endorsed for edexcel Edexcel A level CHEMISTRY 2. Cliff Curtis Jason Murgatroyd David Scott PEARSONPublished by Pearson Education Limited, 80 Strand, London, WC2R ORI. ‘www pearsonschoolsandtecolleges.couk Copies of official specifications for all Edexcel qualifications may be found on the website: www. edexcel.com ‘Text © Pearson Education Limited 2015, Edited by Ashley Craig and Alison Sleigh Designed by Blizabeth Arnoux for Pearson Education Limited ‘Typeset by Techset Lid, Gateshead (Original illustrations © Pearson Education Limited 2015 Mlustrated by Techset Ltd and Peter Bull (Cover design by Elizabeth Arnoux for Pearson Education Limited Ficture research by Alison Prior (Cover photo/illustration © Front Science Photo Library Ltd: Ramon Andrade 3DCiencia ‘The rights of Cliff Curtis, ason Murgatroyd and David Scott to be identified as authors of this work hhave been asserted by them in accordance with the Copyright, Designs and Patents Act 1988. 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The Science of Champagne, Princeton University Press (Liger Belair, G. 2004) pp'37-39, reproduced with permission of Princeton University Press in the format Book via Copyright Clearance Center, Extract on page 78 after How does Toyota's fuel cell vehicle work? by Joe Clifford, 17 November 2014, http: /blag toyota couk/how-) OF information that you How could a reader find out more information about these terms? manos em | Are they all eq, hoe Now we will look at the chemistry in detail. Some of these questions will link to Book 1, 50 you \ retispiee 1! ally may need to combine concepts fiom different areas of chemistry to work out the answers. Some " questions wil also ink to topics covered later inthis book. Dont worry if you are not ready to give eee answers to these questions yes. You may lke to return to the questions later 2. Consider the two equilibria shown below. COs) = COxaq) H,0()) + CO,(aq) = HCO,"{aq) + H"faq) K,= 45 «107 mol dev? 2. How would you expect an increase in the partial pressure of carbon dioxide to affect, both equilibria shown above? b. What happens to the position of both equilibria when the champagne corkis popped? | | in science in order to | 3. a, If0.5g.0fCO, is dissolved in 1,0 dm: of water, calculate the pH of this solution (use | | make sense of comm the K, value given above) stating any assumptions made. ]{ Problems. tn face \ b. The pressure inside a bottle of champagne can each about 6atm. How would this <+_|) 2°°¥" Po" and models affect the pH of the champagne? “Th Reaver important | c. With reference to the equations above suggest why itis better to open a bottle of, | method The ae champagne that is chilled rather than warm. 4. The concept of equilibrium is also an important one when it comes to the flavourand | aroma of champagne. For example, ethanol can react with ethanoic acid to give an ester. | { | thing is tobe aware o | sumptions you | fa Write an equation for the reaction Between ethanol and ethanolcacld'o ghe aneser | | | 8°) why they are / and name the ester formed | eee b. The enthalpy change for this reaction is -3.5k| mol’'. Explain why a change in aes temperature will have very litte effect on the position of the equilibrium in question 4a 5. The structure shown below has the common name malic acid. Malic acid is one of the compounds that contributes to the acidity of champagne. ee 2. Give the IUPAC name for malic aci. chiral centre in malic acid. & c. How many esters could be formed between ethanol and OH malic acid? Explain your answer and draw one of the structures. fig Trestuctue of malic a Activity Didyouknow? _ ( Iris surprising what can be In many cases foods have additives called E numbers that are intreduced for reasons of preservation, added to food. For example, Jimproving colour, flavour or texture. Some E numbers can be used to regulate pH. Such combinations £173, E174 and E175 are the include the following: E200/E202, £710/E211, £221/£222 and E280/E281. Choose one pair of E numbers elemental forms of aluminium, land camplete the following tasks silver and gold, respectively! India alone is reported to use + Identity the chemical compounds giving their structures, es erent about 1 tonnes of culinary Lae a ee oe ug ,iis 1. Nitrogen and hydrogen react together to form ammonia in a reversible reaction that can reach a position of equilibrium. The equation for the reaction i: Ng) + 3Ha(g) = 2NHsa) A= ~92kI mol“! (@) Which change would affect both the value of the equilibrium constant, K,, and the proportion of ameonia present in the equilibrium mixture? i A Adding a catalyst of finely divided iron B Adding mote nitrogen atthe same temperature anc volume. © Carrying out the reaction at « lower temperature atthe same pressure and volume. 1D Carrying out the reaction ata higher pressure atthe same temperature and volume. (b) Ata fixed temperature and a total pressure of 5.00 tm, @ sealed vessel of volume 2000 dmn* contained 1.00 mol of N{g) 2.00 mol of Halg) and 1.00mol of NH) () Calculate the value, stating units of the equilibrium constant, for hs reaction. to) (@) Caleuate the valu, stating uns, ofthe equim constr, K, for reaction 65) (Total: 11] 2 When phosphorus(V) chloride, PCI, is heated to a constant temperature in a sealed vessel it forms a gaseous equilibrium mixture with phosphorus(Il) chloride, PCL, and chlorine. The ‘equation for the reaction is: PCl(g) = PClg) + Chis) (2) The eouliorium constant may be expressed in terms of either concentration, K, or partial pressure, K, () Waite an expression for K;. a (ii) If the units of partial pressure are atm, state the units of J, for the above equilibrium, iH) (b) Explain, in terms ofthe expression for A, the effect on the position of equilibrium of increasing the pressure at constant temperature, oy (@) The relationship between and &; is given by the expression: = K.(00821 TY ‘ihere T= the absolte temperature in Kelvin (K) ‘n = the change in number of moles from reactants to products Calouate a value for K- if the value for K, at 500 Kis o8i0atm. (3) (Total: 9} Exam-style questions 3. Ethanol is manufactured in industry by the direct hydration of ethene in the presence of a phosphoric acid catalyst. The equation forthe reaction is CHa) + H,0(8) = CHLOH(g) ‘The table gives some details of various experiments carried cout under different conditions in order to determine the percentage of ethane converted to ethanol at equilibrium atm of ethanol at] guiibeum 1 ul 573 n | 2 z 12 a7 x | 40 a 13 aa ae a 12 a [a6 5 12 a [8 is 12 5 a 7 12 623 30 [38 (2) Deduce, using the data in the table, how the position of equilbrium varies with changes in concentration of reactants, temperature and pressure. 6) (0). (9) White an expression forthe equilibrium constant, fr this reaction. tt) (i) Calculate value for K, under the conditions used in Experiment 2in the table. State the units, la) [Total: 11] 4. A chemist has discovered a method for making a commercially ‘important chemical, R. The reaction involves the following reversible reaction: 2P\g) + Qle) = Rig) ‘The process is normally carried out in industry at a pressure of 500 aim and a temperature of 573K. (2) (9) Write an expression for K, for this reaction, i) (i) Give the units of K, in this expression a (>) During thei initial research the chemist carried out several experiments all at 500 atm pressure, using mixtures of P and Q starting with 2.0mol of P and 1.0 mol of Q In each case they allowed the reaction mixture to reach equilibrium before determining the percentage of Q converted,‘The table shows the results of two of his experiments. Experiment 1 | Experiment 2 “Temperarare/K 423 373 Percentage of Q 30 7 converted (@ Calculate, using the results from experiment 1, the value of K, (4) @ Deduce the conditions of temperature and pressure that would give the highest yield of R, (2 (ii) Explain way the conditions you have suggested in part (i) may be different from those used industrially. [2] (Total: 10] 5 Hydrogen and iodine react together in the presence of a suitable catalyst, in a reversible reaction, ‘The equation for the reaction is: Hy(g) + 1,(g) = 2HIig) AH = 9k mol {a) ‘The graph shows the changes in concentration when 20 x 10-?mol of H, were mixed with 2.0 x 10 mol of | ina sealed container of volume 1 dm’ and left to reach equilibrium, HL Hand > 2 4 & § & “Time/houre (@) Write the expression for the equilibrium constant, K., fortis reaction al (ii) Use the graph to determine the time at which equilibrium was established. a (ii) Use the graph to determine the equlibrim concentrations of Hl(g.H,(g) ane Lis) a (iv) Calculate a value for the equilibrium constant, K. State the nits al 6 (b) Explain how the value of K. changes wher: {i) the total pressure at equilibrium is increased at constant temperature. (i) the temperature is increased at constant pressure (c) Which statement about the effect of a catalyst on a reversible reaction is correct? ‘A It increases the value of the equilsrium constant of the reaction B It increases the equilbrium yield of product. € Itincreases the rate of both the forward reaction and, backward reaction. (2) 2) 0) D It increases the rate of the forward reaction, but not that of the backward reaction. {Total: 11] (One of the stages in the contact process for the manufacture of sulfuric acid involves a reversible reaction berween SO,(2), (Og) and $O,(g). The equation for this reaction is: 280,{2) + Ox(8) = 280,(2) ‘The equilibrium constant, X,, for this reaction is given by the expression (P50, % Gallo) (s0,)*Po,) “The table shows three values of K, at different temperatures, ‘Temperature/K K/atm 298 40 108 500 25% 10" 700 30x 10° (2) Use the data to comment on the percentage of $0,(g) present in the equilibrium mixture at 298K. 2 (b) Use the data to deduce the sign of the enthalpy change for the forward reaction. 3 (c) Explain, using the expression for K., why an increase in pressure increases the percentage of SO,(g) present in the equilibrium mixture, (4) (Total: 9]BBB ite and death, we need to understand acids and bases and the reactions they undergo. In this topic we shal TOPIC 12 Acid-base equilibria Introduction ‘Acidsand bases play an important part in our lives. They are of fundamental importance in industry, and life depends on the complex networks of acid-base reactions taking place inside ling organisms To understand build on the knowledge you have gained so far on the properties of acids and bases. In particular, we shall use ‘the concept of equilibrium constants ta look at their properties quantitatively. We shal also see how the strengths of acids are related to their molecular structures, ‘When your bos is working normally the pH of your blood plasma is kept fairly constant at around 7.4 ‘You are likely to die if itrises oF falls by more than O. from this nermal value. The pH of your bloed plasma ‘can fall asa result of disease or shock, both of which can generate acidic conditions in your body, You are alsa likely to ce f the pH of your blood plasma rises; this could happen during the recovery from severe burns.To survive, yout body must contro its own pH. fyour natural control systems fil then medicine must come immediately to the rescue by for example, intravenously administering electrolyte solutions In this topic we wll look at how different ions affect pH and how they can be used to controlit. All the maths you need + Recognise aed make wse of appropriate units in cakclatons Be ar ka coe or acces Bic of et poe, eget gare es + Usean appropriate number of significant figures + Change the subject of an equation + Substitute numerical values into algebraic expressions using appropriate units for physical quantities ae eee Use logarithms in relation to quantities that range over several orders of magnitudeATE UMass Coleg STE ATT aE cg erence es eee ee eee treet co a erepemeneenons ee eee ey ome ee Poceearer mere iets eee oe as ee eee? oe) temperature on the value of equilibrium ere ees stants oie Pe ere ee rd See See EL a Perea et) ‘The difference between strang and weak acide Se eet ete Ser eee See eeeThe Bronsted-Lowry theory By the end of this section, you should be able to.. ‘© understand that a Bronsted-Lowry acd is a proton donor and Bronsted-Lowny base is a proton acceptor @ recognise that acid-base reactions involve the transfer of protons © identify Bronsted-Lowry conjugate acid-base pairs @ understand the difference between a strong and a weak acid interms of degree of dissociation Bronsted-Lowry acids and bases in 1923 physical chemists Johannes Nicolaus Bronsted in Denmark and Thomas Martin Lowry in England independent proposed the theory that cories tir names. Inthe Bromste Laviry theory acids and bases are cefind by the way they react swith each otter fig A Jonannes Nicolaus fig Thomas Martin Lowry. ‘They defined an acid as a substance that can donate a preton, i.e.a proton donor (hydrogen ion, H’), and a base as a substance that can accept a proton. Le. a proton acceptor. ‘We might expect that any substance containing hydrogen could act as an acid. In practice, a substance behaves as an acid only if the hydrogen carries a slight positive charge. As an example, this is the case when itis bonded to a highly electronegative atom to the right of the Periodic Table, eg, oxygen ora halogen, 24 In order to accept a proton, a base has to contain a lone pair of, electrons that it can use to form a dative covalent bond with the proton, So, a base must contain an atom to the right-hand side of the Periodic Table, and this is often exygen. Conjugate acid-base pairs ‘When hydrogen chloride dissolves in water an equilibrium is, cstablished that can be represented by the following equation HeVaq) + H,00) = H,0"%eq) + Cea) In the forward reaction: + HClis acting as an acid because itis donating a proton to H,0 + H,Ois behaving as base ait is accepting a proton from HCL In the reverse reaction + H,0" isbehuvingas an acid because it fs donating a proton to CI- + CI" is behaving as a base because itis accepling a proton from 1,0" ‘When the acid HCl loses a proton it forms @ base, Clr. These two species are called a eonjugate acid-base pair. ‘When the acid HO" loses a proton it forms the base HO. These two species also form a conjugate acid-base pait ‘So the equilibrium mixture above contains two conjugate aci base pairs. conjugate pair H+HO o> Ho +c" t____f fig Conugsteacct-bose pairs foxmed fam hycrochlanc acd and water Cis the conjugate base of HCI; H,0 is the conjugate base of HO’ Hydrochlorie acid can donate one proton — itis called a manoprouie ‘ermonobasic acid ‘Sulfuric acid can donate avo protons and is therefore called a diprotie or dibasic acid, Step: -H,SO, +H" + HS0,- Step2, HSO, > H' + SO, ‘Similar, some bases such as the carbonate ion can accept more than one proton: Step 1: CO, +H? + HCO; Step2; HCO, + Ht + H,CO, ‘The carbonate ion is therefore described as a dprotc or diacidic base.ee Didyouknow? ‘+ Acids that donate a maximum of one, two or three protons are called monoprotc,diprotic or triprtic respectively. They ae also called monobasic, dibasic oF tbasic. “+ Bases that ean accept ane, two of three protons are called ‘monaprotic,diprotic or triprotic respectively. They are also called ‘monoacidic. diac or tracidic. We will use the terms monobasic, dibasic et. for acid throughout the book, Another example of a conjugate acid-base pair When ammonia dissolves in water an equilbrium is established that ean be represented by the following equation: NH,(ag) + H,0() = NH,"(aq) + OH (aq) In the forward reaction’ + NHL is acting asa base becauseit is accepting aprotoa rem HO + HOis acting as an acid because itis donating a proton to NH. Inthe reverse reaction: + NH is behaving as an acid because itis Gonating @ proton to on + OH is behaving a base because itis accepting a proton from NH. So the equilibrium contains two acid-base conjugate pas conjugate pair N+HO ===> NH + 0H _——__if eoniugate pair figD Conjugate acid-base pars formes ftom ammonia an water ‘Amphoteric substances In its reaction with HC, H,O behaves as a base by accepting a proton, However in its reaction with NH,, H,O behaves as an acid by donating a proton. ‘A substance that can act as either an acid or a base is described asbeing amphoteric. Didyouknow? 0 You may also come across the term amphiprotc. An amphiprotic substance’ one that can both donate and accept protons. So water | described as being amphiprotie Other examples of amphipratic substances are amina acids and the hydrogensulfate ion, HSO, All amphiprotic substances are also amphoteric, but the reverse is not uve. There are amphoteric substances, ike aluminium oxide, that do ‘not donate or accept protons when they act as acids and bases cespectively. These substances fll into the category of acting as acids and bases according tothe Lewis theory, which tates that an acids, an electron pair acceptor and a base isan electron pair donor. The advantage ofthe Lewis theory is that it shows the similarity between acid-base reactions that involve proton transfer and other acid-base reactions that do not. It is a useful way of explaining why some reactions in organic chemistry that are catalysed by acids can also be catalysed by some substances that can accent a pair of electrons. For example, the nitration of benzene is catalysed by sullric acid, but the reaction also takes place if nitric acid is used in cenjunction with boron trifluoride, BF, [Neither the term ‘amphiprotic’ nor the Lewis theory of acids and bases is required learning for your A level course. Nitric acid as a base ‘The most common method to nitrate benzene (see Section 17.4.2) s to use the ‘nitrating mixture’ of concentrated nitric acid and concentrated sulfuric acid, This mixture forms the equilibrium: H$0,+ HNO, = HSO,- + H,NOs Acid! Base2 Base Acid 2 In this reaction: + H,SO,is an acid: its conjugate base is HSO, + HINO, is 2 base: its conjugate acid is HNO. lt seems strange to refer to nitric acid as a base, but in this reaction that is exactly what itis behaving as. Strong and weak acids A strong acid is defined as one that is almost completely dissociated in aqueous solution Ina cilute solution of hydrochloric acid. virtually all the hydrogen chloride molecules are dissociated. We usually represent this by ‘using a single direction arrow in the equation for the dissociation: HCl{aq) — H*(aq) + Cr-(eq) Learning tip From now on weare going to use H aq) to represent the acid protons in aqueous solution, rather than H,0" It's debatable how ‘many water molecules are bonded toa given hydrogen ion, The formula could just as easily be H;0," or HO. For this reason, Haq) is possibly the best representation of acid protons in aqueous solution it makes no difference to your understanding ofthe concepts involved, whichever formula you use. a ‘The conversion of acid molecules ita ions when an acid issalves in water i also called ionisation, and you may see this term used in other books. Didyouknow? Although, strictly speaking an equilarium exists between HCl ‘molecules, ions and Cl fons, the acid is considered to be completely dissociated in cilute solution, So strong acids are often said to be 100% dissociated, 2526 By contrast, a weak acid is defined as one that is only partially dissociated (often less than 10%) in aqueous solution. Organic acids such as ethanoic acid are typically weak acids. We represent partial dissociation by using the reversible arrow sign ( dissociation: CH,COOH{aq) = CH.COO-(aq) + H"(eq) 11 Give the formula of the conjugate acid of each of the following species (@) CH.Coo- (&) CHANH, (©) HS0, inthe equation for the 2 ive ne foul ofthe conjugate base of ach fhe folowing species (a) HOO, (b) 0° (©) Hs0¢ 3. ineachot he tllowing xampls idan he two conjugate aid-bse pin. each at en tha specer ut are acing 2 Uorsted Lowry ee 6) HCO, #0 = HCO, + HO (b} HCO,” + HO = CO," + H.0* (©) CH,¢00H HNO, = CH,COOH, + Noy 4. Explain why the following reaction may be described as an acid-base reaction: NH" NHy > 2NHS Key definitions An acid isa proton donor. ‘A base isa proton acceptor. ‘A conjugate acid-base pair concets of either a base and its conjugate acid or an acid and its conjugate base, ‘When a base accepts a proton, the species formed isthe conjugate acid ofthe base, ‘When an acd donates a proton, the species formed isthe conjugate base of the acid ‘An amphoteric substance is one that can act both as an acid and as a base.Hydrogen ion concentration and the Py ae By the end ofthis section, you should be able to... © define the term pH ‘© calculate pH from hydrogen fon concentration, and vice versa © calculate the pH of an aqueous solution of astrong acid © deduce the expression for the acid dissociation constant, Ke, for aweak acid and carry out relevant calculations © calculate the pH of a weak acid making relevant assumptions © define the term pk, Hydrogen ion concentration and pH Strong acids ‘As already mentioned, strong acids are assumed tobe dissociated completely when they ate dissolved in water. This means thatthe Jydrogen ion concentration is related directly to the concentration of the acid For example, a solution of HCl of concentration 0.100maldm-? ‘wil produce a hymen ion concentration of 0,100 mol den-* ‘The pH of an aqueous solution is related to the hydrogen ion, ‘concentration by the following equation: si " =e pH = IH] or pH= Ig ‘The hydrogen fon concentration, (H*] is measured in mold. ‘Which equation you decide to use is purely a matter of personal preference. Did youknow? Logarithms can only be taken of a number, nt a quantity with a unit. So, strictly speaking, the hydragen ion concentration has ta be divided by the standard concentration, c®, which has value of ! mol dn Hence, the correct expression for calculating pH is “Ig [H'V.c®. This, however, is not something you need to consider at this level. ‘Learning tip —____ Do not worry ifyou are unfamiliar with the use of logarithms. They are merely away to convert a scale of numbers in powersol 10 to a linear scale. For example: 4g 100 =2 (a5 1001510") 10-1 (as 101s 101) 1g =0(as1 is 105) g0.01 = -2 (as 0.01 is 102) The |g of a number can easily be found by sing the i or‘og’ button on your calculator. ‘Although the accepted abbreviation for logarithm tothe base 10s, Ig, you can also use logic er even log. women bavi 1 Calculate the pH of aqueous solutions ofthe following monobasic, strong acids. In each case assume the acid is completed dissociated. Give your answers to two decimal places. {a} 0.00100moldm"* HCI {b) 0.0500 mol drs HNO, {q) 0.150molim-* HBr Answer @ = +g (0.00100) 3 0, (0.00100) = + 300 00 fo) p= -tg(0.0500) 1g (0.0500) = -1.30 pH=130 (0 pH=te(o150) tg(0150)--082 pH 082 2. Calculate the pH of an aqueous solution of 10.00 mol dm-* of HCL. In this solution the HCI is 55% dissociated Give your answer to two decimal places Answer [H4] = 055 » 10.00 mold’ = 5.50 moldm pH =~Ig(6.50) 1g (550) 0.74 50, pH = -074 Did youknow? pH and activity “The measured pH of a concentrated acid is never as low as the calculated value, even though te acid may be completely dissociated. Ths is because the ions tat are close together in solution interact with ane another. This makes their effective | concentration less than the actual concentration, This effective concentration is called the activity. For example a solution of HC of 1.00 mel di” has an effective hydrogen ion concentration of (0.81 mol dm, This makes the pH of this solution 009, not 0.00, as, calculated from a hydrogen ion concentration of 7,09 moldmn™ Only at concentrations below 0.10 mol dm” do activites and concentrations have similar values. “This activity effect means that the minimum pH and maximum pH that concentrated solutions can have are 0.30 and 14.30, respectively ‘Thisactvity effect can be ignored a A level hence the calculation of -074 above, 27677A Calculating hydrogen ion concentration from pH 1tisa simple matter to calculate the hydrogen ion concentration fom a given pH value “The following equation should be used (H"(aq]) = 20°*" Dee ‘Calculate the hydrogen ion concentration of solution witha pH off (H(aq)|= 10-8 = 1.58 x 10° mol dm? The key to solving this calculation is to press the 10% or 10% button on your calculator and then entering the negate pH value, followed by the equals buon. The answer wil then be displayed Weak acids Determining the hydrogen ion concentration of an aqueous solution of a weak acid is more complicated because a significant amount of undissociated acidis present in solution. tis necessary toreferto the acid dissociation constant, &, for the acid. Acid dissociation constant IE we use HA to representa weak acid, then the equation for its dissociation in aqueous solution is: Haag) = Haq) + A(2q) By applying the equilibrium law to this reaction we obtain: [H (aq) (aq) (Ale) “This constants called the acid dissociation constant andi given the symbol K, ‘Weshal now calelate the hyde ion concentration of en ‘aqueous solution of ethancic acid of concentration 0.0500 mol ém® “The value of X or ethanoi acids 1.74 % 10° mold? a 208 K. CHHyCOOH(aq) = CH{COO (a) + H(aq) [CHsCOO“faq)I[H*(aq)) . [CH;COOH{(aq)) Every time s molecule of CH,COOH dissociates, a CH,COO™ion and a H* ion are formed. =a constant “This means that [CH,COO"(aq = (H"(eq)} So, the expression for X, can be simplified to =a (CH.COOHfaq] Itis important to recognise at this stage thatthe concentrations in the expression for X, are the equilibrium concentrations. However, if the value of X; is very small (as itis in this case) then the concentration of the undissociated acid at equilibrium is very similar to the initial concentration of the acid. Itis therefore reasonable to take the concentration at equilibrium as being the same as the initial concentration, 28 Therefore, (Haq)? cual HG = 1.74 x 10-5mol rw (H"@q)] = (0.0500 x 1.74 x 10°)= 933 « 10-¢malam? This gives a pH of 303, Aearningtip Ifyou are concemed thatthe approximation we made in the ‘alelation s not justified, then its possible to solve the precise ‘equation: , = [H*(aq]?(0.0500 ~ Haq) = 1.74 « 10 mol dav? ‘The solution to this equation gives a value for [H aq] of 9.327 « 10+ moldny” ‘The difference is significant enly fr very accurate work, ‘There is also one other approximation that we made in both the Srna clean and ths calaation As we shal sen Seton 3, water ionises very slightly to form hydrogen ions and rs ions. We have ignored the contribution tothe total hydrogen ion concentration from the dissaciation of water. However, unless the acd i very dilute, this approximation is also justified. If you are good at remembering equations, then the following, ‘equation can be used to calculate the hydrogen ion concentration, cf an aqueous solution of a weak monobasic acid: (H*(aq)] = VR, * Taig) ‘where K, is the dissociation constant forthe weak acid. K,and pk, values “Table A (rox page) sts some weak monobasic onan ais together with their k, and p, values at 298K, were: 0K, = —Ie Ke You will notice that te lager the value of the stronger the acid, By contrast the smal the vale ofp te stronger the acid Calculating the pH of a dibasic acid Suifuric acd is the most common dibasic acid. It dissociates in two stages: H,SO,(aq) —+ H(aq) HSO,-[aq) HSO, (aq) = H"(aq) + $0 (ea) H.$0 js a steong acid and is therefore fully dissociated HSO, isa ‘weak acid (K, = 0.0100mol dm) Ja 0.500 mol dm? aqueous solution of H,S0, the contribution tothe [H"(aq)] from the H,S0, willbe 0.800 mol den. If we assume that the contribution to the (H'(aq)] fom the HSO,- ion is xemol dm’, then we have the following relationship: K, (HSO,°) = 0.0100 = (0.500 - x)x/0.500 Solving this quadratic equation gives x = 0.0098. ‘This gives a total (11(ag] of 0.05098 mold” with a subsequent pH of D298,fee) Ener ee popancic acd CH.CHCOOH | 135107 | 487 eftance acid cHcoon | iraxto™ 476 benoic ad cui,cooH | baie | 420 mathe acd HcooH —|_160%10"" | 380 inane ctlorethncic asd | CHCICOOH | 13810 | 206 diclorostnoicacid | CHC,COOH [6.19107 | 129 tiehleroetiale act | CChCOOH | 2.20107 | 05 table A, [tis interesting to perform this calculation in order to recognise that the contribution to the (H"(aq)] from the HSO;- ions is negligible. This is because its dissociation is significantly reduced owing to the high [H*{aq)] from the full frst ionisation of the H,SO. ‘A second interesting reason for performing this calculation is because many books state thet 0.5 mol dm~* H,SO,(eq) can be used as the acid solution in a standard hydrogen electrode (see Section 14.1.1 on standard electrode potentials), As the standard hydrogen electrode requires a (H(aq)] of 1.00 mol dm-? (pH = 0.00), this is clearly incorrect. 11 Calculate the pi ofeach of he following aqueous solutions af strong monobasic aids Assume the acid is uly dissociated in each case. Give your answers to two decimal places (@) 00100mol dew? Hi (b) 0500mol dm? HNO, (©) 0.00405 mel day Hel N Calculate the pH ofa mixture of 200 em? of 1.00 mol dm HCKag) and 5 cm of 1.00 mol dm> NaO Hag). w Calculate the pH of each ofthe following aqueous solutions of weak monobasic acids. Give your answers totwo decimal places. (@) 0.100mol dm? HCOOH [K,(HCOOH) = 1.60» 10! meld) (©) 1.00mol dav* HF [K,(HF) = 5.62 « 10° mol de] (€) 0.505mol dna” NH,CI [,{NF,) = $62. 10° mal da 4. The pl ofan aqueous slain ofa weak cd HA, of concentatlon 0305 melden is 457 Cleat the dissociation constant Ror this weak acd ‘Keydefinition ‘The pl of an aqueous solution is defined asthe reciprocal ofthe logarithm to the base 10 ofthe hydrogen ion concentration measured in moles per cubic decimetre, pH = ~ig[H' This definition is dificult to ‘remember, s0 either ofthe two equations given on page 27 can be used to define pH. PKe= “Ig ks Didyoulnow? Its interesting to note that the chloro-substituted ethanoic acidsare stronger than ‘ethanoic acd itself, and that the acid strength increases withthe number of chlorine Atoms present. This wil be ‘explained in Section 13.33 29lonic product of water, K,, By the end of this section, you should be able to.. @ define the ionic product of water, Ky © define the term pk, @ calculate the pH of an aqueous solution of a strong base using Ky. Learning tip __ ‘The pH of a neural solution is often quoted a being 7.00 However, thisis true only fora solution that has a temperature of 298 K, ‘As with all equilibrium constants, Ky varies with temperature At.288 K ithas a value of 45210" mok dmv, Atthis temperature, IH'Gag)l= 672 «10 mold, wing pH of 7.17. So, at 288 K a neutral solution hasa pl of 717, Similarly itcan be shown that 3308 K the pH of a neutral solution is 684, are ‘The equation should strict be PR. = Ig Kel(e*¥ in order to be able to take the logarithm ofa dimensionless quantity However we will use the simplified version ofthe equation 30 Dissociation of water Pure water has a slight electrical conductivity soit must contain some ions It selFonises according to the following equation 1,00) = H'(eq) + OH (aq) If we apply the equiliorium law to this reaction we obtain [Ht{aqJOH-faq)) THOM constant As [H,Ol))] is constant ata given temperature, the expression may be simplified to: (H*(aq)J[OH -(aq)] = a constant ‘This constant is called the ionic product of water and is given the symbol Ky ‘The value of K, at 288 K is 1.00 x 10" mol? dn ‘A neutral solution is defined as one in which the hydrogen ion concensration is equal to the hydraxide fon concentration, ‘This isthe case for pure water, ‘AL 298 K, [H*(ac)] = 1.00 x 10-7mol dra [(1.00 x 10-2] So, the pH of pure water at 298 K is 7.00 [-Ig (1.00 « 10-7) K,,and Pky ‘The relationship between K, and pXyis given by the following equation PK, = gk ‘Ar 298 K, when K, Table A gives the values of K,, and pi, at various temperatures. (00 x 10" mol dm’, px, = 14.00 fame 73 283 293 303 313 [anna 1.14% 10" | 293% 10" | 681 x 10-8 | 147 x 10 | 292% 10° Ee 1494 1453 1417 13.83 1353, table A pH of aqueous solutions of strong bases When an acids issoved in waterit produces so many hycrogen ion thet he smal contbaton ffom the wateris insignificant unless the acd concentration is very smal However te fact that water ionsess the reason why even the most alkaline schtions contain some hydrogen ions. Soctur hyroxie is a strong hase, son lute aqueous solutions we can consider its ions tobe complecly dissociatedee A sodium hydroxide solution of concentration 0.100 mol dm” therefore has a hydroxide fon ‘concentration of 0.100 mel dm IF[OH (aq) = 0.100mel dm”* and [H"(eq)][OH-(aq)] = 1.00 > 10-™ moF dm. then (H(aq)] = 1.00 x 10-*/0.100 mal dm? = 1.00% 10-* meldém™* ‘The pH of this solution is therefore 13.9. eaten Calculate the pH, at 298 K, of an aquecus solution of potassium hydroxide of concentration (00200 mol dry K, (298 K) = 1. Answer ‘As poassum hydroxide fsa strong base we may assure tat itsions ae completly dissociated ot (aql = 00200 mol dar? 50, (H'(aqll= 100» 10""y00200 pH = Ig (500 «10 + 10™ mol den 5.00 « 10" mol dmn-* 123 Learning tip Ifyou are not happy working with logarithms of small numbers, you can use the logarithmic form of the equation [H"(aq) OH" (aq) = 1.00% 10", which is pH» pOH = 140, where pOH = Ig [OH-(aq), So, in the worked example above: pH= 140 - pOH = 140 (-Ig(0.0200)) «(140 1.70) = 123, 1 The ionic product of water, K,, has.a value of 1.00 = 10" mol? dm at 298 K and a value of 681» 10 " mold at 293K. Use this information, where relevant, to answer the following questions. (@) Calculate the pH of water at () 298K and (i) 293K (&) Even though pure water at 296 and at 293K has diferent pl values, both samples of water are said tobe neutral Explain vy. (©) Isthefollowing reaction exothermic or endothermic? H,0{) — Hr(aq] + OF (aq) Explain how you arrived at you 2 caeulte tn tat 298X ofeach ofthe following aqueous oktons of tong bases Assume the busi fly disoate neachense Ce Your anes ots decimal paces. {a) 0.0100mol dm? NaOH (b) 0.0500 mol dm? Ca(OH)» (©) 0.0315 mol dm? KOH [ke= 1.00 = 10-™ mo? din at 298 K] Key definition K,=[HaqOH (eal 31Analysing data from pH measurements By the end of this section, you should be able to.. © analyse data from the following experiments: (i) measuring the pH of equimolar aqueous solutions of strong and weak acids (i) measuring the pH of equimolar aqueous solutions of strong and weak bases ‘measuring the pH of equimolar aqueous solutions of various salts (iv) comparing the pH of aqueous solutions of strong and weak acids after dilution © calculate K, for a weak acid from experimental data given the pH of an aqueous solution ‘containing @ known mass of acid Comparing solutions through pH measurement Strong and weak acids ‘The relative strengths of different acids can be determined by measuring the pH of equimolar aqueous solutions of the acids, t the same temperature. ‘Table A shows the pH of 0.100moldm® aqueous solutions of various acids at 298 K. GE Ceee Mmm HC) | CHCLCOOH | CHCICOOH | HCOOH | CH.COOH | CH.CH,COOH Perms 00114 193 287 293 Pera) Perera decreasing acid strength table ‘The higher the value of the pH, the weaker the acid, Strong and weak bases ‘The same method can be used to determine the relative strengths of bases. ‘Table B shows the pH of 0.100 moldm” aqueous solutions of various bases at 298 K, eee ip [ CHANE, [ (CHNH [ CH.CH,NH, | CH,CH,CH,NH, [NaOH aia3] 11.82 increasing base strength table B ‘The higher the value of the pH, the stronger the base. Salts ‘Table C shows the pH of aqueous solutions of various salts of concentration 0.100 mal dm at 298 K Fe 2c! | NO; | CH.COONa | NHACI | CH:COONH, Fcrermcrmms 700 | 700 888 513 700 table ‘The pH of NaClis 7.00 because the salt is made from a strong acid (HCI) and a strong base (NaOH), 32ee ‘The same is true for KNO,, which isa product of the strong acid HNO;, and the strang base KOH. ‘An aqueous solution af CH,COONa is alkaline because it is a product of a weak acid (CH{COOH) and a strong base (NaOH). ‘An aqueous solution af NH,Clis acidic because it is a product of a strong acid (HC) and a weak base (NH3) ‘An aqueous solution of CH,COONH, is neutral (pH = 7.00) because its a product of a weak acid {CH,COOH) and a weak base (NH), and the relative strengths of the acid and base are the same. ‘Learning tip ______ ‘This is shown by their dissociation constants. , a measure of acd strength CH.COOH: K, = 1.74 « 10 moldar? and ky isa measure of base NH k= 1.74% 10-%moldmr® sats Summary table for aqueous solutions at 298 K B ? (Golution is neutral) ‘he reason why some sat form Are pH > 7 (solution is alkaline) eee ED sal acid and a weak base <7 (solution is acid an ae aac (ea Ce ee To lean more about this, Pare ete eer ears pH depends on relative strength of acid and base; | esearch salt hydra if =K,pH=7 a cteerartte eeomaee vet if > K, pHe7 erent cals have cerent pi KS K, p> 7 values because this wll explain why, for erample, the pH ofthe fableD ‘olkton formed when song . 3 7 ac reacts with an equivalent Effect of dilution on the pH of aqueous solutions of acids et tae ; than 7. We shal met this Strong acids ‘concept when we look at acid~ ‘Table E shows the pH of five aqueous solutions of hydrochloric acid. In ezch case the acid has been base tiation curesin Section diluted by a factor of ten from 1.00 (1.00 x 30°) to 0.000100 (1.00 * 10~)moldm-*. All solutions 1221. huave a temperature of 298 K. (00 » 105) | 0.100 (7.00 « 10") | .0100(1.00 « 10) | 0.00100 (1.00 = 10) | 0.00100 (7.00 « 10%) 0.00 1.00 200 300 4.00 ablee ‘You will notice that the pH increases by @ factor of one unt for each 10-fold decrease in concentration. IF we follow this to its logical conclusion, then an aqueous solution of hydrochloric acid of concentration 1.00 x 10-¢mol dm”* should have a pH of 8.00. This is clearly nonsense because this, ‘would mean that a solution of an acid was alkaline, Earlier in this topic we mentioned the fact thatthe contribution to the lyydrogen ion concentration from the dissociation of water can usually be ignored. When solutions are as dilute as 10-* mol da this is no longer the case, The pH of 10-* mol dm”* lydrachlorie avd is very close to 7, as the contribution ¢o the concentration of hydrogen ions frorn the water (10~" mol dm”) is now greater than that of the acid Weak acids ‘Table F shows the pH of five aqueous solutions of ethanoie acid (CH,COOH), In each case the ‘acid has been diluted by a factor of ten from 1,00 (1.00 10*) to 0.000100 (1.00 x LO~4 mol dm. ‘Once again, all solutions have a temperature of 298 K. BEM 1.00 (1.00 = 109) | 0.100/7.00 « 10°) | 0.0100 (1.00 = 109 [ 0.00700 (1.00 » 10°) [ 0.900100 (7.00 » 10%) 238 288 338) 3.88 438) table With a weak acid the pH value increases by a factor of about 0.50 for each LO-fold decrease in ‘concentration, 3B121 Determining K, of a weak acid from experimental data “The folowing experiment canbe performed to determine K, of benzoic acd (C,H. COO!)~a week monobasic aid + Accurataly weigh between 040 and 0.0 of benzoic acid and then cssave icin a smal volume (30950 erm} of deionised water contained ina beaker (Benasic ai snot very sohble soit may be necessary to warm the water to gett 0 Aissolve. fsa. allow the sohton to cool before performing the nent stage) «Transfer the soliton to @ 250m? volumetric ask. Add several ‘washings fom the beaker using deonised water and then mak Upto the mark win detonised water: + Mix the solution by iverting the ask several ies. + Withdraw a sample of the siuton and place itn a small beater + Using a calibrated pH meter, measure the pH of the solution, Ses Mista 049g DH 300 Analysis of results CH,COOH(ag) = C.H.COO"(aq) + H'(aq) ‘molar mass of benzoic acid (C.H.COOH} = 122g mot n{CsHCOOH) in 250 cr of solution = 049/122 mol $0, [CH COCH{aq)] = (049/122) « 4 mol dm pH=3.00 50,[H"(aq] = 10° » [C.H_COO (aq}] K,= (1O*F + (049/122) x4) = 6.22 10° mold ‘The Data Book value is 6.32 « 10% moldm™ at 298K. ‘The result obtained is close to the accepted value, but that does not necessarily mean that we have performed an accurate experiment, There may have been a number of errors that have, bby chance, cancelled out one another ‘To start with, we have assumed that the [C,H;COOH(aq)] at equilibrium is identical to the original concentration of ‘benzoic acid. Obviously this is not correct because it must have dissocieted slightly to produce a solution of pH = 3.00 ‘The major uncercainty inthis experiment is the measurement of the pH value, Even a small errr leads to a large discrepancy in the final answer. A pH of 3.10 would give a final answer of 392 * 10", whereas a value of 2.90 would give 987 10° for the value of K, “Transfer errors may also be significant when weighing out small amounts. 34 1 predic wheter aqueous soktion ofthe folowing sats willbe neutral, acidic or alkaline. Justify your answers. {a} Ammonium nitrate, NH,NO; (b) Potassium propanoate, CH.CH,COOK (c) Sodium nitrate, NaNOs what information is required in order to make a prediction bout the pH of an aqueous solution of ammonium methanoate, HCOONH,? Calculate k, for chloroethanoic acid from the folowing data 1.89 g of chloroethanoic acid was dissolved in SOcm® of water and the solution was diluted to 250cm? in a volumetric flask. The pH of thissolution was 199.Acid-base titrations, pH curves and indicators By the end of this section, you should be able to... (© draw and interpret titration curves using any combination of strong and weak monobasic acids and monoacidic bases © ssclecta suitable indicator, usinga titration curve and suitable data Acid-base titrations End point and equivalence point When you carry outa simple acid-base tration, you usually use an indicator to tell you when the acid and base are mixed in exactly the right proportions to react in equivalent amounts, as dictated by the stoichiometric equation. When the indicator changes colour this is often described as the ‘end point’ ofthe tivation ‘The ‘equivalence point’is when the acid and base have reacted together in the exact proportions as dictated by the stoichiomeuie ‘equation, When titrating an aqueous solution of a monobasic acid with an aqueous sclution of a monoacidic base of the same concentration, 25 cm°ofacid will react exactly with 25 cm’ of base. ‘The pH at the equivalence point depends on the combination of acid and base used. For example, if you are titrating aqueous sodium hydroxide with dilute hydrochloric acid then the pH at the equivalence point is 7.00 (at 298 K), as both the base and the acid are strong, The solution at equivalence point will contain the salt sodium chloride I however, ethanoic acid (a weak acid) is titrated against sodlum. hydroxide (a strong base) the solution at the equivalence point will ‘contain the sale sodium ethanoate, and the pH willbe greater than 7 (see Section 12.1.4) If hydrochloric acid (a strong acid) is tated against aqueous, ‘ammonia (a weak base], the solution at equivalence point will contain the salt ammonium chloride, and the pE willbe less than 7. Leamingtip ‘The term ‘neutralisation point should not be used to describe the ppoint at which the acid and base have reacted inthe exact proportionsas dictated by the stoichiometric equation. Ax seen by the examples listed, the pH ofthe solution formed isnot always, ‘neutral (.e. does not always have a pH of 7.00 at 298 K) Remember thatthe tem ‘end point refers to when the colour of the indicator just changes colour - this does not always occur at the equivalence point (se discussion of indicator choice later in this section), Titration of a strong acid with a strong base ‘As you add an aqueous solution of an acid to an aqueous solution of a base, you might expect there to be a gradual change in the pH of the solution formed. This is not the case. The shape of the ‘curve when the pH of the solution is plotted against the volume of acid added depends on the nature of the acid and base used ‘The curves so produced are called ‘pH titration curves! fig 4 2H mete ‘We shall scare by looking at the pH titration curve when a strong, acid is added to a strong bese. “The following graph is produced when adding 1.00 moldm”* HCi{aq) to a 25m! sample of 1.00 moldm* NaOH(aq). The pH ss measured using a pH meter such as the one shown in fig A. 13 2 tL 10. ° & oH? << eniralence 6 point 4 2 L ° Ca ee ee ee) Volume of acid ade /em? igB pH cunefor asrong aci-strong base tration You can see that the pH only falls a very small amount until quite near the equivalence point. Then there is a really steep plunge. If you calculate the values, the pH falls all the way from 11.30 ‘when you have added 24.90 cm: to 2,70 when you have added 25.10 cr ‘There is a large ‘steep section’ to the curve. As we shall see Jater in this section, ths is an important point ro consider when ‘choosing an appropriate acid-base indicator to determine the end point ofthis titration. 35Pe) Titration of a weak acid with a strong base For this example we shall add 1.00mol dm”? ethancie acid to 25cm! of .00moldm” sodium hydroxide. 1 8 2. in 0 ° 8 pi 7. 5 4 5 2 1 0. Titration of a weak acid with a weak base For this example we shall add 1,00moldm” ethanoic acid to 25cm} of LOOmol dm” aqueous ammonia. pli oS mm as wa oD Volume of acid added/em? fig pH cuve fora wash acd-svong base tivation, “The curve is the same as that fora strong acid-strong base up 10 ‘the equivalence point, but there isa difference once the acid is [presentin excess Past the equivalence point the solution contains a mixture of ethanoic acid and sodium ethanoate. This mixture acts asa buller solution and hence resists any large change in pH upon addition of further acid (See Section 12.2.2), Note that the pH at the equivalence point is between @ and 9; itis not 7 Titration of a strong acid with a weak base For this example we shall add 1.00 mol di hydrochloric acid to 25cm? of 1.00moldm-* aqueous ammonia. os Bm" do Volume of acid ase /om* figD pHi cune ora srong acid-nesk bate tation ‘When the acid is fist added the pH starts to fall quite sharply but the curve quickly levels out. This is because a buffer solution thas been formed, containing ammonia and ammonium chloride (egain, see Section 12.2.2) Notice that the pH at the equivalence point is less than 7 because the salt formed, ammonium chloride, is composed of a strong acid and a weak base 36 ee a Volume of acid added/em? Age pH cuve fora wesk acid-weak base tration Notice that there is not any steep section to this graph. Instead, there is what is kmawn as a ‘point of inflexion’. The lack of a steep section means that itis dificult to do a titration of a weak acid against a weak base using an indicator. The reason for this will be explained in Section 12.2.3, Acid-base indicators Earlier in this section, we looked at the pH titration curves ccbrained when an aqueous solution of an acid is added to an aqueous solution of a base, The four cases we considered were: + strong acid-strong base + weak acid-strong base «+ strong acid-weak base + weak acid-weak base ‘We are now going to use these four curves to help us understand ‘wy different indicators ate required for different types of titrations, ‘An acid-base indicator is either a weak acid or a weak base. Most indicators are weak acids (Hin). For an indicaror that is a weak acid, its dissociation in aqueous solution can be represented as Hin(aq) = H'(aq) + In-{aq) ‘The molecule, Hin, and its conjugate base, [n~ have different colours in aqueous solution. For methyl orange these are red and yellow respectively: Hin(eq) = H'(eq) + In (eq) red yellow ‘When [H"(eq)] is suficiently large the equilibrium will shift far ‘enough to the left for the red colour to predominate. If [H"(2q)] is very low then the equilibrium will ie far over to the right and the yellow colour will predominate. Hence, the indicator changes colour according to the pH of the sotation0 ‘There will he a stage at which (Hn(aq)] = [In-(aq)], and the indicator will appear orange. The exact pH at which this stage is reached can be determined using the equilibrium constant, Kis, for methyl orange. (H"@q)]fta"[eq)) 7 [Hin(aq)] ‘When (Hin(eq)] = [In"[aq)], the expression becomes: ([H*(agi] = 2.00 x 10-4 mold ‘This gives a pH of 3.70 for the ‘haliway’ stage. So, methyl orange wil change colour at a pH of 3.70. 00 x 10-* mol dm# Note this pH value is also the same as the value of pi, for methyl orange. Therefore, the pH at which different indicators will change colour can be determined from their pX;, values. pH range of indicators Asa ‘tule of thumb’, the red colour of methyl orange will first predominate when [Hin(aq)] i ten times (In-(aq), and the yellow ‘colour wil predominare waen [In-(aq}] is ten times [Haag] ‘The approximate pH at which each colour predominates can be caleulated as follows, When [Hln(aq)] = 10[la-(ae} UH eq)lin“taa)] i9fia-faal (H*(@q)] = 200 « 10-* mold? So the pH at which the red colour first predominates is 2.70 = 2,00 x 10-4moldm-# A similar calculation will show thatthe pH at which the yellow colour frst predominates is 4.70, ‘The ‘pH range’ of methyl orange is therefore approximately 2.70 10470, ‘The exaat pH range of methyl orange is 3.10 to 4.40, This means that at pH below 3.10, methyl orange will appear red. At pH above 4.40, methyl orange will appear yellow. Between 3.10 and 440, methyl orange will be a shade of orange. Table A shows the pk, values, pH ranges and colours of several common indicators a] ra nge Colour 1} 3.70 | 310-440 | red methyl orange yelow bromophenolblue | 400 | 280-460 | yellow | blue bromothymol biue | 7.00 | 600-760 | yellow | blue phenol red 790 | 680-840 | yellow | red phenclphthalein | 930 | 820-1000 | colourless | red table Choice of indicator ‘A good indicator shows a complete colour change upon the addition of one drop of acid from the burette. This is necessary in order to accurately determine the end point of the titration ‘Therefore, there has to be a minimum pH change equivalent to the pH range of che indicator in order forthe indicator to successfully determine the end point. Strong acid-strong base titration Lets fit ofall consider the use of methyl orange anc penolthalein as indicators fora strong acié-strong bage tation. Fig F shows the pH titration curve for 25 em? of 1.00molden-* NaQH(aq) titrated with 1.00 mold“ HClaq). The pH ranges of methyl orange and phenolphthalein have also been included! 44 _ phenopalin TF ry eae Volume of acid added fig Song acid-stiong base pH curve ‘You will notice that the pH range of each indicator falls within the steep section of the curve, where a large pH change is occurring ‘pon the addition of just one drop of acid. This means that both indicators will change colour at the end point and therefore both are suitable indicators to use in this titration. Weak acid-strong base titration We shall now consider the suitability of each indicator for a weak aci-stong bas tivation, Fig G shows the pH titration curve for 25cm? of 1.00 mol drm-# NaOl(aq) trated with 1.00 maldm-* CH,COOH(aq), Once ‘again, the pH ranges of methyl orange and phenalpathalein have also been included. ou OS bh hb Ss hb Sh Volume of aid added? fig Weak acd-strong base pH cure 37‘This time, only the pH range of phenolphthalein falls within the steep section of the curve, So, phenolohthalein is suitable, but methyl orange is not. Strong acid-weak base titration Fig H shows the pH titration curve for 25 em? of 1.00 mol dm~* NH,(aq) titrated with 1.00 moldm-+ HC\(aq). Again, the pH ranges cf methyl orange and phenolphthalein have alsa been included. pH oP he ah a we a so Volume of acid added fig Srong acid-woak base pH euve. ‘This time, only the pH range of methyl orange falls within the steep section of the curve, So, methy! orange is suitable, but phenolphthalein is not. Weak acid-weak base titration Fig I shows the pH tivation curve for 25.em' of 1.00 moldmm-* NH)(aq) titrated with 1.00moldm-® CH,COOH(aq). Again the pH ranges of methyl orange and phenoiphthalein have also been, included 8 on? é 5 — metry one 3 =e z a a oe ee a ae Volare of si deem? fig Wook 204-weak ise pH ane As there is no prominent steep section to the curve, neither indicators suitable In fact, the end point of a titration of a weak acid and a strong bbase cannot be determined using an acid-base indicator The end point of such a titration is best determined by measuring the temperature changes (thermomettc titration) or electical conductivity changes (conductomerric titration, 38 2@ Choosing the best indicator ‘The best indicator to choose for a particular titration is the cone whose pi, value is as lose as possible to the pH at the ‘equivalence point. Bromothymel blue (pK, = 7.00) is a particularly good indicator for a stroag acid-strong base titration. 1 The equation or the ection between hydrochloric acid and Cag) + NJaq)— Neg) 25 0em? sample of 0.0200 mod HCl) was placed ina conical fla Adueous ammonia was added gtachaly roma bare andthe pH as meauredfter each addon uni the pH rolonger change The pH cue forth traton shown below 4 8 a pl "2 D &" do ‘Volume of ammonia gelation aed em (a) State how the curve suggests that ammonia i weak base, (b) Use the information given to calculate the concentration ofthe ammonia olution. (c)_ The pH ranges for three indicators are: Thymol biue: 1.21028 Methyl red: 42 to 63 Thymolphthalein: 93 0 105 Explain which of these three indicators is the most suitable for this titration Calculate the pH at 298 K of an aqueous solution of CH;COOH ‘of concentration 0.100 mol dm. [k= 1.74» 10-5 mol dm at 298K] ‘Sketch the pH tration cure forthe addition of 50.0cm? €f 0.100 mol dm? NaOH(aq) to 25.0¢m} of 0.100 mol dav? CH,COOHiaq) (4) State two differences inthe pH curve that would be obtained if the titration were repeated using 25 0m of 0.0500 mal der? CH,COOH(aq) instead of 25.0 cm? of 0.100 mol dm? CH,COOHIaq), (6)Buffer solutions By the end ofthis section, you should be able to. © understand what is meant by the term ‘buffer solution’ (© understand the action ofa buffer solution © calculate the pH of a buffer solution given appropriate data © calculate the concentrations of solutions required to prepare a buffer solution of a given pH © understand the roles of carbonic acid molecules and hydrogencarbonate ions in controlling the pH of blood Whatis a buffer solution? Many experiments, particularly in biochemistry have to be performed in aqueous solutions of fairly constant pH. Unfortunately ‘tis impossible to make a solution whose pH is totaly unaffected by the addition of even small amounts of acid or base. However it {is possible to make @ solution whose pH remains almost unchanged ‘when small amounts of acid or base are added. Such a solution is called 2 buffer solution, ‘There are many ways of making a buffer solution but two of the ‘most common are + tomix a weak acid with its conjugate base + tomix a weakbase with its conjugate acid ‘A buffer made from a weak acid and its conjugate base ‘The simplest example ofthis is ethanoic acid and sodium ethanoate, The salt of the weak acid has to be soluble in ‘water, which is why sodium and potassium salts are commonly sed fo make buffer solutions ln this mixture the acid is partially dissociated, whereas the satis {uly dissociated. The relevant equations are: CH.COOH(aq) = CH,COO (eq) + H'(aq) CH,COONa(aq) ~+ CH,COO"(aq) + Na"(ag) ‘This mixture will praduce a buffer solution with a pH less than 7 “The exact pH depends on the concentration of both acid and is conjugate base, and can be calculated as follows. Calculating the pH of a buffer solution For our example we shall use a solution that has been made by mixing equal volumes of 1.00mol dm ethanoic acid and 1.00 moleim* sodium ethanoate at 298 K. If we assume thatthe extent of dissociation of the acid is negligible, then the concentration of CH,COOH at equilibrium wil be 0.500mol dm ‘Also, agsn because the dissociation of the acid isnepligil, the concentration of the thenoate ions at equllbrium can be considered to be entirely made up fom the sodium salt. So, the concentration of ethanoate ions at equilibria is also 0.500 mol dr* Note the concentration of both acid and salt inthe mixture is half of the concentrations used because equal volumes of each solution were mixed, The total volume of the mixture is twice that af the original volume of each solution used A298 K, (CH,COO“(aa)IH"(aq)] [CHCOOH(eq)] Reatranging this equation and substiuting values for {CH,COOH(q] and [CH,COO"(aq) gives (Haq = (1.74 » 10°* x 0:500)/0500 mol dew 74% 10° moldm* Ke = 174% 107 meldm* ‘This gives @ pH forthe buffer salution of 4.76 aa [potential trap when calculating the pli ofa buffer solution f not appreciating that when two solutions are mixed there isa dilution, IFS0 cr of one solution is mixed with 50-cm? of another solution, then the total volume ofthe mixture wil be 100em®.So, the concentration of each solution will be halved on mixing. How does the buffer action work? When a small amount of acid is added to the buffer solution, the ‘majority of the Hi ions added react with the CH,COO™ ions 10, form CH,COOH molecules: CH,COO-eq) + Haq) + CH,COOH|ag) ‘When alittle base is added, the majority of the OH" ions added react with the CH,COOH molecules: CH,COOHIaq) + OH (aa) + CH,COO (ag) + H.0() Anew exulibrium mixture willbe established in which the concentrations of both CH.COOH and CH,COO- wil have changeel slightly from their orginal values So, there will be a change in pH, but ‘this wl be minimal. Ths is show by the flowing amument “To show that the pH has changed very litle, we once again need to make use of the expression for K, or the acid c= CHCOO eH) *[CH;COOH(aq)) Rearranging this equation gives: tag) 2.x, x EBCOOHLea)} (eal = & * TeH,COO-tea)] [As there area relative large number of CH,COOH molecules in the solution, as the extent of dissociation of the acid is very small the change in [CH,COOH|aq)] will be negiigible. 39)Also, as there are a relatively large number of CH,COO- ions present, resulting from the total dissociation of the CHCOONa, the change in [CH.COO-(aq) will be negligible. [CHCOOH(eq)), ‘This means hat hereto. COD aq] constant. ‘will remain facly If this ratio remains fairly constant, then (H_ (aq) remains fairly constant because, ata given temperature, Kis also constant, Jf (H*(aq)] remains fairly constant, then the pH remains fairly constant “To summarise, buffer solution of a weak acid and its conjugate ‘base maintains fairly constant pH because the ratio of| [CH,COOH(aq)] to [CH,COO (aq) remains fairly constant when smal amounts of either acid or base are added. ‘The best way to demonstrate the effect of adding a small amount of acid on the pH of a buffer solution is to caleulate the pH of the buffer both before and after adding the acid We have already calculated the pH of a buffer solution made ‘by mixing equal volumes of 1.00melém”# ethanoie acid and 1.00 moldm-+ sodium ethanoate at 298 K. It is 476. Let us imagine that we have mixed 500 cm* of each solution to make 1 Gr! of buffer solution, The amount CH,COOH and CH,COO™ in this solution will both be equal to 0.500ma} Let us imagine we have 1 dim? of this solution and we add 1.00 10° (0.0100) mol of HCI to it. To make the mathernatics, ‘easier, we shall assume that the volume of the solution does not change. 0.0100mol of HC! will provide 0.0100 mol of H’ ions. These will react with the CHCOO- ions in the bufferin a 1:1 molar ratio: CH,COO-(aq) + H"(aq) — CH,COOH(aa) “The amount of CHsCOOH present will now have increased from 0.500 to 0.510 “The amount of CH.COO™ present will have decreased from 0.500 v0 0490 mol. So, the new concentrations of acid and base present are: [CH.COOH(aq)] = 0510 mol dm? and [CH,COO (aq]] = 0.490 mol den? ‘The new hydrogen ion concentration is given by: etl ava nee Ne (Haq) = 1.74 « 10° x B38 ‘The new pH = Ig (1.81 x 10°) = 4.74 (to 3 significant figures) ‘The pH has changed by 0.02 units from 4.76 10 4.74 “To appreciate how effective the butter solution is in controling the pH, let us consider adding 0.0100 mol of H” fons to dm of deionised water 81 x 10% moldar? ‘The pH, at 298 K, of deionised water is 7.00 so: [H*(aq)} = 1.00 x 10° moldm=> 40 ‘Adding 0.0100 mal of H’ ions gives: (Haq) = (1.00 » 10-* + 0.0100) = 1.00001 x 10-* mol dm* ‘The new pH is given by: pH =~ Ig (1.00001 x 10-2) = 2.00 ‘The pH has dropped by 5 units as opposed to 0.02 units with the buifer solution, A considerable difference! The Henderson-Hasselbalch equation If you are convinced that you can remember equations, then the Henderson-Hasselbalch equation can be used to calculate the pH of a buffer solution Fora weak acid, HA, and its conjugate base, A", the following equation applies sony 2 x HiMea)) Hed = Tg “The concentration teens inthe equation ar, technically speci he concentrations a equa, However for easons we have already clscussed tis easonable 19 tals the orginal concentrations. ‘The original concentration of A” willbe the same as that of the salt, providing a sodium or potassium salt has been used. The ‘equation can nov be rewritten as: teeny =, « 20H = KX ait) If we take the logarithm to base ten of both sides of this equation we get ceo (ec g(tea) =e Ray Or. . fac “ald =— 18k la Tay Or: acid) H= PK ~ Ie Tay Or: = px, + 1g PH PK, + 18 Fecid} ‘This last equation is the most common form of the Henderson Hasselbalch equation ‘Leamming tip Do nat worry if you did not follow the derivation of the Henderson Hasselbalch equation. You de not need to perform this derivation but you may use this equation if you wish. The equation is also given in another form in which [base] replaces salt} since Ais the base in the butter. 1F we use the Henderson-Hasselbalch equation to calculate the pH of our solution containing ethanoic and ethanoate ions, both 6f concentration 0.500 mold we obtain: pH = 476 + Ig (0500/0500)= 476 (pk, = “Ig X, = ~Ig (.74 x 10-9 1g 1= 0] ‘This is the same answer as we obtained earlierA buffer made from a weak base and its conjugate acid ‘The most common example of ths type of buffers ammonia and the ammonium ion. The ammonium ion i usually supplied in te form ammonium chloride. This mixture will provide a buffer solution witha pH greater than 7. ‘The most convenient equilibrium to considers: NH,“ (eq) = NHyaq) + H(aq) ‘This mixcure provides a relatively high concentration of both NH, molecules and NH,” ions “The buffer works ina similar manner tothe weak acid-conjugate base system and the adcltion of acid results in the added H” ions reacting with NH) molecules NHfaq) + H’(aq) ~ NHe"(aq) ‘whereas the addition of base results in the added OH ions reacting with NH," ions: NH."(aq) + O (aq) —+ NH,(aq) + H0(0) ‘As there is a relative high concentration of both NH molecules and NHL” ions, the ratio of [NH(aq to [NH,"(eq] remains relatively constant upon the addition of small amounts of ether acid or base. Th results in the pH remaining fay constant because itis piven by the equation: (NFxCaq)} (NHa)) ‘As pK, i constant at a given temperature, the pH of the solution depends on the ratio of (NH.{aq)] to (NH, (a9) pH = pK, +g How to make a buffer solution with a required pH ‘To make a buffer solution with a pH less than 7, you need tose a rminture of a weak acid andits conjugate base. Conversely, to make a buffer solution with a pH greater than 7, youneed to use a mixture of a weak base and its conjugate acid Imagine we are faced with making a buffer solution of pH 5.00 ata ‘temperature of 298K, To make this solution, we need a hydrogen ion concentration, (H'(aq)) of 1.00 x 10° mold, The hydrogen ion concentration ofa buffer solton ofa weak acid andi conjugate bases calculated using the formula: vj} -k, «81 ee] = kay F we use ethanoic al asthe weakaci then K,= 174% 10-%molden IF we now substitute our known values into the equation we obtain. 100 105-174 105 86 [sat] This gives a value for fac] m r ay (100 105-174 «10 (to 3 significant figures) =0574 0 ‘o,f we were supplied with an ethanoic acid solution of concentration (0574moldm” and a sodium ethanoate solution of 1ODmoldm®, ‘we could mate a buffer solution of pH 5.00 by mixing equal volumes ‘of the two solutions. Tis would ge usa solution in which the acid ‘eencentrason was 0287 moldny" and the salt eoncentrason was ‘asdomaldm” (0287 - 0500) = 0574] eee] eee ee Oe eR and ammonium chloride be mixed to obtain a butler of pl 9.807 [K, for NH,*is 5.62 10°? mol dm) litle INHeteg] (Nea) "Naval INH INH The solutions therefore, have to be mised in a ratio by volume of, 355 NH,(aq) to 1 NH,Cllaq). pH =pk,+ 055 Controlling the pH of blood “The human body operates within a narrow range of pH values. For example, the pH of arterial blood plasma needs to be in the range of 7.35 to 7.45. Ifthe pH of this blood plasma were to ‘change significantly, particularly if i were to fall the way that the vehole body functions would be affected, ‘The pH of blood is controled by a mixture of buffers, the most important of which is the carbonic acid-tydrogencarbonate buffer mikcure. In this mixture the earbonie acid molecule, HsCO,, acts asthe ‘weak acid. The hydrogencarbonate ion, HCO", isthe conjugate base of H;CO., ‘The equilibrium that exists is represented by the equation: H,CO{eq) = HCO}(aq) + Haq) ‘Under normal circumstances the amount of HCO,” ion present is approximately 20 times that of H,CO:, As normal metabolism [produces more acids than bases, this is consistent with the needs ‘of the body. Any increase in the concentration of hydrogen ions inthe blood, by for example the production of lactic acid in the muscles, results in the equilibrium shown above moving tothe lft as the added H* ions react with the HCO; ions, ‘The pH of the blood can also be raised by a variety of respiratory and metabolic causes, For example, the overuse of diuretics increases the amount of urine exercted from the body, If the urine contains large amounts of acids then the pH of the blood will increase, If this happens, the equilibrium shown above will move to the right as the H,CO, molecules ionise to increase the H” ‘concentration and restore the pH to its normal level aa2 ‘This is considered to be the most important buffer because itis coupled with the respiratory system of the body. Carbonic acid is not particularly stable and in aqueous solution it decomposes to form catbon dicxide and water: H,CO,{eq) = CO,(aq) + H,0(aq) Ilis the respiratory system that is responsible for removing carbon dioxide from the body. Aqueous carbon dlaxice exists in equilibrium with gaseous carbon diexide: CO,{g) = CO,faq) ‘Combining these three reactions gives us: CO.(g) + H,0faq) = CO,{aq) + H.Ofaq) = H,CO,aq) = HCO+ (aq) + H"(aq) ‘When these equilibria shift tothe left as result of an increase in hydrogen ion concentration, the concentration of carbon dioxide in the blood increases. The carton diaxide leaves the blood in the lungs and is then exhaled, thus maintaining the normal pH of the blood 1.) explain what is meant by the erm ble sltr! (0) Explan howan aqueous oon contig a miu of methanok acid, HCOOH and ptasum neurone HCOOK acs asa olen (0) bute slain contin equal concentrations of methanol aid and ptasium methanoate Explain te effec onthe pt ofthis solution of adding some solid potasium methanoat. (6) caelte the pi, at 298K, of bul slution madeby mixing qual lume of 100 meld methane act and @500mol dn potas retaoate (sHCOOH) «179.10 mold] 2 A student prepares two solutions Seaton As prepared by mixing SOcr’ of 0.100 mol dm*CH,COOH(aq with 25m’ of 0.100 old NaOH Solution B us prepared by mixing 25cm of 0.200 mold *CH,COOH{aq) wth SOc of 0.10 mold NaOH(aq). Esplin iy Slatin Asa buffer soto, but soliton B isnot 3 A bufer solution wat made by mixing SOem? of 0 200 mld? aqueous armenia, Neg wth sem? efaqueousammonium chore, Nice) The li othe resulngsokrion nas 938 Cleat the coneantatono the NHChag) sed [KANH,') = 5.62 « 10" mol dav] 4 cataate the pt of a bul slation containing 1220 of beac acid {C.H,COOH) and 720g sodium benaate(H,COON in LO dno soon [pK.