OCR A level hematin 4. bn BCDC = David Scott coe Mie miied PEARSONPublished by Pearson Education Limited, 80 Strand, London, WC2R ORL. ‘worwepearsonschoolsandiecolleges cake “Text © Pearson Education Limited 2015 Eaited by Sue Gardner and Sharon Thorn Designed by Elizabeth Arnoux and James Handion for Pearson Education Limited “Typeset by Tech Set Lid, Gateshead Original ilustrations © Pearson Education Limited 2015 Ilustrated by Tech Set Ltd, Gateshead Cover design by Juice Creative Picture research by Chrissie Mertin Cover photo/illstration © Selence Photo Library Ltd: Eye of Science ‘The sights of Samantha Holyman. Victoria Stutt and Dave Scott to be identified as authors of this ‘work have been asserted by them in accordance with the Copyright, Designs and Patents Act 1988. First edition published 2008, ‘This exition published 2015 1817 1615 10987654321 British Library Cataloguing in Publication Data A catelogue record for this book is available fiom the British Library ISBN 978 1 447 99081 9 Copyright notice Al rights reserved. No part of this publication may be reproduced in any form or by any means (inchiding photocopying or storing itin any mediumby electronic means and whether or not transiently ‘or incidentally to some other use of this publication) without the written permission of the copyright ‘owner, except in accordance with the provisions of the Copyright, Designs and Patents Act 1968 or ‘under the terms of @ licence issued by the Copyright Licensing Agency, Saffron House, 6-10 Kirby Street. London ECIN 8TS (www.cla.couk). 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For more information about the endorsement process please vist the OCR website wwwtoccorgukAcknowledgements ‘The publisher would like to thank Adelene Cogill, Chis Curtis and Chris Ryan for their contributions to the Maths sklls and Preparing for your exams sections of this book. ‘The authors and publisher would like to thank the following individuals and organisations for permission to reproduce photographs: (Key: b-bottom; c-centre; Heft; eight; Heop) ‘Alamy Images: Justin Kase 208x 112br Michael Neelon 111, Simon Dack 138: Fotolia.com: ‘Alex Yeung 93 (2-L), fla 52-3, Philippe Devanne 48; Getty Images: David Becker 84, Stockbyte / Comstock 44; Martyn F.Chillmaid 65, 74,93 (3). 94, 105, 107, 108, 109, 110, 164; Pearson Education Ltd: Trevor Cifford 67br 184: Science Photo Library Ltd: 83-9, 101, Andrew Brookes, [National Physical Laboratory 182-3, Andrew Lambert Photography 8-9, 73bl, 73br, 7,112, 115, 132, 134, 136, 137t, 148-9, 172d, 172bl.173tr, Astrid & Hanns-Fiieder Michler 95t, Biophoto Associates 144, British Antaretic Survey 116, Charles D. Winters 29, 38, 96, Cive Freeman, The Royal Institution 170, Colin Cuthbert 188, Dennis Schroeder. NREL. / US Department of Energy 187, Dick Luria 95b, Food & Drug Administration 185, GIPhotoStock 67el, JC. Revy, ISM 106b, Jerry Mason 104, Laguna Design 120-1, Martyn F Chilimaid 16,24, 34, 1376), 173cr, 173br Patrice Latron / Look at Science 123, Paul Rapson 165, Power and Syred 106t, Sebastian Kaulitzk 154; SciLabwere Ltd: 172th Shutterstock.com Martin Kemp 93 (2-R), Ron Ells 93 (2-C), $ Borisov 93 (1), Syda Productions 70 All other images © Pearson Education ‘We are grateful to the following for permission to reproduce copyright material, Article on page 48 from Mussels don’ stick around in acidic ocean water, http: /wwwdeilyclimate, (org/tde-newsroom/2014/09/acidification-mussels, Sep 9, 2014. By Miguel Llanos and The Daily Climate; Article on page 84 adapted from Hydrogen gets onboard, Chemistry World, Merch (Gutowski M, Autrey T 2008), Royal Society of Chemistry htrp:/ wirwrsc.org/chemistryworld/ Issues/2006/March/HydrogenOnBoard.asp. Article on pege 116 adapted from Survie Bratally Cold Temperatures Posted by Stefan Sirucek in Weird & Wild, http./ /newswratch nationalgeographic. ‘com/2013/07/10//olue-biood-helps-octopus-. National Geographic. Article on page 144 adapted from Pesticides linked to