE A ORC Det ‘A tangent tothe curve haa been drawn at dime organ tanec ate of reac ram grap of eo aon ‘To find the rate at thistime poing, drav as lage a tangle as possible and then measure x andy. send y = —1.60mol dm”, ehange in concentration af reactant time rata Loa 10° mold ence Sorat shen ° ‘Cencericiin of in nba ants a0 490 eo el oo 120 HY 150 tenn Tinsls (a) State what is meant by the ter halflife of reaction {b)lUsethe grapth te shew that the dscrmpesition oP ie aft orforresetion. 4) Explain the effect an the half fe of doubling the nial concentration of P (0) Calculate tne rae constant. k for this weacbon using the fotoming expression: 593 k Include units in your arsine, (6) Wawa the ate equates toe ts reaction 46/0) Usethe graph ta determine the concentration of Pat 800s {i Use the rate equation irom (e} and your answers to (dl) and ffi) to calaulate tre rate of reaction at 800s. Include unis In your answer () Deccribe Rawr could you determine thereaction rae at BOUscrecty from the graphHEED rena ess cet) aCe 2. The equation forthe reacven between bromideiancane bramstet¥) ins in acidified aqueous sation i Br (ag) + BrOs(ag)-+ GH-(aq) —+ 3Brlaq) + 3H-000 ‘The table shows the results of four experenents carried out using diferent concentrations ofthe three reactants Cr a) vol 020 0 2a «10 aro 3610 4 020 96610 (a) Deduce the order of reaction with respect to (OB (0) B05 ca (blritethe rate equation for the reaction, {6} Using the results from experiment 1, calculate the sate constant, k forthe Yeaction. Include unite inyour answer, Ea Ihalfife (ta reaction) the time taken forthe concereration of the reactant to falta ane-half ofits ints value instantaneous reaction ra the gradient ofa tangent dawn to the line ofthe grant of concentration aginst ima. The inctantanaous rite vanes as the reaction proceeds capt fora zero order reaction)EWU 14 MECHANISMS Pe a) 1 Deduice the rate-determining step fram a rate equation and vice versa. BH Deduce a reaction mechanism, using knowledge of the rate equation and the stoichiometric equation for a reaction, 1M Understand that knowledge of the rate equations for the hydrolysis of halogenoalkanes can be used to provide evidence for $1 oF Sy2 mechanisms for tertiary and primary halogenoallane hydrolysis. Understand how to: (@) nbtain data to calculate the order with respect to the reactants (and the hytirogen ion) in the acic-catalysied lodination of propanene (il)_use these data to make predictions about species involved in the rate-determining step (ii) deduce a passible mechanism tor the reaction. REACTION MECHANISMS ‘You will remember rom Book 1 that the basic view asto how a reaction takes place at a particulate level if that particles (atoms enolecules ions or racicals) fret have to colle in the correct ovientation fad with sufficient energy far produces ta be formed, For the fallowing reaction: P+Q-> products we expect the rate law tobe: rate = {P1IQ] In other words, we might expect the meaction 10 he frst order with respect to each veactant anc second order cversll ELEMENTARY REACTIONS ‘A reaction taking place inthis manney (a single collision between the two reactant particles) is doacribed aabeing elementary. If we know that a reaction is elernerary then we can deduce the rate law directly frormthe stoichiometric equation. For example, the following reaction is known to be elermentary. NOjg) + Ox(e) + NOxta) + 0.8) sa the rate equation is rate = KNOJO,) The reaction takes place when a molecule of NO collides with a molecue of Q,, If the reaction is not elementary, itis nat possible to deciuce the rate equation by simply looking at the stoichiometric equation forthe reaction, For example, the decomposition af diniuogen pentoxide inta:nitrogen dioride and axygen ts firs coder with respect to dinitiogen pentaxide, not second 2N,O,(g) + 4NOfg) + Ox(g) The expetimentally determined rate squation i: rate = {NO [A reaction that is mot elementary tates place via a series of interconnected elementary reactions that are collecively called the mechanism forthe reaction. You will have abready come across a nurnber of suck mecharisms fx your study of organic cherristey For exarrple the radical substitution reaction between methane and chlorine to form chloromethane (CHC) is thought to have the following, ‘mechanism:eae ui) ceaht Step Cl, + 2Cle Step2 Cle + CH, HCL+ CH, Step) C+ +CH, Cle + CH ‘The overall staichicenetrie equation for the reaction is: CH. + Ch, CHG + HCI “The species C1+ and CH, ave called fatermediais They da not appear in the everail equatian for the reaction, but are involved in reactions that ultnately result mi the reactants being cosrerted Inco the products Ifthe experimentally determinad rate equation does not match, the overall stoichiometry then iis almiet certain thatthe resetion isnot elemanrary, For example, the sete equation fr the following NOjlg)+ COlg) — NOigh + COM) is rate = INDE “This sugges that only malecules of NO, are imohved inthe retedetermining step, and that neu molecuiesaf NO, are imealwed inthis sep, ‘The onder indicates the number ‘of molecules involved in the 7 tier sep rate = NOP “S__Incates thro molecules af NO, are invaived inthe rate determining step rove in the ate determinngstee B FigA Notes {Using our knawledge of molecules that do exist two posable rate-determining steps are: 1 NOy + NO, — NO, oF 2 NO.+NO; + 2NO +0, Boch of these reactions are equally valid, and we have n0 way of oaving. without carrying out fusther investigations, which is the move fkely to be taking place ‘We also have no way of knowing what is involved in the rematning steps, but we do know thatthe sur of ail the steps must add up ta the overall stoichiometric echation {Using the second af the two possible rate-determining steps. the following mechanism is consistent with the dara: NO,+NO,—2NO4O, SLOW 0C040,-CO40 RAST NO+0— No, BAST ‘This shows how the patticles in the proposed mechanism cancel to produce the overall equation, NO, + Ber — we + NO = gr w+ 5 +e yes yet NO, + co NO» CO, As it happens, further investigations into this reaction have Identiied the mechanism a. NO,4NO,—NO,4NO SLOW NO,+CO—NO,+ C0, FAST ‘This is not what we would immediately suspect as the mechanism because the existence of NO, fs not something with which we ‘would he 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 far the folowing gas-phase reaction: 2N,Oi{g) — 4N0.(8) + Oa) rate = &{N:0%) Vet, the reaction is thought to involve several steps and a number of intermediates, ALKALINE HYDROLYSIS OF HALOGENQALKANES The hytrolysis of halogenoalkanes by hydraride ices is 2 reaction \ne introduced in Topie 10 (Book 1: 1AS). The hytroade ion acts asa micleoptile and reptaces the halogen in the halogercalkanes, ‘The reaetion, therefore, can alin be desenbed as muelsaphile subetiuon, HYDROLYSIS OF A TERTIARY HALOGENOALKANE The equation forthe alkaline fycrolyis of 2-chloramethylpropane i (CH),Ccl + OH (CHy,COH 4 cr ‘The experimentally determined rate equation for this reaction is rate = K{(CH,.CC) The reaction is fist order with respect to 2-chloromethyipropane but wero ofeer with respect tothe hydrox ion. The sensible conclusion ta reach s thatthe 2chlnremethyleropare undergnes iow ionisation as the rate-cetermining, sien Thisis then followed by a veryfat step imeling attack bythe byte ten on thecarhceation formed in Step | Spe (CHEE (CHA +cr slow Step (CHC + OH —(CHCOH FAST Ths type of mechanism is named Sy, Le, Substitution Nucleophilie varmolecular The rete-determining stepis said to be unimolecular because there is enly one reactant particle present. (CH.