{CsHsCOOH) = 4.20) 5 ike water iu aera undergone sociation DN == NH = Ny (0) explain why amimoniacan be casted as an ampheterie substance. (2) For each ofthe folowing substances indicate whether a soto of Iqid anmonia willbe‘! base ot ea! {i) Ammonium chloride, NH CI (ii) Sodium amide, NaNH (i) Potassium hye, KOH Key definition {A buffer solution is 2 solution that minimises the change in pH when a small amount of ether acd oF base Isadded.Buffer solutions and pH curves By the end of this section, you should be able to... (© understand how to use a weak acid-strong base titration curve to: (i) demonstrate buffer action (i) determine k, from the point at where haifthe acid is neutralised Buffer action during a titration Fig A shows typical pH curve cbtined when a weak acids rated against strong base 1 t A 4 in ° : wa ‘ : | ‘ / | of amram | 1 r OTE bb hs ee OB ‘Volume of base added em A Svong base-neak acid pH cur shoning bul range In the region marked ‘buffer range’, the change in pH as the base is added is gradual. Over this range there is @ considerable concentration of both acid and conjugate base molecules, This mixture is displaying buffer action, Determining K, from a pH titration curve ‘This experiment involves performing a titration with an aqueous solution of a weak acid in the conical fiask. A standard solution of a strong base, such as sodium hydroxide, is added from a burette and the pH of the solution is measured after each addition, ‘A graph of pH against volume of base added is then plotted. From the graph, the minimum volume ‘of base required to completely react with all of the acid is determined. Thia is the volume at the ‘equivalence point. ‘The graph is then used to determine the pH at the half equivalence point. This pH value is equal to the pX, value of the weak acid. From this it is a simple matter to calculate X. for the aca. Atypical pH titration curve is shown in fig B, ‘The volume at the equivalence point is 25 cm, so the volume at the half-equivalence point is 12.5 cm. The pH when 125 em* of base is added is 4.80. ‘The pk, of the acid K,for the acid 58 x 10-?meldmr* Bequivalence point pH oD a a do a5" So ‘lume of nase aded/cm? ig Sirong baco-wol ac pH curve showing equiaience a 5 equtalence pon, ‘Supporting theory ‘The theoretical justification for determining K, for a weak acid by the method shown above is quite straightforward ‘The mixture atthe half equivalence point is a buller solution (as stated above). The pH of a buffer solution is caleulated using the folowing equation: salt ptt ‘Atte half-equivalence poine [salt] = facial, so [salt/facia = 1 ‘The logarithm to the base 10 of 1 (ig 1) = 0. So, the equation becomes pH= pk, Alternative method ‘This method has been called the ‘half-volume method. + Using a volumetric pipette, place 25.0 cm? of an aqueous solution of the weak acid into a conical flask + Add a few drops of phenolphthalein indicator + Titrate against a solution of aqueous sodium hydroxide until the end point colour is obtained, + Note the volume of sodium hydroxide required. This is the minimum volume required 10 completely react with the acid, + Use a fresh 25.0.cm? sample of the same aqueous solution of the wealc acid and the same aqueous solution of sodium hydroxide, bur this time do not add the phenolphthalein + Add only hal/the volume of sodium hydroxide requited to react with the acid ‘+ Measure the pH of this solution. This pH value is equal to the pX, value of the acigaldarV omar Me) MULT lien cole strong and weak acids By the end of this section, you should be able to... (© understand why there is a difference in the standard enthalpy changes of neutralisation values for strong and weak acids Standard enthalpy change of neutralisation In Book 1 we defined the standard enthalpy change of neutralisation as follows: ‘The standard enthalpy change of neutralisation (gas) is the enthalpy change measured at 100kPa and a specified temperature, usually 298 K, when one mole of water is produced by the neutralisation of an acid with an alkali We also explained that the standard enthalpy change of neutralisation of a strong acid with a strong base will always have 2 very similar value, because strong acids and strong bases are almost fully dissociated in aqueous solution. This value is around -97.6k) mol" ‘Table A shows the values of the standard enthalpy changes of, neutralisation for various weak acids with the strong base, sodium hydroxide, ‘CH,COOH 552 HEN “12 He 686 table a, [cis interesting to note that for two of the weak acids, CH,COOH, and HCN, the magnitude of the value of A.,..A® is less than that for a strong acid-strong base (ie. less than 57.6), but the ‘magnitude of the value for HF is greater than 57.6. ‘The equation for the reaction between a weak acid, HA, anda strong base such as sodium hydroxide can be represented as: HAfag) + OF (aq) — A(aq) + H00) ‘The major difference in this reaction, compared to that of a strong acid with a strong base, is that the majority of the acid molecules are uncissociated. Obviously energy will be required to dissociate them, and this may explain why less heat energy is given out when both CH;COOH and HCN are neutralised by NaOH. However it does not explain wity more heat energy is given out ‘when HF is neutralised by NaOH. There must be at least one other energy term involved. Inthe above argument, we have ignored the fact chat, once the acid molecules are dissociated (which is an endothermic process. the ions formed will then be hydrated by the water molecules present inthe aqueous solution. Hydration of ions is an exothermic process, so heat energy willbe generated. The two processes can be represented by the following equations for a ‘weak acid of formula Ha: Haag) — H'(g) + A(@) AW = ted mol” DISSOCIATION (endothermic) H'(g) + A (g) + H'(aq) + A (aq) AH = -yk) mol HYDRATION (exothermic) 1F the magnitude of xis greater than that of y, then the overall heat energy change involved in dissociating the acid molecules and then hycrating the ions wil be endothermic. Tiss the case with CH,COOH and HCN, However with HE the enthalpy change of hydration of the ions releases more heat energy than the dissociation of the molecules takes in, Hence the overall effect is thatthe standard enthalpy change of neutralisation of HF by NaOH is greater than 576kImol 1 pin why reactions betucen strong cid and tong basal fave values forthe andar enthalpy change of revaleaion of about 57H) mol 2 explain wy the standard ental change of eutalsation forthe reacion bohween aqueous ammonia and aqueous hese ted 52 2y)mot and at met 3 the standard enttalpy change of neualtaton of HCN() eth KOH(aq) is -11.7K] mal”, predict value forthe standard enthalpy change of neutralisation of HCN(aq) with NH, (aq) 45NG A GROWING PROBLEM Ocean acidification impairs muss abilty to attach to surfaces. This is an alarming prospect for commercial mussel growers who farm in the waters around Puget Sound, USA. cide erp PENN COVE, Wash, — Cookie tay in hand and lifejacket around ches Laura Newcomb looks more like a confused baker than « marine biologist Bul the University of Washington researcher is dressed for work. Her jobs testing how mussels inthis idyllic ny, hoe to the nation’s largest harvester of mussel by changing ocean conditions, especially ‘warmer and more aed waters. IS a question criieal to dhe future of rmssel farmers inthe region, More important, i's key to understanding ‘whether climate change threatens mussels around the word aswell asthe {ood chains mussels support and protectin the wild ‘Along the West Coast, mussels ae well-known ecosystem engineers, said Bruce Menge, an Oregon State University researcher who studies how climate impacts coastal ecosystems, ‘They provide habitat for dozens of species, thoy provide food for many predators and occupy’ large amount of space, so are truly dominant 20 million years Carbon dioxide from greenhouse gas emissions has steadily turned seawater more aid, disrupting organisms accustomed tothe sig alkaline waters of the past 20 milion yeas In the case of misses an arlier Unversity of Washington lab study found tht inereased Oat pe IT ce eee! Where else will] encounter these themes? 46 MUSSELS LOSE FOOTING IN MORE ACIDIC OCEAN cathon dioxide weakens the sticky fibers, called byssus, that mussels ive by clinging to objects like shorelines or the ropes “IF byssal dread weakening does eventually become important! Menge added, the consequences wok he major i rot catastrophic, Newcomb's goal sow isto apply in the eal world what was learned inthe Ia. “Instead of spending alo of time tightly controlling the remperatu and pH conditions mussels grow in, Tuse the natural seasonal varation to | ‘uy to assver the sume questions, Neweomb said, | [Neweomb's fed office isthe rear deck ofa harvesting boat ~ right between the toilet and the microwave. The quarters are cramped, but the view is grand: The blue waters of Penn Cove oa Washington sa ‘Whidbey Island aro st gains rolling bluffs and snow-capped mountains, 30 percent increase in acidity ‘The University of Washingron marine biologist i there courtesy of Penn Cove Shellfish, sibich is also the oldest and best know mussel operation in the United States. If you're a mussel fan, you've probably had few ~ they'te sold at Costco as well as upscale restaurants ueross the country Placing justharvested mussels on her tray, Newcomb samples for size, ‘hioknoss and strength, The mussels are grown on 21-foot-long fopes hanging ftom several dozen rafts in the bay, and Newcomb takes samples from two depts: 3 feet and 21 feet. She also samples water temperate and pH levels at those dep Prior tothe Industrial Revolution and the explosion of manmade COs, ‘ocean pH averaged 82, Toki 8.1, «30 pereent incr the logarithmic scale, Computer models peg ocean acidity at 7.8 7.7 by weinacidiy on | the end of the century at the current ate of greenhouse gas cmissions. ( 2 ‘Washington State isa bit ahead of that curve becanse ancien carbon stores in the deep ocean are periodically chumed up by local currents The surprising lab discovery was that mussel byssus weakened by 40 ent when exposed ta a pH of 75. At Penn Cove, low pH Teves aro common ~ Newcomb has even scen 7.4 in the year that shes Been sampling. “We're worried they're going to se it more Frequently said Emily Neweombs graduate adviser and leader ofthe University of ir lab ress, f { 3 P 3 velear Let us start by considering the nature of the writing in the article UTE 1. This article is not taken from a scientific journal buts instead designed to draw a wider ip SOU oUUsyYy audience's attention to a pressing environmental problem. Identify writing techniques in LL premier ‘tary the text that the author uses ta make the science more accessible een when the Now we will look atthe chemistry in detail, Some of these questions wil ink to topics eater in this || SCl€%Ce has implications book er Book 1, so you may need to combine concepis from diferent areas of chemistry to work || "decision making in) ut the answers: Some questions wil also link to topics covered later inthis ook. Dont worry if you { \S0cicty ; are not ready to give answers to these questions yet. You may like to return to the questions later 2. Write an equation for the reaction of carbon dioxide with water to form hydrogencarbonate ions and H'(aq) ions. 3. a. Using the relationship pH = -Ig [H'] show that a change in pH from 8.2 to 81 is approximately equivalent to a 30% increase in acidity b. Calculate the pH of the ocean ifthe acidity increases by 100% from a starting pH of 82, 4, Many sea organisms form shells made of calcium carbonate. Use the equation belowto | (PWV. IVy. explain why increasing levels of carbon dioxide inte irare making ths process — ee i increasingly difficult. et Tit about how an a“ CO,{aq) + COF*(aq) + H.0()) = 2HCO; (aq) | | diovice vous sti 5. Many organisms use intracellular HCO,” ions to buffer changes in pH. Use equations to the equilibrium oF this show how HCO,” ions can buffer small changes in H"(aq) and OH (aq). (easton. and theretone 6. The equation for the dissociation of carbonic acid in water can be represented as: { ( aes o} H,COs{aq) = H(aq) + HCO¥ (aq) en a. Write an expression for K, for carbonic acid b. Given thatthe value ofthis pk, is 63 and thatthe pH of blood is 74, calculate the ratio of hydrogencarbonate ions to non-dissociated carbonic acid molecules in blood plasma. ‘c. What assumptions have you made your answer to question 6b? Activity Did you know! March 2014 waste fist trom in which te average timospherc carbon donde ‘The molecule histidine fs one of the 20 amino acids that make up all proteins Histidine residues in haemoglobin molecules are also involved in buffering the blood's pH. Research and create a presentation suitable for GCSE Chemisty students addressing the questions below. lt earl soon + What does a histidine molecule lock like? milestone. But carbon dioxide + Which part of the molecule acts asthe proton donor and which as the proton acceptor? is notalonein causing climate change. oxides of niteagen and methane and minute trace amounts of other gases such as SF, are factored in, the ‘equivalent CO, atmospheric concentrations about 480 ppm. + Histidine can frequently be found at the catalytic centres of enzymes. Can you supgest why? (© From The Daily Climate by Miguel snes iw dal yliateerfe-newssoom 201A sciiestiommusels2 1A fruit juice contains a monobasic acid HA. (2) The fruit juice has a hydrogen ion concentration of 250 x 10-!moldm-%, Calculate the pH of the fruit juice 2] (b) A.25.0cm sample of the fruit juice reacted exactly with 26.70cm of 0.0100 moldr sodium hydroxide. () Write a chemical equation for the reaction taking place, State symbols are not required. i) (i) Calculate the concentration, in mol dir, of HA in the fruit juice (3) (ii) Compare your answer in (o\i) to the hydrogen ion concentration and hence make a deduction about the strength of the acid, HA. in the fruit juice. a (c) (Write an equation to represent the dissociation of | HA into its ions in aqueous solution in} (@) Write an expression for the acid dissociation constant, K,, of HACaq), ty (ii) The value of K, for HA(aq) is 6.00 10-*rnol dm" Calculate the concentration of the undissociated acid under these conditions. 2) (Total: 12] 2 A mixture of ethanoie acid, CH,COOH, and its sodium salt CH,COONa, can act as a buffer solution, (a) State what is meant by the term ‘buffer solution a (b) Explain how a mixture of ethanoie acid and sodium ethanoate acts as a buffer (4) (c) Abuffer solution is made by adding a solution of sodium hydroxide, of concentration 1,00mol dm, toa sample of 1.00mol dm”? ethanoie acid until half of the amount of acid present has reacted. Calculate the pH of this buffer solution, [K, of ethanoic acid at the temperature used is 1.70 x 10-Smoldm-4] 3] [Total: 9] 3 The values of the ionic product of water Kare 1.00 10" moF dm”? at 298K and 5.48 x 10"'mol?ém-* at 303K. (@) Calculate the pH of water at each of these two temperatures. (4) (b) Using your answers to (a), comment of the validity of the following statement: "Pure water is neutral because it has a pH of 7. (a) (c) Show that the data supplied can be used to deduce the sign Of AH for the dissociation of water into ions. ia) (Total: 8] Exam-style questions 4 In 1923 Johannes Bronsted and Thomas Lowry proposed. independently a theory that wien an acid reacts with @ base the acid forms its conjugate base. The theory is known as the ‘Brensted-Lowry’ theory. (o) State what is meant by the term conjugate base. [1] (0) (0) Ineach of the two equations identify the species on the left-hand side of the equation that is behaving as a Bronsted-Lowry aci. re) Equation 1 CdHsCOO™ + HF = CcH.COOH + F Equation 2 CH COOH + CN" = C.H.COO™ + HCN Gi) Explain the relative strengths of the three acids involved in the two equilibria. [Assume that both cequilbria lie well to the right hand side “ (c) Liquid ammonia, like water, undergoes self-ionisation, according to the following equation: NH, + NE, = NEU" + NH." For each of the two substances listed, explain whether solution in liquid ammonia would be ‘acidic’, basic’ or ‘neutral () Ammonium chloride, NHC (i) Sodium amide, Na*NH,- (4) (Total: 11) 5 Sullur dioxide reacts with water to produce sulfurous acid, H,SO,, which is a weak, dibasic ac ‘The equation for the fist dissociation into ions is: H,SO aq) = Haq) * HSO;(aq) Ko (298K) = 120 x 10-?moldm? (a) Calculate the value of py for H.SO,, u (0) Use Ky) t0 calculate the approximate pH of an aqueous solution of 0.500 mol dm H,SO; at 298 K (3 (c) The measured pH of 0.500 maldim* H,SO, is slightly lower than that calculated in part (b). Comment on a possible reason for tis difference. ti) (2) The constant Khas a value of 1.00 x 10°" mol? dm at 298K (0) Give the name of the constant K. i) Gi) Write the expression for ky a (e) Potassium hydraxide, KOH, isa strong base in aqueous solution, Calculate the pH of 0500 moldm-* KOK. 3] [Total: 10}6 Hydrochloric acid, HCi(aq), is usually sold as a solution. The solution is made by dissolving hydrogen chloride gas in water A chemistry technician bought 25.0dm* of 10.00 aol dma? hydrochloric acid {a)_{) Calculate the volume of hydrogen chloride gas that is required to make ths solution, (Assume that the molar volume of hydrogen chlavide is 24.0drs?mal- under the conditions used) 2) (Describe how the technician could make 5,00 den# of 0.0200:mol dn hydrochloric acd from the 10.00mol de® stock solution of ytrochloric acid. [3] {b) Calculate the pH of 0.0200moldm”* hydrochloric acid. (1} (6) Hyerochlovie acid reacts with ammonia to form ammonium chloride NH (aq) + HCi(aq) = NH,Claq) A.25.0cm? sample of 0,020 mol dm” hydrochlorie acid is placed into a conical ask. The pH of this solution is messured using a pH meter Aqueous ammonia was gradually added and the pH was measured after each addition, until the pH no longer changed ‘The diagram isa graph of the results cbtained im ie wo 8 pi 0 0 5 10 15 20 25 30 35 40 45 50 Volume of aquesus ammorin adced/ern! (@ Explain how the pH at the equivalence point shows that ammonia isa weak base, ei (i Calculate the concentration of the aqueous ammonia, 2) (ii) ‘The table shows the px, values for three indicators Indicator PKa thymol blue LT. methyl Fed 51 ibymolphihalein | 97, Explain which of these three indicators is the most suitable for the titration 2) [Total: 12]Introduction People lived very simply in the Stone Age, with their energy needs being supplied by the Sun and by plants and trees that could be burned. Because the plants and trees were continuously renewed, and populations ‘were small, energy supplies during the Stone Age period were plentiful. However, this simple lifestyle has almost completely vanished, and people today cannot survive without abundant fuel Today, most ofthe worlds energy is supplied from fess fuels, which consist of natural gas, coal and products from crude ol such as gasoline, diesel and kerasene.Fossl fuels ae not renewable and will one day aun out ‘To manage these energy resourcesand develop new fuels we need to understand how energy is released or Used in chemical reactions, including the reactions in plants animals and our own bodies. Energy is the very essence of chemistry as well as of civilisation as we know it. In chemistry it determines vihich reactions can occur and which compounds can exist. You have already met a large number of chemical reactions Allo these reactions either absorb or release energy. In this topic we shall develop an Lunderstanding ofhow to measure and report these energy changes, Have you ever wondered why water evaporates? Why hot objects cool? Why hydrogen combines with ‘oxygen? Why green leaves turn red in the autumn? Why anything happens? Part ofthe answer is related to energy. We need energy to think, to move and to live. Every chemical reaction makes use of energy to rearrange the bonding between elements in compounds. Thermadynamics deals with questions lke these. In the second hal of this topic we shall deal withthe second law of thermodynamics, which goveens the direction of natural change, The second law enables us to predict whether or not a reaction has a tendency to ‘occur, and to what extent itil occur. This law is oF fandamental importance in chemistry sine it provides a basis for discussing explaining and predicting equilibria, the subject of Topics 11 and 12 in this book. Its also the foundation of the whole field of electrochemistry, the subject of Topic 14 All the maths you need rere eae cere eee ee eet eter err eaee eee trate Seer ee etre il aR rat chino + Usean appropriate number of significant figures + Change the subject of an equation + Substitute numerical values into algebraic equations using appropriate units for physical quantities + Solve algebraic equations + Use logarithms in relation to quantities that range over several orders of magnitude aS jae Rs es be toat pee Sil La Pre torelr Standard conditions of temperature and pressure ema Cen Ree ere Meee ee oo See a Can 1 | Mirae nares er pesonrieny aa A RIC Re) pee ee es Se ener) viens ee ee ee eee eee reeset ar cer ee ee een Cy arene tae * ByLattice energy, Ajaiice4, and Born-Haber cycles By the end of this section, you should be able to: © define lattice energy. Sea © understand that lattice energy provides @ measure of the strength of ionic bonding © define the terms: (i) enthalpy change of atomisation, S.H ) electron affinity, E., © construct Born-Haber cycles and carry out related calculations © understand the effect of ionic charge and ionic radius on the value oflattice energy Lattice energy In Book 1, we sw that bond enthalpies canbe used a a measure of the strength ofthe covalent bonding in molecules. The feaivlon enetay change lor onic boling ionic compounds is Tati energy. Sonar late enthalpy) “The lattice energy of a compound isthe energy change when one ‘mole of the ionic solid is formed from its gaseous ions. If standard conditions of 100kPa and a stated temperature (usually 298 K) are applied (as indicated by #), then the energy chang is called the standard lattice energy. “The equation that represents the standard lattice energy of| sodium chloride is: Natig) + Cr(g) > NaCl) For magnesium chloride iis: Mgi"(a) + 201 (g) + Macs) SussceH!® = ~780 I mol! Mvicell® = ~2526KJ mol” Learningtip ‘The terms “attice energy and atice enthalpy’ are commonly used as If they mean exactly the same thing - you wll ften find both terms used within the same textbook article or website, including some University websites. Infact there isa difference between them that relates to the conditions under which they are calculated. However, the diflerence issmall.n fac, ts negligible compared with the differing values for lattice energies that you will ind from diferent data sourees.| Unless you go on to study chemistry at degree level, the difference between the two terms eed not concern you. 52 Didvou know? There are two ways of defining atice energy. The one mentioned in the specification i the one we have srescy cefined. Theis sometimes called latice energy of formatin, since the compound is being formed from ts ions. Using this definition, the energy change wilalways be negative. However, ome books define itas latice energy of dsocation in lich te he energy change when one mole ofthe compound fe broken down (or dissociated) ito its ions this case the energy change wl be positive. Factors affecting the magnitude of lattice energy ‘You will ave noticed that the lattice energy of magnesium chloride, Mge"(CI?) is much lager (-e. more negative) than that of sodium chloride, Na*CI-. A number of factors are responsible for this ciflerence ‘The first thing to realise is that a magnesium ion carries twice the charge of a sodium ion. Secondly, there are more cation-io-anion interactions in ‘magnesium chloride because there are twice as many chloride ions per cation than in sodium chloride, A third factor that determines the magnitude of the lattice energy is the distance between the centres ofthe cations and their neighbouring anions. which is equal to the sum of their ionic radi ‘This distance is determined in part by the relative sizes of the ‘ons involved (the Mg?” ion is smaller than Nat, thus reducing the sum of the ionic radi) and also by the type of lattice structure the ‘compound has In fact, the relative ion sizes determine the type of lattice structure. "The effects that both the interionic distance and the changes on the ions have on the lattice energy are illustrated in table A. Send eee ee ri ro 7 Ta 15 a8 cr as a0 7 wa a ni oa ae as a a ach ‘Comparison of LiF and Naf. where the charges on the ions are the same, shows that a decrease in the distance between the centres of the two ions (the inter‘onie distance) results in a more negative value forthe latice energy.ER Comparison of NaF and CaF, where the interioio distances are almost the same, shows that an inerease in charge of even one Of the ions (Ce'* as opposed to Na") results in a more negative value for the ionisation energy: Similar comparisons can be made between Li,O and MgO and also between Li,0 and Al,O,. Finally as we shall see later in this topic, there are also covalent Interactions between the ions, and these affect the magnitude of the lattice energy. The values quoted in table A take these interactions into consideration since they are caleulated values using a Born-Haber cycle (see later inthis section) ‘earning tip Lattice energies are determined by «the magnitudes ofthe charges on the fone + the sum of theionic radi + the ype ofltice structure «the extent of covalent interactions between the ions [A Aleve, you ae not required to know the different types of lattice steucture.Inadltion, the extent of the covalent interactions already taken into consideration in the quoted values for lattice tenergy. Therefore, you need only consider the magnitude of charges fon the tons and the sizeof the ions. Standard enthalpy change of atomisation, AyH* The enthalpy change measured ata stated temperature (usually 298 K) and 100kPa when one mole of gaseous atoms is formed from an element in its standard state is called the standard enthalpy change of atomisation o the element Its given the symbol f= Equations representing ome standard enthalpy changes of axmistin a 298 Kate given below Ce) Cig AH = +717 mol Nafs) > Nalg) Aye? = +107) mot* 4HAg) Hl) Agdf* = +218kJ mol! Fh) Clg) Ay? = +1204) mor? hearmingtip Note thatthe standard enthalpy change of atomisation isthe enthalpy change when one male of gaseous atoms formed. nthe ‘ase of elements that exist as polyatomic molecules, itis not the enthalpy change when one mole of gaseous molecules is atomised Electron affinity ‘The first electron affinity of an element, 2, is the energy ‘change when each atom in one mole of atoms in the gaseous state gains an electron to form a —1 ion, ‘The equations below represent the first electron allinties of some elements Cig) te = Cre) Egy) = “349% mol Brg) + €- = Br(@) Egy = 825K) mol Og) + OK) Fg) = 141 KI mol ‘The first electron affinity has a negative value for many elements, including the alkali metals. As examples, the E,4y) of Liis 60kJ mol and the £4) of Ne is ~33kJ mol". There is @ notable exception with the noble gases, For these, repulsion ‘caused by the elecirons already present inthe valence shell results| ina positive value for te fist electron affinity as the additional electton would have to occupy a new valence shell In contrast, second electron affinities, Fag, tend to be positive, For example: O@+e 0%) Eos ‘Therefore, the formation of the oxide ion, O, in the gaseous state {rom its ator inthe gaseous state is an endothermic process overall Ofg) + 22° + Og) Eugs) + Fagpj = +657) mol ‘This raises an interesting question: why does exygen form O* ions in its binary ionic compounds rather than O ions, as the O- jon would appear to be the more energetically favourable state? We will attempt to answer this question later inthis topic. 798k) mol! Born-Haber cycles “We are non a position ro consider the overall eneray changes that take place when an ionie compound is made rom its elements, These energy changes are surmaried in an eneTgy level diagram called the Born-Haber eye Fig A shows the Bom-Haber cyte fr sodium chore. Na") + e+ CMG) Nev) + 19 Naw Cre) +496 Enesay Nap 301 Nats) #018) fig A Bom-Haber cycle for sou chloride ‘The cycle includes the following energy changes, all of which can bbe determined experimentally: + The enthalpy change of formation of NaCl(s), AdifNaC(s)] = 411k mol! + AgHINals}] = +107KJ mol! 53Learningtip __ Note: see Book 1 Section 1.1.4 and 8.1 fora reminder of these definitions, 54 + The first ionisation energy, Ey (Na(g) + AGHICI3(g)] = +122 mol + E-{Cilg)] = -349kI mol Applying Hess's Lav to the cycle gives us: +107 + 496 + 122 + (—349) + Miyscel = —411 Hence: AegceNACKS)] ALL — 107 — 496 ~ 122 + 349k mol” 187k mel" Did you know? ‘Why is calcium oxide CaO and not Ca°O"? ‘You may be wondering why we have asked this question and think thatthe ansivers obvious Surely, you might sy, itis CaO because that way both ions will have a stable noble gas electronic configuration, If this is what you believe, then the following may come asa surprise. Acquiring a noble gas electronic ‘configuration is not a reason for electronic changes to take place when atoms and molecules react ‘together. Afterall, many ions exist in stable compounds, in particular cations ofthe transition metals, in hich they do not have the electronic configuration ofa nable gas. In fact, compounds in which the ions do havea noble gas electronic configuration are in the minority. So, why does calcium oxide formas CaO and not as Ca°O°, and why are we asking the question? ‘You may remember that we have mentioned thatthe formation of ©) from Ofg) is exothermic: fg) +e +O) Faq)= 141) mol” However, the formation of O*() from Ofg)is endothermic: lg) + 2 O%(g) Fag) Eagy = +6574] m0! ‘Since more energy is required, why is the formation of the O*- ion preferred over the formation of O°? ‘A similar pattern is observed with the formation of Ca’(g) and Ca*(g) from Calg]: Calg) Cag) +e (ey = #5901) moi Calg) Cag) +20 (egy #y= #17354) mal Similac, since more energy is required, why is the formation ofthe Ca”* ion preferred over the formation cofthe Ca ion? To answer this question tis necessary to consider al ofthe energy changes involved in the formation of Anionic compound from is elements -not|ust those involved in the formation ofthe gaseous ions from the gaseous atoms. In other words, we need to look atthe information supplied by the Borr-Haber cycle foreach compound Using the equation MACAO'S = A, HCL] HegfCal) + B,HFOLG!] + Exe / OL * Ses) we can calculate a value for 4,H{Ca‘0 (3) using a theoretical value for Ave.,H{Ca'0 (6) of -650K) mol In this way, the value calculated for A. H{Ca‘O (sis: 178 +590-+ 249+ (-141) +(-650)= +226) mat" Silay, the value calulated fr 8 H{Ca""O* (lit ~635 kl mat" From these values tis lar thatthe formation of CaO is energetically more favourable than the formation of C2°0 “The extra energy required ta form the 24 snd 2-ionsie more than compensated for by the much larger (.e. more negative lattice energy of a2*O* (3401 KJ mol) compared to that of CaO (-650 mal). itis the overal energy change involved, and not the incorrect notion of desirability to obtain a noble gas «lectronic configuration, that determines how atoms and molecules wl interact with one another to frm compound However, it isimporantto recognise that the conditions under which a reaction takes place will infiuence the overall energy change involved and hence the nature of the compound formed. For example fron is heated in chorine gas, ron chloride ithe product However, fhydrogen chloride gas is used in pace of chlorine, onl chloride i formed, Therefore, changing the conditions of temperature and/or pressure can aso have an effect on the exact ‘compound formed.CC EE Lattice energies can be used to compare the strength of bonding present in anionic compound {@) State whats meant by the term ‘lattice energy’ (b) Explain the effect of ionic charge and ionic radius on the magnitude ofthe lattice energy of anionic compound, 2. The Born-Haber cycle can be used to calculate the lattice energy, Aey.cH, for magnesium oxide. Meg) + 22> + O18) aso, 1a) + 20° + JOLe) SccIMGO] jo br + & + 10,6) AH, = +7384 mol" ) + 10,6) AH, = +1481) mol sae) + 104) AH, = 602s mor" {@) {9 State the names foreach of the enthalpy changes labelled AH, AH, and AH, (i) Give the formula missing atthe top of the cycle, indicated by a question mark (2). Give the state symbols (6) The equations representing the first and second electron affinities of oxygen are: OG) +e 01@) Eye 41 mot Ole 074g) Eg +798K mol Suggest whi the second ofthese processes is endothermic. (©) Use the information in the Bon-Haber cycle shown above to calculate the lattice energy of magnesium oxide, AvcialMgOU) (@) Explain hows the lattice energy of barium oxide differs from that of magnesium oxide. Key definition ‘The standard enthalpy change of atomisation of an element isthe enthalpy change measured ata stated temperature, usually 298 K, and 100 Pa when one mole of gaseous atoms is formed from an element in its standard state 55Experimental and theoretical lattice Titles By the end ofthis section, you should be able to: ‘© understand that a comparison ofthe experimental lattice energy value (obtained from a Born-Haber cycle) with the theoretical value (obtained from electrostatic theory in a particular ‘compound indicates the degree of covalent bonding ‘© understand the meaning of polarisation as applied to ions, © understand that the polarising power ofa cation depends an its radius and charge © understand that the polarisabilty of an anion depends on its radius and charge Experimental lattice energy ‘The Rom-Haber cycle allows us to calculate a value fr the lattice energy of an ionic compound fiom knowledge of the other energy changes. al f which can be determined experimentally ‘The value of the lattice energy calculated this way is called the ‘experimental tice energy. Theoretical lattice energy ‘The type of lattice structure and the interionic distance can be found by X-ray crystallography: Using this information itis possible for us to calculate a value forthe lattice energy of an ionic compound However, we fist need to make the following assumptions. + Tae ions are in contact with one another + ‘The ions are perfectly spherical + The charge on each ion is evenly distributed around the centre so that each ion can be considered as point charges. ‘A value forthe latige energy can be calculated using the principles of electrostatics, There are three ‘main methods for performing such calculations. If you are interested, you can research them under the headings of ‘The Bom-Lande equation, ‘The Born-Mayer equation’ and “The Kapustnski equation Table A shows & comparison of the experimental latice energies (obtained by using a Born-Heber cycle) with the theoretical lattice enemies (calculated using the principles of electrostatics) for various compounds. Ser lattice energy/kj mot"! | Theoretical lattice energy/KJ mol Naf 918 912 Natl 780 “770 NaBr ~7AD 78 Aer 958 =920) Agcl =905 833 Ager -891 =816 table A ‘You will notice that there is good agreement between the experimental values and the theoretical ‘values forthe halides of sodium. However, the agreement is not so good for the halides of silver ‘An agreement between the experimental and theoretical values of lattice energy for a compound indicates thatthe ionic model is a good one for that compound. A significant difference suggests that the ionic model needs to be modified. In such compounds, the bonding in the lattice has a considerable covalent character, which makes the experimental value for the lattice energy rmore ‘negative than the theoretical value. 56ER ‘The covalency in bonding is caused by polarisation of the anion by the cation. Polasisation resulrs in distortion of the electron density within the anion, resulting ina higher electron density near the cation. This means that there is some electron density existing between the two ions. That is to say, there will be a degree of covalent bonding in the compound. The extent of covalent character: polarisation of the anion In an ionic lattice, the positive ion (cation) will attract the electrons of the anion. If the electrons Cation Anion are pulled towards the cation, the anion is said to be polarised because the even distribution of its electron density has been distorted, ‘The extent to which an anion is polarised by a cation depends on several factors. The two main factors are summarised below, These are known as Fajan's Rules, Polarisation will be increased by cation aa + ahigh charge and small size of the cation (ie. a high charge density of the cation) + ahigh charge and large size of the anion, High charge and small size of cation ‘The ability of a cation to attract electrons from the anion towards itself is called its ‘polarising Caton Anion power. A cation with a high charge and a small radius has a large polarising power. An appeeximate ‘value for the polarising power of a cation can be obtained by calculating its charge density {sometimes called surface charge density). The charge density ofa cation isthe charge divided by ‘the surface area of the ion. If the ion is assumed to be a sphere, its surface area is equal to 4nr?, ‘where ris the ionic radius Region where electrons are existing ‘A rough approximation of the charge density can be determined by dividing the charge by the square Reon where ctos se of its ionic radius. This calculation is beyond the scope of your A level course. charge fig 4 representation af cation charge density ~ racing the electons fan r ‘nian inan onc atice ‘Table B compares the extent of covalent bonding in sodium chloride and magnesium chloride. Theoretical Percentage Pree of cation ory differen cern fl Nec <1 770 013 very it a wos ery lie = 556 ~ ~ ‘more than in Nat Mecl, oer 2526 27326 792 than in NaCl table@ "The charge density of the magnesium ion is lager than that of the sodium ion, resulting in greater polarisation of the chloride ion and increased covalent bonding in MgC, than in NaCl. High charge and large size of the anion ‘The ease with which an anion is polarised depends on its charge and ts size. Anions with alge charge anda lage size are polarised most easily ‘Table C compares the extent of covalent bonding in silver fluoride and silver iodide. Compound | Charge of | Radius of | Experimental lattice | Theoreticallatice | Percentage | Extent of covalent Sache L fee Peed AF | 013 958 920 413 feiiylage | Pal [eas [8898 1249 eater than inf | table ‘The larger iodide ion is more easily polarised, which leads to a greater degree of covalent bonding in silver iodide. 3758 ‘The interesting case of silver compounds ‘Table D compares the extent of covalent bonding in sodium chloride and silver chloride, eee er ees Eo oss | wevlitle ‘gp much greater 492 | thanin NaCl tabled Despite the polarising power ofthe Ag’ ion being less than that of the Na“ ion, there is considerably more covalent bonding in gC ‘This iseuplained by considering the valence shell electronic configurations ofthe two ions concerned Nav 158258 2pe Ag [kr] 34° ‘Al configuration offers les shielding than a p electronic configuration, so compounds which have a d® ‘configuration show a greater tendency toward a covalent character. For the same reason zinc compounds ao contain a significant degree of covalent bonding. 1 theeperinental and thereat ener n mot of caktam lute, Cay and ser ride, Agta pen below experimental value theoretical value car, -2630 -2609 Agr 958 920 Suggest why there is good agreement between the two values for CaF, but there i a significant diference betvieen the twa values for Ag 2 Aniosin anionic tie can be poled by the cations adjacent to them The een of polation depends the nate of bathe arin and enton involved (a) Explain what smart bythe em ‘polare inh conte. (2) Ste whether the ond on O oF the slide nore esl plated (0) Pace the folowing cation (wth onic radi shown n parenthesis) inorder of eensigpolarsing ome ‘Mg (00720) AD* (0053) (0074) ‘Nat (0.102.nm) Ca** (0.100 nm) k° (0.1381nm) Suppo your cancion by suitable eleavons, 3. sugges ay th oid Na"O* doesnot exist state what further energy change, oer than thse quoted inthe data Books you would equ morro con your suggeston,Enthalpy changes of solution and hydration By the end of this section, you should be able to... ‘© define the terms enthalpy change of solution, AM, and enthalpy change of hydration, Aya (© use energy cyces and energy level diagrams to cary out calculations involving enthalpy change of solution, enthalpy change of hydration and latice energy (© understand the effect of ionic charge and ionic radius on the value of enthalpy change of hydration Enthalpy change of solution, A,.H “The soubiltes of oni solids in water show avery wie variation and there sno obvious pater, (ne of the factors that determines solubility isthe value ofthe enthalpy change of solution, Ava. the enthaley change when one mole of an ionic solid dissolves in water to form an infinitely dilute solution. “The enthalpy change of solution for sodium chloride isthe energy change associated with the following process NaCl{s) 2% Na*(aq) + C-(aq) [cis important to specify the extent of dilution of the final solution when quoting a value for the enthalpy change. Upon dition, the ions in the solution move further apart (an endothermic process) ‘and also become more hydrated (an exothermic process). The relative importance of these two processes changes with dilution and they affect the value of 4.u/fin a complicated way. For this reason the quoted values for A.s// refer to an infinitely dilute solution. This value cannot be determined ‘experimentally and is found by a process of extrapolation. In practice, there comes a point wien further dilution has no measurable effect on 8, This is known as the point of infinite dilation Enthalpy changes of solution can be either negative or postive, as is showm in table A. Equation NaCI) = Narfaq) + CHaq) NaOH) “ Na‘(ag) + OH faq) NH,NO4s) “4 NH,"(aq) + NO3"{aq) MgSO4s) “Ss Me(aq) + SO,*Caq) table A Enthalpy change of hydration, AyygH “The enthalpy change of hydration, 4... is the enthalpy change when one mole of an ion in its gaseous state is completely hycrated by water In practice, complete tyaration is said to have ‘occurred when the solution formed is at infinite dilution (see the definition of enthalpy change of solution) For the sodium and chloride ions, the enthalpy change of hydration is the enthalpy change for the following processes: Nag) Natta) and Ch(g) % Cr(aq) 59)‘When an ion is placed in water it immediately interacts with the water molecules. Water molecules are polar (see Book 1 Section 2.2.4) and are attracted to both positive and negative ions. Fig A. shows the hydration of sodium and chloride ions. HK fig A. Hydration of sodium and chlerde iors In the case of the sodium fon, the interaction isthe result of the attraction between the 8 oxygen atom of the water molecule and the cation, Such an interactian is often referred to as an ion-dipole interaction. With some other positive ions, notably those of the transition metals, a dative covalent bond is formed between the water molecule and the cation using one of the lone pairs of electrons. con the oxygen atom, lon-dipole interactions exist in the hydrated chloride ion, but some hydrogen bonds are also formed betneen the 6+ hydrogen atoms of the water molecules and the chloride ion, making use of the Ione pits of electrons on the chioride ion (see Book 1 Section 2.2.5) Enthalpy changes of hydration are always negative, Some examples are given in table B. [a = Equation rE Net 0.102 Nag) Na‘ag) 40s © 0138 K@ = kag) “322 Rr 018 Roig) = Roraq) 301 Me 0072 Mgn(a) 2 Mg*laq) 1920 cae 0.100 cag) Coq) =1650 se ons S@ shea) 1480 a 0180 CHa) = craq) =368 r 0195 Brig) Br (aq) =335 0215 r@ 2 req 28 table B Factors affecting the magnitude of the hydration enthalpy “The fis thing you will notice from the values in table Bis that A, gis much more negative for 2+ ions than for I+ fons. Tis makes sense because we would expect a doubly charged ion to have a stronger interaction with the water molecules compared witha singly charged ion. That is to say the electrostatic force of attraction between a doubly charged ion and water molecules will be greater than that between a singly charged ion and water molecules ‘As-we go down a group (eg, Na’ to Rb! or Cl to [the magnitude of Ay,H7becomes less negative. This seems to correlate with an increase in ionic radius, Ths rend can be explained using a simple electrostatic model for hydration, similar to that used to explain the variation in lattice energies for ionic solids As the ions become larger the electostatic force of attraction between them and the ‘water molecules decreases, and hence the energy eleased upon hydration decreasesAs with latice energy, there isa strong correl and the charge densities of the ions. Table C shows this for four cations. SI ee wo . way “~ Me wasop ope ce 1650 table ‘The greater the charge density of the cation, the more negative the value of ByaH. Relationship between A,.H, Aj,gH and Arattice!t ‘The relationship between 4,7 Ayu and Ay. is best shown by an energy level diagram similar that of @ Bom-Haber cycle asshovn in fg B Rew® + Cre) A, HIN +3, ICME] Sef NACI) 05 + (369) et mol" = “70k mot Na‘ (aa) + Cah al AHINGCI fig Energy level diagram forthe dssahing ef socium chloride ‘Applying Hess's Law. AsacflNeClS)] + Asaf [NaCl] = ArjchNa"(g) + SyaICre] AvafNaC\s)] = ~406 + (-363)kJ mol! ~ (-780) kJ mo +11 mol” ‘The relationship can also be shown in the form of a Hess cycle {shown in question 3), ion berween Ay,ift EE ‘| When potassium fluoride dissolves in water, the lattice breaks up and the potassium and fluoride ons become hydrated (@) Draw diagrams to represent) a hydrated patassium ion and (ia hydrated fluoride ion. (6) Name the type of interaction that occurs between the water ‘molecules and the on for bath the hydrated potassium ion and the fluoride ion, Describe how each interaction occurs. 2 These data refer to some of the energy changes involved when magnesium chiride dissolves in water. MgC) “2. Mgaq) + 2Crag} SoHiMe(CH{s]]=-155¥) mot ag(g) + 2CF(@) = MECH) Sect g'(CI 6) = -25261) mot Mente)“ Mg"aq) Sua] = 19201) mot! Use this information to calculate the enthalpy change of hydration ofthe chide ion, &cH{C! (} 3 The diagram below isa Hess cycle for the dissolving of lithium fluoride in water. W@+ Ure) iF (@) Complete the cycle by filing in the empty box. (b) State the name of the energy change represented by AH, (6) Apply Hess Law ta obtain an expression for A. in terms of 3H, and 4H, () Calculate 4,,HIL"F(S)] given that AM, = -1031 | mol” 4 The standard ently change of slaion of sodium Wurideis 03H mot ‘sample of sour ford of mass 1g isadded to 250 of ‘rater beater and sted wih thetmometet graduated in ineralsaf Expan vat key to happen tothe reading on the thermometer elnesodum fuorde dares Ne claen is ecesy Keydefinitions ‘The enthalpy change of solution, 8,aH, i the enthalpy change when one mole af anionic solid cssclves in water to farm an infinitely dilute solution, The enthalpy change of hydration, AygH, isthe enthalpy change when one mole of anion in its gaseous state is completely hydrated by water aIntroduction to entropy By the end of this section, you should be able to.. © understand that, since some endothermic reactions can occur without the input of heat, enthalpy changes alone do not control whether reactions occur @ recognise that entropy is a measure of the disorder ofa system and that the natural direction of ‘change is increasing total entropy (positive total entropy change) © understand why entropy changes occur during changes of state What makes a reaction occur? Pechaps one of the most important questions to ask in chemistry is Willa reaction occur? ‘We know that, once started, some chemical reactions simply ‘go ‘with no further, continuous help from us. For example, ammonia gas and hydrogen chloride gas react ‘together at room ternperature ta form the white solid, arnmonium chloride: NHJg) + HCIg) > NH,Ci(s) Magnesium. once ignited. will burn in oxygen to form magnesium oxide Mats) + 30,4a) > MgO(s) In other reactions, rather than the reactants changing completely into the products @ position of equibrium is reached, with the final mixture containing a measurable amount of bath reactants and products. For example, ethanoie acid dissociates in water In a 0.1 mol dm? solution of ethanoic acid, only about 1% of the ethanoic acid molecules are present as ions: CH,COOH|aq) = CH,COO-(aq) + H*(ag) Another example is the dimerisation of nitrogen dioxide in the gas phase: 2NO,{z) = N,O.(2) ‘At a temperature of 298 K and a pressure of 100 kPa, the equilibrium mixture contains about 70% N;O, “There are other types of reactions that simply do not occur at all atleast not without some help. For example, ammonium chloride does not spontaneously decompose into ammonia and hydrogen chloride, Magnesium oxide does not break apart ro form ‘magnesium and exygen without some continuous intervention from us inthe form of heating. If we consider all of these types of reaction together, we see that the real difference between them isthe positon of equilibrium that is established. For some reactions, the position of equlibrium is, ‘90 far over to the products sie that. to al intents and purposes, the reaction has gone to completion. For some other reactions, 62 significant amounts of both reactants and products are present at cqulibrium. For other reactions the equilibrium lies so far to the Jeft that they appear not to take place at all So, pethaps, the better to question to ask is nor Will a chemical reaction occur”. but ‘What will be the position of equilibrium? “This isthe question we hope to answer in this topic. Exothermic and endothermic reactions ‘The reaction between magnesium and oxygen is exothermic and can bee represented by the enthalpy level diagram shown in fig A. Enttaloy Maid + 209 Reaction pathway fg Erthalpy level diagram fer the reaction bewicen magnesium and oxygen, As the products have less energy than the reactants, we often say that the products are more energetically table than the reactants, Itis very tempting to conclude that this reaction occurs because the magnesium oxide is energetically more stable than its clerents, magnesium and oxygen. However ternpting this, argument may be, we must ciscard it, because experience tells us that many endothermic reactions occur at room temperature. Let us consider the dmerisation of NO) at 298 K: 2NO,{g) = N:Oug) “The enthalpy level diagram for this reaction is shown in fig B hal Resction pathway fgB Eeuhalpy ove cagram fr the dimeraton of NO‘This reaction is readily reversible and reaches a position of ‘equilirium at 298 K, The forward reaction leading to the formation of N;O,(g)is exothermic. However, the backwards reaction is endothermic. [As we discovered in Book 1 Section 10.1.1, the position of ‘equilibrium can be reached from either direction, This means, that if we place some N,O4() ina sealed container at oom temperature, some of it wll decompose to form NO,(g). So, an endothermic reaction i taking place at room ternperature without ‘any continuous intervention from us. We say thatthe reaction is spontaneous (see later in this section), Clearly i is not only exothermic reactions that can take place spontaneously. Te driving force for spontaneous endothermic reactions cannot be the formation of more energetically favourable, ie. lower-energy, products but must involve another {actor we have yet to consider ‘That factor is @ quantity known as entropy, and is governed by the Second Law of Thermodynamics. But frst, we need to appreciate what is meant by the term spontaneous process. Spontaneous processes A spontaneous process is one that takes place without continuous intervention from us, A good example of a spontaneous process isthe freezing of water to formice. If water is placed in an environment at 20°C it will turn inta ice. However, the reverse will never happen: at ~20 °C. ice will never melt to form water Another example of a spontaneous process is the mixing of gases. If two unreactive gases are present in a container, they will mix completely in a process known as diffusion, ‘We can bring about the reverse of spontaneous processes by intervening, For example, we can melt ice by heating it, and ‘we can separate a mixture af gases by liquetying followed by distillation, ‘The key point, however, is thatthe reverse of a spontaneous process never happens on its own. A mixture of gases will never separate of their own accord. {At the beginning of this section we stated that, in ehernistry, we are concerned with whether or not chemical reactions will occur and we suggested that perhaps the most important question to ask in chemistry is ‘Why does @ reaction occur? rom the point of view of thermodynamics, all reactions are reversible so we suggested that en even better question to ask is: When a reaction reaches a poiat of equilibrium, wat determines whether the equilriam will favour the reactants or the products, and to what extent? ‘This question is answered using the Second Law of ‘Thermodynamics, in which the concept of entropy is introduced. I Entropy ‘The Second Law of Thermodynamics allows us to predict whether a process is likely to occur tis, therefore, the key ‘to understanding what drives chemical reactions and what determines the position of equilibrium. The Second Law of ‘Thermodynamics introduces a term called entropy, which is 2 ‘property of matter just lke density or energy. The simplest way to describe entropy isto say that itis a quantity associated with randomness or disorder. The natural direction of change is toward increasing total entropy (positive total entropy change), “The greater the degree of disorder, the greater the entropy. A gas has a greater entropy than its solid because, in a gas, the ‘molecules are free to move around randomly The entropy of a liguid is higher than that of its solid but lover than that of its gas. ‘This is because the molecules in a liquid are freer to move than those ina solid. but less free to move than those in a gas. So, as ice changes first of all nto liquid watet, and then into water vapour the entropy increases at each stage. “The Second Law of Thermodynamics is sometimes misquoted, You may have come across the statement that in a spontaneous change, entropy always increases. ‘This cannot be true: if it were, ‘water could never freeze because this change involves a decrease in entropy. Another example is the reaction between ammonia gas and Irydrogen chloride gas: NELAg) + HCl(g) — NH,Ci(s) Clearly there is @ reduction in the entropy of the system, since two _gases are forming a solid, yet this reaction occurs spontaneously at room temperature. “The statement entropy always increases is almost corvect. It needs to be expressed more carefully to give the Second Law of “Thermodynamics: Ina spontaneous process, the iota! entropy increases, In Section 13.2.2, we explain what is meant by the term ‘total entropy’. 1 reach ofthe following pede whether th change i ttcorpanld by antnceae ora deren mal enaopy @) H.0@) —H.0() (6) 1) = Le) (6) Nath) Nais) Key definitions Entropy isa property of matter thats associated withthe degree of disorder, or degree of randomness, ofthe particles. ‘spontaneous process is one that takes place without continuous intervention from us, 8BTolE Malice) ois By the end of this section, you should be able to.. ‘© understand that the total entropy change in any reaction is the entropy change in the system added to the entropy change in the surroundings, as shown by the expression: AS.aat™ ASaotem + ASurourdings @ calculate the entropy change of the system, AS, ina reaction, given the entropies of the reactants and products © calculate the entropy change of the surroundings, and hence 4S. using the expression: AH AS moming = Total entropy change, ASiou ‘The toxal entropy change of a process is comprised of two components: + the entropy change of the system. ASem and + the eniropy change of the surroundings, ASaraassey Ina chemical reaction, the system is the species that are taking part in the reaction. ‘The surrouncings is everything else. In practice this usually means the reaction vessel, eg, test tube or beaker, and the air in the laboratory. ‘The total entropy change is defined as the sum of the entropy change of the system and the entropy ‘change of the surroundings. Thet is: ASvoui = BSoynem + ASpurcunnge For a reaction to be spontaneous, ASau, must be positive. This is another way of expresing the Second Law of Thermodynamics Entropy change of the system Didyouknow? __ Fie ctncnléeranononipe 7 SSisen!® Calculated using the exresion official definition of the “ . Second aw of ASiyuen = 3S (products) ~ ZS (reactants) ‘Thermodynamics does notuse here S represents entropy and © represents ‘the sum of’ the term total entropy change’ Instead itrfersto the entropy The slandar entropy values of some substances are shown in table A. change ofthe universe. These standard refers to = a ane chee (Standard refers to conditions of 100 kPa and 298 K.) meaning, We wil use the term oy rate Poy ‘al entropy change’ fon Pian eaoio es Usbes H,0lg) 188.7 H,0() 639 H,0(5) 479 Hs 1306 CH.OH 2387 __| Cldiamond) 24 O, 7080 CH.CHON | 1607 | Clraphite) 57 Ne i916 Hs 8 0 37 ch 1650 CaCO, 929 CO 736 NHs 1923 tablesRT Learning tip Note that entropy values are usually quoted in K~! mot, whereas enthalpy changes are usually quoted in lj mol" So, in aay equation linking AS and AH, one of the energy terms will need a conversion of units. Eeseeee T Use the values in table Ato calculate AS*,4, forte following reaction CaCO,fs} -+ CaO) + CO.ig) AS pum = SEICAOE] + S1CO,il]- SA{CACOYS)] =397+2136-929 = +1604) K* mot a Use the values in table 10 calculate AS® a fr the following reaction Na) + 24) = 2NHYe) AS 2am ~ 2 $*{NH,(g)] - S*IN, (gil - 3 = S*1H.(5)] (2 « 1923) - 191.6 - (3 « 130.6) -1988) K" mol" Entropy change of the surroundings ‘The entropy change of the surroundings, ASyma. i elated tothe enthalpy change of the reaction, AH, by the expression: ‘where Tis the temperature in Kelvin, For an exorermic reaction, where AH is negative, A Syarnaas: Will always be positive, so the entropy of the surroundings ineveases Conversely, for an endothermic action, AS. ronan: Will always be negative, so the entropy of the surroundings decreuses WORKED Baries CALCU AS ern at 298 K when one mole of hydrogen gas s burned in oxygen. H,@) + 40,3) + H,0() AH = -2864) mol! -288 MSerandres” Gop = +0960 4! mat" of +960) K! mol Calculating the total entropy change, AS, Now that we know how to calculate both MS fd A Surcucing» We Are in & position to calculate the total entropy change, AS.aa, fora reaction ES ee Using the information in tale A, calculate the 1otl entropy change at 298 K forthe folowing reaction He@) +J0:le) + HON), AH = -2861) mol? H.010]- Stile] -4 «FO. 59.9 ~ 1306 - (» 205) 1632) K" mol 1632) K! mol! + 960) K! mol! 7968) «mot 65Summary Si, il be postive i + oth ASsreuunp td ASyann ae positive + Syren positive and AS, 8 negative but the roagmitade of ASvranu > the magnitade of MS. © ASccanay i nepEE ad AS, postive, but the magnitude of ASerenang < the magnitude of AS ry The role of temperature “The inoease in entropy obtained by supplying a certain ammount of heat energy to an object depends on the temperature of the system IF an objects very cold the molecules are not moving eround very much, Supplying some heat energy tothe abjct will make the molecules move around more, so the entropy increases IF we supply the same amount of heat energy to a much hotter ject, the entropy wil sil increase, but not by as much as with ‘the cold object. This is because in the hot abject the molecules are already moving around vigorously and the increased degree of ‘movement i less for the hot abject. Why does water freeze? fig. Why coes water feene? We will now apply these principles to explain why, under certain conditions, water will freeze Joe has lower entropy than liquid water 80 AS... i negative, “The process is exothermic, 0 AS wrongs 8 POstve IF the magnitude of AS.uasys > the magnitude of AS,jyay then Sua is positive and the water wil freeze. We will now calculate AS,, +5°C and —5°C using the following data HOU) +H,0(s) AH'= ~6010J molt + S*(yrater) = 69.9, K! mol“ + Sfice) = 47.9) K! mol) AL+5°C (278 K} MSyyuon = (47.9 ~ 698) for the change of water into ice at 22.0) K"' mol 10 ASumonsios = “373 +218) K" mor Sua =-04JK? mat! 66 ‘The total entropy change is negative, meaning that the change is not thermodynamically spontaneous. The water will not freeze, AL~8°C (268 K) AMSsyatm = (47.9 — 69.9} = — 22.0) K-' mol" 6010 MSreniea =~“ 24224) Kt mot! Sou = #04 K! mol ‘The total entropy change is positive, meaning that the change is thermodynamically spontaneous. The water will feeze. Itis interesting to note that what has changed between +5°C. and ~5°C isthe entropy of the surroundings. The reason that ‘Surana has changed in magnitude is simply because of the temperature change. The same amount of heat energy has been transferred to the surroundings but, because the entropy of the surroundings has a higher temperature when at +5°C than when ‘at -5°C, the change in entropy is smaller, as explained earlier So, the reason we put water into a freezer when we want to ‘make ice is because the entropy change of the surroundings. (le. essentially the air inside the freezer) is large enough to ‘compensate for the decrease in entropy when the water freezes. 1 Hyerated cobalt) chloride dehydrate on heating according othe folowing equation Coc; 6H,0() ~ COC) + 6HLO) Aap = 8814) mol (8) Cala the standard entropy change ofthe tem, AS” ‘S?(CoCI.6H ,O(s)] = 343.0) K mol ‘S°(CoCls)] = 109.2) K" mol" ‘S°{H,0(I)] = 69.9) K" mot" (0) Calelte the standard entropy change ofthe suroundings, 85% ane st 38K (€) Calelate te standard total entropy change, Sy a 298K forths reaction (d) Explain whether hydrated cobalt(|!) chloride can be stored at 298 Kwithoutt dehydrating? 2 sete data providedto calculate the tot standard entopy change, 85308298 forthe falouing reac Fels) + 130g) — Fess) SH? = 8224 mol S*ffts]= 272) K" mol o,f - 2050) «° mot” S+FFe.0,)]=900) «metUnderstanding entropy changes By the end of this section, you should be able to... ‘© understand why entropy changes to the system occur during: (i) reactions in which there isa change of state {i) reactions in which there isa change in number of moles from reactants and products the dissolving of ionic solids in water ti Reactions involving a change of state We have already mentioned that, n general. entropy increases in the order: solid H.O[s) A= ~6010J mol and AS = ~220J K+ mol? AL 49°C (278K) AG = ~6010 = (278 x ~2200) = +108 mol AGis positive so the process isnot thermodynamically feasible, Water will nt freeze at +5°C (278 K). AL~9°C (268K) AG = ~8010 ~ (268 220) AG is negative so the process is thermodynamically feasible. Water will reeze at ~9°C (268 K) ‘You will notice thatthe outcomes ate identical to those obtained by the calculation of Six. ‘However the calculations are much easier because we have to think only of the system and not the surroundings. 114J mol Summary AG will be negative when + AH0 + AH<0, AS< Out the magnitude of AM’> the magnitude of TAS + AH> 0, AS> Olbut the magnitude of AH < the magnitude of TAS. AG will always be positive when: + AH>OandAS<0. + AH> 0, AS> Out the magnitude of A/Y> the magnitude of TAS + AH<0, AS< O but the magnitude of A/T < the magnitude of TAS 70er Thermodynamic feasibility of chemical reactions Lec wsnow apply this concept toa chemical reaction: the thermal decomposton of calcium carbonate CaCOss) — CaO(5) + CONg) AN = +178) mob The entries of CaCO) CaO(s) and CO.) are 89,40 and 214 * mol” respectively Caleulate AG forthe reaction at 25 °C and comment on the value obtained 40+ 214 ~ (+89) = +165) K mol (178 x 1000) ~ (298 x 165) = +128 830, mol Since AG is positive, the reaction is not thermodynamicaly feasible. So calcium carbonate is thermodynamically stable at 25°C. We can also determine the minimum temperature at which the decomposition becomes thermodynamically feasible because at this temperature AG is zero When AG = 0, AH = TAS, a. Rearranging this expression gives AH__ 178000 165 T= = 1079K So, calcium carbonate starts to decompose ien heated to a temperature of 1079 K (806 °C). [eis interesting to note that the value of AH does not vary much with temperature, but the value of AG changes significantly. The change in AG with temperature forthe thermal decomposition of calcium carbonate is shown in fig A. AG Pk mot figa ch: 1 Inthe Haber process fr the manufacture of ammonia, a mixture of trogen and hydrogen is heated toa temperature of 823 K Ng) + 3H) = 2NHg) AH? = 9204) mol? “The standard entropies of nitrogen, hydrogen and ammonia are: Sr[Nfg)]= 191) moll; SefHl] = 132) 4% mo SHINE] = 192) x" mo {@) Show thatthe formation of ammoiafrom nitrogen and hycrogen gasis thermoynamically feasible 1298. (b) Explain why this reaction i not thermodynamical feasible at high temperatures. (©) Suggest why a temperature of 823 Kis used despite the reaction being feasible at 298 K in SG wth tempes 2 (a) The standard enthalpy changes for the melting and boiling of water ar: H,0[s) -H,0() AH" = +601 | mol" HO)» H,Olg) AH? = +40.7Kj mot Explain wy AH® for each of the changes is positive. (b) The standard entropies of water in its three states are: $°[H.O(g)}=189) K-" mol", S°{H,O(l]]= 69.9 K mol"; $°H,O(s]] = 48.0) K" mol (i) Explain why there is an increase in entropy when water melts. (i) Explain why the increase in entropy for the change H,0}|) ~» H,O(g)s greater than that for the change H,0(s) — H0(). (6) Use the data from parts (2) and (b) to calculate the minimum temperature at which water will freeze at standard pressure nGibbs energy and equilibrium By the end of this section, you should be able to.. © use the equation AG = -RTInK to show that reactions that are thermodynamicaly feasible have large values for the ‘equilibrium constant and vice versa © understand why a reaction for which the AG value is negative may not occur in practice © understand that reactions that are thermodynamically feasible may be inhibited by kinetic factors. Relationship between the equilibrium constant, K, and the Gibbs energy change, AG ‘The equlvium constant and the Gibbs energy change are relaed by the equation: AG=-RTINK where R is the gas constant (8.31 J mol"? K- ‘This equation can be rearranged to give Kas: kel Learningtip You may not have previously come across the concept of. It isan important mathematical constant that is approximately equal 10 2718. The ‘natural logarithin’, In, isthe logarthim to base e. Using this information, you could have a go at rearranging the equation yourself If AGiis negative, the exponent (the expression in brackets) is positive, The equilibrium constant wil be greater than 1, which ‘means that the products are favoured. However if Ais positive the exponent will be negative giving an equilibrium constant of less than I. In this case the reactants are favoured, Notice that we are suggesting that if AG is negative, the reaction vail each a position of equilibrium that favours the products and if AGis positive the reaction will reach a position of equilibrium that favours the reactants. We are not suggesting that if a reaction hras a positive AG, then no reaction takes place. Itis perfectly possible for some of the reactants to be converted into product, ‘but impossible for them af! tobe converted into products ‘This situation can easily be understood by observing the change in Gibbs energy with the percentage of B present for the equilbnum: A=B for which AGis positive. 22 ‘The change in Gisbs energy for such a reaction is shown in fig A. Gite energy position Or equi. — pure A at pure B fig Charge in Gibbs energy agains the percentage of 8 nthe equilibrium ‘acu forthe reaction & == B Going from pure A to pure B would involve an increase in Gibbs ‘energy and so is not allowed, However, going from pure A to the equilibrium mixture involves a crease in the Gibbs energy (AG is negative) and is allowed. Areaction witha positive AGis not forbidden’ but simply comes, to a position of eenilibrium that favours the reactants, Learning tip In the equation AG = -RTINK, K has no units. This value of the ‘equilibrium constant is known as the thermedynamic equilibrium Constant, as opposed tothe experimental value of K which does have units (see Section 11.1.1), Calculating K for a reaction For the following reaction at 298 K: $0.{a) + [0sg) — SOs) AG=-TikI mol" Kao Fl = el aire) = 2.83 x 1012 “The equilibrium constant is very lange, suggesting that the ‘equilibrium position will be almost rorally in favour of the products in this reaction Both the sign and the magnitude of AG tell us something about the position of equilibrium of a reaction. Because of the ‘exponential relationship between AG and K, once AG becomes more negative than a certain value, K becomes so large that the reaction has effectively gone to completion. That i, al the reactants have been converted into products, Similarly. once AG becomes more positive than a certain value K becomes so small that the equilibrium lies entirely to the reactants side. That is the reaction does not proceed to a significant extent and hardly any reactants, if any at all, have been converted into products,Fig B shows the relationship between Kand AG favoured fig Relstiorship between the equiloriur change, 86. stant Kan the Gib energy (Once AGis more negative than about ~40kJ mol, Kis solerge that all of the reactants have effectively changed into products. ‘Once AGis greater than +40k) mol", Kis so small that essentially none of the reactants have changed into products. Relationship between the equilibrium constant and temperature The two equations AG=-RTnK ond AG= SH TAS ren both involve temperate. If we combine the two we obtain the “RT Hi — TAS, Dividing both sides by ~A7 gives — at, BS yen nk =-38 4 ‘This equation demonstrates thet the way the equilibrium constant varies with temperature depends upon the sign of M/Z. If the forward reaction is exothermic, AHis negative, and the Ai ' WH term — iis postive. If the temperature is increased, — 7 will become less postive and so InX, and hence X decreases, ‘Thus, increasing the temperature for an exothermic reaction results in the equilibrium shifting tothe lef, that i in the endothermic direction, If the forward reaction is endothermic, psn tb tempee since 2 ytbecome es gate ado nk an Ais positive, and the term. hence K, increases. Both of these conclusions are in agreement with the qualitative statements we made in Book 1 Section 10.1.2. Special cases “There are rwo factors to consider when applying the concep of Gits eneray change to predic the thermodmamic feast ofa chemical reecion ee 1 Kinetic stabilit ‘A negative value for AG indicates thatthe reaction is ‘thermodynemicalyfeasile, but i does not necessarily mean that the reaction will take place ‘An examples the reaction between hydrogen and caygen at 296 K Hg) + z0x(@) + H20() AG* = -229kJ mor “This reaction has a large negative AG value, but a mixture of hydrogen gas and oxygen gas does not spontaneously react to form water at 296 K This because the activation energy for the reaction is very high, so very feu if any, colisions result in reaction, We say that the reactants are kintcaly sable. 2 Non-standard conditions Standard Gisbs energy changes, AG®, are calculated fora speciic set of standard conditions, usually 298 K and 100 kPa pressure. Any solutions invelved would be at a concentration of mel dm. ‘The following reaction between hydrochloric acid and ‘manganese(]\) oxide is not thermodynamically feasible under standard conditions because the value for AG" is positive 4HC\(aq) + MnOfs) > MnCl,{aa) + H,0() + Che) However: this reaction is commonly used to generate chlorine in the laboratory. If concentrated hydrochloric acid (~10 mol dm} is uged and the reaction mixture is heated, the reaction becomes ‘thermodynamically feasible because AGis negative under these conditions. 