vitamin D deficiency, Chemistry World, January (King, A 2012), Royal Society of Chemistry hitp / /wwwrse org/chemistrywoild/News/2012 /anuaty /pestcides-celt- vitamind- deficiencyasp: Article on page 178 adapted from The sweet scent of success, Chemistry World, February (Davies, E 2008), Royal Society of Chemistry htte://www1scorg/chemistryworld/ Issues/2009/February /TheSweetScentOfSuccess asp: Article on page 202 adapted from Making pain history, Chemistry World, March (Sutton, M), Royal Society of Chemistry httpe/ /wwvkrsc.org/ hemnistryworld/2012/12/aspirin-historyHow rouse this book Module 5 Physical chemistry and transition elements 5.1 Rates, equilibrium and pH S.1.1 Orders, rate equations and rate constants 5.1.2 Concentration-time graphs 5.1.3. Rate-concentration graphs 5.1.4 Rate-determining step 5.1.5. The ellect of temperature on rate constants 5.1.6 Equilibrium 5.1.7, Equilibrium and X, 5.1.8. Equilibrium constants and their significance 5.1.9 Bronsted-Lowry acids and bases 5.1.10 Acid-base reactions and K, 5.1.11 Calculating pH of strong and weak acids 5.1.12 The ionisation of water and K,, 5.1.13 Buffers 5.1.14 Neutralisation — titration curves Thinking Bigger: Ocean acidification Practice questions 10 4 16 19 2 23 26 28 a1 33 36 39 42 45 48 50 52 5.2.1 5.22 5.2.3 5.24 5.25 5.26 5.2.7 5.28 5.29 5.2.10 Standard cell pot 5.3 5.3.1 5.3.2 5.33 5.34 5.35 5.36 5.3.7 5.3.8 Energy Lattice enthalpy Born-Habet Further Bor le calculations Haber cycle calculations Enthalpy change of solution and hydration Entropy Fiee energy Redox Redox titrations Standard electrode potentials, hinking Bigger: Hydrogen fuel cells ‘Transition metals yansition metals Transition metal compounds ansition metals and complex ions Ste Ligand substitution in complexes Ligand substitution and precipitation reactions Redox reactions sting for ions Thinking Bigge Practice questions isomerism in complex ions Dctopus adaptations 52 54 58 60 62 66 69 n 3 1 80 04 86 88 80 93 97 100 104 106 109 114 116 118Module 6 Organic chemistry and analysis 6.1 6.14 on 6.1.3 6.1.4 6.1.5 6.1.6 6.1.7 6.1.8 6.1.9 Aromatic compounds, carbonyls and acids Benzene and its structure Naming aromatic compounds Electrophilic substitution Helogenation and Friedel-Crafts Phenols Electrophilic substitution in aromatic compounds Reactions of carbonyl compounds Characteristic tests for carbonyl compounds Carboxylic acids 6.1.10 Esters 6.1.11 Acyl chlorides 62 6.2.1 6.2.2 6.2.3 6.2.4 6.2.5 62.6 6.2.7 6.2.8 6.2.9 ‘Thinking Bigger: The impact of pesticides Practice questions Nitrogen compounds, polymers and synthesis Basicky and the preparation of amines Reactions of amino acids Amides Chirality Condensation polymers Hydelysis of polymers Extending carbon chain length Reactions of nitriles Substitution reactions in aromatic compounds 6.2.10 Practical skils for organic synthesis 6.2.11 Synthetic routes in organic synthesis ‘Thinking Bigger: Chart toppers Practice questions 120 122 124 126 128 130 132 134 136 138 140 142 144 146 148 150 154 158 158 160 164 168 163, 170 172, 174 178 190 as 6.3.1 6.3.2 3.3 634 635 6.3.6 6.3.7 Analysis, Chromatography “Tests for organic functional groups Introduction to nuclear magnetic resonance Carbon-13 NMR spectwoscopy Proton NMR spectroscopy NMR spectra of OH and -NH protons Combined techniques Thinking Bigger: Making pain history Practice questions ‘Maths skills Preparing for your exams Glossary Periodic Table Index 182 184 186 187 189 193 197 199 202 204 206 210 218 zai 222How to use this book Welcome to your OCR A level Chemistry A student book. In this book you will find a number of features designed to support your learning RATES, EQUILIBRIUM Chapter openers aoe Each chapter starts by setting the context for that chapter's learning, + Links to other areas of Chemistry are shown, including previous knowledge that is built on in the chapter and future learning that you will cover later in + The All the maths you need checklist helps you to know what maths skills will be required, Main content The main part of the chapter covers all of the points from the specification you need to learn, The text is supported by diagrams and photos that will elp you understand the concepts. ‘Within each topic, you wll fd the following features: + Learning objectives at the beginning of each topis highlight what you need to know and understand + Rey terms are shown in bold and defined within the relevant topic for easy reference. + Worked examples show you how to work through toxi0* aoxi domi ° rte/molern”*s"! 