Raffles Institution Year 6 H2 Chemistry 2018 Lecture Notes 14a lonic Equilibria 1 — Acid-Base Equilibt ‘Lecturers: Ms Lee Mei Yin Mr Jeremy Ng Content Arrhenius, Bronsted-Lowry and Lewis theories of acids and bases Acid dissociation constants, Ka and the use of pKe Base dissociation constants, Ki and the use of pK The ionic product of water, Kw pH; choice of pH indicators Buffer solutions Learning Outcomes Candidates should be able to: (2) Show understanding of, and apply the Arrhenius theory of acids and bases. (b) Show understanding of, and apply the Bronsted-Lowry theory of acids and bases, including the concept of conjugate acids and conjugate bases. (c) Show understanding of, and apply the Lewis theory of acids and bases (including non-aqueous system, e.g. reaction between BFs and NH). (4) Explain qualitatively the differences in behaviour between strong and weak acids and bases in terms of the extent of dissociation (e)_ Explain the terms pH; Ke; pKs; Ke; pK; Kw and apply them in calculations, including the relationship Kw = Kak (Calculate (H*(aq)] and pH values for strong acids, weak monobasic (monoprotic) acids, strong bases, and weak monoacidic bases. [Calculations involving weak acids/bases will not involve the solving of quadratic equations.] (a) (i) Explain how buffer solutions control pH (ii) Describe and explain their uses, including the role of H2COs/HCOs" in controlling pH in blood. (h) Calculate the pH of buffer solutions, given appropriate data, (Explain the choice of suitable indicators for acid-base titrations, given appropriate data. (@ Describe the changes in pH during acid-base titrations and explain these changes in terms of the strengths of the acids and bases, Lecture Outi e References 1 Introduction * Chemistry. The Molecular Nature of Matter and 2 Theories of acids and bases Change (by Silberberg) 3. pH Calculations for strong acids and bases + Chemistry in Context (by Hill & Holman) 4 The ionic product of water + Alevel Chemistry (by Ramsden) 5 pH Calculations for weak acids 6 pH Calculations for weak bases 7 Relationship between Ka and Ko Website 8 Degree of ionisation 9 Salt hydrolysis ‘+ www.chemguide.co.uk 10 Buffer solutions 11 pH Calculations involving buffer solutions 12. More on buffer solutions - 13 Acid-base titration and indicators 14 Acid-base titration curves 15 Summary 16 AppendixEiintroduction 44 Acids a ae oben {a) Strong acids and weak acids ~ An acid can be classified as strong or weak, based on its extent of diss: in aqueous solution. - Strong acid Weak acid Definition | A strong acid is one which undergoes | A weak acid is one which undergoes complete dissociation in aqueous solution. | partial dissociation in aqueous solution, Examples_| HCi(aq), HNOs(aq) _ CHsCOOH(aq), HCN(aq) fe Equations | HCi(aq)—> H*(aq) + Cr(aq) CHsCOOH(aq) = CHsCOO"(aq) + H*(aq) or or HCi(aq) + H20(I) —> Hs0*(aq) + Ci-(aq) | CHsCOOH(aq) + H20(!) = CHsCOO (aq) _ Z _ + H0"(aq) Note ‘TH'1= initial (HC At equilibrium, [H"] < initial [CHsSCOOH} (b) Concentrated and dilute acids The concentration of an acid in aqueous solution is the amount of the acid per unit volume of the ut solution. - he} atl + Aconcentrated acid is one in which the proportion of acid to water is high. _ enh * A dilute acid is one in which the proportion of acid to water is low. Note: strong acid concentrated acid # centration of acid voc ewig tf Latenath of ci concentration of aci “lute ana refers to extent of refers to amount of aci dissociation of acid per dm? of solution z (c)- Basicity of an acid We oe Fao hen ork Number of H atoms ionisable (as H’ ion) per molecule Examples monobasic (or monoprotic) acid a sw Na‘(aq) + OH-(aq)+ Aweak base is one which undergoes partial ionisation in aqueous solution. Examples of weak base: NHs(aq), NazCOs(aq), CHsCH2NH,(aq) NHs(aq) + H2O(1) = NHs*(aq) + OH"(aq) menor bis * Mao diosa bara + Neo, Bato), EE theories of Acids and Bases 2.1 ‘The Arrhenius theoryofacids and basési (a) Defi ions In 1884, the Swedish chemist Svante Arrhenius suggested the following definitions: Acid Base * An acid is a hydrogen-containing substance that ionises and releases hydrogen ions (ie. Hons) in aqueous solution. + Example: HCi(aq) > H'(aq) + C-(aq) * A base is a hydroxide-containing substance that ionises and releases hydroxide ions (ie. OH" ions) in aqueous solution. *__Example: NaOH(aq) -> Na*(aq) + OH(aq) (b) tions of Arrhenius theory: * Itrestricted acid-base reactions to those which occur in aqueous solutions. NH, + Itdid not account for the basic properties of ammonia and some organic substances (such as the amines) that do not contain the hydroxide group. * It focused on the existence of the hydrogen ion, H*, in aqueous solution but no such ion can exist in aqueous solutions, (c) The hydrated proton Wg) + Hho — Hot + ur wy), + The hydrogen ion is a bare proton, a fundamental particle. It is very small (10- m diameter) and has a relatively high charge density such that it attracts any molecule with unshared electrons such as H.0. ‘ + Therefore, in aqueous solution, a water molecule forms a dative covalent bond to the H* ion to produce the hydronium ion (also known as ‘hydroxonium ion’), H;0°. HO) + HY(eq) ——+ H:0'(aq) y ° r( —-. a wD + Haq) H Note: - - 9 + * When talking about acidic solutions, the term ‘hydrogen ion’ is often used. Strictly speaking, we should always remember that protons do not exist in solution and should talk about the hydronium jon, writing HsO*(aq) instead of H*(aq) + In practice, H*(aq) is commonly used for simplicity sake. We will use H*(aq) and HsO*(aq) interchangeably. This means that any equation you see written with ‘H*(aq)’ has an equivalent form with 'HsO*(aq)’ and vice versa2.2 Thé'Brensted-Lowry theory of acids and bases In 1923, J.N. Bronsted and T.M. Lowry proposed the proton transfer theory of acids and bases. Definitions Bronsted-Lowry Acid ~Bransted-Lowry Base _ A Bronsted-Lowry acid is a proton donor. A Bronsted-Lowry base is a proton acceptor. In this case, an acid-base reaction involves the transfer of a proton (i.e. H* ion) from the acid to the base. An acid is only an acid in the presence of a base, and a base is only a base in the presence of an acid. Examples: HCi(g)_ + NHs(g) ——> NH.Ci(s) acid base HCI(aq) + H20() —> Cag) + H0°(aq) acid base Yao w anplaproie — om lly nade oy auapt a pk, Whe nultg ov a C wh wv © bee CHsCOOH(aq) + OH-(aq) —> CHsCOO"(aq) + H20(/) base CO:*(aq) + H:0() + HCOs (aq) + OHaq) base acid 2.3 Lewis acids and bases In 1938, the American chemist G,N. Lewis produced a theory which extends the concept of acids and bases even further than that of Bronsted and Lowry, Definitions. Lewis Acid Lewis Base ‘A Lewis acid is any species that can accept a pair of electrons from a