1 The equation the sproporionttonct eabon monesie inte Carbon and carbon done 2CO4g) = Cis} O8) Sem thermodyraml data for hs reaction igen below 591298K)=-1750) Ket! (298K) =-17254) mat S6*296K)=-12014 mei! (2) Coleuate the equim constant forths reaction (0 Calas the temperature above ich he dproportination ci catbon monoutde cease: tbe themedyramialy eae (€) Sumpet why exbon mononde doesnt spontaneous disproportionate at 238 2 Consider the reaction: ls) + H:0{g) = COlB) ~ Hala) ‘Some thermodynamic data for this reaction are given below: 45°(298 K) = -142.9) K"' mol* AH™(298 K) = -135.0kj mob” {a} Calculate the minimum temperature at which this reaction becomes thermodynamically feasible. What assumptions have you made in your calculation? (b) The Gibbs energy change for this reaction at 500 K is + 633.04) mol, Calculate the equilibrium constant, K, for this reaction at 500K BSome applications of Gibbs energy: further understanding By the end of this section, you should be able to.. © understand why some ionic salts are soluble in water whilst others are insoluble “© understand why hydrofluoric acid is classified as a weak acid © understand the trend in acid strength of the chloroethanoic acids 74 ‘This section will take you beyond the scope of the current A level course, but has been included in ‘order to show you some useful applications of the concept of entropy. Solubility of salts Soluble salts In Section 13.2.3 we saw that by considering entropy changes of both the systern and the surroundings we can explain why a salt such as ammonium nitrate dissolves in water despite the fact thatthe process is endothermic. We are now going to revisit the question of why some salts are soluble and others are not, but this time view it by considering the Gibbs energy change of the system. ‘When trying to predict the extent to which a salt, for example M"X°, is soluble, we simply need to look at the Gibbs energy of solution, A...G*, for the process: M°X(6) 2 Me(aqh + X-(eq) IF &,aG* is negative then the products are favoured at equlibrium and the sl is soluble. If AiG" is positive, then the solid sat is favoured at equilbrium and so the saltis insoluble (or more accurately sparingly soluble, as we have already identified that a process with a positive Gibbs energy change can take place to a certain extent as long as the magnitude of AGis not too large). ‘The equilibrium constant for the reaction is given by the expression: R= [M*(aglX(eq)] (You will remember that in ¢ heterogeneous equilibrium the solid does not contribute tothe expression ] ‘This equilibrium constant is called the solubility product and is usually given the symbol K.,. ‘The relationship between A, Gand Kis given by the expression: AnG* =-RTInk,, ‘The relationship between 46% Aland AS, ai given by BnuG* = MoHl*~ TSS yncn Let us first ofall consider thre soluble salts, calcium nitrate, magnesium sulfate and sodium nitrate. ‘The relevant data for each is given in table A. ("= 299 K) CalNOy, | -19000 15 313.000 410000) MgSO, -31 000 =210 63000 82000 NaNOs $21,000 +90 +2700 1 table Aer Each of these salts is soluble at 298 K, as is shown by the negative AG and the lange values of K, Let us now consider why each of these salts is soluble in water Calcium ate A.M? is negative 50 A,,.ff of the ions must be greater than Ayyi..Af oF Ca(NOs), ASseaar 8 positive, so the increase in entropy produced by the breaking up of the lattice must be {greater than the decrease in entropy of the water produced by the hycration of the ions, Since AH < Vand ASiyzan > 0, SuaG* is negative (see Section 13.2.1), Calcium nitrate is soluble ‘in water as both the enthalpy and the entropy terms are favourable. Magnesium sulfate Again, A.M? is negative. However this time AS.,.on is also negative, since the ordering of the water ‘molecules around the hydrated ions is much greater because both ions have a double positive charge and the charge density of the magnesium ion is that much greater than that of the calcium ion, However, dG is still negative because the magnitude of 4/1 is greater than the magnitude of TAS youn (S22 Section 13.2.1 Magnesium sulfate is soluble because the favourable enthalpy term outweighs the unfavourable ‘entropy term. Sodium nitrate Acad and ASzpam are both positive, However, the magnitude of &,,/4* is less than the magnitude of TAS sen 50 O70e agai 8.6 is negative (see Section 13.2.1). Sodium nitrate is soluble because the unfavourable enthalpy term is outweighed by the favourable entropy term. Sparingly soluble salts Ee Ca acl | ~66000 710000 256000 | 15*10 6250, | ~19000 =105 =31000 251000 | 1x10 caco; | -12000 200 59000 247000 | 57x10? tables Each of these salts is only spatingly soluble at 298 K, as is shown by the positive A._,G" and the very small values of K,, Let us now consider why each of these salts is only sparingly soluble in water Silver chloride Avi? and AS, 21, are both positive. However, the magnitude of A.,#/* is greater than the magnitude Of TAS yeuny 80 A.G* is positive (Section 13.2.1). Silver chloride is only sparingly soluble because the unfavourable enthalpy term outweighs the favourable entropy term. Barium sulfate Avail? is positive and AS, eqs negative, However the magnitude of TAS... is greater than that of AGH®, wich leads to a positive value of A, ,G* Barium sulfate is sparingly soluble because both the enthalpy and the entropy terms are unfavourable.16 Calcium carbonate vai? and ASyomn are both negative, but the magnitude of TAS;mum is greater than the magnitude of Aval#®. Hence, A.C? is postive (Section 13.2.1) Calcium carbonate is sparingly soluble because the favourable enthalpy term is outweighed by the unfavourable entropy tern, Strength of acids Hydrofluoric acid, HF(aq) ‘Why is hydrofiuorc acid a weak acid, whereas hydrochloric acid isa strong acid? Its often stated that hydrofluoric acid is a weak acid because of the high strength of the H—F bond: ic, that the incomplete dissociation of HF molecules in water is enthalpy driven, The following dara should convince you that this is not cortect, and that entropy plays the predominant ral. Let us first ofall loa at the ease of hydrochloric acd, which we know tobe a strong acid in die aqueous solution, The two important energy terms for the dissociation of HCl in water are: Enihalpy change Haq) — Haq) + Cl-faq) AN? = ~58Kd mol! Entropy change: Haq) H"(eq) + Cha) AS ‘The dissociation in water of HC] has a favourable (Le. negative) 4/72, but an unfavourable (le. negative) AS*, From these values we can calculate AG® at 298 K as follows. AG? = AH TAS? 58 ~ (298 « 85 10") 98+ 164 416k) mol ‘This gives a value for the equlbrium constant, K, of 1.98 > 10", which is consistent with the description of HCl as a strong acid. The favourable enthalpy term outweighs the unfavourable entropy term. 85K mol Let us now turn our attention to hydrofluoric acid, The tv important energy terms this time are! Enthalpy change: HP{aq) — H'(aq) + F-{aq) AH? = -9kJ mol“! Entropy change: HP(aq) — H'(aq) + F'{aq) AS? = -71 K mol! Calculating the value for AG® at 298 K, we obtain AG?= aH?- TAs? 9 = (298 x =71 x 10%) 94212 +122k) mot"! ‘This gives a value for & of 7.73 x 10°, which is consistent with the description of HF as a weak acid (On this occasion the entropy term, TA.S®, dominates making AG® positive. Hence, itis the entropy term that isthe deciding factor in making FF ¢ weak acid. Since the H—F bond strength is incorporated into the enthalpy term, we can discount this as the major contributing factor Another factor that contributes to the acid strength of HF is hydrogen bonding, The hydrogen bonding in HF is strong and this has an effect on the dissociation of the HF molecules in aqueous solution.er The chloroethanoic acids Ethanoic acid, CH;COOH, is a weak acid. However as chlorine atoms are substituted for the hydrogen «atoms in the methyl group the acid strength increases, as shown by the pC, vales in table C. free tee a ‘ethanoie acid CH,COOH 476 chloroethanaic acid CH.CICOOH 286 dichloroethanoie acid CHCLCOOH 1.29 tiichloroethanoic acid CCYCOOH 068 table ‘A simple explanation for what is happening is thatthe electron.withdrawing chlorine atoms are polarising the O—Hi bond in the carboxy group, making it easier to ionise. It can also be argued that the electronegative chlorine atoms are helping to stabilise the anion formed upon ionisation. Did you know? Here we can use enthalpy and entropy to explain the pr, trend observed forthe chloroethanolc acids Consider the equibum CHs.C1,COOH{aq) == CH, .€,COO (aq) + Haq) where n = 01, 20°3 aH*/) mol 2108 “46 #12 AS%)) 7 mal “16 “702 “58 TaS®/4j mot 214 208 a7 AGM mal waz 463 29) tabled ‘The important observation to make is thatthe enthalpy terms, AH®, forall bl CC_COOH are negligible ‘compared to the entropy terms, TAS®. The varation in pk, values, and hence strength of acid, i therefore entirely an entropy effect and has nothing to do with the strength or polarity of the OH bond in the carboxy! group. ‘The explanation forthe increasing acidity must centre on the \S® values, which are becoming ess negative from CH,COOH to CCL.COOH. The electron-withdrawing chlorine atoms are producing a spreading out ofthe negative charge across the whole ofthe anion, The charge i therefore less Concentrated and so the water molecules ate les tightly held, leading to a smaller reduction in entropy. The case of CC1,COOH is litle different from the others because the AH and TAS values are comparable. However, AH" for this acd isthe only one that i positive and therefore unfavourable. Despite this CCLCOOH is the most acide. The less unfavourable entropy term is predominant over the enthalpy term 7HYDROGEN REVOLUTION Like many car manufacturers, Toyota is looking to build a lead in the next generation of hydrogen- poviered cars. On sale since 2013 is the new Toyota Mirai eco-car. The following extract from the ear manufacturers blog explains ho the nearest hing yet o an ultimate they work | HOW DOES TOYOTA'S FUEL CELL VEHICLE WORK? oe fig. the Toyota Mire ful cal car can ‘ward second inthe What ‘The revolution starts here... The countdown to he launch of Toyota's advanced new fue cell vehicle has finaly beg ‘Onsale in 215, the Teyota Miri fas been deseribo as the nearest thing yet tothe ukimatsceo-ar and a key stp in nding solution to energy demands ‘and emissions issues associated with tations) petol and diesel engines. But Toyota’: new fuel coll vehicle is much more than the realisation of cutting-edge seience theory. How do fue cell vehicles actually work? A fel cell converts fuel into eleticity by forcing it wo react with oxygen ydrogen sth most common fuel used in eds ful cells, but los ay hydrocarbon, including 2s and slot am be used. Fut ool require a ‘eanstant supply of fuel ancl oxygen ssn the elotcty goncrting reaction 1's wort pointing out thatthe idea of fue cells is nothing new: in fae, ‘the frst examples were designed in the mid-1800s, Howver, i 00K more ‘than 100 years forthe idea to get off the ground —liteally,as NASA refined thei use for the Apollo Moon projec. This environmentally ficndly and highly encrgy-fficient process of spencrating elcetrcity in a ful cell produces no tailpipe emissions, but Tots of pure water ~ great news, ifyou are running one inside a spaceship. [Back on Earth the same qualities make fucl cell vehicles ideal for achieving sustainable mobility which is why Toyota has been striving to take this ecology widely available as soon as possible, “That understand its now necessary to explain the furetions ofthe two primary components used ina fuel cell vehicle Nance pce AT ce a OTT aT EP ee ITE Where else will] encounter these themes? 78 extemal load srogen side siesde requires almost pute hydrogen .——— oer B~ poous cathode Fuel cell The fuel cell generates electricity through a chemical reaction between hnydrogen and axygon. This is achioved by supplying hydrogen to the ‘negative anode ofthe fue ell and ambient air othe postive cathode A fal cell consists of individual ces within a membrane electeode assembly (MEA) sandwiched between separators, The MEA consists ofa polymer clectrolyte membrane with postive and negative catalyst layers on ether Side, Eh cel yields less than one vol of electricity, so several hundred cells fare connected in sros to increase the volage, This combined bod of cells is called a stack, which i commonly referred to as a fuel cll unit ‘Though itis possible vo use other elements in a fuel cell, dhe advantage of Inydrogen i ts high energy cfciency. Since electricity can be produced dlrcelly from hydrogen without combustion, itis possible to convert 83% of the energy within a hydrogen molecule into elecrieity. This is more than double the enorgy efficiency of a petrl-powered engine High-pressure hydrogen tank Hydrogen is stored in te high-pressure (70 MPa) tanks. The innermest layer features a polyamide esin line that has high strength and superb resistance to hydrogen permeation, This s necessary becanse he diameter ‘of hydrogen molecules isthe smallest known fo science and tend to escape ‘Hough inferior materials usher use of optimal matrials has incense tank capacity historically most FCVs have needed four separate tanks to improve capacity and therefore ‘cising range) and euced woigh. This ean be seen in the winding angle, teasion, volume and wall thickness oft earn fbr used in the ocr shell. aonLet us start by considering the nature of the writing in the article Ways remember to Consider the source 1. Write a lst of any advantages and disadvantages of fuel cell vehicles that are mentioned in the blog post. Do you think that the post provides a balanced viewpoint of the you read seins Ge” | technology? Justify your answer. Does the author have oi? wearst npecee = | \ Particular viewpoints Now we will look atthe chemistry in detail. Some of these questions will link to topes earlier in this book or Book 1, so you may need to combine concepts from different areas of chemistry to work cour the answers 2. a. Write a balanced chemical equation for the reaction between hydrogen and oxygen to produce water. a b. Explain why the volumes of hydrogen to oxygen must bein the ratio of 2:1 toensure_ |S #°¢ “expt complete combustion. a 2 question, your The enthalpy of combustion of one mole of hydrogen to produce water is A justification +9 etude ~286N) mol” under standard conditions, The extract says that'83% of this energy can be || soi 20”, Me cous converted int electric raul cel Calculate the energy converted toclectrityby | mga = mathematical expe '50 dm? of hydrogen (measured at standard temperature and pressure) using the enthalpy of combustion value given 3. Use the data in the table below to answer this question. Half-equation Standard electrode potential/eV JO;+ 2H" 2e = H,0 7123 a, Write down the balanced equation for the reaction of hydrogen with oxygen in a fuel cell and calculate the cell emt. The AG for this reaction can be calculated from the expression: AG = -nFE where Fis the Faraday constant (96 500 mol") and n b. What does AG represent and what i its significance for a reaction? . Caleulate a value for AG from the information above giving units for your answer. \umber of electrons transferred. 6, How do the values calculated in questions 2¢ and 3¢ compare? Why would you expect them to be: (i similar, (i) diferent? | Didvouknow? 4, State two challenges that manufacturers of fuel cell vehicles may face. ‘Akhough predicted a ealy as 1935, was only in 2011 that the creation ofthe metalic state of hydrogen was finaly reported. Ata pressure of Activity 260 billion Pa, seients atthe ‘Max Planck institute in The concept Gibbs nergy AGis acetal one to chemist inthatitinksa numberof areas othe ylabuss Germany reported that this + AG RTI form of hydrogen had filly © Age -nFE been made. Metalic hydrogen a helps explain, among other Coie things, the strong magnetic choose one ofthe thre equations above and gvea shor (S-8sides) resentaton onthe applcatonctthe fed generated by the'gas equation toan aspect ofthe chemistry you have covereé ta date. You should ao pont out the limiationsof lant Jupiter, which unite sng the equation in making predictions about chemical reactions Earth has no iron core (© From Tete The Oficial Blog of Tae UE by Joe lita bog sayotncoskihow-loetoytarfeeheell-veice-work13 1 (a) Identify which equation defines the lattice energy of the compound X*Y~, uy A Xig) + ig) > VG) B X(5) +) — X-¥(9) CX) + VU) + X19) DX) +¥9) KY) (b) Identity which of the fllowing compounds has the langest (the most exothermic) lattice energy. it) A caesium iodide B lithium fuoride © rubidium chloride D sodium bromide (c) The Born-Haber cycle shown can be used to calculate the lattice energy for magnesium oxide. 2 glOG8)+ IO +657k) mol” x Neate +0@) AO,@) = 4248 mot A Mee) + 20° +20,0) TE [Mete)) +1450 kd mat te +20 a fADMS-O* to] AH, = +7361 mol Mele) + 30,2) au, = +140 mol Mais) + 20.48) AM, = 602K) mol MgO () Give the name of each of the enthalpy changes labelled Av, AH, and Af, 3) Wite tie missing formulae tom the top ofthe Bora- Haber cycle. Include state symbols. ia) (i) The equations for the fist and second electron affinities of cxygen are: Ofte =O) Ea O@Fe HO) Hyg = 4798kImor Suggest why the second electron alfnity of oxygen is endothermie. al (ie) Use the data in the Born-Haber cycle to calculate the lattice energy of magnesium oxide, (2) [Total: 11] Exam-style questions 2. Lattice enengies can be found ether via experimentally determined energy changes, using the Born-Haber cycle, orby theoretical calculation using the ionic model for the crystalline compound. (a) State the energy changes that need to be determined in order to find the lattice energy of sodium fluoride, using. the Born Haber cycle. ro (0) The table ists the experimentally determined and theoretically calculated lattice energies for some compounds, Experimental value/J mol |=938 |=705 |=958 ‘Theoretical value/kJmol” — [=912[=0a7 [-920 Comment on the discrepancies between the experimental and theoretical values of the lattice energies. (4) (c) The enthalpy changes of hydration, in kJ mol, of the ions in the compounds listed in the table in part () ae: Nat-406 Ag'—464-F--506 I -293 (0) Using the experimental lattice energy values, show by calculation which of the four compounds is the most sohuble. Q) (i) Explain what other information is necessary in order to make a valid comparison of the solubility of the four compounds, by [Total: 12] 3 Entropy changes are important in determining the feasibility of a process (2) For each of the four processes, predict the likely sign of the entropy change of the system, ASynq-In each case [justify your answer. (4) (0) Na) + 3Hlg) — 2NHg) @ 1,06 = H,00) {ii) No(s) + Ox(g) + NozOx5) (i) S69) + Og) — 250)(©) Magnesium oxide s used as arefiactory lining for furnaces Ican be made by heating magnesium carbonate MgCO,fs) ~MgO(s) + CO,(g)AH* = +117dmot “The table shows the standard entropies at 298 K of MgCO,(s), MgO) and CO,(e) [Hammer 00,9 | ad |SeKtmor | 65.7 27.0 (@) Use the dara to show that the magnesium carbonate is| cow | 2140 _| stable at 298 K. (4) (i) Calculate the minimum temperature at which ‘magnesium carbonate will decompose i] [Total: 10] 4 (a) The overall equation for the reaction between two chemicals, Jand M.is J+2M>Q+R ‘This reaction occurs spontaneously at room temperature, entity which of the following must be true? ie A AH? is negative B AH*is positive C AS? pais negative D AS%q is positive Barium carbonate decomposes at high temperature to form barium oxide and carbon diorde: BaCO,(s) > BaO(s) + CO,{g) Barium carbonate is thermodynamically stable at 298 K because fr this reaction: {A the activation energy is high. B the standard enthalpy change of reaction, AH, is, positive C the standard entropy change of the system (AS can) i8 positive D the standard entropy change ofthe system (AS yuan) is negative, a {6) The equation forthe combustion of hydrogen is Hyg) + 304g) + H,00) AH? =~ 285k mol “The table gives the standard entropies at 298K fo Hi), 0,@) and HO) Substance He) | Ox [00 SK'mor* | 1310 [| 2050 | sao ) (@ Calculate the standard entropy change of the system at 298K. AS*saen for the combustion of hydrogen. [2] (i) Calculate the standard entropy change of the surroundings at 298K, AS®syangy fF the combustion of hydrogen, al (ii) Calculate the total stendard entropy change at 298 K. ‘85° forthe combustion of one mole oF hydrogen. Give your answer to an appropriate number of significant figures 1 (4) Explain why hydrogen does not react with oxygen unless the mixture is ignited 0] (Total: 10] ‘Ammonia ean be made by reacting together nitrogen and hydrogen. The reaction is reversible. Ny) + 3Hg) = ANH Ye) 44° (700) AS (700 K) = ~78.7 JK! 0! (@) The * symbol represents standard conditions of a specified temperature and standard pressure. In this instance. the temperature specified is 700 K State the standard pressure for thermodynamic measurements (i) (b) Calculate AS, reaming: (700). ia} (c) Calculate AS*, 4, (700K) ial (4) If the reaction mixture is left for long encugh, in contact with a suitable catalyst, itis possible to establish an equilibrium between the nitrogen, hydrogen and the Comment on what the value of £5... (700 K) indicates about the relative proportions of nitrogen, hydrogen and 110.2kJ mot” ‘ammonia inthe equilbrium mixture at 700K. a] (2) Deduce how the valve of AS én Changes as the temperature inereases above 700K in] (i) Explain how this change affects the value of AS": and the equilibrium constant, K., as the temperature inereases, el (ii) Assuming thatthe reaction reaches equilibrium, use ‘your answer to (ei) to give a possible disadvantage of using a temperature higher than 700K ty (i) State one advantage of using a temperature higher than 700 K, 1) (Total: 12]Introduction In Book 1 Topic3, you learned about one of the main types of reactions ~ redox reactions. Now that we have studied equilibrium and thermodynamics, we can investigate these ceactions in more depth. Redox reactions keep us alive. They capture the energy ofthe Sun by photosynthesis and we can then use that energy. However, redox reactions can also kill- they can result in explosions. Redox reactions are used throughout the chemical industry, for example to extract metals rom their ores. However, redax reactions are also responsible fr the corrasion of metals What redex reactions can achieve, they ean alsa destroy. In Tope 13, we saw that some chemical reactions take place spontaneously. In this topic we shall look at the branch of chemistry know as electrochemistry, which deals with the use of spontaneous reactions to produce electricity ‘This topic also has a link to Topi 12 In that topic we saw that a great deal of chemistry can be discussed in ‘terms ofthe transfer of protons. n this topic we shall see that another large area of chemistry can be Lnderstood in terms of the transfer of another fundamental particle - the electron, Praton transfers the basis ‘of acid-base reactions electron transfer isthe basis of redox reactions, All the maths you need ee eer eee eee ere eee te comet ieete tetera \ + Solve algebraic equations 82STE are Nar ieg cote eye tc eee eee eotia SE ee Using oxidation numbers to name compounds Seo Piette eet pene ee ey What will | study in this topic? [eee errr Perera ee trey) een eee ee cen feasibility of chemical re Sood PeersStandard electrode (redox) potentials By the end ofthis section, you should be able to... (© understand what is meant by the term ‘standard electrode (redox) potentiat, £* (© understand that the standard electrode potential, E*, refers to conditions of {i) 298 K temperature (i) 100kPa (1 bar) pressure of gases (ii) 1.00 mot din concentration of ions © Understand the features of a standard hydrogen electrode and understand why a reference electrode is necessary © Understand that different methods are used to measure the standard electrode potentials of (i) metals or non-metals in contact with their ions in aqueous solution ) ions of the same element with different oxidation numbers © understand that standard electrode potentials can be listed as ‘an electrochemical series Revision of oxidation and reduction You should remember from Book 1 that there are two very useful definitions of oxidation and reduction. One isin terms of loss ‘or gain of electrons. The other is in terms of changes to the oxidation number of an element Interms of electrons: *+ Oxidation is the loss of electrons. + Reduction is the gain of electrons. In terms of changes in oxidation number + An element ina species is oxidised when its oxidation number + An element ina species is reduced when its oxidation number decreases ‘These definitions apply to all elements whether they are in the s+, p-or diblock of the Periodic Table, How well you will understand the topic of electrode potentials depends very heavily on your appreciation of redex reacrions. If ‘you are at all unsure of your understanding, then we suggest that ‘you revisit the topic ia Book 1. Standard electrode (redox) potential “The two terms ‘standard electrode potential’ and standard redox potential’ mean the same, The reactions involved in the measurement ofa standard electrode potential are redex reactions. Hence the term redox potential is also commonly used, Inline ‘standard electrode potential throughout the book. 84 ith the Edexcel specification, we will use the term ‘There are many ways of teaching this topic, but very often a fundamental mistake is made at the outset, [tis sometimes forgotten to emphasise thatthe reactions involved are equi ‘Too often you wil find that the equations are written as if they were one-way reactions, rater than reversible. This very simple mistake can make the whole topic much more difficult 0 understand than is necessary ‘Throughout this topic we shall avoid this problem by always talking in terms of equilibria Background: the different tendencies of metals to release electrons to form positive ions ‘When a metal such as magnesium or copper s placed in wate, there is avery small tendency fr the metal atoms to lose clectros and go into solution as positive ions Ms) 1 M(aq) + ne~ (where M= Mg or Cu) ‘The electrons will remain on the surface of the metal Ina very short time there will be a build-up of electrons on the surface of the metal, and the resulting negative charge attracts postive ios. In this way a layer of positive ions is formed surrounding the metal Some of the postive ions will regain their electrons from the surface of the metal and return to form part of the metal surface Mag) + ne~— Mis) Eventually, a dynamic equium will be established in which the rate at which fons are leaving the surface of the metal to go into solution is the same as the rate at which they ar joining i from solution. Ths equilbrum is represented by the equation: Mag) + nem = M6) Mis) A. Metal Mimmarsed in water: represents metal ions "The equations for magnesium and copper are Mg*(aq) +22” = Mg(s) Cut (aq) + 26° = Culs) The difference betvieen magnesium and copper is that the ‘equilibrium position will be further to the left-hand side for ‘magnesium than for copper, because the tendency of magnesiumCO 10 release electrons is greater than that of copper So, with ‘magnesium there will be a greater negative charge on the metal, ‘and more positive ions in solution. Learningtip [Note how the two equillria are written. By convention they are \wrtten withthe electrons on the left-hand side. Make sure you stick tothis convention atl times In the case of both magnesium and copper, there is @ potential difference between the metal and the solution. However, the potential difference is greater with magnesium than with copper In each case, we would like to measure the potential difference between the metal and the solution. This is called the absolute potential difference. However it is not possible to measure the absolute potential difference between 2 metal elecrode and its solution. The reason is that although tis a simple matter to connect the metal electrode 1oone terminal of a voltmeter, the other terminal would have to be connected tothe solution, and the only way of doing this isto dip another piece of metal into the solution. This second piece of ‘metal would create its own potential difference. So, you would be ‘measuring the potential diference between the two pieces of meta, ‘and not between the original metal and the solution, ‘The way to solve this problem is to create a reference electrode and then measure the difference in potential between this| reference eleetrade and the metal electrode. The standard hydrogen electrode ‘The reference electrode of choice is the standard hydrogen electrode. This electrode consists of hydrogen gas at a pressure of 100Pa (1 bar) bubbling over a piece of platinum foil dipped into solution of hydrochloric acid (or sulfuric acid) with a hydrogen ion concentration of 1 mol dm”*, at a temperature of 298 K. ‘The surface ofthe platinum fil is covered in porous platinum Porous platinum basa large surface area and allows an equlbrum between Jhycrogen ions in solution and hydrogen gas tobe established quickly (aq) + e° = 2Hyla) [eis this equilibrium that we ae going compare with all thers FFigB shows cross-section of a typical standard hydrogen electrode. hydrogen gas ——> ar 100k | plainum }— tyetochvic act lainum fll covered [F(oa)}~ Imoldmy* fn porous platinum B.A standard hyérogen elecrode The importance of using standard conditions ‘You will remember tht the position of an equilibrium can be changed by altering the conditions. If we are going to make fair comparisons i is therefore necessary to standardise the conditions used. The standard conditions are: + gas pressure, 100kPa (bar) + temperature, 298 K + concentration of ions in solution, 1 mol dm “These standard conditions apply to all equilibria Measuring a standard electrode potential We are now in a position to appreciate how to measure the standard electrode potential of a metal ion | metal system, such as that between magnesium ions and magnesium (Mg | Mg). “To do this, we connect the standard hycrogen electrode to the magnesium electrode via a cireult containing a high resistance voltmeter Fig C shows the arrangement of the apparatus vege: i PEE i teen hydrochloric acid [H*(aq)] = 1motdm- ‘magnesium sulfate solution (Ma’*fa)}= tmelém~* fig € Using a sandard hydrogen electodeto measuea standard elected potential ‘The two components of the apparatus are known as half-cels, ‘The two hall-cells combine make a camplete cell. “The salt bridge is needed to complete the electrical circuit. I usually contains @ concentrated solution of potassium nitrate in the form of liquid or a gel. It functions by allowing the movernent of ions. Theoretical, the sat bridge can contain any ionic salt, but neither of the ions present should interfere with the components of the alf-cells. For example ifthe right-hand hal-cell contains a solution of silver nitrate, then potassium chloride would be unsuitable forthe salt bridge because the chloride ions would interact withthe slvr ions to forma precipitate of silver chloride. ‘There is @ reason why a high resistance voltmeter is used, Ideally the voltmeter should have infinite resistance so that dere Is, 85Didyouknow? _ The best instrument to use to measure the potential difference ie a potentiometer. No electrons flow when this instrument s used, so both half-cell reactions are in equtlbrium However, the best practical way of measuring the potential difference isto use a high resistance voltmeter. 86 no flow of electrons ((e. no current lowing) around the external circuit, If this were possile, the reading on the voltmeter would represent the difference in potential between the two half-cells when. ‘both reactions ar in equliérium, The two reactions concerned are: Hifaq) +e = Hila) Mgi*(aq) + 26° = Mats) ‘With the magnesium halfcell connected to the standard hydrogen electrode, the reading on the voltmeters 2.37V, If the magnesium hal-cel is replaced by a copper hal-cel (ie. copper metal dipped into a solution of copper sulfate with (Cu?{aq)] = t mol dm), then the reading on the voltmeter wuld be 0.34 V. ‘There is, however, a further issue to be considered. In the case of magnesium, if the voltmeter was taken out of the circuit, electrons would flow from the magnesium electrode to the hydrogen electrode. Thais means that magnesium is the negative electrode of the cell. ‘With copper electrons would flow ftom the hydrogen electrode tothe copper electrode, making copper the positive electiode ofthe cell ‘This difference in behaviour is recognised by using a sign convention, A negative sign (—) indicates that the metal electrode is negative with respect to the hydrogen electrode, whilst a positive sign indicates the reverse, ‘The difference in potential measured, together with the appropriate sign, is called the standant electrode potential of the metal. Standard electrode potential is given the symbol £. ‘Standard electrode potentials are quoted together with the relevant half-cell reaction, For example, for magnesium and copper they are: Mgi"(aq) + 26° = Mala) Cul(aq) + 2° = Cals) By convention, the standard electrode potential ofthe standard hydrogen electrode is zero. Haq)+e = Fg) B*=000V -2a7V +04V Some other £° values, together with the relevant hal-cell reactions, ae shown in table AL E Agrfaq) +e = Agts) 40.80 AIM(agh +3 = Ale) ~168 Pag +36 = Gis) -074 Fem (aq) + 2 = Fels) “044 Ni*(aq) + 22° = Nils) 025 Zn (aq) +26 = Zn) -076 ‘The sign of standard electrode potential indicates the polarity of the electrode relative to the hydrogen electrode. Ths sign is fived and does not change ifthe equation for the halfcell reaction is reversed, as ‘sometimes stated elsewhere. Remember, standard electrode potentials are measured when no electrons ‘are flowing and hence both half-cell reactions are in equiliium. So, the haf-cell reaction for magnesium is represented as: Mg(s) = Mgiaq) + 2e, the €° value is stil -237 V. doesnot change to +237. Standard electrode potential is described as being a sign invariant quantity. This means that however the reaction is represented, the sign remains the sameWhat do €* values tell us? {tis important to remember that the standard electrode potential of @ metal ion | metal hali-cell is the potential difference measured when the half-cell is connected to a standard hydrogen electrode. ‘The potential difference provides a comparison between the position of the metal ion | metal equilibrium and the position of equilibrium in the hydrogen electrode. ‘Tillustate this point, let us consider the following two standard electrade potentials: Mg?(aq) +26" = Mg(s) F*=-237V Haq) +20" = Hig) = 000 CuP(aq) +22" = Cus) = +034 ‘The negative sign for Mg"(aq) | Mg(s) indicates that the equilibrium position of this reaction is further to the left than the equllrium position of the reaction in the hydrogen electrode ‘The positive sign for Cu?*(aq) | Cu(s) indicates that the equilibrium position of this reaction is further to the right than the equilibrium position of the reaction inthe hydrogen electrode. ‘This is another way of saying that magnesium releases electrons more readily than hydrogen (and also than copper), but that copper releases electrons less readily than hydrogen, Magnesium is, therefore, a better reducing agent than both hydrogen and copper In addition, hydrogen is a beter reducing agent than copper This point will be developed later inthe topic. hearningtip A teducing agentisa species that reduces another species by adding one or more electrons ta it. When a ‘reducing agent reacs it loses electrons and is, therefore, oxidised. ‘An oxigsing agent isa species that oxidises another species by remaving one or more electrons from it. When an oxicising agent reacts it gains electrons ands therefore, reduced, ‘Leamingtip Remember, a negative E> doesnot suggest thatthe equilibrium ofthe hale reaction lest the eft. ‘merely means that ilies further tothe left than the equilibrium ofthe standard hydrogen electrode. Inthesome way, a postive €° means thatthe equlrium of the haf-celleatin ies frther othe right than the equilbrium ofthe standard hydrogen electrode Summary ® values provide a method of comparing the positions of equilibria when metal atoms lose electrons to form ions in solution, + The more negative the ° value, the further the equilibrium lies to the left, ie, the more readily the ‘metal loses electrons to form ions. + The more positive (or less negative) the £° value. the further the equilibrium lies to the right. ie. the less readily the metal loses electrons to form ions. Later in this topic we will extend this to include both molecules and ions losing electrons. Electromotive force ‘As already mentioned, when we are determining a standard electrode potential, the potential difference ‘is measured when no electrons are flowing (i.e. no current is flowing) through the external circuit. The potential difference measured uncer these conctions is called the electromotive force (emaf) of the cal ‘The stancard emf of a cellis given the symbol £®,a ands sometimes called the standard cell potential mf values can be positive or negative, depending on the reference point against which the potential difference is measured. When measuring standard electrode potentials, the reference point is the potential of the standard hydrogen electrode, whichis set at zero, The emf of a cell in which the hydrogen electrode isthe positive electrode will have a negative value, Conversely, the emf of a cell in which the bydrogen electrode is the negative electrode will have a positive value, 87141 ‘This now allows us to define standard electrode potential as follows: ‘The standard electrode potential of a half-cllis the emf of a cell containing the hal-cell connected to the standard hydrogen electrode. Standard conditions of 298 K, 100kPa pressure of ‘gases and solution concentrations of 1 mol dm? apply. Measuring standard electrode potentials of more complicated redox systems Systems involving gases Suppose we wanted 10 measure the standard electrode potential of the following redox system Aci {g) +e" = Crag) ‘We can do thisby seting up a half-ellin which chlorine gos is ‘bubbled into a solution containing chloride ions. However in order to.estabish an equlibrium between the chlorine molecules and the chloride ions, and also to provide an electrical connection to the external circuit, we would need to place a piece of platinum into the solution, Fig D shows the set up + corn ga ot pain 00a sakiton of ae Sodium code o| Le [CP faqy] = totam? i [Hie | retina fot covered © | _ inporas plain fig 2C)[g)|CHag) halle ‘This half-cell is then connected to a standard hydrogen electrode and the emf is measured in the usual way. The measured emf is +1.36 V, Hence: 3Chia) +e Crag) Be = 41.360 Other systems |. Non-metal elements and their ions in salution Examples: 3Br,(aq) | Br-(aq) and 31,(aq) | I-(aq) “To determine the £° of the redox system 4Br, | Bra hallcell containing a solution of Br, and Br ions, each of concentration ‘mol dm-* is connected to a standard hydrogen electrode, ‘similar so: up is used to determine the £® of the redax: system qhit 4Br{eq) +e = Brag) £°= +109 Ayfaq +e = aq) EP = 4054 2.fonsof the same element with different oxidation numbers Example: Fe™(aq) | Fe™(aq) “The half-cell is arranged as shown in fig E 88 platinum wie [Fe "(aqh] = mst? - =} Fe agi = teeta? ‘ 'n porous platinum (gE Fe()| F(a hal-cl "Note that each ion has @ concentration of 1 mol dm” Fe'(ag) +e" = Fe*(aq) £°=+0.77V The electrochemical series Arranging redox equilibria in order of their €° values ‘The electrochemical series is built up by arranging various redox ‘equilibria in order of their standard electrode (redox) potentials. ‘The most negative £ values are placed at the top of the series, and the most positive at the bottom. ‘Table B shows part of the electrochemical series. CR U'tag) +e" = Lis) Kilag)=e = Kis) Ca(aq) + 2e = Cals) Na‘(aq) +e" = Nas) ‘AP (aq) 36 = AIG) Zi (aq) +26 = Zig Cag) = 3e = Cs) Fem (aq) + 26 = Fels) Haq) +e = JH.) Cu*(aq) + Ze" = Cus} Hig) +e = aq) Ag'lag)+e" = Agts) Brlaq) +e = Brlag) aq)+ © = Cag) Reducing agents and oxidising agents “The species on the right-hand side of the hall-cel actions are all capable of behaving, as reducing agents because they can lose electrons, ‘The most powerful reducing agent in table Bis lithium because its redox system has the most negative £* value; the equilibrium position of its half-cell reaction is furthest to the let.he least powerful reducing agent inthe lists the fluoride ion, F-(aq) because its redox system has the least negative (most positive) £* value. The position of equilibrium of its half-ell reaction is, furthest to the right The species on the left-hand side of the half-cell reactions are all capable of acting as oxidising agents because they can gain electrons ‘The most powerful oxidising agent is fuorine and the least powerful is the lithium ion, Li"(aq). ‘Table C surnmarises these statements, Teast powerful oxidising agent reducing as} mast powerful oxidising agent tabl c Summary ‘The more negative the £* value, the more the equilibrium position lies toward the lft ~ ane the more readily the species on the right loses electrons. The more negative the B° value, the more powerful the reducing agent ‘The more positive the £° value, the more the equilibrium position lies toward the right ~ and the ‘more readily the species of the left loses electrons, The more positive the value, the more povierful the oxidising agent. 1 Draw atabeled agar of apparatus tha could bused to measure the standard leo potential oa Coa) hale 2. The standard electrode potential of the 48r,(aq)| Br-(aq) half-cell is +1.09 V. Explain what is meant by this statement and state the sgnficance ofthe postive sgn 3. What smeantby the term electromotive force (emf). How isthe electromotive force ofa cll measured? Didyou know? _ The standard electrode potentials oflithium, sodium, caleium and potassium cannot bbe determined experimentally because exch of these metals teacts to completion with water ie. they do not establish an equilibrium. The E° values for these metals are calculated from thermodynamic data ‘The same s true for fluorine, Which also reacts with water, Key definition ‘The electromotive force (em) Js the standard electrode potential ofa hal-cel (measured under standard Conditions of 298 K, 100 kPa pressure and concentrations of mol dar) connected toa standard hydrogen electrode. 89,Electrochemical cells By the end of this section, you should be able to.. © write cell diagrams using the conventional representation of, half-cells @ calculate a standard emf, Es, By combining two standard electrode potentials, Electrochemical cells ‘An electrochemical cell is a device for producing an electric current from chemical reactions. It is constructed from two half-cells Fig A shows the apparatus used to consiruet an electrochemical cel from a Zn%* | Zn half-cell and a Cu®* | Cu hral-cell under standard conditions ow of electrons copper (2naq)} = 1molémn [Cua] = 1 meld temperature = 298% fig. fn eletochemical cll consisting of Zn 2n and Cu Cu hates ‘The relevant standard electrode potentials for the redox systems involved are 1g) + Je" = Znfo) B= 0.76 CuM(aq) + 20° = Culs) £2 = 4034 ‘The £* value for the Zn** | Zn halt-cell is the more negative, 30, the zinc electrode will be the negative electrode of the cell. When the call is in operation, ie. itis generating an electric current, electrons will flow through the external circuit from the zinc electrode to the copper electrode. ‘The reactions taking place under these conditions are shown below, ‘At the negative electrode: Znjs) —> Zn?¥(aq) + 2e Atthe positive electrode: Cu:*(ag) + 2e- + Culs) ‘The overall cell reaction is: 90 2n\s) + Cu" (aq) — Zn**(aq) + Culs) Cell diagrams Itis not always convenient to draw a diagram of the fll apparatus fora cell To simplify matters, chemists use a shorthand notation to represent lf cells, The hal-cll made from zine ions and zine metal is writen as 2a) |Za(s) 76 The solid vertical line indicates a phase boundary in this case berween an aqueous phase, Zn*(aq), and a solid phase, Zs) Some other examples are Mg*(aq) | Mats) cu fag) | Cus) (aq) | Alls) Agtlaq) | Agts) ‘When the electrode, ie. the electrical connection between the solution and the external circuit, is apiece of platinum fol the following convention is used Pus) | Fe™(aq), Fe (ea) Ersoy Norice that because theres no phase boundary berween Fe!(aq) and Fe?"(aq), a comma is used to separate them, not a solid vertical line ‘The standard hydrogen electrode is represented as fllows: (eq) | SH) Pls) ‘These shorthand notations can now be used to representa cell comprising of 0 hal-cells, Convention dictates two things: 1 The two reduced forms of the species ae shown on the outside ofthe cel diagram 2. The positive electrode is shown on the right-hand side of the cell diagram, Applying these conventions produces the following cell diagram {ora cell formed by combining the Zn”"(aq) | Zn(s) and the Cu(aq) | Culs) half-cells: 2n(s) | Zn#(aq) # Cu**(aq) | Cuts) ‘The double vertical lines (i) represent the salt bridge. ‘The emf £%., of this cells simply the difrence between two standard electrode potentials of the two half-cells. 2n(s) | 2n2*(aa) # Cu?*(aq) | Cuts) E°=-076V E7= 4034V ‘The difference between these two numbers is 1,10, 80 the emfof the cells 1.10. To indicate thatthe right-hand electrode, ie ‘the copper is the postive electrode of the cell, the emf is given a positive (+) sign. So, the complete cell diagram is: Zn(s} | Zn*{aq) # Cu**(2q) | Culs) Eu = +1.I0V Learningtip Note thatthe sign for the E® of the Zn® |Z half cellisstil given as, negative, despite the half-cell being written in reverse. As mentioned in Section 14.1.1, the sign ofa standard electrode potential mains the same no matter how the haf-cellis represented Didyouknow? 0 Itis also posible to calculate the emf of the cell from a cell diagram by subtracting the E> value ofthe left-hand half-el from that of the right-hand half-celk Fret = Ein = i Itis important to remember, however, that you must not change the sign of the E° value ofthe left-hand half-cell, even though the reaction i written as an oxidation and nota reduction, What is meant by the ‘difference’ between two standard electrode potentials? ‘The easiest way to explain this isto represent the two values on a ‘number scale, such as the one shown in fig B. + 1.00 +034 0.00 aiterenee = 1.10 076 00 fig Example ofa number scale wo calculate ane ‘To move from one number to the other on the number scale involves a change of 1.10 units, Breaking the cell convention (Chemists always reserve the right to break convention if it suits their purpose. This is exactly what we do when we draw cell diagrams to represent the measurement of a standard electrode potential. In this case, the standard tydragen electrode is always vwrlten on the left-hand side “The cell diagrams for the set-up used wien measuring the standard electrode potential of the Zn**(aq) | Zn(s) and the CuF*(aq) | Cu(s) half-cells are therefore Ptfs) | pala) | H*(aq) { Zn**(aq) | Zn{s) Fe Phjs) | $Hs(@) | H(aq) i Cu*(aq) | Cals) Ba = = -0.76V 034V As before, the sign of «indicates the polarity of the right- hhand electrode, Zinc is the negative electrode of the cell formed in combination withthe standard hydrogen electrade. Copper is the positive electrode of the cell formed in combination with standard hydrogen electrode. 1 (a) Draw abled gram of apparatus that an be wed to constvuctacellundersandavé condions, rom a 21 [2n hl tel anda feet hae (b) The standard electrode potentials for the half-cells are Zné|Zn = O76 Feet |pt € 240.77 Explain the direction of electron flow inthe external circuit when this ell isin use (€) Give the cell diagram for this cell and calculate the emf E*.a) of thecal, 2. Chlorine may be prepared in the laboratory by reacting dilute pr ry 8 hydrochloric acid with potassium manganate(Vil). The standard electrode potentials that relate to this reaction are- 10g) +e" = Crag) B= +1.36V Mn0,aq) + 8H*(aq) + Se" == Mnfaq) + 4H;0(0) (@) Calculate the emt, E°.x, ofa cell constructed from these two redox systems. (b) Explain the direction of electron flow that would take place in the external circuit of this cll when in use. (€) Give the cell diagram for this cel east aStandard electrode potentials and thermodynamic feasibility By the end of this section, you should be able to. © predict the thermodynamic feasibility ofa reaction using standard electrode potentials © understand how disproportionation reactions relate to standard electrode potentials © understand the limitations of predictions made using standard electrode potentials © understand the importance of conditions when measuring the electrode potential, E © understand that E°,,, is directly proportional to the total entropy change, AS°,.,,,and to Ink for cell reaction Making predictions using standard electrode potentials Using standard electrode potentials is one way of measuring how easily a species loses electrons ‘This method provides information on how fr tothe lett an equi um i relative to the equilibrium in the standard hydrogen electrode. For example fo he felling two equioria, the equibrium of the top reaction ies futher to the left than that of the hydrogen electrode, and the eqibrum forthe bottom reaction lies further othe right than tat ofthe hytrogen electrode. Za"(aq)+ 26 = Zs) B= Cut(oq) +20 = Cols) IL follows, therefore, that the position of equilibrium of the Zn#*(aq) | Zn(s) reaction les further to the left than that of the Cu#*(aq) | Cu(s) reaction If these two equilibria are linked by combining the two hal-cells to make an electrochemical cell then electrons will low from the zine electrode to the copper electrode. Therefore, the equilibria will be disturbed and the following reactions will tke place in each half-cell Zals) > Zn?*(aq) + 26 Cu{aq) + 26° —+ Cus) Electrons flow from the half-cell with the more negative E> value to the half-cell with the less negative (ie. more positive) & value. flow of eleton salt ridge cooper (2naq)] = tml Znis) —> Zn"(aq) fig A. Becrochemical cell showing direction of flow ofl 92CO Linking this to a test tube reaction Is the following reaction thermodynamically feasible? Zn{s) + Cu{aq) > Zn?*(aq) + Cubs) ‘That is, will zine displace copper from an aqueous solution containing copper(I) ions? ‘To answer this question, we will look atthe £® values for the relevant haltcell reactions: Zn™(aq) + 2e° = Zn(s) £7 =-0.76V equilibrium 1 Cuaq) +20" = Cus) F°=4034V equilibrium 2 ‘The ° value for equilibrium 1 is more negative than that for equiliorium 2. So, the position of equilibrium 1 will shift to the lef, releasing eleetrons, and the position of equilibrium 2 will shit to the right, accepting electrons. This means thatthe reaction between zinc and copper(ll) ions is thermodynamically feasible Fig B illustrates this process. ‘This is the move negative valu, so the equa ‘moves to the le. ‘These are the species you ate stating wie anaer of 22 420 Cys) B= Fav Thisisthe more postive value s0 the equim exes io the ight Reaction of ine with copper) ins in aqueous slain, Will zinc react with dilute sulfuric acid? “To answer this question, we need to consider the following, reaction, Zn(s) + 2H"(aq) — Zn?(eq) + Hila) “Thooe are the species you are sarang with Thisis the move negative value, so the equilbrum moses tothe lef. y gs= -076¥ Carta 26 +20 =H) F000 ‘Tals isthe move positive value, s0 the equlbriam roves to the right fig € Rescton of are with dlse sui act ‘As E*{2a°"(aq) | Zn()] is more negative than E°(2H"(eq) | HG} the reaction is thermodynamically feasible, a zine will lease electrons to the hydrogen ions. Will copper react with dilute sulfuric acid? ‘To answer this question, we will consider the following reaction: Culs) + 2H"(aq) — Cu" faq) + Hale) “This ithe more positive valve, so the equlbrium tends to mave to the nig. ‘These ae the species yu ae starting ath, ere today Tater of 2 $e Hyg) ov This the more negative al, so the equliurn tends to move t| the le fig Cooper does not react wth die sulfuric cid ‘This time, E {Cu**(aq) | Cu(s}] is more positive than F°(2H"(aq) | He(a)), 80 the reaction is not thermodynamically feasible because copper will not release electrons to hydrogen ‘ons. The two equilibria tend to move in the opposite directions to those required for reaction, Interestingly, the reverse reaction: Cu (ag) + Hale) + Cuts) + 2H"(aq) isthermodynamicelly feasible. However, no reaction takes place ‘when hydrogen is bubbled into an aqueous solution containing copper} ions because the activation energy forthe reaction is very large. The reactants are therefore kinetically stable The reaction between manganese(IV) oxide and hydrochloric a (One method of preparing chlorine in the laboratory i to react ‘manganese(1V) oxide with hydrochloric acid: MnOs) + 4HCi(aq) + Mn(ag) + 2CI-(aq) + 2H,0() + OL) However the standard electrode potentials suggest that this reaction isnot feasible. MnO) + 4H*(aq) + 26 Mni*(aq) + 2H,0(), equiltorium 1 L(g) + 2° = 2Cr-(aq) Fe= +136) equilibrium 2 “The £* value for equiliorium 2is more positive (ie. less negative) than that for equlbrium {. So, chloride ions cannot release electrons to MnO, and this required forthe reaction shown above to take place. The reaction isnot thermodynamicaly feasible under standard conditions, in waich the concentration of the hydrochloric acid. and therefore the concentration of both the Ihydrogen ions and chloride ions, is L mol dm” ‘The key to making the reaction take place isto increase the concentration of hydrochloric ac. If concentrated hydrochloric acid (~10 mel dm“) is used, then ‘the concentration of beth the hydrogen ions and the chloride ions increases, The effect isto shift the position of equilibrium 1 to the right, and the position of equilibrium 2 to the left B141 cli shits tothe sight MnO,{s) + 4H*(aq) + 2e- = Mn#*(aq) + 24,00) Chg) + 2e- = 2CHaq) Tel his tothe let fig Equlbra forte reaction of manganeseV} axe with hydrecivic acid ‘As a result, the electrode potential, Z for equilibrium 1 becomes more positive because the redox system is now a better electron acceptor ‘The electrode potential for equilibrium 2 becomes less positive ‘because the redox system is now a better electron releaser ‘The net effect is thatthe electrode potential of equilibrium 2 ‘becomes less positive (more negative) than that of equilibrium 1, so the chloride ions can now release electrons to manganese(IV) oxide, The reaction has become thermodynamical feasible Under these non-standard conditions Summary + ‘The thermodynamic feasibility of a chemical reaction can be predicted using standard electrode potentials, + Although the standard electrode potentials indicate that a reaction is thermodynamically feasible, it may not take place for two reasons: the reactants may be kinetically stable because the activation energy for the reaction is very large, and the reaction may not be taking place under standard conéitions. + Areaction that is not thermodynamically feasible under standard conditions may become feasible when the concitions are altered + Changing the conditions may alter the electrode potential. £. of 2 hall-cell because the position of equilibrium of the half-cell reaction may change Disproportionation reactions In Book 1 Topic 3, we learnt that a disproportionation reaction isone in which an element in a species is simultaneously oxidised and reduced inthe same reaction. ‘A ypical disproportionation reaetion isthe conversion of copper() fons in aqueous solution into copper(!) ions and capper atorns. Cur(aq) + Cur(aq) — Cu**(aq) + Cus) ‘This reaction can be explained in terms of standard electrode potentials, CuM(aq) +e" = Cuvfaq) £9 = +015 Curaq) +e = Cus) B= 4052 ‘The £° value for equilibrium 1 is more negative than that for equilibrium 2, 50 the position of equilibrium 1 will move to the lef and the equilibrium position of 2 will move to the right. Therefore, (Cur ions will Both release and accept electrons to one another to form Cu* ions and Cu atoms. That is. Cut ions disproportionate into Cu** ions and Cu atorrs. equilibrium 1 equilibrium 2 94 This ithe more negative value so the equibrium moves tothe le. i 018 ‘These ae the species you ae saring with cua) + ° — =o) Fr = sos Thisls the mort postive vale, so the equilibrium moves tothe ig, fig Disproporionation of Cu ions into Cu ions and Cu atom. Relationship between total entropy and Eau ‘The standard Gibbs energy change, AG®, taking place in a cell and the emf of the cell, 2": are related by the following expression: AG! AE. ‘here nis the number of moles of electrons invalved in the cell reaction and Fis the Faraday constant. AG= AH ~ T&S sen But ASseromines therefore, AH = ~TAScninans and hence: AG=—TASranaeg: ~ TASyaen = ~TASuramiegs + ASiyz) TAS AS AG? = ~TAS%.y, the expression can be written as TAS? = MEE ‘As mis a constant for a given cell reaction, and Fis also a constant, it follows that, at a given temperature, the total entropy cchange of the cell reaction is proportional to the emf of the cel BS Et 1F £%q:is positive, the reaction as written from lef to right in the cell diagram is thermodynamically feasible because AS will be positive For example, forthe folowing cell diagram: 2n(s) | 2n?*(aq) # CuP(aq} | Culs) Ey = 41.10 the half-cell reactions that will ake place in the cell re: Zojs) + Zn" (aq) +26” and Cu" (aq) + 22° — Cus) aiving an overall reaction of Zals) + Cu (aq) — Zn (aq) + Culs) In the folowing cell digram: PU(s) | Hale) | H"[aq) Zn™*{aq) | Znis) E%q =-0.76V the halfcell reactions as written from left to ight will not occur, ‘as Ea is negative, Instead the half-cell reactions will occur from. right to left: 2Zn(s) > Zn*(oq) + 26° and (aq) + &° — 4H)giving an overall reaction of Zn{s) + 24"(aq) — Za”(eq) + Hite) ‘This means that £,., can be used to predict the direction of a cell reaction Relationship between the equilibrium constant and Ex ‘The standard Gibbs energy change for a reaction and the equilibrium constant, K. are related by the following expression AG?= -aTink However: AG*=-neE*, ‘Therefore: RTM = NEE RT Asa, Fand Rare constants it follows that al given temperature, 7: Ink is proportional to Ink x Eo >,., can therefore be used to calculate the thermodynamie equilibrium constant, K, for a cell reaction, 1 (a) Use te fotowing data to expan why, under standard conditions, VO"can be used to reduce MnO, in atic sohason VO,"{ag) + 2H‘(aq) + e° = VO™laq) + H,0(l) E*=+1.00V MnO (aq) Bag)» Se" == Mri“aq) + 4H0{) E> = 1.51 (b) Wiitean ionic equation forthe reaction tha lakes place 2 Use the follwing data to explain o which oxidation state vanadium). in he for of VO, cn be reduced by zine vos‘) + 24-aq) ve" = Vo") H,000 VO*(aq) + 2H‘(aq) + e° = V"{aq) + H.0(!) Vag) +e" = V*(aq) vag) + 26° = V6) Za(aq) + 2e" = Za(s) e= -076V 3 (a) Usethe folowing data to explain why hydrogen peroxide, HO, decompose into water and oxygen in aqueous soltion HO.) + 2H"(aq) +2 = 2H,0() = 177 Ole) = 24"aq) +26 = H,0,) £° = +068V (6) Waite an equation for this decomposition. (©) Explain, using oxidation numbers, why this reaction i cased as dsproportionation. 4. Fea) ions canbe reduced by (aq ions. The equation forthe reaction Fea) + P(aq) — Fe™aq) + Jaq) “The standard electrode potentials for Fe(aq) Fea) an $ aq) faq) ate 60.77 Vand «054 respectively [The gas constant, 831) mol" K". The Faraday constant, F= 96 500€ mot] (@) Calculate the emt of a cell made by combining these two hal-cel (b) Calculate the standard Gibbs energy change. AG°, for thecal reaction (©) Calculate the value ofthe equilibrium constant, K, forthe cell eaction. 95Storage cells and fuel cells By the end of this section, you should be able to.. © understand the application of standard electrode potentials to storage cells @ understand that the energy released on the reaction of a fuel ‘with oxygen is utilise in a fue! cell to generate a voltage @ understand the electrode reactions that occur in a hydrogen- oxygen fuel cell Storage cells A storage cel, or secondary cel is cell that canbe recharged by passing a curTent though tin the opposite Grection fo te ow Of curent generated by the cel Storage cells, often commonly called batteries, ae used in appliances such as torches, battery operated radios, electronic calculators, cordless house phones and mobile phones to generate an electric current, One of the first storage cells to be invented was the rechargeable nickel-cadknium (NiCd) cell, which was invented in 1899, It uses a nicke] compound, NiO{OH}) for the positive electrade, cadmium. for the negative electrode and aqueous potassium hydroxide as the electrolyte. ‘The two hal-cell reactions are: CA(OH)As) +2 = Cals) + 20H-(aq) Ee = NiO(OH(s) + H,Of) + &° = NI(OH),(2) + OH-{aq) “The E* value of the upper equilibrium is the more negative of the ‘two, Hence, the equilibrium position of this reaction shifts to the lft when the cell is generating a flow of electrons (ie an electric current) So, when the cel is generating a flow of electrons the two reactions that take place are: Cals) + 20H-(aq) + CALOH),(5} + 26° NiO(OFKs) + H,O() + e° + Ni(OH)fs) + OH (aq) giving an overall cell reaction of Ca{s) + 2NIO(OHY(s) + 2H,0() + C4(OH),(s) + NHOHs) “The equations must be multiplied up 90 the number of electrons in each half reaction is the same Under standard conditions, the emf is 140. Under the conditions present in a commercial cell, the potential ctference produced is about 1.2V. ‘To recharge the cell, an external potential difference is applied that reverses the reactions shown above 96 ‘The major disadvantage of these cells that cadmium is very toxic. ‘Therefore, great care needs to be taken when disposing of them, Many other storage cells are now produced, including the nickel metal hyeride (NiMH) and silver-zine (Ag-Zn) cel. Perhaps the mast widely known storage cells the lead-acid accumulator, which is commonly used for car batteries fig A carbstery Fuel cells ‘A fvel cell produces a voltage from the chemical reaction of a fuel ‘with oxygen, Several fuel cells have been developed, with the most ‘common using hydrogen as the fuel (the hydrogen-oxygen fuel, cell). In this fuel cell, hydrogen is supplied externally as.a gas and the cell ean operate as long as the fue! supply is maintained. Other fuel cells use methanol/ethanol as the fuels, The hydrogen-oxygen fuel cell dectron ow exude. EE cca J] Sal hydrogen — wh ed sake — proton exchange sleewolye i sembrane wl, t + water im fig Abysragen-onygen fel al In the hydrepen oxygen fel cell both metal electrodes are coated ‘th platinum, whieh catalyses the reactions that rae place atthe electrodes. The to reactions that take place in the presence of an acidic electrolyte are shown belo [Atthe negative electrode: Hg) > 2H'(aq) + 26 the postive electode: 40,4g) + 2H"(aq) + 2e~ + H,0¢) ‘The hydrogen ions (protons) pass through the proton exchange ‘membrane, which allows them to enter the compartment containing the postive electrode, where they can react with exygen,0 ‘The overall cell reaction i: Hyg) + 04(g) > 1,00) ‘There is also a hydrogen-cxeygen fuel cell that has an alkaline electrolyte, The electrode reactions for this cell are shown below. 2H, + 2e + H,0() At the negative electrode: H,(g) + 20H (aq) At the positive electrode: }0,{g) + 2H*aq) + 2e7 ‘The overall cell reaction isthe same as above: Hala) + 302{8) > H,0() Advantages of hydrogen-oxyen fel cells + They offer an alternative to the direct use of fossil fuels such as petrol and diese ‘+ Unlike fossil fuel, their products do not include pollutants, such 4s carbon monoxide, carbon dioxide and oxides of nitrogen. ‘+ They are lighter and more efficient than engines that use fo fuels. Problems associated with hydrogen-oxygen fuel cals Hydrogen is explosive, so great care has to be taken when transporting it. We will consider he following options in turn, + compressing the gas + adsorbing it onto the surface of a suitable solid material + absorbing itinto a suitable material Comprossing the gas has disadvantages in torms of safety. ‘Transporting hydrogen under pressure is particularly hazardous Many metals adsorb hydrogen, but so far no firm conclusion bas, been reached as 1o the best one to use. One of the most promising ‘eas of research is the use of carbon nanorubes to adsorb hyiragen, Many metal hydrides absort hydrogen, which can be released under the correct conditions. The problem is that high ‘temperatures are required to release the hydrogen Another problem is the supply of hydrogen. At the rnoment most of the hydrogen is produced fram methane, which isa finite source. It can be produced using renewable sources, but itis an expensive process. Integrated wind-to-hydrogen (power-to-gas) plants, using electrolysis of water are exploring technologies to deliver costs low ‘enough, and quantities great enough, to compete with traditional energy sources, Fig C shows a prototype car that uses fuel cell technology fige Aca 1 Nickel-cadmium (NiCd) cells are used in many electronic devices because they ae very reliable, economical and easy use ‘The standard electrade potentials forthe redox systems in NiCd calls are Cw(OH),(6)+ 26" = Cils)* 20H (aq)? =-0.88V NiO{OH)« H,O1) + e° = NIOH),5)+ OF aq) E*=~052V (a) Whatis the standard call potential, Ea ofa NiCd cl? (b) Construct the overall action that takes place when a NIC call is producing an electric current. (€) Use oxidation numbers to show which element is oxidised and which seduced during the decharge ofa NiCd cel 2 Fuel cels are being developed as an alternative tothe use of petrol and diesel in cars. The most commen fue used in these cls hnydrogen, but cel using other ful are being developed. Ina methanol fuel el the fuels supplied atthe negative electrode, with oxygen atthe positive electrode The ionic half-equation forthe reaction of oxygen atthe postive electrode is: 3048) + 2H (aq) + 2e"— H,0() (@) Writea chemical equation forthe complete combustion of methanol in ongen (b) Use the equation in) and the ionic hall-equaton forthe reaction of oxygen atthe positive electrode, to deduce anionic halt equation forthe action tat takes pace at the nepotive electrode Give two advantages of using fuel cls compared with the combustion of pevol or diesel Give an advantage of using methancl, rather than hydrogen in a fuel cell forusein cas. ©) @ w Whats the essential difference between a fuel cell and a conventional electrochemical cell? (b) State two ways that hydrogen might be stored asa fuel for use (c) Suggest why some scientists consider that using hydrogen as 2 fuel for cars uses up more energy than using petrol or diesel as the fuel 7Redox titration By the end of this section, you should be able to.. © carry out structured and non-structured titration calculations including Fe®/MnO,- and 1/502 @ understand the methods used in redox titrations Redox titrations with potassium manganate( Vil), KMnO, Pouassium manganate(VI) isa poverfl oxidising agent. is used for the quantitative estimation of many reducing agents, especialy compounds of iron) and for ethanediole acid and itssalts Inacidie solution, the hall-equation for the reduction of the ‘manganate(VI ion is: MnO, (ag) + 8H"(aq) + Se” — Mn**(aq) + 4H,00) In alkaline solution, potassium manganate(Vil) yields ‘manganese(IV) oxide as a brown precipitate, and this interfores, withthe end point colour. For this reason, therefore, potassium rmanganate(VI) is almost always used in solutions that are sulfciently acidic to prevent the formation of manganese({¥) oxide, ‘As the titration proceeds, manganese(Il) ons, Ma**, accumulate bur, at the dilution used, they give a colourless solution. As ss00n a8 the potassium manganate(Vl]) is in excess, the solution ‘becomes pink. I therefore acts as its ov indicator ~ the end point is the first permanent pink colour. Titration of potassium manganate(VIl) with iron(II) ions In this reaction, the xon(l) ions are oxidised and the rmanganate(VIl) ions are reduced “The ionic hal-equations involved are: Mn0(aq) + BH"(aq) + 5e~ + Mn*aq) + 4H,0() Fe2'(aq) — Fe(aq) +e “The overall equation forthe reaction is: MnO, (aq) + 8H(aq) + 5Fe" (aq) “+ Mn™(ag) + 4HL0() + 5Fe™(aq) An aqueous solution containing MnO, ions is purple, In reasonably concentrated scltions containing Fe". Fe!" and Min the ions have the following colours Fet(aq) ~pale green Fe™(aq) yellow Mn#*(aq)— pale pink However. the solutions used in titrations are usually so elute that they appear colourless 98 ‘The method of performing the titration is: + Pipette an accurately measured volume, usually 250cm*, of the iron(l) solution into a conical flask and then add a small volume of dilute sulfuric acid + Slowly add potassium manganate(VIl) solution of accurately known concentration from a burette and svt the mixture, + ‘The potassium manganate(VIl) solution will tum colourless until all of the iron) ions have been oxidised + ‘The addition of one more drop of potassium manganate(VII) solution will tur the mixture pale pink figa eee 25 0enr of iron(l) sulfate solution reacts with 22.40.cn! of (0.0200 mol dir potassium manganate(VIl) solution, Calculate the concentration of the iron) sulat= SFe™(aq)= MnO (aq) 250cm* of xmol div Fe = 22.40cm* of 00200moldm'* MnO, 250r 8 a= 00200 22.40% 250 [FeSOsaql = 0.896 mol dens spol colour in 3 potacsiam manganae( Vl trati 0396 Titration of potassium manganate(Vil) with ethanedioic acid In this reaction, the ethanedioic acid is reduced to carbon dicxide ‘The ieic halfequation for this reduction is: H,C,0 aq) 2H (aq) + 2CO,{@) + 26 “The overall equation forthe reaction is 2hIn0, (aq) + 6H"(aq) + 5H,C,0.aq) + 2Mn**{aq) + 8HO{]} + 10CO,(g)0 ‘Aqueous ethanedicic acid is pipetted into the conical flask (Care: ethanediic acid is extremely poisonous, so a pipette filler mustbe used) and is then acidified with dilute sulfuric acid. Aqueous potassium manganete(VIl} is added from the burette, However, the reaction is very slow so the ethanecioic acidis heated to around 60 °C before starting the titration. Even then, the reaction is slow to begin with and the pink colour does not immediately disappear when the first sample of potassium manganate(VII) is added. This may lead you to erroneously think thatthe titration is ‘complete. After the inital sample is added, the Mn#* ions produced act as a catalyst and the reaction speeds up allowing you to titrate normally and obtain an accurate end point. Did you know? Potassium manganate(VII) can also be used to estimate the amount of ethanedinate ion present in a Aeaction in which a product solution. The equation for the reaction is: actsas a catalysis sid to be 2MnO,-(aq) + 16H"(aq) + 5C,0-(aq) autocatalysed. Autocatalysis is = 2Nin*“(aq) + 8H,0() + 10C0,{g) decimedin section.16-15 Investigation ‘Aredoxtitration the determination of the number of moles of water of erystalisation per mole of hydrated iron() sulfate crystals Procedure 11 Bring tothe boll 100 cm? of dilute sulfuric acid and then allow it to coal to room temperature. 2. Weigh accurately a weighing bottle containing approximately 7g of hydrated iron() sulfate crystal 3. Dissolve the crystalsin the cool acid and reweigh the bottle. Transfer the solution to a 250m? Learning tip —_ volumetric flask. Add several washings from the beaker and then makeup to the mark Shake wel The dilute sulfuric acids 4 Tiatea 25.0 cn sample ofthe ion( solution, as before, withthe standard potassium manganate(Vil) boiled to remove dissolved solution ‘oxygen that might otherwse 5. Perform repeat titrations until you obtain concordant results one: pa Gilat) Calculations — 1 Calculate the mean titre from your concordant results 2 Calculate the concentration of the ironjl) sulfate solution, 3 Calculate the mass of iron) sulfate inthe 250cm* of solution, 4 Calculate the mass of water in the mass of crystals taken and hence calculate the number of moles of water per mole of alt. Sample results Concentration of potassium manganateVIl) olution = 0.0198 mel dr? Mass of hydrated iron] sulfate = 6 84g Mean titre = 24.95 em* [Molar masses: FeS0, 51.9 mol"sH,0 = 180gmor'] 5FeS0, = KMnO, 250m? of xmol dr FeSO, = 22.40 cm? of 00198mol der? KMD, 2505 2435 «0.0198 “1 {FeS0,(ag) = 0.0988 mol dm ‘Mass of FeSO, in 250cm* 52495 x00198 250 Mass of water = (684 ~ 375) = 303g Ifthe formula ofthe hydrated salt is FeSO,.yH0, then ‘Mass of FeSO, in 250cm? = 0.0988 x 151.9 x 250. «3.758 1000 18ay 309 {519° 375 3091519 20375, =695 The formula of hydrated iron) sulfate is FeSO..7H,0 = 0.0988 99)100 Redox titrations with iodine and sodium thiosulfate ‘Thiosuifate ions reduce iodine to iodide ions. The ionic hal-equations invelved are: 28,0," (aq) — S,0,* aq) + 2e° faq) + 22° + 2I-(aq) ‘The overall equation for the reaction is: 25,0, (aq) + (a9) —+ 8,0, (aq) + 21-(a9) ‘The reaction can be used for the direct estimation of iodine, or for the estimation of a substance that can lake part in a reaction that produces iodine. ‘The indicator used in titrating iodine with sodium thiosulfate is starch solution, With free iodine it produces a deep blue-black colour The blue-black colour disappears as soon as sufficient sodium thiosulfate has been added to react with all of the iodine, ‘The procedure is as fellows. + Add sodium thiosulfate solution from the burerte to the iodine solution until she original brown ccolour of the iodine changes to pale yellow. ‘+ Add a few drops of starch solution to produce a blue coloration, + Add the sodium thiosulfate solution drop by drop until the blue-black solution turns colourless, If the starch is added too eal. it adsorbs some of the iodine and reduces the accuracy of the titration. If starch were not added, it would be very difficult to detect the end point. The colour of the iodine solution becomes very faint towards the end of the reaction and this makes it dificult to accurately ‘assess when the end point has been obtained, Investigation ‘A redox titration - determination of the percentage of copper(l) ions in a sample of hydrated ‘copperti) sulfate The copper sulfate solution must be re from anything but a trace of mineral acid otherwise the end point isnot accurate. This solution produces iodine when potasium iodide is added, The ionic equation for this reaction i 2Cu"{aq) + aq) — 2Culs) + faq) ‘The odie produced is then titrated with standard sodium thiosulfate solution, Procedure 1 Weigh accurately a weighing bottle containing approximately 6 g of hyérated copper sulfate crystals 2. Transfer the crystals toa 250 cm! volumetric faskand reweigh the borte. 