0 02 04 G6 OB 1 (| / moter» Figure 6Cc Rate-determining step By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: © explanation and use of the term: rate-determining step » fora multi-step reaction, prediction of: (i) a rate equation that is consistent with the rate-determinina step (id. possible steps in a reaction mechanism from the rate equation and the balanced equation for the overall reaction Pccy perivrioNs ‘reaction mechanism sa series of steps that together make up the overllreaction The rate-determining step i Ue slowest step inthe reaction mechanism of 2 multi-step reaction. ‘intermediate is 2 specios formed in one step of a mutt step reaction thats used up ina subsequent step, and is ot sen as either a reactant 0¢a product ofthe overall ecuation. The rate-determining step Reactions can occur in one step or in many steps. Experimental results can be used to predict how many steps will occur during a reaction, The series of steps that occurs during a reaction is called @ reaction mechanism Some of the steps involved in the reaction mechanism can be slower than others +The slowest step in the reaction will dictate how quicky the reaction can proceed, This slowest step is called the rate- determining step. + When you measure the rate of any reaction that has a mult step reaction mechanism. you are effectively measuring the rate of this rate-determining step. Predicting reaction mechanisms from rate equations ‘As you have learnt in previous topics, some reactants have no influence on the rate of reaction. These reactants have an order ‘of ze70 and do not appear in the rate equation. If they have no influence on the rate, they cannot be involved in the rate- determining step. Consider the hydrolysis of bromomethane: CH,Br + OH CHLOH + Br ‘The rate equation is: rte = & [CHsBr] ‘+ This shows that only the concentration of CH,Br influences the rate. Therefore, only this molecule is involved inthe rate- determining step. + This suggeste that the rate-determining step must involve the C-Br bond breaking, before the OH” can take its place: Step 1: CHsBr + CH,* + Br ‘Step 2: CH," + OH” — CH,OH + In this exemple, CH," must be involved inthe second step in order to be ‘used up’, as it does not appear in the overall equation. + The species involved in the two steps cancel one another to leave the overall equation. ‘Areaction mechanism isa detailed description ofthe way in which a reaction occur. Isa sequence of steps which leads from reactants to products. ‘Chemists propose mechanisms using rate equations derived fem ‘experimental data and balanced equations fr the overall reacton. Mechanisms can be proven wrong, though! They are, at best ‘educated guesses’ and tentative explanations of chemisty that fe the ‘experimental evidence. Orders and the rate-determining step For any reactant shown in the rate equation, the order attached ‘wit tells us how many molecules of it are involved inthe rate- determining step. If we again consider our example of the hydrolysis of bromomethane, the rate equation is: rate = & [CH,Br] + (CH,Be is raised to the power of 1 (remember a 1 isnot shown in the rate equation). + ‘This means thatthe rate-determining step involves just one molecule of CH,Br + If the order is 2-with respect 10 a reactant. eg rate = &(X there will be two molecules of this reactant involved in the rate-determining step. Doubling the concentration of each of the two molecules will double the rate