base to form a dative bond, ie. a Lewis acid is an covalent electron-pair acceptor. A Lewis base is any species that can donate a pair of electrons to an acid to form a dative covalent bond, ie. a Lewis base is an electron-pair donor. Examples: cdekiud pe, 4 Lewis acid H+ Lewis acid AIC + Lewis acid NH; ———> HsN->BFe Lewis base H,0: ——> H:0* Lewis base Cr ——> ACh Lewis base The Lewis theory of acids and bases is much broader than the Arrhenius and Bransted-Lowry definitions. It extends the range of acid-base reactions to include those which do not involve protons.2.4 Conjugate acid-base pairs * We are primarily concerned with aqueous solutions in which acid-base phenomena involve proton transfer, and so the Bronsted-Lowry theory of acids and bases is of most use to us. * Consider the following reaction between an acid HA and a base B. HA + B= A + HB acid base conjugate conjugate base of HA _acid of base B Note:- In the forward reaction + HAis an acid as it donates a proton to B. + Bisa base as it accepts a proton from HA. In the backward reaction + HB" is an acid since it donates a proton to A. + Arisa base since it accepts a proton from HB". Conjugate acid-base pairs + HAand AX HB’ and B Notice that in each conjugate pair, the acid and base differ from each other by a proton, H*. + Examples loses H* gains H Reaction (forward reaction) aca | SoMiugate | 4... | conjugate base acid 1 | HCi(aq) + H20()) > Cr(aq) + Hs0"(aq) Her cr H.0 H:0* 2 | CHsNHz(aq) + H2O0(1) = CHsNHs"(aq) + OH*(aq) | HzO ChaNH, | CHaNHs® 3 | NHs(aq) + CHsCOOH(aq) > CHsCOO-NH«"(aq) | (H, Woo (Hy Loo , aH,” KEMDpH Calculations for Strong Acids and Bases 314 "The pH scale * The concentration of hydrogen ions in a solution is a measure of acidity or alkalinity of the solution. Most hydrogen ion concentrations fall between values of 10° and 10-" mol dm. + The Danish biochemist S.P.L. Sorensen (1909) realised that this wide range of hydrogen ion concentrations could conveniently be expressed by the numbers 0 to 14 using the pH scale. ‘The pH scale o 4123 45 6 7 8 9 0 ahi neutral (at 25 ec) increasing acidity 412 increasing basicity 13143.2. Definition of pH 2 # + The pH of a solution is defined as the negative logarithm to H= Ig [H'] base ten of the hydrogen ion concentration in mol dm=. Cima!) * If the pH ofa solution is known, the concentration of hydrogen ion (in mol dm) in the solution can be calculated. LK 40-4 (H] Note: ~ «The higher the [H*] in a solution, the lower is the pH ofthe solution. => A solution with a lower pH is more acidic than a solution with a higher pH. * An aqueous solution with pH = 7 at 298 K is considered to be neutral because ta [OH]. (refer to Section 4.4) - We dqedd oe TT A ark / base > net «food evliahy F urd [bose rnp 3.3. Calculating the pH of a solution of a strong acid © @ Worked Example 1 @| (a) Calculate the pH of 0.200 mol dm*HCi(aq). | (b) Calculate the pH of 1.00 mol dm-* H2SO«(aq). HCi(aq) —> H"(aq) + Cr-(aq) H2SO«(aq) —> 2H*(aq) + SO,*(aq) [H*] = [HCi(aq)] 200 mol dm-* axhow a.m ie PH = —Ig [H*] = Ig (0.200) = 0.699 pH= - tH} = -ly-) = — 834 3.4 Calculating [H'] from pH me Worked Example 2 om (a) Calculate the [H*] in urine of pH 4.1 (b) Calculate the [H"] in pancreatic juice of pH 8.1. (H'] = 10%"= 10" THT 10S pap. ao) wel de” | | .94 x 10° mol dm* | me Exercise 1 @m [N2014/1/12] 10.cm* of 2 0.01 moldm”* solution of nitric acid is diluted with 90.cm* of water. What is the pH of the resulting solution? Al B 2 SO D4 © tH) =n HN) = gry KOM = bone wd thy} = a neve 2 001 nol dn moc lg CA) 4 Lol) = 33.5 Definition of pOH The pOH of a solution is the negative logari the hydroxide ion concentration of the solution in mol dm 3.6 Relationship between pH and pOH at 25 °C Experimentally, it has been determined that at pH + pOH= 14 Hence pH = 14 — pOH and pOH = 14 — pH at * Refer to Section 4 for more details. 3.7. Calculating the pH of a solution’of a strong me Worked Example 3 @m If the pOH of a solution is known, the concentration of hydroxide ions (in mol dm-*) in the solution can be calculated. ithm to base ten of POH =-1g [0H] 25°C, 25°C. base a 3 (a) Calculate the pH of 0.100 mol dm? KOH(aq). KOH (aq) —> K’(aq) + OH-(aq) [OH] = 0.100 mol dm? | POH = -Ig (0.100) = 4 pH=14-1=130 (b) Calculate the pH of 1.00 mol dm Ba(OH)(aq) | Ba(OH)2 (aq) —> Ba*(aq) + 20H (aq) [OH]= 2x 199 52.00 ml de? pOH = “4 Gem) = - 030 poe - (0.9) 203 3.8 Calculating [OH] from pH or pOH me Worked Example 4 om (a) Calculate the [OH"] in KOH{(aq) of pOH 3.0. pOH = 3.0 [OH] = 10-7 = 10-9 1.00 x 10° mol dm-3 (b) Calculate the [OH] in baking soda of pH 8.4. pH = 8.4=> pOH= wht. MRE est fon = 2S tort mel da? ‘3{9"Méastiting the pHi lof a'solution "> * Main methods available to determine the pH (ai ind hydrogen ion concentration) of a solution: © using universal indicator paper or solution for an approximate pH value. ® using a pH meter for an accurate pH determination.+ The pH values of some familiar aqueous solutions are shown in the diagram below. Note: The diagram gives the pH values of a number of familiar items. Keep in mind that because pH is on a logarithmic scale, every unit cchange in pH represents a tenfold change in [H). Thus lemon juice is approximately 100 times more acidic than tomato juice. 1@ Exercise 2 @! pH values of some familiar substances 1.0 moldm? NaOH. (0:1 mol dm? NaOH: household bleach, limewater “nik of magnesia baking soda human blood, tears, pure waterat 298K saliva, fresh mik rainwater (normal) black coffee tomatoes vinegar lemon juice stomach juices’ (contains HCl) 1.0moldm® HCi(aq) (N2005/V/9] pH “4 Hy Jno de? 1x10" 1x108 1x10 1x10" 1x10” 1x 108 1x 108 1x 108 tx 105 1x10! 1x10 1x10? 1x 107. 1x10 [oH Imol dev? 1x 10° 1x 10% 1x 102 1x 102 1x 104 1x 108 1x 106 4x40% 1x 108 1x 108 1x10 1x10" 1x10 1x 108 1x10" pOH 10. " 8 18 ‘The pH of normal human blood is 7.4. Strenuous exercise can cause the condition called acidosis in which the pH falls. If the pH drops to 6.8, death may occur. How many times greater is the hydrogen ion concentration in blood at pH6.8 compared with that at pH7.4? A 14 ZO 40 B 20 cee tol ees ne CH day tom D 600 3.4%Ei The tonic Product of Water, Kw 44 Deriving the expression for Kw @ a a The electrical conductivity of even the purest water never falls to exactly zero. This is due to the presence of ions produced from the self-ionisation of water as represented by the equation below. H20() + H20(I) = H:0"(aq) + OH-(aq) base acid or for simplicity: H:0()) = H'(eq) + OF-(aq) H*J[OH] At equilibrium, the equilibrium constant, K, = “10H i 1 Rearranging gives: Ke [H20] H*] [OH] ‘Since water is a weak electrolyte, the amount of water ionised is very small such that [HzO] is effectively constant. Hence K [H20] is another constant. Let Kw = Ke [H20] Then [ Kw = [H'] [OH] Kj is termed the ionic product of water, It has units of mol? dm® The exact value of Ky depends on temperature. | At25°C, Ky = [HY] [OH = 1.0 x 10- mol dm | The following expression for Kw is also commonly used. H20()) + H20(I) = HsO*(aq) + OH(aq) Ku = [H30°] [OH-] | Note: =a = * For all aqueous solutions at the same temperature, [H"] [OH] = constant = Ku at that temperature + If [H*] becomes larger, [OH"] becomes smaller and vice versa. and {OH]=“" Las [tH] [OH]4.2 Calculations involving Kw me Worked Example 5 (a) Calculate the [OH] in 0.10 mol dm? {b) Calculate the [H"] in 0.020 mol dm-* Ba(OH)a(aq). HCi(aq). [OH] = 2 x 0,020 = 0.040 mot dm Ku= (HOH ~ Kuo = (H"] [OH] Ke, Ox 3B I= Dd yy ED X10 rol din 4.3. Relationship between pK, pH'and pOH + By definition, pKj is the negative logarithm to base ten of Kw. PKw = ~I9 Kw © pKw can be expressed in terms of pH and pOH. Ku = (H"] [OH] —Ig Ky = = Ig [H"]-Ig [OH] PKw = pH + pOH = PKy = pH + pOH = At25°C, ° AL 25°C, Ky = [H"] [OH"] = 1.0 x 10° mol? dmv? ’ = pKy = pH + pOH = -Ig (1.0 x 10-14) = 14 PKy = pH + pOH 4.4. pH and pOH of a neutral aqueous solution at 25°C + Foran aqueous solution, Kw = [H'] [OH] + For aneutral aqueous solution, [H*] = [OH] = Consider a neutral aqueous solution at 25 °C. 0 1.0.x 10™ mol? dmr® For a neutral aqueous solution at 25 °C, 4.0.x 10 mof? dmr® V¥1.0x10 = 1.0 x 107 mol dm? [H}=[OH7} = -lg [H4]=-1g (1.0 x 10”) =7 = 1.0.x 107 mol div = [H'] = 1.0x 107 mol dm? pH = pOH =7 ~lg [OH] = =Ig (1.0 x 107) + For pure water (at 25 °C) which is neutral, ‘ d [H"] = [OH] = 1.0x 10-7 mol dm => pH =pOH=7 (at 25°C) -10-Note: The pH seale| 67s 90 1 increasing basicity 213 14 A neutral solution has pH 7 only at a temperature of 25°C. neutral solution [H"] =[OH] | pH=7 at25°C acidic solution [H'1> 10H] | pH <7 at 25°C 4.5 The effect of temperature on Kw. {_basic solution | [H"]<(OH] | pH >7 at25°c + The table below shows the variation of the ionic product of water, Ky, with temperature, Temperature /°C [_Ky/ mol? dm pH of water=-ly Tew 10 0.29 x 10° 7.27 20 Z 7.08 : 25 1.00 x 107% 7.00 30 [4.47 x 10-4 6.92 40 2.92 x 10°" 677 7 50 5.48 x 10 6.63 7 100 | 81.3x 10" 6.14 + The value of Ky increases with temperature as shown in the table. This is because the self-ionisation of water is an endothermic process. H20() + H20() = or H20(I) = H0*(aq) + OH(aq) H*(aq) + OH (aq) AH>0 AH>0 timp thd Ath, UJ) $> pL + As temperature is increased, the equilibrium position of the above reaction shifts to the right to absorb the heat added. This is in accordance with Le Chatelier’s principle. concentrations of H* and OH" ions. me Exercise 3 @m [N2013/I/11] The dissociation constant, Kw, for the ionisation of water, below. : ‘temperature/’C Ku! mod oO 1.45 x 107% 25 1.00 x 107 50 5.50 x 10-4 What can be deduced from this information? Only at 25 °C are [H*] and [OH] equal The forward reaction is exothermic, com> Nocted > THY = Len] ‘The equilibrium lies furthest to the right at 0°C. ‘The pH of water decreases as temperature increases A With the forward endothermic reaction favoured as temperature is increased, there will be higher ‘Since Kw =[H"] [OH], the value of Ky increases as temperature increases. = Ht + OH>, at different temperatures is givenTERI Calculations for Weak Acids + Although the pH of a solution provides some measure of the strength of a constituent acid, the use of pH is very limited in this context since its value will change as the concentration changes. + Consequently, chemists looked for a more useful, yet quantitative, means of representing the strength of an acid. They found this by considering the dissociation equilibria of acids in aqueous solution, 5.4 Acid dissociation constant, Ky ; 89 ‘ ‘+ Consider the dissociation of a weak monobasic acid HA (e.g. CHsCOOH) in an aqueous solution HA(aq) + H20(!) = Hs0*(aq) + A(aq) Or for simplicity: HA(aq) = H'(aq) + A*(aq) Note: = + Ky is a measure of the strength of the acid HA. + Ksprovides a quantitative indication of the extent to which the acid is dissociated. + Kshas units of mol dm. + The value of K; is dependent on temperature. ‘+ The following expression for Ks is also commonly used (Hs0°1 1A HA(aq) + H2O(I) = HsO°(aq) + Ar(aq) THA] + The K, and pK; values of different acids can be used to compare the strength of the acids. + The pk of an acid is the negative logari K, of the acid. m to base ten of the me Worked Example 6 om Ethanoic acid is an organic acid with K, value of 1.8 x 10° mol dm~*. Write down the K, expression for ethanoic acid, cd £41 Hblay) Hoy) + Arby) Ke * Hay Solution CHsCOOH(aq) = CH:COO*(aq) + H"(aq) y= EoarSOPL THs UV]5.2 Interpreting K, values . * The Kz values of some acids at 298 K are shown in the table below. Acid K.1 mol dav pK HCiaq) 1x 107 a HF(aq) i 5.6 x 10 il 325 | a HNOz(aq) 45x 104 3.35 strength (CeHsCOOH(aq) 63x 105 420 | eee CHsCOOH(aq) 74.8 x 10% 474 NH«(aq) 57x10 924 HCN(@q) 49x 10-8 931 CeHsOH(aq) 743x109 9.89 Note: — ‘The larger the K; value, the stronger the acid. ‘The larger (i.e. more positive) the pK, value, the weaker the acid, + Consider HF(aq) and HCN(aq). HF(aq) = H’(aq) + Faq) wal) HCN(aq) = H’(aq) + CN*(aq) 2) Since Ks of HF > Ky of HCN, * HF is a stronger acid than HCN * For HF(aq) and HCN(aq) of the same concentration, ~ the equilibrium position of reaction (1) lies more to the right. - HF dissociates to a greater extent than HCN. : ~ HF dissociates to yield a higher [H"] at equilibrium, = pH of HF(aq) is lower than pH of HCN(aq) §.3 Acid dissociation constants of weak polyprotic acids i titel ¥ + Polyprotic acids such as HeS, H;CO and HsPO, have more than one Ka values. * For example HsPOs, which is a triprotic acid, has three Ks values. These are called first (Kyi), second (Kz2) and third (Kas) acid dissociation constants respectively. Dissociation | __ Equilibrium in aqueous solution | Ka/moldm® | _pKs First HsPO«aq) = H"(aq) + H2POr(aq) | 7.5x102 | 24 Second | HePO«(aq) = H'(aq)+HPO(aq) | 62x10* | 7.2 Thit HPO«*(aq) = H"(aq) +POe(aq) | 42x10 | 12.4 ital Yergly aged em > dubly aslo + Itcan be seen that Kay > Kae > Kes + Successive K, values become smaller because successive dissociations involve acidic species that are increasingly more negatively charged, making the donation of positively charged H* ion increasingly more difficult. 13.5.4 Calculating the pH of a weak aci = Problem: Consider a Co mol dm~* HA(aq). Calculate its pH given the K, of HA, * Solution: Let [H"] = x mol dmv at equilibrium. 