CHRIS LAU Topic 6 : Equilibrium B) Acid-base Equilibria 1) Definition of acids and bases t. Arrhenlus’ definition (Neutmlisation) ¥ OW (04) ‘Acid [ Compounds that dissociate in water to produce HT Tons Base [ Compounds that dissociate in wate to produce OFT ions, = Limitations: i. Cannot explain the acid/base properties of certain compounds that do not contain OH of H Eg: NHs (Alkali), AICIs (acidic) ii. Only restricted to aqueous solution. b. Bronsted-Lowry Theory (Acid-base Equilibria) HW’ Jone [0st 69 Bronsted acid = Proton or H” donor Bronsted base = Proton or H acceptor Eg HCl, HNOs, HF, anionic or eationie| Eg: Negative ions or neutral molecule with a fone salts that have proton to donate | pair of electrons that can form dative covalent (NH HS.) bond with proton, such as HO, F. NH: CHCOOH + 505 CH;COO + HO” NH; +H30 = NH + OH Acid : CH;COOH Acid : 1:0 Base: HO Base : NH; Conjugate base: CH;COO" Conjugate acid : NH." Conjugate acid: HO" Conjugate base : OH" ~ Conjugate acid : species formed when a His added to a base = Conjugate base: species formed when aH” is removed from an a ‘Advantages: Can be used to de and bases in gaseous phase Eg: HCI (g) + NH3 (g) > NHACI (s) 2. Can be used to discuss the strength of acids and bases HA (aq) + H20 (€) * H3O" (aq) + A’ (aq) If degree of dissociation, a increases, equilibrium position shifts to the right. 3. Hexaaqua complexes, [M(H;0)6]" which have small highly charged cations (such as AP", Fe”, Cr’*,Be™) act as Bronsted-Lowry acid in water. Eg: [Al(H:O)s]°" + HO = [AI(H:0); OH" + Hs0" Limitations: Les\s > 1. Chemical species that do not contain H+ are not defined as acids, eg: BF & B(OH); BF;+:NH; — — BF;-NHy B(OH); + H,0 = BOH)s +H" ©. Lewis Theory (bonding) Lewis acid = electron pair acceptor Lewis base = electron pair donor Species that ean form dative covalent bond by | Species that has an unshared e* pair which ean be accepting €” pair from a base. donated to form a dative bond with a spec Eg: - _ all positive ions Eg: - all negative ions = Molecules with incomplete octet | Molecules with lone pair of electrons electrons such as BF3, AICI, BeCl: such as NH3, HO, R-OH = Oxidising agents = Reducing agents ‘Advantages 1. Acid-base reactions can be extended to include reactions in which protons are not involved. BF;+:NH; — — BFs-NHy 2._Lewis bases are also Bronsted-Lowry bases as all electron pair donors can accept a proton.3. Lewis acids (eg: metal ions) need not be Bronsted Lowry-aeids (proton donor). Lewis acid include not only substance containing H+ ions but also cations and molecules with empty valence orbitals that can accept electron pair from Lewis base. tion: 1 cannot accept an electron pair: HCI (g), Bronsted acid is not an acid from the standpoint of Lewis Theory because it 2) Types of acids and bases Strong Acids Weak acid = Dissociate completely in aqueous solution to produce large amount of 10° ion (= 1 of 100%) Dissociate partially in aqueous solution to produce small amount of HO" ion (a <1 or < 100%) = Most mineral acid = organic acid Strong base Weak base = Dissociate completely in aqueous| - Dissociate partially in aqueous solution to produce large amount of OMT ion (a= 1 or 100%) solution to produce small amount of OH ion (@ <1 or < 100%) Amine (RNH3) 3) Comparing the strength of acids and bases x PH=- log(tt*] Degree of dissociation, Dissociation constant, Kor Ky & pKy = whereby ~ pH J acid strengtht ‘Temperature,T must be constant. y [ ] must be the same and smount dissociated anne original amount preasiekee KemeaKy ALIS*C, ~a@ varies with [] “Kit, -KeT, acid strength 1, | base strength 1, neutral ~if [J isthe same, at, |_pKat py acid/base strength T = Dissociation constant only -pH value changes with [] depend on T, it will not vary with [] 4) Dissociation 1 Ostwald ~ formula that shows the relationship between the [ ] of weak acid/base, dissociation constant and degree of dissociation, « HA + HO By ern Initial [] © [reacted / formed Equilibrium [] (ws0sita (waltr20) bs041104 Ke= cana) Teal Oe ie a oe For wetk acid/base, ? > [Kaew ca ca =ca? Vkaxe4.2 Dissociation constant of polyprotic acids - The acid molecules dissociate in stages and each stage has its own dissociation constant. One stage dissociate I proton. - The acid dissociation constant for the combine process : Ky =Ki x Kaz, Kar > Ker ‘4. Determination of acids and bases ‘Strong acids ‘Weak Acids Sirong bases ‘Weak bases (i) Determine [H"] Directly from [] | (H"]=VKaxc Directly from [Jo | [OH] =VKbxe of strong acid eee strong base a Gi) Determine pit pH=-ig [it POH = -Ig [OH], p= 14 -pOH 6. lonie product of water. Ky, 6.1 Derivation of Ky HO # H+ OH 6.2 Factor affecting Ky : Temperature, From dissociation of H:O to form H® and OH", when TT, Kuh Relationship between K,, Ki K, A'+H;0 — HA + 0H Ks of the conjugate base = HATCH) Kx Ky = Ky =[H"] [OH] +The weaker the acid, the stronger the conjugate base. ‘The weaker the base, the stronger the conjugate ac. 8. Relationship hetween pK, . pKy .and pK, Kx Ky =Ky Ky=[H"] [OH] slog Ku=-logK,+(-log Ky) -log Ky =-log [H+] + (log(OH-}) PK. = pK, + pKy pK, = pH + pOH = log 10" 14= pH + pon 4 procedure used in quantitative chemical analysis to determine the concentration of either an acid or a baseSN SEKOLAH MENENGAH KEBANGSAAN SACRED HEART 4a) 50 Se». SACRED HEART SECONDARY SCHOOL Eg. The acid dosociaon constant, Ka, Kea and Ke of phonporc ac, HsPO« are 79x 10° 6.3 10* and 40x 10" mol dm? respectively. {G). Vitte balanced equetions to represent the three stages of dissociation of HsPO., (0) Wite expressions for Kus, Ks and Kes fe) Caleuiate the acid dissociation constant forthe dissociation of HxPO. 2s flows: Hs, —=———= 3H’ + POW 4, Caleulate the pH of 0.10 mol dm solution of sodium ethenoate (Ke for CH:COOH = 1.80.x 10° mol de?) 2. Calculate the pt of e solution obtained from adding 26.2 em of 0.1 nol:im'* 20H solution to 25.0 em of 0.05 mol dm’ 7 | Ga) Saget: HsPO, +H20 = HetOu 4 sO" by Ka= UeroeIL HoT Soge 2! HsPO,7 +H:0 = HP0q* + H30* Vag = TARE EHO | Stage2 HPO HO PO + HO" Keg » SE pr? Se 1 Kae ee TW od = Koy X Kaa x Kas = 29x10 x 6,3¥10® x Hoxton ® . = 199 X10 mold? bi | “1 pH= D-pod ha? kaxk, oth +ha( Te xc ) Loni’ = 1sx® x¥, | = ht loq( eto x oo) Ky 5 5b x0 Oa dni? = 83t 2 LNodH + H280y > NaSO4 +50 hd aealkD 25:0(0.05) “206. akan = 1d5x0° From enuation, Irmo! H>S0q + 2mo) Nao 125K Oo) Hoty. * 2.5010 vef NAO nlNaOA) unreaded = 3520 d.69xt0> Pu = = poH = 2.00 x10 Sma | = DY +lo9(3.98'x0™) = Woh TNaoH] = 22. 399 K00* M es = ‘Calon hendakiah menggunakan Kedua-doa bela moka surat. (Condes are eed tows hth sues of he paper [REJUJURAN MENCERMINKAN KEPERIBADIAN ANDA | HONESTY ISA REFLECTION OF CHARACTER3. What isthe pHi of 1x 10" mol dm"? HNOs 7 4. Aqueous dimethylamine of concentration 0.010 mol dm’ has a pH of 7.69 at 288K. Calculate {a) the degree of dissociation , and (b) the base dissociation constant, Ks, for dimethylamine. 5. Calculate the concentrations of all the species prosont in 1.0 mol dm” CH:COOH at 288 K (i, of CHCOOH = 1.80 x 10 ") 3) HNQS* = BENDS” SHA oH” tal HED eto Sem 1xto7 Hw 8aa}” — Tete Spo) io pi =~ Tog ht = Log f-1x10 : a Habe Gledote HFT in H>0 when HA 1s too dilute AL pus WH +begd Rene Co) ky = Col™ 184 = 14 +log (Tk, 0.00 ) 6.03410" = (0.010)( o )™ 0) Ki, = 6.03 x10" mot nS L = WIGYT™ mol dm ® ~ 5) Cs@on =, cry to0"+ H* CHs(00H © = TCUsto0n + - «AT TH =dRaxe Intel] 1.0 0 0 = [Tee 0 [Vowel reacted 4-000 Ames a saxo TT 10-94 0° =0.94b Haw xis 4H sero =A.at x10 at dae? 6,a)in sn aqueous solution solution, the ethanoate fon reacts with the dihyérogen phosphate ion according to the following ‘equlliblum.: CHjCOO(aq) + HPO, aq) = CHsCOOH(aq) + HPO,” Give the formula of the acid-base conjugate palrs for the forward reaction. [2] (0) 4-aminobenzoic acid is found in many sunlight protecting preparations. The H” concentration of an aqueous solution ‘of 4-aminobenzole acid of concentration 0.03 mol dm fa 8.1 x 10% mol dm. (Write the structural formulae of 4-aminoberzoie acid. Write an equation to represent the dissociation of 4.aminobenzoie acid in aqueous solution (ili) Calculate the pH of the aqueous 4-aminobenzoic acid. [5] (312001) ~ ba) aod 2 HPO, bse Cligt00™ Con}paete base : HPO.” conjugate acid! Cy 00H tbe) pies ot ct) NH<2-cood 430 = NHSXLBYCOOT+HEOF u = “4 i o*) = *74a) Boric acid, B(OH),, Is an antiseptic found in some eyewash. In an aqueous solution, boric acid acts as 2 Lewis acid. y () Define Lewis acid. (W) Explain the aciaic property of aqueous boric acid. [6] 3 {(0) Phenol,CgH,OH, isa woak organic acd, A solution containing 0.3859 f phenol in 2.00 dm° of water has a pH of 6.29 at25"C. (ll) Calculate the acid dissociation constant Ky of phenol at 26°C. [9] (12002) Toy oy OH a Lan ci) HO REO, 40 = [ro- bao] +H0" ba = be In aqueous cokation, Bovic acnd vs tothe bem of BLO BOH)y. A will dssoaate in vereor to form HO". Fermatin of H30" exes shows the ache property « PFS este esd ce. sao eae oe lec pei trom base chyen) phe 624. ~~ log Ti" [ Gaeon= ( any as) 5.05 x10 pao dav Ka = 1:3§ ¥10"" wal et tye) Ethanol acids an example ofa weak acd aes “(adie tie properties of ebanok si ays Bronte ct,“ (c) A solution is prepared by mixing 250.