OCR A level hematin 4. bn BCDC = David Scott coe Mie miied PEARSONPublished by Pearson Education Limited, 80 Strand, London, WC2R ORI. ‘www pearsonschoolsandtecolleges.couk ‘Text © Pearson Education Limited 2015 Ecited by Sue Gardner and Sharon Thor Designed by Blizabeth Arnoux and James Handlon for Pearson Education Limited ‘Typeset by Tech Ser Ltd, Gateshead Original illustrations © Pearson Education Limited 2015 Ilustrated by Tech Set Ltd, Gateshead Cover design by Juice Creative Picture research by Chrissie Martin Cover photo/illustration © Science Photo Library Ltd: Eye of Science ‘The rights 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. 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For more information about the endorsement process please vist the OCR website www.ocrorgukAcknowledgements ‘The publisher would like to thank Adelene Cogill, Chris Curtis and Chris Ryan for their contiibutions to the Maths sills 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: e-centre; Heft right; top) ‘Alamy Images: Justin Kave 2D8z,112br, Michael Neelon 111, Simon Dack 138; Fotolia.com: ‘Alex Yeung 93 (2-L), aula 52-3, Philippe Devanne 48; Getty Images: David Becker 84, Stockbyte / Comstack 44; Martyn F Chillmaid: 65, 74,93 (3), 94, 105, 197, 108, 109, 110, 164; Pearson Education Ltd: Trevor Cifford 67br, 184; Science Photo Library Ltd: 88-9, 101, Andrew Brookes, National Physical Laboratory 182-3, Andrew Lambert Photography 8-9, T3b, 73br 77, 112, 115, 132, 134, 136, 137t, 148-9, 172cl. 172b1, 173, Astrid & Hanns-Frieder Michler 95t, Biophoto Associates 144, British Antarctic Survey 116, Charles D. 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Revy, [SM 106b, Jerry Mason 104, Laguna Design 120-1, Martyn F Chillmaid 16, 24,34, 137b), 173cr, 173br Patrice Latron / Look at Science 123, Paul Rapson 165, Power and Syred 106t, Sebastian Kaulitz 154; SciLabware Ltd: 172th Shutterstock.com: Martin Kemp $3 (2-R), Ron Ellis 93 (2-C), $ Borisov 93 (1), Syda Productions 70 Al other images © Pearson Educetion We are grateful to the following for permission to reproduce copyright material -Atiele on page 48 from Mussels don stick around in atte ocean water, hit://wwwrdallyiate, org/de-newsroom/2014/09/acidifcation-musses, Sep 9, 2014, By Miguel Llanos and The Daly Climate; Article on page Bd adapted from Hydrogen gets onboars, Chemistry Weld, March (Cutoviskd M, Autrey T 2008), Royal Society of Chemistry hep: //wrerse.org/chemistryworid/ {ssves/2006/March/HydrogenOnBoard.asp; Article on page 116 adapted from Survive Brutally Cold Temperatures Posted by Stefan Sirucek in Weird & Wild hitp://newswatch.nationalgeographic. ‘com/2013/07/ 10/blue-biood-helps-octopus-. National Geographic, Article on page 144 adapted from Pesticides linked to vitamin D deficiency, Chemisiry World, January (King, A 2012), Royal Society of Chemistry hetp/ /wowesc omp/chemistryworld/News/2012/ January /pesticides-dat- vitamind- defciencyasp; Article on page 178 adapted from The sweet scent of success, Chemisry World, February (Davies, E 2003), Royal Society of Chemistry htp://wwwsc.org/chemistryworld/ {ssues/2009/February/TheSweetScentOfSuccess asp: Article on page 202 adapted from Making pain history. Chemistry World, March (Sutton, M), Royal Society of Chemistry htp://wwwassc.org/ ‘cheenistrywork/2012/ 12/aspinn-historyHow to use this book Module 5 Physical chemistry and transition elements 5.1 Rates, equilibrium and pH Sil Orders rate equations and ate constants 5.12 Concentation-time graphs rivaton graphs 5.14 Rate-determining step 51.5 Theeffectoi 5.16 Equibrum 5.17 Equilibrium and K, 5.1.8. Equilibrium constants and their significance 5.1.9 Bromsted-Lovery acids and bases 5.1.10 Acic-base reactions and K, 5.1.3. Rate-con erature on rate constants 5.1.11 Calculating pH of strong and weak acids 5.1.12 The ionisation of water and K, 5.1.13 Butlers 5.1.14 Neutralisation ~ titration curves ‘Thinking Bigger: Ocean acidification Practice questions 10 14 16 19 a 23 26 28 31 33 36 39 42 45 48 50 52 5.21 5.22 5.2.3 5.24 5.25 5.26 5.2.7 5.28 5.29 Energy Lattice enthalpy Born-Haber evel le calculations Further Born-Haber cycle calculations Enthalpy change of solution and hydration Entropy Free energy Redex Redox titrations Standard electrode potenti 5.2.10 Standard cell potentials 53 5.31 5.3.2 5.3.3 5.34 5.3.5 5.36 5.3.7 5.38 Thinking Bigger: Hydrogen fuel cells Practice questions ‘Transition metals Transition metals, Transition metal compoun Tyansition metals and complex ions ‘Sterecisomerism in complex ions Ligand substitution in complexes Ligand substitution and precipitation reactions Redox reactions Testing for ions ‘Thinking Bigger: Octopus adaptations 52 54 58 60 62 66 6 n 2B 7 80 a4 36 88 90 93 97 100 104 106 109 114 116 118Module 6 Organic chemistry and analysis 6.1 Aromatic compounds, carbonyls and acids 6.1.1 Benzene and its structure 6.1.2. Naming aromatic compounds 6.1.3 6.1.4 Halogenation and Friedel-Crafts 6.1.5 Phenols 6.1.6 Hlectrophilic substitution in aromatic compounds 6.1.7 Reactions of carbonyl compounds 6.1.8 Characteristic rests for carbonyl compounds 6.1.9 Carboxylic acids 6.1.10 Baers 6.1.11 Acyl chlorides ‘Thinking Bigger: The impact of pesticides Practice questions lectrophilic substitution 6.2 Nitrogen compounds, polymers and synthesis, 6.2.1. Basicty and the preparation of amines 6.2.2 Reactions of amino acids 6.2.3 Amides 6.2.4 Chirality 6.2.5 Condensation polymers 6.2.6 Hydrolysis of polymers 6.2.7 Extending carbon chain length 6.2.8 Reactions of nitriles 6.2.9. Substitution reactions in aromatic compounds 6.2.10 Praciical skills 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 46 148 150 154 156 158 160 164 166 168 170 172 174 178 180 Analysis, Chromatography ‘Tests for organic functional groups Introduet nto nuclear magnetic resonance Carbon-13 NMR spectroseopy 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 182 184 186 187 189 193 197 199 202 204 206 210 218 221 222How to use this book some 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 aot Each chapter starts by setting the context for that chapter's learning. + Links to other areas of Chemistry are shawn, Including previous knowledge that is built on in the chapter and future learning thar 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 help you understand the concepts. Within each topic, you will find the following features + Learning objectives at the beginning of each topic highlight whet you need to know and understand. + Key terms are shown in bold and defined within the relevant topic for easy reference. + Worked examples show you how to work through ‘questions, and how your calculations should be set + Investigations provide a summary of practical experiments that explore key concey + Learning tips help you focus your learning and help you remember the key concepts. Atthe end of each topic, you will find questions that cover whet you have just learned. You can use these questions to help you check whether you have ‘understood what you have just read, and to identify anything that you need to look at again, Answers (0 all {questions in this student book are available ar hrp:// viwwipearsonschoolsandfecolleges cauk/Secandary, Science/16Biology/OCR-A-level FreeResources/FreeResources aspxThinking Bigger AA the end of each chapter there is an opportunity to read and work with real-life research and ‘writing about science. These sections will help you 10 expand your knowledge and develop your own research and writing techniques. The questions ‘and tasks will help you to apply your knowledge to new contexts and to bring together different aspects of your learning from across the whole course. The timeline at the hotiorn of the spread highlights which other chapters of your baok the ‘material relates to These spreads will give you opportunities to: + read real-ife material that's relevant to your course + analyse how scientists write + think critically and consider relevant issues + develop your own writing + understand how different aspects of your learning piece together Practice questions At the end of each chapter there are practice questions 10 test how fully you have understood the learning Answers to ll questions inthis student book are avalable at itp //vwpearsonschoolsandfecolieges: ‘couk/Secondary/Science/ 16Biology/OCR-A-levl- Science-2015/FreeResources/FreeResources asp Maths Skills At the end of the book there is a Maths Skills section that focuses on key mathematical concepts to provide {greater depth of explanation and enhance your understanding through worked examples. Preparing for your exams The book coneluces wih a section that offers some practical advice about preparing fr your exams, including sample questions and answers that alow Jouto see where corunon mistakes are made and how you can improve your responses Getting the most from your ActiveBook Your ActiveBookis the perfect way to personalise your learning as you progr level Chemistry course. You can: through your OCR A. + access your content online, anytime, anywhere + use the inbuilt highlighting and annotation tools to personalise the content and make it really relevant to you + search the content quietly Highlight tool Use this to pick out key terms or topies so you are ready and prepared for revision, Annotations tool Use this to add your own notes, for example, links to your wider reading, such as websites or other files. Ormake a note to remind yourself about work that you need ta doPhysical chemistry and transition elements RATES, EQUILIBRIUM AND pH Introduction y do some reactions happen quickly and others slowly? How do we find out which reactants wil change the Speed of 2 reaction? How do we know how many steps are involved ina chemical reaction? Why are some acids Depts weak and others strong? Do all reactions go to completion. and can we affect this? Ife can find out exactly how 2 reaction occurs and what factors affect it, we can manipulate it to make itas effective and efficient as possible. This is why chemists study reaction kinetics, including rates and equilibriu Acids and bases have been known about for many yeas, but i ha taken a lot of research to fin out exactly ‘what itis that makes an acid an acid and a base a base, Aid and base reaction are some of the most important processes in many chemical and biological systems, so itis helpful to study these reactions in some deal In this chapter, you wil eatn about rates of reactions and the ways in hich ceaetions at influenced by ‘temperature, You wil aso team about the information (about reactants and reaction mechanism) that can be obtained from rate equations, rate constants and rate graphs You wil eam about how to use an equilibrium expression to determine the extent of an equilibrium reaction, and you wil find out about the role ofthe equilbelum constant in controlling the position of equilibrium, You will also lean what acids and bases are, how to calculate their pH and why theirstrengt all comes down to gulibum. All the maths you need To lock the puzzles ofthis chapter you need thefllowing mats + Recognise and make use of appropiate units in calculations le. determining te unt fo equim quoting equi + Recognise and use expressions in cecimal and ordinary form Ce + Use an appropriate numberof significa figures (e.g ng pl values) mounts using equilibrium constants) + Change the subject ofan equation (e.g. ning eq {Use exponential and logarithm functions (e.g. calculating i) + Use logarthmie scales (eg. calevating px, values) + Plot and translate graphical information, including gradtents, intercepts and tangents (.. rate graphs)How colision theory c ‘anges in conditions influenc . Dynamic eq How an equilib wre tie xan .Chatelier’s principle aleulate a ate wsing spression is wnittn Je of K, can tll yo position of equilibrium Nhi tudy in actions and How titrations and indicators ean be used to determine concentrations of ins such as Fe? é “he acidic behaviour of some organic compounds. Including phenol and carboxylic acids The basic behaviour of amines anys The acid-base behaviour of amino acids Orders of reactions: what ate determined ey ae and how they How t i ate grap, including how todetermine the rate constant for ist order What. mining step is, and how to predict rate equations that are consistent withthe ate-detsimining step How to calculate futher rate constants, includ Ko Keats Equllxiur and equlitrium constants ‘Acids and bases, including how to determine theirpH Titration curves and how they can be used to choose suitable indicators10 Orders, rate equations and rate dees By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: use of the terms: rate of reaction, order, overall order, rate constant » explanation and deduction of (i) orders from experimental data Ai) a rate equation from orders of the form: rate = KIAIPIBI?, where m and mare 0, 1 or 2 © calculation of the rate constant, &, and related quantities, from a rate equation including determination of units Rate of reaction is the change in concentration ofa reactant ora product per unit time. “The order with respect toa reactants the power 10 which the concentration ofthe reactants ralsed in the rate equation. ‘The rate constant, kis tne constant tat links te rate of reaction with the concentrations ofthe reactants raised to the powers oftheir orders inthe rate equation. The rate equation fora reaction A-+ 8 — Cis given by: ate = KAP(B)” ere m isthe order of reaction with respect to A and mis the order of reaction with respect 18. “The overall order ofa reaction is the sum ofthe individual orders, m+ 1 ‘You learnt about collision theory in Book 1. topic 3.2.7. You will recall that reactions only proceed when successful collisions occur — that is, particles must collide with the correct orientation and with ‘enough energy :o overcome the activation barrier (ie. the activation energy), How frequently these successful collisions occur will determine the rate of a reaction. Rate of react ‘The amount of reactant that is used up, or the amount of product that is made, over a given time is known as the rate of reaction, rate of reaction = S°="eeit cc reactant or product Rates are usually measured in moldm-*s-! (mol per dm? per s) but other units may sometimes be more appropriate, If 2 reacsion is very slow, a larger timescale (such as rninures) may be used. [n this case, the units would be moldm"* min". If itis dificult to measure the concentration, you may use another ‘measurement wiich allows you to monitor the amount of a product or reactant. For example if a gasis produced in reaction, you could measure the volume of gas produced ever a time petiod. In this case, the units would be om! s- Orders of reactions If more than one reactant is involved in a reaction, each reactant can affect the rate of the reaction differently. The effect of the individual reactants is described by stating an order with respect to each reactant, Consider a reactant, A. Its concentration affects the rate of a reaction, This can be expressed ‘mathematically as: rate % [AF“The orcer is always specifi to each of the reactants present. There are three main types of order Zero order If the order is 0 with respect toa reactant A. then: rate % (A) + The rateis unaffected by changing the concentration of A. + Note that any number to the power Vis equal to 1 First order If the order is 1 with respect to a reactant B, then: rate « (BJ! ‘The rate is diectly proportional to the concentration, + If [B] increases by 2 times, the rate also increases by 2 times + If [B] increases by 3 times, the rate also increases by 3 times. Second order If the order is 2 with respect to a reactant C, then: rate % (CF ‘The change in rate will be equal to the change in concentration squared, + If [C] increases by 2 times, the rate increases by 2° = 4 times. + If [C] increases by 3 times, the rate increases by 3° = 9 times. Rate reactions and overall orders ‘Chemists use rate equations to mathematically express the influence each reactant has on a reaction. ‘Take the reaction A +B + C— products If the orders for A, B and C were x, » and 2 respectively, you could write the following expression for the rate: rate = (AMBPICE “The sign for proportional can be removed if a constants added into the equation, Chemists use the rate constant, k The rte constant links the concentrations and orders of reactants to the rate. The ‘expression then becomes a rate equation: rate = MAPB)ICE If any reactant is 2er0 order then it will not appear inthe rate equation. This is because it does not affect the rate, For instance, in our example above, where the orders are O, 1 and 2 with respect t0 A, Band C, the rate equation would be: rate = HAPIBY'(C?2 However because any number raised to the power zero = 1. that reactant can be removed. Powers (of 1 can also be omitted from outside the brackets. Do not remove the reactant from the rate equation though! Therefore this rare equation would become: rate = KBI[CP Overall order ‘The averall order of a reaction is the sum of the individual orders, In the example above, rate = K(B)'{C} and the overall order is 1+ 2, whichis 3 ‘The rate equation can be determined only from experimental results. Note that the orders are not the same as the numbers used to balance an equation. Calculating the value and units for rate constants ‘The rate constant is calculated by substituting values for concentration and rates into the rate ‘equation and rearranging to find ‘The units of & depend on the overall order of the rete reaction, The units of k are determined by substituting units for rate and concentration into the rate equation, rate Zero order, rate = HA) =k units of £= molds = moldms (molds!) First order, rate = HA] units of f= order, rate = H(A] ts = MAP _iliaskeers) = dm*mor'st Second order rate = &{A) atts 0 Ta = dm'mol ia (aot *5") Third order rae = HARB) = [garg unisof k= Sao émimolts [ne eee aay 1 LOx10 | 10x10 10x10" 3.0 « 10° 2 20x10 | 10x10? 1.0% 107 6.0 10° Loxio 20x10 1.0107 3.0% 10" 10x10? | 10x10? | 20x 10° 12.0 x 10Remember that any number raised to a power of 0 is 1. Also remember thatthe power 1 does not need to be wate, You can check your conclusion by comparing other pars of experiments. LS ‘The reaction between hydrogen, Hand nitrogen monaside, NO, has te fllowing rate equation: rate = AHoINO‘g)? Ina Ld reaction vessel. 