1 Define x as unknown [H"] at equilibrium. Concentration/moldm™® | _HA(@q) = __H'(aq) + AY@q) | > Construct the ICE" Initial Co - - table. oe -* oe “ 3. White the Ka Equilibrium [(o-) x expression. [H]1A] _ @& x 4 Substitute values into SGA eee Sa the Ka i THAD * Gorn) 7 Con 1 Ka expression, Since HA is a weak acid with a relatively small Ke, assume x << Co. : ed to Then (Cox) ='Ce 2 calculation. x ta a 6 Solve forx and ° determine [H’] Fee wba Wat 2 NIE eapldbinan 7 Calculate pH. [H*] = /K.Co pH = -Ig[H']= -la/KaCo + There are two key assumptions made to simplify the arithmetic. 1) The [H*] from the self-ionisation of water is negligible and ignored, ‘+ This is usually justified since the presence of H'* from HA will suppress the setf-ionisation of water. ‘+ This assumption is not valid if HA(aq) is very dilute. 2) The degree of dissociation is negligible, i.e. x << Cs such that (Co - x) = Co where Co = initial [HA] and x = [H"] = [HAlésoxtes Degree of dissociation, ia Validity of assumption (&) (100%) ) (100%) = 5% | The assumption is valid and approximation can be used > 5% | The assumption is not valid and x has to be found by (100%) > 5% | solving the quadratic equation + Note: e * This formula is useful for solving multiple-choice questions. + This formula is useful for checking if (Co — x) ~ Co 14me Worked Example 7 om Calculate the pH of a 0.200 mol dm ethanoic acid solution (K, = 1.8 x 10° mol dm~), Solution 4 Let (H"] mol dmv at equilibrium. Concentration / mol dm-* | CH;COOH(aq) = _CHsCOO“(aq)_* _H(aqy) Initial 0.200 = 7 "Change ~ x + Equilibrium 0.200 -x x x [CHCOO-IH'] __ [CH3COOH] — (0.200-x) = 1.8 x 10-5 mol dm? ‘Since CH:COOH is a weak acid with a relatively smalll Ks, assume x << 0.200, Then (0.200-x) ~ 0.200, 2 Check x oan = 18x 10° 0.200 (H") 1.897 x 10° Doon ) (100%) = ( === ) (100%) x = (TEXT O20 = 1.897 x10 | (200) 190%) = (“Gao —) (100%) [H'] = 1.897 x 10-8 mol dm “0.249% < 5% pH = ~ig (1.897 x 109) = 272 = Assumption is valid, Solution 2 Alternative way to CHsCOOH(aq) = CHsCOO-(aq) + H'(aq) : present the working for the calculation of pH of At equilibrium, [H*] = [CH3COO7. a weak acid. Since CHsCOOH is a weak acid with a small Ka, aoe assume that at equilibrium, [CHsCOOH] = 0.200 mol dm feaction equation. + State clearly the THA|, [H*] and [A] at equilibrium including 1H") [H" any assumption LL eto ave + Apply (HY) = JRC. CHT= Jager Po ae = 1.8974 107 galdes? ems a Rat + Calculate [H'} and PH = oly (L847. 107) = 2.72, then pH. if tat) = * Use this method for | Solution 3 Hd = The wea [H*] = VK x[CH3COOH] = J(1.8x10")(0.200) = 1.897 x 10 mol dm PH = ~Ig (1.897 x 10%) = 2.72 + Compare the above answer with that of Worked Example 1(a) on page 6. + Note: The pH of a weak acid is higher than that of a strong acid of the same concentration. 15.5.5 Calculating the K, of a weak acid me Worked Example 8 ‘The pH of a solution containing 0.35 mol dm-* hydrofluoric acid is 1.82 = Calculate the Ks of hydrofluoric acid Solution 1 pH = 1.82 = [H']=10°'* = 0.01814 mol dmv? Concentration moldm= | _HF(aq)_ = Hi(aq) + Faq) Initial 0.35 = = Change = 9.00514 t0.005it 40.0151 Equilibrium - 0.55- 0.0151 stsly paistt FY Co. ost )* = re oft = MEL, OOo a5 c107 sa de? {HF} 0.35 -9.0151¥ Solution 2 (Alternative way to present the working) HF(aq) = H'(aq) + Faq) pH = 1.82 = [H*]=10** = 0.01514 mol dm* At equilibrium, (F+] = [H*] = 0.01514 mol dm-® and [HF] = (0.35 — 0.01514) = 0.3349 mol dm (HLF _ (0.01514)? THF] 0.3349 Ky of HF = = 6.85 x 10“ mol di Note: For this question, there is no need to assume (Co ~ x) = Co since x = [H'] can be calculated from the given pH of the solution. 5.6 Calculating the pH of an extremely dilute strong acid me Worked Example 9 Calculate the pH of 1.0 x 10° mol dm HNOs(aq) at 298 K. Solution ‘+ The given nitric acid solution is very dilute. Hence the contribution of H’ ions from the self-ionisation of water is not nealigible and has to be taken into consideration in calculating the pH of the solution, + There are therefore two sources of H" ions: 1 from the complete dissociation of HNOs: HNOs(aq)—+ H*(aq) + NOs(aq) 2 from the setf-onisation of water: H-O(1) = H*(aq) + OH-(aq) The presence of H' fons from the complete dissociation of HNOs wil suppress the ionisation of H:O. Let [}"] from the selfionisation of water = y mol dm Then [OH] due to the self-ionisation of water = y mol dm. ‘A Simplified Approach Hence [HJ = [H"Jiseass + [H"Tuaw = (1.0% 10 + y) motdm? | assume [H"] from the settionisation of es 7 ‘3 At 298K, Ke = [H"}aa [OH"] = 1.0 x 10" mol? dv-® Loca Reto CO ae ee (Hot = [HT aca + Hut y? + 1.0x10y - 1.0 x 10° 0 = (1.0 x 10° + 1.0x 107) Solving using GC, =1.1x 10-7 moldm? 51 x 10* ory =-1.05 x 10” (rejected since y > 0) {HJ = (1.0 x 10 + 9.54 x 10) = 1.051 x 10° mol dev? pHs ig [H pH = Ig [H"] = ig (1.051 x 10”) = 6.98 Hig (1.1.x 1077) -16-[GI pit Calculations for Weak Bases 6.1 Base dissociation constant of a weak basé'B * Consider an aqueous solution of a weak monoacidic base B (e.g. NH) in which the following equilibrium is established: B(aq) + H20(!) = BH"(aq) + OH"(aq) Eg.: NHa(aq) + H20(\) = NH4"(aq) + OH"(aq) * Deriving the expression for Ky: {BH*}(OH - {BI[H20] [BH'JOH] Ke [H20] = —— = [HO] 1B) Since [H2O] in aqueous medium is effectively constant, Ke [H20] is another constant. Let Ko = Ke [HzO]. — BHIIOH] [8] At equilibrium, Ke = Then Ke BH*]IOH fy = BHTIOH] + Forthe above reaction at equilibrium, Bi + Kyis termed the base dissociation constant of the base-B. Note: — — * Kis a measure of the basic strength of the weak base B. + Kis a measure of the ability of the Bronsted-Lowry base B to accept a proton. + Kohas units of mol dm. + The value of Ki is dependent on temperature. * The ky and pK values of different bases can be used to compare the strengths of the bases. + The pk, of a base is the negative logarithm to base ten of the Ky of the base, pK Ky me Worked Example 10 om ‘Write the Ky expression for the following reaction: CO;*(aq) + H20(!) = HCO; (aq) + OH-(aq). CHL, “1E 041 tor to,*) - Solution: , AT6.2 Interpreting Ky values ‘+ The table below shows the base dissociation constants of some bases in water at 298 K. Base Kol moldm® | pko Note: CHsCH2NHa(aq) | 5.1 x 10 3.29 + The larger the Ky co;*(aq) 24x 104 3.68 value, the stronger is NiHs(aq) 1.8x 104 474 basic the base. HS-(aq) 18x 107 674 atenath + The larger the pK» CHsC00-(aq) 57x10" 924 ae value, the weaker is the base. Orneve 42x10 9.38 ‘= Consider NH and CH;COx. NHs(aq) + H20(!) = NH,*(aq) + OH-(aq) CHsCOx(aq) + H:0()) = CHsCOzH(aq) + OH-(aq) .. (1) (2) Since Ky of NHs > Ke of CHsCO>", «Nb is a stronger base than CHsCOz. For NHs(aq) and CHsCO;"(aq) of the same concentration, - the equilibrium position of reaction (1) lies more to the right. - NHs ionises to a greater extent than CHsCOz- ps -§ UsH"} ~ NH, jonises to yield a higher [OH] at equilibrium. phew pot ; pH ab His < poll dU, OO 6.3 Calculating the pH of a weak base z phot ts > pH dd HU” * Problem: Consider a C. mol dm~ B(aq). Calculate its pH given the K, of