so overall the rate is quadrupled.Determining the reaction mechanism ‘The overall balanced equation does not tell you anything about the reaction mechanism, The reaction mechanism must be ‘worked out by looking at the rate equation and ensuring that: + arate.determining step is given that involves the number of molecules show by the orcer for that reacta + subsequent steps are shown that eventually generate the products shown in the balanced equation + any intermediate generated is not present in the overall ‘equation (ie. it is used up within subsequent steps) Ee ‘Whiting reaction mechanisms caa feel a bit uncomfatable as you may ed to se species that are nat present. in the overall equation and steps that you are not familiar with. Use the reactants you have identified that ae in te rte-determining step In your frst step and then introduce other molecules from the overall equation in the Later steps In each step, ty to generate atleast one product which appears in the overal. equation. Its unusual for more than two molecules to colide during a reaction so try tolimt steps to: + one molecule (eg. decomposing) + 1mo molecules (eg, colliding). RON Niogen donde. NO reac wit carbon monoade. CO to form ntogen ‘monoxide, NO, and catbon dice, CO, NO{) + COG) —- NOI) + COs) The ovr balancod equation tolls you that 1 met NO, eaets with 1.mol Cota to produce 1 mol NO) and 3 mol CO) ‘The results of tate expaiments cate out on ts reaction show thatthe reaction i: + second ordar with espace NO, + zero order with spect 10 6. This ives the at equation rate = KINO, Ts ate equation tls us that two molecules of NO; wl be invlved in the ate determining step The two mecules of NO; goon the Ltchand side ofthe equation for the ote determining stp, Use this ste frst step in your eaction mmechenism. NO, +NO, — 2= the stow, ratedetemining stop + The ate-etermining tep muse flowed by fut fas steps. + Tooethet the sum of all the teps musta up to ive the overall equaton ‘We ul propose a tuo stap mechanism for this action We fst Summatse what we know so fa. + sts NO,+NO, +? slew, rate dotermining step + 2ndsiep atts + Overall equation NO, +CO + NO «CO, 20 (CO end CO, must be involved inthe secend step because they ae in the overal equation: + The CO must be used up In order to praduce CO, + Any intermediate we make fiom tie two molecules of NO, must also be used up, NO; must be a product of the second step because one molecule of NO; ‘sn the overall equation First addin CO: + Aststep NOp+NO» =? slow, ate-deerrining step + 2nd step 2 £00 NO, 4C0, fast + Overall oquation NO, +O —> NO + CO, "Now work out nhac was formed inthe fist rae-devermining) step. + NOs must be present in the second step to react with CO to form NOs and Co,, + So, to gonerate NO, forthe second step. the first step mst be NO; +NO, = NO; + NO. + This gves us the products ofthe fist step, NO and NO, The completed mechanism is: + Aststep NOp+NO» NO-NO slow rete-deterrining step + ndstop NO, +CO + NO, +-CO, fast + Overall equation NO, +CO > NO + CO, Notice that NO, was generated as an intermediate. Intermediates ere shortsved speces. The NO; intermediate in this examples used up an therefore doos not appoar in the overall equation, The rate-detesining step isnot neces: ‘mechanism, the fst step in a reaction Que: © tre catedernng sto eatn etnen Xan Yi: 22 Predict the ato equation fr tis eatin © ss12520 manos an oygonreas oat: inte on taunt 20.) 