},CCL The carbocation, (CH,},C", formed in Step | isan incermeciate {oce Section 114.6), HYDROLYSIS OF A PRINIARY HALOGENGALKANE ‘The equation for the allaline hycrctysis of 1-chiarobtane CHCH,CH.CH,C1 + OH — CH,CH,CH,CH,OH + Cr The experimentally determined rate equation for this reaction is rate = K{CH,CH.CH,CH,CITOETOPIC ‘This time the reaction is fie creer with respect to each reactant, zo itis reasonat ‘one particle of each reactant is prosent in the rate-determining step of the mechanism, The aocepted mechanism far the reaction is oxpace eae oACH EA, Sa +r 3] Woo to wet Av 4 wh, saan atua & fg 5.2 rechenirial eae hey feo ‘Thintype of mechanism is named S,2, Le. Substiution Nuckeophic bimolecular The rate-determining step is-bimclocular because there are avo reactant partides present, Inis.a continuous single one-step reaction. The complex shown in square brackets isnot an intermediate (le the carbocation formed in the 3,1 mechanism), but is a. wonsticn state (see Section 118.6) ‘A study of the acid: catalysed iodination of propanone The maction betwean prepanone an! :odine in aquecus solution ray be ach catalysed: I{ag) + CH.COCH Jag] + Haq) —~ CH,COCK,Naq) + 2H"(aq) + ra) The infivence ofthe iodine on the reaction rate may be studied ifthe concentrations of propancneand hydrogen ions effectively cemain constant during the reaction, Thisis achieved by using alarge exces of bath propanane and acid in the onginal reaction mixture. You wll vestigate this im: CP9A Following the rate ofiodine-propanone reaction by a titrimetric method Procedure 1 Mig2Senv ef mal dm2.aquscus prapanone with 2Serr? af 1 me! dm sure ci, 2 Start the stop cloclethe mamient you act! 50. of 0,02 mot em fotine solution. Shake well, 1. Why ports lh dia Con arpa and pace ina conkal Wk Sop therectoby digs | a ‘ou esr osm hyeregen vooate No ibe eae tine thi esechumyoge aon nees Serer estiee 4 Titrate the remaining adine preien inthe samplewith 7 mal de? ecium thiosulfate) soltion, “Saute defen mats for Goce vesting cfrencion. eee eT en slit. alwaysnaving the exact time at which the sodium hydrogen carbonateis added, Waste should Between wihdiandng.a reaction ibe coetoined iva ares expbneed. sample by pipette and pear Treatment of resus i accein ea The Lin sok can geal gua ithe wstned Aaa vette «lot ah sre sqle te (Thar propeionl tha concanvion odin} Deuce from the graph the ede of reaction wh respect toiodne Analysis of rests The gaps plediced shows thatthe reucon ato orer with rspetts one. inlay patvnmashow vata nico ie cdar ah pac bth profane nd Wynn 1h ae tog ine rate = {CH.COCH JH") Thi would srgget thefolloving reaction a theft of thereat: CoH, ove = Oe J J Sila ecto in hee mechani are vary sot actin suey to bee ate deen bene earchrr eae ee Ue) ‘Thesecond step prebably controls he rate ofthe eactoniand produces that. being a catalyst, i not used up in theresction sow This rearrangement(s Heel to be very slow and hence s probably the ‘ate: determining step ofthe reaction. lodine — CH,CHYOHION Mechanism 2 Step], CH.CHO ~CH —[CHiCHOCNE Step 2. ICH:CHOCN) + H’ — CH.CH(OHICN The rte equation far the reaction ix rate « {CH,CHOJCN' IH) (@) Explain which ofthe two mechanismsis consistent with the rate equaion. (b) hich step inthis mechanism isthe rate-determining step? The equation fr the reaction between hydrogen and nitrogen monoxide is: 2ktlel ~ 2NO\g| — 2H:0g)+ NB) The rata equation for tharaaction ii rate = {HaTNOP ‘proposed mechanism for his reaction is ‘step 1; 2NOIgl—- N08) rast Step 2: NiOdgl +Hde) = H,O1 + N0lg) SLOW Step 3. M.Olg)+H4a) — Nig) H,0lg) FAST \sthis mechanism consistent withthe rate equation? Explain your anamer ‘Assume the flowing propased reaction mechanism iscomect 20 slow rast fase (a ite the overall equation forthe reaction (by Wit arate equaven for the reaction that és consistent with the mechanism, (e1¥hat ould be the effecton the ate of reaction of doubling the concentration of CL? (a) what would be the effectan the rate of reaction of doubling the concentration of Hi? The nuceoptilic substitution reaction between equimolar (quantiles af CH land GH second onder overall, However i the reaction i cared out using alarge excess of OH" the reaction becomes firs arse overall, Sugpest an explanation fer these ‘sbseriations Laeemine can be formed by the oxidation of hydiogen bromide with onygen. ‘Aprepased mechanism for this reaction tx Stgpl: — HBr+ Q— HBO; Step2—HBrO, + HBr —- 2HBr Step HBO + HBr — By, + H,0 Step: HBrO + HGr— Bs, HO (a repeat of Step 3} Thera equation for ths reaction is rate = KHBr[03) (al Explain which of the above four steps is the rate-determing. stop for this reaction, (b) Write the overall equation forthe reaction,ml par Ve CHEV Malacca ae) rang 111) eV eit Understand the terms: (@) activation energy (ii) heterogeneous and homogeneous catalyst 1 Understand the use of a solid (heterogeneous) catalyst for industrial reactions, in the gas phase, in terms-of providing a surlace for the reaction, ACTIVATION ENERGY, £, In Topic 9 (Book 1: IAS), we defined activation energy, E, as the minimum eneray that colbdling parctes must possess for a reaction te occur The activation energy represenés the cnetgy that the colliding particles mast obtain in order to reach the energy level of the dursiion sate (see Section 11A.6 for mere details). Once the encrey level of the transition state has been reached, the particles can react to form the products and release energy as they do sa "Tae entergy profile diagrarn for art exctermic reactiom is show in fig A. Enemy 9 ronaon teste proaucts Progess a ation eA. A reaction pine or ansiementary exothermic eactan CATALYSTS In Topic 9 (Book 1: IAS), we defined acstalyst as a subecance that increases the rare of a chemical reaction but is chemically unchanged atthe end of the reaction. ‘We then went on 10 explain that a caualyst works by providing an alternacive raute forthe reaction, and that this alternative route has a lower activation energy than the original route. Although the Cciginal route is still available forthe reactants, most collisions. resulting in reaction will accu by the alternative reute, since the fraction of particles possessing this lower activation energy willbe greater Catalysts can be divided inta re groups + homagencous catalpsts + hateropensous earslyst HOMOGENEOUS CATALYSTS. A Bomogeiaeous cota isin che sarne phase (soll, liquld. solution or gas) as the reactarsa,‘Many reactions in aqueous solution are catalysed by the fydrogen jon, H'(ag). An example i the iodinasion of propanone, a reaction ‘ye diceusted in deta in Section 118.4 CH,COCH, (a4) + 1,(0q) CH,COCH, faq) « Haq) + Feet “The prnduction of chlorine radicals rom: chioraucroeattons CFCS) is responsibie forthe destruction of oznne.n the wer almosphere, Uitaviotet adiaticn fora the Sun produces chlerine radicals, Cle, fram CFCs such as cichiarodifuoromethane, CCE uilraviok OCLE Ye) “Soe sCCIRfa) + Clg) “The chlorine rackcals then take part na chain reaction with Gaone: Crlg) + O,f6h + C1O*ig) + O8) O+(a) + O.fg) — 204e) + Clete) ‘The chlorine radicals reenerated and s0 is acting axa catalyat ‘Since the catalyst is in the same phase, ie. the gas phase, as the Teacing species its dassified as a homagencous catalyst The averall resctic 204) — 30,6) “Another reaction involving a homogeneous catalysis the ane between peroxydisuliate ions and indide ions i aqueous salution: OF aq) 2I-faq) —- 250} faq) « 