6 0 x 10 mol of Hg) and 30x 10 mol NOIg] were reacted together. The initial rate ofthis reaction was 4.5 x 10"? moldnrs Calculate the rate constant, k; fr this reaction and state it units Answer ‘+ Reartange the equation to make kthe subject rate Rg NOE 45% 10% ‘Substitute values and calculate: k= Anotdn 5) ‘poke mol 2 + k= 83 x 10cin$mol 25+ axa + Units of k= = dmémol?s Da [tis a mathematical convention that positive indices are written fst. In this example, the units were determined tobe s-tmoldm® but, following the convention thi is witen as dn‘ mols" Where there 's more than one. unit withthe same siga, they are wetten alphabetically, so mol? comes before s" Ina reaction between R, § and: ~ when the concentration af Ris doubled, the rate Is unchanged when the concentration of is quadrupled the rate increases by 16 times \When the concentration of 1s halved, the rate is halved, [a Dede he rts ith spect Sand i) Hence we dun the ate equation orth ecto, @ ete cauaton ra reacion beeen P and sate ~ APIA How wil ate change a he concanaon of is doubled 1 the concern of Qi ttt [0 th concantatons of and @ te bt let © ean betvean azoe, O44) and thee C40 has the follwing rate ean: rate ~KO¥elIC 0 baring econ, 5.0» 10 ol v2 0foeacted with 2.4 x 10% mol dv Cg The nl ate of ths maton was 10> 10-5 Cola the rate constant for hs econ ad sate its ntsunderstanding of: © from a concentration time Concentration-time graphs By the end of this topic, you should be able to demonstrate and apply your knowledge and ‘graph (i) deduction of the order (0 of 1) with respect to a reactant from the shape of the graph (ii) calculation of reaction rates from the measurement of gradients from a concentration-time fora frst order reaction, det using the relationship: ‘raph of a first order reaction, measurement of constant half-life, t, termination of the rate constant, &, from the constant half-tife, ty». ined ba the techniques and procedures used to investigate reaction rates by the intial rates method and by continuous monitoring, including use of cotorimetry The half-life ofa reactant is the time taken forthe concantation ofthe reactant to reduce by hall Chemists can use concentration-dime graphs (see Book 1, topic 3.2.7} find out about the rate and order of reactions, The shapes cof concentration-time graphs depend on the order of the reaction. Finding rates from concentration~ graphs Chemists ean use many experimental techniques ro measure concentrations of reactants or products in reaction ime For reactions involving acids or bases, we can measure: + pH changes by carrying out rtrations + pH changes by using a pH meter: For reactions that produce gases, we can measur + the change in volume or pressure + the loss in mass of reactants, For reactions that produce visual changes, we can observe + the formation of a precipitate + a colour change. Visual changes are usually monitored using a colorimeter, as the intensity of colour is directly related to the concentration of & coloured substance. Consider the example of sulfur dichloride dicxide, $O,Cl,. This decomposes to produce sulfur dioxide and chlorine: ) + SO.) + Clg) Inan experiment, the concentration of SO,Cl,(g) was monitored every 500 seconds, The results were then plotted asa graph (see Figure 1). 80,¢! ‘The rate of reaction can be found by taking the gradient of the plotted purple line, As the data have produced a curve, tangent lines must be drawn against the curve, us ‘The graph shows tangent ines at ¢= 0 (the intial rate) and at sto 1000 10 2do0 Figure 1 Aconcansation-time graph fr $0, evo 3000” 3s04do0 ‘The rates are then calculated as follows: + Alter := 0 (shown by the red, steeper tangent line change in concentration of SO.Cl time for the change to take place (0500.00) [3300 9) = 15x 10-'meldm + Aller := 3000's (shown by the green, shallower tangent line) ‘change in concentration of $0,Cl inital rate ‘32 = “Gime fr the change to take place _ (038-024 ~~ 000-0) =60 x 10-'moldm-"s Half-life ‘The time taken for the concentration of a reactant to decrease by half is known as the halflife of the reactant, Half-life is given the symbol ty, ‘You can find the order of a reaction by looking at the halPlfe on a concentration-tine graph,Zero order reactions AA concentration-time graph for a zero order reaction will have the following characteristic shape. Figure 2 Azor0 ardor reaction produces astraght Une graph with the concentration decreasing a constant rate he halite decreases with time. First order reactions A-concentration-time graph for a first order reaction will have the following characteristic shape, Figure 3A fst oer reaction produces a curved graph with constant halite and halving ofthe reactant concenvaton accuting at equal te interval Nitrous oxide decomposes wien strongly heated. as follows: 2N,019) — 249) + Osi) Determine the order of reaction for the decompesition of nitrous oxide using the following graph 1000 0.900. 0.400. 0.700 0.600. 0500 ei time/s The time is determined for every halving ofthe concentration. n this ‘example the initial concentration is 1.000 mol cn" + Half of this concentration is 0.500 mol dm 2. This concentration ‘occurs at 54. The hall- ile is 54s, + When the concentration halves again to 0.250 mol dm the time Is 108s The half life is again 54s, + When the concentation halves again to 0.125 mol da # the time is 1625. The halflife is again 54. Because the hati is constant, ths 1s an example of frst order reaction. INO(ei}/e0 dr Zo Using half-lives to find the rate constant [Because first order reactions have constant half-lives the value of the half-life can be used to determine the value of the rate constant, The halflife and the rate constant are related by the following equation: In2 “This only applies to fist onder reactions, Reaetions with other orders do not have constant halves. Presence Remember, ‘in’ stands for ‘natural lug’. There will bea button on your ‘calculator fr this function ~ usualy labelled Ln. Re ‘Work out the rate constant forthe decomposition of an alrborme pollutant that has ahalf-ufe of 3 minutes. $385 «1075+ Notice the unit for kiss. ln, which does not have units is being divided by time, which has the units. A @ sutstace x cecomposes spontaneous The concerto of subtance was monitored over tne {a ota rah ote flowing rests o | 15 | 30 040 0.28 0.19 {) Suggest whether this reaction is zero or fst order, given the shape of your srap. {o) Determine the hal-Ufe ofthe reaction and use this to explain your answer to part). (ch Ifthe initial concentration of substance X had been {L460 mol dm, what would its concentration be after 84 seconds? Tod 60 0.07 | 0.03 180 0.01 © - sev meine oun to havea gal ale of 80s (a) os ong wl take te evel fhe ruin th bay fl thon berth of agate (Clete neat constant kote reso fs dg 19 Use yr anes ea sigs hot mig eeeunderstanding of: Rate—concentration graphs By the end of this topic, you should be able to demonstrate and apply your knowledge and » from a rate-concentration graph: (i) deduction of the order (0, 1 or 2) with respect to a reactant from the shape of the graph ii) determination of rate constant for a first order reaction from the gradient Initial rates “The rate at the very start of a reaction, given the shorthand 1'= 0 (which stands for time = 0), is known as the initial rate. If a tangent line is drawn at ¢= 0 on a concentration-time graph, the _gradient ofthis line is equal to the initial rate, “To determine the order with respect to each reactant, you carry out the reaction several times. Bach time, you vary the concentration ‘of one of the reactants. You can then obtain the inital rate for each ‘of these different concentrations and plot the results eon a graph 10 [produce a rate-concentration graph for each reactant. Clock reactions Some reactions will produce visible changes, such as the formation of @ precipitate or a dramatic colour change. Measuring the time taken for such changes to occur can be used to find out how concentration affects the inital rate. Only the initial rate is considered, asthe visible changes that occur are assumed to occur asthe reaction fist happens, when the rate is generally fastest In these instances, the time taken for the visible event to occur is inversely proportional to the initial rate: the shorter the time taken for the change, the faster the reaction must be. “This ean be expressed mathematically as rato = 2 “This means that when a graph is plotted, is taken as a good approximation of the initial rate ‘ ‘An example ofthis is the reaction between sodium thiosullate, Na,S,0:, and hydrochloric acid, HCL Na:S,0 ae) + 2HCKaq) — 2NeClaq) + Ss) + SO,(aq) + 1,00) ‘Across is drawn on a piece of paper and placed under a beaker ‘The reactants are then added together in the beaker The products form a cloudy solution as a precipitate is formed, so a stopwatch is used to time how Jong it takes for the cross under the beaker to be ‘obscured by the solution. ‘The experinentisthen care ou! using varios concen OT bo sodium telltale sido determine how th eoncenvansaifet he ate graph of © apo concenon plone 16 Four 1 The wacnhewee sodum hestie ad hye ed an ‘amp la clk acto tan oe prec fomed obscure ne os eae tg aca oneentaons hen tied vn puna the ilar ech efectos Ee ‘The iodine clock reaction Ifa solution of hydrogen peroxide. 0, is added to 2 solution of potassium iodide. KI inthe presence of starch, acid and sodium thiosulfate, Na,5,0, the colourless solution will suddenly tun blue. The reaction acer in two steps H,04aq) + 2baq) + 2H" — tae) + 24,010 25.03 aa + faa)» 5,02 (eq + 21100) “The ammount of time that passes before this colour change occu isa measure of the inital rate, Plan an investigation to determine the effect thatthe concentration of each ofthe reactants has on the initial rate Orders and rate-concentration graphs ‘The order with respect to reactants can be determined by poting rate-concentation graphs The resulting graphs wl have unique Shapes foreach orderZero order If the order is 0 with respect to a given reactant, A, the rate-concentration graph will appear as in Figure 2: Figure 2 Zero ocerrate-concentiaton gh + "This graph shows that rate = [A + Changes in the concentration of this reactant have no effect on the rate. First order If the order is 1 with respect to a given reactant, B the rate-concentation graph will appear asin Figure 3: Figure 3 Fist order rato-concentraton graph, + This graph shows that rate & (B] + the concentration of reactant B is doubled, the rate will double + If the concentration of reactant Bis tripled, the rate wil bile + If the concentration of reactant B is inereased 100 fold, the rate will increase 100 fold. Determining the rate constant from first order rate-concentration graphs If a rate-concentraton graph sft order with respect toa given reactant, iti possible ro use the graph to determine the rae constant, k For frst order reactions + rate & [reactant] «this means that rate (reactant) If we rearrange this to find ke bee ‘Concentration Rate is plotted on the y-axis on a rate-concentration graph and concentration is plotted on the x-axis, 80 calculating the rate isthe same as calculating the gradient, as gradient = change in y divided by ‘change in x “The units for &will depend on the rate equation forthe given reaction,18 ‘Second order If the order is 2 with respect to a given reactant, C, the tate-concentration graph will appear as in Figure 4 Figure 4 Secané order rate-concentration gap. + This graph shows that rate % (CE. + If the concentration of reactant C is doubled, the rate will increase by 22 + If the concentration of reactant B is tripled, the rate will increase by 32. + Ifthe concentration of reactant Cis increased 100 fold, the rate will nerease by 100% (@ > ecion sence wo eas, an, ve the ate-conenztion ars show in Fgue 5 rote Figure 5 concentration (a) Determine the oer with respect to P and Q. (b) Hence write the rate equation forthe reaction Te rate equation fora reaction between Rand Sis ate (@) Determine the oder with respect to Rand S. (b) Sketch the rate-concentiation graphs for reactants and S. es ihe rent gach rosa tc ston aro Nad Yio eer soma (@) State the order with espect to X and write a rte equation (b) Use the raph to determine the rate constant forthe rection (C1 Give the units for the rate constant. 180 x 10”. 160% 10 140% 10° 120% 10° 100 x 10° 20x 10° 80% 10 40x 10". 20x 10°. a remota 25 d 02 04 08 of 1 [x/ moter” Figure 6By the end of this to understanding of: Rate-determining step you should be able to demonstrate and apply your knowledge and © explanation and use of the term: rate-determining step © for a multi-step reaction, prediction of: (i) 2 rate equation that is consistent with the rate-determining step 4) possible steps in a reaction mechanism from the rate equation and the balanced equation for ‘the overall reaction ‘reaction mechanism isa series of steps that together. make up the coveral action The rate-determining stop the slowest step in the reaction ‘mechanism ef a multi-step reaction. ‘an intermediate i species formed in one step ofa mult-sep reaction thats used up ina subsequent step. and is nt seen as ether a reactant ra product ofthe overall equation, The rate-determining step Reactions can cccurin one step or in many steps Experimental results can be used to predict how many steps will ccur during a reaction. The series of steps that occurs during a reaction is called a reaction mechanism. Some of the steps involved in the reaction mechanism can be Slower than others +The lowest step inthe reaction wl dictate howr quick the reaction can proceed. This slowest step is called the rate determining step. + When you measure the rte of any reaction that has a mut step reaction mechanism. you are effectively measuring the rate ofthis rate-determining step. Predicting reaction mechanisms from rate equations As you have learnt in previous topics, some reactants have no infitence onthe mate of reaction. These reactants have an order of zero and donot appearin the rate equation If they have no infuence onthe ate, they cannot be involved in the rate determining stea Consider the hydrolysis of romomethane CH.Br + OH CHLOH + Br ‘The rate equation is rate = k (CHBr) ‘+ This shows that only the concentration of CH,Br influences the rate. Therefore, only this molecule is involved inthe rate~ determining step + This suggests that the rate-determining step must involve the C-Br bond breaking, before the OH” can rake its place: Step 1: CHsBr —+ CH" + Br Step 2: CH," + OH” — CH,OH. + In this example, CH." must be involved in the 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, [ip Vou Now? ‘reaction mechanism isa detailed description af the way in which a reaction occu. tis a sequence of steps which leads from reactants to prodtets. Chemists propose mechanisms using rate equations derived from ‘experimental data and balanced equations forthe overall reaction, Mechanisms can be proven wrong. though! They ae at best. ‘educated guesses’ and tentative explanations of chemistry that fit the ‘experimental evidence. Orders and the rate-determining step Forany reactant shown in the rate equation, the order attached to ittells 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 = k[CH,Br] + (CH.B5] is raised to the power of I (remember a | is not 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 to a reactant, eg. rate = kX, there wil be two molecules of this reactant involved in the rate-determining step. Doubling tae 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: + amate-decermining step is given that involves the number of ‘molecules shown by the order for that reactant + subsequent steps are shown that eventually generate the ‘produers shown in the balanced equation + any intermediate generated is not present in the averall equation (ie. its used up within subsequent steps), Picsnnincrie ‘Writing reaction mechanisms can feel a bituncomfortable as you may need to use species that are nt present in the overall equation and ‘steps that you are not familiar with, Use the reactants you have identified ‘that ar inthe rate-determining step in your fist step and then introduce ‘other molecules from the overall equation inthe later steps. In each step try to generate at Least one product which appears i the overall equation. leis unusual for moce tan two molecules to colide duing a reaction so ‘ry to Limi steps to: ‘+ one molecule (e.g. decomposing! + two molecules (eg, colliding) Ponceau Nitrogen dioxide. NO. reacts with carbon monoxide. CO. to form nitrogen ‘monoxide, NO, and carbon dioxide, CO; NOx) + COlg) —+ NOV) + COs) ‘The overal balanced equation tells you that 1. mol NO) reacts with 11 mol CO( to produce 1 mol NOlg) and 1 mol CO:(9 ‘The results of rate experiments caried out on this reaction show thatthe reaction is: ‘+ second order with respect to NO; +2010 order with respect to C0, This gives the rate equation, ate = KINO, This rate equation tells us that two molecules of NO, wil be invalved in the rate-determining step. ‘The two molecules of NO, go on the left-hand side of the equation for the rate-determining step. Use this as the fist step in your reaction machanism, NO, + NO, —2= the slow, rate-determining step ‘+The rate determining step must be followed by further Fast steps. ‘+ Together, the sum of al the steps must add upto give the overall equation, ‘We wil propose a two-step mechanism for this reaction. We frst summarise what we know so fr + Aststep NO; #NO, >? stow, rate determining step + andsiep c a) fast + Overall equation NO, +CO — NO CO, 20 C0 and CO, must be involved inthe second step because they ae in the overall equation: *+ The CO must be used up in order to produce CO, + Any intermediate we make from the two molecules of NO; must aso be used up NO, must bea product ofthe second stop because one molecule of NO, ‘sin the overall equation Fist add in CO: + Aststep No, +NO, =? slow, rate-determining step + 2nd step 2 +00 —-NO,+C0, ast ‘+ Overall equation NO; +CO — NO + CO, Now work out what was formed in the first rate-determining step, ‘+ NO, must be present in de second step to react with CO to form NO, and CO, + So. to generate NO; forthe second step. the frst step must be INO NOs — NO, + NO. + This gues us the products ofthe fst step, NOand NO, The completed mechanism is: + Aststep INO; +NO; — NO +NO,_ slow, ate-dtermining step + 2nd step NO, +CO —NO,+C0, fast + Overat equation NO; +CO — NO + CO, Notice that NO, was genetated as an intermediate. Intermediates are shored species. The NO; intermediate in this example is used up and therefore does not appear in the overall equation The rate determining step is not necessarily the fst step ima reaction ‘mechanism, Qe ca determing tof aero betwen Xan Vs oe Pred teat equation for ths cn, © six.» monoxide and onsen ac together sn te overall 8 20 + O40) ~ 260) Tes euation rian as = AN (ila who aby at tering se (Wat does the ate equation ely abou ote determining ses! (© Suggest possible wo step mechanism rth reaction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 © a qualitative explanation of the effect of temperature change on the rate of a reaction and hence the rate constant © the Arhenius equation: (i) the exponential relationship between the rate constant, k and temperature, T, given by the Artvenius equation, k= Ae-**" (il) determination of €, and A graphically using: In equation 5 aL where In kis ‘An Arrhenius plots a graph of in k= In A= x 4, plowed aga The rate constant, k Reaction rate depends on both the rate constant and the concentrations of the reactants present in the rate equation: rate = (AFB ‘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 are more frequent, and more of the collisions exceed the activation energy of the reaction, This was explained in terms of the Boltzmann distrioution (see Book I, topic 3.2.9) ‘The key factor 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 from any increased frequency of collisions. Look at the rate equation above — if the rate increases with increasing ternperature wien the concentrations are the samme, then the rate constant must increase with temperature «+ Raising the temperature speeds up the rate of most reactions by increasing the rate constant, k ‘+ For many 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, k £,/RT+ in A derived from the Arthenius Letus look at an example reaction, Sodium thiosulfate and ydrochloric acid react as follows: Na.