B. = Solution: Let [OH+] = y mol dm at equilibrium. Note: See The approach Concentration/moldm> | B(aq) + HO) = BH'(aq) + OH(aa) | simiarto that of Initial Co = = finding the pH of Change = a 4 a weak acid. Equilibrium (Co-y) y k = BHIOK] | OW _ (8) (Co-y) (Cory) Since B is a weak base with a relatively small Ks, assume y << Co, Then (Co~y) = Co. Ke y= VKCo z © [OH"] = VRC. pOH pH = -Ig [OH] = pKw—pOH “gy KC. “18.me Worked Example 11 om Calculate the pH of 0.100 mol dm™ NHs(aq) at 25 °C. Ki of NHs is 1.74 x 10 mol dm. Solution 1 Let [OH"] = y mo! dm at equilibrium. SSS Concentration/mol dm? | _NHs(aq) + H.O() = _NHe(aq) + OH(aq) initial 0.100 - - change -y 4y 4y equilibrium (0.100 -y) y y. [NH4"] (01 yo: = a = 2 74x 10° 2 Ky INH} @100-y) x 10°° mol dav Since NHs is a weak base with a relatively small Ky, assume y << 0.100. Then (0.100 - y) = 0.100. y? Check aro Te (2H (100%) = (2222 ) (400%) y = (74x 10-)(0.100) = 1.319x 107 0.100) 100) = [OH] 1.319 x 10 mol dm* = 132% <5% pOH = ~Ig (1.319 x 10) = 2.88 pH = pk, ~pOH = 14~2.88= 11.1 = Assumption is valid - ~~ | Aitemative way to Solution 2 present the working NHs(aq) + H2O(I) = NH«‘(aq) + OH-(aq) for the calculation of pH of a weak base. [At equilibrium, [OH] = [NH«"] Since NHs is a weak base with a very small Ky, assume that at equilibrium, [NHs] = 0.100 mol dm-®. + Write the relevant reaction equation, + State cleariy the [NH] {HJ _ [OH] [OH] _ {8}, [BH] and efor Nis = TH] 0.109 = 174 x 10° mol dm [OF] at equim including any [OH] = (4-74 x 1070-100) = 1.319% 10 mol dm? assumption made. + Apply [0+] = JG POH = —Ig (1.319 10%) = 2.88 Apply [OH] pH Kw — pOH = 14— 2.88 = 11.1 * Calculate [OH], _ POH and then pH. Solution 3 + Remember the [OH ‘Ky x[NH,] = 5 No. = (31 > 3 formula and use it [OH] = JK, x INA] Ite Jeo.100 110? sel dn won ereworieg McQ. POH = -fy (1319 X10) = 2.64 PH = phy - pif = Wf-2.g6 = 12 + Compare the above answer with that of Worked Example 3(a), page 7. + Note: The pH of a weak base is lower than that of a strong base of the same concentration. -19-6.4 Calculating the Ky of a weak base me Worked Example 12 @m “The pH of a 0.200 mol dm" sodium ethanoate solution is 9.02. Calculate the Ky of ethanoate ion Solution 4 At 298 K, pOH = 14~pH = 14-9.02 = 4.98 [OH] = 1048" = 4.047 x 10° mol dm? Concentrationimol dm | CHsCOO"faq) + H:0() = _CH:COOH(aq) + OH(@q) initial 0.200 - - change -1,047 x 10 41.047x10% —-+1.04Zx 10% equilibrium 0.200 - (1.047 x 10-5) 1.04 aad ‘7 al “=0.200 47 x 10° 1.047 came __ [CHsCOOH] [OH * [CHsCOO 5.48 x 10-19 mol dm: Solution 2 (Alternative way to present the working) CHsCOO-(aq) + Hz0(I) = CHsCOOH(aq) + OH (aq) pOH = 14-9.02=4.98 [OH-] = 108° = 1.047 x 10% mol dm * 3 At equilibrium, [CHsCOOH] = [OH] = |.0#Tx (0 nd din [CHsCOO] = 9.240 - LOY x10 = 0.200 pul dn” : 1x 107) ° (CHSCOOH OHI USHA Lg oy [CHsCOO7} 0.200 Ko Note: For this question, there is no need to assume (Co —y) = Cosince y = [OH] can be calculated from the given pH of the solution. Ei Relationship between Ka and Ke for a Conjugate Acid-Base Pair TAK, Kyand Kw + There is a simple relationship between the ionic product of water and the dissociation constants of an acid and its conjugate base. This relationship can be derived by considering the dissociation of ethanoic acid and ionisation of ethanoate ion in water. * For ethanoic acid, we have CHsCOOH(aq) @ CHsCOO"(aq) + H"(a r {eHsCOO at (aq) Is (aq) + H*(aq) Ky of CHsSCOOH = Toe COOH] -20-* For ethanoate ion, which is the conjugate base of ethanoic acid, we have CH:COO-(aq) + H:0(1) = CHsCOOH(aq) + OH (aq) wcoo- = [CHsCOOHI [oH] Kot cHicoo: = KEROT By multiplying the above two expressions together, we have [CHsCOO7] [H*) yc LotsCOOHT OH [CHsCOOH] [CHsCOO} = [H'][OH] (Ka of CHxCOOH) (Ke of CHsCOO7) = ( + Hence, in general for a conjugate acid-base pair, we have For an acid and its conjugate base | K, of acid HA x Kyof conjugate base A” = Kw For a base and its conjugate acid Ke of base B x K,of conjugate acid BH = Ky Ku KyofB = K, of BHY = + Note that a relationship also exists between pK, and pK, for a conjugate-acid-base pair. = 7 At 25°C, Pee Kix Ko= Ku = 1.0.x 10" maar | and pkw = pK + pk and pkg + pK = pKy = 14 i me Worked Example 13 @m (a) The Ka of CHsCOOH is 1.80 x 10 mol dm-*. | (b) The Ky of NHs is 1.74 x 10-5 mol dm Calculate the K, of CHsCOO-, Caloulate the Ka of NH." Solution Solution Kw ts Ky of CHsCOO- = ee coon Ky of NHet = 10x ~ {80x10 2 5.56 x 10° mol dar? 5-15 «107 meld * -21-7.2 Relative strengths of acid and base ina conjugate acid-base pair * Consider a conjugate acid-base pair at 298 K. ps 1.0 x 10-14 Ka x Ko = Ku = 1.0.x 10" mol? dm? Ky = Be MOE From either one of the equations, + the larger the K, of an acid, the smaller is the Ky of its conjugate base. * the stronger the acidity of the acid, the weaker is the basicity of its conjugate base ‘* Consider two weak acids, HA and HB. + IF HA is a stronger acid than HB, then A” is a weaker base than 8. + Reasoning: HAisa stronger acid thanHB => Ka ofHA > Keof HB Kook 7” kof => Kota < Kyof => Avis aweaker base than B- IF HA is a stronger acid than HB, the reaction between HA and B> will occur to a greater extent than that between HB and A-. HA + B = HB + & stronger stronger weaker weaker acid base base acid ‘+ The table below shows the strengths of different conjugate acid-base pairs. — BASE | sa | apes i ea Sa sscalfscans | ee | oe 3 moe | Sos HS i sa 880) |e | era ac steroi | stele | i | wai x Ror GH.c0o [panting | TAKOH\ HO) Hc, [HOO Hs rs ae Ns Ho ont 3a] a ne a) Sa sania | comgate pexncin | booed cae | ake De WH & oH” + Ni + Ingeneral, Hd + AH, 3 2 cde aoe strong Bransted- * HCTis a strong acid Ka of HCI= 1x 107 mol dm Lowry acids have weak conjugate bases 1ox10" 1107 ‘+ Chis said to be a weak conjugate base Ky of Cr 1.00 x 102 mol dm-* ‘weak Bronsted-Lowry acids have strong Conjugate bases ‘+ CHsCOOH is a weak acid ‘*CHsCOO™ is said to be a strong conjugate base. Ka of CH:COOH = 1.80 x 10° mol dar? ax to" Ko of CHsCOO- = LEE 8.56 x 10 mol dm? 22.KEM Degree of ionisation, « 8.1 Defining degree of ionisation # + The degree of ionisation (or degree of dissociation), a, of an electrolyte can be defined as the fraction of molecules which is ionised at equilibrium, are ionised at equilibrium number of moles of molecules present initially + For strong acids/bases which ionise completely => a =1 + For weak acids/bases which ionise partially => 0 Ks * Consider a weak acid in which «is very smalll such that a << 4 Then (1a) ~ 1. In this case;the K, expression is simplified as shown below. * Since K is constant at a given temperature, it can be seen from the last expression that for a weak acid, a increases with increasing dilution (i.e. decreasing concentration of acid) and is therefore not