edexcel 3 Ey Peer Edexcel A2 Chemistry Revision Guide REVISION GUIDEL ae este Edexcel A2 Chemistry Revision GuideContents 2w 10 use this Revision Guide ision techniques Answering multiple-choice and extended questions: Unit 4 General principles of chemistry I - Rates, equilibria and further organic chemistry Topic 1 How fast? ~ Rates Rate of reaction Activation energy and catalysis Mechanisms and rate-determining steps Topic 1 Checklist Topic 1 Build better answers Topic 1 Practice exam questions Topic 2 How far? - Entropy Entropy Feasibilty, stability and inertness Enthalpy changes and dissolving Topic 2 Checkiist Topic 2 Build better answers Topic 2 Practice exam questions Topic 3 Equilibria Equilioium mixtures Gaseous equilbria and K, Mote on equilibrium constants Topic 4 Application of rates and equilibrium Rates and equilibria in industry Topics 3 and 4 Checklist Topics 3 and 4 Build better answers Topics 3 and 4 Practice exam questions Topic 5 Acid/base equilibria Acids and bases iH and dissociation constants Titration curves, indicators and buffers Topic § Checklist Topic § Build better answers Topic § Practice exam questions Topic 6 Further organic chemistry ‘somerism, chirality and optical activity Aldehydes and ketones Reactions of carbonyl compounds Carboxylic acids ters and polyesters Acyl chlorides Topic 7 Spectroscopy, spectrometry and chromatography Spectroscopy UV, mass spectra and chromatography Topics 6 and 7 Checklist Topics 6 and 7 Build better answers Topics 6 and 7 Practice exam questions Unit 4 Practice unit test 5 6 10 12 14 15 18 22 24 24 25 26 28 30 33 36 38, 39 41 44 46 46 46 48 49 50 54 56 Unit 5 General principles of chemistry II - Transition metals and organic nitrogen chemistry Topic 1 Redox and the chemistry of the transition metals Redox reactions and titrations Redox and electrode potentials Feasibility and extent of reactions Applying electrochemistry Transition metals Chemistry of chromium and copper Uses of transition metals Observations on transition metal ions Topic 1 Checklist Topic 1 Build better answers Topic 1 Practice exam questions Topic 2 Organic chemistry - arenes, nitrogen compounds and synthesis Benzene chemistry ‘Amino compounds Amides and polyamides ‘Amino acids Organic synthesis Organic synthesis techniques Topic 2 Checklist Topic 2 Build better answers Topic 2 Practice exam questions Unit 5 Practice unit test Unit 6 Chemistry laboratory skills Answers Answers to in-text questions Answers to practice unit tests Index ‘A2 Chemistry Revision GuideHow to use this Revision Guide A2 Chemistry Revision Guide Welcome to your Edexcel A2 Chemistry Revision Guide. This unique guide provides you with tallored support, written by Senior Examiners They draw on real ‘ResultsPlus' exam data from past A-level exams, and have used this to identify common pitfalls that have caught out other students, and areas an which 10 focus your revision. As you work your way thraugh the topics, look out for the following features throughout the text ResultsPlus Examiner Tip These sections help you perform to your best in the exams by highlighting key terms and information, analysing the questions you may be asked, and showing how to approach answering them. All of this is based on data from reablfe A-level students! ResultsPlus Watch Out! The examiners have looked back at data from previous exams to find the common pitfalls and mistakes made by students — and guide you on how to avoid repeating them in your exam, Quick Questions Use these questions as a quick recap to test your knowledge as you progress. Worked Examples ‘The examiners provide step-by-step guidance on complex equations and concepts Each topic also ends with: Topic Checklist “This summarises what you should know for this topic, which specification point each checkpoint covers and where in the quide you can revise it. Use it to record your progress as you revise ResultsPlus Build Better Answers Here you will find sample exam questions with exemplar answers, examiner tips and 2 commentary s0 you can see how to get the highest marks. Practice Exam Questions Exam-style questions, including multiple-choice, offer plenty of practice ahead of ‘the written exams, Both Unit 4 and Unit 5 conclude with a Practice Unit Test to test your learning. These are not intended as timed, full-length papers, but provide a range of exam-style practice questions covering the range of content likely to be encountered within the Unit test. Tre final Unit consists of advice and support on the practical exercises which assess your chemistry laboratory skills, giving guidance to help you make inferences from qualitative observations, carry out quantitative measurements and prepare a named substance, ‘Answers to all the in-text questions, as well as detailed, mark-by- mark answers to the practice exam questions, can be found at the back of the book: We hope you find this guide invaluable. Best of luck!Revision techniques red can be the hardest part of revision, but don’t leave it too late. Revise 3 often! Don’t spend too long on any one section, but revisit it several times, 's something you don’t understand, ask your teacher for help. Just reading your notes is not enough. Take an active approach using some of the revision suggested below. ‘Aatve Summarise| works be when Test yourself Summarising key ideas ¢ sure you don’t end up just copying out your notes in full. Use some of these <>niques to produce condensed notes. es and lists to present information concisely. 12x cards to record the most important points for each section. ‘arts to identify steps in process. grams to present information visually. der diagrams, mind maps and concept maps to show the links between ideas. -mionics to help you remember lists aries to make Sure you know clear definitions of key terms. page references to your notes or textbook. Use colour and highlighting to pick terms, Active techniques It you use resources from esewier, tak sure bay cove the ght cortert atthe ight ove vatiety of approaches will prevent your revision becoming boring and will make of the ideas stick. Here are some methods to try in ideas to a partner and ask each other questions. .¢ a podcast and play it back to yourself. PowerPoint to make interactive notes and tests. arch the Internet for animations, tests and tutorials that you can use. ‘rk in a group to create and use games and quizzes, Test yourself {cu have revised a topic, you need to check that you can remember and apply you have learnt ‘the questions from your textbook and this revision guide someone to test you on Key points. + 7 some past exam questions.Answering multiple-choice and extended questions Section A of Unit tests 4 and 5 contain objective test (multiple-choice) questions. Section B contains @ mixture of short-answer and extended-answer questions, including the analysis, interpretation and evaluation of experimental and investigative activities. Section C includes data analysis questions (Lint 4) ar includes contemporary context questions (Unit 5). In all sections you may be requited to apply your knowledge and understanding of chemistry to situations that you have not seen before. Multiple-choice questions For each question there are four possible answers, labelled A, 8, C and D. A good ‘multiple-choice question (from an examiner's point of view) gives the correct answer and three other possible answers, which all seem plausible The best way to answer a multiple-choice question is to read the question and try land answer it before looking at the possible answers. You may need to do some calculations — space is provided on the question paper for rough working, If the answer you thought of or calculate is among the possible answers — job done! Just have a look at the other possibilities to convince yourself that you were right, If the answer you thought of isn’t there, look at the possible answers and try to eliminate wrong answers until you are left with the correct one. You don’t lose any marks by having a quess (if you can't work out the answer) — but you won't score anything by leaving the answer blank. if you narrow down the number of possible answers, the chances of having a lucky guess at the right answer will increase. To indicate the correct answer, puta cross in the box following the correct staternent. If you ‘change your mind, put a line through the box and fill in your new answer with a cross. How Science Works s ‘The idea behind "How Science Works's to give you insight into the ways in which scientists \work: how an experiment is designed, how theories and models are put together, how data is analysed, how scientists respond to factors such as ethies and so on, Many of the HSW criteria require practical or investigative skills and will be tested as part of your assessed practical work, However, there will be questions on the written Units that cover all the HSW criteria. Some of these questions will involve data or graph interpretation, including determining quantities (with appropriate units) from the gradient and intercept of a graph ‘Another common type of HSW question will be on evaluating various steps in an experiment, For example, = explain or justify why a particular piece of apparatus is used - identify possible sources of systematic or random error explain why we use an instrument in a particular way - what safety precautions would be relevant, and why? You may be asked questions involving designing an investigation: these are likely to involve pieces of familiar practical work. Other HSW questions may concentrate on issues surrounding the applications and implications of science (including ethical issues), or on using a scientific model to make predictions a A2 Chemistry Revision GuideExtended questions 2 units — Unit 4 and Unit 5 ~ you will come across questions with larger numbers ‘haps up to 6 marks in one part of one question. in these Units are designed to be synoptic —in other words, they are designed 0 show knowledge gained in the earlier units. Bear this in rind when you answer on: ty to include relevant knowledge from your AS course when answering ons, too, that if part of a question is worth 6 marks, you need to make six 2 tworthy points. Think about the points that you will make and put them together in a quence when you waite your answer. On longer questions, the examiners will be 9 at your QWC (Quality of Written Communication) as well 2s the answer you give. A2 Chemistry Revision GuideUnit 4: General principles of chemistry I— Rates, equilibria and further organic chemistry ile Mey ma -y-La dela) A study of reaction rates (chemical kinetics) allows us to understand exactly how reactions work. You cannot deduce a reaction mechanism simply by examining the ordinary balanced chemical equation. Experimental work to determine the reaction rate leads to the rate equation, which, in turn, leads to the reaction mechanism (see page 12) Cr ay Examiner tip ke care with nits; mars are ofan given for cect nits in adton othe correct ue Theis rate ate SOBRE, gig mold Note tha Pusitive indices are always ease Rate equations —_———— Rate equations show the relationship between the rate and the powers to which the feactant concentrations are raised. If two reactants, A and B, react together then measurements of reaction rates with different concentrations of A and B (see below) could give the rate equation change in concentration ac rate of reaction = fi time At rate = MAyIBY In this case: * Kis the rate constant, which is constant at a particular temperature # [A] and [@] are the concentrations of substances A and B © xis the order with respect to A, and ys the order for B © The overall order of reaction is the sum of the individual orders, +y. Cy Studies of some reactions gave the following rate equations: a rate = MAIBP b rate = KAPIBP ¢ rate = HAPIBP d rate = KAI[B) ‘Which reactions have the same overall order, and which rate is independent of the concentration of one reactant? Leo ta Ty Examiner tip Since any value raised tothe power 1s simply 1, youcan omit zero odor reactants when writing rate equations Reactions a, b are both third order overall. Reaction b is zero order with respect to reactant A, and so its rate is not affected by varying the amount of reactant A. We can write rate = KBP Measuring reaction rates fate =.ia]—tns Rates of reaction are measured by monitoring the ves straight line fate of change of an observable property. * Colorimetry measures the intensity of a colour in a teection mixture with time, such as in the oxidation of iodide ions to give brown iodine. In clock reactions the reaction is timed until a fete=Ha"= x1 Sudden colour change happens when a certain cheaeucinen amount of product is formed, depend on [4 Mass change is used when a gas is produced. For example, when calcium carbonate reacts With acids to release carbon dioxide the mass of the flask decreases. + Volume change is an alternative to mass changes for gases. For example, magnesium reacts with acids to release hydrogen, which can be collected in a syringe. Rete Rate ~ MAl'~ this produces a cure whichis parabola al © Titrimetric analysis uses titrations to measure How the reaction rate varies forthe concentration of A for zero, first and changing concentrations of a reactant second order reactions or product ~ for example, the fall in acid concentration during esterification, mm A2 Chemistry Revision GuideGraphs and tangents The simplest type of relationship between variables is the linear one of general form y= mx + c, where m is the slope or gradient and c the intercept on the y-axis. # The gradient of a curve is found by drawing a tangent. The gradient of the tangent to the conceniration-time graph at a particular time gives the rate at that moment. + The initial rate of reaction is found from the gradient of the tangent to the concentration-time graph at t = 0. «© Itis often difficult to monitor reaction rates or concentration continuously. In practice you carry out a series of reactions where you vary the initial concentration ‘of each reactant in turn. You then piot a graph of intial rate against initial concentration for each reactant. ‘» You can find the orders from the shape of each graph, and the value of & and units by substituting your measurements into the rate equation (e.g. k = Tate t a quation (29 k= Tapiay jow fast? — Rates ee a Td arora ero, fist and secand order reactions ‘roduc graphs with dtforont shapes. Both concetration-time and rate— conceriration graphs have distinctive shapes. Loam these shapes to correctly identify the order of reaction with respect to each reactant. You should also ba abl to fnd the rata constant ‘fom experimental data This is examined inthe Unit 4 paper, and also If the gradient is constant, showing ifthe gradient changes | concentration falls. The gradiont is the rate = HAR, rate constant k, so the rate equation is Ifthe gradient changes from very that the rate is unaffected by the ‘exponentially itis 2 first order —_| high at t= 0 and then slows down, concentration of a teactant, itis a zero | reaction. it a second order reaction, order reaction for that reactant. The halFlife is constant andthe | The halflife increases as the The halflife decreases as the rate = KIA! ‘concentration falls and the Tine Time Concentratan-time grgohe Tine How the reaction rate varies with tine for zero, fst and second order reactions Half-life The halflife is the time needed for any reactant concentration to fall to haif of its initial value. Calculate the haltlife for the decomposition of SO,Cl, starting with concentrations of (a) 0.50 mol dm”, (b) 0.30 mol dm-> and (¢) 0.20 mol dm”? 50,C\(gvmol am-* 125 mol den 8.10% 0625 mol an? | ideo 200 3dn0 ado S000 600070008000 “hess Haleife oF SO;C) ina reaction Find the time taken for the initial concentrations to halve (e.g. from 0.50 moldm~* to 0.25 mol dm. The value is constant, 2300s, shawing that this sa first order reaction. AQ OE. _| 11 Whatis the order of a reactant whose doubled concentration doubles the rate? 2 Why does the addition of starch make it easier to follow the rate of a reaction producing iodine? 3 What is special about the half-life of a first order chemical reaction? Does this include radioactive decay? 4 Describe the shape of a rate-concentration raph for a zero order process Chemistry Revision GuiUnit 4: General principles of chemistry I~ Rates, equilibria and further organic chemistry PCat EL iol alas alae meh NCI TST, Wen reactant molecules collide, it may result in a chemical reaction. There isan energy requirement before this can happen. The activation energy is the minimum Natural gas methane) and &Me"SY needed by reactant particles (molecules or ions) before products can form, air react exothermicaly in ‘ aa Bunsen flame. Explain why mixtures of these vation gases do not ignite energy without spontaneously at room & cata temperature. : The activation energy reactants barrier for this combustion reaction is too high Pear at room temperature Colliding molecules have insufficient eneroy Reaction pathway fr an exothermic reaction torreact. Once ignited, the Bunsen flame heats artiving gases before they react so that enough molecules have energy equal to or greater than the minimum required for reaction, Catalysts and reactants can be in the same ahysical state, called homogeneous = for example, al liquids. Or they can be in diferent states, when they are called heterogeneous. ($F The diagram shows that the reaction is exothermic - the products are ata lower energy level than the reactants «subject to an energy barrier, the actvation energy, in route 1 + able to follow an alternative pathway in route 2, with a lower barrier A catalyst increases the reaction rate by providing an alternative reaction pathway ‘with a lower activation energy. Such catalysed reactions are faster. ResultsPius aI Process Reactants, Catalyst Type of catalysis | Cees) Haber synthesis Nitrogen, hydrogen | on Heterogeneous Moke clea inansnvers that catalysts Gatalicconverter | exhaust gases Platinum Heterogeneous con be ecoverd and rose since hey | > 3 no part ofthe reaction produc ntact process, are not par ofthe rection products concep manufacture Sulfur dioxide, oxygen cas Vanadium(v) oxide | Heterogeneous Solutions of acid, Esteritication Pan Hydrogen ions Homogeneous Many catalysts are transition metals (or their compounds) because they have variable oxidation states and can alter the numbers of bonds available to reactants, Reactant molecules are adsorbed onto the metal surface, at points known as active sites. This weakens the bonds between atoms in the reactant molecules, which reduces the activation energy for the reaction, Example of heterogeneous catalsis oe 2 Chemistry Revision GuideTopic 1: How fst? — Rates ff Effect of temperature on rates When the temperature incteases, the rate of a reaction increases too because the rate constant increases. The rate constant kis only a constant for a particular temperature, Changing the temperature changes the value of k because the proportion of molecules that have the required energy (greater than the activation eneray) is increased and the colliding particles have a greater average energy. The Arthenius equation shows the relationship between the rate constant k and the ‘temperature T (in kelvin). The logarithmic (In) form of this equation is: : pee ea Weed Femenber to give the wits of ‘ctvation energy oryou may lose a ‘mark, The units ae k mol“, which you shoud be able to verify rom substituting units for Tand Bin the equation Ink = E> + a constant tet cia toy Eis the activation energy for the reaction Sse ti © Ris the gas constant and has the value 2 8.31JK~' mol! + Tisthe ken temperature (absolute ‘ fee eee Tisthe tn ae «Gradient = —F* s are asked to determine the activation “4 ‘energy of a reaction. This is examined feline pep. dale Unt + Activity c. : 2 Wing ute fon cat rae } This shows thata plot of ink against“ gave a at TASBPRT 8 IDC at 7 8 8 oN RD ste ne whose greet = ei et Investigating the activation energy of a reaction If we know the rate equation for a reaction, itis easy to calculate the rate constant k using the rate of reaction for a known concentration of reactants, Calculating the activation energy requires the results from experiments at a range of different semperatures, to give values of the rate constant k at each temperature. {A suitable reaction to study is the oxidation of iodide ions by iodateV) ions in acidic solution. The equation is: 105-(aq) + 5I-(aq) + 6H*(aq) — 31x(aq) + 34,010) ‘A small known amount of sodium thiosulfate is added at the start of the reaction together with starch as the indicator, The iodine released by the oxidation of the iadide ions first reacts with the thiosulfate, so the mixture remains colourless initially but then suddenly turns starch blue-black when all the thiosulfate has reacted. This is an example of a clock reaction with a built-in time delay that denends only on the concentration of the iodide and iodate ions, The relative initial rate of production of codine can be found from 1/t, where ts the time delay. The value for the activation energy can be found graphically as described above. Se OEE. _ : 1 Identify the type Use the data to find the value of the activation energy. of catalysis in ‘Temperature Rate constant K/dm?mol-"5* hydrogenating oils to a 73 104 give margarine using a - nickel catalyst. 