A: Ina hard water area, enough limescale is ;water pipes kettles end boilers in your house small bucket! _ | When you add soap solution to a bottle of water and shake it, soap bubbles may form. We say that the sample of water is ‘soft’. If a greasy solid (scum) mins on the surface of the water and the water looks swe say that the water is ‘hard! (Figure 21.1) Hard water is caused by dissolved calcium ‘hydrogencarbenate, magnesium hydrogencarbonate ‘fr magnesium sulfate. The scum is an insoluble ‘compound of calcium or magnesium ions with the long-chain: carboxylic acids present in soap. When hard water is boiled, the soluble ‘hycrogencerbonates change to insoluble carbonate GIHCO,) (aq) + CaCO,9) + H,0() + CO,/g) 21.1 Conjugate a and conjugate bases An Chapter 8, we Considered acids and bases in terms of ‘the Bronsted-Lowry theory. Acids are proton donors ‘bases are proton acceptors, feaction at equilibrium, Products are being " feactants at the same rate as feactants are 40 products The reverse Teaction can lerms of the Bransted—Lowry, water supply coming into the magnesium ions in the hard for the sodium ions in an equilib 2RSO, Na“) + Ca”“(aq) = R80, The position of equilibrium i in G products. So the positive calcium ions farm bonds with the negative charges oh thet the sodium ions are released The are soluble in hot water, so no. solidig: boiling the water. Qu for discussion Discuss with another leamer or group ofle Work with another learner to make disadvantages of hard water. Use textbooks or the internet to find other ways of making the water softer: Jse the ion-exchange equation shown © suggest how you could conver thers beck to its original form. Consider the reaction: NH,(g) + 1,0() = NH Gq) > In the reverse reaction, the NH,*ion do to the OH ion, So NH,” is acting’#s i acting asa base. NH3(@) + H200) —= base acidH-(ag)+ OFF faq) cn expression for this reaction ix n of water is very low. The ns and hydroxide the value of K) is extremely can regard the concentration porate this into the value of K sum expression then becomes: {OH s called the leaie product of water. Its value at 1.00 « 10“ moF dm We can use this equation to find the hydrogen: concentration in pure water, oe, oa eae es ‘water that ionises, onc Hthis equation [H] in pure water: i T]= JK, = f00x10* - 21.2 pH calculations We know that the lower the by the higher the pH. The pif values c ‘Bqueous solutions arc shown in His defined as the negat tydiogen ion concentration. pH=-log.. [H'] Note: # the negative sign is introduced to m positive in most cases culate the pH of a solution ncentration is $.32 = 10*mold Solution pH =-log. (8 = Jog, ($32< 7) =327“Caleulate the pH of the following yilutions: a [HP =3.00 © 10 mol dm & [H']= 1,00. 10% mol dav! 00 * 10" mol dav? £40 10°" mo dn? 80 X10 mol dav? {You should tote that the solutions in Question ¢,dand are alkalis They all have pH values greater than 7, Even though they are alkalis, they each have small goncentiation of H” ions, anid this concentration is used to falculate the pH. They each hive a small concentration of tions because HO =H? + OH isan equilibrium, Even Figure 21.2: 4 pit when there is an excess of OHL ions, there gescentration of H” ions In the same way, the solutions ‘Question 2, partsaand b, have a small concentration of © pH of 0.1 mol dar? HCTis (Off ions even though the solutions are a Jog (1 x 10° mol dm!) = pH t ite determing pH still small ately my HClis pH2 * pHof 0,001 mol dar HE is jog (1% 10° mol dim") = pH 3 * pHof 0.01 Rte l Jog (1 ¥ 10? mold f the use Here is an example c hydrogen ion concentration from pH. Use your own taledlator to-check that you get the correct » Question 3° Caleula nition of a solutions havin 2 plt2.90 b pH3.70 © pHIl2 d pHs.a0 pi 129 % The < Ifyou 101), check with Monobasis acids contain only one replace fin Booklel, oF ask your i 5 