3. Add sodium carbonate solution until a ight permanent bluish precipitate of coppe carbonate is formed. 4. Acidity the miure witha litle dilute ethanoic aid until a clear blue solution is formed. Make up the solution to 250 cm with deionised (or disiled) water and stake wel 5. Pipette 25.0.’ of he solution into a conical flask and add about 15g of solid potassium iodide. 6. Titvate the iodine produced with sodium thiosulfate solution adding starch solution justas the colour of the mire changes to pale yellow The end point achieved when you can se 8 white sspencon of insoluble copper) iodide, Cuil). in a colourless solution. 7 Perform repeattitratons unl you obtain concordant results Calculation Calculate the percentage of copper(l) ons in the sample of hydrated copper) sulphate crystals.0 Sample results Concentration of sodium thiosulfate solution = 00995 mol dm” Mass of hydrated copper) sulfate crystals = 5.85 3 Mean ttre = 23.45¢m? [Molar mass of Cu = 625g mol] 2c Na,S,0 Cu = NaS.0, 25.0¢m) of xmol dnr” Cu = 2345 em? of 00995 mal drs”? Na,$,05 250x- 2345 «0.0995 x= 0.0933, den" « 635g mol! x 259 Solution = 00933 mol! dv’ «635g mob" « 250-1483 ice eeros Percentage of Cu inthe sample= 48 « 100= 25.3% 1 An iton nail of mass 1.50g was reacted with dilute sulfuric acid. The resulting solution was transferred toa ‘volumetric flask and made up to 250cm? with deionised water ‘A250cm° sample of this solution reacted with exactly 2440 em’ of 0.0218 mol dm potassium rmanganate(Vl) solution The ionic equation for the reaction between the iron nail and the acid is Fels) + 2H"(aq) — Fe™aq) + 418) Calculate the percentage by mass of ron in the nal [Molar mass of iron = 558 g mot] 2. A0cm* volume oa solution of ogen provide mas diluted wth alert 100d A25.0cn sample cfs soln was afed anther rated against 00200-ol dt? potassium manganat) ‘he mean hr valle nas 23 90m Clea the concenation a ma fhe oral ston of Tyslogenperonce The onichaequation or the cxdton of drogen peroxide H.0jaq) — 24'(aq) + Oulg) + 26 3. Calculate the volume of a 0.0200 mal dm solution of potassium manganate(VI\) required to completely oxidise 1.00 g of iron(l) ethanedioate (FeC,0) [Molar mass of FO, = 1438 mol] 4 an aqueous solution contains a mixture of iron(l) ions and iron(l) ions. A25,.0cm? volume of the solution required 21.60 cm of 0.0210 mol dm? potassium manganate(VIl) for oxidation, ‘A separate 25.0 cm’ sample of the solution was reacted with an excess of zinc amalgam in order to reduce the iron(Il) ions to iron(l). This sample, after filtration to remove the excess zinc, required 44.40 cm’ of 0.0210 mol dmv potassium manganate{VIl) solution for complete oxidation. Calculate the concentrations, in mol dmv, of both the iron) and ironitI) ions in the aqueous solution. 5 When bleaching powder reacts witha dilute aid chlorine is liberated. This chlorine availabe for bleaching and is known as ‘aalable chlorine. ‘A250 sample of bleaching powders added to an exces of potassium iodide solution and the moure is then acidified. The solution fs placed in volumetric ask and made upto 250 with deionised water A25 em volume of tis solution required 23 20cm of 0.10 mal dm sodium thiosulfate Seluiton to axle the iodine present. Calculate the percentage of availabe chlorine in the 250 g sample of bleaching powder (Chia) + 2M(aq) — 2CH{aq) + LXaq) [Molar mas of Cl = 71.0 mol} © A25.0cm sample of of 0.0210mol dm potassium perowpdisufate.K,S,0, was treated with excess potassium jodie, The iodine liberated reacted with 21,00cm? oF .0500mal cn sodium ticsulfate solution Suggest likely ionic equation for the reactian between $,0," ions and I ions. 101ELECTROLYTE EVOLUTION (One of the reasons that your laptops and smartphones are significantly lighter and slimmer than. those of 10 years ago is not so much because of advances in computing power but because of advances in rechargeable battery technology. @* BATTERY POWER Primary cells ‘These are the disposable cells - they are discharged once and igearded ~ that for ever a eentury powered small and portable ‘equipment. Nowadays as we become more waste conscious we find ‘that many of these cells are giving way to rechargeable (secondary) cells and batteries, “The most common primary cells are based on the zinc-manganese Gioxide couple: either zine-carbon cells or alkaline manganese cells. Fora short period some manufacturers offered mercury cells, which were replaced by zine-air batteries, and some companies now produce 3V Kithium-MnO. cells, Zine-carbon “This cell became commercially available inthe late 1800s and was ‘ary cell version of the orignal wet Leclanché cell (The later was made up of a conducting solution (electrolyte) of ammonium chloride with a negative terminal of zine and a positive terminal of ‘manganese dioxide.) Replacing the liquid electrolyte with a gel and then sealing the whole cell made it suitable for domestic applications where portability was a key feature. These cells were developed and marketed by Ever Ready for use in tadios and torches and ate still ‘popular today, though Ever Ready has now changed to Energizer and, ‘many other makes have become available ‘The dy cell zine-carbon chemistry performs well in applications where there is intermittent use such as flashlights but performance {is not so good in devices that put a heavy drain upon the cell. In such applications polarisation and loss of output results. However, the cell chemistry recovers when left idle for a while ~ the well known ease of the dead battery that comes back to life. Polarisation 4s caused by the products of the electrode reactions building up on the eleetrode surface and preventing new reactants arriving. On standing, dilusion occurs and new reactants reach the electrode as the products disperse Anode: Zn metal Cathode: MnO, powder with graphite powder for electrical eonduction Electrolyte: NH,Cl(ag) and/or ZaCl(aq) a ae Where else will] encounter these themes? In eatlier cells the zine doubled as the outer can which tended to leak as the cell ran down and the zine passed into solution Zos) + 4NH(ag) + 2MnO,(s) + 2H,0'(aq) [ZnNH)**€aq) + 2Mn(OH),(s) fig Alaine manganese baci Alkaline-manganese ‘These batteries developed from the zine-carbon cell and became available for domestic use inthe 1960s and quickly gained in popularity because they were less prone to polarisation, had greater capacity and were less likely 10 leak. Here the anode is powdered zine, which provides a greater reactive surface area and thus more power. The electrolyte is an alkali in ‘contrast to the previous cell whi Anode: Zn metal powder Cathode: MnO, powder with graphite powder for electrical conduction Electrolyte: KOH(aq) Zo(s) + MnO-{s) + 2H,O(0) ( Ma(OH).{s) + Zn(OH) 6) E, Development of these batteries continues and recently P introduced a vacuum forming process to compact manganese dioxide and graphite powders, which the company claims gives ‘improved eapacity. +15eV TN ETP 7rr Let us start by considering the nature of the writing in the article R (Tink about the role oF ~ | | the scientific ‘Community in validating new knowl “ge ort ledge ensuring integrity Nove we wl ook at the chemistry in detail. Some of these questions willink to topes caierin his [PURVIS LITET Tey took or Book 1 90 you may need to combine concep fom diferent areas of chemistry to work eee ei ‘out the answers, eitione, dlagrams ana | } ioe cab | an answer pegs iestity ower particularly UCStion yes the | command words “exsiug" or “ustty when a a op sin’ SEE SUIS Think stout the clectroniz | Eoiguration ofthe ze 7 Wish to revise | ‘One ofthe major technological developments over the last few years has been thelithium ion battery. This pi 2 thas enabled mobile devices ta be rechargeable and light-weight Produce a presentation on the Dic voulsonw? —_ technology acing lithium ion batteries Your presentation should be 5-8 lide in length ar should In2013samevebilion include ithium ion batteries were so +o supply electronic devices + the reactions involved in generating the voltage Ee ee + the advantages of lithium ion batteries over earlier secondary cells blebs carnerest eter oot + any disadvantages associated with lithium ion batteries. and even electric cars. (© From After Ratery Power by Tony Hargresvespwwwineomledacation! iliac 2008Ma/ Baten PowersUe 1 Brassis an alloy of copper and zinc. Itis used to make decorative ornaments, (@) A-sample of brass is analysed to find the percentage of copper it contains. ‘This is the method used: + 0.500 g of brass was reacted to form a solution containing coppertll) ions: Cals) + Cu®*(aq) +The solution is reacted with an excess of potassium iodide to produce iodine: 2Cu*(aq) + AI-(aq) — 2Culls) + Lfeq) + The iodine is titrated against sodium thiosulfate(VI), using starch indicator Ix(aq) + 28,0? (aq) ~» 2I (aq) + $40," (aq) + 22.3 cm’ of 0.200 mol dm? sodium chiosulfate(VI) is required, Use the data to calculate the percentage of copper in the sample of bras. (5) (b) A student carries out the titration but forgets to add the starch indicator (i) Prodiet the colour change that the student observes at the endpoint without the starch indiceror 2) (@) Comment on wiy the colour change atthe endpoint is easier to observe if starch indicator is used, i (Total: 8] 2. The table shows the formulae of some vanadium ions that can exist in aqueous solution, together with the colour of each ion. VO (aa) | VO"(aa) | Veta) | Vea) caaon number of vanadium ‘colour of jon yellow | blue | green | violet (2) Complete the table by inserting the cxidation numbers. [1] (b) tron powder is added to an acidified solution of ammonium. vyanadate(V), NH,VO, and the mixture is shaken unl no further change takes place. Use the following data to explain what you would expect to observe in the sequence of reactions that take place. Your answer should consider all of the electrode reaetions listed, 1 Exam-style questions Electrode reaction EW 1 Vit(aq) + 2e = Vis) 118 7) Vila) Fe = Vaq) 926 3 VOR (aq) + 2H aq) + & = (ag) +034 4 [VOr (aa) + 4H (aq) + & = VO" (aq) + 2H,00) | +100 3 Fevaq) + 26 = Fas) ~ oad (Total: 6} 3 An electrochemical cel is set up based on the following two half-cell reactions: Magi (aq) + 2e" = Mgfs) Nit(aq) + 26” = Nis) Fe (2) () Draw a labelled diagram of the cell operating under standard conditions. a) (i), Explain the eitection of electron flow in the external cireut. 2 (ii) Wihte anionic equation to represent the overall reaction in the cell when currents flowing uy {b) Calculate the standard emf, £°,. of this cel i) (c) Explain how the emi ofthe cell changes when water is added to the Mg?(aq) | Mets) half-ell. (3) (Total: 11] 4 (a) Dravy a suitably labelled diagram to show how you ‘would measure the standard electrode potential of the Cu(eq) | Culs) hali-cel (6) (b) The table contains some standard electrode (redox) potentials involving copper and its ions, Electrode reaction | 2°/V 7 [Gag te = Cure | +015 2 | Ci aq +26 = Cus) [034 3 | Gregre Cus) [+052 {9 Use the data inte table to explain why the following reaction is likely to occur 2) 2Cu"(aq) — Cu (aq) + Cuts) {i)_ Use oxidation numbers to explain why this reaction is classified asa disproportionation reaction (3) [Total: 11)5 Chlorine gas can be prepared inthe fame cupboard of a laboratory by reacting hycrochlorc acid with potassium manganate(Vl). The two standard electrode (redox) potentials ‘hat relate to this reaction are ECkig) += Cred) Fe= +1360 ‘MnO, (aq) + 8H*{aq) + 5e~ = Mn2*{aq) + 4H,0() F*= +1.52V (0) Store whats meant by he term standard electrode potential a {o) Calculate the standard emf, £*,.., for an electrochemical cell constructed from these two redox systems a (©. 6) Construct an ionic equation fo the reaction that takes place between hydrochloric acid and potassium ‘manganate(VIl), Include state symbols, (2 (i) Use oxidation numbers to explain which species is, acting as the reducing agent in this reaction. @ {@) When very dilute solutions of potassium manganate(V'l) and hydrochloric acid are added together, there is no visible change. Explain, using the changes in electrode potentials that occur, why no reaction takes place when the solutions are diluted (3) (Total: 10] 6 Vanadiuen(¥),n the form of vanadate(¥) ions, can be reduced in acidified solution by adaing sulfur dioxide. [A student carries cut an experiment to determine the new oxidation state of the vanadium after the reaction has taken place. He uses tis method + He dissolves 2.24 g of ammonium vanadate(V), NHAVO,, (molar mass = 116.9 gmot~) in water and makes up the solution to 250 cm’. + Ina fume cupboard, he bubbles sulur dioxide through the solution until there is no further calour change. + He then boils the solution for five minutes and allows the solution to cool + He labels this solution ‘Solution Y. + He then titrates 25.0cm of solution ¥ against 0.0200 mol dm-* KMinO, solution. He finds that 38.40.om* of KMnO, are required to oxidise the vanadium tn this titration + The manganate(Vl) ons are reduced from the 47 to the +2 oxidation site +The vanadium in solution Y is oxidised to the +5 oxidation state. {@) Givea reason why the student carried out the experiment in a fume cupboard i) {b) Use the data to show that the exidation state of the vanadium in solution Y is +3 1 7 The diagram shows a hydrogen-oxygen fuel cell bydroge (c) The student repeats the experiment with the same mass of| ammonium vanadate(V) but this time he boils the solution for only one minute. He finds that the volume of potassium ‘manganate(Vl) solution required in the titration has increased. Explain this observation. 2] (Tota: 8] ower A = cpr ae negative postive clecwose cece (@) Identity the particles represented by A and B. iB} (b) The two elecirodes are coated with @ metal catalyst Name a suitable metal to use as the catalyst ial (c) State two advantages of fuel cells over the use of fossil fuels in cars. 2 (4) Apart from cost, state two disadvantages of using fuels cells, rather than fossil fuels in cars, fa (e) The zinc-silver oxide cell is used in button cells for watch batteries, tis based on the following al-cll reactions Zn?(oa) + 26° = 26) Fes -076V Ag, 016) + H,Ol) + 2" = 2Agls)+ 20H (aq) £°= +03 (0) Wiite the coll diagram fr this cel ia} (i) Write the equation forthe overal reaction taking place inthe cell when sin use. Include state symbols. [2] (i) Calculate the standard emf, Ea, thecal] (@) Use your answer t part (i to calculate the standard Gibbs energy change, AG®. fr the rection occuring inthe cell. [F = 96500 C mol] (2 (0) Use your answer ro par (ty) 0 calculate the equitorium constant, K, forthe reaction at 298K. (R= 8.31 Jmol" kK") (2) [Totat: 16]TOPIC 15 Transition metals Introduction In Book 1, you learned about the Periodic Table, and in particular the elements of Groups 1, 2and 7. These | three groups show typical properties of s-black and p-black elements and clear trends in physical and chemical properties. For example, in Group 1, the first ionisation energy decreases down the group, and in : Group 7 the reactivity decreases down the group. You learned to understand simple chemical reactions of these elements and their compounds and hav totes fr ions such as chloride and iodide, In this topic, you wil learn about transition metals in particular thase inthe first row between the s-block element calcium and the p-black element gallium, Transition metals have some distinctive properties and Uses not generally found in s-block and p-block elements, for example + the elements have important uses as industrial catalysts + they help to remove pollutants from car exhausts = + they ae important structural metals, such as iron and copper - * they are used in jewellery, especialy platinum, gold and silver + their compounds have bright colours. such as copper sulfate + they form ions and compounds with different oxidation numbers, such as iron(l) and ironll) compounds O + they form complexes, some of which are vital to lie, such as haemoglobin, and cisplatin, whichis used in “~y cancer treatment = Many of these properties will be explained, especially those that involve complexes. The term ‘complex will be carefully explained, ut don't think that complex’ means ‘complicated - it doesnt! | Allthe maths you need + Investigate the geometry of afferent transition metal complexes 106AE aar Mail te Belek te Crt Ce aa parity ee ee a er ee) What will | study later? CR ee Hstiearuclarceeeaucn ad datia peter eta SE ee es Porat Cee ea eas Pepe erties eee. wind turbine Predicting how changesin conditions affect the Peer ata Marr Nau RTen ited ee eee eee Sener erent eee ee er) complex, monodentate and multidentate How carb Pees) eres 107Transition metal electronic configurations By the end of this section, you should be able to.. ‘© recognise that transition metals re d-block elements that form one or more stable fons with incompletely filled d-orbitals @ deduce the electronic configurations of atoms and ions of the d-block elements of Period 4 (Sc-Zn), given the atomic, number and charge (if any) @ understand why transition metals show variable oxidation numbers Which elements are the transition metals? Where are they found in the Periodic Table? You willbe familiar wit the Periodic Table, and the numbers of the diferent groups. Group 1 ison the fer left, and on the far right are the noble gases, which are in e group numbered 0 (or sometimes 8) When you studied periodicity using the elements in Periods 2 and 3, you ignored the big gap between Groups 2 and 3, However, when you look at Period 4 you can see that there are elements besween Groups 2 and 3 ~ some of the transition ‘metals arc there You will also be familiar with the idea of classifying elements as ‘belonging to one of the blocks (s, p, d or ) of the Periodic Table, ‘The transition metals are in the d-block of the Periodic Table. In this topic we will concentrate on the 10 elements in Period 4 What is a transition metal? It is easier to list the characteristics of transition metals than to explain fully what they are, To describe them as being in the block only indicates their location and not their characteristics. Most definitions of a transition metal refer to the electronic configurations of their atoms or ions (see the Key definition for a simple definition) A fuller definition is quoted in the Edexcel specification: “Transition metals are d-block elements that form one or more stable ions with incompletely filed d orbitals, fig. These ae some veel oectecontan ing sls and ther alloys 108 Characteristics of transition metals ‘Transition metals + are hard solids ‘+ have high melting and boiling temperatures + canactas catalysis + form coloured ions and compounds + form jons with different oxidation numbers + form ions with incompletely-filled d-orbitals. (Of the 10 diblock elements in Period 4, the first and the last (scandium and zinc) do not have some of these characteristics, so although its correct to describe them as d-block elements, they are not considered to be transition metals. In particular, each forms only one ion and their compounds are not coloured. Electronic configurations The elements You learned in Book 4 Topie , how to write the electronic configurations ofthe elements fom hytiogen to krypton, which incudes the 10 dblock elements in Petiod 4 Forrelerence, we Show these in filin table A using the spe notation. wth electon- inbor agrams forthe electrons nthe fs and 3d oral Copper and chromium do not flow the expected patern. Where ireguartes nthe spd notation exit, they are shown i edn the electro inbox agama, paired electrons ae shox wth a seen background, and unpaired eleczons with a bie background. Ins sometimes acceptable to use an abbreviated form of electronic configuration which represents the complete shells with reference to the previous noble gas. For example, the electronic configuration of titanium is shown in fll as Is*2s*2p"3s*3p"4s"34" bout can be abbreviated as [Ar]is*3de The ions ‘When these elements form ions, they lose one or more electrons, ‘Scandium loses both of its 4s electrons and its only 3d electron, forming the Sc ion. Zine loses both of its 4s electrons and none of its 3d electrons, forming the Zn" ion, Because these ‘two elements form only one ion each, and these ions have no incompletely-flled d-orbitals, they are not classified as transition metals.oe Ps Electrons-in-box diagram for Poetry Preerererecret seandiom | 21 [1s 2s'2pe as'ape4sad' [TET] ET 1. 1d titanium — [22 [1s 2s 2p*as'ap'asaé [[PI) (Fit 7 | | 1 vanadium | 23 | 1s'2s' 2p*as'ap' asad’ [[) [it it. | | chromium | 24 [1s 2s'ap' aap? as [PP] [It 1? It 11] manganese | 25 | 1s 2st 2p? ast 3p' as 3d | [I] [lhl tlt) iron 26 [is aap sap asaa [TET] [Et 11 it it | cobat | 27 fis astap*as'ap°4s' aa | [i] ERDLRN DET 1h nickel ae [tear ap aeaparar [TT] PEI) it) it 11 copper__| 29 [is 2 ap asap ass” |[F_] (UIP IT SIT 110] ine 30 [1s 2s 2p 3s ape asa” [PD] PLITT 11 It 11121 table A Gecronic coniguation ofthe erent candhum to 2n6 ‘When the other eight elements form ions, they lose their 4 electrons before their 3d electrons Bach element can lose a variable number of electrons. and so forms ions with diferent oxidation ‘numbers. The higher oxidation numbers are not found in simple ions ~ for example manganese forms ‘an ion with oxidation number +2 (the Mn‘ ion), but the manganese ion with oxidation number +7 is MnO, not Mn". Transition metal ions invoivng higher oxidation numbers usually contain an electronegative element, often oxygen. Table B shows the most common oxidation numbers and ‘examples of compounds formed. Eo Eimer ann 1 af TO; Th Vv 2s l Volk V0s c 8 6 CC, K.CO, Ma 2 4 “7 [Macl, MnO, _KMnO, Fe 2] 3 FeCl, Fa. c 2] 3 C280, Col Ni 2 NSO, G a [2 CuO C150, table B The most common oxdaton numbersand compounds for Period 4 arson elements ‘You can sce that the highest common oxidation number increases from Ti (+4) to Mn (#7) as all he 4s and 3d electrons become involved in bonding, From Fe to Cu, the increasing nuclear charge means that the electrons are attracted more strongly and are less likely to be involved in bonding, Therefore, ions with higher oxidation numbers are less common, 1 Wt othe fll and abbreviated electonic configurations forthe element chromium, 2. Desai, wit reference tots electrons aan stom of manganese becmes anon withan cxation numberof + ‘Key definition ‘transition metal isan element that forms one or more stable ions with incompletely filed d-orbtals See 109Ligands and complexes By the end of this section, you should be able to.. @ understand what is meant by the term ligand’ © understand that dative (coordinate) bondingis involved in the formation of complex ions © understand that a complex ion isa central metal ion surrounded by ligands © understand the meaning of the term ‘coordination number’ Symbols and equations without ligands ‘An example ofthe symbol of a metal ion s Na", the sodium ion ‘You wil also have used the symbol Na*(a), which shows that the ‘sodium ion is dissolved in water. You may have had the process of dissolving solid sodium chloride in water explained in terms Of the aightly negative (-) oxygen atoms inthe water molecules being attracted 0 the postvely charged socium ions and keeping them in sition, You may have a mental picture of Na being surrounded by en unspecified numer of water molecules, with these water molecules leaving and being replaced by others. woe, ot fig A Posie socum iors suroundedby 8 eaygen ater in water molecules and negatvechacide ns surtunded by 8+ Fysrogen atoms in water molecules. ‘When you write equations forthe reactions of transition metal fons, you can sometimes use the same method. For example, the iron(il) ion can be shown as Fe. or Fe*(aq) to show that itis dissolved in water “The equation for a daplacement reaction imolving transition metal oni: Male) + Pe"(aq) — Mig (ag) + Fe(s) ‘This equation clearly shows that the reaction is an example of redox, as magnesium transfers electrons to rn} ions. However itis often better to consider the reactions of transition metal ions in a different way in order to better understand the reactions. This method will be described next. 110 Symbols and equations with ligands “The ions of non-ransition metas tend to have larger ri than those of transition metas in the same period ofthe Perot Table, For example, te onic radius of K" is 0.1331, endthat of Fe" is 0.076nm. The relatively small sie of transition metal tons enables them to atractelecton-nch species more song. inca the water molecules present in aqueous solutions. These water molecules are attracted to the transition metal ions 80 Stony thc tey form a specie number of bonds usally, firing a structure that can be represented in Gagras such as oH, a On, a figh Here ae uo waysto epretent acomplesien,Thecne on thelet shows one ofthe lone pas ef eleczons on the oxygen atoms and the dative covalent bonds with arrows The oe onthe right shows the 30 aangemencof bonds and water maecules around the metal ion In fig B (let). + the bonds are shown with arrow heads, indicating that they are dative (coordinate) bonds — one of the lone pairs of electrons, (on each oxygen atom is used to form the bond + the whole structure is shown inside square brackets, and the original charge of the Fe?* ion is shown outside the bracket + the water molecules are arranged in regular pattern around the Fe — this arrangement can be explained in terms of the electron pair repulsion theory In fig B (ight + solid wedges represent bonds coming out of the plane of the paper + hatched wedges represent bonds going behing the plane of the paper Although it is often useful to think about diagrams like this, ‘ben writing equations it is more usual to abbreviate them. The example above would be shown as [Fe(H,O),|*. Notice that the square brackets and the position of the charge are the same inthis abbreviated form. ‘These water molecules, and other electron-rich species that can form dative bonds in the same way, are called ligands, The complete formulae are called complexes. As mast complexes have charges, they are often called complex ions, but where there is no overall charge, itis better to use the term ‘complex. ‘The total number of dative bonds around the meta ions called the coordination number.Examples of ligands Many species can act as ligands, but those that we will meet mast often are shown in table A, which also shows how the name of the ligand changes when used in the name of a complex. (SS nydronide ammonia NH ammine chloride a chloro tablen Note these points about the names used in complexes: + ligands with a negetive charge end in-o ‘+ ammine should not be confused with the organic term amine. Naming complexes ‘Table B shows some examples toilustrate the naming system used {Fe(H:O\" hexaaqualront(t * the name of the metal ion he oxidation number af the metal {Fed} tetrachlorofer The overall charge is 1- b he ion is formed fe * ion and four Cl ions. “ate is added to the metal name to show that itis now part of a negatively charged complex As it is nepatively charg 1 name the metal is used (in Latin, iron is feerur] no cliferent ligands, they appear alphabetical order (50 ammine before aqua), ignoring the tetra-and di- pans of etraarmminediaquacopper(i) | Wi 1 Explain why the methane molecule cannot act asa ligand. Leaming tip ____ 2. Anequaton fora reaction inolvng 2 tanstion metal cmplet i You can work out the charge [Cu(HO}* + 204+ — [Cu(HO)OHY] + 24,0 cn the metal on in a complex Explain why the fist products a complex but not a complexton. by considering the overall charge on the complex and knowing the charges on the $y en ts gard "For example, (FCP ‘ligand ia species that uses a lone pair of electrons to form a dative bond with a metal on. hasan overall charge of2-, ‘Acomplexs a species containing a metal on joined to ligands and there are four clone fons each with a charge of -, 50 the charge on the metal ion ‘The coordination number isthe numberof dative bondsin the complex. rake ba 7 ‘A.complexion isa complex with an overall postive or negative charge, mThe origin of colour in complexes By the end of this section, you should be able to.. © understand that transition metals form coloured ions in solution @ understand that the colour of aqueous ions, and other complex ions, results from the spliting of the energy levels of the d-orbitals by ligands @ understand why there is a lack of colour in some aqueous ions and other complex ions A complex explanation! Colours very importntin our world think of traffic lights, paint carts othing and the colours of flowers, There are scientic explanations for colour n plants, paints and dyes but these explanations ae often specific tothe typeof chemical substance being consiered {As far as transition metal complexes are concerned, full explanation includes three main concepts + the electromagnetic 5 + the connection bet + the electronic configurations of transition metal ions. srum and the colour wheel colour, energy and wavele The electromagnetic spectrum We first need to find out about the electromagnetic spectrum, You are probably familiar with the idea that the visible part of the electromagnetic spectrum (sometimes described as ‘white light’) ismade up of a mixture of colours (sometimes described as the colours of the rainbow), Frequency () 5"! 21? ax10" 3x10" 3X10 radio TV) ‘mio ita Keays rays i? 1 wavelength Gm oa roonm fig Thed 300m rar shows how the visible part of the spectrum fis int the electomagnetc So, how many colours make up white light? A traditional answer is red orange yellow green blue indigo violet 12 However, seven is a purely arbitrary number and ths ist of colours dees not contain some that are now more familar, such as cyan and magenta. ‘The real answers that visible light is made up of an infinite ‘umber of colour! If we take red light to have a wavelength of, 700 nm and violet light to have a wavelength of 400 nm, then ‘each precise value within this range (such as 651.0 and 438.4) represents a different wavelength and therefore a different colou ‘There is clearly no limit to the number of values in this range The colour wheel The colours in a colour wheel Now consider the colours inthe visible spectrum shown as a ‘wheel, with the red and violet ends of the spectrum next to each other. There are many different colour waeels with varying numbers of colours (ust iry @ web search), but here is one that contains seven colours corresponding to those listed above. Clockwise from the top, they are shown in order ftom red to violet fig This sone ple ofac Complementary colours n colour wheels, complementary colours ate shown opposite to.ach other. In this one, red is opposite blue and green, When ‘white light is passed through a solution containing a transition metal complex, some wavelengths of light are absorbed by the complex. The light emerging wil therefore contain proportionately more ofthe complementary colour So, if @ complex absorbs red light, the light emerging wil look blue or green fige Aran CP E.0- Mir ‘of tanchion meal soluvors. From et rg: TP VO" MiOx, Fe, Ca. NF and CuColour depends on electrons in 3d energy levels ‘A complete explanation of colour or absence of colour in aqueous soitions of metal ionss qute complicated bt the folowing explanation shoud help you to understand the basis, We will use an aqueous solution containing copper(II) ions as an example ‘An aqueous solution of zine sullate is colourless but an aqueous solution of copper(I) sulfate is blue. As the sulfate ion is present in both solutions, we can assume that any difference in colour is ‘caused by the zinc ions and capper(l) ions. Zinc and cope next to each other in the Periodic Table, so way should copper, but not zine form coloured ions? ‘The electronic configurations of the Zn? and Cu?* ions are shown below in the electrons-in-boxes format. iii Nt 1d 34 electrons in r RITES [ons tht have completely filled 3d enengy levels (such as Zn”) and ions that have no electrons in their 3d energy levels (such as ‘Sc*)are not coloured. However, the copper!) or Cu, ion has only mine electrons in the 3d energy level, so it is not completely filled. When water ligands are attached to the copperil) ion, the ‘energy level splits into two levels with slightly eifferent energies. ‘The lower energy level contains six electrons and the higher ‘energy level contains three electrons. TUNE Ut My gE In sh2 Cu" onthe waterigands spt the 2d eneray lv higher energy levels NM MN) Principles of transition metal che IF one of the electrons in the lower energy level absoros energy from the visible spectrum, it can move to the higher energy level Movement from a lower energy level to a higher energy level is called ‘promotion ‘or ‘excitation’. When an electron moves to a higher energy level, the amount of energy it absorbs depends ‘an the difference in energy between the two levels — the bigger the energy difference, the more energy the electron absorbs. It js important to know that the amount of energy gained by the electron is directly proportional to the frequency of the absorsed light and inversely proportional to the wavelength of the ligt. In the case of the Cu* ion, the small difference in energy levels ‘means that Jow frequency (or high wavelength) radiation Is absorbed from the red end of the spectrum. Therefore, blue light TUT MITT ii My Jectron has moved fom the aver ene fig Note that Ingher enorey aa Try to find away to remember that red light has a longer wavelength than violet light The Red Sea (between Africa and Asia) ia long (and narrow) sea. Pethaps you can find better way! 1 solusons containing Fea ions are ello xplan which pat of the clecromagnete spectrim s absorbed by these ons 2 state whysolutors containing Ag) ons arecsourss Key definitions The electromagnetic spectrum isthe range ofall wavelengths and frequencies of al the types of radiation. Complementary colours are colours opposite each other on a colour wheel 3Common shapes of complexes By the end of this section, you should be able to.. ‘© understand why complexes with six-fold coordination have an octahedral shape, for example those formed by metal ons with H,0, OH- and NH, as ligands ‘© understand that transition metal ions may form tetrahedral complexes with relatively large ligands such as Cr Predicting the shapes of complexes Using electron pair repulsion theory ‘You are already familiar with the use of the electron pair repulsion theory to predict and explain the shapes of simple molecules and ions It is quite easy to extend this idea to precicting and explaining the shapes of complexes. A ligand bonds to the central metal ion by donating a pair of electrons to form a dative bond. The only differences are that you should ignore the 8¢ electrons in the transition ‘metal ion and the overall charge on the complex —just count the number of electrons donated by the ligands. Table A shows how this theory can be applied in exactly the same way to predict the shape of a transition metal complex and the shape of a simple molecule, es cere a eed 12 | octahedral | 90° | IColNH).F* SF, 4 @ | terahedral | 1085" | (cul? cH, 2 4 linear | 180° | [AgINHL Bec, table A The elcron par repulsion theory can predic the shapes cf simple molecules and complexions Octahedral complexes ‘The most common ligands in most octahedral complexes are water, ammonia andthe hydroxide ion, Although these ligands have different numbers of lone pairs of electrons (ammonia has one, water has two and the Hydroxide ion has three), each ligand uses only ene lone pair to form a coordinate bond with the transition meal ion, As they contain sx ligands, the complexes are sometimes described as having six-fold coordination. Note that the electron pair donor in each of these ligands is an clement in Period 2 ofthe Periodic Table, so all hee ligands are of approximately ‘equal size. Table B shows some commen examples. not oo na [Mn(H20))" hexaaquamanganese(} very pale pink (usualy described as colourless) [Fe(HOMIOH)] tetraaquadihydroxoiron(l) pale green (Alou hexahyroxoaluminate(l) colourless table B Examples of ecahecral complewes ‘Note that the last example contains an element that is nota transition metal ion, nor even a block clement. This example shows thatthe names and shapes of complexes of nom-transition metals such as aluminium can be predicted in the same way as those of transition metal ions. m4Fig A shows the shapes of these complexes. OH, at OH 3 HO.,, KO.., OH om | Nou, no | Sou ba ba fig A The stricures of some ortaheds Note that + Solid and harched wedge bonds are used to indicate the shapes, although the 3D shape can be shown in other ways + The overall charges are all different —this depends on the charge on the original transition metal jon and on how many negatively charged ligands there are + Allthree structures use square brackets, although is neutral + ‘The water ligands are shown as both H,O and OH, ~ the important point is that the bond must be shown to come from oxygen because it supplies the lone pair of electrons for the dative bond. ‘are sometimes omitted when complex Tetrahedral and linear complexes These are much less common than octahedral complexes. The only tetrahedral complexes that you are likely to come across in your course are those in which chloride ions act as ligands, such as in the (CuCl J ion. Note that because chlorine is @ Period 3 element, its ions are much bigger than water, ‘ammonia and hydrexide ions. So, there is usually insuflicient room around the central metal ion for six chloride fons to act as ligands The only linear comples Tollens' reagent (sometimes called ammoniacal silver nitrate). An explanation of why the Ag" ion has only two ligands, and not six, is beyond the scope of this book, but note that silver is @ transition ‘metal in Period 5 (not Period 4) of the Periodic Table. It therefore behaves differently from t transition metals in Period 4 you are likely to come across in your course is the reactive jon present in Fig B shows the shapes of these two complexes. Leamingtip _ a 2 You can usuallyassume tata | complex wth sx igunds cu HN —+Ag-+—N ‘ectahedral,ane with four 7a ic 8 earner talteet ora ey sth ign nea figB Tesrucues of atevahecal complexand ainear comple 1 Acomplex that forms between cobalt ons and nitrite ons (NO}) has the abbreviated formula [Co{NO.).. Predict its shape and the oxidation numberof the transition metal ion, 2 Acomplet fous betwen nickel) ons and cove fons red its shape ame and formula ‘Keydefinition Six-fold coordination refers to complexes in which there are sb igands forming coordinate bonds with the transition metal ion. usSquare planar complexes By the end of this section, you should be able to.. ‘© understand that square planar complexes are also formed by transition metal ions and that cis-platin isan example of such a complex @ understand why cis-platin used in cancer treatment is supplied as a single isomer and not in a mixture with the trans form Square planar molecules ‘You are familiar with the idea thatthe electron pair repulsion theory can be applied to predict the shapes of simple molecules and ions. However. you may not have core across an example of a square planar shape. One example is xenon tetrafluorde, XeF, Although xenan isa noble gas, it does form some stable cormpounds. ‘An atom of xenon has eight electrons in its outermost energy level, and each fluorine atom uses one Of its electrons to form a covalent bond. The outer energy shell now contains 12 electrons. These ate arranged in six pairs, forming an octahedral arrangement. Two of these pairs ae lone pairs, which repel each other and are therefore located opposite each other So, the fourbonding pairs arein a plane, with the four fluorine atoms at the corners of @ square and an F-Xe-F bond angle of 90°, as, shown in fg A. fig A The square planar shape of the xronttrlluorde molecule Cis-platin Square planar complexes are much less common than octahedral and tetrahedral complexes. One particular complex of this type, ciplatin, has become well known in recent years because ofits use as an effective treatment for some types of cancer, especialy testicular cancer ‘An explanation of why the four ligands in this complex form a square planar shape, and not a tetrahedral shape, is beyond the scope of this book It is not easly explained by the electron pair repulsion theory Part of the explanation is that platinum is a transition metal in Period 6, and so bbchaves differently from the transition metals in Period 4 Cis-trans isomers ‘You have leamed about £-Z and cis.ans isomerism in Book 1 Topic 6. Your understanding of this type of isomerism can now be applied to inorganic compounds such as ci+platin and its isomer, ‘rans-platin These consist of a platinum(ll) ion, two ammonia ligands and two chloride ion ligands. ‘The diagram shows the structures of these isomers and the relationship between them. + The cis- prefix indicates that identical ligands are next to each other + The trans prefix indicates that they are opposite each other 5 NH, fe si “HW” FN era pyr awn Nc, ae (Nn, cs Trans fig8 Stacurestessitn ac anion, HN, 116oe Anti-cancer action ‘A full understanding of how cisplatin kills cancer cells is beyond the scope of this book. Put simply: + Allcells, including cancer cells, contain deoxyribonucleic acid (DNA) + During cell division, the two strands of DNA must separate from each other to form more DNA. + The structure of cisplatin enables it to form a bond between the two strands of DNA, which prevents them irom separating and so prevents the cancer cells from dividing, fig € DNA stands are shown in grey andci-platinin pink Trans-platin ‘The isomers iraneplatin and cieplatin have different structures. The difference in structure means that rane-platn is a much less effective cancer treatment than ciplain, Iti also more toxic. So itis ‘important to use ony the a- isomer in Ue cancer treatment You should know the structures of ct-platin and trans-platn, but you do not need to know exactly why ci-platin i effective at treating cancer but trans-platin is act 1 explain why you would expect the I; ion to havea square planar shape 2 (a) Drawthe structures ofthe two cis-rans isomers ofthe IF; ion (b) Why are there no cis trans isomers of the IFC ion? ‘Key definition ‘Acquare planar shape contains a central atom or ion surrounded by four atoms or ligands in the same plane and with bond angles of 90” uwMultidentate ligands By the end ofthis section, you should be able to... © understand why H,0, Cl- and NH, act as monodentate ligands © identify bidentate ligands, such as NH.CH,CH,NH, and multidentate ligands such as EDTA © understand that haemoglobin isan iron(l) complex containing a multidentate ligand © understand thata ligand exchange reaction occurs when an oxygen molecule bound to haemoglobin is replaced by a carbon monoxide molecule © understand, in terms of the large positive increase in AS.yaew that the replacement of a monodentate ligand by a bidentate or multidentate ligand leads to a more stable complex ion. Denticity Dentcity is a rarely used Fnglsh word, but it isa property of ligands that you shoul be aware of It comes from the Latin word dents (meaning ‘tooth, frorn which we get the familiar word ‘dentist’ ‘There isa connection! ‘When ligands were introduced earlierin this book, we could have described them as monodentate ligands, You can think of monodentate as meaning ‘one tooth’ or ‘one bite’, which means that the ligand uses one lone pair of electrons on one atom to form the dative bond with the metal ion Now for bidentate ligands. 8 means two, soa bidentate ligand has two atoms, each of which can use alone pair of electrons to form a dative bond with the metal ion. You can imagine that @ bidentate ligand has two atoms that can ‘bite’ onto the metal ion, ‘You can work out for yourself what « multidentate ligand is —@ ligand with several atoms, teach of which uses a lone pair of electrons to form a dative bond with the metal ion. The ‘most common example you are likely to meet has six such atoms, soit could be described as a hexadentate ligand. Bidentate ligands ‘The most likely bidentate ligand you will meet in your chemistry course is the organic compound withthe structural formula NH,CH;CH,NH,. Its correct name is 1,2-ciaminoethane, although for a reason we will soon see, i is sometimes called ethylenediamine— the ethylene comes from the (CH,CH, part, andi is correctly described as a diamine because there are two amino groups. Its svete we yt wood ka fig A The sructue of1.2claminaethane Occasionally its abbreviated to ‘en’ especially when used in equations representing its reactions as, aligand ‘When it acts as a bidentate ligand, it uses the lone pair of electrons on each nitrogen atom to attach to the metal ion. Fig B shows an Ni* ion joined to three molecules of 1,2- — [Cu(H0\(OH] + 24,0 1220 ‘You might think that this isa ligand substitution reaction ~ that ‘wo hydroxide ions have replaced two water molecules. In fact, it isan acid-base reaction ~ the two hydrexide ions have removed hydrogen ions from two of the water ligands and converted them into water molecules, The two water molecules that have lost hydrogen ions are now hydroxide ligands. The terrn amphoteric behaviour is sometimes used to describe this acid-base reaction because of its reversible nature. When an acids added to the blue precipitate, the hydrogen ions from the acid react with the Iydrexide ion ligands and corwert them back to water molecules. Exactly the same observations can be made during the careful addition of aqueous ammonia instead of aqueous sodium hydroxide. The equation for this reaction is: (Cul},0)}* + 2NH, ~> [Cu(H,0}(OH}] + 2NHY [tis much easier to see that this equation involves an acic-base reaction — two of the water ligands transfer a hydragen ion to the ammonia molecules, When aqueous ammonia is acded to the blue precipitate formed, it dissolves to form a deep bive solution. The equation for this reaction is: (Cull4s0) (OH), + 4NH, — (Cu(NIHL)(H-OhP* + 24,0 + 20H ‘This is a ligand exchange reaction ~ four ammonia molecules replace two water molecules and two hydroxide ions. The solutions atthe start and end of the reaction, and the intermediate precipitate are shown in fig B. ES ES o-oo — CulsO) the pale blue precipitate fig The pale Due soliton cor onta ns [Cul HO) OH) ae th (CuINH (4,0 The formation of (CuCl, - change in coordination number “These reactions always involve a change of ligand as well.A good ‘example is the reaction between copper) sulfate solution and concentrated hydrochloric acid. When the acid is added slowly ‘and continuously the colour gradually changes from blue to green ‘and finally to yellow This s the equation forthe reaction: [Culh,O)E* + ACI” = [CuCl + 6H,0 ‘The state symbols all (aq), have been omitted for clarity. You can see that all six water ligands have been substituted by {four chloride ions, This reaction is also an example of a change in coordination number, from 6 to 4, Note that although the charge on the complex has changed from 2+ to 2-, there has been no change in oxidation number. ‘The arrow shows that the reaction is reversible, which helps to explain the colour change observed. The hexaaquacopper(] jon is blue and the tetrachlorocuprate() ion is yellow, so the ‘green colour is due to a mixture of the blue and yellaw complex ‘ons. The solutions at the start and end of the reaction, and the intermediate mixture are shown in fig C. il DL the yl You should remember the colours ofthe species in these reactions but you do not need to understand why the species have the actual colours 1. The equation fora reaction ofa transition metal ion is IFelt,0},?* + SCN” — [Fe(SCNH OK” + HO Explain which of the four main types of reaction ae illustrated by this equation. 2 The complex [Co(H,O}. is converted into [Co(NH cP Explain which types of reaction occur in this conversion. Keydefinition ‘Amphoteric behaviour refers to the ability ofa species to react with bath acids and bases, 123Reactions of cobalt and iron complexes By the end of this section, you should be able to.. © record observations and write suitable equations for the reactions of Fe™(aq).Fe™(aq) and ‘Co (aq) with aqueous sodium hydroxide and aqueous arnmonia, including in excess @ understand that ligand exchange, and an accompanying colour change, occurs in the formation of [CoCl¢F* from [Co(H.0).|* Reactions involving cobalt complexes Ca 4: fig A The bright colour of tase glass bats is caused by blue cobalt compounds Reaction with alkalis ‘Consider the reaction that occurs when aqueous sodium hydroxide is added to a solution containing the hexzaquaccbait{) ion until no further change is seen. The observation is thet a pink solution forms a blue precipitate. The equation for this reaction is: [Colt1,0}sF* + 20H" — [Co(H,0}(0H),] + 24,0 ‘As with copper this is an acid_base reaction — the two hydroxide ions have removed hydrogen fons from two of the water ligands and converted them into water molecules. The two water molecules that have lost hydrogen ions are now hyéraxide ligands. Upon standing, the colour of the precipitate ‘redually changes to pink, “The same observations can be made when aqueous ammonia i used as the alkali, However, when aqueous ammonia is added to excess, there is an observation not made with aqueous sodium hyerexide ~ the precipitate dissolves to form a brown solution. The equation forthe acid-base reaction is: [ColH,O}sF* + 2NEts + [Co(HsO)(OH),] + 2NHi* “The equation forthe ligand exchange reaction forming the brown solution is [Coltt,0]{OH),) + 6NH, ~» [CO(NH,),* + 4H, + 20H Some features of transition metal chemistry are impossible to explain without going well beyond an ‘Alevel understanding. One of these is why six ammonia ligands are involved in the reaction with the cobalt complex, vikile in the corresponding reaction with copper only four ammonia ligands are involved. Upon standing this brown solution changes colour because of oxidation by the oxygen in the atmosphere. The exidation number of cobalt increases from +2 t0 +3, and the yellow [Co(NH)* ion forms, Unfortunately, the resulting solution usually looks much darker than yellow, as there are other products whose formation is dificult to explain 1240 Reaction with concentrated hydrochloric acid ‘This reaction is very like the one with the (Cu(H,O)"* ion. When concentrated hydrochloric acid is slowly added to a solution containing the hexaaquacobali(II) ion, the pink solution gradually changes ) to blue. This is the equation for the reaction: } [CH,O\* + ACI [CoC + 64,0 ; You can see that all six water ligands have been replaced by four chloride ions. This reaction is also or an exarple of change in coordination number fom 6 104 Note hat ahnough the charge on the Complex has changed fom 2+ t02~ there hasbeen no change in eidationmurber, ( Reactions involving iron complexes Sg Reaction of iron(II) complexes with alkalis Consider the reaction that occurs when aqueous sodium hydraside is added to a solution containing en This is more noticeable the hexaaquairon(lI) ion until no further change is seen. The observation is that a pale green solution you look though 2 forms a green precipitate. The equation for this reaction is: considerable thiciness of as [Fo(H,0)sf* + 20H — (Fe(H,0) (OH),] + 2H,0 ‘As mith copper and cobalt, this is an acid-base reaction ~ the two hydroxide ions have removed hydrogen ions from two of the water ligands and converted them into water rnalecules, The two water molecules that have lost hydrogen ions are now hydraxide ligands, fig Ordinary glass soften very pale cantaning ron The same observations can be made when aqueous ammonia is used asthe alkali, The equation for the acid-base reaction is (Fe(H,O)q!" + 2NE, — [Fel (4.0) OH) + 2NE Upon standing, the colour of the green precipitate gradually changes to brown as oxygen from the atmosphere causes oxidation, forming [Fe(H0) (OH) ~ this is the riaquatinydroxoiron(t) complex Reaction of iron(II!) complexes with alkalis Consider the reaction that occurs when aqueous sodium hydroxide is added to a solution containing the hexaaquairon(lll) ion until no further change is seen. The observation is that a yellow-brown, solution forms a brown precipitate, The equation for this reaction is: [Fe(H.O},}"* + 30H — [Fe(H,0)(OH)s] + 3H,0 As with iron(l), this is an acid-base reaction — the three hydroxide ions have removed hydrogen ior from three of the water ligands and converted them into water molecules ‘The three water molecules Learning tip ‘that have lost hydrogen ions are now hydroxide ligands, Note that atmospheric The same observations can be made when aqueous arnmonia is used as the alkall, The equation for oxidation occurs with the acid-base reaction is: complexes containing a transition metal ion with a+2 ‘oxidation number, but not For those witha +3 oxidation number. (Fe(HsO)ef* + 3NH, — [Fe(H,0}(OH),] + 3NH. ‘There are no further reactions when an excess of either aqueous sodium hydroxide or aqueous ‘ammonia is added and no further changes upon standing. 1 Wen aquous ammonia is adden exes solution contining[CIM,OLP*ing an ch-base renclon beau elowed byalgand tchange enconWrte an eeaontoesrbe ha escion, 2. student wrote tisequation to expan the fomation of the brown precpate when aqueous ammonia tras added toa solution containing Fons [Fe(H,0},P* + 30H" — [Fe(H,0),(OH):] + 3H,0 Why isthe above reaction ess el to occur than the one shown blow? [Fe(H,O},P* + 3NH3 — [Fe(H,0),(OH),] » INH,” 12sThe chemistry of chromium By the end ofthis section, you should be able to... © record observations and write suitable equations for the reactions of Cr"(aq) with aqueous sodium hydroxide and aqueous ammonia, including in excess ‘© understand, in terms of the relevant E* values, that the dichromate(Vi) ion, r,0;2 (i) can be reduced to Cr’ and Cr*ions using zinc in acidic conditions {ii) can be produced by the oxidation of Cr* ions using hydrogen peroxide in alkaline conditions ‘© understand thatthe dichromate(V) ion, Cr50,?, can be converted into chromate(V}) ions as a result ofthe equilibrium, 2CrO, + 2H" == Cr, +H,0 Introduction Some of the reactions of chromium are similar to those we have already met for the ions of copper cobalt, iron(I) and iron( Il), However, chromium has ons in which the metal has an oxidation numer Of +6, so reactions involving these ions must be considered in a different way. Aword of warning We have already met the idea that there is an infinite number of colours in the spectrum of visible light, although we sometimes refer tothe seven colours ofthe rainbow The perception of colours by humans vaies considerably A specific colour might be described as pink or purple by different people, and a colour deserted as blue-green by one person might be described as blue, green or turquoise by others. ‘The situation withthe colours used to describe chromium compounds is futher complicated by these factors: + Some compounds have different colours a solids and aqueous solutions. + The colour ofa solution depends on concentration + The presence of dssolved oxygen in an aqueous solution can affect the colour ebserved. ‘This means that the colours used in this book may not always correspond to those in other books, and may be different from those observed in test-tube reactions that you see. Reactions involving chromium(III) complexes Reaction of chromium(III) complexes with alkalis ‘Consider the reaction that occurs when aqueous sodium hydroxide is added to a solution containing the hexaaquachrorium({II) ion until no farther change is seen. The observation i that a green or Violet solution forms a green precipitate. The equation for this reaction is: [CH{H,O),}* + 30H” — (Cx{H,0)(OH),] + 3H,0 ‘As with iron), this isan acid-base reaction ~the three hyeraxide ions have remeved hydrogen ions fiom three of the water ligands and converted them inta water molecules. The three water molecules that have lost hydrogen ions are now hydroxide ligands. ‘The same observations can be made when aqueous ammonia is used as the alkali, The equation for the acid-base reaction i: [Ce(H,0),P* + INH, — (Cr(H,0) (OH) + NH 1260 When an excess of aqueous sodium hydrexide is added, the green precipitate dissolves to form a _green solution, The equation for this acid-base reaction can be represented as: [Cx(H,0),(OH),] + ON" — [Cx{H,0]{OH) + HO If the aqueous sodium hydroxide is more concentrated, further acid-base reactions occur such as [CX(H,0) {OH} + 20H” — [Cr(OH)|*" + 2H,0 although there is no further change in colour ‘The reactions involving hydroxide ions can be reversed by the addition of acid, ilustrating the amphoteric nature of the neutral complex. When an excess of aqueous ammonia is added to the green precipitate, the precipitate is slow to dissolve, but eventually 2 violet or purple solution forms [Cx(H,0),(OH),) + 6NH, ~+ (Cx(NH,).}** + 3H,0 + 30H™ Inall of the reactions so far, the oxidation number of chromium has remained unchanged at +3. ‘However, providing that the solutions are alkaline, oxidation is easly achieved by the addition of the ‘oxidising agent hydrogen peroxide. In this reaction the solution changes fiom green to yellow as the ‘ehromate(V} ion, with oxidation number +6, is formed. The equation for this exidation i 2[CHOH),]* + 3H,0, — 2Cr02 + 20H" + BH.O Note that although the chramate(V!) ion is a complex, itis not enclosed in square brackets, Chromate(V1) and dichromate(VI) ions CChromte( VI) ions are stable in llaine solution, but in acicic conditions the cichromate(¥/] on is more stable. Saif acid is added there isa colour change from yellow to orange asthe following reaction occurs: 2CrO, + 2H* Cr,0 +H:0 ‘This reaction is eaily reversed by adding alka. When considering redox reactions, itis often easier rouse simplified formulae by omitting square brackets and ligands that do not undergo rede reactions especialy weter The reduction of dichromate(V!) ions \When zine metals adéed to an acidic solution containing éichromate(V) ions reduction reactions ‘occur in which the oxidation numberof chromium decreases fst to +3 and then to +2 “The ist stage of the reduction involves 2 colour change fom orange to green, as this reaction CHOP" + 14H" + 8Zn — 2CP + THO + 3zn* “The second stage ofthe reduction involves a colour change from green to blue, as this reaction occurs: 208" + Zn 208 + Zn Explanation of redox reactions using E° values [tis often helpful to explain way redox reactions occur by considering the standard electrode potentials of the different recox systems involved, For chromium, we need to consider these values: 1 Zn +26 Zn Ee -076V 2 Che ace Eo=-041V 3 CrO¢- +4H,0 +3e° + COM), +5OH- £9 =-013V 4 H,O, + 2e° = 20H" Be s124V 5 COP + 14Ht +62" = 2Cr+ + 7H,0 BP = 4133 If you have already learned about standard electrode potentials ealir in this book, you may remember that when hall-equations are arranged from high negative &* values atthe top to high positive values at the bottom, then the best reducing agent is atthe top and on the right, and the best ‘oxidising agent is atthe bottom and on the let 7128 Explaining oxidation from +3 to +6 ‘The simplifed equation for the exidation of chromium) by hydrogen peroxide in alkaline conditions is: 2CrOH), + 3H,0, + 40H + 2CrO e+ 8H,0 ‘How can this equation be obtained from the half-equations? ‘The relevant half-equations are 3 and 4 (see previous page). In these equations, the best reducing, agent is Cr(OH), and the best oxidising agent is H,O,, For these two species to react together, we need to add half-equation 3 (teversed) to hall-equation 4. When adding hal-equations, they may ‘need to be multiplied so that the number of electrans is the same in both. In this example, we need {to multiply equation 3 by 2, and equation 4 by 3, so as to obtain 6e in both: 2CHOH) + 1OOH” = 2010" + BHO + be" 3H,0; + 62° = 60H" ‘Adding the ha-equations and cancelling identical species on both sides gives: 2CH(OH)y + 3H;0; + 40H — 2Cr0¢- + 8H;0 Since the * value for half-equation 3 is more negative than the &* value for halF-equation 4. CH); is electron releasing with respect to H,O, and hence the reaction is thermodynamically feasible. Explaining reduction from +6 to +3 ‘The simplified equation for the reduction of chromnium(Vt) by zine in acidic conditions is CO} + 14H? + 320 — 208" + THO + 32a? How can tis equation be obtained from the half-equetions? ‘The relevant half-equations are 1 and 5 (see previous page). Ia these equations, the best reducing agent is Zn and the best oxidising agent is Cr,0,#”. For these two species to react together, we need to add half-equation 1 (reversed) to half-equation 6, bearing in mind matiptying half-equations: Zn = 3Zn"* + 66 CrOS- + 14H + Be = 20 + 7H,O ‘Asin the previous example, adding gives CHOP + 14H? + 3% 2CP + THO + 32a? Since the Z® value forhalf-equation 1 is more negative than the £® value for half-equation 5. Zn is electron releasing with respect to Cr;O;* and hence the reaction is thermodynamicaly feasible Explaining reduction from +3 to +2 ‘The simplified equation fr the reduction of chromium(l) by zin in acide conditions ix 2CH + Zn 20" + Zn How can this equation be obtained irom the hal equations? “The relevant half-equations are 1 and 2. In these equations, the best reducing agents Zn and the best oxidising agent is Cr. For these two species to react together, we need to add half-equation 1 (ceversed) to haléequation 2, bearing in mind multiplying hal-equations ‘Zn = Zn** + 2e7 2CP* + 26 = 2Ce* As in the previous example, adding gives: Crt + Zn 2Ce + Zn Since the £* value forha-equation 1 is more negative than the Evalue fr hal-equaton 2, Zn is electron releasing with respect to Cr" and hence the reaction is thermodynamicaly feasible0 Chromium chemistry summary ‘Table A surimaiss the important reactions of chromium complexes in four sequences Reagent | Intermediate | Reagent IcnH.O}P add NaOH(aq). | [CHH;O}{0H)] | add NaoHlaq) | [COM 100" solution seen precipitate teen solution (cH. ANH (CAH,OM(OH),) | add NAslaqy (CAN) green solution green precipitate violet soto (cnor add 10,700 croz aah crOF 1227 solution yellow solution orange solution co, add Zn" iCrH.O}f 3d ZH [cuH.0). yellow solution green solution blue solution table A (a) (b) «© (d) b) contains the re Tube ced by teducion using 2 othe a very pale blue [CrHLOMP* ion {Ojon whch ienaemaly aren, but can appear wet i th rains the [Cx{OH). ee inalalne solitons. The tubes in ( icaon number +6. The oran Understanding chromium chemistry involves more effort than for some other transition metals because of the number of different ions. As wells all ofthe complexes involving Cr" and Cr, there are two complexes with oxidation number +6 (CrO,-ané Cr.0) 1 Excess ci saddled toa green solution containing [HOH lors Wie an equation forthe reaction In which adferent green chrorsium-containng sltion i formed 2. The standard electrode potential forthe redox system Mri” +26" <2 Mnis 1.184. ions tothe element Ma. Explain whether or not zine can reduce M 129The chemistry of vanadium By the end of this section, you should be able to.. ‘@ recognise the colours of the oxidation states of vanadium (+5, +4, +3 and +2) in its compounds ‘© understand redox reactions forthe interconversion of the oxidation states of vanadium (+5, +4, 13 and +2), in terms of the relevant E* values Redox reactions Like chromium, vanadium is a transition metal that forms ions with several exidation numbers. ‘Table A shows the important ones. Cs nr Namé Etre 42 a vanadium) purple 8 ve vvanadiuin(ti) green 44 vor xovanadium(tv) blue 6 vor" doxovanadium(V) yellow table A Unlike with chromium and the other transition elements the focus with vanadium is purely on redox reactions. Vanadium is a good choice for this because there is one distinct colour for each of the ‘main oxidation numbers found in its compounds. So itis relatively easy to demonstrate the change in oxidation number by observing the change in colour during the reaction. As with chromium, we will consider the feasibility of these redox reactions in terms of £ values. Although most of the species involved are complexes and some contain water ligands, the square brackets and water ligands are omitted for clarity. Reducing vanadium from +5 to +2 "The usual source of vanadium with cxidation number +5 is the compound ammonium vanadate(V}, NH.VO,. An acidic solution of this compound contains the diaxovanadium(V) ion, VO,”. When zinc is added to this solution, reduction begins and there is a gradual colour change from yellow, through blue and green, to purple as the oxidation number decreases from +5 to +2, All of these colours are Of solutions ~ there are no precipitates involved. The test tubes in fig A show the colours. bin fig A Tho tube on helt (yellow) corsa the VO,” ion The second tube (blue) canains the WO ion, The tic tbe (ger) contsinethe Von, The tube onthe right purple) contanethe Von 130Explanation using E° values For vanadium, we need t consider these vals 1 Vie HV Ee=-1.18V 2 Unit + 20° = Zn Fe=-0.76V) 3 Ve eave F°=-026V 4 VOF+OHt+ e = VEHHO P= 4034 5 VO,)+2H'+ @ 2VO"+H,O Ee=+100V If you followed the explanations for the redex reactions of ‘chromium in the previous topic. you should be able to understand {an abbreviated explanation for each stage that just shows the two relevant half-equations and then the overall equation. Reduction from +5 to +4 VO," +2H' +e VO" + Zn nt + De Overall reaction: 20," + 4H! + Zn 2V0% + Zi + 2H, Since the £ value for half equation 2 is more negative than the ° value for half-equation 5, Zn is electron releasing, with respect to VO,* and hence the reaction is thermadynamically feasible Reduction from +4 to +3 VO# + 2H! +e V+ HO Zn— Dnt +e Overall reaction: aVO# + 4H" + Zn av +21 +2H,0 Since the £° value for half-equation 2 is more negative than the E° value for halfequation 4, Zn is electron releasing with respect to VO* and hence the reaction is thermodynamical feasible Reduction from +3 to +2 Vite ovr Zn 2ni* + 20 ‘Overall reaction: 24 Zn » 22 4 Zn Since the £° value for half-equation 2 is more negative than the ° value for half-equation 3, Zn is electron releasing with respect to V*" and hence the reaction is thermodynamically feasible, 0 Reduction from +2 to 0 Vile Vv Zn Zn? + 26 Overall reaction: Dv + Zn + DV + Zn Since the £* value for hal-equation 2 is less negative than the £* value for half-equation 1, Zn is not electron releasing with respect to Vand henee the reaction isnot thermodynamically feasible, Predicting oxidation reactions A similar method can be used to prediet whether @ given oxidising agent will oxidise a vanadium species to one with a higher oxidation number You can see how to do this in Question 2 inthis, topic. Learingtip leis important that you do not get confused between the two oxo ions of vanadium: VO,’ and VO", 1. The standard electrode potential for the redox system Sn +20 = Snis-O.14V, Explain why the use of tin asa reducing agent will not obtain V™ from a solution containing VO," ions. 2 The standard electrode potential for the redox system CaP" + 2er = Cis 0.34¥, Explain whether coppertl) ons can be used to oxidise VO** ions to VO," ions. 31By the end of this section, you should be able to.. @ understand that a heterogeneous catalyst isin a different phase from the reactants and that the reaction occurs at the surface of the catalyst © understand, in terms of oxidation number, how V;O. acts asa catalyst in the Contact process © understand how a catalytic converter decreases carbon monoxide and nitrogen monaxide emissions from internal combustion engines by. {i) adsorption of CO and NO molecules onto the surface of the catalyst (i) weakening of bonds and chemical reaction (ii) desorption of CO, and Nz product molecules from the surface ofthe catalyst Different ways to understand catalysis When you ist learned about catalysts, you probably recognised them as substances that increased the ate of a reaction without being chemically changed daring the proces. This desertion s fine a an intoduction to carlsis burt s incomplete ane not always correct Jn Boole 1, you learned about catelysis in terms of its effect on the activation energy of a reaction, and how to represent catalytic action using MaxwelBoltzmann energy distributions and energy profiles. In this topic and the next one, we will consider catalysis in more detail by looking atthe two main types of action: heterogenous and homogeneous. Transition metals as heterogeneous catalysts 4 heterogeneous eatalyst is one that isin a cferene phase from that of the reactants. You cen probably remember an example of tis type of catalysis from many years ago. gas can be made in the laboratory by decomposing a cagen peroxide solution, The catalyst used in this reaction is usually manganese(I¥) oxide ~ note that this is a compound of a transition metal, Howevez, what males this an example of heterogeneous catalysis is that manganese(V) oxide is a sold anc hydrogen peroxide solution is aliqud. Many transition metals, and their compounds, are used as solid catalysts. Their action can be explained in terms of what happens con the surface of the catalyst. The fact that the action takes plac only on the surface explains why many of them are used in a 132 finely divided form, including powder) rather than as large hurnps, Sometimes, they are used instead as a thin ccoating on an inett support material The Contact process Sulfuric acid is one ofthe most widely used chernicals, both in terms of the quantty produced and the narser of industries that use Is biggest ingle se isin the mantfacare of ferisers ‘Accomplete description ofthe Contact process used to ‘manufacture sulfuric acid is beyond the scope of this book but the key reaction in the process is the conversion of sullur diode to sulfur tioide inthis reaction 280, + 0, = 280. ‘At the temperatures and pressures used in the process, all of the substances are in the gas phase, and the mixture of reacrants is ppassed over a catalyst of vanadium(V) oxide, V2O., usually known in industry as vanadium pentoxide. fig Sample varacium(V}o: Surface adsorption theory The way that a heterogeneous catalyst works i often explained with reference to this theory. which s usually considered as having three steps 1 Adsorption, in which one or more reactants becomes attached to the surface of the catalyst. Reaction, following the weakening of bonds in the adsorbed reactants, 3. Desorption, in which the reaction product becomes detached fiom the surface of the catalyst In the Contact process, the reaction step has two parts: Part 1: sulfur diaxide adsorbs onto the vanadium(V) oxide and « redox reaction occurs V,0, + $0, + V,0, + $0, Note that the oxidation number of vanadium decreases from +5 10 +4, The sulfur trioxide then desorbs.Part 2: oxygen reacts with the V,O, on the surface of the catalyst and another redox reaction occurs! V0. + 40, + V.0, Note thatthe original cata 1 is regenerated as the oxidation number increases from +4 to +5. Catalytic converters The problems One of the major problems associated with the steady growth in road vehicle usage over several decades is the increased emission of pollutant gases from vehicle exhausts. In some cities, the quality of air breathed by humans is below acceptable levels. Without catalytic converters, the situation ‘would now be much worse. Although many different pollutants come from vehicle exhausts, two of the most significant are carbon monoxide and nitrogen monaxide + Carbon monaxide is a toxic gas that interferes with oxygen transport from the lungs through the bloodstream to vital organs in the body (see Section 15.1.6) ‘+ Nitrogen monoxide is easily oxidised in the atmosphere to nitrogen dioxide, where it can act as a respiratory irritant and contribute to the formation of acid rain Carbon monoxide forms through the incomplete combustion of hydrocarbon fuels, and nitrogen monoxide forms through the reaction between nitrogen and oxygen at the high temperatures that xst in an internal combustion engine The solutions For over 20 years, all cars sold in EU countries have been fitted with catalytic converters in an attempt to alleviate the effect of vehicle emissions on air quality The main transition metals used in lytic converters are platinum and rhodium, and sometimes pelladium. The method of action can be explained by the surface adsorption theory described above. In one type of catalyst, molecules of 1bon monoxide and nitrogen monoxide are adsorbed onto the surface. Then, because their bonds akoned, they react together to form carbon dioxide and nitrogen, which are then desorbed trom a the surface of the catalyst. The overall reaction can be represented by this equation: puatnny rhadniood 2CO + 2NO = 2C0; +N, Learning tip ‘Try not to confuse absorb/absorption with adsorb/adsorption. Very simply, absorption involves one substance becoming distributed throughout anather (far example water in a sponge), while adsorption only happens atthe surace ofa substance, 1 How des the destin fhe cate oe of vanaiun(V exe show that th stateent nat re? ‘Aatalsinceases tne rt ofa heal enon but dors ht ake prt nthe reac 2 Write an equation to show how nitrogen monoxide can form acid rain Key definitions ‘Aneterogencous catalyst sone thats ina different phase from the reactants. ‘Adsorption isthe process that accurs when reactants form weak bonds witha solid catalyst. Desorption s the process that occurs when products leave the surface of a solid catalyst. 