700 5x10 Sohne 780 15x 107 ‘temperature affect the rate constant &? Platting a line graph of In k (y-axis) against 1/T gives a straight line of negative 3 What is the purpose of adding sodium ‘thiosulfate in the E,.as about + 190k) mol, depending on how you draw the line. jodine clock reaction? ‘A2 Chemistry Revision Guide a slope. Putting the negative gradient equal t e ives the activation enerayPRB rit: sere crcl of chemistry | ates, equiv and futher orgie ces UU CTe ele e-lae Me iC mrelsa cali: Bod ce) oy Reactions do not just happen whenever all the relevant molecules collide at once ~ rd they happen in steps. The slowest step controls how fast the overall reaction occurs ~it Gath) is called the rate-determining step. Kinetic measurements establish the arder of the reaction for each species. For a expected be ale 10 reaction between A, B and C the rate equation could be sible reaction machanisme observed rate emuatin rate = MAIC? Since substance B does not occur in the rate equation, any step involving molecule B must be fast. This rate equation demonstrates that: «the reaction is fist order with respect to A ~ so A is involved in the rate-determining step ‘the reaction is second order with respect to substance C - so two moles of C are involved in the rate-determining step. Nucleophilic substitution mechanisms of halogenoalkanes ‘Two substitution mechanisms are possible when-an iodoalkane reacts with aqueous alkali R-1+ OH" R—OH +> Only the experimental rate data can show which mechanism actually takes place K mp 20H Mucteoph substitution ofa primary halogenosikane ‘© The single step illustrated for the substitution of 1-iodopropane, a primary halogenoalkane, involves two different species - both the hydroxide ion and the primary halagenoalkane. ‘The reaction will be second order — it depends on the concentration of both the hydroxide ion and the primary halogenoalkane. So, rate = KIRI[OH"] We call this an $42 mechanism, meaning substitution/nucleophilic/second order. Tertiary halogenoalkanes hydrolyse by the alternative Syimechanism, meaning substitution/nucleophilic/first order. tH Hs cs CAG of ES Ho chy determining Hs Nucfeophilc substtution ofa tertiary halogenoatkane «The C —halogen bond breaks first (slow step) followed by attack by the hydroxide ion (fast step). ‘The slow step involves only one species and does not depend on the concentration of hydroxide ions. Hence the reaction is first order overall rate = ARI] AD Chemistry Revision Guide1 How fast? — Rates The mechanism must be consistent with the evidence: : ‘= # the reaction is second order overall it must involve two different species € reaction is fist order overall (only one species in the rate equation) then this is he rate-determining step and it must be a two-step reaction, Kinetics of the reaction between propanone and iodine in acid solution I, + CHCOCH, = CHICOCH, + HI Hydrogen ions catalyse this reaction. The rate equation has the form of rate = KICHCOCHs FllsMH*P Varying the concentration of each species in turn gives the order of each species ~ x, yandz. The reaction can be followed by titrating the remaining unreacted iodine with | standard sodium thiosulfate using starch indicator. Alternatively, a colorimeter can ; bbe used to monitor the brown colour of the iodine imental data shows the reaction to be first order with respect to both propanone and hydrogen ions, but zero order for iodine. The reactant iodine is nat in the rate equation at all but hydrogen ions are present, despite not being reactants. ° A 1 j Benen | a ia oes | % 0.006 O12 0.6 ka Uns 3 0.006 18 06 ) aw | Data from the reaction of iecine with propanane in acid solution Use thi data to establish which species ate involved in the rate-determining step. Within the limits of experimental error, we can see that: « (Expt 1+2) doubling the concentration of propanone doubles the rate (First ' order) : ‘+ (Expt 1-4) doubling the concentration of hydrogen ions doubles the rate (frst order) ‘© (Expt 15) doubling the concentration of iodine has no effect on the rate (zero order) The rate-determining step involves both propanone and hydrogen ions, but not iodine. Using a colorimeter to study rates The chosen filter should let through only the wavelength to be absorbed by the coloured iodine solution. Since iodine solution is brown-red, a blue-green filter is used. SOME 1. Why are some species in the stoichiometric equation absent from the rate equation? What is the meaning of the term ‘Sy1 mechanism’? Suggest two practical techniques to monitor a reaction involving iodine solution, 2 3 oe ca Examiner tip You willbe expectod to deduce orders cof reaction from experimental deta, making reasonable allowance fo: ‘exporinontal oor For example, the relative ratio 1:1 Srepresents 1:2, 6 tubing of the rate ResultsPlus ie You willbe expected to identity possible sources of measurement uncertainty or systematic errs in ‘any determination of reaction at. Possible era in using a colorimeter include variation in tho way cffcont reaction tubes transit Fight heat rom the Lamp causing temperature variations that affect & ‘© changing the output of light from {tele ‘A2 Chemistry Revision oery Unit 4: General principles of chemistry |— Rates, equilibria and further organic chemistry 's topic you should be able to: | checkpoints Revised Practice exam questions Rate of reaction Understand these terms: rate of reaction, rate equation, order of reaction, rate constant, half-life Describe one experimental method to abtain rate data, choosing from colorimetry, mass change or gas volume change 43 Describe a reaction thatis used to find the rate of reaction and its halflife, e.g. a clock reaction Draw and interpret graphs of concentration or volume against time 43c Oo Draw and interpret concentration-time and rate-concentration graphs aad Use experimental data from zero, first and second order reactions to work out the: )half-ife, i) order ii) rate equation a3t ‘Activation energy and catalysis Understand these terms. activation energy, heterogeneous znd homogeneous catalysis 43a Use experimental data from zero, first and second order reactions to work out the activation eneray given the Aathenius equation 43t Know how to cay our a practical investigation to find an ‘activation energy, for example in the oxidation of iodide tons by iodatet\) fans 439 oO] oO] oO Mechanisms and rate-determining steps Understand the term rate-determining step 43a 1) Describe the reaction between iodine and propanone in ‘acidic solution i) Use experimental data to find the orders, and hence discuss a possible mechanism for this reaction 43e ojo oO} oO] OO o|o Use experimental data from zero, first and second order reactions to work out the rate-determining step in a reaction mechanism 43t a QO Study the hydrolysis reactions of halogenoalkanes to Understand the different mechanisms, and deduce proposed ‘mechanisms that ere consistent with experimental data for ‘the orders of reactions 43h and | oO Oo Explain what we mean by $1 mechanisms and 5,2 ‘mechanisms in the nucleophilic substitution reactions of hhalogenoalanes 43 [ AA2 Chemistry Revision Guidelow fast? — Rates ResultsPlus Ce eeu 1 Two gases A and B react according tthe equation: Aig) + ZB(q)—> AB) [A satios of kinetics experiments performed at constant temperature gave the folowing results: Experiment Initial concentration Initial concentration 3 rate/mol dm? * ‘of Alot dn? of Biol dr? 1 "500 0.100 1.00 x 10 2 500 0200 39210" 3 0.1000 0100 195% 10 Caleulate, showing your working, the odars of reaction with respect to A and 108. a \Wite the rate equation fr the reaction. i Calculate the rate constant kor the reaction using the results from experiment 3. State its units, a 81 Looking at experiments 1 and 2, as concentration of 8 double, the rte inseases fou times so the reaction is second ord with respecttoB. (1) Looking at experiments 1 and 8, a3 concentration of A doubles, the rte doubles so itis rst arderwith respect. A {1 "You must icicate that te concerration of une of the reactants steys the same for the pair of values chasen for comparison to gain the thirdmark (1) The rate eqatonis ate = HAIEP— (1 Note that this now presents the sama efrmaton as (ain aclilerert fom. your values for (a order, butte rte equation in (aH matches thas velus, you may stil gt the consequent marks 1.95 x 10-tmoldm“?s~1 ee 1.1000 mol dm? x (0.100 mal dm” =} pale 0 Answers tote sigcnt pres would be aprepat with this data but examiners may ct insist on is in avaring mars. ‘common eoris agnor the suet in the question a calolat he vlu of kor experiment 3 are tong, say both second dn mol 1b Explain, in terms of collision theory, why the te of rection increases with an increase in temperature, ‘1 ‘hore are 3 aks available here so think about saying thee distin things, Note that this question aso tests knowledge from AS Unit 2 ‘+ Inareasng the temperature means tat molecules code wth greater anergy. {1 ‘© This means that a greater froportion of tho coliding molecules will have energy anual to or greater than the activation energy the minimum required. {1} ‘+ Consequently «greater proprton ofthe collisions will bo sucessful and result in reaction occuring, (1) Structure your answer with separate lines or bullet pnts so thatthe examiner can see immediately that yu are making Separate points in Your answer Avid feng prose where the danger is that you wal repeat yourself and fail ta gan full marks (From Edencel Unit test 52, June 07) TE A2 Chemistry Revision GuideUnit 4: General principles of chemistry Rates, equilibria and further organic-chemistry ResultsPlus Pe 2 In aqueous solution, propanona and bromine oact as flaws (H,cOcHaq) + Brag] + CH,COCH.Bxan) + HB(aq) ‘This reaction is zero order with respect ta bromine. What can we deuce rom this? Choose the exact respanse ‘A The slowest step involves bramine B Thovato of action has a constant value © Bromine isa catalyst Bromine isnot irvotved in the rate- determining step a The slow rate-detonmining step carnat involve the bromine because itis zero order The answers D. i) 3 When aqueous sodium hydroxide reacts with 2-bromo-2-methypropane, the rate equation i: tate = K[2-bromo-2-mathylpropane) \What sth fist stop in the reaction mechanism? Choose the corect response: ‘A. Electophilic attack by hyroxie ions on te C—Br bond B Breaking ofthe C—Br bond praducng a carbocation © TheC—B; bond breaks as the C—O bends forms | DD Nucleophilcatteck by hydride ions on the carbon in the C—Br bond a This compound reacts by an Sy1 mechanism to givea stale carbocation, The answers B. (1) Check that you can explain the ciferences between Sy mechanisms and Sy2 mechanism: their stabites. This isa common question, rms af how easy carbocations can form and A ~ Chemistry Revision GuidePractice exam questions 1. Inacid solution, ethanedioic acid (oxalic acid) is oxidized by the addition of an aqueous solution of potassium manganatetVi). During a titration, it was noticed that the rate at which the manganateCv!l) decolorised accelerated significantly just after the start of the addition from the burette. This suggests that: A the reaction is endothermic the potassium ionis a catalyst 8 2 product of the reaction is catalysing the oxidation D the reaction is slightly exothermic. O) a In a rate of reaction experiment between two substances A and B, the overall order of the reaction was found to be 2 Write three possible rate equations for such a second order reaction between A and B. 8 b Ata certain temperature, the rate of reaction between nitrogen monoxide, NO, and hydrogen, H, was investigated. The following data were obtained. INO}/mol dm? {H,}/mol dm-? Rate of reaction/ moldm 3s"? 10 10 0.02 10 30 0.06 30 10 018 Use the data above to deduce the rate equation for this reaction, 8) Use your ansiver to (a) () to calculate the value of the rate constant, with its units @ 3. The rate of the decomposition of nitrous oxide: 2N,0(g) + 2N,(g) + 0x9) has been studied at different temperatures. The rate constant k was determined at each temperature, ‘The relationship between the rate constant and the temperature Tis given by the Arrhenius equation: EZ Ink=- 244 Ink=— FA + In where Ex is the activation energy for the reaction, R is the gas constant (8.314)K-' mol~, and k is the rate constant at temperature T. Given values of k at different temperatures T, what graph would you plot and how would you use it to determine the activation energy? @ b Aplotof the data gave a straight line with gradient ~2.95 x 10K Find the activation energy for the reaction, in kJ mol", to three significant figures. Q) (From Edexcel Unit test 5 Q2, June 08) 12 Chemisty Revision oeates, equiltria and further organic chemistry Ls! vi \ Unit 4: General principles of chemistry Entropy Entropy (symbol 5) is a measure of disorder in a system. You can also think of it as a dispersal or spreading of eneray between the particles in a system, or between @ system and its surroundings Tne entropy of a substance can only be zero at zero kelvin (absolute zero), and this assumes a perfectly ordered crystal. As the temperature of a material increases, the particles gain energy and the'r motion also increases. Higher temperatures, therefore, increase the disorder of the particles. —_ | we lowed FB Lauics Gases Entropy increases with change of state to greater distance between particles and consequent increased disorder. The ions in solid sodium chloride are more ordered than the same ions dissolved in water. Dissolving sodium chloride causes the entropy to increase, Entropy also increases when the number of particles increases. ng freedom of movement increasing csorder a aie pT eS canes be eRe nae al euce Resor bis Reaction releasing 2_| Zine with sulfuric acid | Positive (increasing | Gas molecules are ie cyan |aaen Ree cenect in Panes ne ston Gas reaction where Haber process for Negative Fewer product molecules combine, | making ammonia ‘molecules than re a Reno sana eT The greater the disorder resulting from a process, the more likely the process. The natural direction of change is one of increasing entropy (positive entropy change), Calculating changes in entropy, AS Entropy values depend on temperature and physical state, Entropy values also increase as the complexity of a substance (the number of bonds) increases. For example, the entropy of ethanoic acid (CH;COOH) is greater than that of methanol (CH,OH). A standard entropy 5° is the entropy of a substance at standard temperature and pressure, and is expressed per mole of substance. The standard entropy change for physical or chemical processes isthe difference in the entropies of the products and reactants measured under standard conditions: ASSirem = LSzoaves ~ LSreecans Par ARTI Examiner tip Calculate the standard entropy change for the thermal decamposition of Use the same number of significant caldum carbonate. Explain your answer. fguresin your clean and ser a ad as there are in the data you are given. CaCOx(s) + Cals) + COA} Marks may 6 lst for giving an Standard entropyJK-'mol-. +929 $39.7 $213.6. inappropriate number of significant ‘The positive value for the entropy change shows that the entropy increases. Each ‘igures mole of solid calcium carbonate procuces 1 mole of gas, with greater disorder. 7 Sram = Sposus ~ Stscunes AS = 89.7, JK-1 mol! + 213.6) K-' mol“!) — 92.9) K-? mol +1604 K-! mol" (3 sig. figs) ResultsPlus Teeter) Ha balanced chemical reaction shows ‘the formation af two moles of product, 2g. n Ng} + 3Hzg} = 2NHl then ‘he calculated entropy change forthe reaction shouldbe divided by 2 to get ‘he standard entropy charge. ResultsPlus Coin ‘You willbe expected tobe abe to usa supplied entroay data to calculate overall entropy changes. You wil lose marks if you us the wrang unis entopy has tho uits of JKT mol~ Alay includ the sign when writing a vale for 4S, even itis postive. A2 Chemistry Revision GuideTopic 2: How far? — Entropy Spontaneous reactions, enthalpy and entropy ‘Spontaneous processes are often exothermic. Exathermic reactions give out heat negative AA), which increases the disorder of the surrounding particles. fer, some endothermic reactions are also spontaneous at room temperature hey have a positive value for AH. Wether reactions occur spontaneously or not cannot be explained in terms of ‘lpy changes alone. s the total entropy change that determines if a reaction is spontaneous: ASrori = ASsptam + ASssraundings | + For any spontaneous change AS. must have a positive value. Total disorder must ncrease. = valve of AS.raunings depends on the temperature (in kelvin) and the energy ‘erred to the surroundings, AH: Saveindngs = fe minus sign is there because exothermic reactions have negative AH but transfer ray to the surroundings, which increases their entropy. ce. Use the expression: AH tl = AS yen to calculate the total entropy change when 1 mole of hydrogen burns in oxygen at 298K. Explain the sign of your answer Peere eet ge toe You wl se marks by failing to convert 2.86 x 105) mol"! Celsius temperatures into kelvin fr Substituting gives: calculations ite these. Convert Calsius Sui = ~44,53-? moh ( peeeaa a = +915JK-! mol! cl The combustion of hydrogen is exothermic. The expression =M4 represents the entropy change of the surroundings. Taken together, ASi.,1 is positive and the overall entropy increases. Feas' ity of reactions Spontaneous changes can occur if the total entropy change AS, > 0. This can happen even if one of the entropy changes is negative, as shown in the table. a acne) SOE ‘BS carouninge | AS: endothermic a change spontaneous? | 1 How does the entropy Dissohving | Endothermic | Decreases [Increases | #ve ‘Sys ilonget of the system change sodium nitrite hhecause the when ammonia is inwater erystaline formed from nitrogen latte is and hydrogen? cesnyed 2 Howis the entropy of Sodium meal [Bctheic inceses [Decreases | He MSarananei a system affected by urning in ecause 3 larger reaneratge? nies our 3. How does the enropy formed of the surroundings “Ammonia gas | Exothermic [increases | Decreases | rve ASvrosntogs Cie wey and hydrogen because a larger hydrogen burns? chloride gas lattice forms 4 explain why the combine to transition from water give solid to steam is not ae spontaneaus at room temperature Thus the feasibility of a reaction is related both to enthalpy and entropy changes A Chemistry Revision Guide 74 \ Unit 4: General principles of chemistry | ~ Rates, equlria and further organic chemistry ETS SAYA Coli Laat aCe a aCe A feasible reaction has ASiquj > 0. BECAUSE Awa = ASaaten 44, the key factors for ‘the feasibility of a reaction are: the entropy change in the system, ASyem ‘© the temperature measured in kelvin the enthalpy change with the surroundings, AH. Spontaneous reactions can only happen for AS,,.) > 0. The value of AS... depends con temperature. This is why a chemical reaction that does nat happen at room temperature may become feasible as T increases. ResultsPius STC ror Magnesium turnings react with cilute sulfuric acid to release hydrogen cas. Youll got the wrong answer ifyou The temperature of the acid rises considerably. Explain why this reaction is use Calsus instead of ein in these spontaneous at room temperature. calulations. Remember that Celsius ‘tamperatues can have negative values but kelvin temperatures cannot. Kelvin temperatures start at absolute ze and nezessatily have positive values. The reaction is exothermic so the term AH will have a negative value, The metallic lattice of magnesium metal is destroyed as it reacts with the acid, producing free ions in solution and a gas. This means that the entropy of the system increases it has a positive value, and this reaction is spontaneous. Se The decomposition reaction given on the previous page: CaCOsls) + CaOKs) + CO,g} does not occur at room temperature, Given the standard enthalpy change for the reaction, AH® = +178k)mol-", calculate the lowest temperature at which this reaction becomes feasible. ResultsPius ree) ‘The units of Aare given ink mol ‘and the units of AS are given in Jmol You need to convert kl 10 by rltpying by 1000, Note also that Tis the absolute temperature, ink. ASyceq Can be calculated as before. ASSoiem = Spretues ~ Srecans 39.7 K-*mol-* + 213.6) mol") ~ 92.9) K-! mol? 160.4)K-'mol-? ~ AH = ASaaem = FE He ] For AS > 0, ASSien > SHE > 110K Gig. figs) 178 x 1081 mol~! 