$,Ojaq) + 2HCKaq) — 2NaCleq) + Sis) + $0,(aq) + 1.01), "The change in k with temperature for this reaction is shawn in Figure 1 30 @ 90 60 70 a 90 1b temperarure/"C Figure 1 The rate constant forthe reaction betwen sodium thiosulfate and hytiochionc acid increases wit increasing temperature, The Arrhenius equation ‘The Arrhenius equation is used to describe, mathematically, ‘the exponential relationship between the rate constant and the temperature. The Arrhenius equation is k= Aertver where + = rate constant, té + A= pre-exponential factor tivation energy + ‘R= gas constant + T= temperature (in kelvin) + = mathematical constant with the value 2.71828, This is, Town 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 colide with enough energy to evercome the activation energy. It has been found that at any igven temperature, 7, the rate constant, k; is proportional to 50" This is expressed mathematically as k = e"*" ‘This can be turned into an equation by adding a constant, the ‘pre-exponential factor’, A, giving k= Ae'"\/"” Ths is the Arrhenius equation. ‘The Arrhenius equation tells us thet ‘+ temperature, 7, and the rate constant, k ae related exponentially + as temperature increases, the rate constant increases. ng spadient = -£/2 ‘Adding a catalyst provides an alternative reaction path with lower activation energy, £,. If you follow this through ‘mathematically, 2 lover value of £, increases the rate constant, k - 0012 ‘0014 0018 one Arrhenius plots vr “Taking logarithms of the Archenius equation: Figure 2A typical graph on against 1/7, Using the expression Ed {y's equal ton x's equal to 1/7. mis equal tothe gradient. -G/R. and cls Ing=Ina~ xh equal tothe interent. A, Uf a given reactions careied out tvrying temperatures and the ‘alu ofthe rate constant is ealelted foreach temperate j7aph of In Lean be plored against, Such graphs ae refered ‘bas Arrhenius plot, ‘This logarithmic version of the Arihenius equation follows the general pattern y= me + Pay k Daa Qey or yee me ‘hn Arteria plot canbe uted ta ident: eS + Atheinterceptonthe graph sequaioln Use the esis fm te exrimento dow an Ae ot + the activation ener, f,: the gradient is equal to ==> where Ris the known gas constant, so dis can be earanged lo easly to find &, 10 2.49 1 [20 L710 «10 30 184% 107 40 1475107 45 745 «107 Oi er eee ener aaa see eee a ee oo, © crests ie pre erpoertia tc teeta on the rane a pees eseoral 6) elit eye) understanding of: By the end of this topic, you should be able to demonstrate and apply your knowledge and © the calculation of quantities present at equilibrium, given appropriate data © the techniques and procedures used to determine quantities present at equilibrium ® expressions for K. and K, for homogeneous and heterogeneous equilibria » calculations of K. and K., or related quantities, including determination of units Te equilbrium tw sats tht forthe equlisium aA 6B = oC + dD «ome ine ‘homogeneous equilibrium isan equllbium in ict al the species "aking up the reactants and products ae in the same physical state, ‘Ahheterogeneous equilibrium is an equllbsium in which species making Up the reactants and products ae in diferent physical states. Dynamic equilibrium and K. Not ll actions go t0 completion. An enulibrium may be established. This's when the totes ofthe forward and reverse reactions are equal auilrium does not aceur straight away The reverse reaction cannot ake place unt the forward reaction has produced «high enough concentration ofthe product. Consider the decomposition of dinitrogen tetraoxide, NO, (a colourless gas) ro nitrogen oxide, NO; (a brown gas) N,O\(e) = 2NO,e) ‘+ Atirst the concentration of NO, is high and the concentration of NO, is zero. + Asthe reaction proceeds the concentration of NO, falls and the concentration of NO; rises. The reaction mixture appears colourless intially then a pale brown colour will appear ‘+ Once equilibrium is reached the concentration of each substance remains unchanged ~ the reaction has a brown appearance. Thisishown nFgwe 3 at the start, J, sand no NO. 1 equiv 1 chieved| Figure 1 Graph to show how the concentrations of N,O, and NO, change until ‘auilium sachioved + IF conditions change, the equilibrium will need to be re-established. A colour change will be observed until the equiliorium is restored Remember, according to the equilibrium law, for the reaction: ah +B = eC+aD the equitrium constant, X, can be calculated as follows: _ (cry “are! + Once an equilibrium is established, K, remains constant unless the temperature ofthe reaction changes Units of K, “The units for K, expressions have to be worked out afresh for each cifferent reaction. Each concentation term in the K. expression is replaced by its units + Forthe equilsrium described above, the expression for Ks: NO.) (mole NO.) fooler) Note thet one ofthe concentration terms, mal dm, cancel. + Forthe reaction: 280,(@) + 0,(g) = 2802) (SOs yyy se SO, (0f@) |" GnokernF (mol a Note that positive indices are placed before negative indices, so the units are drs! mol" rather than mold K = moldm x, in? mol «For the reaction: H,(g) + l(a) = 2HI(g) __ le? {mole} FG) ()) [nelér[imotae} Note that all the units cance! Units: = no unitsES In Book 1 you met Le Chateler’s principle, Remember this can be used to predict now changes in cenditions wil affect equilibrium Figure 2 A colorimeter monitors the conoentation of a reactant or product by measring the amount of ght passing trough a substance. 28 Determining concentrations at equilibrium Inorder to determine a value fr K, the concentrations of the reactants and products at equilibrium need tobe known, Chemists can determine the concentrations of reactants and products in a ‘number of ways, The most common ways are «tration + using a colorimeter Titrating one of the reactants or products against a substance with a known concentration will tenable us to find out how much of the reactant or product is present. There are drawbacks with this ‘method however Reactant or product has to be removed from the reaction mixture, and this will alter the position of the equilibrium. Also, other substances may be present that can affect the results of titrations. For example, if an alkalis used to titrate against the equilibrium substance in question and an acid catalyst is also used, both equilibrium substance and catalyst will react with the alkali, The ‘amount of any such substance must be carefully determined when the titration results are used t0 determine equilibrium concentrations. A colorimeter can be used to monitor the concentration of a reactant or product throughout. This ‘works because coloured substances alter the amount of light that can pass through a substance; more intense colours mean the substance has a higher concentration and absorbs more light. ‘Often the equilibrium concentration of one substance only is determined and compared with the initial concentration. Other concentrations can then be calculated using the balanced equation Da Equilibrium investigation Ethanol and ethanoie acid eact, inthe presence ofan acid catalyst to form the ester ethyl ethanoate through the following equilibrium reaction: CCH.COOH + CH,CH,0H = CH,CODCH.CH, + H.0, CChoose suitable starting amounts and concentrations and set up the above reaction. Leave itn a sealed reaction vessel to prevent evaporation for at least a weok to allow the equilibrium to establish. Using a standard solution of sodium hydroxide and a phenoiphthalein indicator, cary out a tation to find out ow much ethyl ethanoate has formed and hence the equilibrium concentations ofall the substances involved Calculate a value for K forthe reaction, Calculating K, from equilibrium concentrations PS slg) and Lg) were mixed in a sealed container of volume 2m and allowed to reach equim, Hig) + Lig) = 2H) “The number of moles at equilbrum was: + Hg)0.280mot + 11g) 0.080 mot + Hllg) 0640 mol Calculate K and work out the units fo this reaction. Frstly. calculate the concentrations at equilibrium: ‘+ H{g)0280 mol/2 dm = 0.140.mot dm * + 1) 0080 mol/2 dm? = 0.040 mol dow? + Hilg) 0640 mol/2 dm = 0.320 mot do * ‘ite the exeression for K. and work out the units. Then caleulate K. under these conditions Hon? + Units: —_ tal no units fall cancel ‘wal de) kd) ee + Use the equilibrium concentrations to calculate a value for: o2208 “= qiaaxoom “8?Calculating unknown equilibrium concentrations in Book 1 you cartied out calculations involving stoichiometry and reacting quantities From the balanced equation you can find: «+ the reacting quantities needed to prepare a required quantity of a product | + the quantities of products formed by reacting together known quantities of reactants, For reactions that go to completion, you can assume that all the reactants are converted into products, This isnot the case in ‘equiliorium reactions. We still use the balanced equation, but we need to do a litte more work to find the amounts of reactants and products present at equilibrium, ‘The equilioium constant, K,, can be determined fom ‘experimental results. Worked example 2 shows how to determine ‘the equilibrium concentrations of the components in an equilibrium mixture, Lwonccpexampier H,(g fg) and Hg exist in equillbium: Hg) + Lg) == 2H) (0.60 mol of Hg] was mixed with 0.40 mol of Ig) ina sealed container with a volume of dm. The mixture was allowed to reach equilibrium and it was found that 028 mo of H,(9 remained. Fin the concentrations ofall three components inthe equilibrium rmisture + tis useful to summarise the information ina table. At the start only 4g) and L(g are present and these values have been added ta the table below in blue. + You are also told how much Hf is present at equilibrium and this, value has been added tothe second row ofthe table in green, Hag) lA) nitial amount/m We now need to find the equilibrium amounts of I; and HL ‘+ You can use the information inthe table to find out how much H,lg) has reacte, “+ Amount of H, reacted = initial amount ~ equilibrium amount 0.60 - 0.28 = 032 mol You now use the balanced equation to ind out how much I; has reacted and how much HI has formed. + From the equation: ImolH, + Imoll, + 2mol HI + Therefore: 032molH; + 032mol ly -+ 064mol HI You can now workout the equilibrium amount of I using the same ‘method a fr H, above. + Amount off temaining = intial amount - amount of reacted 040-032 =0.08 mol + From the equation, the equilibrium amount of Hl = 0.64 mol Finally, convert the amounts to concentrations. Here the volume ofthe container ts 1.00 dm, so we already have the amount in 1d. The Cconcentiation numbers are the same asthe equlirium amounts. + Therefore, at equiliium, Hal = 0.28 mol dm; TQ) = 0.08 maiden; = 0.68molém> LL If you are given equilibrium amounts in moles (as in Worked examples 1 and 2) and you know tie total volume, you vill need to fst calculate the ‘concenttions. For example, a sample of gas contains substances A and B at equilibrium, There ara 0.03 moles of A and 05 moles of 8. The total volume of gas is 500 om The number of moles of each substance can be converted to ‘concentrations using the formula: wmber of moles volume in dm 0.03 ‘Therefore, concentration af A= 003 (09/1000) = 1 mol di (06 mol dm? and 5 (00/1000) ‘concentration of B= Homogeneous and heterogeneous reactions Al he equrum reactions we have considered above have invoted eacants and prodocsin the same stato iui, 20) “They are examples of homogeneous equilibrium resctons 1F more than one sate is present then the reaction is called a heterogeneous equilrium, fr example H,0() = H,0(s) When a heterogeneous equim s present, mor concentrations for sods and pure gus donot change because their volume remain constant “Thismeas the expression for K; changes: + the concentrations of solid substances are not incuded inthe expression «the concentrations of poe Tiquids are not ncued inthe expresion Forexample, when phosphorus eects with oxygen, te falling heterogeneous equim sexablishee! Pi(s) + 50a) = P,O.ds) Hence K = [,]* © 4.0004. 04 cH,c006, aH extn eum Gin tc = Geis te 200 els of CH..00H were med wth 300 moles of C,OH tnd thembcare slowed oar elm Arg Da toes eC COOH ean (3 How ray mets of CH;COOH hve ace? {Demin the avium eaeanetons of CCDOH, GOH cHyeDocyts andi aul ted se Vis epese he Sie ioe al rong por = oat) to ence eat ee ee eerste Patras els ea 2604s) = Ca015)+ C0440) (a) Explain wether this reaction i heterogeneous or homogeneous. (5) Write an expression for X forthe reaction26 Equilibrium and Kk, By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: use of the terms mole fraction and partiat pressure © expressions for K, and K, for homogeneous and heterogeneous equilibria » calculations of K. and K, or related quantities, including determination of units Mole fractions, partial pressures and K, Mole fraction ‘The amount of a given component within a reaction mixture is called the mole fraetion and is given the symbol X ‘The mole fraction of a substance, A, is calculated as follows: _ _number of moles of substance A mmole fraction, X= terat number of moles ofall aubstances Partial pressures ‘The pressure of any reaction mixture involving gases (within a sealed vessel) is effectively the surn of the pressures being exerted by each of the gaseous substances involved. ‘The amount of pressure being exerted by an individual species within a reaction vessel is called the partial pressure and is given the symbol P, followed by a subscript denoting the species to which it refers. (Be careful not to confuse this with the chemical symbol for phosphorus or the generic term for pressure of that substance ) If we know the total pressure of a reaction along with the mole fraction of a given substance, we ean calculate the partial pressure of that substance. + Forsubstance A: partial pressure, 2, = mole fraction * total pressure ‘The concentration of a substance is proportional to its partial pressure. La For reactions involving gases, equilibrium expressions can be written using partial pressures instead cf concentrations. This gives a new equilibrium constant, For the reaction a + bE == eC + dD, the equilibrium constant, X,, can be calculated as follows (Po (Po Sexe For the reaction i) + Ig) == 246) __tuh Pe (Pad (Pi)The following equilibrium was established ina 1.dm? vessel, The toal pressure was 41 x 10" Pa + Hig) + fg) = 2H) Te concentations ofthe individual substances were found tobe: + Hytg] =028 mol de> + Th) = 0.08 motdm-* + [Hg = 054 mol de> [As the volume was 1 di, the numberof moles ofeach substance is: The male fraction are 2 alos: mount in matat Hy 028 Tota numberafmot 10 ~ 0 + 1-284 -064 The partial pressures are: +, =mole fraction x total pressure = 028 x A x 10° + P,=008 x 400 =33 x 10°Ps 15% 10" Pa + y= 06x 400= 26% 107 Pa ey % Re = 25 410"Pa? __ 1999 TLS « 10733 «109 Pax Pe unis = PP = no units K,, expressions for heterogeneous reactions The expression for X, when a reaction is heterogeneous will alter as follows: + solids will nt be included in the expression + pure liquids will not be included in the expression. © Wien eaitam eorson fr forthe fovingeaton: Ni) + 400) = NICOL) @ Pe latovng equim was esablshed: PCL) = PCL)» C4) Ata rer of 60795Pa te equllbriam arts were fv tbe PC, = 1.00 x 10-mol C= 203mot Pcl, = 0.7 mol {a} Determine the mole faction for each substance. (by Determine the partial pressure foreach substance. (@ Wite an expression fr, (di Calculate K, a You will notice tat this K, value Is the same asthe value for Ke worked out forthe same reaction nan earlier worked example. This 's not always the case.28 Equilibrium constants and their significance By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: © the qualitative effect on equilibrium constants of changing temperature for exothermic and ‘endothermic reactions © the constancy of equilibrium constants with changes in concentration, pressure or in the presence of a catalyst © explanation of how an equilibrium constant controls the position of equilibrium on changing ‘concentration, pressure and temperature application of the principles for Ke. K, to other equilibrium constants, where appropriate The significance of equilibrium constants ‘The magnitude of the equibrium constants, K and A, indicates the extent of a chemical reaction. ‘An equilibrium constant, X, with @ value of 1 would indicate thatthe position of eaplbrium is halfway berween reactants and products. ‘When Kis greater than t + the reaction is product-favoured + the products on the right-hand side predominate at equiloium. KL -guibrium postion —> Figure 1 When K's greater than 1. the equlium les othe night. When Xs less than L + the reaction is reactant-avoured + the reactants on the left-hand side predominate at equilibrium. ensilorum pest _— Figure 2. When Kis less han 1 the equim es tothe let How do changes in temperature affect K? Previously you wl ave use Le Chater’ principle (Book 1, topic 3.2.10} 0 predict how changes in temperature afer the postion of equlbrium, You used te sign of AF, which means change in enthalpy to make presctons‘+ An increase in temperature shifts the position of equilibrium in the endothermic dection (AH +¥e). ‘+ A decrease in temperature shifts the position of eguiibrium in the exothermic direction (AH —ve), + ‘The AH values for the forward and reverse reactions in an equilibrium have the same magnitude, but have opposite signs. The control of the equilibrium constant Shifts in the position of equilibrium are actually controlled by the rate constant, which changes its value only with changes in temperature. When any other changes occur to conditions, X will remain constant. The way that K changes is linked to AH. Forward reaction endothermic: AH +ve If the forward reaction is endothermic, then K increases as temperature increases: «+ the equilibrium yield of the products, on the right-hand side, increases + the equilibrium yield of the reactants, or left-hand side, decreases. K- increases, —oos ceulbrum shits exothermic endothermic A= Og) = 2NO{2) AH = +58kImot" s8klmol” N, elow darkred Figure 3 Nitrogen dioxide equilium: a change in temperature in tubes of NO, and NO, gases shits the equilibrium between the to species; when more NO, is preduced, the gas mixture inside the tube becomes darker. Forward reaction exothermic: AH —ve IF the forward reaction is exothermic, then K decreases as temperature increases: + the equilibrium yield of the products, on the right-hand side, decreases + the equilibrium yield of the reactants, on the left-hand side, increases: Kdecreases, nd, ‘equim Nig) + 3H,(g) == 2NH(g) endothermic Ait= +92kImor exothermic AW = -s2kImot* ‘Figure 4 Ammonia equllbrum:the foward reaction is exothermic. so an increase n temperature decreases the value of K i Changes In temperature are the nly changes that affect the ‘equilibrium constants, K and Ky ‘+ Kincreases asthe temperature rises if the forward reaction is ‘endothermic (AA +e. 1+ Kedecreases as the temperature rises if the forward reaction is ‘exothermic (Ave)How do changes in concentration and pressure affect K? Although the equlbrium constant, K, is altered by changes, in temperature, the value of K’is unaffected by changes in concentration and pressure Changes in concentration For a reaction misture of the equilibrium N,O,(g) equilibrium concentrations are NOs) = L.60molde® {N,04a}] = 0.200molam-* NOE _ (1.60)? N,O,@~ 0200 IF [NO] is doubled srom 0:200.mo dra + the concentrations in the K, expression now give the ratio (607 0.400 + the system is no longer in equilibrium, 2NO,(g), the ‘Therefore K. 2.8 mold? #t0,0.400 mol dm 4moldm? ‘The equilibrium position must shift to restore ths ratio to the K, ‘value of 12.8moldm-*. The systern must: + increase (NO, ()] (on the top of the expression for K,) + decrease (N,O,(g]] (on the bottom of the expression for K.). “This causes a shift inthe equilibrium postion from left to right, ‘The same will be true for the rate constant K, as this will also remain constant when concentrations, or the equivalent partial pressures, are changed. Changes in pressure 1F the pressure is doubled, the concentrations of both {NOx} and [NO (will also effectively double (for example, there will be the same numberof particles in half the space, "The concentrations in the X. expression now give the ratio (2x 160 (3.20). 