asey }#eH stom per molecule, Strong monobasic acids sgt btroetoric acid are completely ionised in $20 It follows from this that the concentration Fogen ions in soluti a tely th ar ene jon is approximately the Weasg,sS2mcentration of the acid (Figure 21.2) fon, nee ae the concentration of H* ions 2 aed of water molecules is very the «fot the concentration of Ht ions we the acid, teaching group to Diluting the acid ten times reduces the value of the Ht ion concentration to one-tenth and increases the pH by a-value of one,fon) ‘Step 2: Substitute the values és to-caleulaesiry, Mote Nodium hydroxide, ionise [ety = syn Solution, The concentration of hydroxide “ane Hin & solution of sodium hydroxide is therefore GPProximately the same as the concentration of the sodium hydroxide. “To calcula =2.00 107 mo} det Step 3: Calculate the pit Hethe pH af a solution of strong base we need pH = Jog. TH fe ‘ "By fH] the concentration of O ions in solution "Bie (200% 10-8 © ths equilibritm expression for the ionisation ay water: Tick Way (0 get the same anemg * k= [Ht }(01} f Tor whe * fd ~tog,, {1 (here og, * the value of A for water ic, (0.0500) 615) ee ASK, =[H')(OH} * Subtract this value from 14 fi this mek ample 14 1.3129) tu Diy Works because 8, (H"] ~ log, (OH ]= 14, Wecan calculate the (11+) ana then calculate the pf sale 2uestion ic pH of the following strong acusande ong hases 1.00 mol dar? HNO, 0.500 mol dar? HNO, 28 aqueous solution containing 3.00 g HCI per dm! 8.001 00 mol dm? KOH oreK and Ween apply the equilibrium law (see Section 8,3) to aqueciis solutions of weak acids atic weak bases. For Seample. when cthanoicacid dissolves in water the Howinig equilibriuan results: CHCOOH(ag) + 1.01) = H,0°(4q) + CH,COM tag) an simplify this equation to: = Hii{aq) + CH,COO (ag) cH.COOR( brim expression for this reaction i The equi _fie1}CH,c00} coo e 44298 K, th the dissociation of ethan eon (Ha the equilitsriur oral “Alan tor the dissociation of a woak acid 1 , eit = snined . WA molecules and tl anaritively few t \ Ay K, vallios te nayny ay tow, We ein ise 16) CpAANY they aArCA\EA2 small pin tont ofa sy means the negative ii carbonic wid iv hydrogensilicare ton about 40) 1.5% 107 6.0 x 10% CH,CH,COOH = 1.3 x 108 (AlH,0),) [€0,+H.0 =H: + HCO, SiO, + HO =H: + HSiO, 1.0 « 10*LK eh lb of 1 thi oie, WI OWE A Tit Ma pHOGEA (HHH nn THAN WE MO Cig We honinaitiion ot emia Question Te sai vr Fhe equiltvAin epronaian ca Pniatei be La! ee HAT 10.000 iol di* 2oaminebonaald why, WAL whieh haw n pitt AN, iy raion mete, Whol aad w Wi Hosiny litt ptt yy) ; HH 0100 desl ties Saline hetel, Whig Wink A THOM TO CTGTNKE Ne Yate A, we rate t phatase neumptiony bh Calowlate pA), voto fet ogih of the wold, # Weignone the vonnentrunion of pact JweAliwed by the inition of 1) nile PrenenT UH Mie wefition, Hh | hi ’ 1a the otret He nie prcadwet of sawn (1.00 = | Dy vegipible vornpured WOME Welk (eee Table 21 2) © We surne that the ionination «i Hloulite the pH vale Cor (HY) oF a weal wed Av ht The conicantrstion 0f we hao He Beeihos present wt eqyuilibriurn po) SHE Tht Of the original wid : + the conuentrnton OF ie et He value of K for the mold ser gui, we Muke the yanke WhuMptiony aboun he mttationt of; the wok wotd ion Gt Hyulrogen ins prentiveed by thie Jonmation af waiter ind the equilibrium eondentrttion, of the wouk cid. The value of the pH ealeuilatedl will ae i not bo significantly affected hy these factors inieas we vale of K for rettanale nid require great aveurvey (For exaniple, caleulating pte. .ON0 tryol dns * thethanle wold the thitd decina) plack), HH of 2.90, Worked example 5 stows how to calculate pHt fram value of Band concentration of the weak agid,.: 0 SHER IE Write the cquitbrim expression for the sep CLG EW.COOH ay) = pH = lon HY H(aq) * CH,COO (ay) = log, (1.32% 104) Ka WT oe x 2 fia cH,coom 2-8 (C0 3 significant gal Step 