7 F60.43K=? molt Esoteric reaction Stability and inertness and the activation energy Some reactions are puzzling because they are highly exothermic but are not ‘Activation spontaneous at room temperature. An example is that 2 mixture of methane energy and oxygen gases does not ignite spontaneously at room temperature. ‘There are different kinds of stability that can affect chemical reactions. The thermodynamic stability of a compound relative to its elements depends ‘on the enthalpy level of the products relative to the reactants. The diagram (left) for an exothermic reaction shows an example of products that are ‘thermodynamically more stable than the reactants. A negative enthalpy of formation indicates that a compound is more stable than its elements ~ it Course of eaction must form exathermically from its elements. Progress ofan exothermic reaction {= A2 Chemisty Revision GudeTopic 2: How far? — Entropy hemical reaction is feasible when AS, has a positive value. However, this tells thing at all about the rate of reaction. A high activation energy barrier may vent 2 reaction starting, as in the methane and oxygen example. In such cases, the eactants are kinetically stable or kinetically inert (unreactive), nergy must first be provided to start such reactions, for example: a spark ‘* heat (as in the decomposition of CaCO; above) «light (visible or UV). Sc Use the following data to explain why the conversion of diamond to graphite is feasible at all temperatures yet does not occur at room temperature: standard entropy/) K-'mol: Diamond Graphite 24 57 AHiSamont to gropite = ~2 KI mol ‘Asner to gapnee #5 Negative, showing the reactant (diamond) is thermodynamically unstable and that graphite forms exothermically. The entropy change ASsen = Spoocs ~ Steacans 5.7K" mol~" = 2.431 mol = 331K! mol Fora feasible eaction, AS > 0, ASSam pe =2X10Jmol-! 3.3) mol” ‘The reaction will be feasible at all temperatures above absolute zero. Diamonds at room temperature are unstable! However, we have no data about the activation energy of this reaction. This is likely 1o be quite high, as carbon-carbon bonds in the giant molecular structure must be broken in the transformation of carbon from one form to ‘another. So the rate of conversion is negiigible and diamond is kinetically stable. SAOTHRWENM 1. Give the mathematical relationship between changes in entropy and in enthalpy for a system. 2. Give one reason why an exothermic reaction may not be spontaneous at room temperature 3. What can you conclude about a chemical reaction for which MSieui < 0? 4 Explain the difference between thermodynamic stability and Kinetic stability ‘A2 Chemistry Revision Guide es‘When ionic solids, such as sodium chloride, dissolve in a polar solvent, there are two separate enthalpy terms from two separate processes «lattice energy - the solid must separate into individual ions to dissolve (an endothermic change). « hydration enthalpy ~ the separated ions interact with the surrounding polar Lattice energy is dod as an solvent, such as water (an exothermic change’. cxten proves end ef ‘The enthalpy of solution of an ionic compound is: ~ve, The enthalpy change in dissoving is for breaking down the lattice ard is Abowian = —ASMlasce rey + AMhysaton ‘endothermic, sign +¥e. Reversing the When a new lattice forms fram gaseous ions, energy is released in an exothermic ‘irection ofthe reaction reverses the process — this is the lattice energy, When a crystalline material dissolves, the reverse sign of AH. happens. An amount of energy numerically equal to the lattice energy must be put in {to break the crystal and separate the ions. This is an endothermic process. Maun CaN have a postive or a negative value # Apositive AHayun Corresponds to an overall endothermic change ~ dissolving is not favoured. It may still be favoured by an increase in entropy. Solid sodium chloride is a highly ordered 3-D lattice with a low entropy value. On dissolving, the ions separate and move independently; the entropy of the system therefore increases, favouring the change. A negative AH.sjxion Corresponds to an cverall exothermic change and so dissolving js favoured in terms of enthalpy. The products have less energy than the reactants in general, although dissolving is regarded as a physical not a chemical change Ee Use the following enthalpy and entropy data to predict whether the substances will dissolve at a temperature of 298K, Substance Lithium chloride Sodium chloride Silver chloride +66 ‘Magnesium sulfate =213) ‘An ionic compound generally dissolves if AMiausan #5 Negative (AHhysaton > Airc away) Magnesium sulfate and lithium chloride should dissolve as Afta.iosis negative. However, solids with an endothermic AHjs,non may still dissolve ifthe system's entropy change is positive enough to overcome the decrease in entropy of the surroundings because the reaction is endothermic —i.€. AS can be > 0 AH (Gpontaneous change) if ASaeten > AE For Neci, ~8H = -4000;not-* =13.4)K-' molt, so NaCl will dissolve at 298 K because ASouj > 0. 420)K-' mol") For Ag¢l, -AH = -66000Jmol! = —221 JK-'mol”* 50 AgC| will not dissolve at 298 K because 7 298K ASweus <0 (-188)K-! mol") Calculating enthalpy of hydration or solution from Hess cycles The standard enthalpy of hydration of an ion is the enthalpy change when one mole of the gaseous ions is hydrated (interacts with water) under standard conditions, Where further dilution would cause no further enthalpy change, sometimes called infinite dilution, For example: Na*(g) + aq — Na*(aq) A2 Chemistry Revision Guideitis not possible to measure such enthalpy changes directly because ionic compounds contain both cations and anions together, e.g the total enthalpy of hydration of NaCl = Ai(Na*(a)] + BH CIC] We use a Hess's law cycle to find the enthalpy of hydration. SE Enthalpy. cot oars id era y Na“) + Ci-(g) + excess water Bein full marks in Born-Haber eye question by identifying the start and end points of he two altematve routes. Move araund the cyte in one aie = ald mc | ivetin,ading up the energie. | emember—if ain inthe direction of ‘an arrow then use the same sign asthe enorgy if going agains the arrow, use the opposite sign Novag) + chan) Mii. #101 mor NaCle) + excess water Enthaloy changes when dissolving sodium cherie Find the combined enthalpies of hydration of sodium and chloride ions, Explain how, in principle, you can find the value Of AMncgies Of an individual jon such as sodium. Applying Hess's law to the diagram: Atesston or 10kJmal~ MHvcration = AHissice nergy + AMiyeration 780k mol! + x -770kimol In order to find the value for the sodium ion alone, enthalpies of solution must bbe measured for a range of sodium compounds. Cycles can then be drawn from which AHiyiaien Of the Sodium ion may be deduced, Factors affecting the enthalpy of hydration and the lattice energy The lattice enthalpy (or energy) of a compound is affected by: SE «the charge on the ions — larger charges increase the force of attraction between oppositely charged ions 1 How is the entropy ‘=the size of the ions ~ smaller ions fit closer and this increases the force of attraction affected when an ionic «the degree of covalency in the ionic bonding ~ whether the bonding is 100% ionic solid dissolves in water? and the ions completely separate, as the ionic model assumes. 2 Why are hydration Hydration enthalpy is affected by: enthalpies exothermic? '* ionic radius ~ small ions have a greater charge density 3 re See oe ‘onic charge — larger charges increase the charge density. Sanne lons with high charge densities attract more polar water molecules giving more ion experimental values for dipole interactions. These interactions are exothermic and the system shows a decrease jets ere enna 4 Which ion, Lit or k*, Experimental values of lattice energy determined from Born-Haber cycles compared to has the more exothermic ‘theoretical values can identify @ degree of covalent character in ionic compounds (as hydration enthalpy? you saw in AS Unit 1). A mismatch indicates polarization of the anion with a degree of Explain your answer. covalent character. A2 Chemistry Revision Guide a: General principles of chemistry | — Rates, equilibria and further organic chemistry Topic 2: How far? Entropy checklist By the end of this topic you should be able to: Beare amas aa ae ary EDs Ian Sara EMEC Ol a Siboot nasil oy suka heroes tose Cieiasenl aa rchaha af oop svafaen Cc] aaread a c ih torn aad ccee oe sas ‘standard entropy depends on physical state and aaa hess iow aceinis aangeiar enema] is a a cpsal ster toachrceaeteeemoat Sean uscneeb cere se oa Dele he weal Mecian af Spero md aa diffusion as increasing the total entropy 0 a cay su ee SSR SNE enthalpy and dorder 0 Oo Understand that ASwia= AScsum + QSunandnge 44h o oO cake ono) ABS apes hen Fea data needed Oo Oo caalite Bani ioe samosas laa ee o o 18g Smarr = =H Feast stabity | Undestond tion faci aepenran [AAR a A Sedinereast | dobauacs eaeterte Cat tes aan a ae Ding beween Remedi and fheic Jaa stability Oo 0 Calculate ASsren aNd ASinexndins for endothermic | 4.4m. poe eer eee O Oo Ehahalpy anges | Bian hyn ei and ae enepyand [an ana a a dative” [Reeacear ae er Pret cles sng entropy ard ery data [Aap a a ee aT) Build Better Answers 1 Osim earth of ton yf a Le, ae ‘The enthalpy change when 1 mole of gaseous ions (1) is dissolved inis added to an excess of water. {1} ‘Note that if you refer to gaseous atoms when you define enthalpy of hyation you wil lose @ mark. Also note that if you simply say “is ‘hydrated’, this is insufficient to gain the mark. You should also say excess water rot pet dm because adding 1 mole of inst 1 dof water ‘may not completely hydrate the ions, and further dlution may produce a further enthalpy change A2 Chemistry Revision Guide'b_ The table belovs gives some information tout the sulfates ofthe Group 2 elements magnesium and barium. ‘Sulfate Lattice energy/ | Hydration enthalpy | Solubility/mol dm~* kdimol! of cation/k me M0, =2618 1820 | 250, =a =1380 wax | | Use the lattice energy and hydration enthalpy values to explain the difference in the solubilities of the two salts. (4) ‘Write dovm tho equation you ae using, ater wards or syrbos is no Aan = ~AHarcery + Aran (1) Many students got confused withthe signs f the energy changes. You should sketch a Hess's lw eel. If the latice energy fr tha formation ofa compound is dtind as an exothermic process (—e sign, then reversing the direction ofthe reaction n the Hess cycle (e.g, for MgS0qfs)~ Mg?g) + $OF-(al reverses the sign of AHL For MgSO, Aaaien = —(—2674KI mol!) +|—1820k) mol-")= +954kdmol-! ForBo80, Aten ~ {-2874kImal—")+(—1960kImol-Y) = +1014ksmol-! {1} The enthalpy of solution of MgSO; is ess endothermicjmore exothermic/more negative thar for BaSO, so MSO, is more soluble than 8380, ° {i} (From Edexcel Urit test 4 1 part, June 07) Practice exam questions 1. Ifa change is spontaneous then: A entropy must rise B rate constant must have a negative value € enthalpy change must be positive D none of these is correct a 2. The initial rate of a reaction will depend on: A the enthalpy change B the energy of activation the entropy change D the equilibrium constant in terms of concentration a 3. The ester methyl ethanoate reacts with water as follows: 035 CH:COOCH; + HO — CH;COOH + CH;OH | kinetics experiment based on this hydrolysis showed that the ester concentration varied as shown on the graph. The water is both a reagent and the solvent, and is present in excess Show that this reaction is first order with respect to the ester. @ b Explain, giving a reason, whether or not the overall order is also 1 ) Suggest a method by which the progress of this, reaction could be followed. 3 {Ester|/rmol dr? 05 To 15 20 25 3 Timefhe Variation of: hyatobsis ter concentration during (From Edexcel Unit test 5 Q3, June 2004) A2 Chemistry Revision Guide (eeUnit 4: General principles of chemistry | — Rates, equlbria and further orgenic chemistry Tieden mialaeele-4 ‘As you saw in AS Unit 2, when both forward and reverse reactions in a reversible reaction continue but the rate of the forward reaction is equal to the rate of the | reverse reaction, this is called a dynamic equilibrium. reaction may only obtain equilibrium in a closed system, in which both reactants and products are sealed in. For example, hydrogen gas anc iodine vapour react reversibly to form hydrogen iodide gas: Hy(a) + 14g) = 2HKa) When hydrogen and iodine gases are first mixed in a dosed system, the forward reaction alone begins since there are no products present. As the amounts of reactants fall, the forward rate decreases. Once some product molecules have been formed, the teverse reaction can begin. The rate of the reverse reaction increases until forward and reverse reactions are happening at the same rate. This is a dynamic equilibrium (at a constant temperature), Physical changes can also result in dynamic equilibria. For example, iodine in a sealed container at a steady temperature sublimes in a solid-vapour equilibrium: Lis) = 1X9) logine molecules leave the solid phase and enter the vapour phase at the same rate ‘that they return from the vapour phase and enter the solid phase. Important industrial reactions that are reversible include. the Haber process for ammonia - Nig) + 3H,(9) = 2NH3(9) ‘the contact process for sulfuric acid ~ 250,(g) + O,(g) = 250,(9) «esterification — for example CHsCOOH() + C3H 1 means that the products are favoured, and the position of equilibrium lies well over to the product side + IF. <1 means that the reactants are favoured, and the position of equilibrium lies well over to the réactant side. ‘+ IFK.is very large indeed, such as 1 x 10", this means that the reaction has gone ‘to completion, © IF is tiny, such as 1x 107 EE. Use the following data to find a value for K, and its units for the reaction between hydrogen and iodine vapour at a temperature of 650K H,(g) + IL(g) = 2HI(g) ‘this means that no reaction has occurred. eat id ray Material ysouen Todine | Hydrogen iodide ij Equilibrium amount/mol | _029 039 3.00 Athouh the velume Vancals inthis a ase, you wl ove man fo fal {HW@)P cosubstuta Vin this oxesion <" OIL) Let the volume of the system be Vdm? because it ehanges moles into voncentrations, t «= 00m (0.39) (0.39”) =502 SORES Note that both V and the units cancel out. Gas establish equilibrium between hydrogen, ere iodine and hydrogen iodide at room The equilibrium constant K_ for the reaction 250,(9) + 0,(g) = 250.(9) is temperature? 10dm*mol~ at a certain temperature. The concentrations in the mixture were 2 Explain why an airtight found to be [503] = 5mol dm-=, [50,] = 4mol dm-3, [02] =3 moldm2 bottle of carbonated ‘Was the reaction at equilibrium? water (also known as soda water or sparkling water) ifthe concentrations were equilibrium concentrations, we could calculate Kas catteedd bet ae dynamic equilibrium. [soon 3 Write expressions for (OxO)FIO;OH Ke including units, s for "#xa 2 2NOYg) = N,0,9) Spear helt bb steam in contact with red hot carbon, H,0(9) + Cis) = H,(g) + COlg) A2 Chemistry Revision Guide Zz Since the real value of K. at this temperature is 10dm? mol-", the mixture is ‘ot in equilibrium,ResuitsPlus Examiner tip Check thatthe sum of the mole fractions is 1. These values add to (0.98 — good enough agreement Partial pressure af amneria = 0.14 10= 14am. Similar, the patil pressure of ritragen = 2.1 aim, and of hydrogan = 6.4atm } Ponca ty ni Cerca) Note that equlitria canbe writen either way... Heal + Lda = 2a) or Dill = Hg) + Wel tat, wl have diferent vals. You should always caleulte the eculbium constant fom the equation as itis provided to you we poor oe Examiner tip Be careful when you rite expressions for K, that you clay show round brackets. you write bracket hat looks ike a sauarebrackot you may lose ‘marks because it could lack ike you are confusing K wit Unit 4: General principles of chemistry |— Rates, equilibria and further organic chemistry With gaseous equilibria, it sometimes makes more sense to use an equilibrium constant expressed in terms of pressure rather than concentration, You need to be clear about the meaning of the term partial pressure of a gas ina mixture. Partial pressure can be defined as the pressure a gas would exert if it alone filled the container, Partial pressure is used for mixtures of gases that do not react together chemically. © We assume that each gas behaves independently in the gas mixture. «The total pressure of the mixture is the sum of the partial pressures of each gas — this is Dalton’s law of partial pressures. ‘© Partial pressure is defined in terms of mole fractions. For a mixture of two gases A and B, ‘number of moles of A number of moles of A + B the partial pressure of A = mole fraction of A x the total pressure of the system Sec For a mixture involved in the Haber process, calculate the mole fractions and partial pressures of each gas. The mixture contains 24.9g ammonia, 60.2.9 nitrogen and 13.1 hydrogen at a total pressure of 10 atm, + NYG) + 3Hx(g) = 2NH(@) the mole fraction of A First convert the masses into moles, and then calculate the mole fractions: number of moles = —mass__ ‘molar mass hhumbers of moles are ammonia 1.46, nitrogen 2.15, hydrogen 6.55 giving a total of 10.16 ion Abe mole fraction ammania = 148. — 0.14 mole fraction nitrogen = 215. = 0.21 mole fraction hydrogen ae = 0.64 Pressure units Gas pressures can be expressed in a variety of units + atmospheres (atin) # ka (1Pa=1Nm=2) © mmkg © Nm? Standard pressure is taken as 101 kPa, K, for a homogeneous system For the equilibrium Ha(g) + l(a) = 24g) K,, the equilibrium constant in terms of partial pressures is: ___ pIHIP pA x pil) Note the individual terms are raised to the powers that correspond to the number of males in the balanced equation. (Hig? OIG The expressions for K, and for K- are similar ~ the first is in terms of partial pressures, the second in terms of concentrations. To calculate K,, all partial pressures are measured at equilibrium. As with K., the units of K, Gepend on the equation. In this ase, K,, has no units, Compare this with R ‘A2 Chemistry Revision GuideTopi Equilibria AOISIETIM Calculate the value of K, at 720K and 101 kPa for the equilibrium: H,(q) + L(g) = 2Hi(a) Moles at equilibrium: 0.2 0.2 1.48 pit aT) Total moles in the system = 1.88 ikea! ‘You wil ase mars if you mix citferent pressure units together in these caleulations. = PtHP pan sina Ppl.) X pile) = 55 Note that, in this case, the total pressure P.. cancels out so we don’t need to substitute its value Substituting into the exoression for K,: K, for a heterogeneous system In a heterogeneous system, more than one physical state is present, The commonest examples involve solids reacting with gases. The partial pressure of a solid is taken to be constant. Its not included in the exaression for Ky. EE. \Write an exoression for K, for these heterogeneous systems and give the units of each if the pressure is measured in atmospheres. a CaCOxs) = CaOIs) + COx(g) b C(s) + CO,{g) = 2C0(9) a K, = p(CO,) atm BICO? * p(CO,) Note that the solids have been left out of the expressions. im The effect on K, of changing conditions ‘+ Equilibrium constants are exactly that — they are constants. Changing the pressure of a system has no effect an the value of K, or K. although it may affect the position of equilibrium according to le Chateler’ principle (as we saw in AS Unit 2), and hence the yield of product. + The only variable that can change the value of K, or Ke s a change of temperature Equilibrium constants are always quoted at a particular temperature for this reason. * Changing the temperature also alters the position of equilibrium according to le Chateliers principle, Raising the temperature favours the endothermic process. See page 32 What equilibrium constants can and cannot tell us Equilibrium constants, both K, and K,, are useful in determining the position of equilibrium, They tell us how far the reaction has gone. Equilibrium constants do not give us any information about the rate of a reaction, how fast itis going. SORT. 1 Eqplain the meaning of the partial pressure of a gas 2 What is special about the expression for K, in a heterogeneous system consisting of solids and gases? 3 What isthe effect on K, of doubling the pressure at @ constant temperature? A2 Chenisty Revision Guide yUnit 4; General principles of chemistry I~ Rates, equlbria and further organic chemist More on equilibrium constants Calculating K, from experimental data ‘Alcohols react reversibly with carboxylic acids to give esters acid + alcohol = ester + water ‘The reaction can be catalysed by hydrogen ions. Usually, @ small amount of concentrated suifuric acid supplies the catalyst. A common example of the | esterification reaction is ethanoic acid + ethanol = ethyl ethanoate + water cae In esterification, the amounts of substances present can be found using titration: «The concentration of the reactant acid falls as the reaction proceeds. When the acd concentration is constant, equilibrium has been established at that You shoul beable to calulate 8 value forthe equlibum constant fr a reection based on data derived from an cexoeriment, such asi the preparation ofan estar temperature. 