7x 0200 ~ 0400 ‘The system is no longer in equilibrium so the equilibrium position ‘must shift to restore this ratio to the X. value of 12.8 mol dm” ‘The system must: + ecrease [NOs(g)]} on the top + increase [N;O,(g)] on the bottom. = 156moldm™* “This causes a shit in the equilibrium position from right to left ‘The same will be true forthe rate constant X,, How does the presence of a catalyst affect K? ‘Tae short answer to this is ‘It doesn't, for both K, and X., Catalysts affect the rae of a chemical reaction, but not the position of equlbsium Catalysts speed up both the forward and reverse reactions in the equilibrium by the sare factor Equilibrium is reached rare quick, but the equilbeium position, and hence the value of the ccuilbrium constar, is unchanged by the action of a catalyst Predict whether the two reactions, Aand 8, are exothermic or endothermic. plain your answer Tn ns i tion B 500 800 03 © 11s closed yon NoI9, 0/6) and NO) ex neal: 2NO) + 9) = 28049) ta tet xsi for Kad 0 The concent ef Ns nse. plan in toms of Kant tuba ayers tothe ulm compusion, (0 The presen te ssa is deceased alin ites of od shape equa eo pam Oe eet ean) OSS ee eee adage) Bal this statamat nts Kanae understanding of: © Bronsted—Lowry acids and bases By the end of this topic, you should be able to demonstrate and apply your knowledge and © a Bronsted-Lowry acid as a species that donates a proton and 2 Bronsted-Lowry base as species that accepts a proton © use of the term conjugate acid-base pairs © monobasic, dibasic and tribasic acids a ‘A Bronsted-Lowry acd is a proton 1 doncx. [A Bronsted-Lowry hase isa proton. H", acceptor. Conjugate acid-base pairs are two species related to each other by the loss or gain of a proton Bronsted—Lowry acids and bases ‘The Bronsted-Loviry model of acids and bases states that: + reactions between acids and bases involve the transfer of H* ions (known as protons) + a Bronsted-Lowry acid is any substance that ean donate a proton + a Bronsted-Lowry base is any substance that can accept a proton, Models for acids and bases over time Chemists have studied the behaviour of acids and bases over ‘many years, Qur understanding, or model, of how they behave has changed as new research has been conducted + Inthe 1770s many chemists were investigating air and the gases within it Joseph Priestley and Karl Scheele both reported findings thar suggested the existence of the gas we now know as oxygen, Another chemist, Antoine-Laurent de Lavoisier, ‘ound, among other things, that this gas was important in the rusting of metal and in 1778 he proposed that it was the source of acidity Lavoisier was wrong, but it was an early step towards, the understanding of acids, + In 1815 Humphrey Davy showed that some acidic substances, such as HCl, did not actually contain oxygen + In 1832 Justus Liebig defined an acid as a substance containing Iydrogen that could be replaced by a metal - very close to today’s definition, + Inthe late 1880s Svante Armhenius proposed that acids dissociated in water to form hydrogen ions, H*, and that bases dissociated in water ta form hycroxide iona, OH. This is tue for many acids and ‘bases, and they canbe referred to as Arrhenius acids and bases However the model breaks down when the acids end bases are not solutions in water or when bases are not soluble hyckexides. + In 1929 the Brensted-Lowry definition discussed above was proposed by the Danish chemist Johannes Bronsted and the British chemist Thomas Lowry, Even the Brensted-Lowry madel can break down, e.g. for some solvents. The American chemist Gilbert Lewis proposed a more ‘general theory that describes an acid (known as a Lewis acid) as an electron-pair acceptor and a base (a Lewis base) as an electron-pair donor ‘This mode is beyond the scope of your A level studies, Examples of Bronsted—Lowry acids and bases in action When an acid is added to water the acid dissociates (splits up, releasing H” ions (protons) into solution. + Forhyerogen chloride, HCI: HCi(g) -» Haq) + Cr(aq) “The HC) has donated an H" ion it isa Bransted-Lowry acid + Forsului acid, H,S0,° H,SO,(l) ~» Haq) + HSO,-(aq) “The H,SO, has donated an H" ion itis « Bransted-Lowry acid. HSO," can actually go on to donate another H” ion (sulfuric acid is dibasi) — this will be covered later Bacos are able t accept protons. + Forammonia, NH: NH(aq) + H(aq) — NH,"(aq) “The ammonia has accepted a proton (H*)— itis a Brensted— Lowry base lonic equations Because acid-base reactions involve the transfer of H* ions they are usually represented by ionic equations. Ionic equations show: + the H’ ions being donated + the ion thats accepting the H* ion + the products formed + all charges, correctly balanced (ie. they cancel out) + state symbols for al substances, ineuding ionsFor the reaction between hydrochloric acid, HC, and sodium hydroxide (NaOH): HClfaq) + NaOH(aq) — NaCl(aq) + H.0() the ionie equation would be written as follows: Haq) + OH faq) > H,01) Mono, di and tribasic acids Depending on their formulae and bonding, different acids can release different numbers of protons. HClis a monobasic acid because each molecule can release one proton. Hetfeq) 1180 isa dibasic acid because each molecule can release two protons, This is done in two stages: H,SO,(aq) — H*(eq) + HSO, (aq) HSO¢ (aq) + H"(aq) + 50¢"(aq) H,PO. sa tribasic acid because each molecule can release three protons, This is done in tree stages H.PO,(aq) + Haq) + H,PO¢ (aq) H,PO,-(aq) > H*(aq) + HPO,*"(aq) HPOF (aq) + Haq) + POL-(aq) + Haq) + Cea) Conjugate acid-base pairs ‘An acid-base pairs a set of two species that transform into each ther by gain orloss of a proton. Figure 1 gives an example of a conjugate acid-base pair. for the dissociation of nitrous acid, HNO,, Italso shows how the acid and base in an acid-base pair are linked by H ese to species change into one another by Tesing or gaining HNO, No,- cid base Figure 4 An example ofa conjugate ackd-base pale 32 ‘Acid-base equilibria involve two acid-base pairs, Tae equilibrium below shows the dissociation of nitrous acid, HINO, in water: HNO,(a0) + H,0() = H,0"(eq) + NO;"laa) In the forward direction: + the acid HNO, releases a proton to form its conjugate base NO, + the base H,O accepls the proton to form its conjugate acid H.O* In the reverse direction: + the acid H,0* releases a proton to form its conjugate base H,O + the base NO,~ accepts the proton to form its conjugate acid HNO,. HNO, and NO; differ by Hand make up one acid-base pair: acid 1 and base 1 H,0* and H,0 differ by H” and make up a second acid-base pair: acid 2 and base 2. HNO,(aq) + H,0( acid 1 ,0°(aq) + NO (aq) base 2 © te cua for socton of the lowing ais in water: Gite aH, 1) comical H.00, acid 2 entity and explain whether the aids in question 1 ae ‘monobasi, dibasic or tbasic, © vrei is an eal of base eeacts wth boron tte astalows Wy + BF, NA, ammonia acting as isa-Lowy base inthis rexctont slain your ansver @ cerry base pas inte ai-tase qu bev (HO, +1:0 = #0" +10, (8) GKEDOH + 0 — CH,CO0- + Hor (© mi +0 = Mp +ounderstanding of: ase reactions and K, By the end of this topic, you should be able to demonstrate and apply your knowledge and © the role of Hin the reactions of acids with metals and bases (including carbonates, metal oxides and alkalis), using tonic equations © the acid dissociation constant, K, for the extent of acid dissociation the relationship between X, and ok, the application ofthe principles for XK, to other equlbrium constants, where appropriate Dico Dee ‘an alkalis a base that disclves in water forming OH (a9) fons, Neutralisation is 2 chemical reaction in which an acid and a base react together to produce a salt and water A strong acid san acid that completely dissociates in soltion. ‘A weak acid is an acd that partially dissociates in solution ‘The acid dissociation constant. x, of an acid HA is defined x, ital toa) THAGa) PK, = ~loaioK, K-10 Typical acid-base reactions ‘Aqueous acids take part in typical acid-base reactions with carbonates, bases an alkalis. Inall of these reactions, a neutralisation reaction occurs and ‘waler is formed as one of the products When acids release protons in water, they are usually accepted by the water to frm a hydronium ion. Hj0” (sometimes called the oxonium fom. ORE) 7) hhydronium ion, H,O* Figure 4 the nydronium ion. For example, when hydtochlorc acid is add to wate the following reaction curs: Hag) + H,01) + H,0%aq) + Cag) HH and H,0" can be used interchangeably when desenbing aquedus acid Solutions and H 1s usually used in onic equations fr acid-base reactions, Thats why the above equation would be simplified to: Hclag) — H'(aq) + Cla) ave covalent bond Reactions with carbonates In the reactions of acids that fallow, ionic equations are used 10 show the important role of the H* ion, + The ionic equations show only H’(aq) from the acid. This H could be provided by hydrochloric acid, HCI, nitric acid, HNO,, or sulfuric acid, H,SO,, for example + These acids have the same ionic equation for each type of reaction because they all release H"ions when they dissolve in water ‘Aqueous acid react with sold carbonates, forming a salt, carbon dioxide and water: + fll equation: 2HCi(aq) + CaCOYs) — CaCh{aq) + CO4lg) + HL00) + allions 2H (aq) +2C+taqp + CaCO) » Cablaq) +204 (a6) + CO,fe) + H,0)}) + onic equation 2H (aq) + CaCOY) » CaP*(aq) + CO,(g) + H,0() Pesce ‘The sum ofthe charges on either side of an lone equation need net be zero, but must be the same on the two sides. n this example, two H' ons ‘ate balanced by one C2" ion ~ there is a charge of 2+ an each side of the equation. Jf the carbonate is in solution, the final ionic equation simplifies because the carbonate is dissociated: + full equation: 2HC\(aq) + Na,CO.faq) + 2NaCiaq) + CO,(g) + H.0() + allions 2H"(aq) +2CHtaqh + 2NeXtaq) + CO; (aq) Bean) +2CHfan) + COxa) + HOU) + ionic equation: 2H(aq) + CO, (eq) > COg) + HO)Reactions with bases Aqueous acids react with bases, forming a salt and water + full equation: 2HNO,(aq) + MgO(s) + all ions 2H (aq) + INOmteqy+ MgO(s) — Mg" (aq) + 2NOrfaq} + H,0() + ionic equation: 2H-(aq) + MgO{s) + Mg**(aq) + H0() + Mg(NO,),(aq) + H,0(1) Reactions with alkalis ‘Aqueous acids react with alkalis, forming a salt and water: + full equation: H,S0,(aq) + 2KOH(aq) + allions 2H (aq) +-S0,2-fag) +.2K{eq) + 20H (aa) = 2kefeq} + SO2-fa) + 2H,0() + onic equation: 2E(aq) + 20H (aq) — 2,00) + which cancels to: H-(aq) + OF-(aq) = FLO") » K,SO,(aq) + 24,0()) Redox reactions of acids with metals ‘The reaction of an acid with a metal isa redox reaction, so does, not fit in with the acid-base model, However they are a common acid reaction, The general equation is acid + metal —> salt + hydrogen Figure 2 Zinc reacting with hydrochloric ci. an example of a metal-acié resetion. The bubbles are hydrogen ges and the salt i 2inc chloride, ZnCl, 38 Aqueous acids react with metals, forming a salt and hydrogen + full equation: 24Claq) + Mats) — MgCl(ag) + Hits) + allions: 2H" (aq) + 20a + Mg) «ionic equation 2H*(aq) + Male) + Mg*(aa) + Hale) Although most acids react wth metals inthis wey, you have tobe careful Some acids, such ae aulfune and nitne acid, ae powerful ‘aiising agents and other reactions may also take place, expecially ‘when the acids are concentrated. Its best to steer clear of H,SO, and HINO. when giving examples of acid reactions with metals, Ma"{aq) + 2CHad) + Els) Strong acids and weak acids In aqueous solution, acids ssocate and an eqlriam i set up The ‘equilibrium below shows the dissociation of an acid, HA. in water: Haag) + H,Of) — H,O'[aq) + A (aq) cor more simply: HA(aq) — H"(aq) + A-(ea) “The strength of an acd HA is the extent of ts dissociation nto HY and A” ions. Strong acids Some acids are strong — they are 100% dissociated in aqueous, solution. There are comparatively few strong acids; the most ‘common ate listed in Table 1, Almost every other acid is weak, HEL hydrochloric acid HNO, | nite acid H,S0, | sulfuric acid HBr hhydrobromic acid HI hydriodie acid HCLO, | chiloricivi (perchloric acid Table 1 Strong acids Weak acids ‘A.weak acid only partially dissociates in aqueous solution, Many naturally occurring acids are weak‘The equilirium thats set up when ethanoic acid, CH.COOH, dissociates in water is shown below: CH,COOH{aq) = H*{aq) + CH,COO-(aq) + The equilibrium position lies well over to the let + There are only small concentrations of eissociated ions, H(aq) and CH,COO "(aq), compared with the concentration of undissociated CH;COOH (aa). We can actually say that CH,COO™ isa very good base ‘good at accepting the dissociated H" back. itis very The acid dissociation constant, K, In topic 6.18 you learned about equilibrium constants and what they can tell you about the extent ofa reaction. ‘The actual extent of acid dissociation is measured by an ‘equilbrium constant called the aeid dissociation constant, K. ‘A.weak acid HA has the following equilibrium in aqueous solution: Haag) =H"(aq) + (ea) ‘The expression forthe acd dissociation constant is (Haq) [A-(eal} (HACa}] ‘The unis of Kare aivays mol dm, You can show this by canceling the units in the K, expression: (mold) (olden moldm? (molder > ‘The terms ‘strong’ and ‘weak’ describe the extent of dissociation of an acid given by the K, value + alarge X, value indicates a large extent of dissociation ~ the acid is strong + asmall X, value indicates a small extent of dissociation ~ the acid is weak. K, and pK, “The range of values for; i vast. Fr this eason a logarithmic scale is used 19 descrine them. You wl earn mote about tis in topic 51.11 on the pl scale p&, is @ more manageable number than K;, The two quantities are related as follows: ‘+ Alow value of K, matches 2 high value of px, + Ahigh value of X, matches a low value of pX, + The smaller the pi, value, the stronger the acid. ‘Table 2 compares KX, and pXwalues for some weak acids. re) | Relative | K,/mol dmv 7 | strength Phosphoric | Stronger} 79% 10° log (7:9 107) = 210 acid H,P0, | acid ‘Sulfurous 15x10 | log 5x 10%) = 282 acid H,S0, Methanoic 16x10* | log 6x10) = 3.80 acid HCOOH Ethanoic acid | Weaker | 17% 105 | —log (L710) = 4.7 cH,coon | acid ‘Table 2 K, 27d pk, values of some weak acs © Wie ts on gut rte owirg at-hase ee {a) sulfuric acid and solid magnesium carbonate {b) sulfuric acid and aqueous potassium carbonate {0 hydrochloric acid and solid callum oxide (4) nitvic acl and aqueous sodium hydroxide {e) hydrochloric acid ang aluminium, © ech ote towing ai-base qua, wt doun te expression for (a) HCOOHaa) = Htaq) + HCOO"Taq) (0) CH,CH,;COOHaq) = Haq) + CH,CH,COO-taq) © cates px, fom he olowg valves. Give our answers to ‘wo decimal places. (a) K,=23 x 10" moldm* (0) K,=25 x 10° moldm-> (0) K,=48% 10% moldm> © Cite tom he towing pk, ves. Give your answers to ‘hie significant figures. (2) px, =290 (0) pK, = 7.20 (0) 0K, = 10.60FS pH = ~togiHaa)) aa Et Remember tat the shorthand for ‘the concentration of is to use square brackets ||. ES The 10° button i usually the ‘shift function’ on the log button. Check your own calculator to make sure you know where each button is 36 Calculating pH of strong and weak acids By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: the use of the expression for pH as: pk let ~togl#") 10" © calculations of pli, or related quantities, for strong monobasic acids © calculations of pl, K, oF related quantities, for a weak monobasic acid using approximations © limitations of using approximations to K, related calculations for ‘stranger’ weak acids The pH scale Seren Serensen, a Danish chemist, carried out research that involved measuring hydrogen ion ceoneenirations. These numbers could be cumbersome to measure and recor. ‘Aqueous solutions have concentrations of H°(aq) ions in the range: + fom about 10mol dm (10"'mol dm) + to about 0.600.090.090000001 mol dn? (20° mol dm) Sorensen came up with an easier way to measure and denote these concentrations ~a logarithmic scale called the pH scale. The pH ia the negative log (10 base 10) of the concentration of H(aq) ions. This is expressed as: =e =eeiea ‘The related expression for the concentration of H’aq) ions is: + [Haq] = 10% ‘Table 1 shows the (H"] values and corresponding pH values that make up the pH scale. aflolil/2{/3{[4/s5i]6 i | 1 10' 10% 107 10* 10° 10° 7[a)s [wl ul] ei] l wl] is 107 | 10% | 10 | 10 | 10" | | 107 | 10" | 10% Table 1 pi values and comesponding Hvalues Converting between pH and [H'(aq)] ‘Sometimes it will be necessary to work with [H"(aq)] concentrations that are not whole numbers. For example, readings rom a pH probe may not be whole numbers. + If pH = 452, [H*(aql] = 10-4 + If pH = 1083, [H(eq) We need to express the concentration of H” ions in standard form, This will involve the use of @ scientific calculator as shown in Figure 1. =e forpl for (aa) youneed 10° press press = SHIFT to *log TF (oq) value a + pit value Figure 1 The calculator key fr pit calculations may look like ths refer to your ealeulator manual te make sure you ‘now hw o cary ut this type of calculationPT Calculate faq the pH ofa solution is 13.41 + Press shift og (le. the 10 function + Typein: 13.41 + Pross = Te answer shown Is 3.89 « 10°" [Htaqy = 389 < 10° mol de> Dae Calculate the pt if Haq] = 162 » 10% Arse + Press log + Typein 16210 + Press = The answer shown is 579 ph = 579 The order in which you need to complet the operations may vary berween calculators f these Worked examples do not work on your calculator, refer to the instruction manual to make sure you can cary out this type of calculation. What does a pH value mean? ‘The relationship between pH and [E-(ao) is sometimes called a see-saw’ relationship ~ when one is up. the other is down «Allow pH value menns a nrg [Haq] + Abigh pl value means a small (Haq) + ApH change oft changes (Haq) by 10 times + An acid with a pH of 2 contains 1000 times the (H"(aq)] of an acid with a pH of 5 Calculating the pH of strong acids ‘A sstrong monobasic acid, HA. has virtually complete dissociation in water: HA(ag) — H*(aq) + A-(aq) ‘This means that [H'* (aq) of a strong acid is approximately equal to the concentration of the acid, [HA(aq)} [Hail = (HACea)] ‘The pH can then be calculated using pt log[H"(aq)) Pwonccpexampins ‘A sample of hydrochloric cid, HCL has @ concentration of 1.22% 10-?moldm-. What i is pH? Helaq) isa strong acid and completely dissociates Hellaq) — Hriae) + Cl-taq) Therefore Haq] = [HCleq)| = 122 x 10% moldm> pH =-togl aq) nlogft.22 x 10% 191. Calculating the pH of weak acids In aqueous solution, a weak monobasic acid, HA, partially dissociates, setting up the equilibrium: HA(aq) = Haq) +4°(eq) Because we can no longer assume (H"{aq)] is equal 10 the concentration of the acid, we need to work out the value of K, for the reaction - to find the extent of dissociation that has occurred as this will dictae the value of (Haq) {HP (aq) AC) = THAtag) + For weak acigs,(H"(2q)] is much less than [HA(aq] because the extent of dissociation isso smal + When HA molecules dissociate, H'(aq) and A’(aq) ions are formed in equal quantities and itis assumed that any water present will have dissociated to such a negligible amount that it will not affect the concentration of HY + Therefore (H*(aq)) and [A-(aq)] can be considered equal. + This means the expression ‘H*(aq)] [A-(aq] inthe K, calculation becomes [H'(aq)F Because some HA molecules have dissociated, (HA(aq)] will have reduced slightly. + The equilrium concentration of HA(aq) will be [HACC tine ~ [H"(ea)] “The K, expression now becomes: Wea THAGqlndmocnes ~ [ed] Finally, we make an appreximation to simpy the pH calculation. ‘We assume that such a small amount of acid has dissociated thet [HA (aa adescsee ~ [H"(2q)] = [HA(2q)jnitondase Using this approximation, the X, expression now becomes: [H*(aq)? * (HA(ag)) Remember, we are trying to find the pH so we need to rearrange this equation to find (H"(ag)}. The equation is rearranged to give [H(aq)) =, THAGaq)) ‘The pH can then be calculated using pH og(H (ad) RS The concentration of a sample of nitrous acid HNO.. i 0.055 mol m2 K,= 470% 10-‘moldim at 25°C, Calculate the pH Fist we find [aq HNO, ia weak acd and partially dissociates: HND{aq) = Haq) + NO5 eq) 2 n= Hal NO; THN Sagi Htweassume that th Wag and NO, a