2: Enter the 174 1 } : hanoie atid and sodiuin ethanoate jy dy Question on = ; ons act as buffers hetween pH dale We can understand how a builer solution eferring to the equilibria involved (Figuegh joate ions in soli j CH,COOH(aq) H'(aq) + CHCOORm 21.4 Buffer solut tre “= noate is fully ionised in aqueousy OONa(s) + aq Na*(aq) +H i ethinoute a solution that minim changes in pH when moder. or base are added. AA Differ solution is cither « weak acid and its conjugate base ora weak base and its conjugate acid, which Apinimises any change in pH when wn acid or alkitli or Figure 21.4: The pH of this agar pate ixkopt consiankis wa 9 pe of buffer solution is « mixture of weuk acid solution is added into the aga bne OF its salts. An example is an aqueous ruinture cid und sodium ethanoate. Mixturestion to explain how buffer solutions ease in hydrogen ion concentratio HH of water, but when H* jot. « Nf greatly ded 10 ‘of H* ions shifts the position of um to the left because H” ions combine CH,COO™ i ‘dons to form more CH,COOH until the lage reserve supply of CH,COO-en jsoncentration of CH,COO™ ions i ‘aot change significant! n does not change significantly pH does not change signific: fonscombine with H~ ions to form jum shifts to the right ionise to form more H" high enough to cope with 1 Pollution involved. No buffer solution can cope with the of acids or alkalis. If very large amounts: alkali are added, the pH will change: Buffer solutions that resist changes pH im alka regions are usually a mixture of a weak base an? conjugate acid, An example is mixture of ammonia with ammonitit chloride. Aqueous ammonia is a weak base, so there! concentration of ammonium ions in ammonia NH ,(ag) + H,0 (1) = NH "(aq) + OFF (aq) Ammonium chloride is fully ionised in aqueous solution. This supplies the reserve supplies of the conjugate acid, NH," NHCi(aq) = NH,"(@q) + Chg) Question @ — Aymisture of 0,500:mo} dim” aqueots am » S00 mol dav ummoniuny ehloride rf solistion, a shunges in pH on addition of 4 dilute hydrochloric agid Ww dilute sodium. wry b: first find the hydro, then rearrange the equill make [(sodium) “en expression. What is the pH of a butter salt t 100 cm" of 0.1 mot dm*/meth 50 cm? 0.1 mol dm” sodium it K (HCOOH) = 1.6 * 1 al ane buffer solution HCOOH = HCOO-+H: "the salz contains the HCOO. ® ~HEOG=and HCOOH are a con). 0 mol dm Bisons 4 acid und 0, 01800 ma! der sodium propanoate (ky Propanoic acid *10' mol dm”)buffer solutions by adding a solution of to its eonjunite bare or 3 weak bane es coriugete acid until we get the pH thats [required The more concentrated the scid and cone base, the more effective is the butter Spuition at preventing a change in pH Put SO em! of 0.1 mol dir” ethancic acid in a small beaker dd a spatula-ful of sodium ethanoate and stir wah a glass rod until the sodium ethanoate dissolves 8 of universal indicator solution re colour and determine the pH B Sefusinal processes including sdusinal proces ire of dyes dnd in the v * Haemoglobin and plasma proteins ® diydropenphosphate (H,PO,) and iylrogeriphosphate (HPO,*) ion: PBs pHi of the blogd is often checked by doctor S38 gat mformation which helps identify theworkings of the body (Figure 21.5) Ticeli in our body produce carbon dioxide as 3 Prat of aerobic respiration (the oxidation of glucose Tepe ets) Carbon dioxide combines with watet ood to form a solution containing hydrogen ions AMG) H.Ofe9) = Hi{aq) + HCO,{ag) Iydmgencubonate on fe Balec waar a and then dliite the solution very ofad ‘more distilled wator until you get the sarne pH ‘as the pH of the bulfor solution. You may need, to add more indicator to get the ime colour intensity as thie bufler solution: 7 Label the beaker ‘unbuffered solution’. 