4s Titrating a 25.0.cm? sample with standard sodium hydroxide solution and an indicator gives the concentration of acid present at equilibrium. «snowing the intial amounts of acid and alcohol, all four of the equillbrium Concentrations can be calculated using the balanced equation. Using the equilibrium expression gives a value for K, Equilibrium constants for esterification are often close in value to 1. This would ave @ | poor yield of the ester. Yields can be improved by. ® adding an excess of the alcohol — this shifts the position of equilibrium in favour of the ester product ‘» recovering unused alcohol at the end by distillation and re-using it. Equilibrium i atained after several hours when these mixtures are heated in a water bath at constant temperature. Sete ‘At 323 K (50°C) a mixture of 0.5 mol ethanol and.1.0 mol ethanoic acid was reacted until equilibrium was established. At equilibrium, the amount of ester If you are only given the amount of one ‘was 0.4mol. Find the value of K. othe sutsianes inthe eqilum a s 5 triste, you can still workout the Let the volume of the system be Vidi number of moles of the other reactants: CH;COOH()) + CzHsOH(l) = CH,COOC;Hs{l) + H:0(0) | and products from the stoichiometry Initial amount/mol 1.0 OSs 0 oO {ino mol rato) ofthe reaction } Equilibrium amounvinol 0.6 on 04 04 If 0.4 moles of ester have formed, then from the balanced equation 0.4 moles of + water must also have formed, and 0.4 moles of each of the reactants must have canal isappeared z _ [CHsCOOCsHsIIH,01 Remember to convert rumbers of males © [CH,COOHIICH-OH] into concentrations inthe equiibiun | ave EVV.) constant excresion. Usual, 7 tarels ut nis cae but au should 27 always show this step oven fou tne | the volumes wil cancel out Werise ‘An aqueous solution is made by dissolving 1.00 mol AgNO; and 1.00 mol FeSO, in water and making up 10 0.50dm*, An equilibrium Is established Agt(aq) + Fe**(aq) = Fe?"(aq) + Aals) At eouilibrium, the concentration of Ag*(aq) is found by titration to be 0.88 mol dm”. Find K- for the equilibrium.Topic 3: Equilibria =e First, find the number of moles of Ag” (aq) ions at equilibrium: = concentration X amount = 0.88 x 0.5 = 0.44 mol Next, calculate the number of moles of the other ions at equilibriurn (we don't actually need the amount of silver as we don’t include concentrations of solids ere ink) eee ‘Ag’{aq) + Fe®'(aq) = Fe**(aq) + Ag(s) Initial amounvmol: 1.0 10 0 0 Inthis ease, co usa, the volumes Equilloium amounvmol: 0.44 0.44 0.56 dont canal out. Alvays rember ‘Convert the equilibrium amounts to equilibrium concentrations: ee ino concentrations ‘Agtiaq) + Fe?*(aq) = Fe*(aq) + Ag(s) (ian s Mares it 3044 04d 0.56 Equilbrium concimoldm-= 248 9.44 O36 088 0.88 112 [Fe?*(aqi] [Ag *(aqillFe**(aq)) = een 088 x 0.88 =1.45 dm? mol-! Equilibrium using immiscible solvents lodine is soluble in both hexane and in aqueous potassium iodide solution. Hexane and water do not mix ~ they are immiscible. The iodine solute distributes itself between the two solvents: Iy(aq) = (hexane) Solvent A Solute is dstrbuted between immiscibie solvents &and 6 Sbienke ' ies Partition coefficient = 22 inseivent A id meg Isolten sovent 8 i loan s soluble in te mmiscibiesohents Gain full marks by making lear that the dine inthe aqueous layers ina Solvent A is hexane, B is aqueous potassium iodide, but water is acting as the solvent complex anion. f-,because the iodine for a complex ion containing the iodine. is only vr lightly soluble in water ' This is a special case of an equilibrium constant called the partition coefficient: oe eRe gee [iodine in solvent A] [iodine in solvent B] Large partition coefficients (® 1) indicate that iodine is much more soluble in solvent A than in solvent B. partition coefficient lodine concentrations at equilibrium can be measured using titration of samples from each layer with sodium thiosulfate solution Entropy and the equilibrium constant There is a problem with applying the idea of entropy to a dynamic equilibrium because there are two different reactions going on at the same time: reactants = products For such reversible systems: * the balance between the amounts of reactants and products is determined by the equilibrium constant K * the total entropy change, ASixai = ASasien + ASwyronsngs iS 2670 at equilibrium, A2 Chemistry Revision Guide BB|: General principles of chemistry | = Rates, equilibria and further organic chemistry Note it is the total entropy change that is zero at equilibrium, not the total entropy. In fact, total entropy of the system is a maximum at equilibrium ~ any change from this position would result in a decrease in total entropy. ‘The relationship between these quantities is given by ASwua = RlnK, where R is the {gas constant. Since Ris a constant, an increase in ASypuy results in an increase in the equilibrium constant K as well. (This applies to both equilibrium constants, Ke and K,.) Hence, the total entropy change not only indicates the spontaneous direction of 2 reaction, but also the extent to which it takes place (how far it goes towards completion). The larger the positive value of the total entropy change, the larger the value of K, and so the further the equilibrium position shifts towards the products, Using entropy to explain the effect of temperature on an equilibrium constant Both exothermic and endothermic reactions affect the entropy of the surroundings. ‘* Exothermic reactions release energy to the surroundings. iH 245, surendings = The convention for enthalpy changes is that AH is negative for an exothermic change. This double negative makes the Value Of ASynaundnge Positive, in other words it goes up. ‘+ Exothermic reactions increase the entropy of the surroundings. AS = RINK can be writen as Ink = [5 X (BSypen + ASsconn) Ink = (F) x (QSyaumt QAI # When the temperature is raised, the magnitude of —S4 decreases For an exothermic reaction, as Tincreases, In K becomes smaller (this means less product in the reaction, as predicted by le Chatelier’s principle) ‘+ For an endothermic reaction, as T increases, In K becomes larger. # The increase of AS. ainaigs Becomes less significant and the position of equilibrium shifts ‘When the temperature is raised, for an endothermic reaction the significant factor is the increase in S.yzon Hence: for an exothermic reaction, when T increases, K decreases ‘* for an endothermic reaction, when T increases, K increases. AOMEIIMm 1. Which component shauld you titrate to monitor an esterification reaction? 2 What 's meant by the term immiscible? 3. How does an exothermic change alter the entropy of its surroundings? = AA2 Chemisty Revision GuideTopic 4: Application of rates and equilibrium DeVere iver mime iaY ‘Many important industrial reactions are reversible. You should be able to explain how the equilibrium yield, the equilibrium constant and the rate constant of these reactions are affected by changes in reaction conditions, and to justify the choice of reaction conditions chosen in industry, Changes to reaction conditions could include: © temperature © pressure or concentration © the use of a catalyst. Remember from page 29 that the equilibrium constants K, and K, do vary with the temperature but do not change with either concentration or pressure (for gaseous reactions). Effect of catalysts on equilibrium and rate Catalysts speed up both forward and reverse reactions. Catalysts lower the activation energy (see page 10). Catalysts reduce the time taken to establish equilibrium, Catalysts have no effect on the value of the equilibrium constants. Effect of temperature changes on equilibrium and rate Reversible reactions will be exothermic (AH negative) in one direction and endothermic (AH positive) in the reverse direction. The temperature effects on yield can be summarized as follows: © ina reaction where AH is positive, K rises with temperature increase, giving more of the products © when AH is negative, K falls with temperature increase, giving more reactants ‘increased temperature increases the rate constant k (see page 11), so the rate increases with increasing temperature. Se fc In the following equilibria A NAG) + 0219) = 2NO() AH = +185kImol-! B NA(g) + 3H,(g) = 2NH;(g} | AH = —90kJmol-' i What isthe effect of increasing the temperature on the position of equilibrium? What is the effect of increasing the temperature on the size of K,? Which value of K, might change more, and why? Raising the temperature favours endothermic processes. Reaction A shifts to the right, making more products. Reaction B shifts to the left, making more reactants For reaction A there are now more products, so K, increases. For reaction B there are now more reactants, so K, decreases. iii K, for reaction A is likely to change more because the magnitude of the AH term (the enthalpy) is larger. A2 Chemistry Revision Guideseas coger ays Usp euouure u woueueA Swanyeiadua, 098) Or 007, wea = a wieoo1 uaegoe ~~ | ‘une 001 Indo ve Uase16 eLOUNLE 46 (()) ueIsUOD WNuiquInba ajqeuosee: pue (y) axes UONDeE—L ajqe\deDse | ue uaamjaq asiwuoidwiod e axe su0l2eai [eunsNpul 10} uasoUD suORIpUDD aL ae I ‘6se] e 1sfjeve> aug sani6 siys “a2e]sns snouod e Upian scuun) Low st asAjeie> au, “vonDeai Jo ayes auf sal2vajanDe ypiyia *B19ua UONeNNDe au siamo ISh\EIeD 2 Jo asn SL “Uayo1g aq IS) SKU UPIYNA “aINDQ}OWL CN ap UI Pug aja 2UA JO yjBuans ayy 0} anp A6saua uoHenRse YOIy Aan e sey uomea: pasfle\eDUN ata "122, ul ABveu8 uoaemnse aun Jo az 41 40 ates INOge |e Ye UOeWUO}UI OU ANeY aN papaau sisuleuo> Buoss pue 1s09 ABsaUa ~ seunssoid yBiy Avan uleyUIeU ©} 20/0p410% ayi o} snopiezey Ajenusiod pue anisuada SI! YaNeMOH © “vonDeal Jo aye4 ay} sasea;oU! osfe aunssaid yBiy © ‘ajdiaulid §191}}€4 aj Aq par>ipaud se sanow ‘unugiinbs aug pue seinda|ows snoase6 jo Jaquinu ayp siamo] sip asneseq (eluouwe jo pjaik pasea:5ut) uonzeal pienioy ayy Sunoney eunssaid YBIH © ‘s6ueyp Ado.tua aayebou e 51 aiayp os ‘526 Jo sajow ul aseannep = saunjesadwiay mo] 22 fluo snoaueuods aq pynoys UoRDeal PeMUO] ay, © s9InDa|OW ey>e04 ueYA Sajnd9jOW }>npoId Joma, a1e aiayp asnedaq Adonua ul asea,nep e sasnes uoNDea: piemuo} By ‘uoRDea! ayp 40 218 al Bsea:D—p II! saiMeLadUIa} Mo] YanaMOH « eIUOULE Jo SpIaIK YBIY snoA2, jm saimesadway mo] 05 ‘1w9YI0K | eIOUIWe Gulsnpoid uoKDeaI pIeMLO} 24] aoe peut 06 yotuel ae "ap siompoid on pauisop 0 | cumuun sey ago a6 ons seston ng eu eee eee] Hewr06— = HY GFHN = (6)'He + ON 'Sp[aiK 21wW0U938 UleIgO 01 pasn sUORIPUOD ay) ssnNdsIp O} Ado.qua pue Adjeyjua ui seBuey> eu) asn ‘ejuowwe 104 sisayiuAs JaqeH a4) U} NE oe ba Up Hated | “Anwanbayy 230u1 apiijo> Aa) O (uoriesTu=DUO UI asea.DUI Ue O} 1UayenINba) aUIN|OA Lab e ul sejnaajow a10W ave auaYp YeY3 Sua Seb e 10 aunssaid ayy BuIsearul © aidpuud ssJa1je1ey9 2] 01 Burpioa.e wnuqyinba Jo uonysod ayy sjpaye aunssaid ul aBueyD y * ‘y 40 anjen ayy Paye you op ‘sje aunssaid jo sa6uey3 ‘vonesquasu02 st} 01 jeuo;Odoid s Se6 e Jo ainssaid at) @ | ‘pa6uelpun surettias y Jo nyen aya ing paysi}ge3sa st winuq\jnbs Jo uorIsod sau y “dn paads 01 sues uonzeai asiana, 24) ‘se=:5ul sDnpaId yo UNOWe ALA sy ‘UolDe84 puentuo} ayy Sojesa|e0ze aungsiw LunugHINba Ue O} SyueIDee: aso Bulppy & @}e4 pue winliqyinbsa uo sabuey> aanssaid puke 01324349909 Jo 399459, Ansiwayp 2u2010 sayuny pue euqunte Sarey — | Ansluoyp jo sadouud exeua5 rp mun \' Topic 4: Application of rates and equilibrium xe Nitrogen dioxide dimerizes and gives the equilibrium: 2NOg) = Nz04g) AH = -57kJ mol? Which of the following changes would result in a different value of the equilibrium constant? A Raising the temperature B Lowering the pressure Raising the pressure D__ Adding more nitrogen dioxide The only factor that changes the equilibrium constant is the temperature, 50 the answer is A. The atom economy in industry Remember from AS Unit 1 that the efficiency of converting reactants into products can be assessed using the atom economy mass of atoms in the desired product “otal mass of atoms in reactants The atom econamy can be improved by: © Developing an alternative more efficient synthesis —i.c. find an alternative reaction, such as finding a catalyst for a reaction with a better atom economy, or i replacing elimination reactions with addition reactions «© Finding uses for any by-products e.g. in the cracking of decane to form two products, CigHo2 > CoHe + CeHg, the atom economy is improved if commercial Uses can be found for both products, not just the alkene. In fact, octane is a major component of petrol SOMMMm™m™ 1 How does a catalyst affect the equilibrium constant? 2 When the temperature goes up, how does the eouilbrium constant change for the Haber process? : 3 What possible benefit to the yield might result from using a synthesis with a higher atom economy? 4 in the production of ethanoic acid, explain why the reaction CH,OH + CO — CH,COOH Using catalysts of cobalt, rhodium and iridium, has 2 higher atom economy than the production of ethanoic acid from the oxidation of butane and naphtha, which produces a wide range of products including ethanoic acid, methanoic acid, propancic acid and propanone, atom economy (%) x 100% ‘A2 Chemistry Revision Guide 7BY, Unit 4: General principles of chemistry |— Rates, equilibria and further organic chemistry Topics 3 and 4: Equilibria and application of rates and equilibrium checklist By the end of this topic you should be able to: none eae sminaits Teves” ESR Used in manufacturing, such asthe Haber process Oo Oo | distribution of solutes between immiscible solvents concentrations, and work out its units | oO Oo and K, partial pressures, and work out its units Oo Oo constants: constants, e.g. the reaction of ethanol and Oo o ASiow) = RINK a oO | of equilibrium (extent of reaction) uo | Oo | change oO uo | rate | fae si aaa safely and economically. o QO | | a cat Cee eens 1 Fortheequtrum NO = 25049) £21 00K has the numerical value 18 x 10° at 1300K has the nmeial value 28 x Tot Which one ofthe fling statements i coect? : A Theerthapy change A/is negative B A higher temperature gives mae ntogen dioxide | © Khas the units of dn aim* D_isng the prossure wil gve more ntogen dixie 0 | The tempersiure rise causes K, to increase, giving more nitrogen dioxide. The dissciation is therefore endothermic so Ais wrong and B is correct. The units of K, ere just atm here, so statement Cis wrong, Lowering the pressure favours the reaction that increases the number of imakes, so D iselsoincorect. Te answer's B. (1) | A2 Chemistry Revision GuideTopic 4: Application of rates and equilibrium Bees 2 Consider the equlrium N,Odg) = 2NOla) A= +58Kd mol 8 Wit the expression forthe equiixur stant, K, forthe above reaction a Be careful not to use square brackets ~ ths wil lese you marks har, Ifyou use round brackets, make tis clear to the examiner. bi Anoquiirium mitre contains mole fractions of ditregen tetaide NOx pressure ofthe mixtures 1.1 tr Calulat Kat this temperature, stating its units ‘ND, = 080 x 1.1 atm = 088 atm 120, and of nitragen dioxide, NO; = 0.80, The wial ANO| = 020 x110m=0222m (1) a8. Sonam =32 fl) am) ‘You will get eet ityou cary forward a wrong value forthe partial pressures you calculated in (a, provided the Kyou calculate is consistent vith those pail pressures fi Calculate te total pressure required to educa the mola fraction of to 010. AN,O4) = mole fraction x total pressure of the system = 0.1 X Py AN:O4 + A(NO,)=1,801NO=09%P, (1) AN,O,) 10.9 x PP (1x Ped : 352aIm Pa [Many students lose a mark for incorerly rounding the answer ta 0 © 1 Whatis the effect an K, it any of raising the temperature? Inereases because this is an endothe icreacion) (1) fi Use your answer toe) (i) ta explain the eect of increasing the temperature on tha positon of enulibiom, The value of p{NO,F/p(N,0,) nereases So te parialpressu of NO, must nase 2 th anal pressure of 40, decrees, meaning ha tho poston of oglu hs tothe naling more NO.) Note that you ae asked to use your answer toi) in i, so youn ineroas in temperature affects the position of equilbum or yi not gain any matks for using le Chatelia’ principle to explain how an NO, (From June 08 Unit est ¢ 03) ‘A2 Chemistry Revision Guide ZzTopic 5: Acid/base equilibria Acids and bases ideas about acids included that they: ‘© are corrosive liquids, for example concentrated sulfuric acid © have a sour taste, such as citric acid in fruits © give characteristic colours with indicators — such as litmus turning red The understanding of acids has since been extended to include a wider range of materials. Acids in aqueous solution undergo some characteristic reactions. They react with ‘© bases (and alkalis) giving a salt and water ‘carbonates to give a salt, water and carbon dioxide some metals giving a salt and hydrogen. Arrhenius theory of acids Arthenius developed a theory of electrolytic dissociation. It states that when certain materials dissolve in water, they immediately split up from molecules into ions: ‘+ Arrhenius acids give hydrogen ions H* in cqueous solution Arrhenius bases give hydroxide ions OH in aqueous solution. The theory could not be extended to include non-aqueous solvents such as liquid ammonia. | Ideas about the nature of acids and bases have developed over centuries. Simple, early Bronsted-Lowry theory This theory was based on the movement of protons (equivalent to hydrogen ions, H"). It applied to a wider range of examples than previous theories It said that a Bransted Lowry ‘© acid is 2 substance that donates protons ‘© base is a substance that accepts protons. eerie ia Archenius suggested that salt molecules split up into ions in solution Give some evidence that opposes this view of bonding in sodium chloride. b Which species are produced in aqueous solution by Arthenius acids and bases? a Salt (sodium chloride) is ionic in the solid state. Malten salt conducts electricity in the absence of any water. The splitting up of salt into ions is ‘not caused by adding water — the existing ions simply separate as it melts or dissolves 1b Arrhenius acids give hydrogen ions, and bases give hydroxide ions. Conjugate acid-base pairs The Bransted-Lowry theory defines an acid-base pair as follows: «two species that change into each other by gaining or losing a proton * each acid has a conjugate base * each base has a conjugate acid. For example, when hydrogen chlaride gas dissolves in water, a solution of hydrochloric acid is formed: HCi(g) + H,0() = H;0"aq) + Clea) acd base2 acid 2 base 1 Acid 1 is transformed into base 1, its conjugate base. HC! donates a proton to water, leaving the conjugate base CI-(aq), In accepting a proton, water acts as a base (base 2).Itis transformed by this into its own conjugate acid (acid 2), Hs0* 29). ‘A2 Chemistry Revision Guidetates, equilibria and further organic chemistry Unit 4: General principles of chemistry Examples of Brensted-Lowry acids and bases Acids © HNO,(aq) + H,0(l) = H,0*(aq) + NO,~(aq) ‘* CH;COOH(aq) + H,O(I) = H;0*laq) + CH3CO,-(aa) Bases: © NH;(aq) + H20(!) = NH,(aq)* + OH™(aq) © HSO,-(aq) + H;0*(ag) = H,SO,(aq) + H,0il) te How many of the following are acid —base conjugate pairs? ‘ACO? and HCO, B H0° and OH- C/NH,* and NH. D Cl-and HCI oT eT cee) [Moke itctear in your answer what funetion the water i fulfiling, Water can be a proton dana acc or atceptor (base. Confusion over this vil lose you mars, Look for pairs where one can be transformed into the other by the movement of one proton (H*). Only A and D are acid-base conjugate pairs Strong and weak acids and bases Dilute solutions of the mineral acids (hydrochloric, nitric and sulfuric) are almost completely ionized. These are strong acids, fully dissociated into ions. Alkalis such as sodium hydroxide or potassium hydroxide are strong bases. Some acids and bases are only partly dissociated into ions in aqueous solution. These are called weak acids (e.g, ethanoic acid) and weak bases (e.g. ammonia). Ethanoic acid is only dissociated a few per cent (about 2%) in dilute aqueous solution: CH;COOH(aq) + H,0() = H,0"(aq) + CH3CO,"(aq) The equilibrium lies far to the left, favouring molecular ethanoic acid, The acid H,0*is stronger than CH;COOH, Similarly, CHsCO2~ must be a stronger base than H,0. + Strong acids have weak conjugate bases. ‘© Weak acids have strong conjugate bases. AOMETIM 1 How do we recognise a Bransted-Lowry bese? 2 What is the conjugate base of hydrochloric acid? 3 According to the Sransted-Lowry theory, what is special about water? ° & Chemistry Revision GuideTopic 5: Acid/base equilibria a! Pamlico Mel stele lero meaty lacy There are several mathematical relationships relating to the concentrations of hydrogen ions and hydroxide ions in aqueous solutions. Concentrations in moldm~* are wiritten as [H"(aq)}and [OH-(aq)] respectively ‘+ Use of a logarithmic scale allows easy comparison of concentrations that vary very widely ‘¢ pH = —logiolH*(aq)i: similarly pOH = —log,efOH (20) From the definition of the ionic product for water, K, (see below): © pH + pOH = 14 at 25°C, so knowing either pH or pOH gives the other value © PK = l09raKw lonization of water Water dissociates weakly into ions H,0(l) = Ht{aq) + OH-(eq) ‘At equilibrium, we can write an expression for the equilibrium constant: [OHCaq)llH*(aq)] TROT Since the extent of dissociation is very small, [H0(0] varies very litle indeed and itis, Useful to treat this as a constant, and write an expression called the ionic product for water Ky. % [OH-(eq)IIH1*(aq)], this has units mo’ dm-* Note that the ionization of water is endothermic (the equilibrium shifts to the right at higher temperatures), so K,, depends on temperature. At 25°C, Ky =1.0 X 10° mol’dm-6 Taking logie of both sides: Ky = pH + pOH Ky = 1.0 10° moP dm-é at 25°C hence pH + pOH = 14 at 25°C. We can use the value of K, to calculate either the pH or the pOH of a solution See Find the pH of a 0.05 mol dm? solution of the strong base sodium hydroxide. H*(aq)JIOH-(aq)] = 1.0 x 10-"*mol? dm-Sat 25°C [OH-taq)] = 0.05 mol dm because itis fully dissociated into ions. Therefore, 1.0 x 10°!4mol dm-€ = [H*aq)] x 0.05 mol dm-3 [H"(aq)] = 2 x 10-7? mol dm? pH = ~log,f2 x 10-19) = 127 Dilution effects ‘Strong acids are already fully dissociated into ions in dilute aqueous solutions, so [H*(aq)] = [acid], the acid concentration in moldm~*. ‘© Diluting a strong acid by a factor of 10 raises the pH by 1 unit. © For an acid like hydrochloric ac: Concentration/moldm?