133,Homogeneous catalysis By the end ofthis section, you should be able to... © understand that a homogeneous catalyst isin the same phase as the reactants and appreciate that the catalysed reaction will proceed via an intermediate species ‘© understand the role of Fe® ions in catalysing the reaction between |- and S,0,#- ions ‘© understand the role of Mn” ions in autocatalysing the reaction between MnO,” and C0,” ions Transition metals as homogeneous catalysts ‘A homogeneous eatalyst is one that isin the same phase as the reactants ‘This means that they are either all gases, or more often, all in aqueous solution. You will nt have come across many examples of this type of catalyst, compared with those that take part in heterogeneous catalysis. Homogeneous catalysis is also much less common in industry. ‘The key feature of homogeneous catalysis isthe formation of an intermediate species for which a specific formula can be written. Areaction of the $,0," ion ‘The ion with this formula has several names the simplest of which isthe ‘persulfate ion, although itis often known as the ‘peroxodisulfate ion’ We will not use the IUPAC name, which is very complicated! It acts as an oxidising agent in its reaction with iodide ions. the equation for which is S,O_ + 21+ 280° + Ip ‘One reason wity this reaction is slow at room temperature i thatthe two reactant ions are both negatively charged and so repel each other ‘The reaction is much faster in the presence of Fe** ions, ‘which act asa catalyst All of the reactants and products, and the catalyst are in the aqueous phase, so this eaction is an example of homogeneous catalysis The steps in the catalysed reaction Step 1: The Fe? ions are not repelled by the $,0,*- ions because they have the opposite charge. They teact together as fellows: S,Og + 2Fe* 280," + 2Fe* ‘Step 2: The Fe" ions formed in Step 1 nov react withthe I" ions (these also have opposite charges) as follows: 2Fe! 421-5 Fe + by ‘The ron(t ions are used in Step 1 and regenerated in Step 2, so the two steps can repeat continuoosty An alternative mechanism The reaction is also catalysed by Fe" ions, for which the following mechanism can be writen Step 1: 2Fe% + 21> 2Fe* +s Step 2: 8,0," + 2Fe — 280° + 2Fe* ‘The same two reactions are involved, but they occur in a different order 134The oxidation of ethanedioate ions You may be familiar with titrations in which potassium manganate(VIl) in acidic conditions acts as an ‘oxidising agent. For these titrations to work satisfactorily i's important thatthe reactions a that the end point of the reaction can be accurately observed One example of a redox reaction that can be used in titrations is the oxidation of ethanedioate fons by potassium manganate(VII), The equation for this reaction is MnO," + SCO," + 1GH* — 2Mn** + 5CO. + 8H,0 AAs with the $,0,?-/1- reaction, the reacting species are both negatively charged. Therefore, the reaction is slow. However, as more potassium manganate( VII) solution is added, the reaction rate (2) fig (2)t the star.of he tration, the colour ofthe potassium manganate[Vl) solution takes some ime to |The colourof the potass um mangarate(l solution now asappears more quick becaure tre are Mi onsto cay th atthe end ofthe tration there are no more etnanediont ons la act sing polassium manganatVI) solution gues the mature a pink colour Note that one of the reaction products is the Mn ion, This can aet as a catalyst in the reaction, ‘which explains why the reaction rate increases as the titration proceeds, Tae formation of a reaction product that increases the rate of the reaction is sometimes referred to as autocatalysis. This effect Js sometimes represented using a graph. Note that in Section 15.2.1 all of the transition meta catalysts were solids, but that in ths section they are allionsin aqueous solution 1 state why Mg ion do not act a acatystin the reaction between 0," and tons 2 State why autocatalysis of the reaction between MnO, and C,0,* fons does not occur under alkaline conditions Key definitions ‘Ahomogeneous catalysts one that isin the same phase as the reactants. ‘Autocatalysis occurs when a reaction product acts as a catalyst for the reaction. @ Time fig (1) The slow decease catalysed a ft 25 more rapdiy as the 135ctopuses are complex and intelligent creatures. One of their many fascinating att colour of their blood. What is the chemical that causes this eolour and what ists func antcle below to find 0 POWERFUL PIGMENTS BLUE BLOOD HELPS OCTOPUS SURVIVE BRUTALLY COLD TEMPERATURES & Wilden 10 Joy Posted by fig A. 4 Paelacone chareos octopus ¢ ‘ks Researchers at the Alfred Wegener Institute for Polar and Marine Research in Germany have found that a specialized pigment in the blood of Antaretic octopods allows them to survive temperatures that often drop below freezing, 1c all dawn to a sespicatory pigment in their blood called Ihacmoeyanin that allows the octopus ‘to maintain an aerabi lifestyle sub-zero temperatures, said Michael Oellermann, who took part in the researeh, Haemocyanin also has the effect of making the octopods blood blue, “Haemocyanin contains copy binding oxygen, explained Oellermann in an email. “Hemoglobins contain iron insiead, which gives our blood a red color: Blood chilling snot a question of blood free The reason why octopus blood does not freeze at 1.9 degrees C [28.58 degrees Fahrenheit) is that they are isosmoti, which means that their blood shares the same salinity as the surrounding seawater? «explained Osllermann, The prablem in very cold temperatures is that, witho adaptations, the aerobie process would, in most eases, shut down, ‘Cold temperatures increase oxygen alinty to the extent that oxygen ‘cannot be released in the tissue anymore, ¢ ‘making survival in waters that ean drop to a8 low as 29 Fahrenheit a challenge to sy the last. Comparing octopads The researchers looked ata particular species of Antarctic octopodd called Pareledone chareori and compared it with temperate and watm-adapted actopods to observe the difference in how cold-water ‘ctopads transport oxygen in thei blood, “Pareledone charcou decreased the oxy gen afnity ofits haemoeyanin to counter the adverse effect of temperature on oxygen binding accompanied by changes in their protein sequence, to assure sulicient oxygt ‘Octopods likely developed the adaptation because they requite a lot ‘of oxygen compared to other invertchrates, notes Oellermann, and because they are lagely non-migratary and must instoad adape 10 their supply to its issues and organs, explained Oellermann, Inconras, sad Ocllerman,Antarctisiceshsuvnei ihe sme f loves oogenesis tn cy anepet employed By 5 2 ¢ § frigid environieat by dint ofthe through the adapted system of oxy blue-blooded neighbors. be what allows oetopads to 1, such as the tho same adaptation mi survive temperatures on the other end of the thermo rn found near thermal vents,ii Let us start by considering the nature of the writing in the article Pasrcceeeecennn 1. How might an article like the one opposite be used to highlight the importance of species diversity and environmental conservation? Now we will lock at the chemisery in detail. Some of these questions will link to topics earlier in this, book or in Book 1, so you may need to combine concepts from different areas of chemistry to work ‘out the answers. 2. Oxygenated haemocyanin is blue in colour whereas deoxygenated haemocyanin is colourless. Explain this observation using your knowledge of copper chemistry, 3. Describe the type of the bond between copper and nitrogen in oxyhaemocyanin, as shown below in fig B. wl fig An cayhaemacyani 4, Suggest why zinc is unlikely to be able to form a protein complex that is capable of reversibly binding oxygen. 5. a. Use the two half equations below to show that the reaction between oxygen and copper) ions under standard conditions is feasible: cu(aq) +e" = Cur(aq) Oug) + 4H'(aq) + 4e" = 24,04) b. Calculate the total entropy change for this reaction under standard conditions (298 K) (F = 96500 C). Activi Design an A3 poster for he general public to istrate the role of trasiion metals and ther compounds ascatalysts. You could choose to focus on ther role in biological systems (enzymes) or their role in Industral chemistry. In each case, choose a specific ample to illustrate the general principles {© From the ens ofthe magazine National Geverephic.15 1 Scandium and titanium are both d-block elements, but only titanium is a transition metal, (2) Complete the electronic configuration of each of these Sct 19¢25tOp Tit Ist2s#2p! el () Explain why titanium is a transition metal, but scandium is not. @) (c) What isthe oxidation number of the d-block element in each of these compounds? Se(OH), CaTiO, el (a) Which ion is isoelectronic with TH+? A cu BOce c re Dive a) (Total: 7] 2 (a) What is the meaning of the term ‘ligand’? @ (0) Which molecule is not able to act as a ligand? A co BR, c HO DO, a (c)_ (Give the formula of the complex with the name tetraaquacihydroxoiron( Il) a (i) Give the name of the complex with the formula (Coch. a (d) The arrangement of d-electrons in the complex with the formula (Cr(H,0),}** can be represented using this diagram. tT Explain, with reference to this diagram, why a solution containing this complex is coloured. (5) (Total: 10] Exam-style questions 3. Most transition metal complexes have octahedral or tetrahedral shapes. (a) Explain why the complex forrned between one coppertit) ion and six water molecules has an octahedral shape. [2] () Concentrated hydrochloric acd is added to a solution containing the complex in part (a). During the reaction that ‘occurs, there is a colour change from biue to yellow (0) Explain why the number of ligands around the metal jon decreases during this reaction PI (i) State one other feature of the complex that changes during this reaction, and one feature that does not change. el {c) A complex with a linear shape has the formula (Ag(NH:),*, and is used in a test to distinguish between aldehydes and. ketones. (i) State the name of this complex and the reagent that contains it eB (i) State the type of change that this complex undergoes ‘when it reacts with an aldehyde, and the name of the metal species formed PI (2) A complex with a different shape. used in cancer treatment. is cisplatin, and has the formula [P1(NHL):Ch} Dravr the structure of cisplatin and state the name ofits shape. re (c) A muitidentate ligand has a formula abbreviated to EDTA. Its structures: occH, INCH,CH.N- oocc, ‘cH,COO (Explain why EDTA‘ is described as a mukidentate ligand. ) (@ Draw the structure of EDTA showing the Jone pairs of electrons used in the formation of bonds with a transition metal ion 0) (ii), Using the abbreviation EDTA, give the formula of the complex formed when [Fe(H,0),)* reacts with EDTAY, a) (Total: 15} cH,coo}*—4 “The following sequence summarises some reactions, 1, 2.3 and 4, of chromium compounds (cw, o* L [cxt,0)(0H),) 2+ (crOH) 3, cox 4s c.o- (a) State the appearance of the reactant and product in reaction 1 (2) () State the neagent used in both reactions 1 and 2 i (6) With reference to oxidation numbers, identify which reaction is a redox reaction. (2 {@) Describe the colour change in reaction 4, a {©} Write an equation for reaction 4. a (Total: 7] ‘The heterogeneous catalyst used in the Contact process to ‘manufacture sulfuric acid has the formula VO, Explain, with the help of suitable equations and with reference to axidation states of vanadium, the steps in this catalysed. reaction (6) (Total: 6]TOPIC 16 Further kinetics Introduction ‘Your health depends on a complex interplay ofa large number of chemical reactions taking place in the cells cof your body, Ina healthy body, these reactions wil take place atthe correct rate, in the right place and atthe Fight time, These reactions are controlled by enzymes. The branch of chemistry concerned with the rates of ‘chemical reactions i called chemical kinetics. The term kinetics’ implies motion (derived from the ancient Greek word for mavement-kinesis), We can use the information obtained from the study of chemical kinetics to understand the bodys metabolism and to model the effects of pollutants in the Earth’ alosphere. The development of new catalyst is another branch of chemical Kinetics, and is one that is of immense importance to the chemical industry In Book 1 Topic 9, we used a qualitative approach to the understanding of reaction rates, In this topic we shal develop ths further by adopting a quantitative approach. Ths will enable us to begin to understand ‘what is happening during chemical reactions. We know how atoms can bond together to form molecules, but why do the atoms change partners during chemical reactions? What exactly happens when a hydrogen molecule meets an iodine molecule and they subsequently react ta produce hydrogen iodide? thas been reported by scientists that the herb St John's Wort (Hypericum perforaturn) may be just as effective as Prozac at renting depression, Herbs and plant extracts have been used for centuries to cure diseases and. torelieve pain. In many cases they are effective because they control the rates of reactions within the body. In this topic we shall study the rates of chemical reactions and the mechanisms by which they take place All the maths you need 3 CoE Merete ncn ees im cee arene ree tesa ee eee ree ae ican coger pre cae STS PAS eaten crestor tang conte Oe eee he PS + Solve algebraic expressions + Translate information between graphical, numerical and algebraic forms + Plot two variables from experimental or other data + Determine the slope and intercept of linear graph + Calculate rate of change for agraph showing a liner relationship + Draw and use the slope of a tangent toa curve as a measure of rate of change:\ AWE aE UM er Col td Pee Se ead cee Perera een a eo Sees eee eet eee] catalysed reactions STEAL ee acd + How pharmaceutical companies invest heavily in research and development to design new eee Pesca een od some reactions to accur at lower temperatures and pressures than other catalysts eer er eee recs Cee ee ees Sey uci transmission) based on organic compounds Pes Mart auth ited ene ery Selection ofan appropriate technique to follow Peet eee one peer pene ieee ota ryMethods of measuring the rate of reaction By the end of this section, you should be able to.. © understand the term ‘rate of reaction’ © select and justify a suitable experimental technique to obtain rate data fora given reaction, including: () volume of gas evolved (i) mass change (ii) colorimetry (i) titration (¥) other suitable technique(s) for a given reaction. Rate of reaction ‘The rate of @ reaction can be expressed either in terms of how the concentration of a product increases with time, or how the concentration of a reactant decreases with time. So, _ change in concentration of product gg rere or rate = hae in concentration of reactant time “The negative sign in the second expression reflects the fact that the concentration ofthe reactant is decreasing and therefore gives @ positive value forthe rate Rate is measured in units of concentration per unit time, and the ‘most common unit is mol d=! s- For the mathematicians emongst you, the expressions in calculus notation ae sate = Mbroduet) __dlreactant) a a ‘This rate of reaction is somerimes called the ‘overall rate of reaction’ Methods of measuring the rate of reaction Before investigating the rate of a particular reaction itis necessary to know the overall equation, including state symbols, for the reaction so that we can decide what method to use to follow the reaction ‘There are various methods available, such as: + measuring the volume of a ges evolved + measuring the change in mass ofa eaction mixture + monitoring the change in intensity f colour ofa reaction rinture (colorimetry 142 + measuring the change in concentration of a reactant or product using titration + measuring the change in pH of a solution + measuring the change in electrical conductivity ofa reaction rixcure. "The method chosen to flaw the reaction will depend on the nature of the reactants and products, as well as the conditions under which the reaction is carried out, For example, the reaction between calcium carbonate and dilute hydrochlonc act CaCOy() + 2HCKaq) —- CaCaq) + H.0() + COsla) could conveniently be followed by measuring the volume of gas. given off at regular time intervals, or by measuring the change in ‘mass of the reaction mixture with time, However, the reaction between propanone and iodine in aqueous solution, CHsCOCH (aq) + L{aq) + CHCOCH|(aq) + H*[aq) + Cag) could not be followed by measuring change in mass because all, products ofthe reaction remain in solution. It would be possible, however, to follow the reaction by monitoring the decrease in intensity of colour of the reaction mixture, since (aq) is the only coloured species present, Measuring the volume of a gas evolved ‘The two most common techniques for collecting and measuring the volume of a gas evolved curing a reaction are 1 collection over water into a measuring cylinder and 2. collection using a gas syringe. ‘Tae technique chosen will depend partly on the level of precision required. The gas syringe has greater degree of precision, but if a large volume of gas is being measured, the difference in the degree of measurement uncertainty becomes so small that either instrument is sufficiently precise. conleal ask fig Collecting gas over was,| wince gas evolved conical ask fig Colec Measuring the change in mass of a reaction mixture This is anct technique applicable to reactions in which a gas is evolved. The reaction flask and contents are placed on a digital balance and the decrease in mass is 1s the reaction proceeds This technique is most precise when the gas given off has a relatively high density such as with carbon dioxide, With a low-density (Le. low molecular weight) gas such as hydrogen, the mass changes are so smal that the measurement uncertainties become significant. les quis spa Monitoring a colour change (colorimetry) Monitoring a colour change can somesimes be done with sufficient precision using the naked eye. However, under certain circumstances greater precision can be obtained by using a colorimeter A. colorimeter can detect far more subtle changes than the human eye can observe, and provides & quantitative (rather than a subjective) measurement. Analysis by titration This technique involves using a pipette to remove small samples (aliquots) from a reaction mixture at regular intervals. The reaction inthe aliquot is either stopped by adding another substance or slowed down to almost zero by immersing tin an ice bath, The aliquot is then titrated to determine the concentration of a reactant or product species. The process of stopping or slowing down the reaction in an aliquot is known as ‘quenching For example, i the reaction involves an acid, the aliquot, after quenching, could be titrated against standard sodium hydroxide to determine the concentration of the acid. This technique is used to investigate the reaction between iodine and propanone, which is catalysed by acid, Sodium hydrogencarbonate is added to the aliquot to remove the acid catalyst and hence stop the reaction, The remaining iodine is then titrated against a standard solution of sodium thiosulfate CH,COCH,(aq) + Ix{aq) + CH,COCH:I(aq) + H"(eq) + (aq) fige I,{ag) + 28.0;"(aq) + 21°(aq) + 8,0¢ trating tod thesia144 Measuring the electrical conductivity If the total number or type of ions in solution changes during a reaction it might be possible to fallow xy measuring changes in electrical conductwvity of the solution using a conductivity Measuring any other physical property that shows a significant change Possible physical properties that have not already been mentioned include changes in the volume of liquid (diatometry), chirality and refractive index 1. state suitable techniques to obtain rate data for each of the following reactions. (@) Magnesium with dilute sulfuric aci als) + 2409) — Magan) + Hd (b) Eth ethanoate with sodium hydroside ‘CH{COOCH,CH) + OF (aq) — CH/COO'(ag) + CH.CHLOM(ag) (© Hydrogen gas wit iodine gas: Halg) + bole) > 2HI(g) 2. why would the method of messurng the change in mast ofa reaction vessel and contents nat work well inthe reaction between magnesium and dilute sufi aie? 3 The reaction between calcium carbonate and dilute hydrochloric acid can be followed by collecting and ‘measuring the volume of gas produced. The gas could be collected over water in a measuring cylinder or ina gas syringe. Which method would be the more suitable for this reaction? Explain your answer. ‘Key definition 0 The (overall rate of reaction isthe change in concentration ofa species divided by the time ittakes for the change to occur. lleaction rates are positive.Rate equations, rate constants and orders of reaction By the end of tis section, you should be able to... © understand the terms: (i) rate equation (i) order of reaction with respect to a substance in a rate equation (ii) overall order of reaction {iv) rate constant {(v) rate-determining step Rate equation What is a rate equation? “The usval relationship between the rate of reaction and the concentration of a reactant i that the rate of reaction is directly proportional to the concentration. That is as the concentration is doubled, the rate of reaction doubles. Unfortunately this is not always the case. Sometimes the rate will double, but sometimes it vill increase by a factor of four In some cases, the rate of reaction does not increase at all or it increases, in an unexpected way. Let us consider the simple relationship where the rateis directly proportional to the concentration of a reactant. say A. We can. represent this by the expression: rate o [A] rate = A] ‘where kis the proportionality constant. ‘This is called the fist onder rate equation, ‘The constant kis, called the rate constant Every reaction has its own particular rate equation and its own rate constant. Rate constants will only change their value with a change in temperature. (Other common rate equations with respect to an individual reactant are second order rate equation: zero order rate equation; rate rate = Al? [AP orrate = k Zero order reactions do not occur very often and it might be dificult at this stage for you to imagine why they should occur at all. However all will soon be revealed If two or more reactants are involved, then its possible to have a third order rate equation: third order rate equation; rate = MA){B] The units of rate constants ‘Table A shows the units for rate constants, using mol dm” as the unit of concentration and seconds as the unit of time. You find the units by rearranging the rate equation, Zero Fist Second Third rable A ‘The units are obtained by rearranging the rate equation, For example, fora second order reaction: fle kate Inserting the units we obtain: mol dm s+ mnolém- x moldm? ‘This cancels down to mold ‘which equates to dim* mols“! “The majority of reactions involve two or more reactants. If we call the reactants A, B and C, then the reaction may be first order with respect to A, ist order with respect to B and second order with respect to C. The overall rate equation willbe rate = MAYBIC? and the overall order of the reaction is four (1 + 1 + 2) Note ‘that you are adding the povrers Fora general reaction in which the orders are, a and p, we have: rate = MAYBIICP ‘The overall order of the reaction is m+ n+ p. Reaction mechanisms Many reactions can be represented by a stoichiometric equation containing many reactant particles, For example, the reaction ‘between manganate(V/II) ions and iron(l) ions in acidic solution can be represented by: M0, (eq) + 8H"(aq) + 5Fe“(aq) + Min°(aq) + 44,00) + 5Ee**(aq) IF this reaction actually proceeded in a single step, then the reaction would be very slow indeed. The probability of 14 particles simultaneously colliding all with the correct orientation and energy, is so small that we can say itis effectively zero, The reaction is, however, very fast indeed even at room temperature. It ‘must, therefore, proceed via a series of steps, all of vihich follow 45146 (on quickly from one another [tis important to recognise that a reaction involving simultaneous, collision of more than two particles is very rare. ‘The orders of reaction of the individual reactants can help us to suggest a possible mechanism for a reaction. The mechanism cannot be inferred from the stoichiometric equation, since the ‘mathematical relationship betvieen the rate of reaction and the concentration of reactants (ie. the orders of reaction) can only be determined through experiments. Consider the reaction: A+B+C4D+E for vihich the experimentally determined rate equation is: rate = KAIB] ‘This could mean that C was present in such a large excess that changes in its concentration were negligible and therefore had no measurable effect on the rate of reaction. Hf, however, this is not the case, and changes to [C] really do not have any effect on the overall rate of reaction, then a different explanation must be sought for why [C] does not appear in the rate equation, In this case, there must be a step involving a reaction between A and B that has an effect on the rate of reaction ‘There must also be another step in which C reacts, but this reaction has no ect on the overall rate of reaction. This could be explained by assuming that the reaction between A and B takes place éefore C has a chance to react, and that the reaction between A and B is significantly slower than the reaction invoiving C. If this were the case, then the mechanism for the reaction could be: Sept: A+ BZ, sLow Step2: Z+C+D+E FAST Since only Step 1 is rate-determining, then only changes in [A] and (B) will affect the overall rate of reaction. Changes in the rate at which Step 2 occurs, owing to changes in {C}. will be negligible. Important points to remember are that: ‘The slowest step ina reaction determines the overall rate of the reaction "The slowest step is known as the raiedetermining step of the reaction, ‘We shall return to the concept of reaction mechanisms, and consider them in much more detail, in Section 16.1.4, ‘A.useful way of vsualsing the idea ofa rate-determining step isto imagine that three students are arranging some sheets of notes nto sets (fig A. The notes are arranged into ten pies and the fis. ‘student collects a sheet from each of the piles (Step 1). The second student takes the set of ten papers and shuffles them so that they are tidy and ready for stapling (Step 2). The third student staples the set (of notes together (Step 3) ‘The overall ate of this process (Le the rate at which the final srs of notes are prepared) depends on the rae of Step 1, the collecting ofthe sheets of notes, since this is by far the slowest step. I does not "attr within reason, how quickly the tidying up fo stapling is done. For most af the time the second and third students will be doing nothing while they wait forthe firs student to callect the sheets. The mechanism of the process is therefore: Step 1: Student 1 collects sheets slow Step 2: Sudent 2 tiies et of sheets FAST Step 3: Suident 3 staples set of sheets FAST Fig. Analogy fr rate-detrmiing stepCO Learning tip All reactant species involved either in or before the rate-determining step have an effect on the rate of the reaction and wl appearin the ate equation 1 The rate equation for the reaction between peroxydisulfate ions and iodide ions is: rate = KS.02 11 (@) Whavis the order of reaction with respect to () peronydsufate ions and (i iodide fons? (©) Whatis the overall order of reaction? 2. The rate equation for the reaction between Pand Q is: rate = KPIQ? ‘What willbe the increase in rate if {@) [P]is doubled, while [Ql is kept constant? () [Qlis doubled, while[P] is kept constant? (6) [Pland[Q]are both doubled? 3 inthe reaction between R, Sand T: + when the concentration off is doubled, the rate increases by four times + when the concentration of Sis doubled, the rate does not change + when the concentration of Tis doubled, the rate doubles. (a) Deduce the orders of reaction with respect to R, Sand T. (b) Write the rate equation for the reaction. (6) Whatis the overall order of reaction? ‘Key definitions ‘The rate equation is an equation expressing the mathematical relationship between the rate of reaction and the concentrations of the reactants, ‘The order of a reactant species isthe power to which the concentration of the species i raised inthe rate equation. ‘The overall order ofa reaction isthe sum ofall the individual orders ‘The rate-determining step of a reaction isthe slowest step in the mechanism forthe reaction. 7By the end ofthis section, you should be able to... ‘© understand experiments that can be used to investigate reaction rates by: {i) continuous monitoring method {ian intial-rate method ‘© understand the term ‘half-life (© calculate the rate of reaction and the hal-ife of a first order reaction using data from a concentration-time graph or a volume-time graph © deduce the order (0, 1 or 2) with respect to a substance in a rate equation using data from a concentration-time graph © deduce the order (0, 1 or 2} with respect to a substance in a rate equation using data from an initial-rate method © determine and use rate equations of the form: rate = KAP'[E), where m and n are 0, 1 or 2 {© deduce the order (0.1 or 2) with respect toa substance in a rate equation using data from a rate-concentration graph. How can we determine the rate equation? “This question can equalybe phrased ‘How can we determine the order of reaction with respect 10 each reactant?” “There are two methods for determining orders of reaction. They are both experimental, Indeed, orders of reaction can only be ‘decermined by experiment. “The frst is sometimes called the ‘continuous method! ‘The secondis sometimes called the ‘intial-rate method! The continuous method In this method, one reaction mixture is made up and samples of the reaction mixture are withdravm at regular time intervals. The reaction in the sampleis stopped, if necessary, by quenching. ‘The concentration of the reactant is then determined by an appropriate experimental technique, such as titration, + ‘The first step is to draw a ‘concentration-time’ graph, + ‘The second step isto find out the halflife for the reaction at different concentrations. If the halflife has a constant value, then the reaction is frst onder ‘with respect tothe reactant ‘The 1st halflife, forthe change in concentration from 120 10 60, units, is 100 (fig A). 148 concentration of 1203 reactant /arbiary units 0 i 200300 “ine aka tae haltife allie nate figA A grap of concentration af esctntagsinet ine for ist onder ‘The 2nd hal.ife, for the change in concentration from 60 to 30, units, is 1005. ‘The 8rd hallife, for the change in concentration from 30 to 15 units, is 1005. Since all three half-lives are the same, the reaction is first order ‘with respect 10 the concentration of the reactant plotted, If the half-life doubles as the reaction proceeds, then the reaction fs second order If the graph is a straight line with a negative gradient, then the rate Of reaction is constant no matter what the concentration of the reactant. In other words, the reaction is zera order with respect t0 the reactant. CConcentanon cf reactant Time fig A gaph ofconcentaton agains time fora era onder eacion. ‘Atypical set of results is shown in table A for the reaction 2N,Ox(g) — 4NO{(a) + 0.8)naan ea table A wW[H[H [HX], H[H[ HD] 627 [1225] 935 | ea9 | 488 | 368 [274 [216 | 185 ] If you plot a graph of [NOs] against time using the above data, you will find that the line is curved and the hal-ife is constant: hence, the reaction is fist order with respect to NOs, Calculating rate from a concentration-time graph “The rate of reaetion at any given time can be determined fom a concentration-time or volume-time rapa by drauing a tangent tothe curve atthe given time and calculating the gradient of the tangent. Fig C shows the change in concentration of a reactant with time. Concenraton 290 2 recente im? 2 ver} 0. 20 100 oo 060 oa om. 004 SP LEFESLELS SS Tine/s fig¢ Dewsmining an ncanareous tof eacion toma gaphconcenaton of aca gun ‘Attangent to the curve has been drawn at time = 400s. "To find the rate at this time point, draw as large a wiangle as possible and then measure x and y. 1470s and y = ~1.60 mo] dm hange in concentration of reactant time 1.60 mel dm MTs 09 x 10%moldm#s Calculating rate from a volume-time graph “The procedure is exactly the same for a volume-time graph fora gas evolved, This time the curve vill slope upwards not downwards. Volume of sarored gration at time = 1 e Time fig Deternining an iretantaneousrate of reaction from a graph of volume of gue evolved agains time ‘The rate of reaction obtained in this way is sometimes called the instantaneous reaction rate. 149150 The initial-rate method for determining the rate equation In this method, severa reaction mixtures are made up and the initial rate (Le. the time taken for 2 fixed amount of reactant to be used up or for a fixed amount of product to be formed) is measured. From these times, itis then possible to calculate the mathematical relationship between tie rate of the reaction and the concentration of the reactant, Atypical set of results is shown in table B for the reaction: AtBOC Ea Cee aeons 1 a4 a4 0.02 2 a4 02 004) 3 02 a4 004) 4 02 02 008 I we now look at experiments 7 and 3, we can see that [A has doubled whilst [B] has remained constant, The rate of reaction has also doubled, This indicates that the reaction is frst order with. respect to A and hence we can write: rate a [A] If we now look at experiments 1 and 2, or experiments 3 and 4, we can see that [B] has doubled while [AJhas remained constant. The intial rate of reaction has also doubled. This indicates that the rate of reaction is directly proportional to [B). That is the reaction is fist order with respect to B Hence we can write rate ~ [B] ‘The overall order of the reaction is two and the complete rate law (rate equation) is: rate = KALB) ‘You may suspect that the numbers in table B were deliberately kept simple to illustrate a point. Real experimental results rarely ft such an exact pattern and you may have to look forthe nearest whole ‘numbers to obtain orders. Determining order from a rate-concentration graph ‘The method described above to determine inital rates with changing concentrations results in only approximate values forthe ial rates. However. since most orders of reaction with respect to individual reactants have integer values, this approximation is usually acceptable In an intial rates experiment, the time measured i tat fora fixed amount of product tobe formed, oF that fra fixed amount of reactant to be used up. Since the amount of product formed, or reactant used up. is kept constant, the initial rate of reaction is proportional to the reciprocal of the time, ¢ ‘measured. That is: ‘This assumes that the rate is constant forthe whole time period, ¢ However, this is not true because as soon as the reaction starts the rate begins to decrease. The rate calculated from the expression is, therefore, the mean (average) rate overtime, and not the true initial rate of reaction, The approximation becomes poorer with lager values of 1. However, the approximation is good enough to determine integer order It might be possible to determine orders of reaction from just a few measurements, However, itis usual to record a range of results and plot 2 graph of + against concentration of reactant. ‘The shape of the graph indicates the order of reaction.Zero order with respectto A | First order with respect to A_| Second order with respect to A UieO nti cee er ey) Vier cig ia i vi table [tis impossible to determine directly by sight from a rate-concentration graph thatthe reaction is 1 second order Ifthe graph is a curve as shown, ther ary to then plot + against (AF. If this produces a straight line passing through the origin, chen the reaction is second drder with respect 10. fig Agaph of agit he square of he cancenvaton ef ectant fr aseond xr eacton 1A compound P decomposes when heated. The graph shows the change in concentration when a sample of Pis heated. aio ao eto ala —1co0 dbo isto i600 1do0 Tine/s (a) State whatis meant by the term half of reaction (b) Use the graph to show that the decomposition of P is a first order reaction. (©) Explain te effect on the hal-ife of doubling the inital concentration of (a) Caleulat the rat constant, for this reaction using the following expresion 0692 safe Include units in your answer (©) Write the rate equation for this eaction (0) (Use the graph to determine the concentration of Pat 800s. (i Use the rate equation from e} and your answers to (and) to calculate the rate of reaction at 8005, Include nisin your answer (@) Describe how could you determine the reaction rate at 800s directly from the graph 151Tal 152 2. Theequation for the action between bromide ions and bromateV) ions in accifed aqueous solution is 58r-aq) + BOs (aq) + GHaq) — 38r(aq) » 34,04) “The table shows the rests of four experiments carried out using diferent concentrations of the three rwactants. Crea mance rome) (ag) Initial ony oti Git eo 1 0.10 010) 10 12107 2 010 020 010 24102 2 030 210 010 36*10 4 010 020 020 98x10" (@) Deduce the order of reaction with respect te: (Be {i) 8105 (iy He (©) Write the rate equation forthe reaction. (©) Using the results from experiment 1, calculate the rate constnt, k, forthe reaction, Include units in your answer 3. Bromine canbe formed by the oxidation of hydrogen bromide wih onygen ‘proposed mechanism forth eon Step 1: HBr +0, —HBrO, Step 2 HBO, He 240 Siep3) HBO = HBr Br, + HO Step 4. HHO + HBr — By, «HO (repeat of step 3) Therate equation fo ts eactonis rate = KHBrfO,) (2) Explain which of the above ou sepsis the rate determing sep or this eaton, (b) Write the overall equation for the reaction. Keydefinitions The half-life of reaction i the time taken for the concentration of the reactant to fll to one-half of ts Initial value. The instantaneous reaction rate is the gradient ofa tangent drawn tothe line of the graph of concentration against ime. The instantaneous rate varies as the reaction proceeds (except fora zero order reaction)Rate equations and mechanisms By the end of this section, you should be able to... @ deduce a rate-determining step from a rate equation and vice versa © deduce a reaction mechanism, using knowledge from a rate equation and the stoichiometric ‘equation for the reaction ‘© understand that knowledge of the rate equations for the hydrolysis of halogenoalkanes can be used to provide evidence of S,.1 or S,2: mechanisms for tertiary and primary halogenoalkane hydrofysis © understand how to (i) obtain data to calculate the order with respect to the reactants (and the hydrogen ion) in the acid catalysed iodination of propanone {il) use these data to make predictions about species involved in the rate-determining step deduce a possible mechanism for the reaction, Reaction mechanisms You will remember from Book 1 that the basic view as to how a reaction takes place at a particulate Jevel is that particles (atoms, molecules, ions or radicals) first have to collide in the correct orientation. and with sufficient energy for products to be formed. For the following reaction: P+ Q— products ‘we expect the rate law to be: rate = HPQ] ‘That is, we might expect the reaction to be first order with respect to each reactant and second order overall ‘A reaction taking place inthis manner, that isa single collision between the two reactant particles, is described as being elementary. IF we know that a eaction is elementary then we can deduce the rate law directly from the stoichiometric equation. For example, the following reaction is known to be elementary: NO(g) + Ox(g) — NOg) + Og) 0 the rate equation is rate = KNOYOs] ‘The reaction takes place when a molecule of NO collides with a molecule of Os, If the reaction is not elementary, itis not possible to deduce the rate equation by simply looking at the stoichiometric equation for the reaction, For example, the decomposition of dinitrogen pentoxide into nitrogen dioxide and oxygen is first ‘order with respect to dinitrogen pentoxide. not second. 2N,0,(g) + 4NO,(g) + 0,(g) ‘The experimentally determined rate equations: rate = K(N,Os) 153,rT) ‘Areaction that is not elementary takes place via a series of interconnected elementary reactions that are collectively called the mechanism for the reaction. You will have already come across a number of such mechanisms in your study of organic chemistry. For example, the racical substitution reaction between methane and chlorine to form chloromethane (CH,C) is thought to have the following mechanism Step 1: Ch, + 2Cle Step 2: Cle + CH, HC1+ *CH, Step 3: Ch + *CH, Cle + CH,CI ‘The overall stoichiometric equation for the reaction is: CHy+ Ch = CHACI+ HCI ‘The species Cle and +CH; are called intermediates. They do not appear in the overall equation forthe reaction, but are involved in reactions that ultimately result in the reactants being converted into the products. If the experimentally determined rate equation does not match the overall stoichiometry then itis almost certain that the reaction isnot elementary. For example, the rate equation for the following reaction: NOAg) + CO(g} —+ NO(g) + CO.{g) rate = HNO} ‘This suggests that only molecules of NO; are involved in the rate-decermining step, and that nvo molecules of NO; are involved inthis step. “The order indicates the number of molecules invalvedin the ratedteminiag sep. Indotes hat only molecules of KO, ‘re invalved inthe raledeterrining sep figA Molecules moved in therate-determining 2p Using our knowledge of molecules that do exist, 10 possible rate-decermining steps are: 1 NO, +NO,—+N,O, or 2 NO,+NO,—2NO+0, Ether of these two reactions are equally valid and we have no ‘way of knowing, without carrying out further investigations, which isthe more likely to be taking place. ‘We also have no way of knowing what is involved in the remaining steps, but we do know that the sum of all the steps must add up to the overall stoichiometric equation, Using the second of the ‘two possible rate-determining steps, the following mechanism is, consistent with the data NO, +NO,+2NO+0, SLOW CO+0,-C0, +0 FAST NO+O—NO, FAST 154 ‘This shows how the particles in the proposed mechanism cancel to produce the overall equation: No, + Ser per + NO + pf Org 0, +2 ese = ye 10, = CO = NO > As ithappens, further investigations into this reaction have identified the mechanism as: NO,+NO,—+NO,+NO SLOW NO, +CO— NO, +CO, FAST ‘This is not what we would immediately suspect as the mechanism because the existence of NO, is not something with which we ‘would be familiar Even ifthe experimentally determined rate equation is simple. it does not necessarily follow that the reaction proceeds in a single clementary step. For example, the rate expression forthe following ‘gas-phase reaction: 2N,Oj(g) — 4NOAg) + O(a) rate = NO.) ‘Yet, the reaction is thought to involve several steps and e number of intermediates. Alkaline hydrolysis of halogenoalkanes “The hydrolysis of halogenoalkanes by hydroxide ions isa reaction ‘we introduced in Book 1. The hydroxide ion acts as a nucleophile ‘and replaces the halogen in the halogenoalkanes. The reaction, therefore, can also be described as nucleophic substitution. Hydrolysis of a tertiary halogenoalkane ‘The equation forthe alkaline hydroysis of 2-chloromethylpropane is: (CHy,CCl + OH — (CH,),COH + cr ‘The experimentally determined rate equation fo this reaction is rate = (CH) CCl] ‘The reaction is frst order with respect to 2-chloromethyipropane, but 2ero order with respect to the hyéroxide ion “The sensible conctusion to reach is that the 2-chioromethyipropane ‘undergoes slow ionisation asthe rate-determining step ‘This is then ‘ollowed by a very fast step involving attack by the hydroxide ion on the carbocation formed in Step 1 Step 1: (CHysCC1—=(CHyAC*+ Cr SLOW Step 2: (CHysC' + OH + (CH),COH FAST ‘This type of mechanism is named S41, ie. Substitution ‘Nucleophilic unimolecular “The rate-determining step is said to be unimolecular because there is only one reactant particle present, (CH:),CCl “The carbocation, (CHs),C°, formed in Step 1is an imermediate (ce Section 16.1.6)CO Hydrolysis of a primary halogenoalkane ‘The equation fr the alkaline hydrolysis of 1-chlorebutan is: CH,CH,CH,CH,C1+ OH" — CH,CH,CH,CH,OH + Cr ‘The experimentally determined rate equation for this reaction is: rate = {CH,CH,CH,CH,COH"] ‘This time the reaction is fist order with respect to each reactant, so ils easonable to suggest that cone particle of each eaetant is present in te ratedetermining siep of the mechanism ‘The accepted mechanisn for the reaction is: CHCHCH,, CH.CH.CH, cH,CH,CH, a / +a Hd é\ Py A ah Hi transition tate 68 52 mechansn ofthe allaine yess -chrobtane ‘This type of mechanism is named $42, ie. Substitution Vucleophilic bimolecular. ‘The rate-determining step is bimolecular because there are two reactant particles present. leis a continuous single one-step reaction. The complex shown in square brackets is not an intermediate (lke the carbocation formed in the Sy1 mechanism), buts a ranstion state (see Section 16.1.6), Investigation ‘A study ofthe acid catalysed iodination of propanone ‘The reaction between propanane and iodine in aqueous solution may be acid catalysed fag) + CH,COCH, (aq) + H (aa) —: CH,COCH,(aq) 24 (aq) + (aq) ‘The influence ofthe iodine on the reaction rate may be studied if the concentrations of propanone and hydrogen ions effectively remain constant curing the reaction. This is achieved by usinga lange exces of both propanone and acid inthe original reaction mixture, Procedure 1. Mix25em* of 1 mol dm* aqueous propanone with 25 cm? of I mol da sulfuric ai. 2. Start the stop clack the moment you add Oem? of 0.02 mal den" iodine solution. Shake well 3 Using a pipette, withdraw a 10.cm* sample and place it in a conical flak. Stop the reaction by adding a ‘spatula measure of sodium hydrogencarbonate, Note the exact time at which the sodium hhydropencarhonate is added 4 Titate the remaining iodine presentn the sample with 0.01 mol dm sodium thiosulfate(V) solution, Using starch indicator. ‘5 Withdraw further 10cm? samples a suitable time intervals (approx 5 to 7 minutes) and treat them similarly, always noting the exact time at which the sodium hydrogencarbonate is added. Waste should be contained in a fume cupboard Treatment of results Plot a graph of ttre against time. (The ttre is proportional to the concentration of iodine.) Deduce from the graph the order of reaction with respect to iodine. Analysis of results ‘The graph produced shows thatthe reaction is zero order with respect to iodine, Similar experiments show that the reaction is fist order with respect to both propanone and hydrogen ions. This gives us the following rate equation: rate = HCH,COCH IH] 155Tal This would suggest the following reaction asthe first step ofthe reaction: CH—c—cH, + HY + CH—C—CH, I) ° O—H Similar reactions in ether mechanisms are very fast, so this reaction is unlikely to be the rate- determining step ofthis reaction ‘The second step probably controls the rate ofthe reaction and produces H" that, being a catalyst is not used up inthe reaction: +H sLOW o—H This rearrangementis likely to be very slow and hence is probably the rate- determining step ofthe reaction, lodine can now reactin a fas step as follows CH.—C=CH, + 1, > CH—C—CH, + 1 + HY FAST O-H Testing the mechanism We have a proposed mechanism forthe reaction that is consistent with the kinetic data obtained from experiment. This is not the same assaying that the mechanism isthe correct one, or indeed the most likely one. We now need to carryout further experiments to confirm, or deny, or proposed mechanism, Here are three techniques that can be employed in this case. + Use a wider range of concentrations ‘The experimentally determined rate equation may hold over only 4 limited range of concentrations For example, the mechanism \we have proposed forthe iodination of propanone predic that. at very low concentrations of iodine, the order of reaction with respect to iodine will change from zero to fits. This is because the rate of the final step in the mechanism i given by the expression rate = KIJICH,C{OH)=CH, and so the rate ofthe step will decrease as[l, decreases. This has been show to be the case, so ‘supports the proposed mechanism, + Use instrumental analysis “This may be able to detect the presence of intermediates that have been proposed. Nuclear magnetic resonance can be used to show that acidified propanone contains about one molecule ina milion inthe form CH:C[OH)+CH>. This isan intermediate stated in the proposed mechanism. + Carry out the reaction with deuterated propanane, CDsCOCDs Deuterium 'H or (simply D) behaves slightly diferent to hydrogen }H or (simply ‘AC-D bond i slightly stronger. and therefore harder to break than a C-H bond! If this the Bond that breaks inthe rate-determining step, as suggested by our proposed mechanism, then the iodination of CD;COCD, willbe slower than that of ‘CH,COCH, This s found tobe the case. 156 1 The equation forthe reaction between ethanal, CH,CHO, and hydrogen cyanide, HCN, is: CH,CHO + HCN — CHCH(OH)CN ‘Two mechanisms that have been proposed for this reaction are: ‘Mechanism 1 Step 1: CH.CHO + HY — [CH.CHOH} Step 2: [CH,CHOHP’ + CN" = CHsCHOHJCN ‘Mechanism 2 Step 1: CH.CHO + CN* > [CHCHOCN] Step 2: [CH\CHOCN} + Ht — CH,CH{OHJCN ‘The rate equation for the reaction is rate = KCH,CHO[CN THY {a} Explain which of the two mechanisms is consistent with the rate ‘equation. (5) Which step in this mechanism is the rate-determining step? 2 thecquaton or the etctionbeoween hydrogen and aogen manos Hig» 2NOL) ~ 2H,048) + Nd) Therateequton{or the ection rate = KH.INOP A proposed mechanism for ths reaction is Step 1: 2NO(g) —» NO.) Fast Step2: N,Ojg) + Hi{g) — H,0(8)+ N.0(@) SLOW Step 3 N:O(@)+ Hy(@)— Na) Og) FAST Is this mechanism consistent with the rate equation? Explain your 3. Assume the fonng proposed reaction mechanisms cone Ch, 2Ch stow HytGoeH FAST Hee ch— Hel FAST (a) Write the overall equation for the reaction. (b) Write a rate equation forthe reaction thats consistent with the mechanism, (€) What would be the effect on the rate of reaction of doubling the concentration of CL? (d) What would be the effect on the rate of reaction of doubling the concentration of Hi? 4. The ncecpicsubtuton ration between equinola unites of CH,Cland OF i second order ovr However Sherencion caved aut usnga large xe oF ON the eton becomes ison’ oval Suggs an emanation fr hee obseratonsActivation ene By the end of tis section, you should be able to... © understand the terms: (i) activation energy {il) homogeneous catalyst and heterogeneous catalyst autocatalysis Activation energy, E, in Book 1 Section 9.1.1, we defined activation energy, asthe minimum energy that colliding ‘patticles must possess for a reaction to occur “The activation energy represents the energy that the coliding particles must obtain in order to reach the energy level of the teansition state (see Section 16.1.6 for more details). Once the energy level of the transition state has been reached, the particles can react to form the products and release energy as they do so, The energy profile diagram for an exothermic reaction is shovm below, Emery vranstion sae Progress of reaction fig Arexctionprofie for an elemenany exchermic reaction Catalysts In Book 1 Section 9.1.4, we defined a catalyst as.a substance that increases the rate of a chemical reaction but is chemically unchanged at the end of the reaction, We then wont on to explain that a catalyst works by providing an alternative route for the reaction, ‘and that this alternative route has a lower activation energy than the original route. Although the original route is still available for the reactants, most collisions resulting in reaction will occur via the alternative route since the faction of particles possessing this lower activation energy will be greater Catalysts can be divided into two groups ~ homogeneous catalysts and heterogeneous catalysts Homogeneous catalysts ‘A homogeneous catalysts in the same phase (slid, liquid, solution or gos) asthe reactants Many reactions in aqueaus solution are catalysed by the hydrogen ion, H*{aq). An example isthe ‘odination of propanone, a reaction we discussed in detail in Section 16.1.4 ‘CHsCOCH,(aq) + 1,{aq) ~ CH;COCH:Iaq) + H"(aq) + Faq) 157rT) ‘The production of chlorine radicals from chloroftuorohydracarbons (CFCs) is responsible for che destruction of ozone in the upper atmosphere, Ultraviolet radiation for the Sun produces chlorine radicals, Clr, from CFCs such as dichlorodifluoromethane, CLF: cena) Male aeaton coreg) + coma) ‘The chlorine radicals then take part in a chain reaction with Clo{g) + Osfe) = ClO*(e) + Oe) ClO+(g) + O.(g) — 20,{g) * Clea) ‘The chlorine radical is regenerated and so is acting as a catalyst Since the cetalyst isin the same phase, ie. the gas phase, as the reacting species, it is classified as a homogeneous catalyst. ‘The overall reaction is: 20,(8) > 30.48) Another reaction involving a homogeneous catalyst is the one ‘between peroxydisulfate ions and iodide ions in aqueous solution: $,0;* (aq) + 21-(aq) — 2802 (aa) + Lag) ‘This reaction is catalysed by either Fe*(aq) or Fe™(aq) ‘With Fee), the reaction mechanism is: Step 1: $,0," aq) + 2Fe?*(aq) > 280, (aq) + 2Fe (aq) Step 2: 2Fe*(aq) + 2I-(aq) — 2Fe*(aq) + L(aq) With Fe(aq) as the catalyst, Steps I and 2 occur inthe reverse order Learningtip ‘Te action of Fe™aq) or Fe“(aq) as a catalyst inthe reaction between §,0,? (aq) and | (aq) is sometimes explained in terms of standard electrode potentials (E° values). However it is important to note that since standard electrode potentials can predict ony the thermadynamic feasblty of reaction, and not the kinetics. The razon why the ceactions ace faster inthe presence of either Fe" ar Fe is that the activation energies for both Steps 1 and 2are lower than the activation energy for the overall eaction. Heterogeneous catalysts ‘A heterogeneous catalyst is in a different phase 10 that of the reactants, ‘Two important uses of heterogeneous catalysts in industry are in the Haber process and the Contact process, The use of solid ‘vanadium(V) axide (V0), in which the vanadiurn changes its oxidation number, in the Contact process is described in the section on transition elements (Section 15.3.1). We will now deseribe the action of solid iron as a catalyst in the reaction between nitrogen ges and hydrogen gas to form ammonia gas in the Haber process. “The equation for the formation of ammonia in the Haber process is Nog] + 3Hy(g) = 2NHs(a) 158 Iron is able to act as a catalyst because it can form an interstitial ‘nydride with hydrogen molecules. In this hydride, hydrogen atoms are held in spaces between the metal ions in the lattice. The atoms are then able to react with nitrogen molecules that are adsorbed. conto the metal surface nearby. There are three stages in catalysis involving surface adsorption. These are: + Adsorption — the reactants are fist adsorbed onto the surface of the catalyst. + Reaction ~ the reactant molecules are held in positions that, enable them to react together. ‘+ Desorption ~ the product molecules leave the surface. ‘The rate of reaction is controled by how fast the reactants are adsorbed and how fast the products are desorbed. As mentioned in Book 1 Sections 9.1.2 and 10.2.2, once the surface of the iron is covered with molecules, there is no further increase in reaction rate even if the pressure of the reactants is increased. - The efficiency ofa heterogeneous catalyst depends on the surface of the catalyst in particular the efficiency of the catalyst can be affected significantly by poisoning and by the use of promoters. Poisoning Many catalysts are made ineffective by trace impurities, For example, ‘alalysts used in hydrogenation reactions are poisoned by sullur impurities, Thisis one reason why nickel is preferred to platinum asa catalyst in the hydrogenation of alkenes. Nickel relatively inexpensive, so a large quantity can be used. some of itis, deactivated by poisoning, enough will remain for itil to be effective. nthe other hand, platinum is expensive and so small {quantities would have to he used In tis case itis possible fr all of the catalyst to become poisoned. Promoters The spacing on the surface ofthe catalysis important. For example, ‘only some surfaces ofthe iran crystal act as effective catalysts in the Haber process, The addition of traces of potassium oxide and aluminium oxide act as promoters by producing active sits where the reaction takes place most readily. Did vou know? {An interstitial hydride, sometimes called a metallic hydride, isnot slrilly a compound as such, Itis more like an ally than a ‘compound. The hydrogen absorbs ita the metal and can exist in the form of ether atoms or diatomic molecules. For example, palladium absorbs up to 900 times its own volume of hydrogen at room temperature, and forms palladium hydride. This material has been considered as a method to carry hydrogen in fuel cells for use in vehicles (see Section 14.2.1) A heterogeneous catalyst is used in a three-way catalytic converter, which is employed in the exhaust of cars. This converts unburned hydrocarbons into water and carbon dioxide, and carbon and carbon monoxide into carbon dioxide. It also converts ‘oxides of nitrogen into oxygen and nitrogen. The reactions involved are discussed in more detail in Topie 15.Didyou know? The electophilic addition reaction between ethene and bromine vapour (Book 1 Sections 6.26 and 627) was once thought tobe tenticely a homogenous process in which the molecules collided in the gas phase and reacted. Is now known that the reaction takes place almost entily on the surface ofthe walls ofthe reaction Wessel. The reaction takes pace very quell on a glass surface and more quickly when the surace of the vessels covered witha polar Substance suchas cet alcohol exadecan-1-l, CH,(CH,)sOH) It takes place even more quickly ona surface of stearic acid (6ctadecancic acid, CH,{CH;).COOH), presumably because stearic acid molecules are more polar than molecules of cat alcohol However, the walls ofthe reaction vessel are coated witha non- polar substance such as paraffin wax, very litle reaction ian), ‘curs So, a process that was once thought to bea homogeneous {2s phase reaction is now known tobe heterogeneously catalysed itis sometimes stated that a catalyst doesnot change the products of reaction, but only increases the rate at which the Feation takes place. This not entiely true, as demonstrated by the diferent products obtained when hot ethanol vapour fs passed over different Solid catalysts. ‘With copper or nickel as the catalyst at 400°, a dehydrogenation reaction takes place in which the products ae ethanal and hydrogen CHCHON(g) — CHACHO® + fa) Wat the same temperature, aluminium oxide is used as the catalyst, the more familiar dehydration reaction into ethene and water takes place: CH.CHLOH(g) > CHerCHulg) + H.01@) Its interesting to note that the dehydrogenation catalysts, copper and nickel, adsorb hydrogen very strongly, whereas the dehydration catalyst, aluminium anide, adsorbs water in preference. ‘These to examples illustrate that there slot more to heterogeneous catalysis than fs mentioned at level. This might encourage you to de your own research into the topic and lea ‘even more about it The oxidation of ethanedioic acid by manganate(Vll) ions in autocatalysis, the reaction is catalysed by one ofits products One of the simplest examples ofthis isthe oxidation of ethanedioic acid by acidiied potassium manganate(VIl), The equation for the reaction is 5(COOH){a9) + 2MnO(aq) + 6H*(ea) 10CO(g) + 2M" (aq) + 8H;0() The reaction is very slow at room temperature, but is catalysed by manganese({t} fons, Min#*. The Mn? ions are not present initially 0 the reaction starts off extremely slowly at room temperature. However, Mn is @ product of the reaction, As soon as itis produced in a catalytic amount, the reaction rate increases, ‘You can shaw this effect by plosting the concentration of one. of the reactants against time. The graph obtained is unlike the ‘normal rate curve for a reaction. 0 concen [7 esto the reaction then speeds up the reaction then slows dawn before Iy stopping figB A ctophof concentration against for ana ralyed reaction. You can see ie slow (uncatalysed) reaction at the beginning As catalyst begins to be formed in the mixture, the reaction speeds up —it gets faster and faster as more and more catalyst is formed. Eventually, the rate decreases in the normal way as the ‘concentrations of the reactants decrease. a Do notassume that rate curve that looks lke this necessarily shows an example of autocatalysis, There ae other effects that might produce a similar graph, For example, if the reaction involves a solid reacting with aliquid, there might be a substance coating the surface ‘of te solid that the liquid has to penetrate before the expected reaction can happen, Another possiblity i thatthe reaction is strongly exothermic and the temperature is not being controlled. The heat evolved during he reaction speeds up the reaction, 1 pan wy onl smal quantity ofa homogeneous catalysts rmqured nowt for tobe eect, 2. cars in some parts of he wold sillun on leaded petrol. Leaded petil contains a compound alld tetracthy lead (CH,CH)Pb. Tataethy ead eats nthe engine with omen and fr iad and walt oxide, hese sobtances remove radi intermediates inthe combustion reactonsthusincrexsng the octane ating oF the petiol Excess lead and ea) odes emoved by adding T.2ibromoethane. This forms vole lee) bromide that escapes though the exhaust Sunes acca converte ould not be used Wa carcunaing onleaded petrol 159The effect of temperature on the rate constant By the end of this section, you should be able to.. @ use the Arrhenius equation to explain the effect of temperature on the rate constant of a reaction ‘@ use graphical methods to find the activation energy from experimental data The relationship between temperature and rate of reaction In Book 1 we discussed qualitatively why an increase in temperature increased the rate of a reaction ‘There ae two reasons fr this + on increase inthe faction of molecules with energy equal to or greater than the activation enesgy forthe reaction + an overall increase in the frequency of colisions between the reacting molecules ‘The second effects conscerably mote significant than the first so much so that we can effectively ignore the overalincreese in frequency of colisions. In 1999, Svante Arthenis, a Snecish chemist, proposed a quantitative relationship between temperatuce andthe rte constant, fo @ reaction This is desorbed by the Arvhenus equation and is usually expresoed in the form: eH) + Alisa constant know asthe pre-exponential factor which is mensure ofthe rte at which clsions ‘occur irespective their energy It als inches other factors. the most important of which is that reactions cen only occur when the molecules are correctly onentated tte time of colision. +B, the activation energy ofthe reaction + Risthe gas constant + Tis the absolute temperature (ie. the temperature in Kelvin). If we take natural logarithms (ie, logarithms to the base e’) of the Arshenius equation, we obtain: ee ee RE z Ua gapo inks pod aunt a sage tained wha acento ‘This provides an experimental method for determining the activation energy of a reaction, ‘The intercept with the vertical axis gives Ind Example ‘Table A shows some data related to the reaction between peroxydisulfate and iodide ions in aqueous solution: S,0e (aq) + 21 (aq) — 280, (aa) + (aa) mperature/K [ene 7 ome 300 0.00813 ~S21 0.00333 310 0.00833 478 0.00828 320 (0.0128 436 0.00818 330 0201 351 0.00203 340 0.0301 -3.50 0.00294 table A 160Fig Astosint lowed aaa + ono 9003 nonsi—00 0033 0.0034 =390¢— In -3504 ~s004- Ink 450 ~500! 550: fig A gaphof ineagairet 17 ‘The gradient of the line, 2 (350-527) {0.00333 — 0.00298) = ~4538 (R= 031 mol!) B, = {74538 x 831) = 37700 mol! = +877 KI mol” (to 38!) Didyouknow? Instn tat heart betweninkan nse ave actmed at bot and rain coat cn ange eee ee cence oer alge en etme eee eo thee tanperstie onthe ae corsa and so ane no Did you kmow? as Seo eeaaee 298K. of, om 2 3 x 19-1) 0, only one callsion in 3x 10" has sufficient energy to react. Itis often assumed that the faction of colsions with energy equal to (or greater than Eis the same as the fraction of molecules with ths ‘energy. This isnot strictly true, but the diffeenceis insignificant at high ‘enexpis, here the faction i very all. Its, therefore. not ‘unreasonable to draw the molecular energy distribution curve, instead ofthe collsion frequency curve, when demonstrating the effect of temperature on collision frequency. (See Book 1 Section 9.1.3). CO Learning tip The effect of £, on reaction rate: + reactions with a large E, are slow, but the rate increases rapidly with an increase in temperature + reactions with a small E are fast, but the rate does not increase as, rapidly with an inerease in temperature + catalysed reactions have small values ofE Did youknow? Reaction profiles \When drawing reaction profile diagrams for multi-step reactions, itis Important to distinguish between an intermediate anda transition state {An intermediate has an energy minimum, whereas a transition state ‘occurs atthe top of the energy curve and therefore has an energy ‘An intermediate isa definite chemical species that exists for a finite length of time. By comparison a transition state has no significant, permanent Ifetime ofits ov ~itexists fora period of the order 110" seconds, when the molecule are in contact wth one anather. Even a very reactive intermediate, wth alfetime of only 10 seconds, has lang ifetime in comparison with the period that colliding molecules ae in contact with one another. ‘Asimple one-step reaction such asthe 5,2 hydrolysis ofa primary halogenoalkane, has asingle maximum energy. The reaction profile for the hyrolysis ofa primary halogenoalkane, cepresented as RHal, istherefore: Enthay. 11 (anstin state) [Ome Ree Hal Tar OH Progress of reaction fig The reaction prot dngram for he hyralysis ofa peimay halegenonlhare The reaction profile forthe 5,1 hydrolysis ofa tertiary halogenoalkane, R;CHal, which isa two-step reaction involving the intermediate R,C: is: Enthaly, ROOH > Hl Progen olveasion fig The reaction proile cogram for he hyrlyss aa terny halogenoalare, 161162 Learning tip In the 5,1 hydrolysis ofa tertiary halogenoalkane, the fist step ofthe mechanism isthe rate-determining step ofthe reaction and it therefore has the higher actvation energy. That i, €,(1) > £2), Inthe second step in a reaction mechanism israte-determining, £1) <£,(2. Did you know? ‘The relative rates of Sy] and S,2 reactions depend on structure ‘You learned in Book 1 that ally! groups donate electcans by the inductive effect. This means that the stability of carbocations increases in the order 1° < 2° «3°, as the number of alkyl groups donating ‘electrons towards the postive carbon atom increases. 8 k ‘ t mo nee | 4 ‘ t ° x * {As the stability of the carbocation increases, the activation energy for the reaction leading to its formation also decreases. Enerpy aenorar ali on, Progess of reaction figD Reaction pris forthe S,1 hyo of pnmary and tinny halagencalianes We therefore expect the rate of the Sy reaction to increase inthe order I® < 2° 3, No carbocations are formed during the S,2 reaction. Other factors come into play. In an 2 reaction, the transition state has five groups arranged around the central carbon atom, its therefore mote crowded than either the starting halogenoalkane or the alcohol product, each of which have only four groups around the central carbon atom,CO Allyl groups are much larger than hydrogen atoms, Therefore the more alkyl groups around the central Carbon ator, the more crowded will be the transition state and the higher the actvation energy for its formation, We therefore expect the rate of the S,2 reaction to increase in the order 3° <2°< 1° ‘The two effects reinforce one another. The S1 reaction isfastest with tertiary halides and slowest with primary halides, whilst the 52 reaction i fastest with primary halides and slowest with tertiary halides. ‘Overall, primary halides react predominantly via the S,2 mechanism and tertiary halides react predominantly vis the $,1 mechaniem, Secondary halides tend to react via a mixture of the two ‘mechanisms. Relative overall rate 1 +52. fig ES. and S.2 hydrolysis reactions fx nary, secondary and tear halogenoalanes, 1 Use the Arhenus equation te explain whyannereaselnterpertre ests nan inereas inthe te of 2. The rate constant. k, fora reaction increases from 10.05" to 100.05"! when the temperature is increased from 300 K to 400K. Caleulate the activation energy, E, for this reaction, [® = 8 31) mol" i]. 