ons ny come rate aa? isodaton f NOs ten hs prints to + (naa? = Kx HNOxaaT + Haq) = (A, THNO aa = (870% 10% 0055) = 5.08 x 10-*mol de Now we calculate pH: + 9H =-logit ‘aa og 6.08% 10-) =229The limitations of scientific appro jations When calculating the pH for a weak acid its assumed that so litle of the original acid has dissociated that the concentration of the acid at equilbrium is effectively the same as the concentration of the original amount of acid ‘This can be expressed as: [HAJeautcun © [HAJuodanstsd ‘This is an example of an approximation Its actwally the ease that there will be some acid which does dissociate, even if only a small amount. If this amount is less than 5% of the total or [HAlmnincxnes then itis deemed safe to use the above approximation, This will be the case for very weak acids, with very low K, values, Jf however more than 5% of [HA] nasscass dissociates, then the above approximation cannot be used. This would occur with stronger examples of weak acids, with higher K, values. In this instance, the expression for K, can only be solved using @ quadratic equation. This is not required for your A level course but ‘you should be aware of the limitations of the approximation, Calculating K, for weak acids ‘To determine K, for a weak acid, we need to measure the pl ofa solution of the weak acid using a pH meter (see Figure 2). We also need the concentration of the weak acid Figure 2 The pl ot soliton ofthe weak acid methanaic acid bing measured using a pH meter. The concentaton of te methanoic 2c is (0.030 mol dm and the pH reading canbe soon to bo 2.66, 38 @ cae of soon wih te fotowng Pag ales, Give your onsets toto deci places. (a) 338 110 moldm# (473 «10 mote (6.239 10*molén? (6 230mm © cette 2 of sotto wit the folloning pH aus. Give your answers tote sgnian gues, ta phes3 b phe to on9se @ oh-012 @ Fe oF ne ftovingsolston of weak acs (21065 mad CH,COOM X17» 105 eld) 0) 4a 102molem HCO UK = 37 10 mld > © re sates of nap; forte long weak ees (a) 043modnsoluon witha po 352 (78 10?molen solution vith ap of 18ae understanding of: 12) AUTEM CoD TESTU OL VELL BAe By the end of this topic, you should be able to demonstrate and apply your knowledge and © use of the expression for the fonic product of water, Ky * calculations of pl, o related quantities, for strong monobasic acids and strong bases using K, © application of the principles for K.,K; to other equilibrium constants, where appropriate The lonic product of water, K,.s defined as K, = [3"taq) [OH 2q AL25°C, K,= 1.00% 10-mol!dm-® Water — acid or base? Water can act as an acid by donating a proton: HLO() + H*(eq) + OF aq) Water can act as a base by accepting a proton: H,0() + H-(aq) — H,O"(aq) “This back-and-forth transfer of protons happens continuously in water In fact, water exists at equilibrium Ol) = Haq) + OH (aq) “This is known as the ionisation of water ‘The equilibrium lies well to the let and only an extremely tiny amount of water is dissociated at any given time, If we write an expression for K, for this equilibrium we see that: (H"(aq)) [OH “{aq)) x, = Peale ea) [5,00] Because the amount of dissociation, or ionisation, of water is so srmall, [H,0()] is considered constant, just lke K.. We rearrange the equation as fallows to combine the two constants, > (HLO())=[H"(aq] OH (aa)] ‘This can be further simplified by referring to the expression K* (H,O()] a5 ¢ new constant Ky: K, = K «[H,O()] = (H"(eq)) [O14 (29)) ‘This in turn is simplified to: = [H"(aq)] [OH (eq) ‘This expression for K, is called the ionic product of water. ‘The units for Kare always mol! dm* because: ([H*(aq)] mol dm-* x (OH (aq)] mol ém-* = mol*dm-* ‘At 29°C, the measured pH of water is ? and (H"(aq) 10°? mol dm. When pure water ionises, the same number of OH” and H’ ions are released [H"(aq}] = (OH (aq) ‘This means that the concentration of OH-(aq) is also equal to 10°? mol dm So the calculation for K, becomes. K,=[H'(aq] (OH (aq) = 1.0 107 « Lox 1077 = 10"“moP dm? ‘Therefore, at 25°C, K, = 1.00 x 10-MmoF dm-> The significance of K,, “The balance between (H"(ao] and [OH(ag)] can be affected by the addition of extra H* or OH ions that cause the equlibriam to shift. Remember that as with al equilibrium reactions and following Le Chatlior’ principle, the equilibrium wil shift to restore the value of K,.&, changes only i the temperate is altered. X,, controls the balance between (H_(aq)] and [OH-(aq}] in all aqueous solutions AL 25°C, the pH value of 7 isthe neutral point at which Haq) and OH (aq) concentrations are the same, equal to 10-7maldm-> ‘This applies to water and also to neutral solutions, All aqueous solutions contain H*(aq) and OH-(aq) ions: + in water and neutral solutions, (H*(eq)] = [OH (aq)] + in acidic solutions, [H*(aq)] > [OH"(aq)} + in alkaline solutions, [}(aq)] < [OH-(aq)] ‘The relative concentrations of Haq) and OH-(aq) fons in solution are determined by X,, ‘AL 25°C. Ky = [H"aq]} * [OF-(aq)] must always be equal to 1.00 x 10-' moldm”® (This value is provided for you on a data sheet K, in action ‘At 25°C rainwater is actually acidic, Carbon dioxide dissolves in rainwater This forms a weak acid called carbonic acid, H,CO., which is able to dissociate and release H* ions inte the water40 Because (H (aq) has increased, [OH (aq)] rust fll untit [H"(aq)] [OH-(aq)] = 1.00 x 10-! moP dm® (at 25°C) ‘The overall effect is thatthe pHi decreases. Typical rainwater has a pH value of about 5.6, ‘Mineral water contains dissolved ions such as carbonate, CO,#~. These ions typically react with acids and thus remove H' ions and lower ("aq Because (H(aq)] has decreased, [OH (aq]] emust increase until [H*(aq)] [OH-(aq)] = 1.00 x 10-4 mol- mok dn-* (at 25°C). ‘The overall effect is that the pH increases. The pH of mineral water is typically in the range 7.0-80, meaning that mineral water is alkaline The link between [H"(aq)] and [OH (aq)] ‘We can easily find the concentrations of H’(aq) and OH (aq) in solutions with different pH values. + We need to use (H*(aq)] [OH (aql] = 1.00 x 10! mokdm-® ‘+ Table 1 shows how [H"(aq]] and [OH"(aq]] are related at different pH values at 25°C. + Note that the indices of (H"(aq)] and [OH"(eq)] always add up to —14. a[2{[3[4[s5fel7 19% | 107 107 | t0* 107 | 10% | 107 ao [a0 [0% | a0" | 10 | 107 | 10 | 107 9 | to | um | 2 | a3 | a | is 10° 10" | 108 | 10 0" | 108 10% 1o* | 10* | 107 | 107 | 10% [10-1 | 10! Table 1. The relationship between pi (ce and 10H a9 AL 25°C, [H"(aq)] and [OH (aq)] are linked by Ke &, = [H'(aq)] [OW (eq)] = 1.00 x 10-"*mol? dm * Calculating pH for strong bases Just as we measure the strength of acids by how well they dissociate to form H, we measure the strength of bases by their ability to dissociate in solution to release OH” ions, Sodium hydroxide, NaOH, is en example of 2 strong base. In aqueous solution, NaOH dissociates completely: NaOH(aq) ~+ Na‘(aq) + OH-(aq) Bases that dissociate in water to release hydroxide ions are called alkalis. Strong bases are alkalis — they are 100% dissociated in aqueous solution, Strong bases tend to be hydroxides of the metals in ‘soups 1 and 2 in the Periodic Table. + The strong bases most commonly met are NaOH, KOH and Ca(OH), Ammonia, NH, is a wesk base. In aqueous solution, an equilibrium is set up. The equilibrium position lies well 10 the left-hand side: NH,(aq) + H,0Q) = NH,*(aq) + OH"(aq) Using K,, to calculate the pH of strong bases ‘To work out the pH of a strong base we need to know (H_(aq)] and this depends on: + the concentration ofthe base + the ionic product of water K,,= 1.00 x 10° mol? dm~* (because this links [H"] with [OH"),A strong monobasic alkali, eg. NaOH, is completely dissociated in aqueous solution, This means that [OH (aq)] of a strong base is equal to the concentration of the base. NaOH{aq) —> Na(aq) + OH-{aq) So [OH-faq)] = [NaOH(2q)] ‘We can find [H*(aq)] from K,, and [OH"(aq) = [H*(aq)] [OH (aq)} 5 ‘The pH can then be calculated using pH = log (Haq) Do ‘A solution of KOH has a concentration of 0.050 mol dm. What isthe pH? Oda) is 2 strong base, so there wil be complete dissociation. Thereore: + [otrtaqi = (koWaq) = 0.050 motam-> Using Ke First we find [tal from (OH fa Iza [OH-1aq 00% 10" mol de® i K_ 1.00 10- (00 oi agi” 0050 Now we calculate pt pH = logs Hag = ~log:9 (2.0 10° =1270 20% 10% moldmy> DEA RNG When calculating the pit ofa strong alkali, eg. NaOM,IN“aql depends on both [OH-YanH and Ky. [OH-(aa = strong base} & Wea oF eal We can use k to find eltherthe concentration of H'(aq) or OH taql as long as we know the value for Ky and the other concentiation. oe Some aqueous solutions have the following concentrations of Ha). In each solution, what isthe ‘concentration of OH tal? (2) Bagh = 10-*moldnr* (by Prag = 10-% mol de> (Baqi = 10- mot dor? a see ee kere ener nae Cees eter ete oncrtaton ot Hag (2) fot aq = 10° mold? (b) oF aq (0 fortaq 104 mold 10" mol der © iF the atoning ston 225° (00080 mold Kan (356 10° meter NaOH) © Fre te ancentaton not of Oana 25°C taps 1243 to pa 132STE By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: a buffer solution as a system that minimises pH changes on addition of small amounts of an acid ora base formation of a buffer solution from () a weak acid and a salt of the weak acid, e.g. CH;COOH/CH,COONa Ail) excess of a weak acid and a strong alkali, eg. excess CH;COOH/NaOH explanation of the role of the conjugate acid-base pair in an acid buffer solution, e4. CH,COOH/CH,COO in the control of pH calculation of the pH of a buffer solution, from the K, value of a weak acid and the equilibrium concentrations of the conjugate acid~base pal r calculations of related quantities » explanation of the control of blood pH by the carbonic acid—hydrogencarbonate buffer system ‘Abotfer solution is 2 mixture that minimises pH changes on addition of ‘small amounts of acid or base, The word ‘minimises is essential to this, definition. Buffer solutions ‘A buffer solution ‘resists changes in pH during the adition of small amounts of acid or alkali. A butler solution cannct prevent the pH from changing slighty. but pH changes are minimised. at Teast foras long as sorne of the buffer solution remains. Buffer solutions are very important in the control of pH in living ‘Acbuffer solution is a mixture of + aweak acid, HA + its conjugate base, & " CH,COOH(eq) oak acie partially dissociates = _= H(aq) + CH,COO"(ea) => sale of weak acd salt completely cissoiares i. CH,COO"Na'(aq) —» Na'{aq) + CH,COO"(aq) Figure 4 Making a butler solution fiom a waak acid and asa ofthe weak acl 42 Itcan be made from a weak acid and a salt of the weak acid, for example, ethanoic acid (CH,COOH) and sodium ethanoate (CH,COONa), In the CH;COOH/CH,COONa buffer system: + the weak acid, CHsCOOH, dissociates partially: CH,COOHIaq) = H"(aq) + CH;COO (ag) + the salt dissociates completely, generating the conjugate base cH.COO CH,COO-Na*(aq) + CH,COO(aq) + Na"{aq) ‘The equilbviurn mixture formed contains a high concentration of the undissociated weak acid, CH,COOH. and its conjugate base. ‘CH,COO™. The high concentration of the conjugate base pushes ‘the equilibrium to the lef, so the concentration of H*(aq) ions is very small ‘The resulting buffer solution contains large ‘reservoirs’ of the ‘weak acid and its conjugate base. You can see this in Figure 1 " _ O&O CH,COOH(eq) == Haq) + CH,COO-(aq) large reservoir of large reserveir of weal acd conugate base, HA cig bulfer solution weak acd HA + conjugate base:‘Alternatively, buffers can be made from a weak acid and a strong, alkali, [n this situation, a solution containing a mixture of the salt and the excess of weak acid is formed. For example, a weak acid such as methanoic acid, HCOOH, can be partially neutralised by ‘an aqueous alkali, such as NaOH(aq). How does a buffer act to control pH? [iva buffer solution, the weak acid, HA. and the conjugate base, ‘8. are both responsible for controlling pH. The buler solution ‘minimises pH changes by using the equibrium: HA(ag) = H*(aq) + A(a0) ‘The overall principle is simple: + the weal acid, HA, removes added alkali + the conjugate base, A, removes added acial ‘On addition of an acid, H°(aq), to a buffer solution: + [H"(aq)]is increased + the conjugate base, A{aq), reacts with Haq) ions + the equilibrium shifs to the left, removing most af the added Haq) ions. +— Equilibrium shifts to the left HA(aq) = Haq) + 4a) On addition of an alkali, OH~(aq), to a buffer mixture: + [OH (aq)is increased + the small concentration of H*(aq) ions reacts with the OH"(eq) H(aq) + OH (aq) — H,00) + HA dissociates, shifting the equilirium to the right to restore ‘most of the H_(aq] ions that have reacted: > Equilibrium shifts to the right HA(aq) = H*(aq) + A°(aq) ‘These actions of a buffer are summarised in Figure 2 added acid HAfag) = H'(aq) + A-(aq) ‘added alkall Figure 2 shiring the butter equilbium. Calculating the pH of buffer solutions ‘The pl ofa buler solution depends on «the acid csociation constant, X, ofthe bulfer system + the concentration ratio of the weak acid and its conjugate base. Fora buffer consisting of a weak acid, HA, and its conjugate base, A: Hed fA-ea °° Real) [HA(oa “Therefore [Han] = Kx Med = agi We need to check onthe concentrations of FA(eq) and A(eqh Only a very small proportion of HA dissociates 50, as discussed in topic 5.1.11 on calculating the pH of weak acids, we can assume that [HA(2A) gan = [HQ] etscae ‘The salt of the weak acid is ionic and dissociates completely in aqueous solution, or example CH,COO Nac) —+ CH,COO faq) + Na“lea) So effectively [CH,COO- eq) = [CHJCOO-Ne*(eq) Once (H"(aq)]is known, the pH canbe calculated using pH = Jogi ((ea) The carbonic acid-hydrogencarbonate buffer system Healthy human blood plasma needs to have a pH between 7.35 and 748. If the pH falls below 7.35, condition called acidosis occurs. IF the pH rises above 7.45, then the concition is called alkalosis. ‘The pH of blood is controlled by a mixture of buffers. The carbonic acid-hydrogencarbonate ion buler, which is present in ‘Blood plasma. isthe most important buffer system in the blood: + carbonic acid, H,CO,, acts as the weak acid + the hydrogencarbonate ion, HCO,”, acts as the conjugate base. H,CO,{aq) = H*{aq) + HCO,"(ag) ‘weak acid ‘conjugate baseFigure 4 clood sample - heathy ood hes a pH of beowoen 7.35 and 748, a4 Ay increase in [H (aq) ions in the bloods removed by the conjugate base, HO, "(aqh. The ecru, shifts to the left, removing most of the H*(aq) ions: << Enulibrium shifts to the left H,CO,aq) = H"(eq) + HCO.-(eq) Any increase in OH. (aq) ions in the blood is removed by the weak acid, H,CO,(aq). The small concentration of Haq) ions reacts with the OH (ag) ions Haq) + OF (aq) = H.00) + H,CO, dissociates, shifting the equilibrium to the right 10 restore mast of the H*(aq) ions: > Equilibrium shifts to the right H,CO,feq) = H’(aq) + HCO--(aq) ‘These changes are summarised in Figure 3 below. aelded acid H,CO\aq) = Haq) + HCO, (aq) added ala Figure 3 cid-rysrogencerbonate ion equlisium. ‘The acid dissociation constant. Ky for this equilibrium is 4:3 10-T moldm”*. Most materials released into the blood are acidic and the hydrogencatbonate ions effectively remove these materials, by being converted into H,CO,, The eatbonie acid is converted into aqueous carbon dioxide through the action of an enzyme. In che hungs, the dissolved caron dioxide is converted into carbon dioxide ‘gas, whichis then exhaled. The amount of CO;{aq) in the blood can be controlled by simply changing the rate of breathing, heavy breathing remaves more CO.(g): breathing more slowly removes less CO:(g), The acid-base balance of your blood is vital to your survival. If the pH of your blood drops below 7.2 or rises above 76, then you are in deep trouble! A buffer solution is made from propanole ac and sodium propanaate. Explain, using equations, the ole ‘ofthe conjugate acid-base pai inthis buf elution. You should aim to give at least 3 dstnet points in your answet. @ cari ne pw ofa ter stron comaning 0 1Smoldm? methane ct HCOOH. and 2065 mad sodium metarete, HCOONbe) 225° For HCOOH, K, = 16 x 10-4 mol dm at 25°C. © erased produced in he lod, how do utes preven the pifom aling? You shove aim to Inde tes 3 sine pats nyo awe.By the end of this to understanding of: 14) Neutralisation — titration curves you should be able to demonstrate and apply your knowledge and pl titration curves for combinations of strong and weak acids with strong and weak bases, including: (i) sketch and interpretation of their shapes i) explanation of the choice of suitable indicators, given the pH range of the indicator ii explanation of indicator colour changes in terms of equilibrium shift between the HA and A’ forms of the indicator the techniques and procedures used when measuring pH with @ pH meter ET ‘The equivalence point i the point in a tation at which the volume of tne solution has reacted exactly with the volume of the second solution. This matches the stoichiometry ofthe reaction taking place, ‘The end points te point in a tiation at which there are equal concenvations ef the weak acd and conjugate base forms of the Indicator. The colour at the end point is midway between the colours of ‘the acd and conjugate base forms. Titrations When you carry out a titration, you are determining the volume of one solution that reacts exactly with a known volume of another solution. This is called the equivalence point of the titration At this point, the solution in the conical flask has exactly reacted with the solution in the burette. ‘This topic considers pH changes from acidic to basic. ie. a base being added to an acid. Tirations can be carried out from acid {0 base or from base to acid — the sarne principles apply to both routes, Section 1a sight increase inp occurs as bate ade 8 ‘The increases aly sigh because the acid sin such exces vie mporant to ste that thiseeetion ofthe cure sna horzontl pH ing eh. os 0 8 a & wo ® Tho equivalence point the entre ofthe Serta section the ‘raion curve Seaton 2~ ashap ‘oon pH occur, “The acid no longer in exces sony base ‘ed has alarge impact hep a Titration curves ‘pH meters or data loggers can be used to measure the pH of the reaction mixture as solution froma the burette is added overtime. ‘The varying pH values can then be plotted as a graph ~ known, as an acid-base pH titration curve. The curve may be plotted by hand or by a computer attached to a pH data logger ‘Atypical acid-base titration pH curve is shown in Figure 1 for the reaction between a strong acid and a strong base. You will notice that this typical curve shows three distinct areas: + L-aslight increase in pH + 2-asharp increase in pH + 3~aslight increase in pH. Indicators ‘An acid-base indicator is a weak acid, often represented as Hin. ‘An indicator has one colour in its acid form (Hin) and a different colour in its conjugate base form (Ln") Section 3a sight increase _inpH ecu a thor aves wold ‘Tre increase i only i bcaue the bas i in excess new and era tase has ile impact on the pt Ics important to sate however that thi sections et honzontal pH sein sigh S volume of .1meldm-* base adeed/cm? Figure 1 Tiration curve fora stong aid-strong base tivation, showing the vertical section.Linvesricnion Using a pl meter {an indicator suchas universal indicator can only give @ general indication ofthe pl of solution. A pl meter can give an accurate reading for pH, usualy to two decimal places. DH meters contain a protected electrode ithe pH probe), which fs paced Into the solution in question, and a small computer display, which gives, ‘the pH reading. "When using a pH probe its important to calibrate I fst so thatthe results are accurate, Usually this is done through a two- or three-step calibration. ‘+The probe is removed from it storage solution and rinsed with deionised water +The probe is blotted dry and then placed into a solution of a known pH (such solutions are usually manufactured professionally ust for {this purpose. often starting with a solution of pH 4. The pH reading is allowed to sete before checking that a pH of 4 has been registered. + This process is repeated with other solutions of known pH often using prepared solutions of pH 7 and pH 10. This confi that the pH probe i accurately measuring pH across a range of acidic, neutral and alkaline values ‘Some pH meters wll have setings or buttons that must be used during ‘the calibration process and you should always check the instructions for the specific pH meter you are using. For example, for the indicator methyl orange, Hn is red and In-is yellow @-"- When there are equal amounts of the weak acid and the conjugate base present: + (Bln) = [br] + the indicators atts end point, End points are accornpanied by a visual colour change that allows a titration to be monitored easily. For example, the colour of the end point for methyl orange is orange, at which point (HIn] (red) and (Jr) (yellow) are equal Most indicators change colour ever a range of about two pH units. ‘The pH ranges for the indicators methyl orange, bromothymel blue and phenolphthalein are shown in Figure 2. The end point is typically at the middle of this range. penolphthalein z Dbeomothymar biue res ovange ° Figure 2 pl colour anges for some eummon inieatrs. 