constant at a given temperature. + _ For a weak base B of concentration C. mol dm” and degree of ionisation a, the above equations apply with K, of B replacing Ky of HA. -23-Note: —— Which is the best indicator of the strength of an acid: pH, cor Ks? + Ky is the best indicator as it is constant at constant temperature and does not vary with the dincentration of the acid. The K, of a stronger acid is always larger than that of a weaker aci + The pH of an acid varies with the concentration of the acid. The pH of a stronger acid can be larger or smaller than that of a weaker acid depending on the oencentrations of the two acids. + Like pH, the degree of ionisation, a, varies with the concentration of the acid. It increases with decreasing concentration (or increasing dilution) of the acid. Like pH, it can be used to compare the strength of acids only provided if the concentrations of the acids are the same, 8.3 Calculations involving és Worked Example 14 | The pH of 0.20 mol dm-* NHa(aq) solution is 11.30 at 298 K. Calculate Ki, of NHs and the degree of ionisation of Nis in this solution. Solution pH = 11.30 pOH = 14—11.30=2.70 = [OH] = 102” = 1.995 x 10° mol dv Concentration/mol dv®_[ NHs(aq) + H:O() = NH@(aq) + — OH-(aq) initial 0.20 = = change 1.995 x 10% 41.995 10% — #4.995x 107 equilibrium. | __0.198 1995x107 1.995 x 10° ke = INHALIOHT _ (1.995 x10°V1.995X10) 5 494s mot am? © = Nag tg 10" mol die 1.995 x 10 - Hence degree of ionisation = >>> = 9.98 x 10° Alternatively, degree of ionisation, a= [IR IX = peep Co ou me Worked Example 15 om Calculate the pH of 0.010 mol dm* CHsCOOH solution if the degree of ionisation of CHsCOOH is 0.041. Hence determine the Ka of CHsCOOH Solution Concentration / mol dm | CHsCOOH(aq)_= _CHsCOO-(aq)_+_H’(aq) Initial 0.010 - - ‘Change ~{0.041)(0.010) +(0.041)(0.010) —_ +(0.041)(0.010) Equilibrium | 959x102 4.10104 4.40 x 104 pH= urd = = (ale X10) = 3.34 Ky = Latue OHS | (to 10) LY teste) Lag «19 poe da? Co, Coot astxlo> -24-EDM Sait Hydrolysis 9 /TYpes Of salt solution adi RoW: sp A salt may be defined as a compound formed by the reaction of an acid and a base. It contains 2 a cation which originates from the base and = 2 ananion which originates from the acid ‘Some salts, when dissolved in water, form neutral solutions. Others form acidic or basic solutions due to salt hydrolysis, which is a reversible reaction between the salt ions and water. ‘Whether a salt solution is neutral, acidic or basic depends on the type of salt. There are four types in this context as summarised in the table below. = Combination of acid and base Example of Nature of solution which gives rise to the type of salt salt formed and pH of solution at 25 °C strong acid + strong base Nacifaq) noutral, pH = 7 2g. HOI(aq) + NaOH (ag) ~> NaCl) + H:0() 7 strong acid + weak base eae NHuCitaq) acidic, pH <7 eg. HCI(aq) + NHs(aq) —> NH.Ci{aq) weak acid + strong base : CH:COONar(aq) basic, pH >7 9. CHsCOOH + NaOH -» CHsCOONa* + #0 _ * weak acid + weak base + acidic if Keof eation > Ky of anion ©, CHCOOH +NHs—> CH:COONHe + Heo | CHOONHeag) | + neutral Keot cation = Ke of anion A salt will undergo hydrolysis (i.e. reaction with water) if + itS anion is a conjugate base of a weak acid and/or + its cation is a conjugate acid of a weak base The table on the next page summaries how salt hydrolysis gives rise to acidic or alkaline solution. Note that only ions that are the conjugate bases of weak acids or conjugate acids of weak bases hydrolyse appreciably. -25.(a) Salt ofa strong acid and strong base Example: sodium chloride, NaC/ This type of salt dissolves in water to form a neutral solution. In the solution, complete dissociation of NaC! occurs, NaCi(s) + aq. —> Na‘(aq) + Craq) Both the Na* and Ci ions are hydrated but they do not undergo hydrolysis. The solution is meutral since (H"] = [OH"] Nat does not undergo hydrolysis due to its relatively low charge density (as compared to Mg* or AP* ions). Being the anion of a strong acid (i.e. HCI), Cis a weaker base than water and it does not undergo hydrolysis. (b) | Saltofa — ‘Example: ammonium chloride, NHsC/ strong acid ; al This type of salt dissolves in water to form an acidic solution. In the solution, Weak base | complete dissociation of NH4C/ occurs. NHACi(s) + aq. —> NH,"(aq) + Cr-(aq) Being the anion of a strong acid (Ie. HC), Cris a weaker base than water and does not undergo hydrolysis. Being the cation derived from a weak base, NH," is a relatively strong conjugate acid (as compared to water) and it undergoes hydrolysis to give Hs0* ions. NH."(aq) + H:0(1) = NHs(aq) + Hs0°(aq) [H;0°] > [OH7], the slight excess of HsO* ions generated by the hydrolysis reaction causes the solution to be acidic. (c) | Saltofa Example: sodium ethanoate, CH;COO-Na* weak acid and This type of salt dissolves in water to form a basic solution. In the solution, Strong base | complete dissociation of CHsCOO-Na‘ occurs. CHyCOO-Na‘(s) + aq. —> Na*(aq) + CHsCOO“(aq) Nat does not undergo hydrolysis due to its low charge density. Being the anion of a weak acid, CHsCOO- is a relatively strong conjugate base (as compared to water) and it underaoes hydrolysis to give OH" ions. CHsCOO“(aq) + H.0(l) = CHsCOOH(aq) + OF [OH] > [H;0°], the slight excess of OH’ ions generated by the hydrolysis reaction causes the solution to be alkaline. (@ | Saltofa Example: ammonium ethanoate, CH;COO-NH,” a See CHsCOO-NH"(s) dissolves in water to form a very slightly acidic solution. In the weak base | Solution, complete dissociation of CHsCOO-NH«* occurs. CHsCOO-NH4"(s) + aq. —> NH¢"(aq) + CHsCOO"(aq) Both the NH,* and CHsCOO- ions undergo hydrolysis (see reasons given above). The solution is weakly acidic because the Ka of NH.’ is slightly laraer than the Ky of CHsCO%9.2 Calculations involving hydrolysis of a salt me Worked Example 16 om [ The Ks of ethanoic abid is 1.8 x 10 mol dm at 298 K : Calculate the pH of a 0.50 mol dm sodium ethanoate solution. Solution The solution contains ethanoate ions which undergo hydrolysis to give OH- ions. Kw 1.0.x 10-14 Kg of CHsCOOH ~ 78x10 ~ 56x 10" mol dn Ky of CHxCOO- = Let [OH"] = [CHsCOOH] = y mo! dm-® at equilibrium. ‘Since CHsCOO” is a weak base with a very small Ke, assume that at equilibrium, [CHsCOO-] = 0.50 mol dm. = [CHsCOOH] [OH] ~Goncinal 13 |“ GHsCOO (aa) + HOW) = CHCOOH(ag) + OFFag) Ko of CHSCOO™ = TE Coy intial 050 S Change 7 v v _ —Eauitbrium | 050-y ye x ~ 050 = 5.56 x 10 mol dm? y= Messe rioycosn) = L667 x10% Note: 5 Ky of CHsCOO™ is needed here = [OH] = L667 «107 wd de but is not given. POH = -4 (LOT x 4) = 418 Itcan be calculated from the Ree er te ee tibet vat given Ky of CHsCOOH. me Worked Example 17 om ‘The Ky of NHs is 1.74 x 10-6 mol dm~ at 298 K. Calculate the pH of a 0.10 mol dm ammonium chloride