| 0.1 001 0.001 pH fl 2 3 * Diluting a weak acid is different; it increases the degree of dissociation into ions {see below), of ResuitsPlus er Make sure you can calculate (H*taql) frp By eangenen, [H*eqll ~ antlcgid ~pl). You find ‘this by using the 10° function on your caste ResultsPlus ea) Note that a neutral solution has (O}-1 = 1H"), but the pH will only be TaD poor oa Te Pre ‘Students lose mas ty confusing the terms weak and dilute as applied to acids. A weak acids party ionized — a diluta solution has a low cercentation. You van have dilute ar concentrated solutions of weak acids. A2 Chemistry Revision Guide aVE = (01 X 6€)"60)- = Ha au} ¢-UUP }OWy-OL x 6 E = [(b2),H] (WP OW ,-OL X O°L) X (¢-WUP OWL X GL) = ¢{(be).H] -p dors ((O2)HO0Du] x 5 = z{(be),H} iEeen Bub ,{(be),H] Aq doy ayn uo una axp arejdai y 104 uoissaidya aya Ul se days ((be) H] = [.(be}0034) 2U8Y "1:1: S| UOREDDOSSIP siytJO4 ones a;oW ayL -z dors (be),H + (be)_oO3u = (be)}HOODa ‘uoneZessip ayl 40} uoKenbe ay) allin, :1 daas 229 ppm Hon pum_up, 01 xo 8g pinow {ibe}. (payetaossip $0018) re Bunns aS | eens) ee Wp Jou s_OL x O'L 51 pDe au Jo UOENUaIUOD ay} UE ;_WPJOW.-OL x S' ="¥ 224) UBAIB HOODY Pde wWUebIO yeaM e yo Hd aur a12IN>|e> NEE y wow, Hd puy oF 20 "Hid Buunseaui fq *y puy 01 sn smoje sty. AyjentU! [(be)yH] 02 Jenba Ajarewinoidde 1 51 wnuguinbs e [(belyH] ‘Ajued fluo saeNossip yy asnereq, "YeyL BUINSSe OS|e LED aN | Keeyvel nhs ca “foe =} Pewcuas 1510} uossaucxo oy, -uouomssau ypu auujon ) 4 uosaeud pve dseiane en arene {(be)_] = [(be),H] ‘veo nod yeyn pu “aie 883) anno ‘a10yasau, (be) orien e030 "posn yom Jo ue (be),.H Jo stunowe (12jowinba) ajoul jenbo saonpoid poe ain *_¥y PUP ,H suo! ‘aunjon ag pue poe ajo ssew pue PaleDossIp sy pUe UoRNjOS snoanbe UI YH PDE Yeam e UBaMaG WhguINbd AUE UL Seu Jou a ny uomentuansea real ty arenoj2 0 oy mouy nok ans aye 9 Atay gun ose pu vaded FU 4 Ut pau SSIy. ep jenuewuatda cy poe yeam © 205 uy. 07 eg@ 6q os prays N04, poe au 1axe—M aK PUP sryeny ay Ja/PUNS ayy ‘anjen"yd up andisod a1oW ayy yeWA AION Sé'v ="¥'60|— = *yd vay poe rIouRNRe 104 ¢ WIP JOWs-OL x PL SyP'60)— = Syd *y J! ajduiexa 404 'SUO| OWUI s3yeDOsSIp poe UP JeYL 2ua}x9 84 SayeDIPU Y 9sneDaQ ‘PIDe ay) Jo JUE}SUOD UOREDoSSIp UI Se UMOUY s|°y ree ‘¢-WUp [OW SyUN aL sey ®y ‘uoREDOSSIp siY 104 Bd is hs [(be}H009°H31 * (be), H]Ie}-003*H3] Sy queISUOD Lunugiinba au sani6 me] winLguinbs ay) Burkiddy (b2)_003°HD + (be)..H = (be)}HOODEHD [pide 2}oUeYa Jo4 "PDE ayy Jo UONesTUaDUO> ay} 02 jenba 30U 51 [, H] PUE ‘LoRINjos snoanbe UI SUD! OUI pare_ossIp AED Ajuo ale spre yoann °y ‘Spipe 403 JUe}SUO> UOeDOSSIG EL = HO a0uay “pL = Hod + Hd | | =(1'0)"'60|— = Hod [(be)_HO]"Bo|— = Hod uoissaidxe ayy Busn Hod aLeinD|e0 ys114 > Z = (LO0"Bo|— = Hd q | 0 =(O'1L)"60\- = Hd & vl = Hod + Hd pue [(be), H)°60|— = Hd asp Uuonnjos snoanbe ainyp ul suoi ‘jut paxersossip Any ae saseq pue spioe Guons jeyp st apew uondwinsse ou HORN e WP|OW 0 2 FON s-UPIOW LO. | OH e-wipjoworL e ‘28u noK suonduinsse ‘Aue weidxo pue ‘aseq 10 poe Buo.as e jo uonnjos ype yo Hd aya aeIn2je> ERE TOIT ‘Aasiuip >1veB0 ayn, pue euqiinba ‘sarey — | Aysiuayp jo Sajdpuud je2ue9 sp wun,Topic 5: Acid/base equilibria Src The pH of a solution of a weak acid of concentration 0.15 mol dm~3is 2.5. What is K, for this acid? Step 1: Calculate [H*(aq)) pH = 2.5, 50 [H*(aq)] = antilogio(—2.5) = 0.003 mol dm- Step 2: Since equal numbers of [H*(aq)] and [A~(aq)] are produced in the foe fe ted dissociation, the equilibrium concentrations of the dissociated ions are eet ‘the same, 0,003 mol dmm~2 Step 3: Make the assumption that the concentration of the acid [HA(aq)} ‘As always in calulations,don'trourd ‘at equilibrium is the same as the initial concentration of the acid, too earl or your caleulte value wil because it dissociates so litle be inaccurate [HA(aq)] = 0.15 moldm-? a Step 4: Substitute these values into the expression for K;: c= (0.003 mol dm)? *°0.15moldm== = 6.67 X 10-2moldm-? SORE 11 What effect does increasing temperature have on the ionization of water and its pH? 2. What assumption is made about the ionization of strong bases in dilute aqueous solution? 3° Whats the advantage of using a logarithmic scale for pl, rather than simple ' hydragen ion concentrations? 4 Convert the following [H”] values to pH 0.01 moldm=? b 0.001 mol dm? © 2.5.x 10-¢moldm- 5 Calculate the pH of: a 0.5dm-~* HCI b 0.1moldm-? KOH a ‘A2 Chemistry Revision Guide (EaUnit 4: General principles of chemistry | ~ Rates, equilibria and further organic chemistry Titration curves, indicators and buffers 14 2 10: | | fussmasse Pa strong base 4 | 2 ° 2 om? of 0.1 mal dm alkali 14 2 10 6 (2) Strong acid | weak base 3 , ‘ar? of 0.1 old? alkali | ‘added to 25cm?0.1 mol dn-?acid Variation of oH curing trations ResultsPlus y, eae e Dae Sacre Ail sig mars ty choos te won deat tang mut caren ete veri setenen te tetova J Meebo pA) he) ‘acid to 25.m°0.1 mol dm"? acid 14 * Monobasic acids have one replaceable 12 hydrogen atom ~ for example HCI, 10: (al CH,COOH and HNO.. Sulfuric acid, H,S0,, is 8 (b) Weak acids asic. pa strong base The end-point can be determined using : indicators or by using a pH meter or ph! i paper. «A titration curve is a plot of measured pH oar against volume of added base (or vice versa, adding acid to base) The end-point is halfway up the vertical section of the pH curve, where the pH changes most rapidly There is no sharp change of pH with weak car? of 0.1 mol dn alka added to 25em*0.1 moldv?acid® 14 12 ‘a acid-weak base titrations, making it very 8 hard to determine the end-point. me (t) Weak acid Note that: ‘only the titrations of strong acids with strong bases give end-points with pH 7 © neutralization of 2 weak acid or weak base moves the end-point above or below 7 respectively, weak base ol ____ 3 cr of 0.1 mel de alka added to 25cm"0.1 mal dm acid Indicators ‘Colour-change indicators are week organic acids or bases: Hina) = H¥(aq) + in-(aq) colour A colour 8 ‘An indicator and its conjugate base show two colours, according to the pH of the solution, Indicator Colour change | pH range of use Methylorange | Red-yellow | 32-44 Methyl red Red-yellow [48-60 Bromothymol blue | Yelow-blue | 6.0-7.6 Phenol red Yelownred [68-84 Phenolphthalein | Colourless-pink | @3-10.0 Indicator ranges and colours eee E a Choose a suitable indicator for the following titrations, and explain your choices: a ethanoic acid and sodium hydroxide b hydrochloric acid and potassium hydroxide ethanoic acid and ammonia solution, ‘a Weak acid strong base; predicted pH at the end-point around pH 9; use phenolphthalein. Strong acid—strong base; vertical section of the titration curve covers a wide range; any indictor will do. © Weak acid—weak base; no clear pH change at the end-point; no colour change indicator is suitable — use a sensitive pH meter instead. A2 Chemistry Revision GuideTopic 5: Acid/base equilibria Buffer solutions ‘Buffer solutions maintain their pH when small amounts of acid or base are added. ‘+ Biological buffer solutions maintain the optimum pH ranges in ving systems; . changes in blood pH could disrunt biochemical reactions and even cause death, ‘© Buffers contain a mixture of a weak acid with its conjugate base. ‘+ Most chemical buffers are made by mixing a weak acid with one of its salts. Simple buffer solutions work because the salt is fully ionized, supplying ions that are the conjugate base to the weak acid ‘+ Additional H*(aq) ions combine with the conjugate base from the salt, 10 give a largely undissociated acid. This removes the H'(aq) ions from the solution and the pH remains virtually constant. ‘Additional OH~(aq) ions are neutralized by the small number of H“(aq) ions, which disturbs the equilidrium so that more of the weak acid dissociates, returning the pH to its original value Buffering occurs in titrations, for example when a weak acid is titrated with a strong base A (see upper figure, page 44). The pH stats to rise and then becomes less steep once the buffer is present — when both the acid and its salt are present in reasonable concentrations. Sree Explain why pH = pk, at half-neutralization of a weak acid by a strong base For the neutralization reaction: CHsCOOH(ag) + NaH(aq) + CH;COO-Na*{aq) + H,040) [CHsCOO-IH"] [CHsCOOH] But at half-neutralization (when half of the acid present has been neutralized by reaction with alkali) the concentration of the acid, [CHsCOOH], equals the concentration of the conjugate base, [CHCOO-], from the salt. Hence K, = (H*] and, therefore, taking logs: ResultsPlus Cee K You should be able ta use tration ‘curve to fd K, of @ weak acid using the hafneutalization meth. PK, = pH Calculating the pH of a buffer solution ‘The weak acid is partly ionized, so: _ [He@lla@a)) (HAGa)l x [HA(aa)] Wed) = eal Because HA dissociates only partly, [HA(aq)] at equilibrium is approximately equal to [HACaq)] initially. Also, [A~(aq)] will be due almost entirely o the fully ionized salt, so (A~(aci]is approximately equal to [salt] nag. Hence: a Haq = 5% TH Alsat ree lth i ‘A buffer solution is made using methanoic acid and sodium methanoate. What is the pH of a solution | containing equal volumes of 0.100 mal dm-? methanoic acid and 0.400 moldm-? sodium methanoate? , for methanoic acid is 1.60 x 10-4 moldm”3 at 298K. K, x the ratio of the initial concentrations of the acid and its conjugate base = (1.60 x 10-4 mol dm) x (0.05 mol a 0.2 mol dmv Note that the initial concentrations of methanoic acid and sodium methanoate are halved on mixing equal volumes (same number of moles in double the total volume). pH = —Iog,0(4.0 x 10-4) = 4.40 {H*@q)] 0 x 10->mol d= ‘A2 Chemistry Revision GuideUnit 4: General principles of chemistry 1— Rates, equilibria and further organic chemistry Topic 5: Acid/base equilibria checklist By the end of this topic you should be able to: Revision spread ‘Checkpoints Specification | Revised Practice exam points questions ‘Acids and bases Understand the Arrhenius and the 47a Bronsted—Lowry theories | Understand conjugate acid-base pairs in terms of | 4.7b and c proton transfer Know that weak acids and bases are only slightly 4.72 dissociated in aqueous solution pH and dissociation | Explain the meaning of BH, Ky, BK. Kn DK 47d constants ‘Write expressions for the equilibrium constants K, | 4.7eandt and Ky and deduce their units Use logs and antilogs to carry out pH calculations | 4.7d and for a strong acid and a weak acid, including after | dilution Understand the relationship between K, and pH [4.79 andh for weak acids, and discuss the assumptions in the Glaulation Titration curves, [Draw and explain titration curves for diffeent [4.71 indicators and combinations of strong and weak acids and bases | Batters Select suitable indicators for acid-base titrations [4.7] Understand how buffer solutions maintain pHi end | 4.7k ‘calculate the pH of buffer solutions Use tivation curves to relate K, and pH athal [4.71 | neutralization O,O} oO]O} oO} Of} oO; ojo] o.oo} oO OOOO} O] ovojojojyojo Explain the importance of buffers in biological | 4.7m | systems Root cat) Crear’ 11 The following dissociation is sot up when ethanoic ax dissociats in water (CH,COOHteq) = CH,C0,-lan) + Haq) ‘8 Write the exmression forthe aissciation constant, K, fr ethanoic ai a ed K=(CH.COMIN*VICH,COOH| at eculibxium (1) ‘The question asks for K for ethanoe acid. Ifyou write the generic equation you wil lose marks even if you write the generic equation cect bb Given K, ~ 1.8 x 10-Sroldm* for 1.0mol dn ethanoic aid, calculate the pl 2) i ES nis a weak arid so assume that there site dissociation, so thatthe fil corwertaton (CH, COOH], is approximately 1.0 moldm~% (1) Hance: A, = (CH,00eIH*WcH,p00Hl = HH Ps1.0 | (i= \Gax 10min a) pH =—loag(H"1=24 A) [Dont forge to take the square root in orr oealulate the value of [Ham your expression containing (HP. oom, ‘A2 Chemistry Revision GuideTopic 5: Acid/base equiva 2 Arinture which wil act asa butfr is B HNO; and NaNO, c0 Buffer solutions are made from a weak acid and one of foe sla, 0 the answers inn 1D CH,CH.COOH and CHyCH,OH ts salls, so the answer is . (1) The acids in And B naa ae strong nD, one compound is 2 eleahol, 3a. Sketch the tration curve that you would expect if 25.0cn of 0,100 mal dmShydrocherc acid, HCL, is titrated with 40.Dcm? of (0.100 moidn-¥ ammonia slution, NH, @ 4 Mary students can damtity te stzrt pH and the end-point volume, but fran excellent anewor you wl leo need to show the final pi Clearly andthe extant ofthe vertca ange ‘Stating pt strong acc. estimeted nH = fishing pH: an excess of woak base, estimated pl between 10 and 11 ( for both comet (Note —you may be asked to calculate te inital and inal pH in anther part ofthe question inital pH from —iog0.1} = 1) Endpoint vlume: 28 cm® (1) (because the solutions are ofthe same concentration and the reacting ratios are 1-1) ‘range atthe vata part othe grap: eam he shape of curve fora strong act-weak bse tat, whichis quite steep but nots steep ‘9 fora stong ood-strng bose, Here there ere a least thee pH wisn the range 3108, iehas p37, 67 or5+-Blorsmils) (1) ‘Middle of verica pH range: between 4 and 8) because the end-point pH wil be less than 7 fora strong acid-weak bese station. Using our answer to select a suitable indicator fortis titration a oso ie a 1b bromarresol green (for end-point around 5) Srurero] gn ul Note thar you will receive ret fr naming 2 Phenol ed 73 Aifferent indicator ifthe graph you craw has 3 Phenolphihaein 33 vertical range about a ifferent ond point © Suggest why thee is no suitable indicate forthe titration of ethene acid with ammonia i © Rishon stabs ou masta ana weak me ton ee sos cage of | plorpctange oss oiga lune forthe obsoshap sar cangetinieane (From Edexcel Unit test 4,03, une 07) Practice exam questions 1a Define the following terms: i pH ii Ky 2) 'b Explain the meaning of the term strong as applied to an acid or base. a) € Given that Ky = [H*(aq)][OH“(aq)] = 1.0 x 10-'moP dm-® at 25°C, calculate the pH of the following solutions 0.200 mol dm? aqueous hydrochloric acid ay ii 0.800 moldm-? aqueous sodium hydroxide. MO on HA isa weak acid with a dissociation constant of 62 X 10-Smol dm a i Write an expression for the dissociation constant K, of the acid. @ ii Calculate the pH of a 0.400 moldm->solution of the acid ® 8 © A buffer solution contains 0.300moldm~of aqueous HA and 0.600moldm~2 of its sodium salt Na, Calculate the pH of this butfer solution. | 2a Whatis meant by a Bransted—Lowry acid? a2 bb Ave there any hydrogen ions or hydroxide ions in a neutral solution? qe Explain your answer, Cio a a ena. € Identify the type of titration curve illustrated opposite in terms of weak or muleats mcr) pean strong acids and bases, and explain your answer. (2) pcid-base titration curveRecall from AS Unit 1 that structural isomers have the same molecular formula but i different structural formulze. ‘There is restricted rotation about 2 double bond making possible another type of isomerism, EZ isom spatial ( sm. E-Z isomers have the same molecular formula but different ) arrangements of the bonds. : Nay; LN | a 4 trans isomer = groups on opposite sides _cisisomer ~ groups on same side E.and.2 isomers of dichloroethene Optical activity A chiral carbon atom hes four different atoms or groups attached, A chiral centre in a molecule gives optical isomers, able to rotate the plane of polarization of plane- polarized monochromatic (single colour) light. | Eee Which of the following isomers of CyH,0 has a chiral centre? a butan-1-ol b butan-2-01 ¢ 2-methylpropan-1-ol d_2-methy/propan-2-01 q ch a a) ‘Butan-2-0} has 2 chialcarbon ‘The easiest way to decide if the molecules have optical isomers is to draw their displayed formulae. The answer is (b), = Both optical and £-Z isomers are examples of geometric isomers. One optical isomer rotates light to the right (+ or clockwise rotation), the other to the left (~ or anticlockwise rotation) e.g. +5 degrees and —5 degrees rotation. These mirror image structures are non-superimposable. Stee toa Td reset Minor Two mitrorimage optical omer: An equimolar mixture of the + and — forins gives a racemic fnixture (or racemate) ~ this is described as being optically inactive. Optical activity can change during reactions such as Sy1_and $,2 substitutions and in additions to carbonyl compounds. Watttec Suggest why the reaction mechanism shown left would produce @ racemic mixture starting from an optically active, During the reaction there is a planar intermediate. There is 50:50 chance of attack on the intermediate by the nucleophile on either side. This produces an equimolar mixture of the two optical isomers ~ a racemic mixture, Nucleophitc substition mechanism a ° Chemistry Revision GuideAldehydes and ketones both contain the same functional group, the carbonyl group, C—O The carbonyl group is polar because oxygen is very electronegative, In aldehydes, a hydrogen is bonded to the carbon of the carbonyl group, but in ketones there are WO The carboryl group carbons bonded to it In aldehydes the secand carbon band can be to another hydrogen or to an alkyl aon oO and aryl group (based on the benzene ring). Ketones can also have allyl and [PEE eee aryl groups. aa — 4 i 4 Physical properties of aldehydes and ketones "””"*”"40"* The polar carbonyl group influences the aa Ta physical properties. The carbonyl group roeipara tre does not take part in hydrogen bonding i 2 (unless in aqueous solution), unlike the ‘Methanal =21 —OH group in alcohols. Permanent ahaa a dipole-dipole attractions occur in both compounds. The forces of attraction Ethanol (an alcoho) 78 between molecules will increase if they Propanone 56 can align more closely. Straight chain Butanal (straight chain) 76 isomers, therefore, have higher boiling benzaldehyde . met l a ‘temperatures than branched chain eee An any alee isomers Soling temperature comparisons foot ce ty Solubility in water gear The polar carbonyl group allows hydrogen bonding to occur with the polar solvent Take care that you distinguish cleatly water for the short-chain carbonyl compounds - this makes them soluble. The in your witen answers between solubility decreases as the molar mass increases. ‘compounds such a ethanol and cethanal, oF marks wl be lost. eee Account for the boiling temperatures of these one-carbon molecule compounds methane 162°C methanal 21°C ey methanol 64°C — The increasing boiling temperatures reflect the increasing farces of attraction between molecules. Alkanes have only weak London forces, aldehydes are polar and have stronger interactions. Alcoho's have, in addition, extensive hydrogen bonding which accounts for their relatively high boiling temperatures. SOREN 1 What is special about a racemic mixture? 2 What structural feature allows alkenes to shaw E-Z isomerism? 