163Y CATALYST CRAFT In this article you will ook at an example of how an engineered metalloenzyme can improve both ‘the kinetics and specificity of reaction, The extracts from Chemistry Worl, tne print and online ‘magazine of the Royal Society of Chemisty. ENGINEERED METALLOENZYME CATALYSES FRIEDEL-CRAFTS REACTION 3 November 2014, Debbie Houghton Reprogramming the genetie code of bacteria to incorporate an unnatural amino acid has allowed scientists in the Netherlands to.create a new metalloenzyme capable of catalysing an enantioselective reaction. “Nature is extremely good at catalysing reactions with very high rate accelerations bacterial expression using ‘expanded genetic code" ut os 2 and very high selectivity. But it does so, from our perspective, with a relatively limited set of reactions, explains Gerard Rogelies from the University ef Groningen, the Netherlands, who led the study. His eroup is targeting existing reaetions that ‘use traditional catalysts, but fail to achieve the same rate acceleration and selectivity as enzyme catalysed reactions. fig. The arial mecaleensymes were apples ina cataic asymmetric Fectel-Craf aliyation action ‘Motalloenzymes combine the flexibility ‘of metal catalysts with the high activity and selectivity of enzymes. Artificial ‘metalloenzymes are produced by inserting a catalytically active transition metal complex {nto a biomolecular seaffod, lke a protein Roglfes” team engineered Escherichia coli cells to include a eopper-binding amino acid into one of its proteins. This method requites no further chemical modification ‘or purification steps, giving it an advantage ‘over existing methods, The resulting ‘metalloenzyme was tested on a catalytic asymmetric Friedel-Crafts alkylation reaetion, achieving an enantiomeric excess of up 10 83%, ‘Takafumi Ueno, who researches the ‘mechanisms of chemical reactions in living cells at the Tokyo Institute of Technology in Japan, is impressed by the work. “eould be applied not only for rapid screening of artificial metalloenzymes but also for in vivo use of them to govern cell fae in Future’ ‘The group are now looking to develop ‘new artificial motalloenzymes with the capability to perform chemistry that ttaditional transition metal catalysts cannot, Ultimately, they hope to integrate these enzymes into biosynthetic pathways. Where else will] encounter these themes? 1a0 rr Let us start by considering the nature of the writing in the article 1. a. After reading the article for the fist time, write a one-paragraph summary of what you think the article is about, + b. Now write down alist of any words from the article of which you do not know the meaning. Do some research into what they mean. Is there anything about your summary from (a) that you would change? Now we will ook at the chemistry in detail. Some of these questions will ink to topics earlier inthis book or Book 1, so you may need to combine concepts ftom different areas of chemistry to work ut the answers 2. Assuming the reaction is exothermic, sketch an energy profile for the catalysed reaction a. the overall reaction enthalpy change b. the activation energy for the formation of the enzyme-substrate complex 3. Under certain conditions the rate equation for an enzyme catalysed reaction takes the form: Rate = K[EF were [Eis the en2yme concentration and k and n are experimentally determined constants. What does this rate equation suggest about the reaction mechanism under these conditions? 4, Name the type of bond that is formed between the copper ion and the unusual amino acid in the metalloenzyme shown in fig A. 5. Suggest why the use of a metalloenzyme of this type might be a better alternative than the traditional Friedel-Crafts methods for alkylation. 6. Suggest why this method might be expected to increase the enantioselectivity of this reaction. 7. Suggest why the Zn” ion may not be a suitable replacement for the Cu ion in this enzyme. ‘Although the metalloenzyme detailed above is genetically engineered, there are many naturally occurring ‘metalloenzymes that carry out a range of eeactions in organisms, Most of these can be found ina freely accessible online database called the PDB (alternatively, the PDBe), Choose one of the following metals: Fe, Zn, Cu, Mo, CO. + Find a protein that contains the metal + Find out what the protein does. + Find out how much ofthe metals present atypical healthy adult. Give a five-minute presentation on your chosen metal, featuring no more than five sides. You will have the ‘opportunity te display your chosen molecules using some ofthe freely avaiable software packages such as mol showing Pp itnen you are asked mt | 2 Although a typical adult has only about 15 mg of copper per kg of body mass, an inability to regulate copper has disastrous effects For example, the inability to excrate excess copper from the body (Wilson's disease} can be fatal fle untreated. Menkes’ syndrome manifests itself f the body is unable to retain copper. Although not fatal it an lead to developmental delay and neurological problems, (© From Engincered Mesallcnsime Cataes Friedal-CrtisReacton by Debbie Houston, Chemis Work, | November 2014 | L [Parernrnweens | (‘ou may tn that ~ think to get an over Uunderstacki ing OF what 9 |) detailed scicntitc arcs | ' about. You a 2} |} to understz tard cvery single word t0 leam somes | raw sometti 7 thing, craw so make sure), YOU use a sharp HIB pench 50 that your drawing is | | || clear ane us Soa 21d use a nter if you rawing straig16 1 Nitragen monoxide, NO. is a polltent gas emitted from the exhaust of car. tis oxidised in the atmosphere to form nitrogen dione, NO, “The overall equation for this reaction is NOte) + 40s) — NOs) (a) An tvestigation into che rate ofthis reaeton produced the reauts shown inthe table. 1 oxio? | Loxiw? | 6oxlot 2 roxio? | 20x00" | 12x10 3 zoxlo? | Loxio® | 2axlo™ 4 2oxio | 20x10" | 48x10" () Deduce the order of reaction with respect to (i) NO(a) and (i) O,(g). Justify your reasoning, (al (@) Write 2 rate equation for the reaction between nitrogen ‘monoxide and oxygen. tH (b) A proposed mechanism for the reaction between nitrogen, monoxide and oxygen is 2NO(g) + N,O,{g) FAST NOx) + O,{g) + 2NO.ig) SLOW (Comment on this proposed mechanism in light of your answers to part (2). 3] [Total: 8] 2. Propanone and iodine react in aqueous acile soktion according tothe following overall equation CH,COCH, +1, + Ht + CH,COCH,L + 2H + 1- ‘The experimentally determined rate equation for this reaction is rate = H(CH,COCH,][H"] (@) With initial concentrations as shown. the initial rate of reaction was 1.43 x 10-8mol dm!s~+ CHACOCH, 0.400 7 0.200 400% 10 Calculate a value forthe rate constant, for the reaction. [3] (b) Explain the effect on the rate of reaction of doubling the concentration of iodine, but keeping the concentrations of propanone and hydrogen ions constant fa Exam-style questions (c} The proposed mechanism for the overall reaction is: step sep? sep i] o 6 | A Explain which of the four steps could be the rte-determning step. 3] {@) Ada one or more curly arrows to the carbocation to complete the mechanism for Step 2. a 4 ‘Step 2 l — cH—c: + HT (Total: 9} 3. Most chemical reactions involve two or more steps. The experimentally determined rate equation indicates which species are involved either before or in the rate-determining, step. (a) State what is meant by the term rate-determining step. (1] (©) Hydrogen reacts with iodine monochloride in a two-step mechanism according to the following overall equation: Hy(g) + 21Cl(g) + 2HCifg) + Ie) The experimentally determined rate equation for this reaction is: rate = & [H(@)I0CN2)) ‘The rate-determining step isthe first step in the mechanism for the reaction. (0) Write an equation forthe rate-determining step. [1] (i) Write an equation for the second step. a(0) A sevies of experiments were carried out on the reaction A+ B+ C— products, The results are shown in the table. Experiment | Initial concentrations/ | Initial rate/ moldm™ moldm™* a) [| t 0.100 | 0.100 | 0.100 | 620% 10% z o100 | 0200 | 0100 [620% 10% 3 0.100 | 0.00 | 0200 | 249% 109 7 0200 | 0.00 | 0100 | 124% 10 (@) Determine the order of reaction with respect to A. B and C. Show how you obtain your answers. i (i) Write the rate equation for the reaction. a (ii) Which reactant is unlikely tobe inthe rate determining step? ay (Total: 8} 4 Nitrogen pentoxide decomposes on heating to form nitrogen tetroride and oxygen. The equation forthe reaction is N,Os(e) + N.Od(g) + 40.8) ‘The progress of the reaction can be followed by measuring the concentration of N,O present. The graph shows the results obtained in an experiment conducted al constant temperature 20 18 Cr rr a “Time mines (a) () Use the graph to predict the rate of reaction alter 20 minutes and after 90 minutes. (3) (i Deduce the rate of production of cxygen after 20 minutes? i (©) () Plot on the graph two successive half-lives for this reaction, 2 (i) Deduce the order of reaction with respect to N.O; Justify your answer, (2) a) (ii), Write a rate equation for the reaction, (©) (9 Calculate a value for the rate constant, for this reaetion Deduce the initial rate of reaction when the intial concentration of NO, is 1.50moldm”*, Astume the reaction is carried out under the same conditions of temperature and pressure, (1 @ (2) {[Total: 14] 5. Nitrogen dioxide, NO,,is decomposed on heating nto mitogen ‘monoxide, NO. and exygen. The proposed mechanism for this reaction is NO, +NO,+NO,+NO SLOW NO, = NO +0, FAST (2) () Wte en overall equation far the decomposition of nitrogen diexide (i) Write a rate equation forthe reaction. i) 0) (b) The rate constant, k, for the decomposition was determined at several diferent temperatures. The results obtained were used to plot the graph shown below 9. ine to 1 1243 urnek Use the graph and the expression Al Sittin to calculate the activation energy, B,, forthe thermal decomposition of nitrogen dicxide. Give your answer to.an appropriate number of significant figures. ‘A vessel of volume 200ém is filled with 4.00 mol of nitrogen dioxide at a temperature of 650K. The initial rate oF reaction was found to be 12.64 molém”?s* Calculate a vale for the rate constant, at this temperature. La 0 Ink (4) @ (3) (Total: 9]| = ial \ Introduction In Book 1, you learned about the simplest hydrocarbons ~ alkanes and alkenes - and how to name them Using IUPAC rules You then considered halogenoalkanes and alcohol, including important practical techniques used to convert one organic compound into another. You learned how the analytical techniques cof mass spectrometry and infrared spectroscopy are used to determine the structures of organic compounds. In this topic, you will extend your understanding of organic chemistry by considering compounds with functional groups such as aldehydes, ketones, carboxylic acids, cyl chlorides and esters. You wil also learn about aromatic compounds and amines, and condensation polymers such as polyestersand polyamides, ‘Amino acids and proteins will be introduced, together with reaction schemes that enable one compound to be conver into another in a series of teps. Two more modern analytical techniques ~ nuclear magnetic spectroscopy and chromatography - willbe introduced, Here are some important areas of organic chemistry you will encounter: + How measurements of optical activity can be used as evidence for organic reaction mechanisms + How simple chemical tests can be used to identify diferent functional groups +The uses of esters in solvents fod flavourings and perfumes + How commen medicines such as aspirin and paracetamol can be made: All the maths you need | yi + Use percentages and ratios to calculate empirical formulae + Visualise and represent 20 and 30 forms when distinguishing between the diferent types of isomerism, + Translate information between graphical, numerical and algebraic forms when analysing spectra | iemitying chiral centres and drawing structures of isomersSVE CaWU SS NAF ea eee eee re neers a eee esta poorer oe eee eee een ee eet sera peter ieee + How scientists are developing superconductors en nee ere eet el eer ee eee eens os f° Se cee Eee pee eee a eee eee nett er et) efficiency rising, wih partclar importance for eee AWE aE Maes Coleg eee ee ne en me eters + Recognising different types of isomerism, Eaten Eeaeanad cee ee ern) another Pe eee Seen eee eee spectroscopy to determine the structures of pretest A Mam ect antec | ec \oGedneini sn pehieiey o Bicone 0 Hip cet ay ere Fifer ee ers oat Pe ee eee pariee Se Tre eee te ee o eee hs p STChirality and enantiomers By the end of this section, you should be able to.. ‘@ recognise that optical isomerism isa result of chirality in molecules with a single chiral centre ‘@ understand that optical isomerism results from chiral centre(s)in a molecule with asymmetric carbon atoms) and that optical isomers are object and non-superimposable mirror images Different types of isomerism In Book 1, you eared about stmctral isomerism and its dvsion nto chin isomerism and postion isomerism You then considered a afferent type of isomerism ealled ‘geometric somerism, including the terms £2 and as:ransisomerism this is one type of stereoisomers. ‘This chapter locks at a second type of stereoisomerism ~ optical isomerism, Before we introduce this, itis useful to consider al the types of isomerism that you need to be familiar with, inthe form of a family tee, figA The sometism famiy tee ‘Structural isomers are compounds with the same molecular formula but with different structural formulae. Functional group isomers difler because they have different functional groups (eg aldehydes and ketones, alechols and ethers) ‘Chain isomers differ because they have different patterns of branching in their carbon chains, Positional isomers differ because the same functional group is altached to different carbon atoms in the chain, ‘Stereoisomers have the same structural formula but differ because their atoms or groups are arranged diflerenty in three dimensions Geometric isomers differ because their atoms or groups are attached at different positions on opposite sides of a C=C double bond. Optical isomerism How does optical isomerism nent this fry ree? Optical isomers are non-superimposabe mitor images of each other but are otherwise the same. This needs carefull explanation! Chirality ‘This sa term derived fam the Greek word fo hand’, and could be translated as “handedness. Many objects, incding human hands, can be described as chiral Your hands have the same features and you could describe both hands using the same words. Both consist of a palm with a thumb on one 170side, and four fingers of different sizes, However, if you place one hhand on top of the other, you can see that they are different ~ you ‘cannot superimpose one hand on the other Now put your hands together ~ you can see that the thumbs are together, the litle fingers are together, and so on ~ everything corresponds. Next, put your left hand infront of mirvor, then. Jook at the image in the mirror and your right hand at the same time — they should look identical, so your hands can be described as mirror images, or sometimes as an object and its mirror image. Chirality in simple molecules ‘The key to understanding chirality in molecules is to visualise them in 3D, and ideally use models to help you. Consider a ‘molecule consisting of a single carbon atom joined to four different groups or atoms (represented by W.X. Y and Z). If you represent the molecule in two dimensions, with bond angles of 90°, you cannot easly see why there should be two different arrangements. However, you may remember from Topic 20n the shapes of molecules that you can attempt to show the 3D. nature of molecules using different styles to represent the bonds. ‘Ordinary lines are used to represent bonds in the plane of the paper tapered or wedge-shaped lines indicate those above the Plane of the paper, and dashed lines indicate those below the plane of the paper Drawing the two structures side-by-side cleanly shows how they relate to each other as abject and mirror image. rf a & x72 2S x ¥ Y fig This sone way 0 show optical somersin 3D ‘The asterisk indicates that the carbon ator next to it is a chiral centre, also known as an asymmetrie carbon atom, Notice that if the attached atoms or groups are W, W, X and Y {60 two are the same) then although its possible to show that they relate to each other in the same way (they are mirror images), ‘there is no chirality because one can also be superimposed on the other w w | I A 7 = i w . w fig € These stcures are not optical somes because thare are only tree citfrent groups eine tote cental carbon atom How to identify chiral centres in structural formulae You need tobe alle to identity chiral centres in molecules such 4s the examples shown in the following table ~ all you need 10 ‘consider is whether there is a carbon atom joined to four different 107s Or groups, 0 nn The single carbon atom has only three different atorns attached, sa there is no cial cenve. CH,CHBICH,CH, | Carbons 1,3 and in the chain have to or mote hydrogens attached so are not chiral. Carbon 2 is joined to four cifferent groups (meth. hydrogen. bromine and ethyl) so its a chiral centre CH.CH.CHBICH;CH, | Carbons 1, 2, 4and 5 in the chain have 0 OF Mote hydrogens attached so are not chiral. Carbon 3 is joined to only three differen groups (two ethyl, one rydrogen and one bromine] so itis not achiral cenve CH.CH,CHBCCHBICH, | Carbons 1,2, and Sin the chain have ‘mo oF more hydrogens attached so are not chiral. Carbon 3s joined to four diferent groups (ethy, hydrogen, bromine and CHBICH,) soit is achiral centre, Carbon 4 is joined to four different groups (meth. hydrogen, bromine and CH,CH,CHBr) 50 itis also a chiral contre table A If a molecule has a chiral centre, then it can exist as optical isomers ~ each one is known as an enantiomer. Learningtip leis really worthwhile using molecular models to make some models fofeimple structures to check the idea of mirrar images and superimposabiity 11. Whats the main similarity and the main difference between optical Isomers and geometric isomers? 2 How many chiral centres are there in each of these molecules? (@) cHicct.cH, (©) CHCH(OH)COOH (@) CH.C-CHcI-cHFCH, inition: Chiral refers to an atom in a molecule thatallows it to exist as rnon-superimposable forms. it can also refer to the molecule ise. ‘Asymmetric refers to a carbon atom in a molecule that i joined to four different atoms o° groups. Enantiomers are isomers that are related as object and micror image. mOptical activity By the end of this section, you should be able to.. ‘© understand that optical activity isthe ability ofa single optical isomer to rotate the plane of Polarisation of plane-polarised monochromatic light in molecules containing a single chiral centre © understand the nature of a racemic mixture Plane-polarised light In the previous section, we looked at the causes of optical isomerism. Before we consider optical activity, we must have some understanding of plane-polarised light. One wey to consider ight is, as electromagnetic radiation that travels as a transverse wave, This means that the oscillations exist in planes at right angles to the direction of travel, Fig A shows ‘normal’ unpolarised light and plane- polarised light with the oscillations in only one plane. diectons of a fig tn an unpolenses wave. osllavons may occ in any plane, while in a plane: polarwed wave they ecu in ely cone plane ‘Some natural materials, and syntheric materials such as Polaroid (the material used in some sunglasses), cen absorb all of the oscilations except those in a single plane, and so convert unpolarised light into plane-polarised light. For convenience, the single plane that remains is often assumed to be the vertical plane, as shown in fig B. fist Potro sheet second Polaroid sheet a right angles smonociromati ia polis: paca Teh Fig Polarisation on Fig B shows that the second sheet of Polaroid has horizontal lines, which means that only horizontally plane-polarised light can pass through. As the first sheet has produced vertically plane- polarised light, chen no lig can pas treugh the second sheet. Polarimetry Polarimetry isthe use of a polarimeter to measure the amount of optical activity, if any of a substance. Fig C shovis how a polarimeter works. A monochromatic ligat source (light of only one colour or frequency) passes through a polarising filter (such as a piece of Polaroid) This s called the polariser because it converts unpolarsed light into (vertical) plane-polarised light. The plane- 12polarised light then passes through a sample nue containing some ‘of the substance in solution Ifthe substance is optically active {because it contains an enantiomer), then the plane of polarisation ‘wil be rotated so that itis no longer vertical. In this example, the rotation is clockwise, and the substance can therefore be described as ‘dextrorotatory’. Ifthe rotation is anticlockwise, then the substance is laevorotatory’ S analyser x > tame tbe G7 poe light fig You can see how the plane of polrzaon ofthe polarised gt rotated cloclise ast pases through the samp ‘The second polarising filter, known as the analyser, is rotated to position where the maximum light intensity can be seen, ‘The angle of rotation (a) is measured, and is quoted as a positive vvalue if the rotation is clockwise and as a negative value if the rotation is anticlockwise. In fig C, the rotation, a, is approximately 60°, Properties of enantiomers ‘Two enantiomers have identical physical properties, with one exception. The enantiomers rotate te plane of polarisation of plane-polarised ight by equa anges, tn opposite directions 50 if the rotation for one enantiomer is 460°, then the rotation for the other enantiomer is ~00°. ‘Two enantiomers have identical chemical properties, with one ‘exception ~ the way in which they react with enantiomers of other substances. This chemical property may be different for each enantiomer Racemic mixtures What happens if a compound with a chiral centre is present ‘as 2 mixture of both enantiomers? You can imagine that the dextrorotatory and laevoratatary enantiomers have equal but ‘opposite effects on plane-polarised light, and so the analyser does not need to be rotated to allow the maximum light intensity t0 be seen, Without knowing anything about the substance, tis not possible to distinguish between a substance that has no eptical activity and one that has optically active enantiomers whose effects cancel out. A mixture containing equal amounts of two ‘enantiomers is called a racemic mixture, We cannot explain the origin of every scientific term in this book, but let us try to provide a brief explanation of this one! The Latin rd racemus means: a bunch of grapes, What has this to do with ‘optical activity? The French chemist Louis Pasteur achieved much sn his lifetime (1822-1695), and his name lives on in the English 0 ‘word ‘pasteurisation, often associated with milk production “Another of his achievements was to realise that tartaric acid produced during winemaking showed optical activity, ur that tartaric acid produced in other ways did not. He eventually realised that a single enantiomer of tartaric acid was produced from winemaking and that a mixture of both enantiomers of tartare acid was produced in the other ways, Since tartarie acid is present in grapes, the term ‘racemic acid’ was used, and the ‘racemic’ patt of this term was then used to describe an equimolar mixture of the two enantiomers. Voilal Here are the structures ofthe two enantiomers of tartaric acd Gexoujcoon Gexoneoox c C now 17H Ho SoH Coon cori fig The mo enantiomers of tna Learning tip Iti worth spending some time making sure you understand the diferences between these terms: Lnpolarised, polarser,plane-polarsed, plane of polarisation. 1 outline how a polariser works 2 Adextrorotatory enantiomer has a rotation of +43". A mixture of this enantiomer and its lnevorotatory enantiomer has a rotation of =10". What does this information indicate about the composition of this mixture? Keydefinitions A substance shows optical activity iit rotates the plane of polarisation of plane-polarised light Plane-polarised lights monochromatic light that has oscillations in only one plane Unpolarised light has oscilatons in all planes at right angles tothe direction of travel ‘A polarimeter s the apparatus used to measure the angle of rotation caused by a substance, ‘A ppolariser is a material that converts unpolarised light inte plane= polarised light [An analyser a material that allows plane-polarced light ta pass through it. ‘racemic misture is an equimolar micure of two enantiomers that has no optical activity 123Optical activity and reaction mechanisms By the end of this section, you should be able to.. @ use data on optical activity of reactants and products as evidence for Sy and $2 mechanisms Nucleophilic substitution in halogenoalkanes In Book 1, you learned to write mechanisms for these reactions, but the story was taken only so fat "There was a suggestion that the explanation given in Book 1 was incomplete and that there was ‘more to come, Now is the appropriate time to develop the explanation in greater depth, Firs, let us revise what ‘you may remember from Book 1, Fig A shows how we represented the mechanism of the reaction between the primary halogenoalkane bromoetnane and hydroxide ions. fig A Trisisa simple way to represenca rucleephilicsubstturion mechanism, ‘We must now accept that this mechanism is an oversimplification and that we need to consider ‘two alternative mechanisms. This mechanism shows the simultaneous movement of two pairs of electrons ~ those fiom the O of OH ions and those from the C—Br bond. In fact, there are two distinet mechanisms. The $2 mechanism ‘The individual symbols in 2° have the following meanings $= subsituion N= nudleophilc = bimolecular and second order ‘The term ‘bimolecular’ means that there are two species involved in the rate-determining step —in this example, the OH ion and the halogenoalkane. Second order reactions were considered in Topic 16 in this book In this topic. we are going to revisit Learningtip ______the mechanism provided in Book 1, by looking at it in more detail. Here is the mechanism for a femembertoindude square pYimary halogenoalkane that is als an enantiomer brackets and a negative ch outside tetra when Hox cu, cH, writing the transition state in QL | | 1 the Sy? mechanism Using 3+ S6.4¢ + |tomeb] ee ewe and 8- to indicate the polar F7 Br Ni HOT Np 4B H bbondsis good practice, but in this section, they have been. Ths the S\2 mechanism showing the transition sate ‘omitted for clarity, Notice thatthe curly arrows are used in the same way. The mechanism now includes a transition state sowing the HO—C bond forming and the C—Br bond breaking ‘The dashed lines represent parial bonds ~ those being broken and formed, The most important thing to notice is that the arrangement of the three groups that remain attached to the central carbon atom has been inverted (turned inside out) m40 Evidence from optical activity Ifthe reaction actully occurs according to the S,2 mechanism, then, because ofthe inversion that occu, the opical activity of the product is diferent from that ofthe reactant. Ifthe reactant is dextrorotatory, then the product will be laevorotatory and viee versa. So, by measuring the optical activity of the origina halogenoalkane and the alcohol formed, we can show whether the reaction has occurred by the $,2 mechanism. The 5,1 mechanism “The individual symbols in ‘Sy! have the following meanings ‘unimolecular anc fst substitution N= nucleophilic order ‘The term ‘unimolecular’ means that only one species is involved in the rate-determining step ~ in this example, just the halogencalkane, We have used the same halogenoalkane as for the ‘Sy2 mechanism so that you can focus on the differences between the two mechanisms, mechanism, the planar carbocation can be attacked for the om te right, ging apa of enarsiomers ‘The original halogenoalkane has a tetrahedral shape, but the product of the fist step of the reaction isa carbocation with a planar shape. This means that in the second step of the reaction, there is an equal chance that the attacking HO- ion can approach from the left or from the right. There are therefore two products, both of which are enantiomers, These are present in equal ‘numbers, so a racemic mixture is formed, Evidence from optical activity If the reaction actually occurs according to the Syl mechanism, ‘then the optical activity of the product is different from that of the reactant, Whether the reactant is dextrorotatory or laevorotatory tie product has no optical activity. So, by measuring the optical activity of the original halogenoalkane and the aleahol forrned, we ccan show whether the reaction has occurred by this mechanism. Which mechanism? JIn general, the main mechanism for primary halogencelkanes is $)2 and for tertiary halogenoalkanes is Sy1. For secondary halogenoalkanes, both mechanisms can occur although the main ‘one depends on the actual halogenoalkane and the conditions. 1) 2romobutane and eyanielons ect together an 2 mechanism Drew th uctur ofthe waetlon ate formed ints vector 2 2-tromopropane and carideions ect together by an Sy) techni Explain why eso hangin op ely in is Key definitions ‘Amechanism described as bimolecular has two species reacting in the rate- determining step. ‘Amechanism described as unimolecular has one species reacting in the rate- determining step. WsCarbonyl compounds and their physical properties By the end of this section, you should be able to.. @ identify the aldehyde and ketone functional groups ‘@ understand that aldehydes and ketones: (i) do not form intermolecular hydrogen bonds, and this affects their physical properties (i) can form hydrogen bonds with water, and this affects their solubility Nomenclature ‘We met carbonyl compounds brief in Book 1, but only as the [products of the oxidation of alcohols. ‘The carbonyl group (C=O) is a carbon atom joined by a double ‘bond to an oxygen atom. Many types of compounds contain this group (such as carboxylic acids which contain COOH), but only two types are classified as carbonyl compounds ~ these are aldehydes and ketones. Aldehydes carbonyl compound is deseriped as an aldehyde if there is a hydrogen atom joined to the carbonyl group The naming system ‘ses the sufix al, with the carbon chal being named as for alkanes. If locants are used, then the carbon of the carbonyl ‘group is carbon 1 in the chain, Table A shows some examples. eretneny HCHO mmethanal formaldehyde cH.cHo ethanal acealdehyde CH.CH;CHO propanal | (propionaldehyde) (CHcHCHO methylpropanal | (sobutyaldehyde) (CH.CH.CH,CHO butanal (butyraldehyde) GH.CHO table A ‘The general formula is RCHO. benzenecarbaldehyde | benzaldehyde Ketones ‘A carbonyl compound is described as a ketone if there are only Inydrocarbon groups joined to the carbonyl group. The naming system uses the suffix -one, with the carbon chain being named as for alkanes. If locants are used, then one of the end carbon atoms in the chain of the carbonyl group is carbon 1 in the chain. ‘The rules about using the lowest possible numbers, as with alkanes, apply to ketones. Table B shows some examples. 176 CHOC CH,COCH.CH, propanone acetone butanone (meth ethyl ketone) CHCOCH.CH.CH; | pentan-2-one | (methyl propy ketone) CH,CH,COCH,CH, (CH.CHCOCH: pentan-3-one (¢iethy! ketone) 3-methylbutan {methyl isopropyl ketone) table B ‘The general formula is RCOR’, Forboth aldehydes and ketones, the common names in brackets are rarely used Bonding ‘You are familiar with the nature of the C=C double bond in alkenes. It is composed of a combination of sigma and pi bonding, but the bond is non-polar because there are two identical (carbon) atoms involved. The situation in the carbonyl group is very similar except that che bond is polar because of the differing clectronegativities of carbon and oxygen. Fig A compares the two, figA The bondingin an alkene son the eft. The bending ina carkory, compound ison the right. Green is used to preset sigma bondingand blue s used to reeesent pi bonding Note that the electron density in the pi bond of the alkene is ‘evenly distributed across both eatbon atoms, but that in the carbonyl compound the electron density is greater near the ‘cxygen atom than near the carbon ator, Physical properties Aldehydes have distinctive smells. Those with short carbon chains have unpleasant smells (butanal smells of rancid butter). Some Of those with long carbon chains have very pleasant smells and are used in expensive perfumes (nonanal, with nine carbon atoms pper molecule, smells of roses). The smells of the lower ketones, especially propanone, remind most people of solvents. Infact, ppropanone is widely used as a solvent. including as nail varnishSolubility in water ‘The lower aldehydes and ketones are soluble in water because ‘they can form hydragen bonds (shown as a dashed line) with water molecules. Fig D shows hydrogen bonding between ethanal and water HoH H. Sod Noro | i & H fig Hydrogen bonding nenwsen water molecules and erhanal molecves i stronger than the iermolecular bonds nthe pure aldehyde ‘The solubilily of aldehydes and ketones decreases with increasing chain length, as the hydrocarbon part of the molecules becomes more significant fig B Cinnamon (which contains the alebyde cinnamaldehyde) comes from 2 Theres barkof the tee Cinnamornim zeylaleum iis widely sed 352 spice in cookery Learningtip When naming ketones with a chain of five oF more carbon atom, Boiling temperatures Jocant is needed to show the position of the carbon group. When naming aldehydes a locant is never used to show the position ofthe carbon group because the CHO group must be at the end af the chain, Alkanes have only weak intermolecular forces (London forces) because they are non-polar Alcohols have strong intermolecular forces (hydrogen bonding) because they have a very polar O—H group. a strength. They contain the polar C=O group and so have permanent dipole-dipole atractions. They do noc have hydrogen Boncingoecase all thes hyrogen satan ocabon 1 Wetthe diptyed oma for ‘atoms, As with alkanes and aleahols, boiling temperatures (@) propanal increase with increasing molar mass as the extent of London (©) propanone. forces increases. At room temperature, methanal is a gas. The other carbonyl compounds are liquids. Fig C compares the boing temperatures of some carbonyl compounds 2 Draw adagram to explain why propane sll in wate es alcohols . = exes ee} g ‘aldehydes (green line) B90 z anes ie E 012343 Number oferta atoms fig Theboling temperatures of sme allanes, aldehydes, ketones and alcofios, The effet ofthe intermolecular orces an te boing temperatures can be seen cleat withaipole-cipale arracions, which rex fom the carbony! groups cf the aldahydes an ketones, causing higher boiling temperatures than the equivalent alkanes but lower than re aicahols withthe nycregen banding WwRedox reactions of carbon compounds By the end of this section, you should be able to.. ‘© understand the reactions of carbonyl compounds with: (i) Febling’s or Benedict’s solution, Tollens’ reagent and acidified dichromate{V) ions (i) lithium tetrahydridoaluminate (lithium aluminium hydride) in dry ether (i) iodine in the presence of alkali Which reactions occur? You may remember trom Book 1 that carbonyl compounds ormed by the oxidation of alcohols) differ in their ease of oxidation ~ aldehydes (bur not ketones) are easly oxidised to carboxylic acids. In his section, we will look at these reactions in ‘more detail, and also consider the reduction reactions of carbonyl compound. Fig A summarises these reactions [= _ [=| ~~ [=] not easly [== _— ‘oudied fig. Aldehydes canbe reduced and ovdised, but ketones can only be reduced Reduction reactions Both aldehydes and ketones can be reduced to alcohols by the same reagent lithium tetrahyeridoaluminate. This reagent is also know as lithium aluminium hyeride, and ts formula is LIAIH, The reduction reactions are carried out with both the carbonyl compound and reducing agent dissolved in dry ether. ‘Tosimplify the equations, the reducing agent is represented by [H), which isthe symbol for an atom oF hydrogen provided by the reducing agent in an unspecified way. Note that this isa different use of square brackets ~ it does not indicate a complex (as with ‘transition metals), andit does not indicate a molar concentration (as in kinetics) Here are some examples of equations. Reduction of propanal to propan-1-ol CH,CH,CHO + 2{H] - CH,CH,CH,OH Reduction of butanone to butan-2-ol CH;COCH,CH, + 2{H] ~> CHCH(OH)CH,CH, Inall of these reduction reactions, a hycragen atom becomes attached 10 each of the atoms in the carbonyl group. 178 Oxidation reactions Ketones are very dificult to oxidise, and as far as this book is concerned, ketones cannot be oxidised, Table A shows che reagents that can oxidise aldehydes to carboxylic acid, ro ies Aciified corange solution | The colour change is potassium | —+ green solution | due to the reduction of dichromate(Vl) chromium from +6 to #3. Fehlings deep blue solution | In both of these solutions, solution =+ ed precipitate_| the colour change is due Benedics | deep blue solution | © the conversion of a solution —+red precipitate | Copper} complex to copper onde. itisnot necessary 10 understand the difrence betwoon the Chemical compositions ofthese swo reagents: The colour change is de to the conversion of asiver() complex tometai iver which often sticks tothe insce ofthe tube. The reagent s also desenbed ae ammoniacal sver nitrate ‘colourless solution silver mirror Tollens reagent table A All of these oxidation reactions can be carvied out inthe laboratory ina test tube, by mixing the carbonyl compound with the oxidising agent and leaving the mixture in a beaker of hot water ‘As for the reduction reaction equations all of the oxidising agents in table A can be represented by (0). This is the symbol for an atom of oxygen provided by the oxidising agent in an unspecified ‘way, Here are some examples of equations. (Oxidation of propanal to propancic acid: CH,CH,CHO + [0] > CH,CH,COOH (Oxidation of butanal to butanoic acid (CH,CH,CH,CHO + [0] ++ CH,CH,CH,COOH Distinguishing between aldehydes and ketones ‘The oxidation reactions using Fehling’s solution, Benedict's solution and Tollens’ reagent are often used to distinguish between aldehydes and ketones. A positive result, as described in table A, indicates the presence of an aldehyde. A negative result indicates the absence of an aldeiyde I itis also known that the substance being tested is a carbonyl compound, then the negative resuk can be taken as confirmation of the presence of a ketonefig6 cour ‘ee soluton blue soltion ta 2 re ppt froma coiouiless solution 33 We rmaror nthe est for an alderyde, Reactions with iodine ‘Another redox reaction of some carbonyi compounds is rather different ~ it used to be known as the jodoform reaction, but is now described as the tiiodemethane reaction, This is because the product, is CHI, yellow insoluble solid If a carbonyl compound is added to an alkaline solution of iodine and the mixture warmed and then cooled, a pale yellow precipitate sometimes forms. This result is a positive test for carbonyl ‘compounds containing the CH,CO group ‘This group is found in only one aldehyde (ethanal) and in all methyl ketones (thase with the carbonyl group as the second carbon in the chain). This means ‘that the reaction occurs with propanone, butanone and pentan-2-one, but not pentan-3-one, Because oxidising conditions are used in the reaction, this means that some alcohols will also give positive results, Table B shows the results for some common aleohols, Alcohol Result ethanol CH:CHO positive a a Ec aaa propan-1-ol CH.CH.CHO negative ee eo propar-2-ol CH.COCK. positive conversion flees and nest alcohols butan-T-ol CH.CH.CH.CHO negative ‘ : ‘The oxidation reactions are butan-2-ol CH.COCH,CHs positive gael a a na 2-methyipropan-T-ol (CH),CHeHO negative distinguish between aldehydes ine and ketones 1 what are the eamesetthe organic products of hee reactions? {a) The reduction of CH,CH,CH.CHO. (b) The oxidation of CHyCH;CH,CH;CHO. 2 what ectour changes would be observed in thee tat? (2) Heatnga mire ofproranone and aiid potassium dcroratet¥) (8) Heating a mature of thanal and Toles eager 179Nucleophilic addition reactions By the end of this section, you should be able to.. ‘© understand the reactions of carbonyl compounds with: (i) HN. in the presence of KCN, as a nucleophilic addition reaction, using curly arrows, relevant lone pairs, dipoles and evidence of optical activity to show the mechanism (i) 24-dinitrophenylhydrazine (2.4-DNPH), as a qualitative test for the presence of a carbonyl group and to identify a carbonyl compound given melting temperatures of derivatives data The reaction with hydrogen cyanide “The reagent is hydrogen cyanide, and the reaction is caried out in an aqueous akan sluion containing potassium eye (KCN). ‘The equations and mecharisms are the same forbothaldehyces ani ketones Here are some examples of equations [Adtion o propane! (CH,CH,CHO + HCN — CH,CH,CH(OH)CN: ‘Adation to butanone CH,COCH,CH, + HCN + CH,C(CN\OH)CH,CH, ‘These addition reactions involve a hydrogen atom attaching to the ‘oxygen atom of the carbonyl group and a cyanide group attaching, to the carbon atom of the carbonyl group. ‘These products contain a carbon atom joined to the functional ‘groups OH and CN. They are named somewhat differently from other organic compounds we have met so far According t0 IUPAC rules, the OH group should be shown as a prefix and the CCN group should be shown as a suffix. When this happens, the OH group is shown as fydraxy- and not as -ol and the CN group is shown as the ending -nirie, In general, these products are deseribed as hydroxynitriles, Applying these naming rules: CH,CH,CH(OH)CN is 2-hydroxyutanenitrle CH,C{CNOH)CH,CH, is L-hydroxy-2-methylbutanenitile The nucleophilic addition mechanism Nucleophilic addition is ¢ two-step mechanism, illustrated using cthanal as an example, Step 1 involves the nucleophilic attack by a cyanide ion on the carbon atom of the carbonyl cornpound, 4 Hobs a i nore —- ne—c—8 / | He cH, Intermediate 180 ‘Step 2 involves the reaction between the intermediate and a hydrogen cyanide molecule 4H H chen + ne Gon + ew MG pe cH, Using optical activity as evidence ‘A.consideration of optical activity can be used as evidence for this ‘mechanism. The arrangement ofthe two atoms or groups joined toC=0 is planar, which means that in Step 1 there is an equal chance of the cyanide ion atacking from each side of the plane. So, although the product ofthis reaction conlains an asymmetic carbon atom (a chiral centre), there are equal amounts of both Gextrorotatory and laevorotatory enantiomers formed, giving a product mixture with na optical activity Using ethanal asthe example, the product is 2-hyroxypropaneniuile, Fig A shows the formation of a racemic rmisture containing equal numbers of both enantiomers cN CN cH, a atbooe- Co AB, HTN cu. on? fg. sack bythe cyanide ‘on fom the tp leadsta te precuc shown higher up we attack ftom the ottam leadeta se proc shown lower down, Each ethanal molecule allactad by only ene ofthese janie iors, ‘The cyanide ion can attack from above or below, producing equal amounts of both enantiomers. The reaction with 2,4-dinitrophenylhydrazine ‘This compound is sometimes inown as Bracy's reagent. and its name soften abbreviated as 24-DNPH. You do not need to ‘ive equations or mechanisms for any reactions involving tis reagent, but itis useful to show its structure, andthe structure of product of ts eaction with carbonyl compound Fig B shows ts reaction wth propanlcH.cH, NO + OFC — on NO y+ HO H ‘a Na fg Thereacon bye 2A-dnitophenyhyacne and propaal ‘The reagent reacts with most carbonyl compounds to form a brightly coloured orange solid, so the appearance of an orange precipitate is a positive result that indicates the presence of a carbonyl ‘compouné. Melting temperatures of derivatives ‘As well ax providing a visual indication of a positive result forthe presence ofa earbonyl compound, these reactions can also be used to identify individual carbonyl compounds. Tis is because the compounds formed, known as derivatives (oecause they are derived from particular carbonyl compounds), can be filtered, purfied and dried. and their melting temperatures measured, These derivatives have the ending -one, so the derivative of butanal is butanal 2,4-cintrophenylhydrazone By comparing the experimental values of melting temperatures of these derivatives with data book vvalues, the identity of the original carbonyl compound can often be confirmed. For example, the three carbory compounds pentanal, pentan-2-one and pentan-3-one all have the same boiling temperatures and all form coloured precipitates with 2,4-dinitophenylhydrazine. Table A shows the boiling temperatures of the carbonyl compounds and the melting temperatures of their derivatives. aaa fig Ths isthebogrt orange precipiate formed wn 2 bony comaourd 3c wit orn) ene pentanal 102 104 peatan-2-one 502 144 pentan-3-one 102 156 table A ‘You can see that the original carbonyl compound can now be identified by matching the ‘experimental melting temperature of its derivative to a value in the table, Remember that when a cyanide group becomes part of an organic compound, the number of carbon atoms increases by one, which affects the name. So for example. propanal becomes 2-hydroxybutanenitile. 1 whatare the names ofthe organic products ofthese reactions? (a) methaal + hydrogen cyanide (8 propanone hydrogen cyanide 2 compound x reacts wth 24-ydrogen bonding between ethanoic acid and water, z La, TT NEG, h Xe fig Hyikogen bonding between exhanole acid and wate Solubility decreases with increasing chain length, as the >ydrocarbon part of the molecules becomes larger Learmingtig [Note thatthe hydrogen bonding between carboxylic acid and water molecules involves =CmO - H-O-H and -O-H = O-H on where hydrogen bonds are represented by dashed lines. 11. Write the displayed formula for: (a) methanoie acid (6) ethanedicic acid 2 Explain why hexanoic acid is much less soluble than ethanoic acid in water 183ee Leli (eae late mclad loli eeoll carboxylic acids By the end of this section, you should be able to.. ‘© understand that carboxylic acids can be prepared by the oxidation of alcohols or aldehydes, and the hydrolysis of nitriles @ understand the reactions of carboxylic acids with (i) lithium tetrahydridoaluminate (lithium aluminium hydride) in dry ether (i) bases to produce salts (ii) phosphorus(V) chloride (phosphorus pentachloride) {iv) alcohols in the presence of an acid catalyst Preparation by oxidation ‘hough carbanie acids are formed in many chemical reactions, to main methods are used to prepare them in the laboratory. Oxidation uses either a primary aleohol or an aldehyde as the staring materi. The usual oxdsing agents acidified potassium Glehromate(VI, andthe method is to heat the mbure under reflux Ifa primary alcool is used it frst oxicises to an aldehyde, then toa carboxylic acid, but both oxidations occur inside the apparatus use ‘When the cxdation is complet, te reaction mix i fractionally distiled o obtain a pur sample of the carboxylic acd Examples Propanoic acid can be prepared from either propan-I-ol or proparal The equations use [O} to represent the oxygen supplied by acidified potassium dicheomate(V1} From propan-1-ok CH,CH,CH,OH + 2{0] — CH,CH,COOH + 1,0 From propana: CHyCH,CHO + (0) -» CH,CH,COOH. Preparation by hydrolysis Nitiles are organic compounds containing the CN group. “They can be hydrolysed by heating under reflux with ether a dilute acid or aqueous alkali, The same apparatus is used for preparation and purification as for oxidation, JInboth cases. the C=N tiple bond breaks. The carbon atom remains part of the organic product and the nitrogen ator becomes either ammonia or the ammonium ion Acidic hydrolysis Propanoic acid can be prepared from propanenitrle. The equation for the reaction is: CH,CH,CN + Ht + 2H,0 — CH,CH,COOH + NH 184 Alkaline hydrolysis ‘Butanoie acid can be prepared from butanenitile, The equation for the reaction is: CH.CH,CH,CN + OH" + H,0 — CH,CH,CH,COO- + NH, “The products actually the butanoate ion, but this is easily converted to butanoic acid by adding dilute cic: CH,CH,CH,COO- +H > CH,CH,CH,COOH Introduction to reactions ‘There are four main reactions to consider. These are summarised in fig A 2, [nevtratsation redvetion nalogention| T 7 4 | eseriication fig these ste the four main reactions of carboxylic acco form oer ‘organic compounds ‘Some of the products of these reactions, especially acyl chlorides ‘and esters, willbe discussed in more detail later on. 1 Reduction ‘You will remember that carboxylic acids are products of oxidation ‘They can be reduced in the same way as aldehydes and ketones. Carboxylic acids can be reduced to primary alcohols, but not ro aldehydes. Tis is because aldehydes are more easly reduced than carboxylic acids, and so any aldehyde produced during the reduction wil be immediately reduced to a primary alcool ‘The reducing agents lithium tetrahydridoaluminate, and is used in solvent of dry ether Asan example, an equation using butanoic acid is CH,CH.CH.COOH + 4{H) ‘The product is butan-1-ol, » CH,CH,CH,CH.OH + H.0 2 Neutralisation ‘Although carboxylic aciés are weak acids, they can be completely neutralised by mixing with aqueous alkali. The products are carboxylate salts, which have a wide range of uses. ‘The commonest, sodium ethanoate, is used in hend warmers and to make the additive that gives the flavour to salt and vinegarpotato crisps. An equation for the reaction to make sodium ethanoate occurs between etaanoic acid and sodium hydroxide: CH,COOH + NaQH + CH,COONa + H,0 Carboxylate salts are ionic, and are sometimes shown with formulae such as CH,COO™Na’ ‘Their general formula is RCOONa, 3 Halogenation In this reaction, the OH group is replaced by a halogen atom, usually chlorine, so the functional group becomes COC, These products are known as acyl chlorides, They are highly reactive compounds with many uses in organi synthesis, as we will see later on. The reagent is phasphorus(V) charide {old name ‘phosphorus pentachloride’) It must be used in anhydrous conditions because bath the reagent and the acyl chloride preduct react with water The reaction is vigorous, so no heating is ‘equited, An equation for the reaction, using propancic acid as the exemple is: CH,CH,COOH + PCI, + CHsCH,COCI + POC, + HCl Acyl chlorides ere named using the sulfix-oyl chloride, so this product is propancy! chloride, “Their general formula is RCOCL ‘The phosphorus-containing product is phosphorus trichloride oxide (also known as phosphorus oxychloride}. Its liquid that mixes with the acyl chloride, which has therefore to be separated by nis one ofthe most familia and inexpensive mmeciestions but = usta fractional dstilation. The hydrogen chloride gas produced escapes, appearing as misty furnes, eating many medical Conditions tis an example of a 4 Esterification carbonpic ac In this reaction, a carbaxylic acid is mixed with an alcohol and a small amount of an acid catalyst, often concentrated sulfuric acid, Even with a catalyst, the reactions are slow and reversible. Esters are used in industry for many purposes, including as solvents and in making polymers (polyesters). They also occur very commonly in nature they are responsible for the characteristic ‘Leamingtip ___ smells of fruits, and most animal fats and vegetable oils are esters Sei anteater] een make sute that the name and {formula match, CH,COOCH, is ‘An equation for the reaction between methanoic acid and ethanol is: HCOOH + CHCHOH = HOOOCH.CH, + 1,0 aires The nrnes of esters ays conan two words —he fa she alkyl group tam the lool and the HCOOH sei second is the carboxylate from the earbexylie acid, So, this product is ethyl methanoate. 1 Write equations for the preparation of methy|propanoic ac: {@) by the oxidation ofan alcoho! (b) by the hydrolysis of anti 2. Write an equation for the conversion of methylpropanoic acid (@) into an acyl chloride (©) into a methylester 185Acyl chlorides By the end ofthis section, you should be able to... © identify the acy! chloride functional group © understand the reactions of acyl chlorides with (i) water {i) alcohols concentrated ammonia (i) amines Whatare acyl chlorides? These used to be known as acid chlorides, and have the general formula RCC. They are derivatives, of carboxylic acids, and can be imagined as the result of replacing the OH group in COOH with Cl Although, like carboxylic acids, aldehydes and ketones, they contain a carbonyi group, they are not classed as carbonyl compounds. As with carboxylic acids, having two functional groups sharing. the same carbon atom means that the properties are different from both carbonyl compounds and hhalogencalicanes, ‘The commonest example is ethanoyl chloride, CH,COCI, which is stil called by its old name acetyl chloride. You may come across ethers, such as: propanoyl chloride CH,CH,COCI and —butanoyl chloride CH,CH,CH,COCL Reactions of acyl chlorides fig Adangeranoycronce The carbon atom in RCOClis joined to two electronegative atoms and so is electon-deficient sei pedutestines at (B+). Youcan therefore precct that it will be readily attacked by nucleophiles, such as molecules rege cn containing O or Natoma, You need to know about fourreactions of acyl chores, although no mechianisins are needed for any of them. Reaction with water Acyl chlorides react vigorously with cold water forming a carboxylic acid and releasing hydrogen chloride gas, which appears as misty fumes. The equation forthe reaction of ethancy/ chloride with ‘water is as follows: 9 9 o Zé + HOH > cH-c® + HO \ ‘oH Reaction with alcohols ‘Acyl chlorides react readily with ethanol to form an ester and hydrogen chloride gas. The equation for the reaction of ethanoyl chloride with ethanol is as follows: 0 ° ao Zé ons + cHCH-oH + cH + Hoa ro ‘OcH,CH, Notice the similarity between these two reactions. In both cases, the H of the second reactant combines ‘with Cl to form HCl, and the other part of the reactant becomes joined to the carbonyl group, 186C0 Reaction with concentrated ammonia solution Similar to alcohols, acyi chlorides react readily with concentrated ammonia solution. You can now predict the reaction that eccurs: the H of the second reactant combines with Cl to form HCl, and. the other part of the reactant becomes joined to the carbonyl group. The NH, group joined to the carbonyl group produces a different functional group — amide (not to be confused with amine} The equation for the reaction of ethanoyl chloride with ammonia is as follows: o fF \ NH, + NH, — Unlike with water and alcohols, a further reaction occurs, The reactant is a base and the product is an acidic gas, co these react together to form ammonium chloride: NH, + HCI NH,C You could write a single equation that combines both of these reactions: CH,COCI + 2NH, ~» CH,CONH, + NH,CI You wil learn more about amides later inthis book. Reaction with amines This reaction is similar to the previous one. A primary amine ean be shown as RNH,, 80 you can ‘again predict the reaction that occurs: the H of the second reactant combines with Cl to form HC and the other part of the reactant (RNH) becomes joined to the carbonyl group. The equation for the reaction of ethanoy! chloride with the simplest primary amine, methylamine is as follows 9 oO Zé 4 cH + cHNH, —+ cH-c™ + HOC \ . \ ‘al HCH, ‘The product of this reaction is a substituted amide, often celled an N-substituted amide. The capital N emphasises that there is an alkyl group attached to N, rather than the usual situation in which itis attached to another C atom. You can see from the product name (N-methylethanamide) that N- is used as a locant, in the same way as in names such as 2-methylbutane — it shows where the methyl group is attached. ‘Secondary amines (represented as R,NH) react in the same way, although the product will eontain two substituted alkyl groups, A sample equation is CH,COCI + (CH,),NH — CH,CON(CH,, + HCL ‘The organic product is N.N-cimethylethanamide, eaming tip You might be able to predict why this type of reaction does not occur with a tertiary amine (RyN) Be sure nat to confuse amines With three alkyl groups, there is now no H atom to react with Clo form hydrogen chloride. (RNH,) with amides (RCONH). 1 ite te names ofthe crane product fomedin the ou similar reactions propanyl chord with wrter metnnel snmonte and methylamine 2. rte an equation or butanoy code reacting with (a) propan-1-ol (b) ethylamine. 187By the end of this section, you should be able to.. @ identify the ester functional group ‘@ understand the hydrolysis reactions of esters, in acidic and alkaline solution Introduction In previous sections, you have come across esters as the products of reactions of other organic compounds, We will now take closer lock at esters, including their reactions. Naming esters “This is straightforward, but you need to remember these points: + As for carboxylic acids and acyl chlorides (pur not amides), an ester name contains two words. + The fist word comes from the alkyl group joined t0 0 + The second word comes from the alkyl group joined to C ‘Table A shows some examples. eno ao HCOOCH methyl methanoate cH.COOcH ‘methyl ethanoate HCOOCH,CH, ethyl methanoate CH.COOCH.CH ethyl ethanoate CH.COOCH,CH,CH. propyl ethanoate table A Physical properties Eszers are colourless liquids with relatively low melting and boling temperatures, and are insoluble in water All ofthe hydrogen atoms in their molecules ae atached to carbon atoms, 0 hydrogen bonding is not possible. ‘The generally pleasant smells of esters are largely responsible for the familiar odours of lowers and fruits. Examples include: pentyl ethanaste pears S-methylbutyl ethanoate bananas, methyl butanoste apples Esters are present in perfumes, food flavourings, solvents, anaesthetics and biofuels 188 JA. Benzyl athancate is responsible for food flavourings that resemble apples and pears Hydrolysis of esters ‘The only reactions of esters that you need to know about are two sight differen ypes of hydrolysis The term hyclyi means breaiang down (pss using Water (peo) Itean be considered as the revere of estenfiation, You may remember equations Such as this fom a previous section CH,COOH + CH,CH.OH = CH.COOCH,CH, +H,0 ‘This shows the formation of ethyl ethanoate from the corresponding carboxylic acid and alcohol. The reversible arrow indicates that a mixture of ethyl ethanoate and water reacts together to form ethanoic acid and ethanol. This reverse reaction could be described as the hydrolysis of ethyl ethanoate, Hydrolysis in acidic solution ‘We parlly covered this type of hydrolysis in the previous paragraph. For a given ester, warming it with water will cause hydrolysis. As with esterification, the reaction is slow A catalyst such as sulfuric acid will speed up hydrolysis, but will ot affect the position of equilibrium, so the reaction will not go to completion: CH,COOCH,CH, + H,0 = CH,COOH + CH,CH,OH Hydrolysis in alkaline solution ‘The disadvantage of using an alkali such as aqueous sodium hydroxide instead of sulfuric acid is thatthe reaction produces a carboxylate salt instead of a carboxylic acid, However, the advantage easly outweighs this disadvantage — the reaction goes to completion instead of reaching an equilibrium. The equation formethy! propancate is: (CHsCH,COOCH, + NaOH — CH.CH,COO™ + Na* + CHOH Converting the carboxylate salt into a carboxylic acid only needs 2 cilute acid to be acide: CH,CH,COO- + H' — CH.CH,COOH ‘The final organie products are ethanol and propanoic acid,C0 Saponification ‘The Latin word for soap is sapo, so saponification means ‘soap-making’. This isa particular example of the alkaline hydrolysis of esters. Soaps and detergents have similar uses, but the main diference is that detergents use organic compounds obtained from crude ol wile soaps use erganic compounds obtained from vegetable (and, originally. animal) soure Vegetable oils contain large quantities of triglycerides. These are triesters, each of which consists of a lenge ester molecule that can be hydrolysed to one alcohol and three carbaxylic acid molecules. The hydrolysis of a typical triglyceride is shown in fig B. i —0—t— cyt, HoH ° I - CH—0—C—G,,, + aNaoHt > + 3CyHhyc! ° ‘O-Na CH—0—C— C,H, a trighceride ~an ester Propane-L23tiol sodium of long-chain carboxylic {elycerol) octadecanoate acids and atid (sodium stearate) fig An example of sponfemon In this example, hycrolysis produces an alcohol with three hydroxyl groups (glycerol). Glycerol has many uses, including as a sweetener in foods and toothpastes, and in skin care products, It is now also being used as a component of the liquid in electronic cigarestes. The other product ofthis reaction, commonly known as sodium stearate, isa very common ingredient of most soaps. earning tip ‘Acidic hydrolysis ofan ester is a reversible reaction, but alkaline hydrolysis reactions goto completion. 1 whatare the names ofthese estes? (a) CH,CH.COOCH,CH.CH; {b) (CH,),CHCOOCH; 2. ee equations forthe hdl of prop! blanca {a) acidic conditions (b) alkaline conditions. Key definition Hydrolysis isthe breaking of a compound by water into two compounds. 189Polyesters By the end of this section, you should be able to.. © understand how polyesters are formed by condensation polymerisation reactions 190 Addition polymerisation Examples of addition polymerisation were covered in Book 1, so may be wef to remind you ofthis type of pokmerstion. The monomer ropene can combine wth many thousends of otter propene tolecues to forma very long chain, This process can be represented a iF a (One thing to notice is that all of the atoms in the monomer molecules end up in the structure of the polymer fig A Thisequaton represents the polymerisation of propene. Condensation polymerisation ‘There are two main dferencesbetween ition pymerisstion and condensation polymerisation. In condensation polymerisation + each time to monomer molectes join together another small molecule is formed + usualy two diferent monomers eact together In mary examples of condensation polymerisation, the smal molecle formed is water wich the origin of the term ‘condensation’. In other examples, the small molecule formed is hydragen chloride. ‘but the term ‘condensation’ stil used to describe thse examples. (One type of polymer formed in this way is a polyamide, which we will meet in Seetion 17.5.4 Polyesters ‘The example we will use to introduce condensation polymerisation isthe formation of polyesters ‘You will remember that esters are the products of the reaction between alcohols and carboxylic acids, However once one molecule of an alcohol has reacted with one molecule of a carboxylic acid, the reaction is complete. The only organic producti a slightly lager ester molecule Fora reaction to produce a polymer, we need two monomers, each with two reactive groups at either tend, The alcohol usually involved inthis type of reaction, more accurately called a ‘dil’ has two hydroxy] groups, one at each end: H—O—CH>—CH;-O—H One of the most common carboxylic acids used, more accurately a dicarboxylic acid, has the structure below. The common name for this compound is terephthalic aca. H-o—¢: C—O I °0 Consider how these molecules react together The OH of the carboxylic acid and the H of the alcohol react together to form the small molecule, water, and the two molecules are linked together by an ester group. This equation shows what happens during the formation of a typical polyester iG O}- D 0n cco + HOO é 6 —O—CH—CH—O—H This larger molecule that has formed still has reactive groups at both ends, so it can continue reacting with ather molecules in the same way as abave, until a very long polymer chain has formed, The structure of the polymer is: ‘O—C- QO ‘C—O—CH;—CH;—O- rw ° ° Because of the original name of the acid (terephthalic acid), the polymer wi Terylene, ras originally known as Polyesters have a very wide range of uses, including soft drink bottle, food packaging, many types of clothing, and duver filings [cis also possible 1o use a dioyl chloride instead of a dicarboxylic acid, although this is not used as a monomer in industry The reaction occurs in the same way — the only diference is that the small ‘molecule formed is hyéragen chloride, not water. \When showing how a polyester forms, cemember that in the formation ofthe small molecule the H comes from the diol, and the OH from the dicarbowylc acid (or the Cl from the dioy chloride) 1 whyis trot posible to mate a polmer by reacting together molecils of HOOCCH,COOM and chow 2 raw the repeat unit the polymer forme benween molecules of HOOCCOCH and CHLCHOHICHONICH, Keydefinition ‘Condensation polymerisation refers tothe formation ofa polymer, usually bythe reaction of two diferent monomers, and in which a small molecule is also formed. 191Benzene - a molecule with two models By the end ofthis section, you should be able to... ‘© understand that the bonding in benzene has been represented using the Kekulé and the delocalised model, the latter in terms of overlap of p-orbitals to form pi (x) bonds @ understand that evidence for the delocalised model of the bonding in benzene is provided by data from enthalpy changes of hydrogenation and carbon-carbon bond lengths ‘© understand why benzene is resistant to bromination, compared with alkenes, in terms of delocalisation of x-bonds in benzene and the localised electron density of the x-bond in alkenes What are aromatic compounds? ‘The sections in Chapter 17.4 deal with compounds containing a benzene ring. You have already met berwene rings in previous sections, but no detal was given about them. For example, in Section 17.2.3 on carbony! compounds, there was a reaction involving 2,4-dinitrophenylhydrazine, which contains « benzene ring In Seetion 173.5 on carboxylic acas, one of the monomers used to make polyesters as terephthalic acid which also contains a benzene ring Origin of the term You know that the word ‘aromatic’ in everyday language refers to smells usualy pleasant. Some herbs used in cooking are often described as aromatic. The word smellis a neutral word, but when you replace itby aroma it implies that the smells pleasant. On the other hand, if you replace it by odour it implies thatthe smell is unpleasant Think of the aroma of perfume, and the odour of unwashed socks! ‘ Pi Aliphatic and aromatic fig Many orightycoloued dyes drermade trom aromatic compounds With a few exceptions, almost all the organic compounds you have ret so far in this course could have been described as ‘aliphatic’, although this isa term we did not use to describe them because ‘there was no point, You can regard aliphatic compounds as all those that are not aromatic! Benzene ‘The compound benzene is atthe heart of every aromatic compound, so the first thing we must do is understand what is special about benzene, Benzene can be described as an arene, as can many of its derivatives. You already know that -ene indicates, the presence of a C=C double bond in a molecule (as in ethene},so you would expect that an arene also cconlains C=C double bonds. The answer is ~ yes and na This obviously needs careful explanation! Physical properties of benzene Benzene is a colourless liquid with a boiling temperature of 80°C, and it is insoluble in water Itis, present in crude cil and the fuels obtained from itso the petrol tank of a car contains some benzene. ‘The one place you will not find i isin a school or college laboratory, because of its toxic nature: in particular, itis a carcinogen (ie. it can cause cancer, It was frst isolated by the English chemist Michael Faraday in 1625, Within a few years, the compound became known as benzene and its ‘molecular formula was established Ins molecular formula is CH, which suggests that itis highly unsaturated, because the alkane with six carbon atoms has 14 hydrogen atoms. Finding a structural formula to fir the molecular formula, ‘and which was supported by studies of its chemical reactions was a challenge for chemists. 