solution. Solut The solution contains ammonium ions which undergo hydrolysis to give HsO* ions. Ky _ 1.01 Ky of NHy 1.74 x 10: Ka of NH¢ 5.75 x 10° mol dm Let [Hs0*] = [NHs] = y mol dm~* at equilibrium, Since NH." is a weak acid with a very small Ks, assume that at equilibrium, [NH,"] = 0.10 mol dm. eae MO) Comsat cert sc + MoM = _Niieq) + sort ee aaa jaa | a.10 — = = 5.75 x 10°” mol dm= y = [H:0*] = (6.75 x 10°)(0.10) Note: = 7.583 x 10° mol dm K, of NH«’ is needed here but is not given. pH =~ lg (7.583 x 10) = 5.12 Itcan be calculated from the given K; of NHb. -27-EQ Buffer Solutions 10.1. Definition A buffer solution is a solution which is able to resist pH changes upon the addition of a small amount of acid or base. + A buffer solution contains both an acidic species and a basic species (both in relatively large amounts) to react respectively with any base or acid added. In general, there are two types of buffer solutions: © _ acidic buffer which consists of a mixture of a weak acid and one of its salt «Example: an aqueous mixture of CHsCOOH and CHsCOO-Na* ® alkaline buffer which consists of a mixture of a weak base and one of its salt «Example: an aqueous mixture of NHs and NH.C/ 10.2 Acidic buffer (a) Composition of an acidic buffer + Anacidic buffer solution consists of a mixture of a weak acid and a salt containing its conjugate base. + Consider an acidic buffer consisting of a mixture of ethanoic acid and sodium ethanoate. In this solution, ethanoic acid, being a weak acid, is only partially dissociated: CHsCOOH(aq) = CHsCOO"(aq) + H*(aq) (1) On the other hand, sodium ethanoate, a strong electrolyte, is fully dissociated CHsCOO-Na*(aq) —> CHsCOO~(aq) + Na“(aq) (2) + In accordance with Le Chatelier’s principle, the presence of CHsCOO° ions from the complete dissociation of CHsCOO-Na" further suppresses the dissociation of CHsCOOH such that the equilibrium position of reaction (1) lies very much to the left. + Hence the buffer solution contains relatively high concentrations of both CHsCOOH and CH;COO*. The buffer solution is said to contain a large reservoir of CHsCOOH (acidic species) and a large reservoir of CHsCOO™ (basic species). (b) Action of the acidic buffer solution * Addition of a small amount of acid (i.e. H* ions) + When a small amount of H’ ions is added to the solution, the following reaction occurs: CHsCOO{aq) + H*(aq) —> CHsCOOH(aa) etd edo mse zoe the solution ensures that nearly all the = The presence of a large reservoir of CH3CO\ added H’ ions are removed. + Hence [H']in the solution changes very little and the pH is kept approximately constant. -28-+ Addition of a small amount of base (i.e. OH” ions) * When a small amount of OH" ions is added to the solution, the following reaction occurs: CHsCOOH(aq) + OH(aq) —> CHsCOO-(aq) + H-O(\) + The presence of a large reservoir of unioniSed CHsCOCH molecules in the solution ensures that nearly all the added OH" ions are removed. + Hence [OH] in the solution changes very little and the pH is kept approximately constant. (c) Diagrammatic representation of how an acidic buffer works ‘utter soktion just ater Buffer soliton wth relatively high Butler solution just ater the adeton ofa smal concentrations ofboth the weak the adston ofa sma mount of fons ‘eid and its conjugate base ‘amount of OF ions cHicoo- |} crscoon |< | crncoo- |] crscoon | | crscoo- | cHcoon [Gascook <— WF + cHicoo [CHcOOH + OH” —> cHiCoO- +H:0 10.3 Basic buffer ‘ ion of a basic buffer (a) Compo: + An alkaline buffer solution consists of a mixture of a weak base and a salt containing its conjugate acid * Consider an alkaline buffer consisting of a mixture of ammonia and ammonium chloride. In this'solution, ammonia, being a weak base, is only partially ionised: NHs(aq) + H2O()) = NH«*(aq) + OH"(aq) oo... os... (1) On the other hand, ammonium chloride, a strong electrolyte, is fully dissociated: NH,Ci(aq) —+ NH."(aq) + Cr-(aq) oe (2) * In accordance with Le Chatelier's principle, the presence of NH«* ions from the complete dissociation of NH,C/ further suppresses the ionisation of NHs such that the equilibrium position of reaction (1) lies very much to the left. * Hence the buffer solution contains relatively high concentrations of both NH, and NH. The buffer solution is said to contain a large reservoir of NHs (basic species) and a large reservoir of NH@* (acidic species) -29-{b) Action of the basic buffer solution me Exercise 4 ©! = Which of the following could act as buffer solutions? Addition of a small amount of acid (i.e. H’ ions) = When a small amount of H! ions is added to the solution, the following reaction occurs: NHs(aq) + H'(aq) —> NHe"(aq) = The presence of a large reservoir of unionised NH, molecules in the solution ensures that nearly all the added H" ions are removed. + Hence [H'] in the solution changes very little and the pH is kept approximately constant, Addition of a small amount of base (i.e. OH" ions) When a small amount of OH" ions is added to the solution, the following reaction occurs: NH«*(aq) + OH-(aq) —> NHa(aq) + H-0()) + The presence of a large reservoir of NH." ions in the solution ensures that nearly all the added OH" ions are removed. + Hence {OH7 in the solution changes very little and the pH is kept approximately constant. [N2003/1/33] a EEEMI pH Calculations involving Buffer Solutions 14.1 The relationship between pH, pK, and composition of an acidic buffer NaHCOsandNaCO; © 2 CHsCOzH and NaC! 3 HNOs and NaNO; WB (Uy) fo vor, acrd (HDs “) WACO oH) bub nw I " t ce so wad wy she or Consider a buffer solution containing a weak acid HA and a salt of the acid Na‘A~ jam | HAlaq) = Haq) + Ataq) mol NatA-(aq) —> Nat(aq) + (aq) oe HA(aq) = H"(aq) + A(aq) ats Co-y y 26 HA, being a weak acid, undergoes partial dissociation in the solution. The dissociation of HA is further suppressed by the presence of A- ions from the complete dissociation of Na‘A-. Hence at equilibrium, only a very small amount of HA has dissociated. Hence at equilibrium, [HA] initial [HA] | [A‘1 = initial [A] TH] + [AT inthe solution, allthe [In the solution, all | « Inthe solution, due to the presence of A-from_| HA molecules can be | the A-ions can NavA-, {H"] 2 [A] assumed to remain | be assumedto | « ifthe solution contains only the weak acid HA (i. undissociated. come from Na’, NatA- is absent), then (H'] = [AT]. = -30-(HAT © At equilibrium, Ke = THA Taking logarithms to base ten, Ig kK = Ig ttt} +1g (AL) 5 {HA} Multiplying by 1, Ig Ks = Substituting pH = 0 1g (H"] and pk, = Ig Ka, pKa + Rearranging the above expression gives the following expression: LAT) of bow. (HAY [salt] ) pH = pk, + Ig ( inca or PH = pK + Ig (: The above expression is called the Henderson-Hasselbalch equation for a buffer solution consisting of a