109) ‘This reaction is catalysed by elther Fe**(aq) or Fe*"{aqh, ‘With Fe*fan), the reaction mechanism ts: Step t: $,0 (aq) + 2Fe™{aq) ~ 20-(aq) + 2Fe“taq) Step 2 2Fe!faq) + 21-feq) + 2Fe**iacl + Lac ‘With Fe’*(aq) asthe catalyst Steps 1 and 2 oncur im the reverse pices ees Fe (aq) as catalyst in ee Beer aa se aed inter potentals(E* values) However it's mpo tart to nate that standard electiode potentials «an predict only the thermodynamic feasibility ofa rencion, and not ‘the kinetics The reasor-why the reactions ie fasterin the presence of cther For Fes that the activation energies for both Steps 1 and 2 are lower than the activaton energy for the overall reaction, HETEROGENEOUS CATALYSTS A heterogenous catalyst in a diferent phase to thet of the “Two important uses of heterogeneous catalysts industry are In the Haber process and the Contact process. The use of solid ‘vanadium(V} ence (VO) in wich the vanadium changes its ‘dation number in the Contact provess is desenibedt in the section on wansition elements (Tople 17) ‘We will now describe the action of solid fran as @ cetalstin the reaction between mfrogen gas and hydrogen yas form ammonia gas in the Haber process, ‘The eqution fer the formation of ammonia in the Haber process i: Nila) + 3HLLa) = 2NHed Ino ate to act as a eatalyst because it can foreman inzrstual span with hydrogen molecules, In this hyde, tdragee aroma areheld in spaces berween the metal ions inthe lice. The ators arethen able to eget with nitrogen molecules that ere adsorbed nto the metal surface neatby There are three stngesin catalysis involving surace adsorption These are 1, Adtoyption — the reactants are fit adsorbed onto the surface af the cazalys. 2 Renetion the reactant molecules are held in positions that enable them to veact together 3, Detorption — the product niolecules leave the surface The rete of reaction is controlled by how fase the reactants are adsorbed and how fast the products are desorbed, As mentioned In Topie 9 (Boole 1: TAS}, ance the surlace of the iron is covered With molecules, there is no further increase in reaction cate even iF fhe pressure of the reactants increased, ‘00D YOU KNOW? ‘The efficiency of # heterogeneous catalyst depends on the surface ‘ofthe catalyst n particular, the efficiency ofthe catalyst can be affected significantly by poisoning and by the use of promoters, orsonines ‘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 prefered to platinum as a.catayst in the nydraganation of alan. Wicks! is ‘atively Inexpensive, so a large quantity ean be used. if some af itis deactivated by poisoning, enough will remain foci tll to bs ‘efactive. On the ather hand, platinum is expensive, and so small ‘quantities would have to be use. In this case, itis possible for all ‘of the catalyst to become poieonad. ‘PROMOTERS ‘The spacing on the surface of ihe catalyst is important, For ‘example, only some surfaces ofthe Iron crystals act ws effective ‘catalysts in the Haber process. The addion of haces uf potassium ‘tide apd aluininlum ani act as promoters by producing active ‘sles where the reaction takes place most readily (Dip YOU KNOW? ‘A Intersttbal hyde, somtimes cated & metallic hydra, fs ‘ot Sica. cOMpOUNG, Is more PAE an alloy Ma @ gam pou, “Toe hydrogen absorbs into the metal and can exist in te form ‘of ter atoms or diatomic molecules, For example, palladium ‘absorbs up 19.900 times its aryn volume of hydrogen at room emperature, and forms palladium fytride. This mater has been ‘consered as a method to carry hyarogen in fuel celts for use im ‘yhieles (0 Seetion 14.2.1), A heterogeneciis catalyst is used in a tiree-way catalytic ‘converter which is employed in the exhaust of cars unburned hydracerbers into water and carbon dicwide, and carbon and carhon mozoxide into carbon dioxide, Itelso convertsTOPIC cceides of nitragen into oxygen and nitrogen. The rections Involved are discussed in more detailin Topic 17, ‘Bio YOU KNOW? ‘The electophitie action reaction between etnene and bromine ‘vapour (Topic 5 (Book 1:1AS)) was once thought to be entiey a ‘homogeneous process in which the molecules collided inthe gas hase and reacted {18 now known that the reaction takes place almost emraly on {he surlace ofthe walls of the reaction vessot. The reaction takes place very quickly on a glass surface and even mora quickly when the surface ofthe vessel i covered with a polar substance such 2 cof! alcohol (hexadecan-tol,CH,(CH.) 0H). takes place ‘Sven more quihty stil on a surface of stoari acid (octadecanaie ad, CHYCK,) COM), presumably borause stearic acid molecules are more polo than moleoues of cety aeohol. However, if the walls ofthe reaction vessel are coated wth a ‘non-polar substance such as paratfin wax, very litle reaction, i ‘ay, otcurs, So, a proces ence thought to be HoMOgENEDUS Bes [phase reaction Is now krown to be Heterogeneauy catalysed, {tis sometimes stated that a catalyst does not change the products oF reaction, but only increases the rate at which the reaction takes alare. This is not entirely tue, as demonstrated by the different pruducts nbtsined when hot ethanol vapour is passed ‘over gferent soit catalysts, With copper ar nickel as the estalyst, at 400°C, a dehytragenation reaction takes lace in which the products are ethane and Inydeogen: CHCH, OM gh —> CH CHONG) + Hal) Hat thesame temperature, aluminium oxide i used as the scatalys, the mare fara Getydraton reaction into ethene anc water takes plac! CH,CH_OH{g) —» CH-=CH.Agh + H,0(a) {tis interesting to nto that the dohycrogenation catalysts, ‘copper and nick, adsorb hydrogen very stronaly, whereas the dettyration catalyst luninium oxide, adsorbs wator in proforanc. ‘These two examples llustrate that there isa lat more to heterogeneous catalysis than \s mentianed at international ‘ALevel, This might encourage you to-do your awn researc into ‘he topic and learn ever more about i OXIDATION OF ETHANEDIOIC ACID BY MANGANATE(VI) IONS In autocatalysis the reecionis catalysed by one of its froducis One of the simplest examples of thi isthe oxidation of ethanedicic eid by acidied potassium manganate(VU0). The equation forthe resetion i S{COOH (aq) = 2MnOjtac) + GH (aq) MECOu(e) + 2Nte?*ag) + BHO “The reactions very siow at room temperature, but is catalysed by manganese( i) ionx Mn'* The Mn tons are not present inital, so the reaction starts off extreme'y lor at race tempera However Mr®* isa product ofthe reaction. As soon as itis Froduesdlin a cetayic amount, the reaction rate increases ‘You can show this effect by plating the concentration of one tf the reactants against time. The graph obsained is unlike the normal rate curve fora reaction ononren fp PeROREN Hara ont of eta, ane sos doom bale verter nacona 7 2 fig Agrapnstconcenazen against me or an avez eats, In fig B.you ean see the stow (uncatalysed) reaction at the Degiining. AS catalyst begins to be formed in the mixture, the regetion speeds up — it gets faster and faster as more and more festalysts formed Bventuslly the rate decreases in the normal vay asthe concentrations af the reactants decreace, SARNING. Dor tennenn ast onesies te oath ar er shobisan example ofautocatalysi. There are-ether effects that might produce a similar graph For example, the reaction involves sole reacting with aqui, Fiud might have'to penetrate substancecn the surface athe sold before the expected veaction ean happen, Another possibilty thatthe reaction s strongly excthermic and the temperature ist being controlled, The heat evolved during the