192CO The Kekulé structure (One of the better own stories in the history of chemistry is how the German chemist Friedrich August Kekule came to suggest the structure of benzene that stl bears his name. The story goes ke this. Kekulé was dozing in font of a fie. Inte flames, he imagined some snake-lke molecules dancing, one of which held irs own call and whirled arcund in the lames. Inspired by this dream about snakes, in 1855 he proposed a cyclic or ring structure for benzene. Fig B shows the displayed and skeletal forms of this structure H Displayed Kehulé structure of benzene Skeletal cr Perhaps Kekulé was also influenced by Josef Loschmidt. who hhad suggested a ring structure for benzene a fev years earlier Loschmidt’s role in developing the structure of benzene is litte remembered, although you may remember his name from Book 1 1s the source of the symbol J. for the Avogadro constant. Problems with the Kekulé structure ‘We still use the original skeletal structure to represent benzene today. However, sce it was fist used, there has been mounting experimental evidence that does not fit with the structure. Several problems arose in the 19th century, although more became apparent in the 20th century. Problem 1 IF benzene contains three C=C double bonds, it should readily decolourise bromine water in an addition reaction, However, it does not decclourise bromine water When bromine does react vwith benzene, a substitution reaction occurs (see Section 17.4.2). ‘This evidence suggests that there are no C=C double bonds Fig C shows the results of shaking bromine water with a liquid alkane, benzene and a liquid alkene in separate test tubes. mom {ig € The yellow colour i caused by uveacted bromine Problem 2 As more compounds containing the benzene ring were discovered, including those such as dibromobenzene (C,H,Br,), another problem appeared. It the Kekulé structure is correct, there should be four isomers with this molecular formula Br Br Br Br : cr a Br Br fig These are the four somersofC.MyBr, assuming that the Kelulé structure However only three were known to exist. So, the two isorners with ‘bromine on adjacent carbon atoms are identical I is not the case that adjacent atoms in one isomer are joined by C—C and in the other by C=C. This suggests that the bonds between the carbon atoms in the benzene ring are the same, not different. Problem 3 ‘When data about the lengths of covalent bonds in molecules became availabe, there was another problem. Table A shows the bbond lengts in benzene and cyclohexene (a cyclic alkene with five ‘C—C single bonds and one C=C double bond) Bond (C-Cin cyclohexene v 134 139 ran (Cineycloherene Cinber rable A ‘This evidence suggests that the carbon-carbon bonds in benzene are all the same, and perhaps also intermediate in character between C—C and C=C bonds Problem 4 When data about enthalpy changes of hydrogenation became available, there was yet another problem. Table B shows these enthalpy changes for three relevant compounds, eer) Pree cycoheva-1.35-triene benzene (actual) table Al of these hydrogenation reactions form the cyclic allane cydlohexane. This evidence suggests the following + The first two values indicate that the enthalpy change for adding 1 molof H,to 1 mol of C=C bonds is around -120kJ mol! (che value for eyelohexa-1,4-diene ia double that of eyelohexene because there are twice as many C=C bonds} 193174 194 +The Kekulé structure could be named eyelohexa-1,3,5-trene, for which the value should be treble that of cyclohexene, + The actual benzene has a value very much lower (152J mol~ lower) than a theoretical structure with three C=C double bonds would have. ‘The values for cyclohexa-1.3,5-triene (theoretical) and benzene (actual) can be represented on an enthalpy level diagram. as shown below. Kekale’s benzene Expected AH = —360 KF mol Enhalpy ay! = —208 3 mo fig This diagram shows bw enthalpy changes or Kekules benzene and ea benzene Anew model for benzene ‘The weaknesses of the Kekulé structure and growing evidence ftom other areas of chernistry paved the way for a new model of benzene. In Book 1, we explained the C=C double bond in ethene in terms of single sigma C—C bonds and pi bonds formed by the sideways overlap of orbitals. Now consider the situation in benzene afterall the sigma (2) bonds have formed, Each carbon atom. ‘has one electron ina p-orbital. You can imagine the formation of three individual r-bonds, bur instead ‘imagine the formation of one large x-bond made up of all six eleccrons, Three are in a doughnut shape above the atoms and three are in another doughnut shape below the atoms, Together these six electrons form a delocalised «-bond, as shown in Fig F. fig F The deocalsed suvere of bervene foems when the p-orbials evelap sideways forming a r-eecton coud above ana eow the plane cf the carbon atoms Each carzon atom coninbutes one elemron tothe oul, ving a {elocalled apse of six electrons inital Problems solved? Let us see how this new model overcomes the problems associated with the Kelle structure. Problem 1 There are no individual C=C bonds, so there is no addition reaction with bromine. Problem 2. There are three, not four, isomers of C.H,Br, because when the bromine atoms are on adjacent carbon atoms there is no difference in the arrangement of electrons between these atoms. Problem 3 ‘The carbon-carbon bonds are all the same length because they are identical and are not individual C—C and C=C bonds Problem 4 When charge is spread around in a species, there is increased stability, which explains the 152KJ mol" greater stability of benzene compared to cydolexa-1.3.5-tiene.CO ‘The fact that benzene undergoes a substitution reaction with bromine to form C,H,Br, rather than addition to form C,H,Br,, can be explained because substitution preserves the stability of the delocalised electrons in the pi bond, The addition reaction would instead produce a compound with two C=C double bonds, and that would lack the extra stability of the product of the substitution reaction ‘Anew meaning of ‘aromatic’ Now we can use the old word ‘aromatic’ in a new way — it refers to a hydrocarbon ring containing ae delocalised electrons. The traditional skeletal formula for benzene can now be replaced by this: Leaming tip __ ‘When explaining the bonding = inabenzene molecule, be careful to avoid confusion, between electrons in p-orbitals and delocalised electrons in bonds. fig The cicle represents the delocalaed pibonds wth total 1 Using the Kelul stucture for benzene daw the iomersf tibromabenzene C8 2 How many econsina benzene molecule are inhi (@) a-bonding 0) = bonding? ‘The original meaning of aromatic was a description of the smell of certain organic compounds. ‘The new meaning of aromatic isa description of the bonding in a compound - delocalised electrons forming pi (x) bonding in a hydrocarbon ring 195Some reactions of benzene By the end of this section, you should be able to.. ‘© understand the reactions of benzene with: (i) oxygen in air (combustion with a smoky flame) (i) bromine, in the presence ofa catalyst a misture of concentrated nitric and suifuric acids (iv) halogenoalkanes and acyl chlorides with aluminium chloride as catalyst (Friedel-Crafts reaction) Reactions as a hydrocarbon In Seeton 17.4.1, ycrogenation vas mentioned This reaction occusin the sare way mth benzene 2s with alenes. The same's the for combustion Hydrogenation “This is done by mixing benzene with hydrogen and heating under pressure with a nickel catalyst. The equation for the reaction can, be shown using molecular or skeletal formulae Cole + 3H — Cota _9O-*-9 Note the plain hexagon (without a circle) used for the skeletal formula for cyclohexane. Combustion As with al ydrocasbons, benzene burs in aig ltough wih a senoky flame. Thisis peal of mary compounds witha high carbon hyde elo The equation for compete combustion Cyt, + 740, = CO, + 3H,0 Reactions as an arene ‘The most important reactions of benzene are substitution reactions, in which the products are also aromatic. We will consider the mechanisms of these reactions in the next section (Section 17.4.3). Learpingtip Bromination refers to putting bromine into’a molecule, This could be by an addition reaction, but inthis section it refers only to a substitution reaction, 196 Bromination ‘The term ‘bromination’ is ambiguous. It could refer to the addition reaction between benzene and bromine, This reaction does ‘occur in the presence of ultraviolet radiation, but itis of litle Jmportance. In this book, the term refers to a substitution reaction, ‘Benzene and bromine are heated under reflux, in the presence of a calalyst called a halogen carrier. Halogen carriers ae usually ‘metal-halogen compounds such as aluminium chloride, aluminium, bromide or iron(II) bromide, Far bromination, tis enough to ‘add iron filings because they react with some of the brornine 10 form iron(II!) bromide. The products are bromebenzene and Iydrogen bromide. The equation for the reaction is: » Nitration ‘This refers to the substitution of a hydrogen atom by a ito ‘group. The nitro group has the formula NO; and should not be ‘confused with the gas nitragen dioxide. The reaction is cartied out by warming benzene with a mixture of concentrated nitric and sulfuric acids. The nitric acid can be considered as the source of the NO, group and the sulfuric acid as @ catalyst. The products are nitrobenzene and water ‘The equation for the reaction is No, HSO, + HNO, + + HO Friedel-Crafts reactions Reactions with this name were developed by Charles Friedel (a French chemist) and James Crafts (an American chemist) ‘There are several types of reaction bearing their names, but We vil consider only two of them: alkylation and acylation. They both have these features in common: ‘+ using a reagent represented by XY, one of the hydrogen atoms in benzene is substituted by Y, and the other product is HX. + a catalyst is needed ~ often aluminium chloride, although other halogen carriers such as iron(ll) chloride and iron({ll) bromide also work + anhydrous conditions are needed because water would react ‘with the catalyst and sometimes also with the organic product,Friedel-Crafts alkylation reactions Alkylation means the substitution of one of the hydrogen atoms of benzene by an alkyl group. The reagent is a halogenoalkane, and the products are an alkylbenzene (methylbenzene) and hydrogen chloride, The equation forthe reaction with chloromethane is: Friedel-Crafts acylation reactions Acylation means the subatitution of one of the hydregen atoms in benzene by an acyl group The reagent isan acyl chloride, and the products are a ketone (phenylethanone) and hydrogen chloride ‘The equation for the reaction with ethanoyl chloride is S cocH, [O) + cxcoa “(CO + Hel NN Naming aromatic compounds The rules for naming aromatic compounds are similar to those used for aliphatic compounds Prefixes, locants, hyphens and commas, and multiplying prefixes are used in the same way. In some ‘names, you will see ‘phen’ or ‘phenyl’ used to represent the benzene ring vihen itis attached to ‘another functional group. For example, che organic product of the last reaction is phenylethanone: ‘ethan’ refers to the two carbon atoms in CH,CO, ‘one’ indicates that the compound is a ketone and jphenyl' refers to the CyHs group. You might expect ‘benzyl to be used rather than ‘phenyl’, but itis snot. The explanation for ths is beyond the scope of this book. fig. A Shoe polish ip one ofthe 1 Write an equation for the reaction between benzene and 2-bromopropane. 2 whatisthe name ol the ganic produc ormed in the ection between benzene ad butanol ‘horde? ‘Keydefinition 0 A halogen carviersa catalyst that helps to introduce a halogen atom into a benzene ting 197Electrophilic substitution mechanisms By the end of this section, you should be able to.. © understand the mechanism of the electrophilic substitution reactions of benzene (halogenation, nitration and Friedel- Crafts reactions. including the generation of the eletrophile Electrophilic substitution Ahough you have not met hs mechanism sofa you have leamed the meaning of exch word The reaction bebween methane and chlorine inthe presence of ultviolt radiation isn txample of radical sustution. The reaction beoween ethene and bromine isan example of electrophic addition (Once you understand the meaning of each word, itis not a big, step to understand the meaning of electrophilic substitution. Before we consider the mechanisms of the individual reactions, it is worth considering what they al have in common: + The benzene ring is electron-rich. Although its electrically neutral, the delocalised electrons in the pi (r} bond above and ‘below the atoms mean that the molecule attracts electrophiles ~ species attracted to negative charge, + Using ¥" to represent the electrophil, as Y* approaches the delocalised x-bond, it attracts two of the six electrons. waich form a covalent bond wit i. This gives an intermediate species with a positive charge (shown by convention in the centre of the hexagon), in which one carbon atom is joined to both Y and H. Thete are now only four delocalised electrons, and these are represented by two-thirds of a circle + This intermediate species lacks the stability of an aromatic ccornpound (because the cir is broken), so in the next step the Hleaves as H! and the two electrons in the C—H bond join the remaining four to restore the delacalised r-bond (with its relatively high stability) When drawing these mechanisms, or skeletal formulae, a substituent on the benzene ring can be showin in any of the six positions Iris usually shawn at the cop of the hexagon or the next position clockwise. ‘To help you see the similarities and differences in these mechanisms, they are all set out in the same way. Bromination Step 1: formation of the electrophile Bromine reacts with the catalyst to form Br AIC, + B= Bro + AICLB 198 ‘Step 2: electrophilic attack Pe [Note thatthe H atom shown inthe product ofthis step is already present in benzene, although its not shown. It is shown here because it wil be let in Step 3 ‘Step 3: formation of the aromatic product or _ (or: a Step 4: formation ofthe inorganie products AICLBr +H — AIC), + HBr Nitration ‘Step |: formation of the electrophile Nitric acid and sulfuric acid react to form NO,* (the nitryl ion or nitronium ion}: HINO, + H,SO, + NO;* + HSO" + H.0 ‘Step 2: electrophilic attack . ‘Step 3: formation of the aromatic product NO, No, or oy a ‘Step 4: formation of the inorganic products HSO; + H* > H,S0, Alkylation ‘Step 1: formation of the electrophile lloromethane reacts with the catalyst to form CH," AIC, + CHsCl —> CHS* + AICI Step 2: electrophilic attack cH, cH, HCO ‘Step 3: formation of the aromatic product Nt cH, op _ + oH Ne Step 4: formation of the inorganic products Aldl: +H’ — AICI, + HCL Acylation Step 1: formation of the electrophile Ethanoyl chloride reacts with the catalyst to form CH:CO" AIC), + CH,COC CH,CO” + AIC” Step 2: electrophilic attack OP ‘Step 3: formation of the aromatic product oer Cy formation of the inorganic products AIC +H AlCl, + Hel Step Note the similarities between all these mechanisms. The first tep involves formation ofthe elecrophile, and the last step shows what happens tothe replaced Ht. The second and third steps show the actual substitution in the benzene ring. 11 Write an equation for Step 1 in the bromination reaction in which the halogen carriers irontll) bromide. 2. Write equations for Steps 2 and 3 in the alkylation reaction using 1-bromopropane asa starting materia 199By the end of this section, you should be able to.. ‘@ understand the reaction of phenol with bromine water ‘@ understand reasons for the relative ease of bromination of phenol compared with benzene 200 What is phenol? Most aromatic compounds have a benzene ring and an aliphatic par. In previous sections ofthis topic you have covered some important reactions ofthe benzene ing, You know many oF the reactions of aiphatic compounds ftom eater chapters nd ffom Book 1. inthis section, we il look a one more aromatic compound tha fami aliphatic group the byron (OH) gous Phenol consis ofa hyroxs group joined to a benzene rng It has some properties similar to an aliphatic slconel such as ethanol and you would expect it to undergo elecroph substition reactions because it contains abenzee ring is structures OH Bromination of phenol You wil eamember fom Seetion 17.4.2 that benzene undergoes bromination, bt he reaction neds a caclyst andthe reaction miztre has tobe eated under refx. In contrast, the bromination of hen! occurs at oom tempereture without a erly, and worts With bromine water The bromine Wateris decoloursed during the reaction. and ine organic produc forms asa white precitate The tsuaton forthe reaction is on oH Br Br + 3B, — + SHBr Br Another obvious difference between benzene and phenol is that the substitution reaction accurs three times, as there are three bromine atoms in the organic product. You can probably see why the ‘name is 2,46-tribromiophenol. The carbon joined to OH is carbon 1, the other carbons are numbered clockwise, and the three bromine atoms are joined to carbons 2, 4 and 6 in the ring. Inis beyond the scope of this book to try to explain why the reaction involves substitution by three bromine atoms and not any other number However we can try to explain why the reaction occurs ‘much more readily with phenol than with benzene: + The oxygen in the OH group has lone pairs of electrons, and these electrons can merge with the clectrons in the delocalised pi (x) bond, + The eleccron density above and below the ring of atoms is increased, a process sometimes referted to as ‘activation’ because the molecule is now much more reactive towards electrophiles, + Bromine molecules, although originally non-polar, are polarised as they approach the benzene ting, Eventually, the Br—Br bond breaks and the Br' electrophile attacks the benzene ring,Fig A shows how the delocalised electrons in the x-bond change because of the presence of the oxygen. q q fgA Treclecrons inthe porta of th oxygen atom became pat ofthe delocalized eecron eye THsincrese elecron deny above and below te rig and makes he molecule mote stactve 19 eectrop ies such 2 Br Uses of phenol and its derivatives One of the earliest and best known uses of phenol was in antiseptic surgery, especially by the surgeon Joseph Lister Since then, other antiseptics have been developed from phenol. One of the ‘most familiar of these is the product of the chlorination of phenol - this is 24.6-tichlorophencl better known as the antiseptic TCP Nowadays, phenol is widely used in many industries, notably in the manufacture of polymers and pharmaceuticals. Phenolphthalein You will remember ths substance as an indicator in acid-base trations, and will not be surprised to learn that it contains a benzene ting joined to.a hydroxyl group! Although you do not need to know its structure, notice that its colour change invelves a change inthe structure of phenol HO An ° Ay 0 SAAS +20H Ch. SS — MgB Fae: bce on pened ee: 2H CL 6 rae orvening ged 4 of ‘COO Be careful to distinguish colourless pink between the use of benz and ‘phen’ in organic names. In ‘general, benz’ comes after the The colourless form is a molecule with three benzene rings and two OH groups, while the pink form ther groups inthe molecule, ig an ion with no OH groups and two benzene rings. 1 suggest why phenclisaslld at oom temperature and sgt soluble ln wate fig € The phenclphth fsa change inthe suctue ef phone! 2 wte an equation forthe formation oF TCP from phenol 201Amines and their preparations By the end of this section, you should be able to.. @ identify the amine functional group © understand, in terms of reagents and general reaction conditions, the preparation of primary aliphatic amines: (0) from halogenoalkanes by the reduction of nitriles @ understand that aromatic nitro-compounds can be reduced, using tin and concentrated hydrachloric acid, o form amines Introduction to amines ‘These nitrogen-containing compounds have some similarities with ammonia. The three bonding pairs of electrons around nitrogen are distributed in a trigonal pyramidal shape. The nitrogen atom hhas alone pair of electrons and three bonds to one or more alkyl groups. If there is one alkyl group, the amine is classed as primary if there are two, then itis secondary, and with three itis tertiary Fig A shows the structures of the simplest amine in each of these classes. AN AN AK HOCH, CHE YH, CH GAN CH, fig A Those ate te simplest example af pray secondary an teary amines In this book we will focus on primary amines. Methylamine is a gas at room temperature, ethylamine has a boiling temperature of 17°C, and propylamine and butylamine are volatile liquids. This list of ames shows the naming system used ~ the suffix is -anvine and the usual codes methyl, ethyl, propyl butyl ete. are used. ‘We will also meet the simplest aromatic amine, CjH,NH., which is phenylamine. ‘Amines occur widely in nature and many drugs (bath legal and illegal) are amines, inchuding the ‘group of compounds called amphetamines. Preparation of aliphatic amines “Ther are two main ways of making primary aliphatic amines, starting rom halogenoalkanes or rom nites, aT Preparation from halogenoalkanes cnisinamaes Although you do not need to know the mechanisms of these reactions a reference to the mechanism will help you understand why certain reaction conditions are needed. The method involves heating a halogenoalkane with ammonia, Because ammonia is @ gas, this must be done under pressure andl ina sealed container Alternatively, the halogencalkane can be mixed with concentrated aqueus ‘ammonia, The equation forthe preparation of methylamine is: CHC + NH, + CH.NH, + HCI ‘The reaction involves nucleophilic attack by the lone pair of electrons of ammonia on the electron deficient carbon atom in the halogenoalkane. Notice that the amine formed also has a nitrogen atom containing a lone pair of electrons. This means that it could also act as a nucleophile, competing ‘with ammonia inthe attack on the halogencalkane. This would result in the reaction: CH.CI+ CHNH, + (CHL):NH + HCL ‘The product of this reaction is a secondary amine, inthis case dimethylamine, 202‘To prevent such unwanted side-reactions occurting, or at least reduce the chances of them ‘happening, the ammonia is used in excess, so that it outnumbers the molecules of primary amine formed, Some of the excess ammonia reacts with the acidic hydrogen chloride formed, so a better ‘equation to represent the preparation is: CHCl + 2NH, — CH,NH, + NH,Cl Preparation from nitriles Nites can be reduced to primary amines by reduction, using the reducing agent lithium hydrochloric tetrahydridoaluminate, which you may temember from Seetion 17.2.2 can also be used to reduce carbonyl compounds. As before, the reactants are mixed in dry ether, to ensure that there is no water water out that could affect the reaction, The equation for the reduction of ethanenitie is: CH,CN + 4[H] — CH;CHNH; [H] represents hydrogen atoms produced by the reagent in a way that you de not need to know. Preparation of aromatic amines specific method is used to prepare aromatic amines, expecially phenylamine, which is made by veces the reduction of nitrobenzene. In this method, the reducing agent isin mixed with concentrated Dydrochlovic aci, andthe reaction mixture is heated under refux. The reduction is achieved parlly through the oxidation of tin to tn(l) ions and tin(IV) ions, and partly through the hydrogen produced, inthe reaction between tin and the acid. For simplicity, we wil represent the reducing agent by [H._"wovereene— ‘The equation forthe reaction is te CeH.NO, + 6(H] —> CeH:NH, + 2H,0 B rec: As with other amines, pheenylamine is basic and will react with the acid present to form the {© Aoparatusstable for phenylammonium ion, but this can easily be converted into phenylarnine by adding an alkali such as spmvertngnizober sodium hydroxide sclution ine CAH.NH,* + OH" C.HNH, +H, [nthe 19th century, phenylamine was called aniline, and was the source of large numbers of dyes used mainly for clothing. Itis stil used in the manufacture of synthetic indigo, most familiar as the colour of blue cenim jeans. Nowadays, much phenylamine is used in the manufacture of polymers and pharmaceuticals, Learningtip Note that in the name used fora nitrile, the code indicating the number of carbon atoms includes the Cin the CN group, so CH.CH.CH.CN is butanenitrle, not propanenitil, 1 rte an equation ote preparation of propyamine sang om (a) ahalogenclane (b) a nitrile 2. Explain why another organic product would be formed in 1(a) i the two reactants were used in a 1:1 ratio. 203,Acid-base reactions of amines By the end of this section, you should be able to.. ‘© understand the reactions of primary aliphatic amines, using butylamine as an example, with {i) water to form an alkaline solution (i) acids to form salts ‘© understand reasons for the difference in basicity of ammonia, primary aliphatic and primary ‘aromatic amines given suitable data Reactions with water ‘The first few members of the homologous series of primary aliphatic amines are completely miscible (capable of mixing) with water, although as the hydrocarbon part of the moleeule becomes proportionately larger, the solubility decreases, ‘They dissolve in water because they can form hyclagen bonds with water molecuies (se fig A) Phenylamine is only slightly soluble in water ‘As well as dissolving in water, amines also react slighty with water to form alkaline solutions ‘Compare the equations using methylamine and ammonia: CH.NH, +H, = CH,NH.* + OH NH, + H,0 = NH, + OH cchonurn-howsine ‘You can see the similarity ~ this is because the ritrogen atom in both molecules can use it lone pair Fe A cee oftncropen bonds of electrons ro form a dative bond with the hydrogen of a water malecule. The cation in the fist meena piinaryarinesré equation i the methylammonium ion ~ think of it as an ammonium fon in which one hydrogen has water been replaced by a methyl group. So, how do amines and ammonia compare as bases? Whats the position of equilbrium in these reactions? ‘Comparing basicities ‘The basicity (basic strength] of a base can be quantified using the constant &, or the constant p&,. ‘The pk, of water is 7.00, and any value greater than 7.00 indicates a basicity greater than that of water: Water is equally good as a base and as an acid. Table A shows values for aramonia and some ammonia NH, 9.30 methylamine CH.NA, 10.64 ethylarine CHACH.NH, 1073 propylamine CH.CH.CH.NH: 1084 phenylamine CoHsNHs 462 table A ‘What these values show is that methylamine is a stronger base than ammonia, and that extending the hydrocarbon chain causes further, but smaller, increases in basicity. Phenylamine is a much weaker base than any of the aliphatic amines, and is a weaker base than even water Methylamine is a stronger base than ammonia because the methyl group is electron-releasing, and so thas an increased electron density on nitrogen compared with ammonia, The ethyl and propyl groups are only slightly more electron-releasing than methyl, so their effects are very similar Fig B shows the situation 2048 o- o- CH= NH, = CHLCH—=NH, —CH,CH,CH NH, figB Thedagar ‘The equation forthe reaction of butylamine with water is CH.CH,CH,CH,NH, + H,0 == CH,CH,CH,CH,NH,* + OH The situation with phenylamine is very different. Think back to the diagram in Seetion 17.4.4 showing that in phenol the lone pairs of electrons on axygen are attracted to the delocalised electrons in the pi bond. A similar thing happens with phenylamine, and this makes the nitrogen less ‘electron-rich and the lone pair of electrons less available for donating to the hydrogen of a water ‘molecule. Fig C shows how the delocalised electrons now extend above and below the nitrogen, So, as the original lone pair of electrons on nitrogen is now part of the delocalised system, itis less available for bonding to the hydrogen of a water molecule Jone pair pow delocalized vith he rng electrons fig The eiecrons hom te lone par on the nivoge Reactions with acids Even though the amines vary in their basicity, they all react with strong acids to form ionic salts. ‘Sample equations are: CH.NH, + HNO; » CH.NH,* + NO, methylamine ‘methylammonium nitrate (CH,CH,CH,CH,NH, + HCL = CH,CH,CH,CH,NH,* + Clr butylamine butylammonium chloride Note the big difference in basicity between aliphatic amines and aromatic amines, and the all dliflerences in basicity between different aliphatic amines. 1 team equation forthe reaction of etylamine wth (a) water (b) sulfuric acid. 2. Predict, with a reason, whether dimethylanine has a lower or higher basicity than methylamine. Key definition ‘The basicity ofa bases the extent to which it can donate. lone pair of electrons to the hydrogen atom of water molecule. 205,Other reactions of amines By the end of this section, you should be able to.. ‘© understand the reactions of primary aliphatic amines, using butylamine as an example, with: (i) ethanoyl chloride (i) halogenoalkanes copper) ions to form complex ions Reactions with ethanoyl chloride Although you do not need to know the mechanisms of these reactions, the name of the mechanism will help you understand how the reaetions aceur The reaction type is addition-elimination, which means that the wo molecules join together, and then a small molecule is eliminated ~ in these examples, hydrogen chloride. The organic product contains a new functional group ~ amide in which a carbonyl group is next to a NH group. The equation for the reaction between ethanoyl chloride and btyamine i oe & - cic + SNencricH er, —> ci—c@ +H ca N—CH,CH,CH CH HW” Oo ‘We will meet amides in a later section, but we can introduce the naming system here. The most common mice is ethanamide, and the product of the above reaction can be thought of as the result of replacing one of the hydrogens in the NH, group by the butyl group. Its name contains two words the first isthe alky! group from the amine and the second indicates the number of carbon ators in the original acyl chloride. As the butyl group is attached via a nitrogen atom, N is used as the locant ‘The name is N-butylethanamide Paracetamol ‘This is one of the commonest pharmaceuticals used to relieve the symptoms of fever and pain, It is manufactured in a sequence of reactions, one of which is an addition-elimination reaction Its structure is N OH ‘You can see how paracetamol go its name. The ‘paral part indicates thatthe two groups attached to the benzene ring are at opposite ends of the ring The acetam’ part comes fom the old name for ethanamide, which used to be called acetamide. Finally, the ‘ot par indicates the prosonce af a hydroxy] group Reactions with halogenoalkanes [Although you do aot need to low the mechanisms of these reactions, you can see thatthe to ‘would react together because a halogencalkane contains an electron-defcient carbon atom and An amine contains an electron-rich nitrogen atom. Using general formulae, the reaction can be represented as RyNH, + RX — RINHR + HX 206‘where R; is the alky! group in the amine and R, isthe aryl group in the halogenoalkane. The reaction is another example of substitution. The organie product is a secondary amine and the inorganic productis a hydrogen halide, often hydrogen chloride {An example equation using butylamine and chloraethane is (CH,CH,CH,CH,NH, + CH,CH,Cl + CH,CH,CH,CH,NHCH,CH, + HCL Notice that the organic product also contains an electron-rich nitrogen atom, so it can also react with cchloroethane. The equation for this further reaction is: (CH,CH,CH,CH,NHCH,CH, + CH,CH,CI > CH,CH;CH,CH:N(CH,CH,). + HC) ‘The organic product ofthis reaction isa tertiary amine. ‘Once again, the tertiary amine contains a nitrogen atorn with a lone pair of electrons, which can also react with the halogenoalkanes. The equation for this further reaction is: (CH.CH,CH,CH,N(CH,CH,), + CH,CH,CI -> CH,CH,CH,CH.N*(CH,CH,); + Cl Note that the equation is different this time ~ HCl is not formed because this would require the loss Of H from the nitrogen of the organic reactant, which a tertiary amine does not have. The product is an ianie compound related to ammonium chloride (NH,* + Cl) except that all the hydrogens in the ‘ammonium ion have been replaced by alkyl groups. Its known as a quaternary ammonium salt, Reaction with halogenoalkanes does not seem to be a good method of preparation, as it is likely that ‘a mixture of similar products will be formed. If there is an excess of the halogenoalkane, then the sequence of all four reactions is mare likely to occur Producing a quaternary ammonium salt in this sequence is wnat happens in industry. These compounds have many uses, and are usually found in fabric softeners, Reactions with copper(II) ions You will remember fom Topie 15 that ammonia can act as ane pir donor in ts reactions with trandtion metal ons This the overall equation forts reaction wih hexaaquacopper(} ions [Cu(H,O),)* + ANH, — (Cu(NH,)}.H0),)* + 4H,0 ‘Amines also have a lone pair of electrons on nitrogen, so can take part in similar reactions. The ‘observations are the same as with ammonia ~ first of alla pale blue precipitate forms, then with excess butylamine, the precipitate dissolves to give a deep blue solution. The equations for these reactions look. complicated, but the only difference is the use of CH,CH,CH,CH,NH, in place of NH,, Formation of the pale blue precipitate: [Cu(H,0),}* + 2CHyCH,CH,CH.NH, —+ [Cu(H,0) (OH), + 2CH,CH,CH,CH,NH,* Formation of the deep blue solution: [CU(H,0)(OH),) + 4CH,CH.CH,CH,NH, — [Cu(CH.CH,CH,CH,NH,),(H,0),F* + 2H,0 + 20H) 11 rte an equation forthe reaction besweenpropanoy| chloride and propylamine 2. raw he srucrure of the qunersry ammonia sale formed when ein ese wth 1-bromopropane Keydefinition ‘An addltion-elimination reaction occurs when two molecules join together, followed by the loss of a small molecule Leamingtip __ Be careful nt to confuse amines, ammines and amides, all of which appear inthis sedtion 207Amides and polyamides By the end of this section, you should be able to. © identify the amide functional group ‘© understand that amides can be prepared from acyl chlorides ‘© know that the formation ofa polyamide isa condensation-polymerisation reaction © draw the structural formulae of the repeat units of condensation polymers formed by reactions between dicarboxylic acids and diamines Amides ‘We met amides in previous sections as the products of reactions. Amides have a funetional group consisting of a carbonyl group joined to an amino group g Nw, As with otter compounds in which two functional groups share the same carbon, amides have properties that are different from both carbonyl compounds and amines. They are solids (except for methanamide, which isa liquid) and the lower aliphatic amides are soluble in water because they Contain two electronegative atoms and polar bonds and so can forrn hydrogen bonds with water The carbon atom is very electron-deficient because it is joined to both nitrogen and oxygen Preparation of amides ‘A convenient way to prepare amides in the laboratory is by mixing an acyl chloride with concentrated aqueous ammonia. Although you do not need to know the mechanisms of these reactions, it helps to understand the reaction if we refer to the mechanism, The lone pat of electrons on the nitrogen ofthe ammonia molecule is strongly altracted tothe electron deficient carbon ator of the acyl chloride. The chlorine of acyl chloride combines with one of the hydrogen atoms of ammonia to form hydrogen chloride, which appears as misty fumes. The equation for the reaction between propanoy! chloride and ammonia is CH,CH,COCI + NH, ~ CH,CH,CONH, + HCl [Note that ammonia is basic and that the inorganic products acidic, so there willbe a reaction between the two molecules: NH, + HCl NH,Cl So, an alternative equation forthe rection, combining these equations is CH,CH,COC! + 2NH, ~ CH,CH.CONH, + NH,Cl Polyamides eaming tip In Section 17.3.5, ve leamed about polyesters as examples of polymers formed by condensation polymerisation reactions, The formation of these polymers needs two monomers a dicarboxylic acid aerate molecule 1a diol. The formation of polyamides also needs two monomers ~ a dicarboxylic acid and a diamine. formed isuater (fa The simplest examples of a dicarboxylic acid and a diamine are HOCCCOOH and H,NCH.NH, dicarboxylic acid sused) or You can see how these molecules can react together ~ one has acidic groups and the ether has basic tyydrogen chloride (#adioyl_—— groups, so they can react with each other to form @ CONH group withthe elimination of HO. chloride is used), 208Nylon Nylonis almost certainly the most familiar example of a polyamide. Both of the monomers used in the production of its mast common form contain six carbon atoms. Common examples of these monomers are hexanedicie acid (known as adipic acid in the polymer industry) and hexane-1,6-diamine (also known as 1.6-diaminohexane). What both of these monomers have in ‘common isa number of CH, groups with reactive groups at each end of the chain. The formation of this polymer is shown below ° Tan t i a + 2 HLN(CH).NH, —* -C—(CH—C—N—(CHJ—N: HO’ ‘oH Bano ft " hewanedioic acid ——_1.6-dlaminohexane nylon 66 There are diferent types of nylon, and this example is described as nylon 66 because both of the "EA Micon aerclamade/ror monomers contain six carbon atoms Kevlar? If benzene rings take the place of the CH, groups in the monomers used to make nylon 6 6, and a dioyl chloride is used in place of a dicarboxylic acid, chen the monomers and the polymer structure ‘can be shown like this K \ ono. N s\n” SOY n Sx-¢ wl xe 'e e.O*K, Me KOT, =n | a This polymer produced is lnown as Keviar®, and has very many uses, the most familar of which is as body armour (bullet-proof and stab-proof vests), However, the list of applications continues to {grow as a web search will reveal 1 wtetne veal equation for the fomation of thanamidefrom an acl chord, oN 2. Write an equation for the formation of Kevlar® starting from a diamine and a dicarboxylic acd. 209Amino acids By the end ofthis section, you should be able to... © identify molecules that are amino acids ‘© draw the structural formulae of the repeat units of condensation polymers formed by reactions between amino acids © understand the properties of 2-amino acids, including {i) acidity and basicity in solution, asa result of the formation of awitterions (i) effect of aqueous solutions on plane-polarised monochromatic light What are amino acids? ‘The name suggests the presence of an amino group and a carboxylic acid group. Unlike amides, these two groups are separated by a carban atom and so rerain most of their typical properties Below is the general displayed formula of an amino acid. H i, ° \_/ yk wt Non ‘When R (the symbol for an alkyl group) is only a hydrogen, the amino acid isthe simplest one, alycine, Over 20 amino acids are found in humans. Some of these are synthesised in the body, and others must be included in the diet. Proteins are made from amino acids, and these will be considered in the next section. Although R is normally used to represent an alkyl group in the case of amino acids it can represent a more complex structure, Table A shows information about some important amino acids. Structure alanine ala H.N—CH—COOH 60 bu, cysteine oF H.N—CH—COOH 31 busi guameacd | gle HN—CH—cooH 2 cH,—cH, coon slveine ey HN—CH,—cOoH 60 lysine ys. H,N—CH—COOH 97 I CH,—CH,—CH.—Cct table A ‘Amino acids are often referred to as 2-amino acids because the NH, is attached to the second carbon atom in the chain, counting the C in COOH as carbon 1. Note that most amino acids have fone NH; group and one COOH group, although some have two of one and one of the other 210Acidic and basic properties ‘The values of the isoelectric points of the amino acids have been included to help you understand thir aid-base character ‘They are all soluble n water and you can imagine that one of 190 reactions might occur The molecule could act asa base and form in alaine soliton n reaction ike this: H,N—CHR—COOH + H,0 = H,N’—CHR—COOH + OH Alternatively, it could act as an acid and form an acidic solution in a reaction ike this H,N—CHR—COOH + H,0 = H.N—CHR—COO™ + H,0° ‘There isa third alternative ~ an H* jon could transfer fiom the COOH group to the NH, group in a reaction lke this: H.N—CHR—COOH = H,N'—cHR—COo ‘The product of this reaction is electricaly neutral because it has « positive charge and a negative charge that balance each other. Such species are called zwitterions. Zniueris the German word for hybrid, meaning a cross between two things and having the ‘characteristics of both Now to the isoelectric point. This is the pH at which the zwitterion ‘oxists in aqueous solution, A low isoelectric point indicates that the molecule is predominantly acidic (glutamic acid has a value ‘of 3.2), while a high value indicates thar itis predominantly basic (lysine has a value of 9.7). You can see that these values are related to the numbers of NH, and COOH groups in the molecule (glutamic acid has an extra carboxylic acid group and lysine has an extra amino graup), Salt formation Allamino acids ean form salts with acids and bases. For example alanine can reaet with acide Co form this protonated structure HN'—CH—COoH cH, Glutamic acid can react with sodium hydroxide to form three possible salts. This is because there are two COOH groups, so either of them can react, or both can react. One salt has the structure: H,N—CH—COO-Na* CH>—CH>—COOH You may have heard of this salt ~its name is monosodium {glutamate and js often used as a flavour enhancer in food Optical activity Almost all amino acids contain a chia centre the C ofthe CH group ane so are opially active. The exception svcne, ‘which has @ CH, group instead The enantome's rotate the plane of polarisation of polarised ight ~ some enantiomers are dextrorotatory (+) and others are laevorotatory (~). I? an amino acid is synthesised inthe labortory. en racemic mntre i formed Learningtip Practice writing equations for diferent amino acids to show how they can react as both acids and bases. aw the sreture of ying in a skin with (a) apH of 60 (0) averylow pl (€) avery high pH. 2 Draw structures to show how the two enantiomers of cysteine are related to each other. = ‘The isoelectric point of an amino acid isthe pH of an aqueous solution in which itis neutral ‘A.zwitterion isa molecule containing positive and negative charges but which has no overall charge 2Peptides and proteins By the end of this section, you should be able to.. © understand that the peptide bond in proteins: (i) isformed when amino acids combine by condensation polymerisation (i) can be hydrolysed to form the constituent amino acids, which can be separated by chromatography What is a peptide? When two amino acid molecules reac together, an acid-base reaction occurs. The OH ofthe COOH sreup combines wth one of the H ators of the NH, group to form water This a condensation reaction, in which the two amino acids are joined together by an amide group (CO—NH). The bond that forms is known as a peptide bond andthe organic product is acipenice More than one dipeptide ‘When two amino acids combine together to form a dipeptide, there are always two possiites sometimes more. For example, when glycine reacts with alanine, the OH could be lest from either molecule, as shown below. alanine + glycine H.N—CH—COOH + HN—cH, COOH —> H.N—CH—CO—NH—CH,—COOH + 1,0 cH, cH alycine + alanine H.N—CH.—COOH + H,N—CH—COOH —* H.N—CH,—CO—NH—CH—COOH + H,0 cH, cH, Tripeptides ‘When one molecule of each of three diferent amino acids reacts together to form a tripeptide, the sx possiblities can be summarised using the tireeletter abbreviations shown in the table in the previous section, They are: ala-cys-gluala-gl-cys —cysvalarglu — cys-gluvalaghivale-cysglu-cys-ala If you work out the possibilities in wihich two or more molecules of the same amino acid in these three react to form a wipeptide, you will find that there are many more! Polypeptides and proteins Most peptides in living things contain many tens of amino acids joined together, and there comes a ppoint where if the chain is very long the polypeptide is described as a protein. The main difference between a long-chain polypeptide and a protein is that proteins have further levels to their structures ‘These are to do-with the way in which the polypeptide chains interact with each other in three dimensions, to give secondary, tertiary and quaternary structures, but these are beyond the scope of this book 212re Analysing proteins Many proteins have very large molar masses and complex structures In recent decades, more and mote proteins have been analysed, As several milion different proce are thought to exis, cis work. is sll continuing but far rom complete, Table AA shows three examples of proteins, the fist two of ‘which have vital oles in the human bods. ren ae ns Greta neers insulin pancreas 5700 51 haemoglobin blood 56000 574 urease soya beans 480000 4500 table A ‘The first step in discovering the structure of a protein isto find which amino acids are present. The second is o find the order in which they occur in the polypeptide chains, Hydrolysing proteins ‘The polypeptide chains in a protein can be broken down into ther individual amino acids by prolonged heating with concentrated hydrochloric acid. This breaks the peptide bonds between the ‘amino acids, although because of the strongly acidic conditions all the amino acids formed will have their NH, groups protonated as “NH, groups. You can see tis process more easily inthe hydrolysis of a dipeptide. As an example, we wll use the dipeptide formed between alanine and gine referred to earlier in this section. The equation for this hydrolysis ix H.N—CH—CO—HN—CH, Coot +40 + att + ji —p—coott + 8c, coon cH, cH, ‘You can see that this hycolysis reaction is the reverse ofthe original dipeptide formation, except that the two NH, groups are protonated, which explains the inclusion of the two Hi ions in the equation, Using chromatography ‘The different ypes of cheomategraphy will be covered in later sections, but you already know about simple chromatography from your previous study of chemistry A mixture of amino acids produced by hydrolysis of a protein can be spotted onto chromatography paper Using a suitable solvent the individual amino acids wil rie to different heights during the experiment. As amino acids are colourless, the chromatogram can be sprayed with a developing agent so tha the positions of the amino acids can be seen, You may read about the use of ninhycin as a developing agent. Although this works wel is nat normally sed now because of is toxic nature However, once the positions of the amino acids have been established, their & values can be calculated and so the individual amino acids can be identified, Working out how they are all joined together is rather more complicated and beyond the scope of this book. Insulin isa protein with the molecular formula C,s,Hy.:NesO,yS,. [ts made up of a total of $1 amino acids, including 17 different ones. Is structure is shown in abbreviated form in fig A 213he y ate va a ee ce—s—s—es ey the Ku oe val ahr iu s sy Sade 7 ys fig A. Thisdiagam shows the sequence oF amino acid: in nsuln fom a sheop se tac there ave actualy 90 ‘sequences of amino acids in which cysteine molecues ae joined by sulfide b ‘Learning tip ‘Two posible dipeptides can form between two diferent amino acids. Fane or both ofthe amino acids hhas more than one NH, or COOH group, then more possible dipeptides can be formed, 1 wtethesructres of the wo dlpeptides formed when alanine and cysteine reac together 2 Wiitethe seuctrs of th wo amine acid fomed when this dipeptides here by concerted hetero oc H,N—CH—CO—HN—CH—COOH CH,—OH CH,—COOH ‘Keydefinition ‘A peptide bond isthe bond formed by a condensation reaction between the carbonyl group ef one [amino acid and the amino group of ancther amino acid 24Principles of organic synthesis By the end of this section, you should be able to... ‘© plan reaction schemes, of up to foursteps, to form both familiar and unfamiliar compounds {© understand methods of increasing the length of the carbon chain in a molecule by the use of magnesium to form Grignard reagents and the reactions of the latter with carbon dioxide and with carbonyl compounds in dry ether What is organic synthesis? ‘The term ‘synthesis’ the plural is ‘syntheses’ refers to making something new from what already exists In organic chemistry, it usually means using a familiar compound to make an unfamiliar ‘compound. You have already learned many examples of ‘conwerting one compound into another —for example, converting a halogenoalkane into an alechol, In this section, we will consicer ‘converting one compound into another compound that cannot be achieved in one step, but needs two or more steps. To keep things relatively simple, in this book the number of steps will be limited to four ‘The ability to plan a reaction scheme to achieve this synthesis is ‘not easily learned. It is not lke recalling a simple mathematical expression and putting the numbers into a calculator to obtain the answer. Instead, it relies on a thorough knowledge of a range (of chemical reactions and the ability to select the ones that are appropriate to the problem, Hore is a simple example of a two-step synthesis —_hew to convert bromoethane to ethy! propanoate. You could starrby considering the reactions of bromoethane, and then consider reactions in ‘which ethyl propanoate is a product. You could consider the question as a puzzle in which you need to find the identity of X in this sequence: bromoethane + X — ethyl propanoate If you know a product of a reaction of bromoethane that is the same as a compound that can be converted into ethyl propanoate, then you only need to include the reagents and conditions to achieve each of these two steps. When the synthesis involves, three steps, it is more difficult because you need to identify two intermediate compounds in the synthesis. If there are four steps, then we have reached the limit of what is reasonable to expect at this point in your study of chemistry! [nthe example above, X is ethanol, and the steps are: Step 1: bromoethane — ethanol reflux with aqueous potassium hydroxide (hydrolysis) ‘Step 2: ethanol ~ ethyl propanoate heat with propancic acid using an acid caralyst (esterification), Preparing for planning a synthe: (One thing that will help you learn how to plan a synthesis is to put together an oatline ofall the reactions you need to know: You Could leave out reactions that are less useful in synthesis. such as combustion, polymerisation and chemical tess. You could try to produce a diagram (ikea spider diagram) that would include all the reactions, but thar would probably be too complicated to easily use. It might be better to produce a series of smaller ones. For example, fig A shows reactions based on alcohols. a cabo | add halogenoakane ‘lechal _/ \= fig A. Reacions af akcohos aldehyde ‘Where the arrows point in both directions, this means that ‘you need to know both conversions. Note that reactions from Book 1 are included. If you copy this onto a sheet of paper, you can add the formulae of reagents and any special conditions on the arrows. You could use different colours to emplaasise different features, Extending a carbon chain Ikis possible that one ofthe step in your synthesis wil involve extending en existing carbon chain by one or more carbon atoms You have already learned three ways of doing this 1 Reacting a halogenoalkane with a cyanide on forms a nite ‘uth one more carbon atom than the halogenoalkane 2 The addition of hydrogen cyanide to a carbonyl compound. 3. The aliistion of benzene, which introduces anal group into a benzene ring A different way, which is more versatile, invalves the use of | Grignard reagents Grignard reagents Victor Grignard was a French chemist who devised a new way to synthesise organic compounds, His method involved the use oF organometalie compounds containing magnesium, which are now known as Grignard reagents. They are made by heating under reflux the chosen halogenoalkane with magnesium ina solvent of éry ether Haloarenes such as hromobenzene are also used Bromoalkanes are used in preference to other halogenoalkanes. 25figB Victor Grignard won the Nobel prize nchematty lors work Inorganic synmesis, 216 Grignard reagents contain magnesium covalently bonded ta both the alkyl group and the halogen. ‘A general equation for the formation of a Grignard reagent is: ROBr + Mg—> R—Mg—Br Grignard reagents react with water so they are both made and used in a solvent of dry ether Grignard reactions (Once @ Grignard reagent has been made. it can then be converted into a range of organic compounds, depencing on the reagent used, In this book we will consider only two ofthese reactions = with carbon dioxide and with carbonyl compounds. They can be summarised as follows 1 with carbon dioxide RMgBr — RCOOH carboxylic acid 2a with methanal RMgBr—RCH,OH primary alcoal 2b with an aldehyde R'CHO RMgBr—+RR'CHOH secondary aleohol 2c with aketone R'COR” —- RMgBr— RR'R'COH tertiary alcohol RR’ and R represent different alky! groups, although they could be the same, Note that both carbon diaxide and methanal increase the carbon chain by one carbon atom, Both aldehydes and ketones produce a branch, of variable length, on the existing carbon chain. Having made the appropriate Grignard reagent, the second reagent (carbon dioxide or the carbonyl compound) is added. After the reaction is complete, a dilute acid is added to obtain the desired. organic product Examples of Grignard reactions Formation of 3-methylbutanoic acid CH—CH—CH—cOOH cH, ‘This isan example of reaction 1, described above. The COOH part comes from carton dioxide, so the starting compound rust supply the (CH,),CHCH, par, which means using (CH),CHCH, 8, i.e Ltbromo-2-methyipropane. Tae equations for the reactions that occur inthis example are Step 1: formation of the Grignard reagent (CH,),CHCH.Br + Mg — (CH,),CHCH.MgBe ‘Step 2:reaction with chosen reagent (CH,),CHCH,MgBr + CO, Step 3: hydrolysis using a dilute acid (CHy,CHCH,COOMeBr + H,0 — (CH),CHCH,COOH + Me(OH)Br ‘The inorganic product of Step 3 will react with the dilute acid. You do not need to know details of the mechanisms, {(CH},CHCH,COOMgBr Formation of propan-1-ol ‘This and the other examples are abbreviated as reaction schemes, rather than being shown as three steps Propan-1-0l, CH,CH,CH,ON. is a primary alcohol. So, methanal isthe source of the CH,OH part and the starting compound is bromoethane, which isthe source of the CHCH part. Mg/ether HCHO CH,CH,Br. ———> CH,CH,Mg8r. ———+ CH,CH,CH,OH then H,0/H"0 Formation of pentan-2-ol Pentan-2-0, CH,CH(OH)CH,CH,CH, isa secondary alcohol, so ethanel is the source of the CH,CE(OH) part, and the starting compound is I-bromopropane, which s the source of the CH,CH,CH, part Mg/ether cH.CHO CH,CH,CHBr "+ ch,cH,CH.MeBr CH,CHIOK)CH,CHCH, then H,O/H" Formation of 2-methylpropan-2-ol 2-Methylpropan-2-ol, (CH.);COH isa tertiary aleohol, so propanone isthe source of the (CHs):COH part, and the starting compound Mg/ether cH,COCH, CH.MgBr 's bromomethane, which s the source of the CH, part. CH,Br (CH),COH then H,O/H" Learning tip Practice choosing reagents for a Grignard synthesis Fist, identifying the product type (acid or alcohol) tells you the type of compound to react with the Grignard reagent. Then, work out how many carbon atoms are needed in the halogenoalkane used to form the Grignard reagent. See how you get on with the {questions in this section! 1 raw ine structure ofthe organic product obane na Gard synthesis stating fom ‘tbrome-22-dimetyprpane aed propanal 2 craw the rucurtcf the two compounds needed in a Grigard sts of 33-dinthyhean--o 217Hazards, risks and control measures By the end of this section, you should be able to.. © select and justify suitable practical procedures for carrying ‘out reactions involving compounds with functional ‘groups included in the specification, including identifying ‘appropriate control measures to reduce risk, based on data about hazards Safety in chemistry laboratories Incidents that cause harm to people ae rare in schoo! and college chemistry laboratories. One ofthe reasons fr this stat all laboratories must consider the hazards of carrying cut chemistry experiments ane ise safe methods of working “This applies to all chemistry experiments, whether you are given the instructions for doing them, or whether you plan your own ‘When you plan an oman synthesis, you mast consicer the hazards ascocited with the reactants the substance you are synthesising, and with any intermediate compounds formed. Hazards, risks and control measures ‘The hazards of chemical substances relate to the inherent [properties af each substance and the way in which it will be used Most people would consider that water (H,O) is completely safe and has no hazards. [n most situations this is the case. However, consider a beaker of boiling water The steam coming from the boiling water and the boiling water itsel, could beth cause harmful effects if they came into contact with your skin Now consider a substance that most people would consider dangerous. You probably used dilute hydrochloric acid years ago in experiments involving marble chips. You will have been told to ‘wear eye protection when using the acid, because of the harm it could do if it got into your eyes. ‘The hazard exisrs because hydrochloric acid is corrosive ‘The risk is that hydrochloric acid may get into your eyes and cause harm. ‘The control measure is to wear eye protection to neduce the tisk of the acid getting inta your eyes, ‘This simple example should help you to understand the difference between hazard and risk ~ these tno words are often thought, ‘wrongly to have the same meaning. Hazard warning symbols ‘Along time ago, bottles containing certain chemicals were labelled with the word POISON. This early attempt to prevent harm to laboratory workers was well intentioned, but some people ray have thought that boitles without such a label contained hharmnless substances, 218 ‘More recently, symbols (sometimes called pictograms) have been used as labels for bottles to identify the actual hazard of the substance inside. The actual symbols have changed over the years, and you may stil see older ones used, especially those in squares ‘with an orange background, such as these "The symbols in current se are red diamond shapes. Table A shows some of the more common ones, along with a simple scription of their meanings. Sn eatin | indudes warnings on sn rashes, razard | eye damage and ingestion Conese | an cause sin bums and €> permanent eye damage Flammable | can each fei heated or comes into contact wih a ame Raat can cause ife-threatening fects toricty | eveninsmal quantities © table A In some cases, the substance may have more than one symbal, ‘especialy when itis an aqueous solution. For example, you are likely to use hydrachlorie acid in three different concentrations: ‘+ when used in a titration, it will have a concentration of ‘approximately 0.1 mol dm-* ‘+ as.a general laboratory reagent. it will probably have a concentration of approximately 1 or 2mol dm? + bottle labelled ‘concentrated hydrachloric acid’ may have a concentration of more than 10 mol din ‘These very different concentrations have different risks, ‘There are severe! other hazard symbols, including those thet you are more licely to find in biology or physics laboratories.0 Control measures [eis the responsibilty of whoev the laboratory to identify risks and hazards, and 10 prescribe appropriate control measures. This responsibility is shared with the student doing the experiment, who should follow the guidance. There are several organisations that provide advice and suppor’ to schools and colleges, and itis likely thatthe health and safety information you see in your laboratory has come from one of these sources. ‘Asa student, you may be asked to plan an experiment or a synthesis, including identifying the hazards and control eneasures needed, so you need to be familiar with this information. , OVEN CLEANER I DANGER a ' [Ean Ree fig A You wil als find examples of hazards, ke and control measures in your hom Apparatus You also need to consider risks associated with apparatus. For example, mercury thermometers a often replaced by spirit thermometers or digital thermometers, which have much lower risks, Heating ‘may be done using an electrical heating mantle instead of a Bunsen burner You may use glass ‘apparatus with ground glass joints, as these are safer to set up than t You also have to coi that use corks or bungs ider where fo support apparatus with a clamp and stand Learning tip Become familiar with the hazards ofthe substances you use in an experiment and consider how any risks of using them may be reduced. 1 sugges some contol mesures you should use nan experiment comertbromoethane nes ethanol 2 Use your chemical tone to gust wy sling edu hyo shion onto your sin ay cause more ham than hydrochloric acd ofthe same concentration Key definitions ‘Ahazard isa property ofa substance that could cause harm toa user. Aiakis the possible effect that a substance may cause toa user an this will depend on factors such as Concentration and apparatus. The level of risk s controlled using control measures 219Practical techniques in organic ati te Veen laa By the end of this section, you should be able to.. © understand the following techniques used in the preparation and purification of organic ‘compounds: refluxing, simple distillation, steam distillation fractional distilation 220 Different practical techniques In the preparation and purification of any organic compound, there are likely to be several techniques used, Each preparation or synthesis will use one or more of the techniques inthis section and the next. Most of them have been covered in Book 1, but all are included in these sections for completeness. Heating under reflux ‘Some reactions involving organic compounds are slow at room temperature, so the obvious thing to {ois heat the reaction mixture. However, as many organic compounds are volatile, there i risk that they will escape from the reaction mixture during the heating process. The normal way to prevent this happening isto heat the reaction mixture ina flask fted with a reflux condenser This technique is also Jnowm as refusing. Allthe vapours rising from the reaction mixture during heating enter the condenser ‘and change back into liquids and return to the flask so that the unreacted compounds can react old water in —» fig A Apparatus for heating under tei ‘The flask ean be heated using hot water or oil in a beaker heated by a Bunsen burner orby using an electric mantle. The use of anti-bumping granules in the reaction mixture helps to make the boiling smooth. A gentle flow of cold water enters at the bottom of the condenser Methods of separation Simple distillation ‘This is a separation technique used to obtain a liquid product from a reaction mixture that has a boiling temperature much lower than the other substances in the reaetion mixture, Distillation of an impure liquid involves heating it ina flask connected to a condenser The liquid with the lowest boing temperature evaporates or boils off frst and passes into the condenser fist, and so can be collected in the receiver separately from another liquid that may evaporate later The purpose of the thermometer is to monitor the temperature of the vapour as it passes into the condenser. If the temperature remains steady, this isan indication that one compound is being distilled. If after a ‘while the temperature begins to rise, this indicates that a different compound is being distilled.0 ime t distil rats for simple dilaton fige ‘The advantages of using simple distillation, rather than fractional distillation, are tha itis easier to set up and is quicker. The disadvantage is that it does not separate the liquids as well as fractional distillation, [t should only be used ifthe boiling ‘temperature of the liquid being purified is very different from the other liquids inthe mixture, ideally a difference of more than 25°C, Steam distillation Steam distillation is @ technique used to separate an insoluble Tiquid from an aqueous solution I involves passing steam into a reaction mixture that contains an aqueous solution and a liquid ‘that forms a separate layer Tae agitation of the liquid caused by the steam bubbling through the mixture ensures that both the insoluble liquid and the aqueous solution are on the surface of the ‘mixture and so can form part of the liquid that evaporates. The advantage of this process is thatthe insoluble Tiquid is removed from the reaction mixture at a temperature below its normal boiling temperarure ‘An example is phenylamine, a liquid with a boiling temperature of 184°C, During steam distillation of a reaction mixture containing phenylamine, a liquid containing phenylamine and water distls ata temperature of 98°C. An advantage of doing this s chat the ‘temperature at which phenylamine distil is much lower than its boiling temperature, so there is less chance of decomposition, estat rats for steam delaton fig 8 Fractional distillation Fractional distillation uses the same apparatus as simple distillation, but with a fractionating column between the heating flask and the stil head. The column is usualy fled with glass beaks or pieces of broken glass, which act as surfaces on which the vapour leaving the column can condense, and then be evaporated again as more hot vapour passes up the colurn, Effectively, the vapour undengoes several repeated distilations as it passes up the column, which provides a better separation, fig Apparatus fe fractional dsl Fractional distillaion takes longer than simple distillation. Its bbest used when the difference in boiling temperatures is small and when there are several compounds to be separated from @ mixture Remember that there are three types of distillation, and that you need to consider which one to use ina pantcular case. expan bey why the condensers vera in eftuning but neat horizontal inthe three methods of dilation 2 suggest. with a reason, which fractionating column provides the beter separation very small glass beads or larger pieces of glass. 221Practical techniques in organic atti te ae laa By the end of this section, you should be able to.. ‘© understand the following techniques used in the preparation and purification of organic compounds: washing, drying, solvent extraction, recrysalisation, melting temperature determination, boiling temperature determination More methods of separation Solvent extraction As the name suggests, this method involves using a solvent to remove the desired organic product from the other substances in the reaction mixture, Several solvents can be used, but the choice depends mainly on these features + The solvent added should be immiscible (1. does not form a mixture) with the solvent contaiing the desired organic product, +The desired organic product should be much more soluble in the added solvent than in the reaction mixture “The method is this + Place the reaction mixture in a separating funnel, and then add the chosen solvent ~ it should form a separate layer + Place the stopper in the neck of the funnel and gently agitate the contents of the funnel fora short while (puta finger on the stopper invert, open the tap, agitate in a circular motion, close the tap and return the funnel to its normal position, + Allow the contents to settle into two layers. + Remove the stopper and open the tap to allow the lower layer to drain into a flask, and then do the same to allow the upper layer to drain into a separate fask, fig A. Apparatus for separating immiscible liquids If @ suitable solvent is used and the method is followed correctly, ‘most of the desired organic produce will have moved into the added solvent. [tis better to use the solvent in small portions rather than in a single volume (e.g four portions of 25 cm’ rather than one portion of 100 crm) because this is more efficent, Using more portions of solvent, but with the same total volume, removes more of the desired organie product “The desired organic product has been removed fiom the reaction mixture, bu is now mixed withthe added solvent. Therefore, simple distillation or fractional distillation must now be used 10 separate the desired organic product from the solvent used 222 Washing You might assume that washing i a technique used to remove impurites from a solid. Although this is correc, tis also used to remove impurities from a liquid. Washing could involve the use of water or an organic solvent. Whichever liquid is used, it must be chosen careflly so as o dissolve the impurities but as tle as possible of the substance being purified {An impure solids sted in some of the solvent, then the mixture filtered Ifthe solids already ina fiter funnel, the solvent could be acded on top of the solid. ‘Aliguid would be mised with a solvent chosen so that twill lssolve litle, if an, of the liquid tobe purified. The mixture is then shaken in a separating funnel, After allowing the two liquid layers to separate, the tap is opened to allow each layer to drain into a separate container Drying No special technique is needed to dry an organie solid —it just needs tobe let ina warm place or in a desiecator with a suitable drying agent organic solid lying agent fig Drying an organic solidn a desc ‘Many organic liquids are prepared using inorganic reagents, which are often used in aqueous solution. A liquid organic product may partially, or even completely dissolve in water. Therefore, water ‘may be an impurity that needs ta be removed by a drying agent, Obviously, one important feature of a drying agent is that it does not react with the organic liquid ‘Several drying agents are available, but the most common ones are anhydrous metal salts ~ usually calcium chloride, magnesium sulfate and sodium sulfate, The property that these compounds have in common is that they form hydrated salts. So, when they come into contact with water in an organic liquid, they absorb the ‘water as water of crystallisation, “The dying agent is added to the organi liquid and the mixture {is swirled or saaken, and then lef for a period of time. Before use, a drying agent is powdery, but after absorbing water it looks more crystallin. If a bit more drying agent is added and remains powdery, then this is an indication thatthe liquid is dr. The liquid also goes from cloudy to clear when water is removed. ‘The drying agent is removed either by decantation (pouring the ‘organic liquid off the solid drying agent) or by flltration,Filtration [tis likely that after preparation, an organic solid will need. tobe filtered at some stage. This alvays happens as part of recryslallisation, so the two pieces of apparatus (Buchner and Hirsch funnels) that are normally used will be considered under the next heading. The use of a vacuurn pump means that these ‘methods are described as filtration under reduced pressure. Recrystallisation ‘When an organi solid has been prepared, tilly to need purification. A tadtional way of removing impurities i the technique of recrystallisation. The principle behind this technique i that a sold compound is dissolved ina suitable solvent that can cisslve all or most of any impurities but very litle ofthe compound being pared ‘The seeps used ina typical purification ae + Add the impure solid toa conical flask. + Add some of the chosen solvent and warm until the mixture rears the boiling temperature of the mixture, + If there is still some undissolved solid, add further solvent and ‘warm unti] the mixture boils again. + Continue adding further solvent and heating until all of the soluble solid has dissolved, + If insoluble impuritios are present, then hor ftration eould be done using fluted flter paper in a heated funnel + Allow the liquid to cool until erystals of the organic solid have formed, + More crystals can be obtained by cooling the solution below Tom temperature in an ice bath + ‘The mixture is then filtered to remove soluble impurities using a Buchner funnel or a Hirsch funnel, and then dried in a desiecator or oven, organlesolid [erent fier paper amp pump Buchner funnel seh Fane fige 8 ‘earning typ Study the information about recrystallsation carefully Many students do not understand why there might be two hitrations ‘needed, Some throw away the substance they have just purified! rats for ration under recs Testing for purity Having prepared an organic compound, a simple test can be performed to give an indication of whether the compound is pure. If che compound is a solid, then its melting temperature can ‘be measured If itis a liquid, then its boiling temperature can be measured. Determination of melting temperature Forsolid, impunties reduce the melting temperature. If you measure the melting temperature of your organic compound, then you can compare it with the known value of the pure compound, "This will enable you to estimate how pure its. ‘The traditional way to measure a melting temperature of a solid is 10 place some of the solid in a small capillary tube attached to the bulb of a ‘thermometer and then place the assembly in a liquid that quit has a boiling temperature tobe. cotpanic above that of the melting, neal solid ‘temperature of the solic sealed ot In practice, this apparatus ‘ea is often replaced by VariodS ag ge rsrustor dexter et electrical devices, Determination of boiling temperature For liquids, impurities increase the boiling temperature ‘The boiling temperatures of pure organic compounds have been carefully measured and are widely available in data books and online. IF you measure the boiling temperature of your organic compound, ‘you can compare the value you obtain with the knovm value of the [pure compound and then estimate how pure the compound is ‘The apparatus used depends on the volume of liquid available, and whether is toxic or farnmable. The appararus used for simple distillation can be used in most cases. A word of caution. This test may not be conclusive because ‘you may not be able to measure the boiling temperature of ‘your organic compound accurately enough ~ your thermometer ‘might read too low or too high. So, even if your measured boiling temperature exactly matches the one in the data book or online, you may wrongly assume that your compound is pure It is also worth remembering thet different organic compounds can, by coincidence, have the same bolling temperature, For example, both t-chloropentane and 2-methylpropan-1-ol boil at 108°C, 11 Explain why the solvent extraction method will not workif the solvent dissolves the impurities, 2 explain wy in ecstaliaton. insoluble impure are removed froma nto nat coed one 223Simple chromatography By the end of this section, you should be able to.. ‘© understand that chromatography separates components of a mixture between a mobile phase anda stationary phase © calculate R; values from one-way chromatograms Paper chromatography You may be familiar with paper chromatography from your early experiences of chemistry This isa suitable place to remind you of this technique and to explain some of the principles that relate ‘to most types of chromatography. The word ‘chromatography’ comes from the Greek for colour (chroma) and writing (graphen) because mixtures of coloured substances were used in early experiments. However the technique can also be used with colourless substances because these can be detected in other ways without considering their colours. Chromatography is used + to separate a mixture into its individual components + to identify the components of a mixture by considering how far they have travelled up the paper If you have synthesised an organic compound, chromatography is, 2 good way to check whether itis pure and, if not, what impurities are present, Apparatus ‘Allforms of paper chromatography need the following: + Accontainer (usually glass) witha lid. The lid is there to prevent evaporation of the solvent. The container could be a beaker or rectangular tanke + Paper. In introductory experiments you may have used filter paper or kitchen towel, but specially formulated chromatography paper gives better results, There also needs to >be a method of supporting the paper in the container + Asolvent, In some cases, water works well, but often the solvent is a mixture of organic compounds, and is chosen to fit the characteristics of the components of the mixture ‘Whichever variation is used, the mixture is spotted onto the paper a short distance from one edge. Often, spots of known substances are spotted separately atthe same level as the mixture. A small, volume of the chasen solvent is added to the container, and then ‘the paper is inserted and suitably supported. The lid is replaced and the apparatus left until the solvent front has reached almost to the top of the paper The paper is then removed, the position of the solvent front marked, and the paper left to dry. The resulting cried paper is known as a chromatogram. Fig A shows typical apparatus used to set up a chromatography experiment and the resulting chromatogram. 