46 Choosing suitable indicators For a titration, an indicator is chosen so that the pH value of the end point is as close as possible to the pH value of the titration's, ‘equivalence point. In practice. a suitable indicator changes colour ‘within the pH range in the vertical section of the titration curve. ‘This often coincides with just a single drop of the base. ‘You may notice in the following curves that the ranges of the indicators are not actually on the equivalence point. So how can they show when the reaction has reached this point? Because the ‘equivalence point occurs halfway through an incredibly sharp mise (or fall) n pH, the moment at which the indicator passes through its end point is effectively the same as the moment that the ‘equivalence point takes place. ‘Strong acid-strong base titrations ‘An example of a titration curve fora strong acid reacting with a svong base was shown in Figure 1. Let us now look at indicators and their possible sutability Comparisons berween methyl orange ‘and phenolphthalein are shown in Figure 3 1 3 10 15 20 25 30.95 a0 ab 0 volume of mold” base added/ar? Figure 3 pi sitration cuve for tization between astong aid and a strong base wth phenolphtialein and meth orange indieatorrnges. ‘You should notice the following points from this curve. «+ The vertical section of the graph covers a large change in pH, starting around pH 3 and ending around pH 11, with an equivalence point at pH 7. ‘+ Both the indicators, methyl orange and phenelphthalein, have end points that fall within this pH range. + Either indicator would be suitable to use in a tration between a strong acid and a strong base, ‘Strong acid—weak base titrations ‘The curve fora titration between a strong acid and a weak base and the end points of the two indicators are shown in Figure 4 ‘You should notice the following points. + The vertical section of the graph covers a smaller change in pH, starting around pH 3 and ending around pH 7.5, with the equivalence point occurring at a more acidic value, ie. at a pH lower than 7.+ Methyl orange has an end point that falls within this pH range. + Phenolphihalein does nat have an end point that falls within this pH range. ‘+ Only methyl orange would be a suitable indicator fora titration between a strong acid and a weak base 4 2. 10. 0S 1 2a as 0 wD ‘yume of 0.1 mal base aded/em Figure 4 pl cation cue fora tration berwcen a song aed and a weak sate wth phrophtalein ane methyl erange indicator ranges Weak acid-strong base titrations ‘The curve fora tration between a weak acid anda strong base and the endpoints ofthe two inicators are sown in Figure 5 “ 0 3 i 15 20 25 40 35 40 45 50 volue of 0.1mal base added? Figure Spi ration cue fora titration betwsen 2 weak acid anda stong base wth phenolphhaloin and meshyl orange Indicator anges You should notice the following points. + The vertical section of the graph covers a smaller change in pH, and occurs further up towards the higher pH values, starting around pH 6.5 and ending around pH 115. + The equivalence point accurs at a more basic pH, Le. a pH value above 7, + Methyl orange has an end point that falls outside this pH range, + Phenolphthalein has an end point that range within this pH + Only phenolphthalein would be @ suitable indicator for a titration between a strong acid and a weak base. Weak acid—weak base titrations < “The titration curve for a weak acid reacting with a weak base is shown in Figure 6 4 2 10: 8 z 6 4 2 ° OF bm Eo valume of 01 meld bose ade /cm? Figure 6 pil titation curve for ration between a weak acid and @ weak base with phonolphtialoin and met range Indicator ranges. ‘You will notice the following points. + There isno teal vertical section + Neither indicator has an end point near the equivalence point. + Neither indicator is suitable. + An indicator would change colour gradually ver a few er of base added + No indicators are realy suitable for a weak acid-weak base titration, EN Set up trations between acids and alkalis of diferent sengths. You should select some weak acid and bases and some strong acids and bases with guidance from your technician of teacher. Cary out titrations using various combinations of weak and song acids and bases, Usea pH meter to record the pl throughout the titrations. Use your results to Dla acid-base tivation curves. Identity the equivalence points for each tivation, @ ein ty tne end point for tation othe same asthe eauvalenc point © 01 cages oro nator ate shown below erect emilee thymelptalem 9193-105 Use the tivation caves in ius 2-6 0 dey wheter hese indicators ae suitable forthe uration ofeach combination of acl and base,MUSSELS LOSE FOOTING IN MORE ACIDIC OCEAN OCEAN ACIDIFICATION Ocean acihification ienpairs mussels’ ably to attach to surfaces — alarming commercial grawers farming the waters around Puget Sound on the northwest American coastline. Figure 1 Carbon tram greenhouse gas emissions has steaciy tumed seawater more ac, distin organisms accustomed to ce slightly alkaline waters of ‘the past 20 milion years PENN COVE, Wash. Cookie tray in hand and lifejacket around chest, Laura Newicomb looks mo like a confused baker than @ marine biologist. Buc the University of Washington researcuer is dressed for work, Her job testing how mussels in this idyllic bay, home wo the nation’s latgst harvester of mussels, are affected by changing ocean conditions, especially warmer and more acidic waters. 1's a question KCls) AH®= 437i mor ‘The standard enthalpy change of atomisation, 4,H” For the standard enthalpy change of atomisation, &,/*, one mole ‘of gaseous atoms is formed frarn its element in its standard state A,H"* is always an endothermic process because bonds have to be broken For potassium, metallic bonds are broken: K(s) — Kg) AH? = 489k mol For chlorine, covalent bonds are broken: Clg) = Cite) A\H*= #121 kImol The first ionisation energy, A,,H” For the first fonsation energy, Ay#Y*, one mole of geseous 1+ fons fs formed from gaseous atoms Adi*is an endothermic process because the electron being lost bhas to overcome attraction from the nucleus in order to leave the atom, Adi *for potassium is: Ky) + Kg) +e AyH*= +419 kl molt The second ionisation energy, A;H” For the second ionisation energy, Az#1*, one mole of gaseous 2+ ions are formed from one mole of gaseous 1+ ions ‘As with the first jonisation energy, this is an endothermic process because the electron being lost has to overcome attraction from ‘the nucleus, AH. for calcium is Carl) Catig)te A, = +1145 kJ mol” The first electron affinity, Aca: H” Electron afity is effectively the opposite of ionisation energy ~ the addition of electrons rather than the removal of electrons. Forte first election afity, Aza", one male of gaseous 1— fons fs formed from gaseous atoms. Ths is an exothermic process because the electron i attracted into the outer shell ofan atom by the nucleus, Ay? for chlorine is: Clg) + e- + CH) Aca? = -346kJ mol? The second electron affinity, AzaaH” Forthe second electron afrity Au®, one mole of gaseous 2+ ions is formed from gaseous 1= ions, ‘This is an endothermic process because the electron is repelled by_ the Tien. This repulsion has tobe overcome aul for yg O@+te +0") Angell? = $790k) molt Constructing Born—Haber cycles Step 1 Draw a zero line (called a datum line) This is the line that starts ‘your Born-Haber cycle, Onto this line, vite the elements in their ‘Standard sais at 2er0 energy. Under this ine, draw another line. Place the jonic solid on this lin. Join the first ine with this new line, using a downward arrow to represent an exothermic change “This change represents the enthalpy of formation, one mole of the ionic solid being formed from its constituent elements in their standard states. An example is shown in Figure 1 below.56 Nats) + Sele) atum Tne — elements Afinve Nac) ase ofoyte Jowest energy level is the lonie solid s Figure 1 Step 1 in constucting the Born-Haber cycle for sodium chloride Step 2 Draw a line near the top of your cycle, slightly tothe right-hand side. Onto this line place each constituent element needed to form the ionie solid in the gaseous state. Join this line with the line showing the ionie solid, using @ downward pointing arrow to represent an exothermic change. ‘This change represents the latice enthalpy. This second step is shown for sodium chloride in Figure 2 below. Naval +0718) Autre Na) +3048) latice enthalpy: exothermic ° Ganum ne Genes Nac base of cycle wear energy level isthe Tore sl Figure 2. Adding the second step to the Bom-Haber cycle for sodium chloride Step 3 ‘This third step will involve a number of small steps, The overall aim will be to: + make sure each original element is gaseous and on its own as separated atoms (ie. enthalpy changes of etorisation for each element) + onise relevant elements to give the appropriate positive charge needled (ie, frst and second ionisation energies) + lonise relevant elements to give the appropriate negative charge needed (ie. first and second electron affinity), ‘The specific steps you take will depend on the solid ionic lattice being formed. For sodium chloride, the steps required are + atomisetion of soctum: ———_Na(6)—» Nal) endothermic + stomiston of chlorine Clg) -» Cla) endothermic + onisation of sou Nal) Na‘(g)+e° endothermic + electron ality f chlorine; Clg) +e"—+CF{g) exothermic‘The completed Born—Haber cycle for sodium chloride is shown in Figure 3 Nava) + Cie) +e 4 ave Aytitve Nat) + Ca) Nala) + Cha) gaseous ions ~———— add ether steps 10 complete Auiove the eycle Nalg) + $CL{@) AuHeve lace enthalpy exothermic Nag) + #04) ° Gam ine ements a tsve acs) Teweatensigy eval aue oP eye Figure 3. Comploted Bomn-Haber cycle for sodium chard Bom-Haber cycles, such as the one shown above, can be used to calculate an unknown enthalpy change. We can apply Hess’ law (see Book 1, topic 3.2.6) to the cycle such that: A:H?= the sum of all the other enthalpy changes sum of anticlockwise enthalpy changes = sum of clockwise enthalpy changes (green arrows) (purple arrows) © Wire earatonsrorepresent the floving ental changes i th ft ons ane of iam 1 the enthalpy change of fomaton of clean chloe [0th tic ental of calcu char, © e wee ne egrsons or making the ere sal gee 1) fom conser elements under standadcontons ile Heteatiar eee ae 1) Nae the ently changes pesrtedby your wo equations © e210 wy te somiatn of cries poste ently change © o:2n wn you ve to use a Bomar yl to detainee ace ental fan oie so58 @) _Born-Haber cycle calculations By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: use ofthe lattice enthalpy ofa simple ionic solid (i.e. NaCl, MgCl, and relevant energy terms for (i) the construction of Bon-Haber cycles (i. related cateutations Construct a Bom-Haber cyle from the following data and calculate the latice enthalpy for czesium chloride + Enthalpy change of famation of CsCL= -«334Imot* 45) SC4io)-» C30) + Enthalpy change of tomisation of Cs = +79 mot? as) — Cag) + Fist ionisation energy of Cs = +376kmol® Gig > csigh ve + Emhalgy change of tamisation of C= 4121 kdmat* Seu — cu) + Fist elton att of Ck = -386k mot ag +e = cr) Before staring to daw your cyl, you should constuct he equations alngste the data as sown above in blue ‘The question asks you to caleulate the lattice enthalpy fer C516) + CL-(g)—~ C8) The cycle is drawn in steps: + place the elements at zero energy and add the enthaloy change of formation + ad the latice enthalpy + complete the cycle and insert the enthaloy values. The complete Born-Haber cycle for caesium chloride s shown in Figure. co@)+ Ow +e A,HP= +376 kt mal Coty) + Cle) Gig) FCW) AHr(C)= +121 Ki mol Cote) + FL) +79 mol asics) ade=? o 99k met” css) Figure 1 Bom-Hater cyt or zesum chloride Catealatng the lati enthalpy isthe final sage Using Hes! law: sum of anticlockwise enthalpies =sum of clockwise enthalples AyHPICSC = ALHACS) + AHACD + Ay HOICS) + AiyHPCI 4 A,cHCSCD 833 = 479 + 121 +376 + (-366) + AyHPtCsCd Rearanging this to find Ay H!1CsCh AH (CSC = ~433 ~ (79 +121 + 376 ~ 346) Therefore lattice enthalpy of CsCt = ~663 Ki molConstucta Bom Nabe cele ram the folloving dt, and cal the tice entlby for sod cade, Noe hatin he Born-haber + tntalpy chang of oman osodumanida=—4i4Kimel —2Nab)+ 0,6) Nas0) See sow in Worked ample ‘+ Enthalpy change of atomisation of sodium = +108 kJ mot? Na(s) — Natgh 2, the atomization of todiwn hag : Seen oiled. hss because eet areeel ares al eee Teele Jo10) 009 ecg ciety Tae belay + Fisonisaton energy sodum = +96KI mot! al = Nag) +e em oe ace teeereee eee ose 0%) Fate oetateceen omen eeeteeet aye coer ere = OMe) fas bren died becaise Pee Pert eea ate ace The question rates te cleaton fhe atic ently for 2Na'gh« (0) = HO) acai awa +o) csc eae cof oxygen isa postive energy change, so there is an addtional ‘upwards step inthe cycle as shown. 2Nat(g) + Ola) + 26° Bylft= —141 KS mor 2Nalel+ 0@) Nel HOH AIO) = +2495 mot"! 2Nalg) +30,8) 2% AJFTNa) = 2x +1081 molt ; 2Nats) + +040) af Figure 2. Sorn-Haber cyte for sodium exit. Calculating the lattice enthalpy i the final stage. Using Hess law: ‘sum of clockwise enthalpies = sum of anticlockwise enthalpies AWH*tNaO) = 2 x AyHPINa) + AHO + 2 AgHPtNA) + Aug HO) + Aut 0) + OcH*tNa,O) AIA = (+108 x 2) + 249 + (4496 x 21+ 141) + 790 + Au H"ING,O} Rearanging the equation to find A,.HIN2,0} Aye Na,0) = ~414 ~ (4108 <2) + 249 + (4496 x2) ~ 141 + 790) Therefore, lattice enthalay of Na,O = ~2520KI mat-* © ctr he een for dum coi gen he foouing da, ‘ifformation of Rl = ~4354I ma* ‘tatomiston of = 811) ma Fitionsaon energy a Rb = 403 mol? Afatmisaton of C= 4121 Xa Fist eecron atfiy of C= 245 ma© Further Born-Haber cycle calculations By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: © the use ofthe lattice enthalpy ofa simple ionic solid (i.e, NaCl, MgCl.) and relevant energy terms for: (i) the construction of Bon-Haber cycles (i. related cateutations ‘This topic will cover some more complicated examples of Born-Haber cycles and their associated calculations iescuverp | Notice that in Worked example 1 the atomisation enthalpy of The fallawing data is provided for use inthe Bom-Haber cyete for calcium chloride: Helaliaiaaet hy + cats) Cats H= +190ki mol Atomisaton refers tothe formation + Cag)» Cg) +€ ‘H=+550kimol aft molec g2seousatoms.in cag) sca @) +e eee en His qcmnle 2 moles ef css | cece Ha +121 KImol? Pibebeabhale + Cats + CLug)— cach) 795kI mot? ermal + CaPIQ)+ 2CLIg) + CaCI) AH = 2237 KI mol > ‘AW = +242kImat* Draw a Bom-Haber cycle for calcium chloride, and determine the electron affinity of chitin. ‘This double the value of BANC Ca*(g) + 204) + 20 = Selioy = cle) axa ‘AW= 121d mol A= +1145 is mot cat(g) + 201 ‘As with atomisation a factor of + 2c) 2is included forthe election affinity of chlorine. two moles Car(g) + 204g) + A,H*= +590 ks mor of gaseous chloride ions are [colg) + 20g) obtained from gaseous chlorine AG eee atoms forthe enthalpy change. A) Calg) + Cla) 201g) + 26° — 20tg) Wy AJrCa) = +190 eT mot! AW =2x Ault rica) z Poet B= 705i caCys) Figure 1 Born-Haber cyte for calclum chore, Calculating the electron afinity of chlorine fs the final stage. The equation for electron affinity is Clg te cr@ Using Hess law: sum of anticlockwise enthalpies = sum of clockwise enthalpies AYHNCACL) = A,HPICa) +2 « ONC + Ay HCA] + Ag MCA) +2 DayMPICY + A.HICACL) 795 = + 190+ 242 + 590.4 1145 + 2x AgHICl + (-2237) Rearanging to find ACU: = 795 ~ (490 + 242 + 590 + 1145 ~ 2237)= 2x A,.HACD Therefor: 2x AgH®IC = -725kI mol Therefore: Bytercy ==225 363KImol* 60DS Using the enthalpy data below. draw a Bor-Haber cycle and calculate 2 value for the latice enthalpy of In Workes example 2 itis copper oxide. important that you remember ‘twrepresent the two electon affinities comecty ~ the fis is ‘exothermic and the second is ‘Atomisation of copper First fonisation of copper 4745 Sis Second ionisation of copper 1960 Remember: ‘Atomisation of onygen 4249 + endothermic changes are shown First electron affinity of oxygen =14L Seana anoles poleting UE Second election affinity of oxygen +790 lee se cea Using rows pointing DOWN, Formation of coppert oxide ~155 soe curtal +018) Qua) + Ola) + 26° Spf? —141 kl mat 41° = +1000 mat Cua + 0) +e Age 47451 me AAO) = #2491 me SECU) ~ +339 ml” 0 cul) + 206) Figure 2. Bomn-Haber cyte for copper) oxide Calculating the lattice enthalpy i the final stage. Using Hess lave ‘umm of anticlockwise enthalpies = sum of clockwise enthalpies AWH*{CUO) = AHCI] + AHO) + AgHXCU + DaH%CU + AHO) + AgaH"0) + AycHICUO) “155 = 4 399+ 249 +745 4 1950 ~ 141 +790 + AyHCUO) Rearranging to find A, HCuO: AyH®\CuO)= ~ 155 ~ (339 +249 + 745+ 1960-141 +790) Therefore: lattice enthalpy of cope oxide = ~4097 Ki mot Question © 2» Die aap Bon-habr ee or tefmation of ad MC, showing the species present at ech stage (Use te cata below tof the value fe election tiny of chine Enthalpy change of formation of MgCl, | ~642Imot* Lace enthalpy of MgC, “2493 kl mo Fist ionsetion eneray of Ma 276K mot Second ionisation energy of Mg +1450) mol Enthaly change of atomisaton f CL sais mot Enhaipy change of atomisaton of Ma 150i mot®Licey pesnrions ‘The standard enthalpy change of solution, Qa® ithe entlpy change tat takes place when ane mee of solute s completely dissoved in water under standard conditions. Te standard enthalpy change of hydration, 4H" s the enthalpy change that toes place when dsslving ene mole of cases ons in water Standard conditions are ‘considered as 100 kPa and a temperature of 298K, 2 Enthalpy change of solution and Neel aCe) a) By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: © explanation and use ofthe terms. (i) enthalpy change of solution (dissolving of 1 mol of solute, A..,4*) Li. enthalpy change of hycration (dissolving of 1 mol of gaseous ions in water, AnysH®) © use of the enthalpy change of solution ofa simple ionic solid (i.e. NaCl, MgCl) and relevant ceneray terms (enthalpy change of hydration and lattice enthalny fr: (i) the construction of enthalpy cycles lid related cateutations © qualitative explanation of the effect of ionic charge and ionic radius on the exothermic value of a lattice enthalpy and enthalpy change of hydration What happens when a solid dissolves? ‘When a solid dissolves, two processes take place +The ionic lattice breaks doen +The free ions become partof the solution (hydration. ‘A.change in enthalpy occurs when this overall process happens. The enthalpy of this process is known es the standard enthalpy change of solution, 4,.,f/°, end