reaction speeds upthe reaction eas ‘Explain why oxy a mall quantity of w hornagenequs catalyst required in order for ito be effective 2. Carsin some pars the word sll run on leaded petrol, Leaded ‘petal contains a compound called tetraecy lead, (CH,CH,)Pb. Teueethyl lead eactsin the engine with axygenand forms lead ri eae} oxide: These substances remove radical {ntermeczates in the combustion reactors, thus increasing the ‘octane rating ofthe ptr. Excess lead and lead} oxide it remawed by acing 1 2-clbromaethane: The fairs volatile lead) bromide that escapes throug the exhaust. Suggest whya catalytic canverter cauld not be vied ina car ‘rumning on leaded petrol Bee ‘dsorption the adhesion ol atarns, molecules artanato the surface cf solid ‘autocatalysis when areaction product actzas a catalyst forthe reactionFac OR e ees ie Ue | ot ee IM Use the Arrhenius equation to explain the effect of temperature on the rate constant of a reaction, IM 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 @ reaction There are two reasans for this + am increase in the fraction af molecules with energy equal lo or greater than the activation energy for the reaction + an overall increase in the frequency of collisions between the reacting molecules, ‘The second elfect is considerably leas synificant thes the first and means that we can effectively ignore the overall incteasein the frequency af collisions ‘THE ARRHENIUS EQUATION EXAM HIN tn 1989, Svante Artberius a Swe chemist, proposed quaritative relationship between Nod Sarbe grea erersut witht rate corsan fr arscon. Tiss exert iy te Ahead Athens equation itis is ‘needed in an exam question, ead) where + Aisa constant kacem as the pre-exponential Factor, wich is 2 measure of the rate at which collsions ‘accur imespeciive of their enengy It also includes other factors the mast important of which i that reactions can only occur when the molecules are correrty crientatedat the time of calision + E's the actwation energy of the reaction. + the gas constany, + Ts the absolute temperanute (Le, he temperature in kelvin). II wre take natural logevithine (Le. logarithens tothe base'a’ of the Arrhenius equation, we obtain 1 get wag ern potatague Laie atten a cnt Ink=~ R ‘This provides an experimental method for determining the activation energy of a reaction, ‘The intercept with the vertical axis gives Ind, Meats ‘Table A shows same dita related to the fection betwen perondsulatan aqueous 010033 310 ‘ness “000823 3 or 00313 0 ~no201 “0030: 20 0.0301 ®TOPIC nen aa shows reed Fig showsink plone gaia gone 9003 pons! oom aooss cont fig A praphet bi gaint 1/7 5 The grachenta the line, = [Re k3t] mot =>] 15386831) 57700} mat"! = «37714 mot to 34) ‘DID YOU KNOW? ; When we stata thatthe relationship between Ink and —| is neat, we have assumed that both and A ‘romain constamt aver a range of temperatures. Mis isnot stict true. Howeves, tleehange inthe values of and A wth tomperature are nsigniicart compared withthe effect ot temperature on the rate constant, ‘and so ean be ignored. ‘DID YoU KxOW? ‘The significance of he factor ‘The factor e-‘ represents the traction of callistons that have energy equal to or greater than the ‘activation energy, €, Forexample, a reaction with an £,of €OkJ mol gives a fraction, at 298K, of proms +298 9 10-1 ‘80, anly one collision in 3» 10!" has sufficient energy to react. 11s often assumed that me tration of calisions With enasgy equal 0 or ofeater than E, iste same as ‘he fraction of molecules wth ins energy. This Isat sbicty true, but the difterence is insigniicant at ‘high energies, were the fraction is very small Itls, therefore, reasonable to craw the molecafar energy cstribution curve, instead of the cofision frequency curve, when demonstrating the efect of temperature on colision aque. (See Tope 9 (Book 1:1AS). ‘The feet FE, on reaction rite: + reactions witha lage E, ae iow, but the rate Increases rapidly with an increase m temperatuie + reactions wit a small Ear fast. but the rate dws rox cease as apiclywith ap nereasin temperature + catalysed reactions have small values of, Ee x]iYOU KNOW? Reaction protiies: \Wnen craving reaction profile diagrams for mul-step reactons, itis impartant to distinguish between fn irtenmeniate anda transition state: + en termediate as an eneray minimum ‘+e transition state occurs atthe top ofthe energy curve and therefore has an eneray raeximom, An intermediate isa definite chemical spscles that exists fora finite natn of time, By comparison, & {rangition state bas no significant pormanont Hotime of Hs own: exsts for a period of the orcer of 0°" szponds, whan the molecules are in contact witn ane ancther. Even a very reactive imermodiat, wi atitetime af onty 10° seconds, has a bong Ietime in comparison with the period that caliing rolecules are in cantact with one another. A simple one:step reaction, such as the &,2 hydrolysis of primary halogenoaliano, has a single asim energy The réaton profit far the hydrolyse ata primary nalogenoalkane, rpwesonted 5 it, is thoveore: rma rages alveacion a fig mereactny porte cps rar hoger The reection profile for the Sq1 hydrolysis ofa tertiary halogencalkane, RyCHal, which isa two-step Faction invowing the intermediate RC", is: Go Fad Frogessalvescioe 209 pnflodagram fre back of wma lggpretane ‘nthe Sy) hydrolysis ofa tertiary ha fist step ofthe mac ate-determiing “step of the reaction, and it therafere has the higher activation energy. That is, re pitas reaction mechanism is ate-determiring,E11}< &,(2}TOPIC 1 114.6 TEMPERATURE AND THE RATE CO ‘Dio You KNOW? ‘The relative retes ot $y1 and Sy2 reactions depead on structure "You leamed in Book T that alky! groups donate electrons by the inductive effect, This means that the ‘stability of arboeations increases in the onder 1°~< 2° < 3°, ax the number ot aly! groups donating ‘etectrons towards the positwe carbon atom increases, ; ' ; | t i me Eel asl | b ‘is the stabilty of the carbocation increases, te activation energy far the reaction leading to its formatian also decreases. Frege of tsctch ‘A fig Reacton pti forthe’5,) yechas cf penary ad teary halegenodhanes We theretore expect theate of the Sy1 reaction to Increase inthe order 1*-< 2° < a, ‘No cartocations are formed during the Sy2 recon. n an $y2reacton, the transition state as tv ‘cups ararged araurd the central carbon aim. tis therefore more crowed then ether te starting halagenoalkane oF the alcool product each of which have only our groups-arcund the central carbon aoe ‘Alkyl groups are muck larger than hydrogen aioms. Therefore, the mare alkyl groups around ihe ‘central carbon atom, the mare crowed wil be the transition state, andthe higher the actwation energy for is formation, We therefore expect the rate of the $,2 reaction to increase inthe order 3*< 2° < 1% ‘Tho two efforts reinforea one anater, Tha Sy reaction Is fastest wil trary nalites and slowest with ‘rary halides, while the S,2 reacton is fastest wth primary hares and slowest with tera hae, ‘Overall, primary hades react predominantly via the 8,2 mechanism and tertiary halides react predominantly lathe S,1 mechanism. Secondary halides tend ta react laa mbt ofthe two moctanisns. Pte a ae erates FE 5.1 and 5,2 hytclss reactions fr primary secondanyand txt talogernalanes Gets ELD ce T.pUsr the Athen ive equation to explain why ternperature resis in an Increase in the rate of reaction, 2. The rate constant fora reaction increases 1003" to 10005* when the temperature is Increased from 300 to awk Calculate the acsvation