8 Add one dhop of 0.1 mol dey sodhutty hydioxide to each of the beakers. Observe what happens. Add a futher diop of sain hydroxide one ata time, to each of the boakors. Which solution is best at resisting pH ange? This reaction is catalysed bi yme carbonic anliydrase, When the bloga passes through the small blood vessels around our hungs, hydrogencarbonale ions ane rapidly converted to carbon dioxide and water, THE: nofH i left unchecked, would the blood and cause *ucidosis”. This body functions and eventually lead arbon dioxide and ilibeivem. Dewwes carbonate is the most important buffering. : position of this equilibrium shifts 10 the lett mbine with HCO,” ions to form dioxide and water until equilitsrium is res * this reduces the concentration of hydx the blood and helps keep the pH constant If the H’ fon concentration decreases + the position of this equilibrium shifts to the Tight «some carbon dioxide and water combine to form: Hand HCO, ions until equilibrium is restored + this inereases the concentration of hydrogen ions i the blood and helps keep the pH constant,however, are insoluble or only, But even ‘insoluble' ionic compa toa very small extent in water, Sone quoted as the umber of grams orl compound necded to saturate 190, a given temperature, We say that aot whet no more salute dissolves inj Sodium chloride is regarded agg salurated solution contains ey po Lead(Il) chloride is regarded 4s ian inug saturated solution contains 0.99 pari An equilibrium is established when an i Figure 21.5: Anaesthetists monitor the pli of , in contact with hee nus. The ions move from the slit hee = rat the sitme rate as they mae tm ein igure 21.6), Question 3 Wa Oneo . "@ ae HI ‘os Oy Figure 21.6: 4 aid silver equilibrium equation f (Pr= proicin) HPr=H* + pr Explain how this system ¢ Prevent the blood getting molecules ate an act its is butle too acidic ; at of a sparingly soluble sat cu itaSo ween write this equilibrium, expression ayy K,=(Aetaa) [era AK. iscaled the yohiy K. + Vanes are quoted at A= {OMIA (aay where #is the number of © cations in one formula unit ‘of the compound and 6 is the number of Av anions in one formula unit of the compound. So fur Fe,S, (which contains Fe" jons and S* ions) the equilibrium is: FeS\() = 2 and the equilibrium expression is: K,=[Fe"(aq)) 1S" (aq)! The idea of solubility product only applies to ionic oompounds that are slightly soluble e"(aq) + 3S (ag) The uitts of solubility product depend o mt Of each type of fon present in solution A the units out in the same way as f ‘eapressions (see Section 8 aay cancelling. For example, for the expre = [Ma**(aq)) * [OH-(aq)F = mol dinr' x (mot dim) * = nol! dm? The idea of solubility product is only useful for pel soluble silts. The smaller the value of K ‘isthe solihility of the salt, Some yalues of ‘in Table 21 3, ShCO, TOx 107 2ntOH), 20% 107 2n5 1.6% 10% Table 21.3: Saine values of solubility product ot 278K Question Write equilibrium expressions forthe solibility xuets of the following I mits of solubility product for euch of ds in parva, i jons You may be asked to calculate the solubility product of a compound from its solubility, or you may be asked to calculate the solubility of a compound fron its solubility product, An example of each of these types of calculation is shown in Worked examples. Tand 8,aves the equilibrits equation, MeP (5) <= Mitaq) + 2F (aq) 2: Calculate the concentration of cach ion in : solution: Step I: Write down thee ‘When 1/22 « 10°? mol dissotves to form CuStI == CHM agi: 4 dim! of solution the cone Step 2: Write the equitibrum, : each ion ix of one ion only. From the equilibrium: (Cu"| =|") So Step 3: Substitute the wijive gf KL (6.3 * 10) =(Cuep Step 4: Caleulat Step: w ; 3 In this Case We take the sg Step $ Subs [Cu*]= JR, (Cu*]= 6.3310" S255 Culeulage the solubility following solution sulfiche, Z0S. H waaturated aqueous sot (AK, #168 104 noF diy Sulfide, CS (solubitiry Calculate the solubility OF as 146% 10°" mol dm) Agcy, (K,=6.3% 10%) Tip: you havele und sodium carbonate are soluble por barium carbonate is relatively insoluble: We j consider the equilibrium for the insoluble salt in. water: faq) + CO.