¢ 0. cm? of 0.05 mol dm’ nite agin ee ‘om? of 0.05 mol dm calcium Ae otaton Cala the pH ofthe solaton. (6) 12 (6/2003) Sta) OgW00R + H20 = CMs(00%. HOT During dUsscciation tn Water, ethanore acd clofode: H* ron sto fom H30%. fermeation. of H36* okt wade property. ) DHNOs + Od), > 2HsQ + GCNO5)s (Tambor eFiwole of Rigs = S80 C08 0.0195 mol number of mole of Cat0H), = =BOSR2) - 0 o125mol From equation, Amol of HNOz - mol of Calon)> G05 mat of HNOs + 6.25 x10 Sol of CalOH)s. number & mole unreacted GlAUs = 0.010- 6.25xI0> SP tats = =e tea GaSx0 Smal9b) Ammonia is prepared in industry by using the Haber process and itis used to manufacture chomicalfortlisers. i) Stato one physical property of ammonium salt that makes itsultable asa chemical fetliser. ssile wea {iin aqueous solution, ammonia acts as a base. Write an equation forthe reaction involved. Gjve the chemical formulae cof the conjugate base in this reaction and state te type of hybridication ofthe ammonium ion.“ Ul) State the contents of tank of ammonia gas which i lef to sfand in a hot spot fora fow days. Give a reason for your ears ier Rs RAE sass SS Slane et a) ne solr 38, aay in twdter «iy + 10> NHyt + oH” ivgate base 1s ORT WIA? bas of? bypidsation “rs ci) Ns, Na ands. A portion of Als dissociate into Hts elmer? gas dissolves in watar to form carbonic ackd which can further react wit calcium carbonate. The 40 b) Carbon ai equations forthe eatlons areas follows. whenLl,0 eugene, 2 fest oon = COfg) + HOM) = H,COs(aqh “hupowe a rein 2 veastin (ats os dapeattnct H,CO,(aq) + CaCo(s) = CalHi0,),(aa) () How would the above equilibrium equations explain the formation of stalactites and stalagmites ina limestone cave? (i) Carbonic acta is 2 weak acis with dissociation constant 4.3 x 10” mot dav®, Calculate the pH of carbonic acid with eoncentration 010 mol dm 981 (80/2008). 41. Bactorial fermentation of lactose in milk produces yoghurt which contains lactic acid, a monoprotic acid. A sample of a ‘yoghurt deine hao pH 3.82. (@)Befine pH. 11] 9 -ley(t") IDcd)ciy Stolactites aro stalaguites IS the bie lds. When H2D ace =m postion of reaction » <= This promde he =m position in getoed reaction Gales 's deposited: o) pe ~ ait iT n)_ pH =~ lyfe] Be aX , = ae Be 1 Dil g (6) Cateulatethe concentration of hydrogen ions in the sample ofthe yoghurt drink. (1) 3,02 io" M\ {€) 25.00 em’ of the yoghurt drink requires 27.85 cm of 0.1000 mol dm potassium hydroxide solution for complet tation. Phenolphthaiein is used as an indicator for this titration. Calculate the concentration, in mol dm’, of lacte acid in the yoghurt drink. 2] Oude weak aud ~ pateally,, 1c) [mete aud) Or] (G) Explain win the values obtained in (b) and (c) are differént. (2) {) Calculate the acid dissociation constant, Ks, ofthe lactic acid, [2] °° Y"* az (rz01) | Tet] tO HY *OH" > 440 cut] n(on-J = SEPIO:000. 3185 xto"® mo 10 nal de> Irao| o€ Ht! Imol of OH DAS OF mol a HT: O.18S x10 ral of OH @) TW] = TRaxe DAYT = Pate iaay = Osi motes 3.080% = JR x Onn Dace acid = o,mis ml en’ Ko. = 8.19 x10 meal des i: cd) Lactic acid os weak acid andl H+ dssocites portally fo bem Ht ron.9.2, Acid — base indicator 9.2.1 meaning - substances which change colour according to the pH of the solution. - weak organic acids or bases in which both their ions and undissociated molecules have different colours. Hin = Iv Colour A Colour B +H «ln acidic solution, [H"] increases, thus equilibrium position shifts to left More In’ are used for the reaction thus solution turns to colour A When Hin isin alkaline solution, OH" jon reacts with H° to form HzO. [H"] decreases, thus equilibrium position shifts to right. ‘More In’ are formed thus solution turns to colour B. 9.2.2 When do the indicators change colour? = When [HIn] =[In"] or Kyia=[H"] oF PKn= pH. ‘However, in