it corresponds to one mole of solute dissolving in water under standard conditions. ‘The dissolving of a substance can be endothermic (for example, when ammonium nitrate dissolves in water) or exothermic (for exemple, when calcium chloride dissolves in water). The substance that is dissolved is known as the solute, and the substance it dissolves in is known as the solvent. In order to understand why this is possible, we need to consider the stages of dissolving in more detail The breakdown of the ionic lattice In topic 5.2.1 we learned that the lattice enthalpy is the enthalpy change that accompanies the formation of one mole of an ionic compound from its gaseous ions. The process that occurs when the latice breaks down during dissolving is the reverse of this process, We imagine the lattice becoming free gaseous ions. ‘Therefore the enthalpy change of ionic latice brealsdown is equal to ~AsHH® For example, when the fonic lattice of potassium chloride forms: K'g) + Cite) — KCI) Ayplf==T1L kJ mol ‘When the ionic lattice of pocasstum chloride breaks down during dissolving: KCi(s) + K*{g) + Ce) AH=+711k)mol Notice that: + the processes are identical but the reverse of one another + the enthalpy change has the same value but different signs lattice enthalpy bas a negative sign and is exothermic + the breakdown of the ionic lattice has a postive sign and is endovhermic.What dictates the size of the lattice enthalpy? "The magnitude of any lattice enthalpy is dependent on: + the size of the fons involved + the charges on the ions + jonicbond strength (which is dependent on ionie size and charge), ‘Smaller ions, ie. fons with a smaller ionic radius, ean get closer together They will attract one ‘another more strongly and give rise to more exothermic latice enthalpy values, ie. more negative values ‘This is illustrated in Figure 1 using the sodium halides NaC], NaBr and Nal as examples. lace enthalpies (kJmol~) cr) er Latice enthaipy becomes less exothermic and es negate as casi |) theszeorthe ngative ons straction bereen ions a ence ‘weaker ion bonding Figure 1. The latie enthalpies ofthe sodium halides [ons with higher charges cause greater electrostatic attraction and in turn more exothermic lattice enthalpy values. The most exothermic lattice enthalpy values arise from small, highly charged ions, ‘This is illustrated in Figure 2, using ions of period 3 elements as examples we . d “The smallest, most highly charged ions wil give nse to the largest lattice enthales asthe can pack ‘eser to oppositely charged ions, with higher attraction. Latice enthalpies willbecome more fxotherm'e more negative Figure 2 The effect of charge on latice enthaloes Hydration of ions ‘Once the ionic lattice as broken dovmn into its constituent fons, these have to become part of the solution. This is known as hydration, The ions are able to do this if the solvent (water in the case of hydration) can interact with them in similar ways to the bonding in the lattice ~ remember ‘tke dissolves lite’. [onic solids are therefore able to dissolve in polar solvents, such as water Pr Charge density describes how ‘spread out @ charge is aross an Jon. If we consider two ions with the same charge, the smaller of the two ions would have a greater charge density as the charge | found ina smaller are, The larger ofthe two would have a lower charge density and be less attractive as the charge is more dispersed.‘During hydration: + the positive fons wil be attracted tothe slightly negative (3-) oxygen inthe water molecules + the negative ions will be attracted to the slightly positive (5+) hydrogens in the water molecules + the water molecules will completely surround the ions. ‘The hydration of potassium ions, K*, and chloride ions, Cl" is shown in Figure 3 seg oa \. i fos be ere ae ye oR ae Figure 3.The hycration afk and cl-ons occurs when porassium chloride Is dissolved, ‘An enthalpy change occurs when ions become hydrated, Energy is released when new bonds are formed between ions and ‘water molecules. This is the standard enthalpy change of hnydration, AyeH". and isthe enthalpy change when one mole of agueous ions are formed from their gaseous ions. under standard conditions For example A, ® for potassium ions is Ka) PK aq) ypl¥® =~922 41 mol" Agel!®for chloride ions is crte) "Fer taq) aff? = 9634 mol Notice that both have negative values for A,®. Ths is because 64 hydration is an exothermic process, ‘The magnitude of the enthalpy of hydration is dependent on: «the sizeof the ions involved + the charges on the ions. Jons with smaller ionic radi can get closer to the water molecules and are able to attract them more sirong'y. Tis means that on hydration, more energy is released and 44H” becarnes more «exothermic, For more information on reduced change density in larger ions, see the ‘Did you know?’ box on the previous page. ‘This trend i illustrated in Figure 4 for the hydration of halide ions, ae increases cr = 388 + Ajyieseroineme | fer = 25 l f= Figure 4 Enttalpy changes fr the hyeraton of alle ons. ‘The higher the charge on an ion, the greater the attraction it will have with the water molecule, This will give a more negative and hence more exothermic value for the enthalpy of hydration. ‘This trend is ilustrated for some common period 3 ions in Figure 5. The enthalpies in these examples will also be affected slightly by the size ofthe ions as there isa decrease in size aevosa the period. + ize decreases Na a + chargeincreaser + 3, Hemore exatrmic| [ME =r oF Tees v Figure 5 Enaloy changes of hyation of sme common cations Calculating a lattice enthalpy from enthalpy changes of solution and hydration “The energy changes associated with dissalving of ionic substances can be shown using Born-Haber cycles ‘The ionic solid and the gaseous ions can be linked by either: + the lattice enthalpy + the standard enthalpy of solution along with the standard enthalpy of hydration, ‘This means that if we know the standard enthalpies of solution ‘and hydration, we can calculate the lattice enthalpy for anionic sold — which, as we learned in topic 522.1, cannot be measured cirectly,‘Figure 6 Determining the enthalpy change of solution of paassium chido using simple apparatis sometimes known a6 cates cp calorimeter. {An example Born-Haber cycle is shown in Figure 7. This shows how the Born-Haber eyele for the dissolution of potassium chloride, KCl, can be used to determine lattice enthalpy. Kota) + Cr) ion otk Ki(ag) + 3634 mol"| hydration of C1 Ka) + Crag) lotce enthalpy F sJentnaipy change 26k mel a ‘of solution Figure 7 Bomar cyte forcalevlating the lattice enthalpy of KC) Notice that + the ionic solid is atthe bottom of the eycle + the gaseous ions are atthe top ofthe cyele + the route via latice enthalpy is shown on the left + the route via enthalpies of solution and hydration is shown on the right + the enthalpy change of solution (upwards arrow) does not correspond to the overall enthalpy change (downwards arrow) upwards = endothermic, downwards = exothermic, ‘The processes that form the Born-Haber cycle for the dissolving, cof potassium chloride in water are: KCIfs) + K'(aq) + Ch4aq) Ayal? = +261 mol-! Ke) Keep Ayal? = 822k mo Chg) > Crteq) Aygll® = -363K mel” KG) + CMG) > KES) AygH°= unknown Using tie Born-Haber cycle and Hess law, we can say that sum of clockwise enthalpy changes enthalpy changes Aaall 1K) + Bag tICH} 322 + (-363 sum of anticlockwise AcaHf(KCI) + AaHtKCI) AveH(KCD + 26 Rearranging to find Ay Ht ~ 322 ~ 363-26 = AccHH°(KCI) ‘Therefore: AeFH(KCI © te eras used to compar the soot oe bonds. Desabe ad ex te elect of ne carge ad onicrads on themida fate ental. 711 kImol © 1:20 ho. nd wan vy. the ently change of hytaton fot os fers om tat fbi ons © 212 vied wt te foovig ently changes. NG) Fig) Nas) AM=-918N mot* nari a) ‘fl = 3904 mot a : ar 8 tag ¢ Fa) d= 473K mat (a Name these tree ety changes, () Write an equation including state symbols, forthe change that accompanies the enthalpy change of hydration of F ions. (0 Calculate the enthalpy change of hydration of F ionsEntropy, 5. is the quantitative measure ofthe degree of disorder ina system. ‘he standard entropy, $°.of a substance isthe entropy content ‘of ane mole ofthe substance under standard conditions ‘Standard entropy change of reaction, AS®.is the entropy ‘change that accompanies 2 reaction in the molar quantities ‘expressed ina chemical equation under standard conditions, all reactants and produets being in their standard states, 66 By the end of this topic, you should be able to demonstrate and apply your knowledge and understanding of: » explanation that entropy is a measure of the dispersal of energy in a system which is greater, the more disordered a system © explanation of the difference in magnitude of the entropy of a system: (i of solids, liquids and gases (i. fora reaction in which there isa change in the number of gaseous molecules » calculation of the entropy change of a system, AS, and related quantities for a action given the ‘entropies of the reactants and products What is entropy? Entropy, given the symbol, is a measure of disorder ina system. System is used to describe the actual particles involved in a reaction or process. Surroundings descr everything outside the system, The more disordered the particles in the system are, the higher the entropy ofthe system. If you think of solids compared to gases, we would say tht the solid has a lower disorder compared to the gas~ the gas is more disordered, Entropy is a key thermodynamic factor that can be used to describe chemical processes. usually alongside enthalpy ‘The standard entropy, 5”, of a substance isthe entropy content of one mole of the substance under standard conditions. Standard entropies have units of JK *mol All substances above 0K possess a certain degree of disorder because they are in constant motion. ‘This means that: + entropy, 5, is always a positive number abave 0 + at OK. entropy is zero for perfect crystal, Most substances are thermodynamically stable atthe lowest energy state, which would correspond to a low entropy. However, entropy always tends to increase; quid water naturally evaporates into ‘gaseous water, Increasing entropy; heat energy spreads out fram hot objects, increasing entropy; salt particles dissaive in water, increasing entropy [cs always more probable that a more disordered system will be found instead of a more ordered system. This is illustrated in Figure 1 oy OO BO, Pile of bricks dropped from a lorry Whit arrangement is the more probable? Disorder is ‘more probable than order Figure 1 Increasing entropy.Often a useful way to think about entropy is ‘+ more spreading out of energy = higher entropy ‘+ more random arrangements of particles = higher entropy. Entropy can change during the course of a chemical process or reaction, These changes would be ieseribed in cerms of the change in entropy, AS. Although there is alway higher entropy (this is the second law of ynamics) itis possible for entropy to decrease, ie. for AS to be negative. For example, wate a tendency towar ing, would represent a decrease in entropy as a liquid has become a more ordered solid, with lower levels of energy dispersal How entropy is affected by temperature Entropy of pure su per kelvin (K-4) ature. The values of ent spendent on the temperature, entropy values are a y are given + Particles at higher temperatures have higher energy and move me + The arrangement of particles at higher temperatures becomes more randor + Entropy of solids < entropy of liquids < entropy of gases When water boils and becomes gaseous its 70kI mn: ropy rises 189 kJ mol"? Entropy changes when dissolving ionic solids that allow more disorder ie, more ways for energy to be arranged or entropy will increase, If a reaction results in product persed far more Cu*(aq) + SO? (aq) + 5H, Figure 2 Cryst of CuS0,SH,015) anda solution of CuSO {eo} wit some undissolved crystals. The blue crystal ate soluble ad cssoluing them produces a Bue solution ~ copprll sulfate ions are spreading out and entropy is increasing How the number of gas molecules affects entropy If the number of gas molecules changes during a reaction, entropy changes. + An increase in the number of gas molecules causes an increase in entropy Eg, CaCO4(s) + 2H1(aq) + Ca?*(aq) + CO,(g) + H-0() Figure 3 Entropy cecreases when +A decrease in ie number of gas molecules causes a decrease in entropy. ‘egnesim tums in oxygen. as there Isa decease inthe number of gas Eg. Ma(s) + Ox{g) — MgO(s) ates present68 Calculating entropy changes ‘The standard entropy change for a reaction isthe change in entropy that occurs when a reaction takes place under standard concitions, with molar quantities of each reactant reacting in theic standard states. Ths is given the symbol AS* ‘The standard entropy of a reaction is calculated using the entropies of the reactants and products as follos: AS= ES%praize~ ES" eecats Gohere 3 = ‘sum of) Entropy is a measure of randomness. Systems that are more chaotic have a higher entropy value + Ifa change makes a system more random, AS's positive, + Ifa change makes a system more ordered, S's negative. a ET sik ' mot ESE +131 @ wars ne sgn oF store owing actions? Ga) NaCl) — Naan) + C10) (©) 25049) +04) = 25046) (0 tl + 124046) ~ BCOAg) + 9,00 © vse he catan the tbe beow to caculte ASfortese actos, (0) 2NO1 + Oxo) ~ N40) (CH + 7040) ~:6C045) «34,010 Pore S173 | 4214Free energy By the end of this to understanding of: you should be able to demonstrate and apply your knowledge and the explanation that the feasibility of a process depends upon the entropy change and ‘temperature in the system, TAS, and the enthalpy change of the system, AW © the explanation, and related calculations, of the free eneray change, AG, as: AG= AH TAS the Gibbs’ equation) and that a process is feasible when AG has a negative value © the limitations of predictions made by 4G about feasibility, in terms of kinetics The free energy change, AG. isthe balance between enthalpy. entropy and temperature fora process: AG= AW~TAS [A process can take place spontaneously when AG < 0. Spontaneous changes Fora process to happen spontaneously ie, nstantanewusy, entropy must increase, But there are many examples of reactions that happen spontaneoust that would seem fo lower entop, or example a metal rusting i exjgen ora gas condensing “To understand why these are able to occur we need to consider the entTopy change of both the system and the surroundings Total change in entropy We calculate the total change in entropy as fellows ASS = WSican + ASS For spontaneous changes to occur, the total change in entropy rust be positive Reactions that have a decrease in entropy can occur spontaneously ifthe change in entropy of the surroundings is positive enough to make the ratal change in entropy positive. Free energy ‘Changes in entropy are linked with energy changes that occur during «teaction or change; remember, entropy isa measure of the cispersal of energy. A reaction that would have a positive entropy change stil may only be spontaneous at certain vemperatures. Reactions and processes have to be considered in terms of enthalpy changes A/i, total entropy changes AS, and temperature T (measured in K) The Gibbs’ equation ‘The energy that becomes ‘ree’ during a reaction is known as Gibbs’ fee energy after the theoretical physicist and ‘mathematician, Josiah Willard Gibbs, and is given the symbol G It is dependent on the total entropy and enthalpy changes that occur as well as being dependent on temperazure. “The free energy change is calculated using the Gibbs’ equation: AG= AH TAS For a reaction to occur spontaneously, AG must be negative. Using the Gibbs’ equation to predict feasibility of reactions Using the Gibts' equation, we can make some assumptions about conditions that will favour spontaneous changes. + Large increases in entropy will cause decreases in AG, because the term ~7AS will become larger + Lange negative values for A/? (Le. highly exothermic reactions) ‘will result in more negative values for AG. However, there isa balance to be struck. If, for example, a highly exothermic reaction causes a large decrease in entropy, AG may ’be positive, in which case the change would not be spontaneous “The effect of enthalpy and entropy changes on AG are ‘summarised in Table 1. negative | positive | alwaysnegative | reaction feasible positive negative | always positive reaction never feasible negative negative | negative at low feasible at low temperatures temperatures positive positive negative atihigh feasible 2t high temperatures. temperatures ‘Table 1 The eect of enthalpy and entropy changes on AG.Tn summary: + exothermic reactions are generally spontaneous — the negative value of A's usually stil able 10 make AG negative, even if the entropy change is postive + endothermic changes are only spontaneous ifthe entropy is positive and the temperature is high enough to make TAS large and postive, ie. greater than AH, worse exw The thetmal decomposition of zinc cabonate,2nC0,, s represented by: ZnCO,'s) + Zn0\s) + C049 AH=471kimot* Use the data in the table to caleuate the minimum temperature, n°, {or thermal decomposition to take place. Step 4 Calelate Ain unis of kK"! mot! AS= 2S" yeten— BS ete =us714-82 76146 matt 017643 mol ‘Step 2: Calculate Then AG= 0 AG=AH- TAS When: AG=0 AH-Tas=0 Therelore: an AS a 0176 403 403 - 273 = 130°C DN In free energy elated calculations. you need to get the units of ules for ‘entropy and enthalpy te same. ‘+ A\His usually ven in ki matt + ASis usualy given in J K-?mot* Fist get ASinto KK mot! + toconvert to Ky, divide by 1000, ‘Also remember that entropy is worked out using temperature in K + toconvert °C 10K, add 273, + toconvertK to °, subtract 273, Limitations of using AG to predict feasibility of reactions Calculating the value ofthe free energy, AG, gives @ theoretical answer for whether a reaction or process will react spontaneously, ice. whether itis thermodynamically possible. 