* faq) “Fhe solubility product is ziven by: = [B81 [CO] = 5.5 * 10°" mol? dav ri" (CO, is greater than 5.5% 10°" mol’ dma peesintate will form 1c Jess than 5.5% 10°!" mol din {Ba**][00, >] Is less than spate al form (see worked exam 9, Remember that solub de to loride. S€empound that has an ion in cc fat This often results in pro P Willa precipitate form if we mix equa volumes B if solitions of 1.00 x 10+ mol dmv? Na,CO ae $0010 mol dn! BaCl,? : ; an the solubility Solution product, so a precipitate of barium carbonate 10) = 500% 10% mol dm fon = 2:50:10 mol dmA 65310" B Lion 10% Cc RT x 108 D 435-1 ‘an ionic compound in aqueous a common ion is less than its The principle of partition of a solute bey ° two solvents helps us to understand me coxa, lubility of barium sulfate, BaSO,,in OW we separate the components in a Bee Sis ael oan the solubility of barium chromatography (see Section 30.1)) Lets Hin 0.100 mol da” sulfuric acid, H,SO,. is only ammonia dissolved in two immiscible soli 1,0 * 107 mol da? Immiscible solvents are solvents that in cach other and so form two separa {We can explain the lower solubility in sulfuric acid by (Figure 21.8), i felerring to the solubility product of barium sulfate: K, = [Ba] [80,7] = 1,0 * 10°” mo! dnx If we ignore the very small amount of SO*(aq) {ro the barium sulfate then [SO,*] is 0.1 mol dns’ (/ sulfuric acid). This gives: ; i 1.0% 10° = (Ba°*] x [0.1] organic {Ba®) = 1.0 10? mol dm” Questions Aa Thallitni(t) chioride is a salt shat is sparingly soluble in water. When hyelrochlori acid i aidded tow sutiirated solition of thalliym(t) Phlonide, a precipitate is formed. Explain why & Procipitate is formed, Sulfate fs a sparingly soluble salt Figure2}-e: Ammonia’ pe ie by mixing solutionsee sacad. The end-point proctor = twas found ta be pica! of asd {What i the partition coefficien ipetween these tro solvents st > Solstion The alkaline snmonit solutic Bute bydrocblors 220. 4 seat NEifaq} + HCH29) Tmo of amon: tspeqotx mol = =9.40* 10 mol Themenber of moles of amor | Biper eres be equal to the jaitia! ou" ack shows an tieat x than in theused in the partitioning. uth of the intermolecular ‘bonds with water. So ammonia is very ;, Ammonia is less soluble in org ‘45 trichloromethane (CHCI,) because the between ammonia and the solvent is permanent manent dipole, which is weaker than Papi Go the partition coefficient; K.= INH,(CHCI, TNH\(ag)) isles than | because the concentration of ammonia in CHG, is less than the concentration of ammonia in water Todineisa molecular element and will not dis: ‘Well in water. In order for it to dissolve. iodin hydrogen bonding between water molecul the strongest intermolecular forces. The iv disrupt the hydrogen bonded structure of w dissolves in organic solvents such a are non-polar molecules lodine forms ins /ipole—induced dipole bonds with cyclolex does appear to dissolve in water to a very tall extent. This is due to the equilibrium PHO = 10-+ 1 + 2H: of equilibrium is well over to the Itself is not soluble-but the ions dd so the iodine appears to dissolve t solutions of iodine in the dissolv f nromatograp In paper chromatography, the difern coefficients of the components id y to their relative solubilities in the two Worked example 10, the relitive soli in water is greater than in the ongalhi chromatography, the mobile phase is The other solvent is the water trappedin structure, which is the stationary phase Fy solute molecules partitioned between. ind a stationary liquid phase on a solid solute molecules dissolved in the stationary liquid phase Figure 21.9: Partition chromatts mmaves over the station liquid particles with it. The filter paper paper chror