practice, indicator changes colour over a pH range (= pKiin= + 1) o25) r is the solution Based on the pH range of indicators Methyl orange — yellow Methy red ~ yellow Bromothymol blue— green Phenolphthalein - colourless @ Gi) Hin =n Indicator [pKwn] pH [| Colowrehange range [Acid | base || x, = Weline) range - S alew)|| ema Wtigfornge |37[32- | Red | Yel peta Methyl red SI [42- | Red | Yellow ape x 63 aT Tal Ta Bromothymol [7.1 [60° | Yellow | Blue n=] im] {n=} blue 16 Colour of | Colour of | Colour of in phenolphthalein [53 | 8.2- | Colourless | Pink Hin Hin 10.0 + Colour of In” the colour ofthe solution ifeach of the tors are added to water at 25°C ? Eg: The indicator dissociation constant, Kin is 1.0 x 10° mol dm’. The colour of Hin ‘molecule is red and the colour of In’ is yellow. ‘What is the colour of this indicator in a solution of pH 4.02 (iin) [w+l_ Loxio-4 100 It is red in colour. ‘What is the range of pH through which the indicator will change colour? pH range = pKin + 1 = 6 | 5-79.24 Choosing a suitable indicator for an acid-base titration so that the end point coincides with the ‘equivalence point - pK, of the indicator = pH at equivalence point on the titration, or - pH range of the indicator should lie on the vertical part of the titration curve / pH at the equivalence point on the titration Equivalenece point = the point when the amount of acid and base present exactly neutralises one another End point = the point at which the indicator changes colour. Ideally, equivalence point = end point 93 itration curves Steps to sketch the curve 1. Determine the initial pH (in the titration flask) Sand 2. Determine the volume used at equivalence point Sb.—10 3. Mark the pH change at equivalence point Wa-7 4. Final pH ‘Types of titrations Sa.— 8b. titration Sa.— wo titration waa. = sb. titration Wa — wb. titration “Sharp increases in pH|- Sharp increases in pH |-Sharp increases in pH (6.5-|-no sharp increase in (3.5-10.5) slightly before | (3-7) slightly before and | 10.5) slightly after and | pH at equivalence point and after equivalence pt. | after equivalence point | before equivalence pt no suitable indicator -pH of equivalence pt=7 | -pH at equivalence point | -pH at equivalence pt >7 <75) E10) 9.4 Acid-base nature of the salts formed and hydrolys ‘Types of titrations S.a.— 50. titration 3.2, — wb. titration ‘wa. —S0. titration Waa. — wo. titration Eg: NaCl Eg: NH.CI Eg: CH;COONa Eg: CHsCOO NH NaCloNa® + Cr NHACI— NH. +CP | CHCOONa + CH;COO'+ Na’ | If K,>Ky, solution (No cationic or anionic | NH," + HzO + NH; +H;0° | CH:C00 = H.0 = CHLCOOH + OF | js acidic hydrolysis) (cationic hydrolysis) (anionic hydrolysis) ki si If Ke>K,, solution Both Na* and CI ions are | Production of Hy0" ions | Production of OH ions from | is pasic ‘not hydrolysed by water. | from the hydrolysis of NHs" | the hydrolysis of the No extra H” ions or OH | ions causes the solution to be | CHsCOO™ ions causes. the | if K,=K,, solution ions are produced. acidic. solution to be basic. is neutral. ‘The solution is basic. The solution is neutral.42. 1,0) Bheolpithalin HP, ean aclstes intor a hep range between 8:2 and 88. Te eli equnon ot heroic magueeus sluton sc lows lntes HPN + HO = Hye + PH aac Expiain how phenolphthalein acts in acid-base titration. [4] 2. Bacteria! formentation of lactose in milk produces yoghurt which contains lactic acid, a monoprotic ack. A sample of yoghurt drink has pH 3.52. 25.00 cm’ of the yoghurt drink requires 27.85 cm? of 0.1900 me! di" potassium hydroxide solution for complete titration. Pnonolphtalia ie used ss anestr nna tsasor (f'Sktehatitabon curve forthe ivaon above twa01) Ich) The thou of HPh moletule ss ad Ph” are colourless andl pink, 1 respectively chhen 2xtess aod ts added, CAI, equiibium postin of the Teaction moves to left. Solution tum tolowless. z = when a abakcts added, OH"+ Ht > 1,0. [H*] deceases. The =m pasition of the above reaction chrfis te the right. So, soktthn turns pink. : LA change in_ colour of indicator, le from caloscless_T2 pink of ‘om pink, to cleus? indicate the enclpoint of rertvn-42 4. Strong acid with strong base ‘0g, 26.0 em of 0.10 mol dm hydrochloric acld, HCI i titrated with 0.10 mol dm”* aqueous sedium hydroxide solution, NaOH (aq). Te 20) } phenolphthalein } bromothymol biue >| Suitable indicator } methyl orange i LR | 25 om? (end-point) fz 3040 volume of NaOH (cm) 2, Strong acid with weak bage ‘eg. 25.0 em of 0.10 mol dm’* hydrochloric acid, HC! is titrated with 0.10 mol dm”® ammonia, NHs (aq). 