3° What feature is shered by all aldehydes and ketones? ‘AZ Chemistry Revision GuideoT aT Caer | inferences from the results of the tests. ‘dentiyng functional group simply from the molecular formule can sore ‘many marks if you make the evidence ‘lear. A formula containing one ‘nygen aton could suggost en sleahol aldehyde or etone. Both alcaols and aldehydes cn be oxide A2 Chemistry Revision Guide Aldehydes and ketones are both carbonyl compounds containing the polar carbonyl group. The main difference in their reactions is that aldehydes are easily oxidized to ‘carboxylic acids but ketones resist oxidation Oxidizing agent Aldehyde Ketone Fehling solution or | Blue to red-brown precipitate No effect Benedicts solution _| Reduction of Cuill)t0 Cut) Tollens' reagent (silver Colourless to siver mirror or silver precipitate | No effect mirror reaction) Reduction of Aa() to Ag Acidified dichromate(V1) | Grange to green No effect solution Reduction of CriVl) to Cri) Reactions with exdiing agents * Aldehydes are reducing agents but ketones are not * Fach reducing agent is itself oxidized. i W i o i p pau te we lf HOW H H H Lad Aldchres ae the excaton product of primary alcoho, and are themselves oxidized to carboryfc acts 4 of ret a Seiten ee lea ee eel a Ketones are the oxidation products of secondary alcohols, and are not ovdied further Ketones can be oxidized under extreme conditions but the acids formed contain fewer ‘carbon atoms —a contrast to the aldehydes where there is no loss of carbon on oxidation Reduction of aldehydes and ketones ‘+ Reduction of aldehydes gives primary alcohols. ‘+ Reduction of ketones gives secondary alcohols. ‘The reducing agent for these reactions is LIA. lthium tetrahydndoaluminate (lithium aluminium hydride), This is moisture-sensitive and must be handled using anhydrous Conditions, in dry ether (ethoxyethane) solvent. a Reduced Shows tse of a Aldehyde mide ee Primary alchol propanal pepan-o Reduction of en aehye oH 4 i | a 4 I i} 4 4 ketone Secondary alcahol pentan--0ne ‘entan 20 Reduction ofa ketoneTopic 6: Further organic chemistry Nucleophilic addition to carbonyl compounds ‘The carbonyl group is poler with an electron-deficient carbon atom Nee Nucleophiles will attack the carbon atom of the carbonyl graup. Hydrogen cyanide, < HIN, is a weak acid with a low concentration of the CN nucleophile, the cyanide ion. // Use of an alkali metal cyanide instead, KCN, gives a high enough concentration af CN- The pole carbonyt group for the nucleophilic addition, : c i tl N N eT oa} id rena Wen you draw curly arows in N ‘mechanisms, itis vry important to Nucleophilc ation to the carbonyl group show whet electrons move from The nucleophilic addition product is called ¢ 2-hydroxynitrile (or cyanohydrin). A eae: i 2-hydroxynitrile compound has two isomers, each of which has a chiral centre and are © bond. In mechanisms inva a therefore optically active. However the product mixture of the reaction shown above is | "w«leerhiles you should also show the Jone pais andthe 8+ and ~ charges not optically active. This racemic mixture (see page 48) is evidence that nucleophilic addition in carbonyl compounds is equally kely to proceed by attack fram either side. Assingle isomer would indicate attack from one side only. intha dipole Many candidate oso marks in mechanisms due to careless ‘rawing of crt arrows, Detecting the carbonyl group | Carbonyl groups undergo addition—elimination reactions, also called condensations. 2.,4-dinitropherylhydrazine (or 2,4-DNP, Brady's reagent) adds to @ carbonyl group with the elimination of water. The presence of a yellow ar orange precipitate on addition of 2,4-DNP to a compound indicates the presence of a carbonyl group — but does not distinguish between aldehydes and ketones. Neh Oo ON 1: Ose N \ Ho \ \ 4 fT 2,4-dinitrophenylnycrazine provanal 2.4-inivophenyihycrazone derivative of propanal Condensation with 2.4-DNe ResultsPlus nea) Try writing out the 240NP addition — elimination equation fora aldetyde ‘ra katone, Marks are atten awarded for coract structures in these complex reactions, ‘The 2,4-DNP derivatives can also be used to help to identify specific aldehydes or ketones. The derivative is first purified by recrystallization from a hot, saturated solvent. Each derivative has its own sharp melting temperature. Data tables of melting temperatures allow us to identify the original carbonyl compound. Haloform test Organic compounds with a methyl group next to a carbonyl group give a positive iodoform (haloform) test. The reagent used is iodine in alkaline solution. A positive test gives a yellow precipitate of triadomethane (iodoform) with a characteristic antiseptic-type smell 11 Describe the colour change and metal oxidation number change when an aldehyde is reacted with acidified dichramate(v) i 2. Suggest three possible functional groups for a compound with a single oxygen atom. 3 What physical property of 2,4-DNP derivatives allows us to identify the original carbonyl compound?Unit 4: Generel principles of chemistry | - Rates, equilibria and further organic chemistry (e-Te Lo aU CeLa (ery The functional group in carboxylic acids is —COOH. Carboxylic acids are named using the same system as { see for the alkanes, 0 © set ieee The names of the salts that can be formed from the NaH || Sow acids are similar to the parent acids HoH methane acid hance acd repancc acid | gems ve ST ARTA | ‘The affects of hydrogen bonding for carbonic acids include the formation | of dimers in which pairs of acid ‘molecules are hydrogen-bonded ‘together. This may give an apparent doubling of he molar mass. I) Teresnso pepe cob acid by heating under reflux is because: not stp a the aldehyde but praceed to the carborye ac A2 Chemistry Revision Guide Methanoic acid | Methanoate Ethanoic acid | Ethanoate Propancic acid | Propanoate Butanoicacid | Butenoate Names of carbosyioe salts Physical properties of the acids Boiling temperatures of carboxylic acids are significantly higher than for other compounds with equal numbers of carbon atoms. Name Formula ‘Molar mass/g mol? Boiling temperature/*C Propanone | (CH:)sCO 58 56 Propanal CH;CH,CHO| 58 50 Propanoic acid | CH,CH,COOH 74 1a The presence of the —OH group in carboxylic acids accounts for two physical properties — higher boiling temperatures than expected from their molar masses and also their solubility in water. The —OH group forms hydrogen bonds between the acid and a polar solvent, such as water. Preparation of acids Carboxylic acids can be prepared by oxidation of alcchals (as we saw in AS Unit 2) or carbonyl compounds (see previous page). Oxidizing agents include acidified potassium dichromate(V)) and potassium manganate(VI). Carboxylic acids can also be prepared by acid hydrolysis of nitriles (cyanides) to] K,C1,0,/ll H,$0.,laq) i A HE a ae : cH,cH,cHf compound V ‘8 Compound V contains two functional groups. Kent both functional groups and state a chomical test foreach Tho result ofeach test shoud als be inued in your answer, Co) '@ ‘Many candidates could identity the furctional groups in compound W as aken contin the carbonyl {C= 0) and hycrayl (OM) groups, but these ar pat of the larg Tha tests aro: C)(th and carbonic acid (7). Be careful ~ the molecule 32" carboyli¢ acd functional group ‘© alkenes ~ change bromine water rom brown o colourless (li Note, « colouiessnot ‘tea’ solution is forme ‘+ carbon acid—on ation of Na lus tums red/warming wit ana Heavy acidified KMn0, solution changes fom purple to colourless) (1) 10030" NaHCO. a gas is evolved which tums fnewater miky(1)-(Akerativey, universal indicator/elve med alcohol plus conc. acid as catalyst) gives afuty este smel) Note, the use of phosphors( cri asa sole chemical test fara Carbonic ec is insufficient because it gives the same result with water and with aleahals, 'b Compound V can be convertad into two carbonyl compounds W and X, shown below. Corpaund W can be reduced in two steps to compound ¥ of molecular formula C40, Kentity¥. a Compound W can be oidzed to compound 2 of maleculat formula C40, dentiy 2 fn {6 Acorect structural forma shaqam is acceptable as an answer and wil help t identity the compounds by name VisCHOHCHOH,orethane--2-iol. 1) ZisHOOCOOOH, ethanotoc acicjaralic sod 1) A2 Chemistry Revision Guide[Unit 5: General principles of chemistry Il — Transition metals and organic nitrogen chemistry Redox reactions and titrations Redox reactions simply involve electron transfers between species. ‘OILRIG’ helps * oxidation is loss of electrons # reduction is gain of electrons. We can follow redox changes using changes in oxidation numbers (or oxidation states). Oxidation numbers for molecules and ions Recall these rules from AS Unit 2: 1 Uncombined elements have oxidation number zero — for example H,(Q), Nats). 2 In monatomic ions, the oxidation number is the charge on the ion — so Fe? has oxidation number +2. Note Group 2 usually +2 and Group 3 usually +3 3 In 2 neutral compound, the sum of the oxidation numbers is equal to zero — for ‘example in NaCl, Na is +1 and Clis—1, and +1 + (—1) = 0 4 Ina polyatomic ion, the sum of the oxidation numbers is equal to the charge on the jon ~ for example in SO.2- has S at +6 and O at -2, and +6 + (-2 x 4) = —2. 5 There are exceptions, for example in sodium hydride Na*H~ the oxidation number cof hydrogen is ~1; in hydrogen peroxide, HsO2, oxygen is —1, Fluorine is always but the other halogens vary. AEE What is the oxidation number of manganese in the manganate ion, MnO,-? ResultsPlus Cotioa Ferember that transion metals often | stows rngeofociefor manirain | theirconpounds — ion can be iro | ori; coppereanbe Cut or Cu. Take caret calla the oxidation rumers carefully bore desciting a | change as xidation r reduetian ‘Oxygen has oxidation number -2 giving (4 x =2) = -8 Manganese is x, where x ~8 = ionic charge of —1, giving x = 7. Redox In a redox reaction, reduction and oxidation occur together’ ‘the oxidation number of one element goes up — it is oxidized ‘the oxidation number of another element must go down ~ itis reduced * the total increase in oxidation number of the element oxidized must balance the ‘total decrease in oxidation number of the element reduced, Mg + Cl, — MgCl, Mgls) + 2HCl(aq)— MgCl,(aq) + H,(9) 3 +2 eidaion(ox ro. neresmd | [0 2 cxtaon g =] eto ono. decreases 7 8 edcon ‘Changes in andation numbers n reectons ~ the oxidation numbers indicate which species is ovcized and whichis reduced Half-equations 'n an ionic half-equation we show either loss or gain of electrons. Combining two | half-equations cancels out the electrons, giving the full balanced equation. . Sree Find the balanced equation for the oxidation of an iron(ll) salt by potassium manganate(Vil) in acid solution, The half-equations are: Fe?(aq) > Fei(aq) +e oxidation MnO,-(aq) + 8H*(aq) + 5e~ > Mn##(aq) + 4H,0() reduction ‘A2 Chemistry Revision GuideTopic 1; Redox and the chemistry of the transition metals ‘The first reaction transfers 1 electron, but the second transfers 5 electrons, | Multiply the first by 5: SFe?*(aq) + Sfe*(aq) + Seu | MnO,"(aq) + 8H*(aq) + 5e~ > Mn?*(aq) + 4H,0() Then add the equations, cancelling out the electrons: MnOq-(aq) + 8H*(aq) + 5Fe®*(aq) > Mn?*(aq) + 4H,0() + 5Fe**(aq) Redox titrations 1 Pe The reaction and its balanced equation in the worked example above can be used erie in redox titrations to estimate the amount of a reducing agent — for example the amount of an iron) satt in iron tablets taken for anaemia. ‘+ Potassium manganate(Vil) is @ powerful oxidizing agent and has an intense purple colour in aqueous solution, ‘+ In acid solution, itis reduced to almost colourless manganesetl) salts + standard 0.02 mol dm-* solution of potassium manganate(Vil is titrated against the solution of ironil) ions of unknown concentration ‘© Ths titration is self-indicating, so no additional indicator is needed. ‘The end-point is when all the irontil) has been oxidized to ironil). The first excess ‘of manganate(Vil) gives a permanent pink colour - this is the end-point. ‘©The reaction stoichiometry gives a mole ratio of 5 mol Fe? to 1 mol MnO, Inthe witten and practical tests (Unit {6 Activity dl you will be expected to cary out and interpret a potassium ‘manganato( tiation, Make sue that you can describe the redox i ‘action between ron fons and ‘manganate(l) ons, make up 3 standard solution and that you can caulate solution encertrations or ‘masses fom tivation resus Redox titrations 2 ‘Mako sure you can evaluate the I Another redox titration is that of sodium thiosulfate, Na,S,03, with aqueous iodine eae ee ce ‘ measurements, a that you 28,0;*-{aq) + I,(aq) — 2I-(aq) + $,0,?-(aq) ‘understand the implications for the © lodine in solution in potassium iodide is a dark brown colour. validity of the calculated result of | ¢ Addition of sodium thiosulfate results in a light brown/yellow colour as the iodine is ‘any assumptions or measurement reduced giving a colouriess solution at the end-point unceratis ‘+ Near the end-point, while the solution is still pale yellow, starch indicator is added | \—___ giving a blue-black solution. The end-point change is now blue to colourless, | showing that all the iodine has reacted ‘+ This titration can be used to find the concentration of an oxidizing agent that oxidizes iodide ions to form iodine ~ copper) ions, Cu?*, for example. ‘To estimate the percentage of copper in an alloy, the copper alloy is dissolved, and the 4 resulting solution is reacted with excess potassium iodide solution to produce iodine. The liberated iodine is titrated with standard sodium thiosulfate. SOTTETTR ons ‘* weighed sample of the alloy is reacted with nitric acid giving a solution containing ‘Cu? *(ag). 1 In the analysis of the This is reacted with an excess of potassium iodide solution: percentage of copper 2Cu?*(aq) + 4I-(aq) — 2Culls) + 1,(aq) a alloy, elie ‘© The amount of liberated iodine is estimated by titrating with standard sodium pata Geena mst thiosulfate be ed. + Overall the reaction stoichiometry shows that 2 moles of Cu#* gives 1 mole of b, which Wher the oxidation is reduced by 2 moles of S,0;2-; this gives a 1:1 mole ratio between Cu" and S,0;2 Ae eEzeE etrcrattar Measurement uncertainty and implications Sees gen: Uncertainty can be caused by poor technique or by the limits of precision of the apparatus. 2 pa HHychnoemiodides Hi ‘© Remember to quote a mean titre or the calculated solution concentration to the same i avldcedi adsdine: number of significant figures as the least precise measurement in the experiment. 1, by concentrated ‘© Repeating the experiment will improve the reliability of the data, but not the sulrane adel 1:80, accuracy if the same conditions and apparatus are used. vifilett isftectaeiead © The larger the measurement, the smaller the percentage error — when using scnhyoues esulfitig apparatus of comparable quality. fbb Beatin Be careful about any assumptions made — e.g. about the alloy sample: Bale ROSS ~ alloy composition is uniform throughout the sample baareeniledaton = sample chosen is representative e.g. not a corroded surface. fovAnereactiGn: ‘They can introduce systematic errors and inaccuracy in the calculated value. ‘A2 Chemistry Revision Guide anUnit 5: General principles of chemistry i ~Tiansition metals and organic nitrogen chemistry Redox and electrode potentials ‘A metal dipping into a solution of its own fons creates a half-cell For a simple cell (battery) two haif-cells must be joined together without introducing another metal Asalt bridge completes the circuit. High resistance voltmeter ResultsPlus nua Examiner tip | Standard conditions means measured at 298K with solution concentrations (of 1 mol dm and a gas pressure of ‘atin, H.(a) at 298K ain arian with Roles intoallow bubbles of Hyla)t0 escape Prati lectrode Acid solution: containing 1.0mal dm? x) Standard hydrogen halal cor ca ty ie Cones You need nat have experience af using salt ridge Copper stip — Zine sti Solution of Solution of CuFGaq) 2n*(a0) (1 mal do) mal de) Assimple cot ‘The half-cell reactions at the electrodes are: © Zn(s) > 2n2*(aq) + 2e- oxidation © Cutaq) + 2e- > Culs) reduction The overall cell reaction is Zn(s) + Cu?* (aq) > Zn?*aq) + Cuts) ‘The electrode potential is the maximum e.m.. (electromotive force) across the halt- cell, in volts, ‘The standard cell potential, Ez, is the e.m.f, between the two half-cells used measured under standard conditions, Standard cells and standard electrode potentials Electrode potentials are relative to each other. A standard half-cell (or reference electrode) is needed to establish the individual cell potentials for the half-cells ‘The standard hydrogen half-cell has a defined em. of zero volts under standard conditions. So, other cells can be compared with it to give standard electrode potentials, E~. £2 is the difference between the standard electrode potentials of the two half-cells, Cell conventions Drawing full diagrams of electrochemical cells is not necessary there is a shorthand convention. © The metal electrodes are written at the ends, with a line separating them frorn their ‘aqueous ions, ‘+ The salt bridge is shown in the centre as a vertical dotted line. ni 2niaicurin [Cue E-s10¥ ee ee tectast seaifein | tecoein nghthond Tis te call f—the ptr Soo eee || sem cmiwh | coxa corm | aomnenenc rar thon” | Serene sepet het ce ‘electrode. Miake clear in your answers electrode electrode measured with zero current flowing | athe oun ae etoan Gioenhyanghessince ‘must be compared witha standard, oabaas: voltmeter must be used). cateanentco ‘on Guide|: Redox and the chemistry ofthe transition metals Eee | Write the cell convention for the electrochemical cell made from half-cells of Electrode Fav a lead and copper Pe aqiPti) | 013 | b aluminium and copper. Pe) lorem | Standard electrode potentials are measured with the standard hydrogen AP Tool) <1 electrode on the let, for example Pi{H(Ql|H*(aq) |] Zn?*(aq)izn(s). A negative [Zntaclaas) | _—076 electrode potential means electrons are transferred from the hydrogen electrode to the electrode in question, | Following the convention: a Ph(s)IPb?*(aq) |! Cu fag)ICuts) b ASAP aq) }} CuP*(aq)|Cuts) Calculating cell potentials, E:. ‘cell Make the more negative potential the left-hand half-cell (LHS), to give the rule: Esau = Enis — Fits You should always show the sign of For example, for copper and zinc half-cells, this gives: ES, values, even if itis positive. Ey = (+0.34V) — (-0.76V) = +1.10V Eee What is the cell potential after combining these two half-cells? Cu (ag)lCuls) = +0.34V Po?*(aq)[Pb(s) = —0.13V [teeth gd The rule puts the more negative (or less positive) lead half-cell on the left-hand, side Ph(s)|Pb?"(aq) 1! Cu?*(aq)ICuts) Hence Ere = Enis ~ Eins = (+034) ~ (-0.13¥) +047V Checking cell potentials If we write this copper/lead cell in the reverse order, the copper haif-cell is on the left Cu(sCi?*(aq) ff Pb?*(aq)IPb(s) Eva = Fins ~ Ets (0.13¥)~(+0.34V) = -0.47V The negative value of the cell potential shows us that we have written the cell backwards, implying that the reaction: Culs) + Pb?*(aq) — Cu?*(aq) + PbIs) ‘occurs from left to right. This reaction does not occur, but it does occur in the reverse direction This shows that for the two haif-equations the more positive E° isthe redox process that ‘goes forwarc; the one with the more negative (or less postive) E goes from right to let. AQHIMIEEM 1 What is the voltage of the standard hydrogen electrode, and why? 2 Given the following standard electrode potentials, explain which metal ion is the strongest oxidizing agent: APt(aq) + 3e7 = Alls) - CuP*(aq) + 2e” = Cuts) Fe'(aq) + &- = Fe*"(aq) 3 What is the cell potential for a cell made from half-cells of lead and aluminium? A2 Chemistry Revision GuideUnit 5: General principles of chemistry Il ~ Transition metals and organic nitrogen chemistty Feasibility and extent of reaction Standard electrode potentials can show if reaction is feasible, They give no | information about reaction rates. A feasible reaction may still be extremely slow and of litle use Thermodynamic stability * Standard enthalpy change and standard electrode potential values both give | information about thermodynamic stability. ‘+ These values suggest whether a reaction is feasible (thermodynamically unstable) — is it actually possible or not? Standard electrode potentials are quoted under standard conditions (at 25°C and | 1 x 10°Pa pressure). Most reactions will not be done under standard conditions | Leck of standard conditions for most reactions limits the use of electrode potentials in predicting if a reaction is spontaneous, Eee Use electrode potentials to predict whether copper metal will reduce nitric(V) acid to nitrogen dioxide gas. NO. (aq) + 2H “(aq) +e" = NOx) + H,0() ES = +0.80V CuPHaq) + 2e- = Cu(s) ca = +0.34V Eee The rules for using elecirode potentials include: ‘¢_the reaction goes forward for the more positive value) is written on the left, CuSICG aq) If NO,-Ceq)INOsla) Fea = Ens — Eins = (+0.80V)~(+0.34V) 4 Multpnghat-cel reaction in oder oy igor aae ee This positive value shows that this reaction is feasible change the electrode potential. The overall reaction is found from the two half-cell reactions by multiplying the first half-cell reaction by 2, giving 2 electrons transferred. : 2NO3 “{aq) + 4H *(aq) + 2e- = 2NO,(g) + 2H,01) Culs) = Cu?* (aq) + 2e- ‘Add to cancel the electrons out: Culs) + 2NO3 (aq) + 4H (aq) = 2NO,(g) + 2H,O(l) + Cu**(aq) Poot a Ty Examiner tip TZ To gain full marks in a question about Predicting it @ reaction wil acu, ‘you must explain the effect of high ‘activation energy, and not simply stato thatthe activation energy is high, This reaction may stil be too slow for kinetic reasons, For example, the eneray of activation may be too high, reducing the rate. Note that the reaction is also unlikely to be carried out under standard conditions. Linking E,. to entropy and enthalpy Recall from Unit 4 (page 19) that the effects of enthalpy and entropy changes in a system are reflected by: © Seat = ASyrum + ASprounding: * spontaneous, or feasible, change has a positive value of ASicu. ‘+ Cell potentials are directly proportional to the total entropy change, ASwrs, of a reaction ‘© Entropy changes are also related to the equilibrium constant K. The value of K indicates the extent of a reaction ~ how far towards completion it goes: Sci = Rin K, where Ris the molar gas constant. ‘* Hence, cell potentials are also directly proportional to Ink. AA2 Chemistry Revision GuideTopic 1: Redox and the chemistry of the transition metals ff Changes of oxidation state and the | electrode potential We can use standard electrode potentials to predict the feasibility of redox changes. | Calculations using electrode potentials can show us, for example, if manganese(Vl) can oxidize iron(l) to iron) in acid solution in a titration. Remember that transition metals have variable oxidation states, e.g. Fe(\/Feill); Man(Vil), Mnilv) and Mn). j Eee ' Use the following data to predict if the reaction between manganateCVil) ions and iron(l) ions is feasible, and deduce the overall equation. Fe*(aq) + e~ = Fe?