70 If 2 reaction is found to have a negative value of AG. it does not ‘mean it will actually go on to react, For example, burning petvol in| a car involves combusting a fuel: itis a very exothermic reaction and produces gaseous products, hence an increase in entropy. ‘Thermodynamicaly it should react spontaneously. Thankfully for all the drivers in the world filing their cars with petra, it does not — it needs to be ignited first! ‘Whether or not a reaction proceeds spontaneously also depends con kinetic factors, + The reaction may have a high activation energy — energy needs {0 be intially supplied to overcome this, eg. igniting a fuel. + The rate of the reaction may be extremely slow. ‘Equally, reactions that have positive values of AG are considered, not feasible. They can be mace to take place however, usually by changing the temperature of the reaction. Figure 1 Some reactions are thermodynamical feasible and have a negative valve of AG but do nt cccur spontaneously du to kinetic factor such as aztvaion bares or slow ates of eactons. An examale fs the buming ofa fue such 3 petro © 1% combustion of thao represented by HOH + 30,6) 200,) + 34,000 796K)" Calculate AG tor ths reaction at 25°C, The equation forthe thermal decomposition af ammonium Chloride, NKQCL i: INH,CUs| — NHY(g)+ HCG) AH=H176kI mol Caloulate the minimum tempereture in °C for thermal decomposition to take place spontaneousty +95, +192By the end of this to understanding of: you should be able to demonstrate and apply your knowledge and © explanation and use of the terms oxidising agent and reducing agent © construction of redox equations using half-equations and oxidation numbers » interpretation and prediction of reactions involving electron transfer Redox ‘You will recall from Book 1, topic 2.1.19, that redex reactions involve both oxidation and reduction. + Oxidation is the loss of electrons — an increase in oxidation umber + Reduction isthe gain of electrons ~ a decrease in oxidation umber Oxidising and reducing agents electrons must be transferred during a redox reaction - they cannot just disappear, they rust be transferred between species. Oxidising agents ‘When a species is oxidised, it loses electrons, These electrons are gained by the species being reduced If a chemicals readily reduced it will gain the electrons in the reaction and is known as the oxidising agent, Reducing agents ‘When a species is reduced, it gains electrons. These electrons ‘have been removed from the species being oxidised. If a chemical is readily cxidised it will provide the electrons in the reaction and is known as the reducing agent, Redox half-equations Redox is essentially two reactions occurring simultaneously: + the reduction of e species + the oxidation of a species. It soften helpful to consider each of these reactions separately, We can use hall-equations to do this, Half-equations show ‘half the reaction, If-we consider the redox reaction that occurs when a metal, such as magnesium, reacts with an ac: Male) + 2HCl{aq) + MgClaq) + He) ‘this overall redox equation can be broken down into two half equations Mg — Mg? + 2e- 2H? + 26 this is the oxidation half-equation +H, this the reduction half-equation Notice thatthe numberof electrons losin the oxidation hal equation isthe same as the nunber of electrons gained inthe reduction half-equation. This must aivays be the case ~ the electrons must balance. Notice also that Cl" is not included in either of the half-equations. ‘This is because chlorine fons are not involved in the redox reaction ~ its oxidation number remains ~1 throughout the reaction, tis mown as a spectator ion and does not need to be included in the hralf-equation. Using half-equations to construct full redox equations We can construct an overall equation fora redox reaction if we know the oxidation and reduction half-equations. “To construct a balanced equation, we must follow a series of steps. These are illustrated in the first worked exampleRe Iron reacts with aqueous copper ions to form irndi) fons and copper metal, ‘Step 1: Identity the oxidation and reduction halt equations. ‘+ Equations forthe separate oxidation and reduction reactions are shown lined up. + fe Fe 4 3e + cue +28 cu ‘Step 2: Balance the electrons. The half-equations are scaled up or down (by multiplying the entre hal-equation so that the number of electrons is te same in each. Here, we need to multiply the oxidation hal-equation by 2and the reduction half-equation by 3: + 2e = DF + 66° + 3c + 66° — 3c Step 3: Add the two half-equations together and cancel the electrons + 3Cut + Fe 4.56 Fe + 3Cu + Be So the balanced equation is: + 30 +-2Fe — 2Fe™ + 300 oxidation (loss of electrons) reduction (gan of electrons) oxidation reduction Using oxidation numbers to construct redox equations Assigning oxidation numbers to each substance involved in a redox reaction allows you to track the movement of electrons + An increase in oxidation number shows a substance has been oxidised + A decrease in oxidation number shows a substance has been reduced + The overall increase in oxidation number will equal the overall decrease in oxidation number By knowing how each species involved in a reaction will behave (ce. its tendency towards losing or gaining electrons, the ions it forms, and so on) its possible to predict the whole reaction that will oceur and write a full redox equation to represent reactions. For example: + metals generally will be the species that lose their electrons + non-metals usually gain electrons + the group number (number of cuter electrons) can be used to predict the ion charge for most elements ~ along with the other rules for assigning oxidation numbers to species involved in redox reactions. We use this information to identify half equations that can then be Joined together to form a full edox equation. An example of using oxidation numbers to construct redox ‘equations is shown in the second worked example. Hydrogen iodide, Hi is oxidised to foie, I, by concentrated sulfuric acid, H,S0,, whic is reduced to hydrogen sulfide, H.S. ‘Step 1; Identify the reactants and products from the information given. + The eactants and products are writin down to give an incomplete at equation: HL H,50,— HS + Ip 2 + Do not wotty that there is no '0" onthe right-hand side ofthe equation we wil sort that out later. ‘Step 2: Identify the oxidation nurnber changes. + Wate oxidation numbers undemeath the atoms that change oxidation ‘umber, + Balance ary atom that changes oxidation number. + Identity the total changes in oxidation numbers. DHL HsS0, > HS +I 46-2 Shas decreased exidation number by 8 from +6 to -2 1602) (2) thas increased oxidation number by 2. ftom ~1 to 0. twice ‘Step 3: Balance the oxidation number changes + The equation must be balanced sot total increase in oxidation number = total decrease in oxidation number + Here, we need to multiply Hl and Iz by 4 to balance the total ‘oxidation number change for S, so that the number of electrons being lose when Hi becomes | s the same as the number being gained when H,S0, becomes: BHI + H3S0, — HS + 4h 46 to1al gain of 8 electrons 18) total loss of 8 electrons 48 ‘Step 4: Check 1 see if anything else needs to be balanced. + Here there are BH and 40 extra onthe left-hand side, We can easily complete the equation by adding 4H0 tothe right-hand sid, + This gives the final equation BHI H,SO, > HS + AL + 44,0 oa PieaRING Te | In Worked example 2, extra substances need to be added into the {equation to make it balance. This will be the case sometimes. The mast ‘common species you may need to add are: ‘+H usually when reactions are caried out in acid conditions| + OH" usually when reactions are cared out in alkaline conditions + H,0 usually wen the equation needs extra O and K tobe added. Simply add the numberof ions needed to balance the equation sie cin tarts aot ha sats assem e2e cu (by 28r + Br, #26 MoOq + BH? + Se — Mn+ 4H0 Or ecco ens (a) Hydrogen bromide. HBr. is oxidised to bromine. Bra. by Comte sui, SO, vc fv ose sie 50, 0 hymgen sue. ded sl 5 by te a 1hDy ics acd wboper moro NOBy the end of this topi understanding of: iClear aod , You should be able to demonstrate and apply your knowledge and © the techniques and procedures used when carrying out redox titrations including those involving Fe2"/MinO,- and |,/S,0,2 structured and non-structured titration calculations, based on experimental results of redox titrations involving (i) Fe®/Mn0,- and L,/S,0,> (il) non-familiar redox systems Redox titrations ‘Titrations are a way of determining amounts of substances, for example the concentration of an unknown acid. They can also be used to determine the amounts of species being oxidised or reduced ~ this is known as a redex titration A known concentration of either a reducing agent or oxidising agent is placed in a burette and titrated against an unknown concentration of the chemical that is being oxidised or reduced, ively. Whilst for acid-base reactions we use an indicator to identify the end point, often for redox titrations this snot necessary. Many redax titrations involve species that selfindicate they change colour between different oxidation states. We will look at some examples of redex titrations below. Redox titrations between Fe?* and MnO, Manganate(VI) MnO, is a common oxidising agent, usually obtained from potassium permanganate(VIl), KMinO,, [thas a deep purple colour but becomes colourless when i is reduced from +7 to +2 oxidation states ‘Mn0,"(aq) — Mn**(aq) (ou (colourless) Figure 1 Colours o sous ions containing MnO, (a) (lft) and nia) ons. ‘This usually occurs in the presence of H' ions, ie. in acide solutions (typically sulfuric acid is used, as hydrochloric acid reacts with MnO, >) MnO, (aq) + 8H*(aq) + Se —+ Mn?*(aq) + 4H,00) MnO," is commonly used to oxidise solutions containing iron(I), but can be used as an oxidising agent in many other chemical ‘The reaction between iron(II) and acidified manganate(VIl) is, shown below: MnO, (ag) + 8H"(aq) + 5Fe*(2q) + Mn"(aq) + 5Fe™(aq) + 44,0()) ‘The end point is seen when excess MnO," ions are present — indicated by a faint pink colour appearing, This occurs because all the Fe ions have reacted and the MnO,- can no longer be reduced to the colourless Ma#* We can use this reaction to determine the concentration of iron in an unknown solution, or indeed other fons that can be oxidised by MnO, or to caleulate the percentage composition of @ metal ina solid sample of a compound or alloy, When calculating the mass of iron in a substance, the molar mass of an Fe ion is taken to be the same as the molar mass of Fe therefore the titration results can be used directly to convert the number of moles into the mass present. iM Figure 2 Measuring the conceniation of ond fn in a solution of rom sultte. You can see the purple colour ofthe MnO,” before it reacts withthe acide Faq) solution inthe conical flask.25.0 of a solution of an iron salt required 23.00 cm? of (0.0200 mol d* potassium permanganate for complete oxidation in ‘acid solution. {al Calculate the amount, in moles of permanganate, MaO,7, used in the tiation ImMMnO%)= eV _ (0.0200 23.00) _ 4 69, 19-4 1000 1000, Sie: {) Deduce the amount, in mos, of ron, Fe inthe solution that was trated, From the equation: LMn0jfaq) reacts with 5Fe*laq) So,theactual moles: 460% 10 mol Mnd; 230% 10" mol Fe Mn0;{aa) + Bla) + 5Fe™*(aq) — Mn?) + 5Fe* la) + 44,010 {cl Calculate the concentration, In mol dr}, of Fe? inthe solution that was titrated trey 100 _ 2:30 10" Vidm') (25071000) 10920 mt dm? Nice that to solve the problem given in Worked example 1. we need to use the equation n= cVfor pats (a and (c) and the balanced equation for pati) Redox titrations between |, and $,0,?" Jodine isa useful substance to use in redox trations as it has a darc blue-black color in the presence of starch bt when tis reduced to iodide ions this colour disappears. oa) 2-(aq) +28 (blue-black colour with starch) —(olue-black colour disappears) ‘This reduction of iodine to iodide ions will occur in the presence of thiosulfate ions, $;0;" 25,02 (aq) + Ix{aq) thiosulfate S,0¢ (aq) +21 (aq) tetrathionate We can use aqueous iodide ions and aqueous thiosulfate 0 determine the concentration of unknown reducible species Often this involves an initial reaction between the unknown oxidising agent and iodide ions (for example by mixing it with, potassium iodide), which has iodine as a product. For example: faq) + 21-(aq) + 2Cr(aq) + Lea) ‘This liberated iodine then goes on to react with thiosulfate ions, from a solution with a known concentration being added fram a burette 25,0." (aq) + Isaq) — $,0,7 (aq) + 21-(aq) Inthe presence of starch, a blue-black colour will remain present as long as there is any iodine. Once this has all reacted with the thiosulfate ions, this will disappear, marking the end point of the reaction. 7” Figure 3 lodine has a blue-black appearance in the presence of starch. During a ration Beaween iodine and thiosufae ons, this ealour wil remain a org asiodine i present Chlorine was reacted with potassium fodide and the solution then tiated against 2027 moLdnr” solution of sodium thiasulfate i the presence of stare 18.0cm of sodium thiosulfate was required forthe blue-black colour to disappear. Calculate the numberof moles of chlorine that reacted, ‘Step 4: Calculate the numberof moles of thiosulfate used 15,02 Step 2: ‘Wite balanced equations forthe reaction between the species being Investigated and iodine and the reaction between iodine and thiosulfate (you may need to deduce these. Ch +2 2ct +t, 25.0%" +p 5,02 +2 Step 3: ‘Work out the stoichiometry of each reaction and the numberof moles ptesent for known substances. Then calculate the number of moles for Unknown substances. +L mol Cl produces 1 mol : therefore 2.43 x 10% mol, must have been produced from 243 x 10°? mol Cl, + Amol reacts with 2mol$,0,¢: therefor, 4.86 x 10° mel S,0,% ‘must have reacted with 2.43 x 10-2mol I Calculations involving unfamiliar redox systems Sometimes you will be required to interpret the results from redox systems you are not familiar with, You willbe given any relevant equations and experimental resuits that you need. The procedures willbe the same: some general steps you may need to use include:‘+ determining the numbers of moles used for any of the substances you have concentrations and volumes for, using a= eV and number of mele Fiala aaaap Whete necessary + identifying the reaction stoichiometry using the balanced equations + deciding on the amounts that have reacted for known substances, and deducing the amounts of unknowns: + using the equations discussed above to calculate unknown quantities or concentrations, ‘An example is given in the next worked example, 'A25.0em® portion of hydrogen peroxide was poured Into a 250 cm volumetric flask and made upto the mark th sills water. ‘825.0 em? portion of ths solution was aciified and titrated against 0.0200 mol dm potassium permanganate solution. 38.00 cm* of the MnO; solution was required for complete oxidation Calculate the concentration ofthe original hydrogen peronice solution. Tie following equation represents the oxidation of hydrogen peroxide: H,0.09) — O,(g) + 2H" aq) + 26 Step 4: You will ned to write the fully balanced equation for the reaction to find the stoichiometry between the ‘wo reactants, The equation for Ma; ions is M029) + BHYaq) + Se Moog) + 44,010 The fully balanced equation -2Mn0aq) + aq + 502g) ~ 26a) + BH,OAD + 50.10) Stop 2: Calculate the amount of Mn, that reacted. mMan04) = 6h = 0.0200 x 3820 = 7.60. 10-+mol 000 1000 ‘Step 3: Deduce the amount of #0, that was used in the ttation. equation 2MonOjlaq)reacts with 50,109) moles from equation 2mol Smal actual moles 7.60 10-* mol 190 = 10°? mol ‘Step 4: Calculate the concentration, In mol dr ofthe hycrogen peroxide solution, 0 190% 10 4902107 _ ga760mol.dnr V~ 250/100 ‘Step 5:The fist sentence ofthis worked example states thatthe solution was diluted by factor of10 atthe start ofthe experiment. Therefore the concentration ofthe onginal hydrogen peroide solution s 0.760 mo dm Estimating the copper content of solutions and alloys Redox titrations can be used to estimate the concentration of a solution containing Cu®"(aq) ions ‘The copper(l) solution is mixed with aqueous iodide ions, (aq), anda redax reaction occurs. This can be shown as two hall-equations: + iodide ions are exidised to iodine, 21” — |, + 2€ + copper{ll) ions are reduced to copper) ions, Cu So, the overall ionic equation is 2CuP(aq) + AI (ag) — 2Cul(s) + Ifa) ‘The reaction produces alight brown/yellow solution and a white precipitate of copper(l) iodide, but the precipitate appears light brown due to the iodine in the solution, ‘The misture of copper iodide and iodine can be titrated against sodium thiosulfate of know concentration. As the iodine reacts, the iodine colour gets paler during the titration. When the colour ssa pale straw, a small amount of starch is added to help withthe identification of the end point. ‘A blue-black colour forms, The blue-black colour disappears sharply at the end point because all the iodine has reacted ‘You wil need to beable to perform structured titration ‘calculations and unstuctures tiation ealeulations. Structured ‘calculations wll have clear stops shown, For unstructured ‘calculations, you wll be given the experimental resuits only and ‘any equations required ~ you will, need to decide the steps to cary ‘out the calculation for youreET In Worked example 4. the rounding ofthe answer was not cated out until the last step in order to give as accurate an answer as possible. Ealy rounding can lead to incomecttnaccurate) The value is given to 3 significant figures as this matches the lowest numberof significant figures sien inthe information provided inthe question. Remember. you are only justified to quote tothe lowest numberof significant figures given 76 ‘You can then use the amount of thiosulfate used to determine the concentration of iodine in the titration mixture, and hence the concentration of copper(l) ions in che original solution, ‘One application for this method isto caleulate (within experimental error) the concentration of ccopperil) ions in an unknown solution, or the percentage of copper in alloys such as brass and bronze. ‘To obtain the copper(I!) in solution, the alley is fist reacted with nitric acid, Brass and bronze can both be reacted ta produce a solution containing copper(I) ions, which can then be reacted with potassium iodide solution. The iodine that forms is then titrated against sodium thiosulfate Dopp Sx ‘A sample of bronze was analysed to find the proportion of copper it contained. (05009 ofthe bronze was reacted with nitric acid to give a solution containing Cu ons. The solution was ‘nouralised and reacted with iodide ions to praduce iodine “The iodine was titrated with 0.200 mol dm-* sodium thiosulfate and 2240 cn was needed to reach the end point Calculate te percentage of copper inthe bronze The relevant equations ae: Cuts) = aa) + 26 2¢u"aa) + Araq) — 2Culs + faq) 25,021) + Lag) 2 aa) + 5,010) Stop 1: Calculate the amount of thiosulfate used. 5,08 Stop 2: Calculate the reacting amounts + 2mol Cu produces 1 mol, wich reacts with 2 mol S03" + mol Cu reacted with nic acid to produce 1 mol Cu + S01 mol Cuis equivalent to 1 mol §,0," Stop 3: Calculate the % copper. Cul = 15,0,2) = 448 x 10-4 mol Mass of copper = nx M= 4.48 x 107x635 0.28689 028443 ‘0500 4.48 x10 mal ‘E eapper in bronze = 100 = 569%, Cand 25.0 ine sia plasm. lectode seid salution solution containing ‘ontaiing 10moldm 10maldm H'G@q) Zni*(aq) Figure 4 Measuring the standard electrode potential ofa Zn? /Zn hal oe Notice that in Figure 4 the two cells are joined by the following: ‘+a wire~ this allows the electrons carrying charge to flow through it + a salt bridge — this connects the two solutions and allows ions carrying charge to be transferred between the half cells, Salt bridges are usually made from a piece of filter paper soaked in an aqueous solution of an ionic substance, usually KNO,(aq) or NH,NOs(aq) The electrochemical series ‘We can lst hal cells in order of their standard electrode potentials ~ ths is known asthe electrochemical series, A small portion ofthis is shown below, The horizontal arrows show each reaction as a reduction reaction as electrons are gained. Ifthe electrode potential isa negative vale, the backward reaction vil cccur when compared withthe standard ydrogen electrode, Ir the electrode potential is a postive value the forward reaction wil ‘occur when compared to the standard hydrogen electrode = preferred direction of reaction Fet (ag) + 22° = Fas) 2H (aq) + 26° = Hale) Cu*(ag) + 2e° = Culs) Brg) +2e” = 2Br-(aq) lig) +26" = 2Chaq) + preferred direetion of reaction £ E “The more negative the E*value, the greater the tendency towards the half cell undergoing oxidation; the more positive the EF? ‘value, the greater the tendency towards the half cell undergoing reduction, when connected in a cell From this small series we could say thatthe half cell Fel + 20 = Fe + has the most negative 2° value + therefore has the greatest tendency to release electrons and shift the equilibrium to the left E* values for standard electrode potentials can be used to predict ‘what will happen when half cells are connected together to form a cell This will be covered in the next topic, 5.2.10 (a) State what a standard hydrogen half cell consist of. {0) When two cfferent half cells are connected, state how the electric curent flows: (between the rwo electrodes 4) between tie twa solutions. © 2 sor ease porn fo the nace Carag) 24" = Cfswas menue as #038 flan how hs vale woud have Bee string