6 © 16 2 2 ‘elu ofan fom) * Suitable indicator: bromothymol blue / methyl orange. © Phenolphthalein is not suitable because its pH range is not within the steep range of pH profile. | © The indicator pH range should lie | on the straight vertical section of | the pH titration curve. The pH change very sharply from to 7.0 a os 1. An indicator has a K. of 4.0 x 10~* mol dm”*. Calculate the pH range over which the indicator changes colour. 1, An indicator has a Ks of 1.0 x 10°* mol dm. Over what pH range will the indicator change colour? noxio*3. Weak acid and strong base = (09. 26.0 em of 0.10 mol dm’? ethanole acid, CHsCOOM is titrated with 0.40 mol dm’ aquoous sodium hydroxide solution, NaOH (aq). 5 + Phenolphthalein is suitable pafrojphthaloin because it will change colour sharply at the equivalence point. Methyl orange and bromothymol ive blue are not suitable Take note: There is a sharp increase in pH, from 6.5 to 10.5 at the equivalence point. 31015 20 25 30 35 40 48 50 Volume 00 10.M NaGH accede? —e 4, Weak acid with weak base 3 £€g. 25.0 cm’ of 0.10 mol dm’ ethanoic acid, CHsCOOH Is ttrated with 28.0 em of 0.10 mol dm”* NHs (aq) 14 | 13 12 mon , [ [phbnolph{halein 8 sf + fi mathymol blue | ‘Take note: 6 No indicator can be used because 5 pH of the titration solution does not 4 + change sharply at the equivalence s methyl ofange poise ae 1 O 5 1018 20 25 30 35 40 45 50 Volume of 0.10 MINHy added / cm! —peston tp xref ‘ Eg 1. 25.0 cm’ of 0.10 mol dm ® phosphoric(¥) acid, HPO, is titrated with 25.0 cm’ of 0.1 mol dm” of NaOHi‘aq). PH range of phenolphthatein (PH range of ‘methyl orange J | formation ot tage, First equivalence point: methyl! orange + Second equivalence point: phenolphthalein No Sequvclene powr beccuse fell ph = 1B 2 30 75 volume of NaOH (cm?) HPO, (aq) + NaOH (aq) + NaH:PO, (aq) + 120 (1) NaH;PO, (aq) + NaOH (aq) — Na:HPO; (aq) + H,0 (1) NasHPOs(aq) + NaOH (aq) — NaPO, (aq) + H:0()) Rages weal base / aerd > £Eg 2 25.0 cm’ of 0.10 mol dm sodium carbonate, NasCOs is titrated with 25.0 cm’ of 01 mol dm hydrochloric ac, Hoag. ® phenolphthalein : if methyl orange 25.0 50.0 volume of HCI Na,CO; + HCl — NaHCO; + NaCl indicated with the use of phenolphthalein NaHCO; + HCl -» H,CO; + NaCl indicated with the use of methyl orange10. Buffer solution 10.1 Me olution that pH does not change signi that can resist the change in pH 10.2 Types of buffer solution ficantly when a little acid or base is added to it / solution Types Acidic buffers (pH<7) Alkaline buffers (p> 7) Components [A mixture of a weak acid and is|A mixture of weak base and its conjugate base conjugate acid. Eg | CHsCOONa & CH;COOH NH « NHACI 103 Actions of buffer solutions 10.3.1 CHsCOONa & CH;COOH When a little acid is added ‘When a little alkali is added CH COOH = CH;COO™+H™ (large amount) CH3COONa CHsCOO'+ Na® (large amount) When a little acid is added to the buffer solution, Hi ions added are removed by CHsCOO™ ions to form undissociated CHsCOOH molecules. H’ des + CH3COO" > CH;COOH pH remains constant. [H+] remains constant CHsCOOH 5 CH;COO+H™ (large amount) CHjCOONa + CHsCOO™+ Na* (large amount) When a little base is added to the buffer solution, ‘OH ions added are removed by CH;COOH molecules to form CHsCOO” ions OW tues + CH}COOH > CH3COO" + H,0 pH remains constant. [H+] remains constant 10.3.2 NH & NH,CI When a little acid is added ‘When a little alkali is added NH; +H20 = NH," + OH (large amount) NH.CI> Cl + NH" (large amount) When a litte acid is added to the buffer solution, Hons added are removed by NH molecules to form NH" ions. H’ aides + NH; > NH" pH remains constant. [H+] remains constant NH +H, = NH," + OH (large amount) NHACI> Cl +NHi" (large amount) When a little base is added to the buffer solution, OH’ ions added are removed by NH," ions to form NHs molecules. (Ol ades + NHe’ + NH + H20. pH remains constant, [H+] remains constant 10.4 Equation used to caleulate pH of buffer solutions. ‘Acidie buffer Alkaline butter pH= pk, + log E>witaets Pas POH = pXy + log Menlogate ae pH=14-pOHDerivation of the formula to calculate pH of the buffer solutions Consider a buffer solution of weak acid, HA