energy for this reaction. [R= B31 Imo! KyPPMP LA em 1 ele ait CATALYST CRAFT ELE crane In thi article you wal look at an exemple of howan enginaered metalloerzyme can improve both the kinetics and speciiciy of 3 renetion, The extract is Hom Chemimy World the print and online magazine of the Royal Seciery af Chemistry. ENGINEERED METALLOENZYME CATALYSES FRIEDEL-CRAFTS REACTION ‘Reprogramming the gence code of bucterigto include an unnatural arnine ueid thas tllowed scicatists in the Netherlands to create anew metalloeazyme capable of ccalalysing an enantioselective reactioa ‘Nature ic extremely good ai caralysing roactions with very high rate accelerations: and very high selectivity, But it does 9, Deets poison sing ‘axganded gues cock fram our perspective, with i relatively limited set of reactions,’ explains Gerard ‘Reelfes from the University of Groaingen in the Netherlands, who led the study. His group is lookin al existing scactions that use traditional catalysts, but fil to achieve: the sume rate acceletation and selectivity as enzyme catalysed reactions. Ah FigA. The weil metalbeneymesuee applied inacatayic armen Friedel-Craltsallyation Meralioenzymes combine the flexibility ‘of metal catalysts with the bigh aetvity and selecivity of enzymes. Arificial metalfoenzymes are produced by inserting 4 catalytically active transition metal complex inio a biomolecular scaffold, lke protein, Roclfes” team eagincered Excherschia cold cells ta include a eapper-binding amino ‘cid into one of its proteins, This method requires no further chemical modification ‘or purication sep, atving it an advantage ‘over existing methods, The resulting retallocnszyme was tested an a catalytic ‘asymmetric Friedel-Crafts alkylation reaction, achieving an enantiomeric excess of up to 3% “Tukafumi Ueno, who researches the rochatisms of chemical reactions in living ‘Tokyo Instiute of Technology in Japan, is impressed by the work. “Ut could be applied not anly for rap sorvening of artificial metallogazsines but also fo in vivo use of then bo gover sell fae i future” calls at ‘The group are row looking wo develop new auifcial mealloenzymes with the ‘capability to perform chemistry tht traditional transition metal catalysts cannot. Uhtimately, they hope to integrate these ‘eaymes into biosynthetic pathways. Adapted (with pension) tum ‘Enginevted Mtlloenzyie Catayses Fridal-Crafis Reaction by Debbie Houghton, Chsusery Whirl, 3 Nowembee 2014aro) Ten a ad DE 1 a} Afierreacirg te atte forthe festtime, write aone-paragraph summary of whatyourhink You may find that it is easier the atic about ‘han you mune to get an {b} Now verte down a lst of any words from the article of'which you do net know the meaning. eel aneeeeneh Do some research inte what they mean. &.there- anything abowt your summary from (a) tar «What. a detailed scientvic you would change? amicle aberut Youdo not need to understand ‘ovary ingle word 10 jean something new and CHEMISTRY IN DETAIL inlA 2 Auuuming the reaction ieesathermic shech an eneyprofisfortnecatzheed reuction shaking When youste asket to draw something rate sute you vse a sharp HB pene 30 that your crawing 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-catalyséd yeaction takes tie foIr) and usea rier ifyou are Rate = {lf where [El i the erayme concentiation and and mare expenmmentaly determined itrawing staight lines. constants. What does ths rateeqjuabon seezrest about the reactor) mechanism uiider these eanditions? 46: Name the ype of ond that is formed between the eopper ion-and the unusual amine acid in the metalloenzyme shown in fig 5 Sugeest why the use of metalloencymeof this type might bea beter altemative than the traditional Friedel-Crafts methods for allylation 6 Suggest wity this medion might be expected to increase the enantuoxelecty Of this reaction, 7 Suggest why the Zi jon may noe be a-sutable replacerment fo! the Cyr ion ih thisenzyme. planed ‘Although the metalloenayme detailed above sgeretically engineered, there are mary naturally (occurring metalloenymmes that camy outa rage ef reactions in organisms, Most of these can De found in a feely accesibée online database called the PDB (alternatively, the POBE) Choose ane ofthe flowing metals Fe: Zn, Cu, Mo. Co + Find.a protein that contains +g out what the protein does + Find out how much of the metals present in atypical healthy adut Give five-minuié presentation on your chesen rea, Fearing no mee than Tveslices You wil have the apporunityto display your chosen eickec ule cing. some af the freely mrlable coftuare packages suchas jmo} 1g meta ‘01D You KNOW? Although typical adult has only sbout 1.8:mg of copper per ka af body mass, an inability to regulate ‘copper has disastrous effects. For example, the inability to exzrete excess copper trom the body (Wilson's ciseage) can be fetal left untreated. Menkes’ syndrome manifests ital ifthe body is ‘unable te retain (hold on to) copper, Although not fata, can lead to developmental delay and ‘neurviogjcal problems.11 EXAM PRACTICE A. An experiment inset up 0 measure the sate of hyralysis of methyl ethanoate, CH;COOCTE CH:COOCH; + H,0 = CH,COOH + CHOH “The hydrolysis is very slowrin neutral aqueous sclution. ‘When cllute hydrochloric acid is added. the reaction is faster, ‘What is thé function of the hycrochloric acid? ‘A tn increase the reaction rate by acting asa catalyst B ta-make sure thar the reaction veaches exuli lum to maintain a constant pH during the reaction D toddisseive tha methyl ethanoate fa (Total for Question 1 = 1 mark) 2 For the gaseous reaction 2Xig}-+ Yq) — Zs), the rate ‘equation is rote = (XPIP. 1f the presaure in the reaction vessel Is doubled but she temperature remains constant. by what facta cows: the rate of reaction increase? AZ B32 C4 Da o) (Total for Question 2 = 1 mark) 3 Thellaline hydrolysis of Be where Re = (CH,),Br, takes place intwa steps RB RY + Br SLOW K+ OH — ROH FAST Which of the folowing rate equations is consistent with this a] (Total for Question 3= 1 nan 4 Thetable gives data for the reaction between X and Yat ‘constant cernperature, ee 1 3 02: 40x 104 a 06 04 1ex 10? 3 06 08 84x10" [What isthe rate equation for the reaction? O) (Total for Question 4 = 1 mark) 5 The reaction af acidified aqueous potassium iodide with aqueous hydrogen peronide 2roq) + H,O,(aq) + 2H"lea) —~ Lda) + ZHOU) is thought to involve three steps HO:+1>HO+0r SLOW or + HY = HOT FAST HOI} HT + 1+ H.O FAST ‘Which of the following conclusions eamnot be deduced fram this information? ‘A The acids a cata, B The reaction iit order with respect ta the iodide ion, C The rite determining step is 0; + > > HO + OF D The rate equstion forthe reaction iat 8 Propanone and iodine react in aqueous acidic solution according tothe following. overall equation: CH,COCH, + p+ HY — CH,COOH +2H* +1 ‘The experimentally determined rate equation for tis reaction i: rate = KCH,COCH,IE] {a) With iniial concentrations as shown, the inital rate of reaction was 143 x 10“'moldm“"s”. COST, aan L 200 x 10% Calculate e-valie fer the rate constant. & forthe reaction. [3] (b) Explaie the effect ow the sate of reaction of doubling the ‘concentration of iadine, but keeping the concentrations of 0400) Popaoane ei lige scott ia {The pope nth othe onal sti ee ee ee owTOPIC Explain whieh af the four steps could be the rate-doterrring step (3) (Total for Question 6 = 6 marks) 7 Mast chemical reactions involve twiror more steps. The experimentally determined zate equatiea Indicates which species ave involved either