*(aq) Fe = +0.77V ‘MnO,(aq) + 8H*(aq) + Se~ = Mn?*(aq) + 4H,0() Ea = +1.51V | The more positive electrode potential is the reaction that goes forward — | therefore Mn(VIl) will be reduced to Mn(ll) and iron(ll) will be oxidized to Feilll). Multiplying the first reaction by 5 to balance the electrons gives overall: MnO,(aq)- + 8H*(aq) + 5Fe2*(aq) — Mn?*(aq) + 4H,O(I) + 5Fe*+(aq) Reversing the direction of the redox reaction reverses the sign of Ey, so iron(ll) oxidized to Fell) has a negative electrode potential. Ey = -O.77V + (41.51V) = +0.76V This positive value confirms that the reaction is feasible. orm 1 What are the standard conditions for electrode potentials? | 2. Use the following standard electrode potentials to explain why irontll) iodide does not exist in aqueous solution: | FePtaq) +e = Feaq) §— E* = 40.77 . Iaq) + 2e- = 2I-(aq) F* = +054V 3 What does it mean if a change has a positive value for AS? 4 Use the following data to suggest why vanadiumill) compounds are more ‘common than vanadium(l) compounds. Vit(aq) + e = Vag) F? = -0.26V Rcherisy eon GiteUnit 5: Generel principles of chemist II— Transition metals and organic nitrogen chemistry ON ie ma dcelsa luli iag Hydrogen and alcohol fuel cells as energy sources Fuel cells are different from ordinary batteries or lead-acid car batteries. In fuel cells, the reactants are supplied continuously and the reaction products are removed as they form. Fuel cells turn the chemical energy of hydrogen or hydrogen-rich fuels, such as alcohols, into electricity. ‘+ The hydrogen-oxygen cell contains an alkaline electrolyte. Hydrogen fuel is supplied to the negative electrode: ‘2 Hy(Q) + 20H (aq) —+ 2H,0() + 28 EG) = +0.83V Heio o.in . Oxygen is supplied to the positive electrode: 29) + HOU) + 26° 20H-(aq) Ey = +0.40V es ‘* The cell produces only water as a waste product Hyckegen-onygen fel ce 2H,(@) + 0,69) ~» 2H,0() Ey= -0.40V + 083V = +0.43V In spacecraft, the ‘waste’ water from hydrogen-oxygen fuel cells is used for drinking | and washing, Sources of fuels for use in fuel cells } ‘+ Hydragen can be obtained from water or brine by electrolysis. | * Natural gas (methane) can also be a source of hydrogen (this is the main UK source Of hydrogen used in the Haber process) * Alcohols can be obtained by fermentation of sugars or by the hydration of alkenes obtained from crude oi. Pere Peay wy Advantages and limitations of fuel cells ‘+ Fuel-cell vehicles are very efficient — up to three times more efficient than petrol Make it clear in your answers that engines, ‘et cel chicas may simpy shit te |g Fuel cells produce no carbon dioxide emissions or pollutants such as CO at the pollution from the cart the power Point of use — although fuel production and pressurization of hydrogen does cause station Feilure to make clear the pollution Serius limitations of current ful ee ‘+ Hydrogen fuel is produced by electrolysis using electricity generated in power plants technology willose you mars. that use fossil fuels or is derived from non-renewable fossil fuels (methane) * During the manufacture of hydrogen from methane, the carbon in the methane is converted to carbon dioxide. '* Fuel cells currently have a limited lifetime and are expensive to replace. + Hydrogen fuel is gaseous and, hence, dificult to transport and store ~ by liquefaction at ultra-low temperatures or in high-pressure storage systems or by Athough mistres of hydrogen and air solid state adsorption are explosive, tbe density of ytrogen is solow tha eked hyragen will icky escape Breathalyser technology In old-fashioned breathalysers, ethanol in a driver's breath was detected by a colour change in the reduction of dichromate(Vl) ions to chromiumilil ions: 3CaHsOH(Q) + 2Cr,0;2-(aq) + 16H*(aq) > 3CHCOOH + 4Cr?*(aq) + 14H,0() orange green ‘The sensitivity of this simole breathalyser was limited and so was open to question when a driver was taken to court, The amount of ethanol in the breath depends on the concentration in the blood, but ‘mouth alcohol’ can give errors in readings Drivers can also be asked to provide a breath sample for infrared (IR) analysis at a police station. Ethanol has an easily recognizable IR spectrum with a peak at 2950cm~? that corresponds to the C—H absorption frequency. The OH group in ethanol is not used for IR analysis because the presence of water in breath affects the reading, ‘A2 Chemistry Revision GuideTopic 1: Redox and the chemistry ofthe transition metas, Fuel-cell breathalysers © This device detects a chemical reaction of ethanol inside a fuel cell. w oO platinum | eters c> 1 acid electroyte ae | | oe ae fava a | Processor eal Fuelcel breathalser © Exhaled air flows past one side of the cell - the platinum electrode oxidizes any ethanol to ethanoic acid, releasing both protons and electrons, © Ameter measures the current flow, The protons combine with oxygen on the other side of the fuel cell, forming water. | ‘* The more alcohol in the exhaled breath, the more is oxidized and the greater the measured current Fuel-cell breathalysers are not as reliable as systems using IR or mass spectrometry, or | ‘the measurement of blood alcohol content (BAC) from blood samples. AQHENWMM | 1 In what ways are fuel cells different from ordinary batteries? 2. White ionic haif-equations for the reactions that take place at the anode and cathode in the methanol fuel cell. ‘A2 Chemistry Revision oeUnit 5: General principles of chemistry I Transition metals and organic nitrogen chemistry Transition metals Be aT eee) Exch d orbital can hold two electron. There ae five d bias ane so the 4 sub-shell can hald 10 electrons, Caer) Chromium and copper have 4s! electonic configurations, nt the expected [A] SHS? or [Ar] 3649? This | lenes halite 4s sel ater ha or complete fling ofthe 3d shal. full coc half full sub sholconfrs greater stability et eT Examiner tip WZ] Although the 4 orbital fil before the 23d inthe fist transition series, the 4s ‘cts have higher energy and are | lost st during ionization tis bttar ta write Sas! ather than 45°34 to show that you understand this Transition metals and d-block elements are not necessarily the same thing. Recall from AS Unit 1 that the outer electrons in d-block elements occupy d orbitals When d-block elements ionize, the outermost electrons are the first to be lost. The d orbitals are inside the spherical s orbitals so the 4s electrons go first. ‘© A transition metal must form at least one stable ion with an incomplete d sub-shell Atoms or ions with electronic configurations that include 4° or dare not ‘transitional in their behaviour. * The common zinc ion Zn?* isa dion and the common ion of scandium, Sc?*, is a d° ion. ‘Manganese 25 1s? 2st apt 36? 3p! 4s? 3c (ir) 45? 3d ! 1] t t I I ‘Copper 29 1s? 2s? 2p" 35? 3pf 4s! 3d" [Ar] 4s! 3c” t i 1] t | Zine 30. 1s? 2s 2p* 35? 3p* 4s? 3d” [Ar] 45? 3 { | t | I | Electronic configurations of some chblock elements. [Ar] is usta shorthand way of vrtng the entire ‘electronic configuration of argon (13?2s!2p33p8), Matec Use zine to illustrate the statement that ‘all transition metals are d-block but not all d-block elements are transitional’ ‘+ A transition metal must have at least one ion with an incomplete d-shell ‘© Zincis @ d-block element, its outer configuration being 3d"° 45? s orbital outermost). ¢ The only comman ion of zinc is 2n** (3d"°) with a filled, not an incomplete, deshell lonization energies The successive ionization energies of d-block elements give evidence concerning the electronic configurations of their ions. Element | 1 1E/ kimol~* | 24167 kimol "| 316/ kimol * fe 760 1560 2960) zn 900 1750 3850 Some c-block ionization energy values There is a major jump in ionization energy between the second and third values ‘or zinc the Zn#* ion is stable (filled outer shell, 3d") but the potential Zn?* ion requires too much energy to form. ‘+ Iron forms stable Fe ions and Fe** ions and we would predict a major jump in ionization energy between the third and fourth values because the outer electronic configuration of Fe** is 3d° and haif-filled orbitals are very stable. = A2 Chemistry Revision GuideTopic 1; Redox and the chemistry of the transition metals Variable oxidation numbers in compounds You should be able to work out the oxidation numbers [fon Oxidation state of V | Colour of aqua ion of the transition element ions found in compounds from | v2= #2 lilac | the rules on page 68. ra 43 Green | Transition metals show variable oxidation states in [Vo +4 Blue. their compounds (see table right): VO5- orvor 5 Yellow in acid solution Vonadium cn est in four abn sates ARNE wt otc icy ea ‘What would you expect to see if a solution of ammonium vanadate(V) was 2 reacted with zinc and sulfuric acid until there was no further change? ‘What further change might be caused by the addition of concentrated nitric acid at the end? Not, electrade potentials for each of the redox half-wactions will show if ‘the reactions feasible fora particular reducing agent. For exarple, tin wil raduce VO "(ao to V2 "(an ane no further, because Zinc and the acid function as a reducing agent for the original vanadium(V) compound. Full reduction would give the sequence: Yellow — green (yellow + blue) — blue — green — flac Vaal +e = Vlas ‘as the vanadium is steadily reduced from the +5 to the +2 state. E* = ~076Vard Concentrated nitrie(V) acid is an oxidizing agent, and the colour would change See eee as the vanadiumil) species was oxdized further. It is not possible to predict a Eel from the avaiable data what the final oxidation state would be. We would cE need access to full electrode potential data for the possible reactions. ili | 4 > Hh 1 Ny igands and complex ions oy, | A. complex transition metal ion has a transition metal ion at its centre with a vik cH, number of other molecules or ions surrounding it. These are called ligands ~ ions Hue | 4 or molecules that can form a dative (coordinate) bond to a transition metal ion by fom in ' donation of an electron pair: i * monodentate ligands attach in one place (to one atom) rs # bidentate ligands have two electron pairs to donate Hy © the number of dative bonds to the central ion is called its coordination number. Complexion with te bidentate ligands aria coordina ‘The overall charge on a complex ion is the sum of the charge on the metal ion and the Wanssanacoosination charges, if any, on the ligands. ‘The most common complex ions are hexaaqua ions. For example, in gt [Cul,O}gF*, 6 water molecules are the ligands attached to the central metal ion Ho. 2304, Shapes of complex ions or Most transition metal complexeshave a coordination number of 6, forming 4, il Nek ‘octahedral complexes so that the electron pairs in the ligands will be as far" apart as possible. Other geometries are also possible for complex ions I 3a, crea fcuns,OuP* one note he SORETE fe dottd ine convention to represent bonds going into the plane of the paper 1 Whyis S@* nota transition metal ion? ai 2 How can we tll when a transtion metal compound Cometex | Coordination, || Balas of vanadium changes its oxidation number? ES a ne Gites 3 Whatis the commonest coordination number and ae geometry of transition metal ions? (Pees, Cl] 4 sor | Penar 4 Wiite the electronic configuration of the following ecu a 10955° | Tevrahedral atoms or ions: Ti, V, V*, CuP* [cure 6 or | oaaieael [ICH 2 Chemistry Revision Guide EPUnit 5: General principles of chemistry Il ~ Transition metals and organic nitragen chemistry Both chromium and copper aisplay many of the characteristics of transition metal ions: '» variable oxidation number in compounds ‘© formation of compiex ions with ligands ‘* susceptible to ligand exchange reactions to form different complexes ‘+ form coloured ions in solution. Bonding in complex ions | Bonetng in a chramiur(t complex Lone pairs of electrons are donated by ligands to the central metal ion forming dative covalent bonds. Many ligands have their own internal covalent bonds. : Colours of complexed d-block ions ‘When white light is shone onto a substance, light of a particular frequency may be absorbed. Colour at this frequency is removed from the white light — for example, When red light is absorbed, a solution will appear blue. Se a Ty ern) {mn an isolated transition metal ion there are five d orbitals, all of equal energy. The addition of ligands to the ion splits the five orbitals into two groups of different energies Some substancos appoar coloured because ofthe light they absorb, No ‘new ight is emitted. ‘Whenever transition metal ions are surrounded by ligands, the electron transitions between the spit energy levels in partly filled d sub-shells give these ions the Two 3dobitals characteristic colours of hydrated complex ions and hydroxides (see page 81). Similar cf higher energy electron transitions are not possible for either d? or di¥ions, such as S* or Zn?*, ead patel: which therefore form colourless compounds and aqueous solutions. cof equal energy Changing the ligand changes the amount of splitting (the size of the energy gap) and so changes the colour of the complex ion Three 34 orbitals cfovercrecy STATE. Splitting of cerita! energies Explain why copperill) compounds have distinctive blue or green colours, but coppert!) compounds have no colour at al In the ground state, the element copper has the electronic configuration [Ar] 3d'°4s! In copper() compounds such as copper) sulfate, the ion is [Ar] 3d? This incomplete d sub-shell allows electron transitions between the split energy levels, hence the colour. Copper( ions have the configuration [Ar] 3d! with a completely filled d sub-shell. No d-d electron transitions are possible and there is no colour. Ligand exchange reactions Some ligands bond more effectively than others to transition metal ions giving more : stable complexes. Ligands can displace each other, aften causing a colour change because the different ligands create a different ammount of splitting between d orbitals : in the metal ion. For example: [Cut,0),2 (aq) + 4Cl- (aq) + [CuCl,2-(aq) + 6H,0(1) blue worse Aout The charge on a complex ion takes into account the charge, if any, on the ligand(s) t The charge on the above coppertl) complexes change from +2 to —2. Neutral ligands, such as water and ammonia, cause no change in the overall charge on a complex ion. ie iS Geet UD, Cdovide ls A2 Chemistry Revision Guide wisite be Ae Mi on avd SA Seth § oot eT reece ‘Don't forgot oalance ionic equations forligand exchange. Many students omit water asa product, or gve an inoorect charge on a complexion,Topic 1: Redox and the chemistry of the transition metals In the following reaction, four of the water ligands are replaced by four ammonia ligands (see page 81): [CulH,0),F*(aq) + 4NH,(aq) — [CulH,O)(NH).1?*(aq) + 44,000 pale blue deep be stom verponsb& fov lhue cobouy Ligand exchange and stability of complex ions + Monodentate ligands, such as water and ammonia, have a single lone pair that they Use to form dative covalent bonds to the metal ion. « Polydentate ligands, such as EDTA (hexadentate), have several lone pairs available \ : EDTA is an example of a chelating agent; it binds firmly to metal ions giving very aan stable complexes. gocch, CH, Cog. \When a ligand is exchanged for a water ligand, we can write a stability constant, The hexadentate gael EDTA known a5 Kap, similar to the equilibrium constant, Ke. Kaas is written omitting the has sicfore pais concentration of water as a factor. For the above example, where ammonia replaces water ligands: {ICutH0),(NH.),)*(aq)] (CulH,O} “(eal x INH, aa) Hf Kshs a higher value then the new complex is more stable than the one it iy replaced, as here. When a single EDTA ligand replaces six separate ligands, the EDTA Compan, ion complex will have a high value of Kea ee Sek gine The additional stability of complex ions following ligand exchange results from an at increase in entropy. When monodentate ligands are replaced by polydentate ligands, lea @dlauy :- CuLHQ, ‘the total number of species (molecules or ions} increases — this results in a positive entropy change K, For example, because the coordination number of transition metal ions is usually 6 ADR compar jove we in their complexes, the mole ratio between the metal ion and EDTA is 1:1. Forevery "py (acyl | mole of a hexadentate ligand that bonds with the metal on, 6 moles of water are produced ~ so the number of moles increases from 2 to 7. Predicting disproportionation from | electrode potentials Copper has two oxidation states in its compounds — capper(l) and copper(|l). Does the copper(|) ion disproportionate? The electrode potentials for the half equations are: b CuP(aq) + em = CuNiag) = +0.15V Cu*(aq) + e~ us) FP= +0.52V The reaction with the more positive electrode potential goes forward. So the overall reaction will be: 2Cu*(aq) — Cu(s) + Cu?*(aq) and Ezy = (+0.52 V)-(+0.15V) = 4+0.37V Eis positive, so in aqueous solution the copper() ion will disproportionate into copper) ions and copper metal -RUNIETITM 41 What are the different types of bonding in a transition metal aqua complex and how do they form? What colour are coppertl) compounds and why? Why is the mole ratio of copperil) ions to EDTA 1:1 in complex ions? How can chromiuum(v}) be reduced 10 chromium)? BUN A2 Chemistry Revision Guide Far‘catalyst isnot changed chemically ya reaction, butt must be dietly involved inthe reaction mechanism. ‘You wil ose marks fr stating that a ‘etalyst doesnot eke patina reaction ~itdoes Unit 5: General principles of chemistry lI Transition metals and organic nitrogen chemistry PUES So) Be TartaCeam (sy e-1 4 Transition metals and their compounds are often good catalysts. In many industrial processes, the reactants are adsorbed temporarily on to the catalyst surface, When the reaction is complete, the products diffuse away leaving the catalyst surface available again, This is an example of heterogeneous catalysis. Heterogeneous catalysts can be poisoned when other materials bind permanently to their surfaces, preventing any other reaction, The variable oxidation state of transition metal ions allows them to bind to reactants to give reaction intermediates. For example, in the Contact process for manufacture of sulfur trioxide, from which sulfuric acid is made, the vanadium(\) oxide catalyst (V;0;) isfirst reduced from the +5 to +4 oxidation state: 50,(q) + 30565) + $05(9) + V,0.