16) ~ 20) tha te pation rn acto t= KINO feria ueteees atte carl (Wha dos ate eatin el you abut te e-em to (6 saps pesble rep mechan sete,constants understanding of: The effect of temperature on rate By the end of this topic, you should be able to demonstrate and apply your knowledge and 2 qualitative explanation of the effect of temperature change on the rate of a reaction and hence the rate constant the Arthenius equation: (i) the exponential relationship between the rate constant, k, and temperature, T, given by the ‘Arthenius equation, k= Ae"s*" (i) determination of E, and A graphically using: in k= ~£,/RT+ In A derived from the Arrhenius equation The rate constant, k Reaction rate depends on both the rate constant and the ‘concentrations of the reactants present in the rate equation: rate = (ABP ‘The larger the value of & the faster the reaction. The effect of temperature on the rate constant, k ‘An increase in temperature gives more energy to the molecules, ‘This means that collisions ate more frequent, and more of the collisions exceed the activation energy of the reaction. This was ‘explained in terms of the Boltamann distribution (see Book 1 topic 3.29), ‘The key fector affecting the reaction rate is the number of collisions that exceed the activation energy. This means that rate increases with temperature by much more than can be explained solely ftom any increased frequency of collisions, Look at the rate equation above —if the rate increases with increasing temperature when the concentrations are the same, then the rate constant must increase with temperature. «+ Raising the temperature speeds up the rate of most reactions by increasing the rate constant. k ‘+ Formany reactions, the rate approximately doubles for each 10°C increase in temperature. This reflects the greater number of reacting particles that exceed the activation energy, + Typically, doubling the rate will double the value of the rate constant, Let us look at an example reaction, Sodium thiosulfate and hydrochloric acid react as follows: Na,S,0 aq) + 2HClaq) —+ 2NaCiaq) + S(e) + $O,{aq) + H,0() The change in & with temperature for this reaction is shown in, Figure 1 2 @ 9 70 a 90 1M temperarure/*C Figure 1 The rate constant for the reaction between sodium thoslface and hpochirk ed increas wit increasing terperare The Arthenius equation ‘The Arrhenius equation is used to describe, mathematical che exponential lationship between the rate consent and the temperatre The Archenss equation where: + k= rate constant + A= pre-exponential factor + R= gas constant cemperature (in kelvin) +e = mathematical constant with the value 2.71828, This is known as the inverse natural log.‘What can the Arrhenius equation tell us? ‘An example is shown in Figure 2. ‘Tobe able to react, molecules have to collide with enough energy to overcome the activation energy, It has been found that at any sgiven temperature, T, the rate constant, & is proportional to 4 This is expressed mathematically as k e"F'*, ‘This can be turned into an equetion by adding a constant, the ‘pre-exponential factor, 4, giving k= Ae “v'"” This is the Arthenius equation. ‘The Arthenius equation tell us that: + temperature, 7; and the rate constant, k are related exponentially gradient = -£/2 + as temperature increases, the rete constant increases. s ‘Adding 2 catalyst provides an alternative reaction path with a lower activation energy. £, If you follow this through ‘mathematically, lower value of E, increases the rate constant, & 1 doa aoara 0.0016 0018 Arrhenius plots ut “Taking loganithms of the Arthenius equation Fgure 2 A typical ai fn Keasinst 1/7, sing the expression a sequal tin x's equal to 1/7 m seal ice graient.~ 6/8 ad os Ink=Ina~ BX qual tothe intercept. In Ifa given reaction is cartied out at varying temperatures and the ‘aloo of the rte constants calculeted for each temperature, a staph of ink can be plotted against. Such graphs are referred ‘as Arrhenius plots ‘This logarithmic version of the Arrhenius equation follows the general pattern y= m+ 5 ESAT py Qu Pie tlecaliy i © A rocionbewoon xand yas card ext trios tempers ‘An Anheis lt canbe wed identi: gies ai eae a a ecto e| + A theintercept onthe graphisequalto ind Use theres om the experimen to daw an Aton lot ‘+ the activation energy. E,; the gradient is equal to—>°. where Ris the known gas constant, so this can be Weatranged easily to find £,. 10 249% 10-* 20 740% 10 (0 184% 107 0 4755107 5 745x107 Or sire cherie ceoreen te ene coo ee © cate pre epneria far, entrap the fates pat als ooas 224