and its salts, MA. Apply the equilibrium law to (2) only, k, = Hee) pH=pk. + (-log fe Sera) is ed = OK, + log Kansuaate base] y-Kx4 pH= pk, + log 4d pH= pK, + log outa nesel ial [MA] Assumptions : (i) [A’] at equilibrium initial [HA] as a of weak acid is very small (i) (HA) at equitibrium [conjugate base} Hence, pH = pk, + log MU arie 10.5 Calculate the pH of the buffer solution for the reaction between the excess weak acid and strong base or reaction between the excess weak base and strong acid. Eg: CH;COOH + NaOH % CH;COONa + 1h Initially Ma, Va Mb, Vb Initial mol wave Mov 7000 7000 Mol reacted/formed y y y Final mole xy 0 y : x-y y Final {] V7 1000 2 V7 1000 conjugate base] ToS Alto calculate pH of buffer solution, Use pH=pK, + log. 10.6 Calculate change in pH of buffer solutions Steps : 1. Calculate initital pH of buffer solution (before addition of acid or base) using pil = pk og EUR or por =p + Tog UE 2. Determine the final pH of the buffer solution ( after addition of acid or base) a. Write the equation involved to remove H” added or OH ions added. b. Calculate the initial mol of weak acid or weak base and conjugate base or conjugate acid ©. Calculate the number of mol of acid added or base added. 4d. Calculate final mol of weak acid or weak base and conjugate base or conjugate acid e. Calculate final concentration of weak acid or weak base and conjugate base or conjugate acid £, Calculate the final pH of buffer solution. 3. Determine the change in pH 10.7 Buffer capacity = amount of acid or base that needs to be added to a buffer solution for its pH to change by one unit. ‘a, Maximum buffer capacity of a solution occurs when faci = [acid] = [sat] or #4 = 1 or pH ofthe buffer solution = pK, ofthe acid = [base] = [salt] or: = = | or pOH of the buffer solution = pKy of the base - Half-way stage of titration10.8 Buffer zones in an acid-base titration 10.9 Determination of K, or Ky from maximum buffer capacity in the titration curve. Maximum buffer capacity pH 7° i 2 2 sqareeicn sce Volume of titrant added (mL) ( v ae osnwauovnogaian, Maximum buffer capacity Equivalence point utter reat" Yo Gquivaiense point Volume of base added 10.10 Preparation of a buffer solution with a specific pH value Steps: 1. Choose a wak acid or weak base which pK, value or pK, value is close to pH or pOH of the buffer solution (within | unit) Choose the suitable salt of weak acid / base, conjugate acid/eonjugate base tate) Cy ALE in 3. Caleulate the ratio of St or REL using pH = pk. + log S2BEEEE] or OH = pk + og emateec 4, Prepare the buffer solution using either method as follows: att] _@ ES facia) b Dissolve b moles of weak | -Mix b em’ of weak acid of I mol dm=& a em” ofits salt of 1 acid & a moles of its salt in| mol dm’ or water to make up to dm? _| -Mix | mol dm® of both solutions in the ratio of a : b by volume 10.11 Importance of buffer solutions in human blood pH of blood is maintained at 7.4 by HCOsHCOS system F:POJHPOS" system ‘Amino acid system HxCO3# HCO; +H" H.PO.' = HPO,” +H" HpN - R- COOH HT iaes + HCOJ—+ HaCO Hace + HPO? HaPOs H’saau + HaN - R- COOH, + Hs'N-R-COOH OWT sases + H2CO; + HCOx +H; | OH atces + H2POS > HPO” + H20 (OFFauset + H2N - R- COOH + H:N-R- COO" +H,0NGSAAN SACRED HEART gm of 20 told tance ac wth 360 emo 50 mol dn® 91: Calculate the pH ofthe solution obtained by snixing Sodium butanoate. (Ke for butanole acid is 1.60 x 10" mo! dm _Zg2 Calculate the pH forthe butfr solution ade by mixing 760 om of 0.20 mol dm NHI with 760 er of 40 mold? ts Solution. ( K, for the NHs’ fon is 6.0 x 10" mol dm) _AcA putter solution is prepared by adding 3.20 g of sodium ethanoate to 1.00 dm ethanoic acid of concentration 0.0100 mol tor ‘dm. Calculate the pH of this solution.. (Ke for CHCOOH = 1.75 x 10"* mol dm) 74.28 9 of ammonium chloride was added to-260 cm’ of 0.500 mol dm ammonia solution, Calculate the pl ofthe resuiting ‘solution. (Ke for NHs = 1.80 x 10 mol dm”, Ky = 1.00 x 10° mol? dm”) { souk . OCOD} TkT Fam batcnectie ) = OT S50" > 0 Smeal con 3 5) p= pe *g “pas pH = hg (UB0 x16) +heg BR [ano ait} = BAB,» OB mol dnc? pHs 4 BOO) s oidmel dm’? pOH= pky-+ bg EE “fe Trier) = Bee ie = leg lias tag 010-5 LNs] =8820). «cotta Ka x Ky = Ke = 5.08 Ts0 4150, (Gono Ke) tO y= Lb? gs pon =H 6.08 = 8.9 1) CUs(OONa | + CHg COOH > [tts (ooNet] = 3855 X17 = 0.039 wel de | EAg(00H\] = 0.0000 mat dm” = [i coon" pe pka + by Fak Gort shy Ib no + by Sooo > 635 >) NBgcl + NHs —> [NWS = 0.500 mol on® Kar Ky = Keo wey Ss) Ko > Kua + Kip =O.32 ma dm> = hooxio +. 