before or in the rate-devermining step, (@) Store wht is meant by the term mate-determining step. [1) (b) Hydrogen reacts with iodine monochioride in a two-step ‘mechanism according ta the following overall equation Halg) + 21Ctg) — 2HCha) + La) "Thee experimenisly determined rete equation for this reaction is sare =a (Hts) 0] The rate-cetermining step is the hist step in the mechanism forthe reaction (i) Write an equation forthe rate-ceterminig step, [1] (i) Write an equation forthe seconsi ster, ny (€) A sories of experiments were carrie eut on the reaction 4B C~ produrta, The results are chown in the tale iol dis? mol des"? s? Jal_|_ fei} tc 1 1m | o100 | aron | aco x 10 z Gamo | a200_[ fiom | 43% 107 3 oxo | axoo | a200 | ata xi07 2 oz | aioe | aion | 128% 10° (i) Determine the order of reaction with respect 0 A. sand C. Show how you obtain your answers, (3) (il) Write the rate equation forthe teaction (Gi) Which resctant i unlikely tobe in the rate determining step? ft) (Total for Question 7 = 6 marks) 4 Nitiogen perce decompose on heating ta form nitrogen tetroxide and axygen. The equation forthe reaction is N.C) + N,Odg} + $0.4) ‘The progress af the reaction can bellowed by rmeasuritig the cancentration of N,O, present The graph shores the results obtained in an experiment conducted ot constant temperature, Tes (2). (), Use the graph to prodier the rate of resetion after 20 ‘minutes and after 90 minutes pl (UW) Deduce terete oF procueuen oF axygen after 20 minutes? a (bo). ()) Ploc on the grat two successive halF- Ives fir this reaction el (i) Deduce the onder of reaction with respect to N;Oy Justify your anne rh (Gl) Wire arate equation for the weaction i (c). (), Celoulme a vatue for the re constant, for this reaction. BI (i) Deduce the Initial rate ef resetion when the initial ‘concentration of NO, 1.80mol dm Assume the reaction isearfied GU under the same conditions of temperature and pressure Bl (Total for Question 8 = 14 marks) 9 Nitrogen diaside, NO.,.1s decomposed on heating ito nitrogen ‘mescoiee, NO, and oxygen. The proposed mechanism for this reactions: NO, +NO.—NO,+NG SLOW NO, =NO+O, FAST (9). () Wete an overall equatina for the deeernposition of ltiogen dioxide. oT (W) Wee a ate equation fer the reaction. Ay (b) The rate constant, & for the decomposition wes determined at several cifferent temperatures. The resulis cbtained were used to plot the graph shown below: yo 8) te 19 tat writo-K ()) Use the graph and the expression ofl, hhke-G pein to calculate the activation energy. F for the thermal decomposition of nitrogen diaside Give your answer teanapproprisie number of significant figures. [8] (i) A vesset of volume 200m! is filed with 100mol of trogen diaxide at avempetature of €50.. The initial rate of reaction was found tobe 12.64 mal din-s~ Calculate value for the ate covstant& at this temperature. BI (Total for Question 9 = 9 marks)a © Saat at] S itt sages) 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 cantinuously renewed, and populations were small, energy supplies during the Stone Age peried were plentiful, However, this simple lifestyle has almost completely vanished, and people taday 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 cwn bodies. Energy is an essential part of chemistry as well as of civilisation as we knowit. 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 auturnn? 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 hasa 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 ard 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 ms in relation to quantities that range over several orders of magnitudeCe ene eee Td eee eee eae Energy level diagrams and enthalpy profile Ce ee eee ee earn St See eee ee ceo Se Lny Sea ee ens ee once ty ey eee eee peererareti|12A 1 INTRODUCTION TO ENTROPY ‘Fara paeraics [Am rz 123 | 124 Paes | Understand that, since endothermic reactions ean occur spontaneously at inom temperature, enthalpy changes alone de nat ‘control whethar reactions accut IB Understand enfropyas a measure of disorder of system in rms of the random dispersal of molecules and of energy quanta between molecules. 1 Understand thatthe entropy ofa substance increases with temperature, tht entropy increases a5 solid — liquid —. gas and that perfect crystals at zero kali have zere entropy, 1M Be able to interpret the natural direction of change as being in the direction af increasing tolal entrapy (postive entropy change), including gases spread spontaneously through aroom. WHAT MAKES A REACTION OCCUR? Pethaps ane of the most important questions to ask in chemistry is Willa reaction occur? ‘We know that, once started, some chemical reactions sintply ‘go ‘with no further, continua help from us. For example, amnmonia gas and hydrogen chloride gaa react together fat room temperature to form the white solid, ammonium chloride: NELigy + HEM) —+ NH,ClS) ‘Magnesium. ance ignited, will burn in oxygen to form magnesium onde: Male) + 30,(a) > MgO) In other reactions, rether than the reactants changing cotnpetely Inco the products, aposition of equlibrium is reached, withthe final mixture containing-a measurable amount of both reactants and products For example. ethannic acid disanciates in water Ina 1 mol drm-* solution af ethancie acid, only about 19 of the ethanove acid molecules are present an ons CH:COOHH{ag) = CHCOO tea) + Hoa) ‘Another exaraple isthe dimerisation of nitrogen diexde in the as phase 2NOgh = NzOulg) ‘Ata temperature of 29H K anda pressue of 100 kPa, the equidriuim mivtare contains abou 70% NO, “Tore ate other types of reaction that simply da net ecewr at atleast not withoursomehelp For example: * ammonium chloride does not spontaneously decompose into ammonia and byelogen chloride + magnesium cite does not bresk apart to form nisgnesium andl cuoygen without some continues intervention from us in the formof heating, if we Consider allo these types of reaction together, me’ see thar the real difference between them isthe postion of equiitsium that Isestablshed, Fer some reactions, the position of equilbramm is so far over tothe procucts side that, 2 all intents and purposes, the reaction has gone to completion. For some other reactions significant zenounts of both reactants and products are present at equilibrium. For other reacsians, the equilibrium lies so far to the leltihat they appear not to take place at all So. perhaps the etter questioe to ase wat WH & chersical reaction secur? but ‘What will be the positian af equllibeluns? ‘Thia i the question we hope to-anevor in this tapie ‘A.camplie is an example of Increases in entropy. Tae solid wood ‘burns and becomes ash, snoke and gases, all of which spread ‘energy outwards more easiy than te solid tel. EXOTHERMIC AND ENDOTHERMIC REACTIONS Tir eacton betweer sruynesium and aoygenis exahesmit and'can be represented by theemtulpy level diagram sown n fg A. ral 7 nui ga) ‘neat energy given out Ms Tracion psoas (AC Tigh.Enihay be diagram tr te As the products haveless energy than the reactants, we often say thatthe products are mate enorgvcaly stabs than the reactant, ben magnet and ‘tis: very tempting to conclude that this reaction occurs cause the magnesium oxide is energetically more stable than its clements, magnesium and oxygen. However tempting this argument may be, we must discard it, because experience telus that many endothermic reactions necur at roar temperature. Let us consider the dimerisation of NO,(e) at 298 K: 2ND ala) = N,04f8)TOPIC ‘The enthalpy level alagram for this reaction