224 spot of mixture baseline solvent paper. solvent font separated components oe manure crip baseline spot of mire KZ fg The chromatogram i showmn a ater del se0 way - the sprs ore often elongated and tei centes ae ficult dently, How does chromatography work? ‘ltypes of chromatography depend on the use of « stationary phase and a mobile phase. Each component in the mixtureis| atacted to both phases, but more strongly to one than the other. ‘+ A.component that is strongly attracted to the stationary phase ‘but wealdy attracted to the mebile phase will not travel very far up the paper + A.component that is weakly attracted to the stationary phase but strongly attracted to the mobile phase will travel a long way up the paper. In paper chromatography, the stationary phase is the water ‘rapped inthe fibres of the chromatography paper and the mobile phase is the solvent ‘We have used colours to illustrate the different substances in he mixture, but most organic compounds are colourless. Chromatography can sil be used, but the components on the chromatogram must be visualised using ultraviolet radiation corby spraying with a chemical reagent that will react with the ‘component to form a coloured product.0 Thin layer chromatography The apparatus and method used in thin layer chromatography (TLE) is very similar to those of paper chromatography. The only difference is that instead of paper, a sheet of glass or plastic lumina is used. coated in thin layer of a solid such as silica or fig This ba TIC pioat Calculating R; values The chromatogram fs analysed andthe distance traveled by the solvent (om the base linet he solvent font) s measared For each component in the mistre te distance it hes traveled (starting fom the baseline) is measured The Rvalue fs caleulted using the expresion: _Gistance travelled by component stance aveledby vaes have no unis because they area ratio of to dances. The leters nthe term refer fo Taran (sometimes etenton a facto” Each component has characteristic vale, on theory diftrent components canbe tented by reference oa abe o ‘now vas Unorunately, aes depend onthe ssvent sed and ober factors. In practice paper and thin yer cromatograpty Ze umually carted out wth nown substances nhded in he same experiment so that a comparison an be made vent ise ‘This chromatogram suggests that the mixture on the left contains three different substances. Two of these three are probably the en and blue substances on the right. The third substance (yellow) cannot be identified by this experiment. Learningtip Remember, when calculating R; values, the distance moved by the solvent is measured from the baseline tothe selvent front. Column chromatography Column chromatography uses the same principles as thin layer chromatography, The stationary phase is alumina or silica packed into a tube (a burette will do) and soaked in a solvent. The mixture is placed on top of the stationary phase and more solvent (the mobile phase) added on top. When the tap is opened, the solvent drips through the tip and the components of the mixture begin to move down the tube and separate. LJ of mature by column chromatogranhy figd Sep More solvent is added at the top, and eventually one component {yellow in this example) leaves the column and can be collected in 2 container If the experiment is continued, the blue component can be collected in the same way. The advantage of column chromatography is that much larger quantities of material can be separated than with paper chromatography. 1 Suggest why, in paper chromatography, the non-polar substance hhevane has a high R value, 2 Calculate the R, value of component x inthis diagram. wl] 2» | .©2@ x baseline solvent frost = The stationary phase in paper chromatography is the liquid or soli that does not move, The mobile phase isthe liquid that moves through the stationary [phase and transports the components 225Traditional methods of analysis By the end of this section, you should be able to.. ‘© deduce the empirical formulae, molecular formulae and structural formulae of compounds from data obtained from combustion analysis, elemental percentage composition and characteristic reactions of functional groups Introduction Chapter 17.6: all bout organic synthesis planning how to convert one organic compound into another, including common techniques used in preparation and purification. In this section we will look at methods of analysis ~ different ways of finding the structure of an organie compound. Modern methods, such as infrared spectroscopy, ae increasingly used. In many situations two or _more methods are used together In this section we will frst consider the traditional methods of analysis, many of which were introduced in Book 1. Determining empirical and molecular formulae Qualitative analysis ‘The purpose of qualitative analysis is to find out which elements are present in a compound, We wil take as our example compound X, which i found to contain only carbon, hydrogen and oxygen. Quantitative analysis ‘One method of finding the percentage composition by mass of @ compound is combustion analysis. ‘A-known mass of the compound is burned, and the masses of carbon dioxide and water formed are found by measuring the increase in mass of U-tubes containing the absorbers (shown in fig A). coygen unas acted compan 0 oxen rere temaysed tenes — heat water carbon dite Tober absorber fig A dpparausfor combusten analyse ‘Table A shows the masses for the combustion of compound X, ET 7 compound X water formed carbon diaxide formed 226‘The first seep is to caleulate the masses of carbon and hydeagen in the catbon dioxide and water ‘The relative molecular mass (44) of carbon dioxide is 44.0, but because the relative atomic mass (4,) ‘of carbon is 12.0, the proportion of carbon in carbon dioxide is 120 ‘ lays 725; Similarly, the proportion of hydrogen in waters Allof the carbon inthe carbon dioxide comes from the carbon in the ‘organic compound. Sivilaly, ll ef the hydrogen inthe water comes fom the hydrogen in the organic compound. So, in this example 353 x 120 40 144 x20 pp = 060g ‘These two masses add up to 1.123 g However the original mass of the onganic compound was 1.98 g, so the difference must be the mass of exygen present in the organic compound (1.98 1.123 = 0.857). ‘mass of carbon = = 09638, and mass of hydrogen Calculation of empirical formula ‘This is done by dividing the mass of each element by its relative atomic mass (there is no need to convert the masses to percentages). Table B is the calculation table. mass of elemenv/g 963 | oreo | 0857 A, v0 | 10 60. division by A, ooso3 | o160 | 0.0536 ratio 15 3 a whole number ratio 3 6 zZ table 6 ‘The empirical formula of X is therefore CyH,O; Learningtip Remember that you can do empirical formula calculations starting. from the masses ofthe elements present. or from the percentage composition by mass. Also, the supplied percentages do not add ‘upto 100, then you should assume that the cemainder is oxygen. Determination of molecular formula ‘To deduce the molecular formula of X from its empirical formula, «an adlitional piece of information is needed — the molar mass of X. Let us assume that this is found by experiment to be 74.0 g mol We can now compare the ‘molar mass’ of the empirical formula (74.0) with the actual molar mass of X. In this example they are both the same, so we can deduce that the molecular formula of Xis GiH.O, ~the same as the empirical formula, Determining structural formulae Fora compound (X) with a molecular formula of CyH,O, there are several posses forthe sructure. Using traitonal methods, we an obtain information from chemical test to help decide which functional groups are present. Although tis no a good idea to jump roan cbs conchision, one way forthe atoms in X tobe arranged CE isas CHy—CH,—COOH. This suggestion could be confirmed, cor not, by a simple chemical test the addition of sodium Irycrogencarbonate, If effervescence is observed, this evidence ‘would support the suggestion that X is CH,—CH,—COOH. If there is no effervescence, then X cannot have this structure, It, ‘would be sensible to test X forthe presence of other functional ‘groups before making a decision about its structure, Table C shows the rests done on samples of X, and the results. Test em 1. [add sodium hydrogencarbonate _| no change 2 [add 24-dinitrophenylhydrazine | orange-yellow solution precipitate ‘add Tolleng reagentand warm __| no change 4 [heat with acidified potassium | colour change from dichromate(V\) orange to green 5. | test product from test 4 with no change Tollens' reagent and warm Test produc: rom test 4 with effervescence sodium hydrogencarbonate ‘able “The conclusions that can be made fom the results of these tests are 1 X does not have a COOH group 2 Xhas a carbonyl (C=O) group 3. X does not have an aldehyee (CHO) group 4 X contains a group that can be oxidised ~ as this is not an aldehyde group, it could be an alcohel group 5 the axidation product of test 5 is nat an aldehyde, but could be a ketone or a cerbaxylic acid 6 the oxidation product of test 5 is a carboxylic acid, so X could contain a primary alcohol group, Asstructure that is consistent with the results of these tests is: CHy—CO—CH,—OH Limitations of traditional methods of analysis Even with this very simple example, you can see how dificult it isto be sure of the structure of X, whose molecules contain only 11 atoms. With compounds whose molecules contain many more atoms than this, you can see that traditional methods of analysis become less suitable We will consider the use of more modern methods in the {following sections. 11 compound Shas he percentage composition by st C= 4000 eer and = 533 kris COU andi ener lervescence Write figA. Apparatus for HPLC As each camponent reaches the detector, a signal is displayed fon the computer sereen, Just as retention factor (R) values can ‘be obtained from paper and thin layer chromatography, in HPLC ‘values of retention time are obtained, The retention time of @ component is the time taken from injection to detection, and these values can be important in identifying the components. However retention times depend on several variables, including + the nature of the solvent + the pressure used + the temperature inside the column, 230 Gas chromatography Gas chromatography (GC) anther refinement of column chromatography. The min ifrences are + The metal tube can be several metres long and is coiled to save space. + ‘The stationary phase isa solid or liquid coated on the inside of the tube. + The mobile phase is an inert carrer gas (often nitrogen or heliuen), + The sample is injected into the column, as in HPLC + The components passing through the column are detected. + ‘The whole process is automated and the results are quickly available on a computer display. fig The comple GC equipment aks up very ile Fig C shows a typical setup. injection por. i i AXXX camer gas supply “ fig Apparatus for 6.CE After the sample is injected, the components vaporise and move through the called tube with the cartier gas. They move at different speeds, depending on how strongly they are attracted to the stationary phase. Those with weaker attractions move more quickly and have shorter retention times. Fig D shows the separation occurring inthe coiled tube. fg D 4 zs cheomatagragh separating tree compan: ‘The relative concentrations of the different components are often displayed on a graph like that in fig E ft Metnanot 2 Banal 5 Bihan) 4 2methylpropan-i-o! 5 Propanone 6 Props Tene/min fg The areas under the peaks represent he relative concentrations of the companen Learning tip Traditional column chromatography (using a burete for example) has one advantage over HPLC and GC = reasonable amounts ofthe Components can be collected, In GC the components are often detected in a flame, so they are destroyed during the detection process. 1 How does the movernent of the mobile phase in HPLC differ from that in traditional column chromatography? 2 sugges reasons why ttenton tines ora given substance may be diferent when ebuined fom ciferet gaschvomatogame 231CO rouieieoyicl eae MCs) spectrometry By the end of this section, you should be able to.. GC-MS (@ recognise that high performance liquid chromatography, ‘As the two combined techniques ate very similar we will focus HPLC, and gas chromatography, GC may be used in conly on GC-MS Fig B shows the stages in a typical setup ‘conjunction with mass spectroscopy, in applications such as E A forensics or drugs testing in sport D oor : Limitations of HPLC and GC c Sample: mix of ‘The two types of chromatography described in Seetion 17.7.3 ee are very use for separating small quate of components in a ‘mixture, bus they are not very goed at pastvely identifying them } ‘This is parsy because of the diel ia contoling al ofthe variables (such as solvent, pressure and temperature) and partly because different substances may have the same retention times. Components are often identified by reference to a database of the graph retention times of known substances. However, if a component has a retention time for which there ig no referenee, then these ‘techniques provide no useful information, Here are two areas in which the results of these chromatography ‘methods have to be exactly correct: + In providing forensie evidence (for use in a court of law) + in detecting banned drugs in sportsmen and women and racehorses. “They are used in other areas, including analysis of pollutants in the environment, detecting explosives in aiport baggage, and in ‘space probes on other planets Because HPLC and GC do not give results that are beyond doubt, they are often combined with a different technique that ‘you learned about in Book 1, This is mass spectrometry (MS), a technique that cannot separate a mixture but which can provide information about the structures of compounds. The Combinations of these techniques are often abbreviated to HPLC- MS and GC-MS. fig A GC-MS widely use fr forensic purpores B Sages in CMS, 232CE Imagine a sample containing a mixture of five different In the 1998 Olympic Games, aver 600 participants were tested substances, A-E. for nandrolone, and none tested positive. In the years that followed, some very high-profile athletes in a range of sports have been banned from competition because of testing positive Stage 2: Each component has a diferent retention time, for nandrolone. However, many scientists believe that the number ‘emerges at a diferent time. cof positive rests is higher than expected. The suspicion is that nandrolone may be an ingredient in some autrtional supplemenss| ‘that participants are allowed to take. Another theory is that a combination of permitted dietary supplements and exercise may Stage 4: Component C has its mass spectrum displayed. increase the concentration of nandrolone in the human body. ‘Stage {:"The mixture is injected into a gas chromatograph Stage 3: One ata time, each component enters the mass spectrometer ‘Stage 5:The m/2-values and relative abundances of components ‘are compared with a database of known substances. ‘Stage 6: When a match is found, component C has been positively ‘identified, Very small traces of substances, or example in a human hair ora paint fleck, can be accurately identified by this method, Problems with drug testing Although the use of GC-MS for detecting small amounts of banned drugs is usually accepted as producing cliable results, sometimes a problem arises. One example involves the anabolic steroid called nandrolone. Anaboli steroids have legitimate uses sn medicine, especially in the treatment of anaemia, osteoporosis tnd some forms of cancer. Is effects include muscle grow, ‘nereased red blood cel production and bone density. fig A urine zampls rom an athlete about tobe tee for legs cg Mainly because of their effects in promoting musdle growth, sporting autores heve prohibited the use of anole sterckls IRsportsmen and women including athletes. When someone eAtMing tip _ takes nandtolone itis converted inthe human body into a Inquoting very rll eoncsrratons of drugs ererber hata similar compound, 19-norandrosterone, which is then excreted ‘microgram (ug) is one millionth of a gram, 1 * 10*g. in urine. Participants may be routinely tested for the presence of 19-norandrosterone in their urine, and the International Olympic Committee has set a limit of 2 micrograms (yg) per er of urine, which is enly 0.000 000 002 g per dm. A participant with a ‘concentration higher than this has ‘tested positive. The skeletal formulae of these two related compounds are: ‘1 What s the main function of each technique in HPLC-MS? OH 2 Which of the two compounds nandrolone and 19-norandrosterone rnandrolone would you expect to react with: (@) bromine water (©)2.4 et 7 eo so 0 ao ao TD ob (Chemical shit 8/ppm A The low resoltion 'H NMR spectrum of propan1-o go oO io lo 0 90 80 70 60 50 40 30 20 (Chemical shit 8/99 7 00 fig 8 The lw rzoution NMR spectrum of propan-2- Interpreting chemical shifts ‘To interpret chemical shifts, you need a table of reference values ‘with corresponding hydrogen atoms or a chart. Fig C shows simplified version of the chart that will be provided in an ‘examination, and you need to become familiar with using itwe [oe] virB rio oo 70 60 50 40 Cherie shit 3/epm fig HNMR chemical shift anges For two of the chemical shift ranges in this chart, tae compounds included show trends in chemical shift values, as shown in this table A. = R.CHF > R,CHCl> R,CHBr> R,CHI RACH > RCH, » RCH, Butanal and butanone ‘We will use the chart to interpret the ow resolution 'H NMR spectra of these isomers with the ‘molecular formula of C40. Fig D shows the spectrum for butana penn) halogenoalkane alkane table, ® @ oo to 10 90 8o_7O e080 40 30 20 TO oo (Chemical sit 8/opm fig The low resclution |W NR speerum of butanl ‘The peak at 6 = 9 8 ppm is within the aldehyde range, so must be due to the H in the CHO group. ‘The peak at 5 = 2.4,ppm is within the range for H—C—C=0, so must be due to the two H atoms in the CH, group joined to the CHO group, ‘The peak at 5 = 1.6 ppm is within the range for H—C—C (alkane), so must be due to the two H «atoms in the CH, group not directy joined to the CHO group. Note that although the spectrum is for «an aldehyde, the shut for an alkane is appropriate because this CH, group is part of the CH.CH,CH, alkyl group. ‘The peak at 6 = L.O ppm is within the range for H—C—C (alkane), so must be due to the three H atoms in the CH, group, 241242 Now for the spectrum of butanone, shawn in Fig E uo 10 10 90 80 70 60 so 40 50 20 10 OO Chemical cit &/ppm {ig The ow resolution 'H NMR speci of but ‘The peak at 5 = 2.5 ppm is within the range for H—{ the CH, group joined to the CO group, ‘The peak at 5 = 2.1 ppm is within the range for HC—C=0, so must be due to the three H atoms in the CH, group joined to the CO group. ‘The peak at 6 = 1.1 ppm is within the range for H—C—C (alkane), so must be due to the three H atoms in the CH, group not directly joined to the CO group. C—C=0, so must be due to the two H atoms in com Law resolution 1H NMI spectra indicate three things |The number of pesks represents the numberof different chemical environments ofthe hydrogen atoms (protons) “+ Theareas under the peaks indicate the relative numbers of protons in each chemical environment. +The chemical shift of a peak can indicate the functional group responsible (eg, aldehyde or ketone) rod ne number peaks inthe NMR spectrum ofeach of the omer of Ci 2 wy does an itegiation race nt aaa rate the actual numbers drogen atoms ina molecule? 3. Hor would youeasily decid toma HNMR specrun wheter a compound isethyamine(CHLCHNH,) orethanamie (CH:CONK,)? ‘Keydefinitions ‘A peak in a°H NMR spectrum shows the presence of hydragen atoms (protons) in a specific chemical fenvironment. An integration trace shows the relative numbers of equivalent protons (ie. in the same chemical environment).Splitting patterns in 'H NMR spectroscopy By the end of this section, you should be able to... ‘© use data from high resolution 7H NMR spectroscopy to: (i) deduce the splitting patterns of adjacent, non-equivalent protons using the n + I rule and hence suggest the possible structures for a molecule {i predict the chemical shifts and splitting patterns of the 'H atoms in a given molecule High resolution 'H NMR spectroscopy In Section 17.7.7 ve introduced NMIR by staring with the low resolution form, although only the high resolution form is actually used now Both forms have two features in common: Peaks at efferent chemical shit values help to identify the different chemical environments of the hydrogen atoms. If the environments are identical then the protons are often described asbeing equivalent (.e they ae equivalent protons) ‘The relative peak area (1. the rato of peak areas) helps to decide the numbers of hycrogen atoms responsble. A high resolution 'H NMR spectrum has one extra feature not seen in a low resolution spectrum ~ the peaks may have a splitting pattern. This means that the peak is split into a group of smaller peaks (sub-peaks) grouped very closely together When considering these split peaks: + you can take the chemical shift to be at the centre of the group ff sub-peaks the relative peak areas are shown in the same way as in a low resolution spectrum — by an integration trace or by showing ‘numbers next 10 the peaks remember that the numbers indicate the ratio of the numbers, ‘of protons — they may happen to be the actual numbers of protons, but ths is mot always the case. What causes the splitting of peaks? [Although the most important thing is for you to be able to interpret the spliting patterns it will help if you understand how the spiting is caused. The fundamental point to be aware of Js that hydrogen atoms (we will all them protons from now on) joined to a carbon atom have an influence on the protons on ‘adjacent or neighbouring carbon atoms. Consider a molecule of Dbutanone, in which the protons are labelle¢ with letters: » C—CH. Il ° fg A The thee diferent chemical environments fr the protons in autarone, CH, —CH, ‘The protons labelled « are not influenced ky any other protons ‘because there are none on the adjacent carbon atom, The protons labelled 6 are influenced by the protons labelled cand vice versa, ‘These influences are vehat cause spliting of the peaks (sometimes referred to as spin-spin coupling), usually considered in terms of the m+! rule. Very simply if carbon atom has m protons, then the peaks on adjacent carbon atoms are split into m1 sub-peaks. “The split peaks are sometimes referred to as multiplets, but more often by a term indicating the number of sub-peals, If the peakis not split, itis called a singlet. If the peak is split into two sub-peaks, it is called a doublet IF the peak is split into three sub-peaks, itis called a triplet. If the peak is split into four sub-peaks, its called a quartet ‘The sub-peaks ina split peal have distinctive shapes, due to splitting into different sub-peak areas, as shown in table A. ry Eee a rT = table A, “The spiting pattern ofa group of protons indicates nothing about the group of protons being split, but relates only to the number of protons on an adjacent atom. Understanding the spectrum of butanone ‘We can apply the information provided above to explain the ‘spectrum of butanone in table B. Proton: o co Ic a singlet | There arena protons on the adjacent carbon atom (C=O), 0 there is na splitting, quartet | There are three procons on fhe adjacent CH, group, so applying then + 1 rule, the peak for the two protons is spit into a quartet. triplet | There are sno protons on the adjacent CH, group, so applying then + 1 rule, the peak far the theee protonsis spit aviplet table 243‘Two more points to remember + We have said that protons cause spliting of peaks on adjacent atoms. While this is generally true, it does not apply in cases waere the molecule is completely symmetrical. For example, there is spliting of peaks for 1.1-dichloroethane. CHCL—CH.,. The single proton spits the peak for the CCH, group into a doublet, and the three protons in the CH, group split the CH peak into a quartet, following the m1 rule. However in 1,2-dichloroethane, CH;C}—CH,C, neither of the CH, groups affects the protons of the other CH, group because all of the protons are equivalent (the CH, ‘groups are in the same chemical environment) + Now consider 1-chloropropane. CH—CH,—CH,—Cl This time, the two CH, groups are in different chemical environments (50 the protons are not equivalent). One is joined to CH and CCH,, and the other is joined to CH, and Cl, so there willbe spiting of peaks by the Cl groups. "However, this example has been included to make a different point. The frst CH, group would be influenced by the CH, group on its left and by the CH, group on its right. Using the nl rule ‘you would predict that the CH and the CH, group acting together would cause spitting into six Sub-peaks — this splitting pattern would be deseribed as a sextet. In other compounds, @ quintet ‘would be formed by four protons on adjacent carbon atoms ~ these could be two CH, groups, or cone CH; group and one proton. Practice makes perfect - again! ‘The way to check how well you understand how to use "H NMR spectra is to try Jots of examples. We will use tree examples all of which require you to use the chart of chemical shits inthe previous section ca eS Predicting the appearance ofa spectrum (chemical shifts and splitting patterns) ‘What would you predict about the appearance of the 'H NMR spectrum of methy! propanoate (CHsCH,COOCH,)? Answer The CH, in the ety! group is part ofan allyl group and is joined only to a hydrocarbon (CH.) group, <0 itshould havea peakin the ange é = 19-01 pp, which is split ia a triplet because of the nwo prozons inthe adjacent CH, group. ‘The CH, in the eth! group i part ofan alkyl group and is joined to a hydrocarbon (CH, group but also to the Cof the COO (ester group, soit shoud have a peak inthe range d= 3.0-1.8ppm, which ssp into a quartet because ofthe three protons inthe adjacent CH, group. The CH inthe methyl group isjoined only an exygen atom in the COO pou, sit shoud have a peak in the range 6~ 43-30 pom, which isa singlet. This peak snot spit because there are no protons €n the adjacent atom. FigB shows the actual spectrum of methyl propancate, so you can check whether the predictions ave correct Singlet of 1 peak from a4 rule, no H atoms on an adjacent C Absorption “Toplet of 3 peaks Quartet of 4 peaks fiom w+ rue A fiom n+ rae CH, adjacent CH, is adjacent 8 4 a Z T a a/ppm fig The HNMR pacirum of met! propanoate 244CE a as ish Predicting the structure of a compound from its spectrum Fig Cshowrs the 'H NMR spectrum of a compound with the molecular formula 4,0, ® ® a a 70 ood 40-50-2070 oo (Chemical hit 3/pe fig The 'H NMR spectuen ofa compoun vith molecular forms co: What ists structure? Remember that the spectrum shows three features + relative peak areas + chemical shits + splitting patterns allafwhich need to be considered together Answer The peak on the leftis a quartet at 6 = 4 1 ppm representing two protons. This suggests a CH, group next to a CH, group and an ©. in an alcohol, ether or este, so O—CH,—CH The peak in the middle isa singlet at 5 = 20 ppm representing ‘three protons. This suggests a CH, group joined to C=O in an aldehyde, ketone, ester amide or acid so CH,—CO— ‘The peak on the right i atriplet at 5 = 13 ppm representing three protons. This suggests a CH, group next to a CH, group, so =CH.-CH, The final step isto put all hese interpretations together. This is often easy to do but difficult to explain. The only structure that fis the interpretations s CH,—CO-O-CH,—CH,, which is the ester ethyl ethanoate ‘Another prediction of the structure of a compound from its, spectrum Fig D shows the "H NIVIR spectrum of a compound with the molecular formula C,H,0, (the same molecular formula asin Example 2) ® ® ® ug io wo eb eo 70 0 s0 40 a0 Zo Chemical shit ppm 10D fig The 1 NMR spectrum of = compound with the formula CHO, Whats is structure? Answer ‘The peak on theleftis a singlet at 8 = 11.9 ppm representing one proton, This suggests a proton in a COOH group, =o COOH, ‘The peak in the middle is a quartet (or multiplet) at = 2.6 ppm. representing one proton, This suggests a CH group joined to a CH, eroup, <0 Cl The peak on the right is a doublet at 6= 12 ppm representing six protons. This suggests wo CH, groupsriext to a CH group, so (CH.-CHe. final step is to put all hese interpretations together. Again, thisis easy to do but dificule to explain. The only structure that fits the interpretations is (CH,),—CH—COOH thisis the acid methyipropanoic ac, 1 Acompound has the molecular formula C,H.0. Its NMR spectrum contains onty three singlets, with chemical shift values of 40, 24 and 2.1 ppm. The integration trace shows the ratio 2:3: What sits structure? 2 Acompound has the molecular formula C,H;sO> Its *H NMR spectrum contains a singlet witha chemical shit of 23 ppm, a quartet with a chemical shift of 15 ppm, and a doublet with a chemical shift of 7.2 ppm. The integration trace shows the ratio 3:1:6. What sits structure? Key definitions Equivalent protons are hydrogen atoms in the same chemical environment A splitting pattern isthe appearance of a peak as a small number of small sub-peaks very close to each other. ‘Muttiplets are the diferent spitting patterns observed (singlets, doublets triplets or quartet) 245MOLECULES OF FRAGRANCE AND TASTE Behind the flavours and scents that we experience every day there is often a complex mix of organic ‘molecules. The following extract ia from Chemisiry World, the print and online magasine of the Royal 5 Society of Chemistry. THE SWEET SCENT OF SUCCESS Chart toppers ‘Tomake a fine fragrance, new molecules are mixed with old favourites But which fragrance camipounds are most valued by industry —a kind of fragrance top 10? e's. dificult question to answer. Gautier has no doubt about the value of Hedione (methyl dibydrojasmonats), used in almost all fine fragrances and Firmenich’s topseller in terms of volume. The ‘compound was discovered at Firmenih inthe early 1960s a an analogue ‘of methyl jasmonate, a key component of jasmine oi. Said w give a warm, ‘oral jasmine note, Hedione has been used in perfumes for over 40 years, fist saring in Diows Eau Savage in 1966 0 o% ~o rect edione fig Sialetal suc fig anc p-damascone at fray components of re 9) “The synthesis of Hedione gives four stereoisomers explains Gautier “Only one of them uly eontibutes to the odour ~ (+)-cis-methyl litydrojasmonate while the others are thought o modulate other fragrances. Over the years we've been able o synthesise new versions of Hedione which have a much higher quantity of the right isomer.” Gautier also has a soft spot for the rose Ketones: damascerone, and alpha an beiadamaseone, Firmenich is Famed for their discovery and syntsis inthe 1960s during a quest to ideotfy the characteristic smell ‘of Bulgarian rose ol. But hatch purity problems meant that damascenone ‘was not released commercially ui 1982, Then eame alpha-damascone (ose apple note) and bets-damascone (blackcurran-plum note). The rose ketones broke new ground inthe 1980s, giving female perfumes suchas Diors Poison their unusual and distintive fragrance. Tod, ‘eta-damascenone and beta-damascone remain (wo of the most important fragrance ingredients. 9 ° Jaclar isomers a-damascone and Pecamascone, fige ‘Chemists are forever improving on the rose ketones, which are still trendsetters, One of Krafts recent and "very successful captives is ‘Pomarose,a‘eut-open”seco-damascone. Pomarose introduced the did: fruit character of Poison tothe male market and had its debut in DKNY'S mule fragrance Se delicious Men ‘Ithas a very specific note of cooked pple, ros, and dried plums, Its very diffusive soit gives a lot of bloom toa fragrance, exthuses Krafl,Givaudan’s process development team had co wy 19 different synthesis routes before it managed to produce Pomarose. “Initially we thought we couldn't produce it It was a eazy idea that originated from a 1 percent impurity for which different structures ‘were proposed based on the NMR specirum, After we had discovered the correct structure we synthesised the “wrong proposal” for fun but it turned ‘out to beso powerful recalls Kraft. Interestingly, it wasnt the impurity itself thar became Pomaraso, hut ane of he alrorative structures. a a ee a Where else will] encounter these themes? 246audience? = Now we will look at the cherisiry in detail. Some of these questions will link to topies earlier inthis, book or Book 1, so you may need to combine concepts from different areas of chemistry to work out the answers 2. a, Deduce the molecular formula of Hedione from the skeletal structure given in fig A. b. Identify the two chiral centres in the molecule Hedione and explain how four isomers, are possible. Write an equation for the hydrolysis reaction of Hedione and 2 mol dm sodium hydroxide solution and draw structures of the products. 3. The mass spectrum below shows the molecular isomers a-damascone and B-damascone both found in rose oil wo. 0 60 omia= 102 20 0. vo 4 6 0 100200 a. Using the structures in fig C. identify which of the two is able to form optical isomers and explain why the other isomer is not. b. Suggest what species is responsible for the peak at m/z = 177. Can you suggest why thision fragment is so abundant in the spectrum? Activity Many diferent molecules are now used in adding or augmenting beth the avour and aroma of foods, Choose one of the fliouing groups of flavour moleculesand write a report for your classmates on their ‘wea favouring and smell additives: (a) Thiazoles (0) Pyrazines| (@) Ketones and aldehydes (@) Furanones and lactones ‘Your report should include the following Molecular structures Some examples of their usage [Any information on how they are either extracted or synthesised (© From Te Sweet Scent of Success by Emma Daves, Chemistry World, Febroary 200, [rrcwveey: Ty te highight son La - sills that you have | | developed throvghens [| eer | |} occ | | | OF chemistry beyond | J Aitinensersa, [ec | Sone ote ae a | | sora Did you know? __ A surprising ingredient for hxury fragrancesis ambergris,a yellonish-grey way substance that forms in the digestive tract ‘of sperm whales, Despite initally having a steong faecal smell the substance develops an unusual earthy scent asit ‘ages Although it has largely been replaced by synthetic alternatives itsstilla sought after substance. In 2013, a dog walker in Morecombe found 3 3kg lamp of ambergrison the beach a find itwas estimated te be worth £10000,ie 1 The structures of three organic compounds, A. B and C are shown, 4 4 4 I | o., c.. Aon CHO ca NB ca Br cH, ch, CH, A B c (@) Explain which two of these compounds are enantiomers [2} (b) Explain why a mixture containing equal numbers of these enantiomer molecules cannot be distinguished from the cther compound of the three in a polarimeter py (c) Compound A reacts with aquecus sodium hydroxide. Explain how measurements of the optical activity of compound A and the organie product of the reaction can be used to confirm whether the reaction occurs by an Sq! mechanism or an $y2 mechanism. (a) treat: 1 2. The srucre oft aon compounds ae eee me iv i td CS yyy Lif Ladd (sine wepnenicropemusaicsaaieriwiis 1H Dy Nita acca ees wate Hecomeanet aioe gail i (i) Bota compounds react with 2,4-dnitrophenyhydrazine Describe how the organic product of each ofthese reactions coulé be used to identify the carbon! compounds a (€) Give the structure ofthe organic product of the reaction of each compound with lithium tethydridoaluminate followed by water al (4) Only one ofthe two compounds reacts on warming with Tollens' reagent. ‘Write an equation forthe reaction that occurs using [0] to represent Tilens’ reagent, and state the observations that ville made when a positive results obtained, ia] (Total: 8] Exam-style questions 3 (a) The structures of three alechols are: cu, cH, cu, HCO CH—cH—CH—OH cH—CH—cH—on ci, D E F Explain which of these alcohols reacts on warming with acidified potassium dichromate{\/l) to form a carboxylic acid, @ (0) Draw the displayed formula of the nitrile that can be hydrolysed co the carboxylic acid withthe formula, (CH),CHCH,COOH a (0) The diagram summarises a sequence of two reactions. rege Ton} frerooa [areas Ta () Dede the name ofthe alcoho. a {i) Explain how the homologous series to which reagent X belongs can be deduced from the dgrar, el (i) Deduce the structural formula of the carboxylic acid. (1] (iv) ‘The yield of carboxylic acid in the second step can be ‘improved by using a different reagent before the acid in a two-step process. ‘Write an equation for each of these steps. 2) (Total: 10} 4 Addition and substnation reactions ae common 3pes of reaction in organic chemistry {2} (Bromine reacts with both propene and benzene Write an equation for each of these reactions, (2) (i) State the type of mechanism in each of these reactions, e) (b) The reagent used in the nitration of benzene is concentrated nitric acid. (0) The reaction is usually carried out wing a catalyst of concentrated sulfuric acid ‘Write equations to show how the sulfuric acid acts as a catalyst Q) (i) Draw the mechanism for the reaction with benzene. (3] (c) Explain why bromine reacts with phenol at room temperature, and without the need for a catalyst. (3) [Total: 12}5 The structures of two amino acids are: HN—CH—COOH —-H.N—cH—CooH crs siyine cystine {@) The isoelectric points of these amino acids are slycine 60 cysteine 5.1 Draw the structure of each amino acid in a solution with apH of 55. ia {o) These amino acids reac to form form two dipeptides. Draw the structure of each dipeptide ia) {6) Deserve how you would identify the amino acids in a tripeptide using paper chromatography. ic} (Total: 10] 6 ‘The compound 1-bromopropane is used as the starting material in some syntheses involving Grignard reagents, {a) Write an equation for the reaction between |-bromopropane and magnesium in dry ether to form a Grignard reagent ol {b) Identify the compound needed to convert this Grignard reagent into a primary alcohol and state the name of the primary alcohol. el {c) Identity the compound needed to convert this Grignard reagent into a secondary alcohol with molecules containing five carbon atoms and state the name of the secondary alechol. el (4) Identity the compound needed to convert this Grignard reagent into a tertiary alcohol with molecules containing, seven carhon atoms and state the name of the tertiary alechol. 2) (Total: 7] 7 The structures of two compounds are: cH, oH, cubic, ondisen, on on (a) Explain why infrared spectroscopy is not used to distinguish these two compounds. 2) (b) Explain how the number of peaks in the °C NMR spectra of these compounds can be used to identify which spectrum is obtained from each compound (4) (c) One of these compounds has a 'H NMR spectrum that shows only two singlets Explain which compound can be identified from this information, al (2) A simplified mass spectrum of each ofthe compounds is showa below. 100 4 100 57 29 at 1 14 ° ° om m © wo 9 a a 6) a 0 Explain how this information can be used to identify each compound (al (Total: 15]eases Temperatre/"C a 250 00 Maths skills 200 0 Im order to be able to develop your sills, knowledge and understanding in chemistry you will need te have developed your mathematical skills in a number of key areas. This section gives more explanation and examples of some key mathematical concepts you need to understand, Further ‘examples relevant 1 your A level chemistry studies are given throughout the book and in Book 1 Using logarithms Calculating logarithms Many formulae in science and mathematics involve powers. Consider the equation: l= 62 ‘The value of x obviously lies between 1 and 2, but how can you find a precise answer? The term logarithm means ‘index’ or ‘power’. Logarithms enable you to solve such equations, You can take the logarithm to base 10 of each side of the equation using the log button of a calculaton wouipaauns 108= 62 logy(10 = 1.792392. 810162) ‘You can caleulate logarithms using any number asthe base by using the log,() button 27 logi2) = log?) x= 2807355. Many equations relating to the natural world involve powers of e. These are called exponentials. The logarithm to base e is referred to as the natural logarithm and written la Using logarithmic plots An earthquake measuring 8.0 onthe Richter scale is much more than twice as powerful as an earthquake measuring 4.0 on the Richter scale, because the nits used for measuring earthquakes are logarithmic. Logerthmic scales in charts and graphs can accommodate enormous increases of decreases in one variable as another variable changes 100 8 ‘Tanpenture*C cSRSEEREE 460500 600700 800 900 1000 1100 Rate of restion/atbizary unis Lote eaction/atbitrary units fig A Logatthmc scales ate wef when representn rates of0 Graphs Understanding that y = mx + c represents a linear relationship ‘Two vatiables have a linear relationship if they increase ata constant rte in relation to one another If youplota graph with one such variable on the xaxis and the other onthe acs you get a straight ine Any linear relationship can be represented by the equation y = mx + e, here the gradient of the line ‘is mand the value at which the line cresses the y-axis is ¢ An example of a linear relationship is the relationship between degrees Celsius and degrees Fahrenheit, which can be represented by the equation F=9/5C+ 32, where Cis temperature in degrees Celsius and F's temperature in degrees Fahrenheit. ee oor 0. . temperature 60 Patnent fig Linear lationship beeen Fatrennet and Ct Js lemperature measuemes Using the gradient as a measure of a rate of change Sir Isaac Newton drew tangents to curves on graphs to find the rates of change of the varebes as part of his journey towards discovering calculus ~a fascinating branch of mathernaics. He stated thatthe gradient of a curve a a given point is exactly equal othe gradient of the tangent to the curve at tha point ‘To ind the gradient ata point on a curve 1, Use a ruler to draw a tangent to the curve at that point. 2, Calculate the gradient ofthe tangent using the equation for a linear relationship This gradient is equal to the gradient of the curve atthe point of the tangent 3, Include the unit with your answer 251Applying your skills ‘You will often find that you need to use more than one maths technique to answer a question. In this section, you will look at wo example questions and consider which maths skills are requited and how to apply them, open panes) The pH of an aqueaus slution is related tothe hycagen ion cancentatian by the following equation pH = -Ig[H") where hydrogen ion concentration, [H's measured in mol dn” Calculate the pH of an aqueous solution of 0.001 mol den? HCI. Assume the acd is completely dissociated. Give your answer ta two decimal places. tel] pH =-(g(0001) le(oo01)=-3 pH=300 el ‘A scientist observes an intresting by-product forming during a chemical reaction: reactant 1 + reactant 2 > desired product + by-product ‘She decides to investigate how the concentration of this by-product changes ducing the reaction by plotting ‘agraph af concentation against tie. She also plots the change in concentration ofthe desied predvet and reactant 1 “a ee reactant 1 oat > =| 9 desired product Hate i i # Fe byproduct a 06 oa oad 03 CConeentration/moldn-? 02 a Oommen eo ayant ie era “Time minutes fig € Concenvation of reactant and products ove the course of reaction. (2 Wat was the concentration of reactant 1 atthe stat ofthe eacton? (®) Calculate the eae of change of concen ation of the by-product afer 10 minutes. Give your answer in olde?! (Q Calculate the rate of change of concentation ofthe desired product after 10 minutes. (2) To answer this question, you need to find the value forthe concentration of reactant 1 when time is equal 0 2er0, That's, you need to find the intercept withthe avs ofthe line forthe concentration cof reactant 1 From the graph, you can see that his is 0.85 mol dar 252Be {b) In orderto calculate the rate of change of by-product concentration during the reaction, you need to find the gradient ofits line. The lines straight, meaning that thee sa linear lationship between the concentration and time. To find the rate of change, you just have to fin the gradient ‘ofthe ine by dividing the change in concentration of by-product by the time taken for the change. ‘Since the line straight, you can choose any 140 valves. Take care to use the correct units. Concentration isin mol dr but ime iin minutes, so you must convert time to seconds fo get the correct answer Concentration after 8 minutes » 0.24 mol dm? concentration after 12 minutes = 036 mol dr change of concentration = 0:12 mol cn? time taken for change = 4 x 60 = 240 5 change in concentration of by-product CE ie time taken for change = 212 mold? _ 9Q¢05 moan +s 20s {c}_ Tofind the rate of change of desired producti alte trickier because the line is curved. To do this, YoU need to draw a tangent to the curve then calculate the gradient of the tangent. simple way 10 4 this to craw a triangle with the tangent asits hypotenuse, centred onthe 10-minute point as asked (fig) a9: ee reactant Je desired product Fe byproduct 08 Concentration mold ° 03 4 6 @ 0 & i a te a Dime/minutes| {gD Fincing he ateof change of concn of th deste produc by craving a angen change in concentration between 8 and 12 minutes = 404 mol dmv time taken for change = 4x 60 = 240.5 change in concentration of sde-product time taken for change = 0,04 mol dm-3/240 s = 0.0001 66..= 0.0002 mol dens? rate of change = 253Preparing for your exams It is important to be familiar with the format of the Edexcel A level Chemistry examinations so that ‘you can ensure you are well prepared, Here are some key features: © You will sit three exam papers, each covering content from both years of your course. The ‘third paper will include synoptic questions that may draw on two or more different topics and. {questions on conceptual and theoretical understanding of experimental methods © You will also have your competency in key practical skills assessed by your teacher in order 10 gain the Science Practical Endorsement. The endorsement will not contribute to your overall grade but the result (pass or fail) will be recorded on your cenificate ‘The table below gives details of the three A level exam papers. A level exam papers Topics 15) Tepies HE Tops Topies 10-15 30% 40% Thour e Thour 45 minutes 2 hours 30 minutes 90 marks. 30 marks 120 marks multiple-choice multiple-chei short oper chart open ‘open-response open-responce open-response calculation caleulatio caleulation extended writing extended writing extended writing synoptic No No Yes ‘A aiinimum of 20% oF the marks across all three papers will be awarded tor mather Level 2 or above. at ‘Assessed by teacher throughout course Does not count towards A level grade but result (pase ofall) will be reported on A level certificate, 254Arrive equipped Make sure you have all of the correct equipment needed for your ‘exam, AS a minimum you should take © pen (black ink or ball-point pen) © pencil (HB) © ruler (ideally 30cm) (© rubber (make sur it's clean and doesn’t smudge the peneil marks or rip the paper) © calculator (scientific). Ensure your answers can be read ‘Your handwriting does not have to be perfect but the examiner must be able to read it! When you're in a hurry it’s easy to write key words that are dificult to decipher. Plan your time Note how many marks are available on the paper and how many ‘minutes you have to complete it. This will give you an idea of | how long to spend on each question. Be sure to leave some time at the end of the exam for checking answers, A rough guide of a minute a mark isa good start, but short answers and multiple choice questions may be quicker. Longer answers might require ‘more time. Understand the question Always read the question carefull and spend a few moments ‘Working out what you are being asked to do, The command \Word used will give you an indication of what is required in your answer Be scientific and accurate, even when writing longer answers. Use the technical terms you've been taught. Always show your working for any ealeulations. Marks may be available for individual steps, not just for the final answer. Also, even if you make a calculation error, you may be awarded marks for applying the correct technique. ane Plan your answer {In questions marked with an *, marks will be awarded for your ability to structure your answer logically showing how the points that you make are related or follow on from cach other ‘where appropriate. Read the question fully and carefully (atleast ‘ovice!) before beginning your answer, Make the most of graphs and diagrams Diagrams and sketch graphs ean earn marks ~ often more easily and quickly than written explanations — but they will only earn marks if they are carefully drawn. © Ifyou are asked to read a graph, pay attention to the labels and numbers on the x and y axes. Remember that each axis isa number line, © If asked to draw or sketch a graph, always ensure you use a sensible scale and label both axes with quantities and units. IF plotting a graph, use a pencil and draw small crosses or dots forthe points. ‘© Diagrams must always be neat, clear and filly labelled Check your answers For open-response and extended writing questions, check the number of marks that are available, I three marks are available, have you made three distinet points? For calculations read through each stage of your working. Substituting your final answer into the original question ean be a simple way of checking that the final answer is correct. Another ple strategy is to consider whether the answer seems sensible. Pay particular attention to using the correct units. 255Question type: multiple choice Which substance has non-polar molecules? 11 A Androgen fluoride 0 B water 0 € carbon dioxide DD ammonia Question analysis ‘© Multiple choice questions may require simple recall, as in this case, but sometimes a calculation or some other form of analysis will be required. ‘© In multiple choice questions you are given the corect answer along with three incorrect answers (called distractors). You need fo select the correct answer and put a cross in the box of the letter next to it (© The three distractors supplied will feature the answers that ‘you are likely o arrive at ifyou make typical or common terrors. For this reason multiple choice questions aren't as ‘easy a8 you might at first think. Ifpossible try to answer the question before you look at any ofthe answers © Ifyou change your mind, put a line through the box with the incorrect answer (8) and then mark the box for your new answer witha cross (5). © Ifyou have any time left atthe end of the paper, multiple choice questions should be put high on your list of priority for ‘checking answers, Average student answer © D ammonia Verdict ‘This is an incorrect answer because: (© The student has shown a lack of understanding of this topic. Question type: short open Complete the electronic configuration for the copper atom Cu ‘and the Cu” ion. Cus Ls? 28 2p Gir Is! 28? pt Ry 2560 Question analysis © Short open questions usually require simple short answers, often one word, Generally, they will be simple recall ofthe chemistry you have been taught © The command word will tell you what you need to do. Here the command word is complete so you simply need to complete the electronic configurations inthe space provided. Average student answer Cu: 1s? 2s? 2p 3s! 3p 3d! 4s? Cu: Is? 25° 2p" 38? 3ph 3a" Verdict This isa poor answer because: © The student has forgotten the electronic configuration of the ‘copper atom, Question type: open response Chlorine and bromine are elements in Group 7 ofthe Periodic Table. Both elements exist in a number of different oxidation ‘numbers and therefore are involved in many redox reaction’. Chlorine dioxide reacts with cold, ditute aqueous sodium Inrdroxide, The equation forthe reaction i 2C1O.faq) + 20H- (aq) + C1Os(ag) + ClO; aq) + HOW) Using oxidation numbers, explain why the chlorine in CIO. has undergone disproportionation. Gl Question analysis © The command word in this question is explain. This requires, justiication/exemplifcation of a point, which in this case is that chlorine has undergone disproportionation, In some cases of this type of question, a mathematical explanation could also beused. Average student answer In C10, chlorine has an oxidation state of +4. When it reacts its oxidation state changes to 43 in CIO, and + in CIOs. This means its oxidation state has both increased and decreased in the same reaction or in other words it has been reduced and oxidised at the same time. Verdict This is an excellent answer because: © The answer is logically structured. © ‘The student has calculated all three oxidation states correctly and shown that they understand the term disproportionation, 2357Question type: extended writing * The equilibrium reaction between carbon diaxide and water is important for maincaining the pH ofthe body by buffering. The equation for the reaction is: CO, + H,0 = HCO, +H Explain what is meant by a buffer solution and explain how a nffer solution works by referring to this equation. [6 Question analysis © In questions marked with an asterisk (*), marks will be awarded for your ability to structure your answers logically showing how the points that you make are related or follow on from each other where appropriate. © Four marks are available for making valid points in response to the question. In mark schemes, these are referred to as, ‘indicative marking points’. To gain all four marks, your answer needs to include six indicative marking points, The remaining two marks are awarded for structuring your answer ‘well, with clear lines of reasoning and linkages between points © Is vital to plan out your answer before you write it down, ‘There is always space given on an exam paper to do this so Just jot down the points that you want to make before you ‘answer the question in the space provided. This will help to ‘ensure that your answer is coherent and logical and that you «don’t end up contradicting yourself, However, once you have ‘written your answer go back and eross these notes out so that itis clear they do not form part of the answer. Average student answer [A butler solution is a solution that resists changes in pH when ‘small amount of acid or alkali are added, So if an acid was added then the pH wouldn't change very much and if an alkali vas added then the pH wouldn’t change very much, Bulflers can do this because they contain something that can react with any acid added and they contain another chemical that ean react with any alkali added so effectively these are removed and that means that the pH doesn’t change very much. Verdict ‘This is a poor answer beeause: (© The student has not used the equation given in the question to explain how a buffer solution works. This will limit the ‘number of marks they are able to obtain, 2580 Question type: calculation A phosphate buffer system operates in human celts The reaction involved is: HPO; =H + HPO; Caleulate the pH ofa 0.10 mol dm solution of HsPOs = 6.2.x 10 mol dm Pl Question analysis © The command word here is calculate, This means that you ced to obtain a numerical answer fo the question, showing relevant working, Ifthe answer has a unit, this must be included. © Always have a go at calculation questions, You may get some small part correet that will gan credit. © The important thing with calculations isto show your working clearly and fully. The comrect answer on the line wll gain all the available marks. However, an incorrect answer can gain all but one of the available marks if your working is shown, and is correct. Show the calculation that you are performing. teach stage and not just the result. When you have finished, look at your result and sec if it is sensible. © Take an approved calculator into every exam and make sure that you know how to se it! Average student answer (P01 = 6.2% 10" [H'] = (2 1080.1) =7.87 x 10+ pH = -log [H" Verdict This is a good answer because: © the student has completed all stops correctly and has shown their working. 259Question type: synoptic A student carrying out a titration wants o identify the piece of ‘apparatus that contributes most to measurement uncertainties in the experiment. The percentage measurement uncertainty is marked on the ipette as +0.06em", on the volumetric flask as +0.2em’, and on the burete as 41105 em®, The average tire was 25.50.em Deduce the most significant source of measurement uncertainty in this procedure. ul Question analysis ‘© A synoptic question is one that addresses ideas from different areas of chemistry in one context. In your answer, you nced to use the different ideas and show how they combine to explain the chemistry in the context ofthe question. "© Questions in Paper 3 may draw on any of the topics in this specification. This question is assessing understanding of ‘experimental methods Average student answer 06 * 100/25 = 0.24 % 2 x 100/250 Percentage uncertainty of pipette Percentage uncertainty of volumetric flask = 008% Percentage uncertainty of burette = 0.05 x 100/25.50 = 0.2 % ‘The piperte has the greatest percentage uncertainty. Verdict This isa good answer becau © The student has used the correet formula to calculate perventage uncertainty. There is only one error, and that is not ‘doubling the percentage for the burett. This is only penalised 260Glossary ‘An addition-elimination reaction occurs when two molecules join together, followed by the loss of a small molecule, ‘Adsorption is the process that occurs when reactants form ‘weak bonds with a solid catalyst. ‘An amphoteric substance is one that can act both as an acid and asa base. Amphoteric behaviour refers to the ability of a species to react with both acids and bases, ‘An analyser is 2 material that allows plane-polarised light to pass through it The original meaning of aromatic was a description of the smell of certain organic compounds. ‘The new meaning of aromatic is a description of the bonding in a compound - delocalised electrons forming pi (x) bonding in a hydrocarbon ring. ‘Asymmetric refers to a carbon atom in a molecule that isjoined to four different atoms or groups. ‘Autocatalysis occurs when a reaction product acts asa catalyst for the reaction, The basicity ofa base isthe extent to which it can donate a lone pair of electrons to the hydrogen atom of a water molecule. A bidentate ligand is one that forms two dative bonds with = metal ion, ‘A mechanism described as reacting in the rate-determi imolecular has two species ing step. A buffer solution is a solution that minimises the change in pH ‘when a small amount of either acid or base is added, Chemical environments of carbon atoms in a molecule are related to whether the carbon atoms are identically, oF differently, positioned within a molecule, ‘The chemical shift of a proton (or group of protons) is a number (in the units ppm) that indicates its behaviour ina magnetic field relative to tetramethylslane. It can be used to identify the chemical environment of the carbon atoms or ofthe hydrogen atoms (protons) attached to it. Chiral refers to an atom in a molecule that allows it to exist as rnon-superimposable forms. It can also refer to the molecule itself. Complementary colours are colours opposite each other ona colourwheel ‘A.complex is 2 species containing a metal ion joined to ligands. ‘A complex ion isa complex with an overall positive or negative charge. Condensation polymerisation refers to the formation of a polymer, usually by the reaction of two different monomers, and in which a small molecule is also formed, ‘When a base accepts a proton, the species formed is the ‘conjugate acid of the base. ‘When an acid donates a proton, the species formed is the ‘conjugate base of the acid. ‘A conjugate acid-base pair consists of either a base and its conjugate acid or an acid and its conjugate base, ‘The coordination number is the number of dative bonds in the complex, Derivatives are compounds formed fram other compounds, especially when the properties of the derivatives can be used to identify the original compound, Desorption is the process that occurs when products leave the surface of a solid catalyst. ‘The electromagnetic spectrum is the range of all wavelengths and frequencies of all the types of radiation, ‘The electromotive force (emf) is the standard electrode potential ofa half-cell (measured under standard conditions of, 298 K, 100 kPa pressure and concentrations of I mol dim) connected to a standard hydrogen electrode. Enantiomers are isomers that are related as object and mirror image. ‘The enthalpy change of hydration, A,, 4, isthe enthalpy change when one mole of an ion in its gaseous state is completely hydrated by water. ‘The enthalpy change of solution, AH, isthe enthalpy change ‘shen one mole of an ionic solid dissolves in water to form an infinitely dilute solution, Entropy isa property of matter thats associated with the degree of disorder or degree of randomness. ofthe particles. Equivalent protons are hycrogen atoms in the same chemical environment. The half-life of a reaction isthe time taken for the concentration of the reactant to fall t one-half ofits initial value Ahalogen earrier isa catalyst that helps to introduce a halogen ‘atom into a benzene ring, Ahazard isa property of asubstance that could cause harm toa High resolution mass spectrometry (HRMS) is atype of mass spectrometry that can produce M, values with several decimal places, usually four or more. A homogeneous catalyst is one that isin the same phase as the reactants. Hydrolysis is the breaking of a compound by water into two compounds. 261‘The instantaneous reaction rate isthe gradient ofa tangent drawn to the line of the graph of concentration against time. The instantaneous rate varies a the reaction proceeds (except for a zero order reaction). An integration trace shows the relative numbers of equivalent protons (ie in the same chemical environment). ‘The isoelectric point of an amino acid isthe pHi of an aqueous solution in which itis neutral i, = [H(aq)JOH (aq) A ligand isa species that uses a lone pair of electrons to form a dative bond with a metal ion, ‘The mobile phase is the liquid that moves through the stationary phase and transports the component. Amonodentate ligand is one that forms one dative bond with a metal ion, Amultidentate ligand is one that forms several dative bonds witha metal ion, Multiplets are the different splitting patterns observed (singlets, doublets, triplets or quartets). Nuclear magnetic resonance spectroscopy isa technique used toffind the structures of organic compounds. It depends on the ability of nuclei to resonate in a magnetic fel. Nucleophilic addition isa type of mechanism in which a ‘molecule containing two atoms or groups is added across polar double bond (usually C=O), and the attacking species inthe first step isa nucleophile. Asubstance shows optical activity ifit rotates the plane of polarisation of plane-polarised light. ‘The order of a reactant species is the power to which the concentration of the species is raised inthe rate equation, ‘The overall order ofa reaction is the sum of all te individual orders. ‘The partial pressure of a gas in a mixture of gases is the pressure ‘hat the gas would exert ft alone accupied the volume of the mixture ‘Apeak in a'H NMR spectrum shows the presence of hydrogen ‘atoms (protons) in a specific chemical environment. ‘A peptide bond is the bond formed by a condensation reaction between the carbonyl group of one amino acid and the amino ‘group of another amino acid ‘The pH of an aqueous solution is defined asthe reciprocal of the logarithm to the base 10 of the hydrogen ion concentration ‘measured in moles per cubic decimetre pH = -Ig(H'] This definition i difficult to remember, so either of the two equations given on page 27 can be used to define pH. PK,» -Ig K, 262 Plane-polarised light is monochromatic light that has cxillaions in only one plane. A polarimeter is the apparatus used to measure the angle of rotation caused by a substance, A polariser is a material that converts unpolarised light into plane-polarised light, Abase isa proton acceptor. Anacid isa proton donor. A racemic mixture is an equimolar mixture of two enantiomers that has no optical activity The rate-determining step of a reaction is the slowest stop in the mechanism for the reaction, The rate equation isan equation expressing the mathematical relationship between the ate of reaction and the concentrations of the reactants. The (overall) ate of reaction isthe change in concentration ofa species divided by the ime it takes forthe change to occur. ll reaction rates are postive. A risk isthe possible effect that a substance may cause to a user, and this will depend on factors such as concentration and apparatus. The level of risk is controlled using control measures. Six-fold coordination refers to complexes in which there are six ligands forming coordinate bonds with the transition metal ion splitting pattern isthe appearance ofa peak as a small number ‘ofsmall ub-peaks very close to each other A spontaneous process is one that takes place without continuous intervention from us. ‘A square planar shape contains a central atom or ion surrounded by four atoms or ligands in the same plane and with bond angles of 90" ‘The standard enthalpy change of atomisation of an clement s the enthalpy change measured ata stated temperature, usually 298 K, and 100kPa when one mole of gaseous atoms formed from an element in its standard state ‘The stationary phase in paper chromatography isthe liquid or solid that does not mave. A transition metal isan element that forms one or more stable ions with incompletely filled d-orbitals. ‘A mechanism described as unimolecular has one species reacting in the rate-determining step, Unpolarised light has oscillations in all planes at right angles to the direction of travel A zwitterion is a molecule containing positive and negative charges but which has no overall charge.Group (4) 6) (7) (3) atomic (proton) number atomic symbol Telative atomic mass 2 agig gest gale sag eis 22] velg raf sag 263Index ‘acid-base indicators 36-7 acid-base reactions 122-8, 124, 125, 126-7 ‘amines 204-5 amino acids 211 acid-base titrations 35-8, 43-4 acid dissociation constant K, 28-9, 33, determining 34 fiom a pH tration curve 43-4 acidic hydrolysis 184, 189 acidic solutions 38 acids Brensted-Lowry 24-5 dibasic 24, 28-9 monobasie 24-5 reactions with amines 205, stiength of 76-7 see als strong acids; weak acids ‘acsivation energy 157 activity effect 27 ‘acyl chlorides 185, 186-7 acylation reactions 197, 199 ‘addition-elmination 206 Adcition polymerisation 190 adsorption 132, 158, airpolltion 133 ‘alanine 210,211, 212, aleohais ‘acyl chloride reaction 186 tatboxyiie acid reactions 190-1 reactions 179, 215, aldehydes 176 oxidation 178-9 aliphatic amines preparation 202-8 reactions 204-7 aliquots 143, allaline hydrolysis 154-5, 184, 169 alaline-menganese batteries 102-3 alkaline solutions 23 alls. complex reactions 124, 125, 126-7, alkenes bonding 176 alkylation reactions 197, 198-9 aluminium oxide 52-3 ‘amides 187, 208, amines 202 cid base reactions 204-5 acyl chloride reactions 187 copper on reactions 207 tthanoyl chloride reactions 205 halogenoslkane reactions 206-7 preparation 202-3 see also butylamine amino acids 210-11 chromatography 213-14 forming peptides 212 ammenia 41 acyl chloride reactions 187, basicity 204 rmanvlacture 158 264 ‘ammonium ion 4 amphiprotic substances 25 ‘amphoteric substances 25, 123, anabolic steroids 233 _antisepties 201 apparatus paper chromatography 224 Fiske with 219 ‘aqueous solutions pHi measurements 32-3 strong bases 30-1 aromatic amines, preparation 203, ‘aromatic compounes 192, 195, nomenclature 197 Arhenius equation 160, ‘asymmetric cazbon atom 171 ‘autocataysis 99,135, 159 ‘avium sulfate 75 ‘base dissociation constant K, 33, bases base dissodation constant K, 38, Bronsted-Lowry 24-5 nie aid asa 25 see alo acid-base entries; trong bases weak bases basicity 204 Dateries 96, 102-3, Benedict's solution 178 Dbenaene ‘elocalised structure 194-5, lectophilc substation 198-9 Kelle structure 103-4 physical properties 192 Feactions 196-7 benzoic acd 29, 34 bidentate ligands 118-19 bimolecular mechanisen 174 ‘blood plasma 41-2 pH 22 Doving temperatures carbonyl compounds 181 carbowyie nies 183 Gerermination of 223, organic compounds 177 bonding carbonyl compounds 175 carborglie acids 182 covalent 57-3 dative 110 Gelocalised moonds 194-5, 198, 200-1 bnydrogen 177, 183, Born-Haber eycles 53-4, 96 ‘bromination benzene 193, 196,198 phenol 200-1 bromophenol bue 37 bromothymol blue 37, 38 Brersted-Lowry theory 24-8 buffer solutions 39-42, calculating the pli 39-40,

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