(5) This alternative mechanism for producing SO3 has a lower activation energy than for the uncatalysed reaction. The intermediate V2O,is then oxidized back to V0. to be Used again: V,045) + 30,{g) — V,04s) Although V0 takes part in the mechanism, the overall reaction SO,(q) + 40,(q) == SO) does not include V;0s and itis unchanged at the end of the reaction Catalytic converters Catalytic converters use a fine coating of a platinum catalyst supported on 2 heat- resisting ceramic honeycomb material to give a large surface area, Advantages Disadvantages Reduce air pollution and smog_| Reduce fuel economy by several per cent (typically 210%) by unburnt or incompletely | Catalyst can be poisoned by just one tank of leaded petrol combusted fuel removing | a te tows Up tere cates pe itegey cries and cabo fay take time to warm up to working temperature, hoa releasing pollutants ‘Advantages and disadvantages of catalytic converters Chemical research on catalysts New and improved catalysts can have many benefits: ‘* lower energy use in industrial processes ‘+ improved atom economy ‘+ use of waste materials from other processes reduced ervironmental pollution This is why research scientists are actively seeking and improving potential catalysts for the future For example, ethanoic acid can be prepared from butane and naphtha from crude oil Using a cobalt) ethanoate catalyst. However, there are many by-products including ethanoic acid, methanoic acid, propanoic acid and propanone. An alternative process producing ethanoic acid from methanol and carbon monoxide has a much higher atom economy because there are no by-products (see Q4 on page 35). Its important that published research findings are as reliable as possible: new research must have peer-group review — other specialists assess the data before itis accepted for publication «© new results must be able to be repeated by other scientists to check the new conclusions. Most scientific research is collaborative — groups of scientists work together sharing ideas and learning from published theories and data. Transition metal compounds have made possible some valuable new products: + aplatinum compound, cis-platin, which is a powerful anti-cancer drug + polychromic sunglasses have a thin reflective coating, often of chromium — the sunglasses can adjust to light conditions, becoming darker in bright sunlight and reducing glare * photochromic lenses respond specifically to UV in sunlight ~ molecules in the lenses, associated with silver halides, change shape according to the UV intensity In artificial ight, the lenses remain transparent. . ‘A2 Chemistry Revision Guide‘* Identifying the type of ion present is qualitative analysis. «Finding out how much (e.g. mol dm~ of a material present is quantitative analysis. Transition metal ions form complexes, often coloured, which allow them to be identified in qualitative observation tests. Addition of either aqueous sodium hydroxide or ammonia solution to transition metal aqua ions forms metal hydroxide precipitates, which are coloured. For example [CutH,0),?aq) + 20H-(aa) [CulOH)(H,0)4) blue precipi ‘© A few metals, such as zinc and chromium, form a precipitate further reaction with excess sodium hydroxide, giving a solution again. This is called amphoteric behaviour — the metal hydroxides can react with both acids and bases. For example: [C1{H,0),(OH)3I() + 30H" (aq) = [Cr(OH)_P-(aa) + 3H,0(0) green precipitate green solution ‘¢ An excess of ammonia solution can cause ligand exchange with many transition metal complexes, giving a new ammine complex. The change in ligand causes a i colour change due to different splitting of d-orbital energies. The table surimarises the behaviour of complex ions with NaOH(aq) and NHs(aq). Aqua lon colour NaOH(aq) ‘Excess ‘NH,(aq) ‘Excess jon NaOH(aq) NH,(aq) ce [Green Green ppt | Soluble green | Green pot | Green ppt Ma? [Pink Cream to flrsoluble | Cream‘to | soluble : brown ppt brown ppt Fo=_ [Pale geen [Dark green ppt [ncotble | Dark green pp | soluble : Fe" [Yellow or brown | Rusty red ppt [Insoluble | Rusiy red ppt_[ soluble 7 Net Green Green ppt Insoluble Green ppt jue solution Ca | atue orgreen Blue pt ‘insoluble | Blue ppt__/| Deep blue soluton aa [eos [We pt [Soubie [wate pot [| sot Goupiam lon el ye> E (eee *S freed] * —~ How might you identify the metal fon in these green solutions that could include Crit), Felt) or Nil)? Use ammonia solution. Only Nil) gives a precipitate that dissolves. If ths fais, ‘add sodium hydroxide and see which of the green precipitates turns rusty red ‘when left in ait, this is Fe(l) oxidizing to Fe(l). SOW 1 What is meant by poisoning a catalyst? 2 How can you recognise amphoteric behaviour? 3 Sodium hydroxide is added slowly to solutions of fa the aqua complex of chromium) 'b the aqua complex of iron). Give the equations for the reactions. Assume that the sodium hydroxide is, added until in excess, teak fov/ Cee! Inthe writen test and in Unit Activity, youneed tobe ble to idem transition metal ions from the characters colour af tho precipitate ofthe yratad yr on reaction with aqueous sodium hydroxide and ‘aqueous ammonia bth added util in excess. See page 104, Dont forget to show the charge on the ‘complex in, and state symbols, when you write equations forthe reactions that you deduce have occured. [orn ci Td arr) Be careful to distinguish between ammines, which are complexes with ‘armenia, and anes, wih awe the funetional group NH ‘A2 Chemistry Revision Guide aUnit 5: General principles of chemistry lI —Transtion metals and organic ntregen chemistry : Topic 1: Redox and the chemistry of transition metals checklist By the end of this topic you should be able to’ Revision spread Checkpoints Redox reactions and | Explain oxidation number, redax and haif-reactions in | 5.3.18 titrations terms of electron transfer Understand how oxidation number changes relate to | 53.1b | mole ratios in equations | Explain the principles of redox titrations, including [53.1 (0 titration of manganatetVi) with Fel) Ai) titration of thiosulfate with iodine Critically assess the uncertainty of measurements in) 5.3.11 redox titrations and how ths affects validity of results Redox and electrode | Define standard electode potential and understand [53.1 potentials the need fora reference hydrogen eectrode Calculate cell voltages from electrode potential and [5.314 | use these values to say i a reaction i tiely Feasibility and Know that electrode potential i proportional e both 53.18 I extent of reactions | entropy change and toink ! Realse that kinetic effects and non Standard Sait . The electrophile is the nitronium ion, NO;", formed from a mixture of concentrated nitrie(V) and sulfuric acids: HNO, + H;50,—+ NO;* + HSO," + HO Sulfuric acid is then reformed, so it functions as a catalyst. The mechanism is similar to bromination. The full equation is CoHy + HNO, — C,H.NO, + H,0 Sulfonation This reaction is carried out with fuming sulfuric acid. This very strong acid reacts Under reflux with benzene to give benzenesulfonic acid, the electrophile being sulfur ‘trioxide, S03, Suifonic acids contain the SO,H group and are important commercially in ‘the manufacture of detergents, Friedel—Crafts reactions These reactions introduce a side chain into the benzene ring. ‘= Alkylation Ethylbenzene is prepared from benzene using a halogenoalkane and an aluminium chloride catalyst CoHo + CoHSCl + CcHsCH, + HCl The electrophile here is CoH. 4 In, : pPi—enc, +» ent, + fl carbocation # Forming te electrophile i the electrophiic substtation ‘reaction of benzene vith choroethane ard AIC, + Acylation Ina similar way, an acyl group, CH,CO, can be added to the benzene ring using an acyl halide such as ethanoy! chloride, CHsCOCI, and an aluminium chloride catalyst: Cols + CHxCOC! + CcHsOCCHs + HCI The presence of the methyl side-chain in methylbenzene (toluene) activates the ring towards substitution reactions (makes substitution easier) Itis easier to substitute into the methylbenzene ring than in benzene itseif so some of the reactions can now happen at room temperature, Phenol In phenol, C.HsOH, the presence of the OH group attached to the benzene ring also activates the ring towards substitution. ‘OH Es + 38n(0q) > 4 HBr 8 Bromination of phenol The reaction of phenol with bromine water is fast at room temperature and does not require a catalyst. The reaction gives multiple substitution at several points on the ring, showing that the ring has been activated Phenol also undergoes nitration — dilute nitric acid alone can be used and sulfuric acid is not needed as a catalyst. A2 Chemistry Revision Guide pena Inthe Unit paper you may be asked to describe how to carry out the steps in the preparation and purification of ‘an organic compound such as met! ‘-irobonzoata This is synthesized bnitvation of methyl berzoate using concentrated suture and ite acids You will need to describe meting temperature determination to confi the putty of cystal, see page 37. You should also beable to calculate a yield Aidt OE 1 What is the typical type of reaction for benzene? 2 What is the function of a halogen cartier? 3 Why does phenol brominate more easily than benzene itself?‘ei Unit 5: General principles of chemistry ll Transition metals and organic nitrogen chemistry Amino compounds ‘Ammonia, NHs, has a lone pair of electrons on the nitrogen atom. itis @ base (a lone-pair donor or proton acceptor). Amines are an important group of ammonia derivatives — the amine functional group is NH Primary amines have only one cartoon chain attached to the nitrogen. They are named according to the group to which they are attached. Butylamine, C,HsNHp, is an aliphatic amine, and pherylamine (aniline), C¢HsNH), is an aromatic amine with 2 benzene ring. ‘Amines are weak bases and behave in a similar way to ammonia i i wep ae It i h Amines as bases Preparation of amines Aromatic amines, such a5 phenylamine, are prepared by reduction of aromatic nitro | compounds, such as nitrobenzene, by reflux with a mixture of tin and concentrated hydrochloric acid. This is a side-chain reduction — the stable benzene ring is unatiected, Cor Ga Tey } Se Properties of amines t You shout! be able to predict and Like ammonia, the amines have unpleasant smells some resemble a fishy smell j sae de dyalal aniseed ‘© Like ammonia, aqueous solutions of amines are alkaline, ‘properties af unfsmiliar compounds The hydrocarbon part of the molecule (residue) is hydrophobic but the amine coda ord ofa tes group is able to hydrogen-bond both io itself and to water. The amine group ‘groups, such as the amine group — for is hydrophilic. The larger the hydrophobic group, the lower the solubility of the ecample thor likely suscoptblty to amine in water. FARSp ote eee ¢ As bases in salt formation. amine + acid — a salt ET STR MM The salts are more soluble in water than the parent amines: eer : 2 CgHsNH,(aq) + HNO.(aq) — CcHsNH5*NO5-(aq) Sing phenylamine phenylammonium nitrate of anines, think of them as cerivaties of the moc ania: ammonia, with Nip + HNO, ——> Nig NOs itslone pir of eleewons ad asi, bavout henyammonium nivate 7 Sale formation from phenyamine and nisi acd Weta Explain why phenylamine is less soluble in water than butylamine. Suggest a way to increase its solubility in water. The hydrophobic (aromatic) group in phenylamine is larger than the d corresponding group in butylamine — this reduces its solubility in water. lonic compounds are generally more soluble in water ~ acidity phenylamine with hydrochloric acid to give its more soluble salt ‘A2 Chemistry Revision GuideTopic 2: Organic chemistry — Arenes, nitrogen compounds and synthesis ‘* Formation of complex ions — amine molecules have a He lone pair of electrons, so they can form dative covalent aan | wel, bonds with transition metal ions, giving coordination SANS ts complexes. curd = (culC HN HOF HCN I Nae Amine complex with copper() ‘« Nucleophilic substitution — the lone pair of electrons on the nitrogen atom in ‘amines gives them some nucleophilic character. Amines can act as nucleophiles in reactions with halogenoalkanes - the lone pair is attracted towards the 8+ carbon in the halogenoalkane. Mixtures of amines are formed. For example, it you start by reacting bromoethane with ammonia, ethylamine is formed, which then reacts with the halogenoalkane to form diethylamine, which can further attack bromoethane. ‘Amines react with acyl chlorides to form N-substituted amides, RCONHR’ (also see age 57) es Oa rs id ay G+ ang : + cence + cae v1 ee mS nse unsons intb witen We lust, yournay be asked to devise ; phenylamine —_propanoy! ‘N-phenylpropanamide e organic product You wil need to learn ‘the reactants and conditions for stops sith a the preparation of amines and One example of such an amide is the analgesic, paracetamol, amides, or the halogenaton of phenol \_aieereiaemar a chloride Forming an amide from propanoy! chloride and phenyiamine Diazotization and synthesis of dyes Aromatic amines, such as phenylamine, can be converted into diazonium salts by reaction with nitrous acid, HNO>, Nitrous acid — nitrc(l) acid — is unstable and is, itu from a solution of sodium nitrite it formed in situ from a solution of sodium nitrite in dilute aci: are tae te a erty N+ 20 Ny + HNO: + 2HCl | ——» Itis the diazonium compound thats Uunstabla, not the dye or phenplamine Ceistc \ | pherylamine benzeneiazonium chiorde, Diazotzaton of pherylamine Diazonium compounds are generally very unstable at room ae ‘temperature and are kept below 10°C for this reason. At the ‘ reduced ternperature, diazonium compounds can be easily converted into a range of useful products such as dyes. Benzenediazonium chloride can be converted into a NaoHaq) coloured dye, an azo dye, by reaction with phenol under alkaline conditions: Reactions between iazonium compounds and an aromatic amine or phenol are called coupling reactions, OH + NaCl + #0 The aromatic rings are joined together through the azo group (—N=N—}. These dyes can absorb light in the visible part of the spectrum and appear coloured. +9) diazo rou Formation ofan az0 dein the reection of pheno! with onzencoiazonium chloride ‘Why do amines form salts with acids? Why are diazonium saits difficult to handle in the laboratory? ‘What kind of bonding allows amines to form complexes with transition metal ions? 'A2 Chemisty Revision Guide aneneral principles of chemistry l— Transition metals and organic nitragen chemistry Amides and polyamides Tae ae The general formula for the amides is RCONM, where R is an alkyl group. Amides are Methane | Heo carboxylic acid derivatives ~ they are named according to the longest carbon chain, Ethanamide | CH,CONH, Sree ee Propanamide | CHCH;CONH: ‘Comment on the likely differences in melting temperature and solubility of the following compounds: ‘A CH,CH,COOH B CH,COOCH; © CH.CH,CONH, These compounds have almost identical molar masses. A contains a polar C=O group that does not take part in hydrogen bonding and an OH group that does. B has the ester functional group RCOOR’ but no OH group. contains the CONH, group and is an amide. Amides have extensive hydrogen bonding owing to the presence of electronegative atoms and hydrogen attached to an electronegative atom and so will, therefore, have higher melting temperatures than carboxylic acids or esters, Both A and € will be soluble in water because they can form hydrogen bonds with water. You should be able to expain the plysical and cherical properties of unfamiliar compounds in tars ofthe functional groups they contain, fr example cifferences in melting end | Amides are prepared by the nucleophilic substitution reaction of an amine with an acyl | chloride (see the previous page and also page 57) or by reacting acyl chlorides with concentrated ammonia solution (see page 57). Condensation polymerisation ef hexane-t 6-doic acid 1,6-claminohexane | one molecule of waters formed for ‘each amide bond formed + 2-1) HO) repeat unit Making a polyamide, rylon-6.6 “ i. f Be benzene-t,4-ioic acid toto cigar gM eee Kevlar | Chemisty Revision Guide 4-O-+ Recall from Unit 4 (page 55) that polyesters can be made from ester monomers by addition elimination reactions. These reactions can also be called condensation reactions. A small molecule (often water is split out as a result of such a reaction, Polyamides are made by condensation polymerisation from amide monomers ~ the amide bond CO—NH joins the monomer units together. ‘The strong bonds in polyamides make the polyamide chains themselves strong. Polyamides such as nylon and Kevlar can be made into strong fibres and are used in making clothing. Kevlar is used for bulletproof vests, 4 H \ / a N MA \ HW iH benzene-t,4-diamine One molecule of ater is formed for ‘each amide bond formes + 2n— #0Topic 2: Organic chemistry ~ Arenes, nitrogen compounds and synthesis Addition polymerisation Recall from AS Unit 1 that alkene derivatives polymerise by addition with no small molecule product accompanying the polymerisation. '* Poly(propenamide), better known as polyacrylamide, is formed by addition polymerisation of 2-propeneamide: Ko=cH I ° c=o > wy, md 2-propenamide polyforopenamice) Adiltion polymerisation of polyioropenamice) '* Polyfethenol) is a special addition polymer whose solubility can be varied: poly(ethenyi ethanoate) + methanol — poly(ethenol) + methyl ethanoate ‘The repeating unit in the polymer chain is shown on the right. ee. What are the differences between adcition and condensation polymerisation? In addition polymerisation, alkene molecules simply join up to give chains and nothing is lost (eliminated) In condensation polymerisation, a small molecule is eliminated as the monomers join. ARISE Which is more likely to polymerise when reacted with a diamino compound — butanoic acid or butanedioic acid? Explain your answer. Molecules with reactive functional groups at each end are needed for condensation polymerisation, so the answer is butanedioic acid (HOOCCH,CH,COOH). Note that the elimination product is often, but not always, water from a hydrogen atom in an OH group at one end, and an oxygen atom in OH at the other. Water solubility It is unusual for synthetic polymers to be water soluble. Poly(ethenol) is soluble because of the formation of hydrogen bonds to the solvent, water. The requirements for hydrogen bonding are: © avery electronegative atom - oxygen here # 8 hydrogen atom attached to an electronegative atom. See What advantages are there for health workers in hospitals through the use of laundry bags made from polylethenol)? Hospital laundry may be heevily soiled or contain pathogens that pose risks ‘o those handling them. The use of bags made from polylethenol) allows the material to be permanently sealed. Since the polymer is water soluble, the bag dissolves when put in the washing machine, allowing the material inside to be washed safely 4 ¢ I 4 9-0-5 palyieteno) Palyetheno) structure Root cy Cena) C4 Practise writing the formulae of ‘monomers and ther coresponding polymers, both akition and ‘ordensation types. tis easy 10 lose marks by leaving out some key part such asthe C= band in ester manomets, of not showing the ectinuaton bonds at each end atthe repeat uit OEE 11 What is the functional group in amides? 2 Explain why the polymer called poly(ethenol) has Unusual properties for a polymer. 3 Write the full equations for: athe formation of ethanamide, CHSCONH,, starting with ammonia b the formation of N-ethylethanamide, CHCONHC;H., starting from ethylamine, A Chemistry Revision Guide Sa). Sg CT, a General formula of an amino acid Check that you can explain the formetion of ewittsions and ther act base behaviour ~ and also that you can Aefne th isoelectric pont, These are ‘cman questions, ‘Amino acids contain both a carboxyl group (COOH) and an amine group (NH,) The carboxyl group has acidic properties but the amine group (ike ammonia) is basic. Since amino acids have two contrasting functional groups, they have some unusual properties. Varying the nature of the R group gives a wide variety of possible amino acids. The simplest is where R = H, glycine (aminoethanoic acid). Many ather amino acids are still called by their common (non-IUPAC) names, such as lysine, which is 2,6-diaminohexanoic acid, Acid—base properties Amino acids are amphoteric because they can react with both acids and bases, At intermediate pH values, amino acids can exist as ‘internal salts’ called zwitterions, Which contain both a positive ion (NHs*) and a negative ion (COO-)— but the molecule has no charge overall vo sh ce 4 a oO Nee og i | foc pi ino as acig fron 29 agg) / nS \ oartay eee Eitan ets, es TH? anti spc Tohyasidee Pte nin sea cnn Sees a, ‘Acid-base behaviour of an amino acid The pH value at which the amino acid exists as a zwitterion is called its isoelectric point. The pH of the solution determines which of the two ions on the 2witterion react with protons in the solution (see the diagram above), ‘In strong alkali, an amino acid behaves as an acid. An example of acid behaviour by an amino acid is the formation of an ester from gjycine: HNCH.COOH + CHjOH — HNCH,COOCH, + H,0 ‘¢ In strong acid, an amino acid behaves as a base. Basic behaviour of an amino acid is shown by reaction with acyl chlorides: H.NCH,COOH + CH;COCI — CHsCONHCH;COOH + HCI een Why do solutions of amino acid awitterions resist pH changes when small amounts of acid or base are added? The added acid reacts with the zwitterion to reprotonate the carboxyl ion, removing the excess acid, Any added base remaves a protan from the NH,* group, neutalizing the base. This s the action of a buffer solution ‘A2 Chemistry Revision Guide-Arenes, nitrogen compounds and synthesis Identifying amino acids Mixtures of amino acids can be separated and identified using chromatography, Comparing the position of the spots on a chromatogram of the mixture with known reference amino acids (or measuring R, values) allows the identification to be made. Amino acid spots in a chromatogram are colourless, so to be viewed they must be stained by spraying them with ninhydrin. This produces coloured spots, such as purple for glycine. Optical isomerism in amino acids All amino acid molecules except glycine have a chiral centre (see page 48) and show ‘optical isomerism rmitror chiral R centre . HW Xoot | wood H Seine Chiral molecules rotate the plane of polarization of monochromatic (single colour) plane-polerized light. The extent of rotation is equal but opposite for two optical isomers. Importance of amino acids ‘Amino acids can polymerise by condensation to give peptides. H 4 Oo H eae, im & iol Oy i \ Y dipeptide wher retiaie a, ra ramets ‘Amino acids are linked together by the peptide link (CO—NH), an amide bond. A peptide link is formed when the COOH group on one amino acid reacts with the NH, group of another. Chains of many peptide groups form polypeptides and proteins. NCH, CONHCHCONHCHCONHCHCONHCHCO— HOH CH CHSH (CHa Cots Ny Four amino acids ina polypeptide chain SOPETWM 11 Which two functional groups are found in amino acids? 2 What is amphoteric behaviour in amino acids? 3 Amino acids are colourless. How can amino acids that are suspected to be in a reaction mixture be separated, made visible and identified? 4. Draw the zwitterion structure of glycine, H,NCH;COOH. A2 Chemistry Revision Guide En