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]