80x06" a cl > 5.5xI07 pi: pKa + beg eT : = bog 6,456 + log, i806 ey ‘Calon endakiah menggunakan Kedua-dua bela muka ura dates ae required owe both de ofthe oper [REJUIURAN MENCERMINKAN KEPERIBADIAN ANDA HONESTY 18 A REFLECTION OF CHARACTERsua ‘ang 10S ini cota “gt: Catia pl ofthe eo inenaten 1 ~ Ea pli of the eolution obtained when 10.0 cm cf 0.100 mol dm? NaOH is added to 60 em of 0.100 mol én ‘CHsCOOM. (plc, of CHsCOOH = 4.75) (4.15) Calculate pH of solution obtained by adding $0.0 cm of 0.040 mol dm” sodium hydroxide solution to 60.0 em? of 0.080 ‘mol di CHsCOOH. (Ke for CHsCOOH = 1.74 x 10° mol dm* ) (4.76) fal NaOH + OAs(00 > OAa(00Na__ + H30 5.0004 EOC) htalwol eo 7900 3 7 0.00) mol = 0.00% ot : evel egasieal 9.001 6.001 : 0,001 Em mol ° 0.0044 0.001 p= pk TAs(OoNG, +g Tabesard EAT + Tag BOO ‘ ia = 4N5 Eq) NaOH + Cs (00H => Cs(00Na +) HO Jaa mo) SACGHO Ene ° = 0.002. = 0.004 a! Sue ° 0.002. 0.002, pH pa + loge aa EHs[00NaT log (1-14 x10"5) + loo) ~3:285- = ANb erga ia at pana Dena aa eto a bap sp ‘Reminder: Pas the anaer opt ogther Wh ahe foe pageSEKOLAH MENENGAH KEBANGSAAN SACRED HEART _ SACRED HEART SECONDARY SCHOOL No. Kad Pengenalan * CHs (OOH + NaCl hniteal mo\ oe 025 x1,0 0.10x1 = 00| Oo = 0.10 mo] reacted 0.01 0.01 = 0.01 gee =m mol 0 0-4 oll Frat pH = pXo hg Teese es tag i Rian) = 5.08 Change in pH = 5illt - 5.08 fo = 0.06- ‘Calon hendakah menazunakan ked-dva blah moka rat "Canes rere ase bth ses of the paper. KEMUJURAN MENCERMINKAN KEPERIBADIAN ANDA HONESTY IS A REFLECTION OF CHARACTERat A solution is mado by mixing 600m’ of 2.0 mo! dia® butanoteacia with 500 cm’ of 0.50 mol dm* sodium butanoate, _— for putanoie acid fs 4.50 x 10" mol dm*. Calculate the change in pH when 100 em of 080 mol dm of HCI is added to £0 ‘dm’ of the buffer solution. (0.12) 3)|Tediam beanocte’] = Feten = pabmoldn® [btonoic acd] = S822. 1.0 mol om3 pH of butler solaton Inttally = pH = pKa + leq, a : = ~ log (1.60 x10) 4 log ( pe) = ID ntHal) = EBS. 6.950 mol Albutaroie add) = 833. 1.9 mol ae 5 (Sodium bytarecte) = SORE = 0:25 mol C3100" + H* —» Gry CooH Initial mol 025 0.05 10 25 -0.05 9.05-0.05 1.04005 Tadlimetiec! O53 Sor? sie Fell 1 pier 0 Etats 000 (ea Fil = le TE ge = — log (150 x10") + log ae > aD (genie00) Charge io ph =~ 4.02 - 4.10 = OID» Patna Ss ali gas om pat pe ap op: ‘Reminder: Pas eth anor sri eter wh he fom page:8 Calulat te (of €.060 mol dm” NaOH to 80.0 cm’ of buffer solution? (9.17, 9.20) / SEKOLAH MENENGAH KEBANGSAAN SACRED HEART SACRED HEART SECONDARY SCHOOL Nd, Kl Pengensian ‘NocPusat/Angks Gilran | entity Card Number, Centre Numberinder Number Kod dan Nama Kertas ‘Tahun STPM. Pengga/Ulangan* oat of STEM = Si. Teresi Saal a = ‘pH of the 0.30 mel dm* irs / 0.96 mot dm NHACI buffer system. What is the pH alter adcition of 20.0 em* Sansa tis Snap ah rang in Denote * nti cotann. . log Gated = N+ pol poy ph e bs et 10.36), a = ries 2) = — ley (18 x10°*) + leq ToSoy = ASL = 418 NHy* + © OH" —> NHs) + Hs0- hited mole “eee Seog awl) = 0.0288 mo} = OD mol — = O24 0h mo| reacted O.do1 0.001 0:0540.001 ‘ (=02 Final mo) BROS = 0.925 Fel LT sto haw ooeDTE? x Fal pow = phe + be Taser poets Firal pH = 14- pou TF beg (10) oy OB > 1479 = AMT tet = 421 dhange in pH = 4.01 - 4B = 003% ‘Caton hendaklah menggunakan Ked-doa blah mika Sorat. "Candidates are reqeied one bo ides of he paper KEJUIURAN MENCERMINKAN KEPERIBADIAN ANDA LHONESTY IS A REFLECTION OF CHARACTER“a a) Calalate the change in pH when lOcnP sf IM NaOH is acldedd to /Ocn® & bufey soletiin cwsisting of 610M MsCoot and 025M Cislo0Na | CKa for Ms(oart =/¢xi0 “$M ) Intel pH of the bullor lation © pk + by Ea 1 + ae = -bqli§xi0'®) + log Br — = = Bae NaH + Cs(00H —> W3l00Na + 20 Inttaal are 200 bapa O.25xl.0 7 = 00! = 010 £0.25 readied Mormed 0.01 0.01 6.01 =m wel 0 0.09 026 Faipt birein = pKa + 4 Mes ~ “bg (18x10) thq — yee e bol E Change in pH = ar GIy = 0.07 evn Sn ar a dps spre Tse Nee anspor th te ot ae1D giSQ SEKOLAH MENENGAH KEBANGSAAN SACRED HEART SACRED HEART SECONDARY SCHOOL ae No. Pus/Angha Gian aisle) iden Cand Number —__ ne MunbetdesMnber Rie gt: How would you prepare a buifersoktion ef pH8.8. pK, of Ny = KvTS a £Eg2: Calculate the volume of a 0.10 mol dm CHi;COONa olution nevded to be acded to 1 dm? of 0.40 mol dm? CHsCOOH to produce a buffer olution with pH 4.0. ( pX, for CH:COOH = 4,74) Delete where appropriate Year of MUET 16.4Q——— Fy): Hoa wd you pupae o baller cotton of gH 7.6? Heme a wixtuve of Bete and NUE is used = l~ pon 5-14 POH pot = eke ths Pale ea pOH= 5 48 = 45+ log EARS pk of Nils <1 THE 086d ~{_Dsssave 01562 mol of NHACl and LO mol NH3 in Idi’ of obstllecl weter I Mix 5b2 om? of J mol olor ® NHL) sokshion with [00 cm? ot I mal chet NHz Solution: E49) pH= pk + log Tattooed 0 = HTH Hoy Beuistcorte eo eee Ets (00H J = 0180 ( Las (oONe | a = = On, Los toort J wore) ee Volurte df Us(00Na needel, V= 182 om? ‘Calon endakiah wenggunakinKedua-dua blah maka surat (Condes are eure 1 use bth ies ofthe pope’ [REJUJURAN MENCERMINKAN KEPERIBADIAN ANDA HONESTY 1S A REFLECTION OF CHARACTER4 at Define buffer solution. (° ((pmpsare of equecue ammonia, Nand asusous armonim chloe, NHAC, an example of bur solton Using sutablo equations explain how the biter solution functons. [7] (caries) _lta)et) Butlorsdlation is a soltion that can resist pH chore on addition do of tile acd ox bast: i) NH +H,0 <= Na’ + OHF “NHeCT NAY 4 clr A mixture of Nis and NHACl solution co a lame amount of NHs aol NHat tons. Win a small aout of aad 2s added tw the mixture , Ht adchd! wre remwed ly reacton with NHs to form NH? ions. Higg + Nie > NH when a emall amount of alkali %s added to the mixture OH” added are. < femovel by reacting with NH Yo form: Nig and HO. OH) Nit > 0 A, In both cases, H4 vr OH” added ave removed. Therefore , gh fhe ol olution romans anthanged © (©) (Barve the folowing expression fr ethanol acllethancataystom, “+ log [CHsCOO"f [CH:COOH} (w calla the pt of Xo dn os tulforsokston propared by dissolving .0 mele of CHsCOOH and 1. mole of CHsCOON in sufficient amount of water. [The acid dissociation constant, Ks of CHsCOOH is 1.8 10“ mol dm >] {i Ceteutata ep ofthe ter solution In (i) ebove when 0: mol of caleum hyéroxid,Ca(ON)n I ded owes an ‘equation forthe reaction. [12] (orte29) We Cs coo = CH COOT+ Haag a 5 U.gx0") hg R= z ‘O's (00-]TH*] Y z E Tots (00H F Glo), > Ca + 20H" c eas Ke Letoon y omol 0200) = “TeHstoo"] : Ons 0H => Cs (00"+ HO wll iT = “ye «(by mae a : Tents (00246) CH,C00H can bo ued to propare a buflersluon ceca, SA {ij State one chemical that needs to be added to CH,COOH to produce a buffer solution. (36 se {H)Give the structural formulae of the species that are responsible for the buffer action of the soiution. (2) 1 AS 3.(ll)_Deseribe the use of ethanole acid in the preparation of a buffer solution. [5] ‘300 tt) (3.(00Na GI) CASC00NA ancl Csfo0H Bei) Wig t0DNa ss adclecl 4 aquecus (He COOH to produce olution. (Us (00Na ~» CHsl00™ Ne f ee Aes sana Ms l00" + H* i mixture contains a large amount of CYS (00H and C300 ins Wun able acd as added, the ue added are’ removed by reacton with WsC00" .-to “form CHRLOOH- Hiay,g° + CH3C00" > Cts COOH, When. litle alkali ig addecl, *he “CH acldedl are remavecl by rxn with “ CUa(00H fo" form EHs60- CH 00" + HO wd In both cases, H* adelecl or ON" addleel are removed. pH cemains unchanged 4.) tetharamine, CHsNH: is the simplest aliphatic amine, It reacts with hydrochloric acid to term metiylammani ‘Shleride. By se‘ering fo both Bronsted-Lowry and Lewis theories, explain the roie of methanamine in the acis-base ‘Waite the equation forthe reection involved. [6] {b)() & solution was prepared by mixing 100 cm’ of 0.03 mol de methanamine solution with 100 em*of 0,04 mol dm? of hydrochlorie acid, Calculate the pH of the aqueous solution formed at 25°C. The bate disseciation constant, Ky for methanaming Is 4.3 x 20 mol dm?at 25°C. (7) (ibexpiain te elect on the pH of te solution In 6) I» rep of Sodium hyéroxde soliton Is acsed toe otuon 612015), Yea) sNH, + HCl —> X3NH3Cl Natom in CHeNH2 has 0 lone pair of electron. Ei is able fo accept a proton “fom HCl by orming olatue bore! with H* ion e . His a brmstecl bas a His alto chon pric conor Gilg -Ni HY e Tk donates eo” tH tn to fom ON? Achy CHgNHa + Het > CsNHsct en) pl remains uncharged Initolo! oloc3) __!0to0) "OH ions added ~are temonod ae oS by the. weacton bela: _ —* aoe = 1Mto"s OH added + CHsNHg> Gtsnu, tHD Em Sha =axi0"> ° yuo 3 Totensct] pOrl= pKb + ley Ton Tay ee bog Te OH fe wi.) = OT