fs shawn in fig B. shale eacion patwrey (Be fig ritalpy Yee! agra lor the dineaticn tO, ‘This reaction is readily reversible and reaches a position of equilibrium at 298K. The forward reaction leading :o the formation of NO g) a exothermic. However the backward renction is endothermic ‘As we discovered! in Topic 9 (Book 1: IAS}. the position of equilibrium can be reached from either dectinn. This means that if we place some N,O,(z) in a sealed container at room temperature, some of it will derompase to form NO,(g), §0.n endothermic reaction is taking place at coor temperature without us doing anything to it Wie say that the reaction is spontaneous (gee later inthis section}, (Cleary. it is not only exothermic reactions that can take place spontaneously ‘The deiving force for spontaneous cndotherrnic reactions cannot be the formation of mare cnergeticaly favourable, ic. lower-cncrey products but must invctve another factor we have yet to consider ‘That factor iva quantity known az entropy, which is governed by the Second Law of Thermodbnanic, But fist, we need ta appreciate what is meant by the teem spontaneous process SPONTANEOUS PROCESSES ‘A spontanenas process is ane that aes place without cantiquetis intervention by uz ‘A good example of a spontaneous procesc is the freeng of water to-fornn ioe. If water Is placed in an entronment at ~ 20°C it wel turn into ibe. However, the rewerse wll nevey happen: et ~20°C fee il ewer melt to forrn water ‘Another example of a spontaneous process isthe mixing of gases If twounreactive gases are present in. container they will mix completely in.a process known as cifusion. ‘We can bring-abour the reverse of spontanecis processes by intervening. For example, we can melt ice by heating it and we can separate a manure af pases by liquetying followed by station "The key point; however is thatthe reverse of a spontancaus process never happens onits own. A minture of gases will aver soparate on their own. ‘At the beginning of this section we stated tha in chemistry. we are concerned with whether or not chertical seactions wil occu and we suggested that perhaps the most important question to ask in chemisuy is Why does a reaction occur? From the point of view of thermodynamics all reactions are reversible, so we suggested that an even better question to ask is When reaction meches « point of equilibrism, what determines whetber the equilbrium wil favourthe reactants fr the praducta, and ta what extent? ‘This question is answered using the Second Law of ‘Thermodynamics, in which the cancept of entiopy is introduced, ‘The Second Law of Thermodynamics allows 1s to predict Whether a process isliely teaccur Itis, therefore, the key to understanding what drives chemical reactions ard what determines the pasion of equibbrum. ‘The Second Law of Thermodynamics introduces.a term called entropy, which isa property of ratte just like density er energy” ‘The simplest way to deseribe entropy isto say that Hi. @.quantity ‘associated with randomness or disortier ‘This definition ig rather basic and has to be uted wath care, Entropy refers not only tothe distrinution-of molecules but alsa To The ways of aistrinuting the energy af che system in all af the energy levels evalatle: “Teshelp you teundorstand entropy, it helps to think about wha happens during the diflsion of gases, DISTRIBUTION OF MOLECULES Fig C shows two gas jars. The bottom one contains bromine gas sand the tap one contains air a fig Gir jrecominngar ‘When the cover sip becwgen the two gas jus is removed, the ‘bromine and air ciffuse so that the molecules of each gas re spread out evenly throughout both gas jars To understand why this happens we eam look at a mach eimploe example where there are anly five molecules Fig D shows two gaz are. The left-hand jar containe five molecules af bramine and the right-hand jar contains no rnotecules,{ci stiafyingto mate inks betoreen topics in chemi, If youmatiply the Botzmann onstant (1.38 » 10-23) by the ‘Avogdro constant (602 + 4023). ‘youvill get 831. This isalso Acuna the gas constant, which you should remernber ‘fom PY = nT in Tope ¥ (Book 1: 145) Ferme of rami stat of he har jar @ @ AB 200" as hve ela mnened, haere as ne ee to ren erwDON a jara Aig. Offuscri ma gat one ofthe yay the matacules present but have not been dhown ange Remeber that sr reales ae als Each molecule has twa possible arrangements con be in either the left-hand jar or the right-hand jae We can-write the number of passible arrangements for molecule 1143 M7, and the number of possible ertangements for molecule 2 03 W, and 30 on Ad there aie two possible arrangements far molecule 1, W = 2. For'malecule 2. W = 2, and ga on. ‘The equation for the toiaf number of ways FY, har the five melecules can be arranged is given by WS Wh Wi WS Wa ‘Most of the 32 passble arrangements have molecules in both jars. Only cne has al five molecules in the left-hand jar It would be surprising if this arrangement happened very often I. we increase the rumber of molecules t0 100, W'becomes 2°, The lef-hand gas jar would comain all 100. molecules only once in every 3.2. 10% years! We would have fo walt for a very long time indeed to see a 100 ractecules:in the left-hand jar You can see that as she number of molecules increases, the nuriber of posable arrangements also inereases very rapidly. To make the numbers easier to work with we need {o.use an equation to helps us, You do not need to remember the equation, but ithelpsus tasee how the spuesding out of the molecules i relaicd io an increase in entropy. Entrooy. 5. feiked to Wby the equation S= xn ‘where Histhe number of ways of arranging the molecules, kis 2 constant called the Boltzmann constant, with a value 138 x 10° K" and in isthe natural loganthm (ie. the loganthm to the base 2 Ennroy is measured in units of JK"! malt Entropy measures the degree of randomness, so you would expect a gas to have a larger entropy than is quid form, and a liquid to haye a larger entropy than its soll farm, The figures in table & show that thi is the case for water vapos, water anc ice. ‘pater vapour I 189 [ 48 ‘table Anes over vapour water naive DISTRIBUTION OF ENERGY “The mpreading out of molocutes in diffusion is an ineveasa in entropy, because the molecules become ‘more randomly dispersed, Inthe esme wry, the epresding out of heat energy also represents an increase in entropy, Enemy exists m ‘packets’ called quanta, You can have a whole number of quanta, butnct halves or frctions of quantaTOPIC aera) The distribution ofthe quanta between molecules is rendam. The more quanta there ae the more ‘ways there are af arranging them between the molecules. Also, the more molecules there are, the more ways there are ef sharing the quanta, ‘As an example, table B shows that there ore five possible arrangements of four quanta between two molecules, Table © shows that there are six possible arrangements of five quanta between to molecules Table D shows thor there are 10 possible arrangements of three quamta between three molecules table B table C table D i EE [2 3 2 Oo [3 o 4 4 Zz oO Ti a oO lz aris, 10 wagers ‘The higher the ternperare, she mors energy substance has: The more energy 4 substance has, the mare ways there are-to distribute the energy The mone ways there arto ciscriure the energy, the higher the entropy So. increasing the temperature will ineresse the entiopy. PERFECT CRYSTALS: A perfect exystal it one in which the imesnal latice stucture i the same at all times In ether wards, the particies (tame, molecules oF ions) are fad ad arenat moving in any way, rotating ce vibvating, ‘The Thitc Low of Thermodynamics stetes that the entropy of a perieet crystal at the Lemperanure of absolute 2eto (12.0 K)is 2810 ‘THE SECOND LAW OF THERMODYNAMICS. ‘The Second Law of Thermodynamics & sometimes misquoted. You may have come aetoss the ‘Satement that ina spontaneous change, entropy abvays increases. This cannes be ue. if Ic were, water could never ‘iteeze because this Change Involves decrease in entropy Another example is the reaction between ammonia gas and hydrogen chlonde ges: NHL(g) + HCA) —- NHC) Clearly there isa reduction in the entropy of the system, since 1we gases are forming aoa, yr thie reaction occur sporansoutly at room temperature “The statement puropy chun ncracee is almest correct It needs to bo expressed marecarellly to ‘give the Second Law of Thermacynamics Ina epontaneous process the loll entropy increas InSection 124.2, we explcin what is meant by the term ‘total entropy! Greats 11. For each ofthe following. predict whetherthe change is accompanied by an increase ora decrease! total entropy, (a) 4.01) =H.00)—(b) We) —Ile) (eal) Nas) 2. Arrange the following in ender of enrapy. wth the lowest fst ‘seam at 110°C; cet “10°C: water at 30°C Ta ed ‘enteopy a property of matter shat i assocated with the dages of diarder or degree fof fandoniness, of partic (te. atoms, malaeulas pr ions), ae ‘alsa with the datribution oF the ‘quanta of energy Letween the aictes sponuaneous process & process ‘hat takes place without ‘eontinucus iiervention by usaaa paeraics PWR OT UML a aa 12.9(i)) 1240 | 4217 Paes | Understand that the tolal entropy change of any ‘eaction Is thesum of the entropy change of the system and the entropy ‘change: the surraundings, summarised by the expeessian: Sci = Aim * ASarciang Im Beableto calculate the entropy change of thesysterr for a reaction, AS na given the entropies ofthe reactants and products, lm Beable te calculate the entropy change of the surroundings, and hence AS... using the expression AS, =H IM Understand that the feas/bilty of areaction depends on: (i) the balance between ASvsun ad AS. $0 that even endothermic reactions can occur spantaneously at room ‘temperature (i) temperature as higher temperatures decrease the magnitude Of45.y..cgnq,S0its contibution to AB, is ess 1 Understand that reactions can occur as lang as. Sy is pasitive evan if one of the other entropy changes Is negative. 1H Understand! and distinguish between the concepts of thermodynamic stability and kinetic stability TOTAL ENTROPY CHANGE, ASii.0 ‘The total entropy change nf a process comprises two component: + the entropy chenge of theaysiem, AS ja. end + the entropy change of the surroundings. A Swen aage Ina chemical reaction, the system isthe species that are taking part in the reaction ‘The surroundings is everything else. th prbttice, this usually means the neacton vessel eg: test tube tarbeaker, end the air in the 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 i: Mus = Apa Seeman Fora reection to be spontaneous, AS,.4 must be positive. This is'anather way of expressing the Second Law of Thermadynamics, iD YOU KNOW? The official definition ofthe Second Law of Themodynarnics daes nat use the term “ote entropy change’. Instead, it refers to the “entropy change of tha univers. These two terms have the same ‘ieaning, We will use the term “tote entropy change’ threwghout this book. ENTROPY CHANGE OF THE SYSTEM Supp '5 calculated using tho expression ASypon = 35 (products) ~ ES yeactants| where § repretencs entropy and represents ‘the sum cf ‘The standard entropy values of some substances are shown in table A, Standard refers to concivions of 100 kPa and'208 K.ars wae Nag Sor An examiner may ask you to Hct) a9 suggest why the sandacd [H0g) HOM. i 1068 cHOH a ‘entropy vaiue cf dlarmond is 7 = ue ——| z Newer than that of sraphite 05.0 CHCHON | 1607 Grice ceceren a tes N 6 GH, 1728 sdimensions [a 30 lace). 1650 - ‘whereas graphite is ordered in = two dimensions and has greater 2136 degrees of freedom between NH, 1523 the layers, table A Cau Use the values in table A to calculite AS%, forthe loliwing reactor ls) C206) + COME! SHCaDIs|| + S4CO.gl ~ S4CACO 36-923 +1404) mot! WORKED EXAMPLE 2 Use the ales i table A to calculate ASS, forthe following action + 2NH Jet STNdall- 3 S*H.i}] =(2 1923) 191 6-(3* 1906) = 1988)! met! ENTROPY CHANGE OF THE SURROUNDINGS ‘The entropy change of the surroundings, AS sears: reaction, Ai by the expression AH ed to the enthalpy change of the MSemmnsigs where Tig the temperanne in kein Foran sraifarmic reaction, where AW s negatve, AS, cf the surroundings sncroases amanda, Wall alvraye be positive, 60 the entropy Conversely for an eiditheric reaction, AS. yenige Wl AWARE be negative, sc The enoopy of the sarmoundings dacmaset Cea us LER CUBE AS, any 2¢298 Kien one mole of hydrogen gas bumes i Oner “Note that entropy values ae eee Hill JOg)—H0)) AH -286 8 rot shereas enthalpy changes cal comune ae any enuation inking AS anch ‘AH, eno the anergy tenn = +0560 8 Koh! or+860} K” mot Wena Nene: CALCULATING THE TOTAL ENTROPY CHANGE, SS, ‘Now that weknaw how ta calculate bath AS... and AS, mistope WEArP i apostion © caleulate the total eniropy change, AS... for a reactionRomar ea Tee ad attr WORKED EXAMPLE 4 Using the information in table A. ca‘cate the eta entropy change at 298 K forthe Following reacton Halal + Ofe)— HLOOL Sits 286 kj mal! O] ~ SIH, lg} EO] 9-9-1306 ~{f = 205) ==1682) 1 md 1632) 6 md! 960) K" mot 247968) a! Sun SUMMARY AS Will be positive i + both SS acs and AS, uy ae postive + ASveranang 3 Positive and AS, qq i Regative, but the magpitude OF AS nq of AS, + ASuanare Of SSyony THERMODYNAMIC AND KINETIC STABILITY ‘The reaction between methane and oxygen is exothermic, and the total entropy change has & positive value CHyg) + 204(g) + COXg] + BHO) AN Sout > the magnitude s negative and Sens noite, butte ragritude oF ASsuminaye the magnitude Since AS. «is positive, the reaction Is thermiodynamically easibie at 298X However the reaction {does nor take place until the reaction mixsure ia ignited. usually with a flame ‘The added heat energy is required to avercome the bigh activation energy of the reaction, ‘A reaction mixture with a high activation energy, where a reaction will not take place spontaneously at room temperature, is sald to be kinetically stable. You cen see here that & reaction micture (such as methane and axyygen) can be therenodynarnieally Unstablebut kinetically table, s0.a reaction dacs not take place under standard conditions THE ROLE OF TEMPERATURE ‘The increase in entrapy obtained by supplying a cestain amount of heat energy to.an object depends on the temperature af the system IF an object is very eal the molecule: are not moving arsund very muck Supplying some hear lenargy to the object will make the malecales move arcune more. go the entropy IF we supply the samme amount cf heat eneagy fo.a mck hotter abject, the entsopy wil sill incease thant by as much as withthe cold object, This is because n the hot dbject the molecules are already moving arcund vigorously and the Incressed degree af movement is less forthe bat cbjec. WHY DOES WATER FREEZE? ‘We wil now apply these principles to explain why, under certain conditions, water wil freeze Joe has lover entropy than liquid water 30 AS. [8 negate: ‘The proces is exothermic. £0 AS, ssanal8 ese themagnitude ot AS oping > emagnitude Of Ay the AS is paste and the water will eeze A AGA Viny