weak acid and its salt. + The Henderson-Hasselbalch equation can be used to calculate the following: + the pH of a buffer solution, * how much acid or salt is needed to make a buffer solution of required pH, * the effect on the pH of a buffer solution when a small amount of acid or base is added, 11.2 The relationship between pH, pK, and composition of a basic buffer + Consider an alkaline buffer solution containing NH3. and NHAC! NHiCl(aq) —> NH¢(aq) + Cr-(aq) NHs(aq) + H2O(!) = NH¢"(aq) + OH-(aq) + Ina similar manner as that in Section 11.1, the following expression can be derived. Pky + Ig (RL oot [salt] ) INHs} [base] pOH or POH = pK; + Ig (- ‘The above expression is called the Henderson-Hasselbalch equation for a buffer solution consisting of a weak base and its salt. “31.14.3 Calculating the pH of buffer solutions me Worked Example 18 om Calculate the pH of a solution containing 0.50 mol dm~ of methanoic acid, HCOOH, and 2.5 mol dm~ of potassium methanoate, HCOO-K’. Ka for HCOOH = 1.6 x 10“ mol dm~*. k= Urdu@o'] Solution Tae HCOO'K"(aq) —> HCOO“(aq) + K*(aa) 4 HCOOH(aq) = HCOO*(aq) + H’(aq) Oe} = ke Citas The given solution is an acidic buffer. idic buffer, pH= pK + | Ceca = Ag (1.6 x 10%) + k (2% = 4.49 For this acidic buffer, PH= PKs + 19 (goon) = 19 (1.6% 10%) + Ia Geo) = 449 me Worked Example 19 om Calculate the pH of a solution that is formed by mixing equal volumes of 0.40 mol dm-> NHs(aq) ana | 0.20 mol dm-® NH n(OH-) added, some CHsCOOH remains unreacted and the resultant mixture contains both CHsCOOH and CHsCOO- = an acidic buffer is formed After mixing, n(CHsCOOH) left = initial n(CHsCOOH) — n(CHsCOOH) reacted = 0.10 - 0.04 = 0.06 mol n(CHsCOO-) = n(OH") added = 0.04 mol a . [CHsCOOH] = 0.06 mol dm? and [CHsCOO*] = 0.04 mol dm [CHsCOO"] For this acidic butter, pH= pks + 19 (or coo a -32-11.4 Calculating the change in pH of buffer solutions }@ Worked Example 21 Calculate the change in pH when 0.001 mol of solid potassium hydroxide is added to 1 dm® of water. “Solution ‘Since water is neutral, pH of water = 7.0 (at 298 K) After addition of KOH, [OH] in the solution = 1.00 x 10? mol dm? POH = =Ig [OH] = -Ig (1.00 x 10%) = 3.00 At 298 K, pH = 14 — pOH = 14-3.00= 11.0 Change in pH = final pH ~ original pH = 11.0 ~7.0 = + 4.00 = increase in pHi of 4.00 units me Worked Example 22 om Calculate the change in pH when 0,001 mol of solid potassium hydroxide is added to 1 dm® of the buffer solution prepared in Worked Example 20. Solution PH of the buffer solution = 4.564 Initial amount of CHsCOOH present in the buffer Initial amount of CHsCOO- present in the buffer 06 mot 0.04 mol Upon the addition of OH: CHsCOOH(aq) + OH-(aq) —> CHsCOO“(aq) + H20()) n(CHsCOOH) left = initial n(CHsCOOH) ~ n(CHsCOOH) reacted 0.06 — 0.001 = 0.0590 mol n(CHsCOO>) present = initial n(CHsCOO-) + n(CHsCOO-) formed 04 + 0.001 = 0.0410 mol At equilibrium in the resultant solution after reaction, [CHsCOOH] = [CHsCOOH] left after reaction = 0.0590 mol dm? [CHsCOO] = [CHsCOO7 present after reaction = 0.0410 mol dm The resultant solution is an acidic buffer. [CHsCOO- For this acidic buffer, pH= pK. + Ig (Gncoont a 0.0410 4.74 +19 SoEa9 ) = 4,582 Change in pH = final pH — original pH = 4.582— 4.564 = +0.018 => increase in pH of 0.018 units + Note: Compare the answers for Worked Examples 21 and 22 Worked E.g. Solution | Original pH_| pH after addition of 0.001 mol KOH | Change in pH 21 | 4dm? of water 7.0 11.0 + 4.00 2 ‘Tam of buffer | 4.564 __ 4582 +0.018 There is a significantly smaller change in pH when the same small amount of KOH is added to a buffer solution than to water. -33-EE More on Buffer Solutions: 424. Buffer capacity and effective buffer range (a) Buffer capacity + The buffer capacity of a buffer is a measure of its ability to resist pH change and depends on both the absolute and relative component concentrations, * In absolute terms, the more concentrated the capacity. Consider the following two acidic buffer solutions. components of a buffer, the greater the buffering ~ [Butter [ Components ina 1 dm® solution pH © | 1 mol dm CH:COOH and 1 mol dm? CH:COO-Na* 474 @ | 0.1 mol dm CHsCOOH and 0.1 mol dmr® CHsCOO-Na* | 4.74 change in buffer © than buffer @ obtain the same pH change. In this case, buffer © has greater buffer capacity than buffer @. + Adding the same amount of H" ions (or OH" ions) to each buffer will produce a smaller pH = A larger amount of H' ions (or OH" ions) will have to be added to buffer © than buffer @ to + Buffer capacity is also affected by the relative concentrations of the buffer components. when they are different = 1 for an acidic buffer or when E24. {acia] {base} + For a given addition of acid or base, the buffer component ratio (i.e. {sat isc {sam itase} or ) changes less (and hence the pH changes less) when the component concentrations are similar than + Itfollows that a buffer has maximum buffer capacity when 1 for an alkaline buffer. | | {sat Acidic buffer Hence maximum buffer capacity is attained at Lat) Tad] Alkaline buffer = pk +ig1 = pk Hence maximum buffer capacity is attained at [power a * A buffer solution is most effective in resisting changes in pH when the following requirements are met: © The number of moles of both the weak acid (or weak base) and its salt are large relative to that of the acid or base to be added to the buffer solution. ® The weak acid (or weak base) to salt concentration ratio is close to 1:1 34.(b) Effective buffer range * The effective buffer range is the pH range over which the buffer acts effectively in keeping pH approximately constant, and it is related to the relative component concentrations. + Inpractice, an acidic buffer is effective provided: 0.1 < {salt] _ - 5 en ag) = Ot PH = pK, +g 0.1 (salt) When Say = 10 PH = pK. +g 10= pk +4 + This means that the effective buffer range is from pH = (pK,— 1) to pH = (pKa + 1) Effective buffer range of an acidic buffer = pKat 1 12.2 Effect of dilution on the'pH of buffer“ BBR a a weak acid HA and its salt Na‘, pH = pKa + Ig Gay 5 * Foran acidic buffer contai ‘+ From the equation, it can be seen that diluting the buffer has no effect on the pH because [HA] A and [A"] are reduced to the same extent (ie. the value of a is unchanged). * Similarly, for an alkaline buffer containing a weak base B and its salt BH’, dilution has no effect ‘on pOH (and hence pH) since (B] and [BH"] are reduced to the same extent, + However, note that dilution has a marked effect on buffer capacity. It reduces the ability of the buffer to cope with contaminating acid and base, 12.3 Preparing a buffer solution i * Consider the Henderson-Hasselbalch equation as applied to acidic buffers. + There are two terms on the right-hand side, which determine the final pH of the solution, * The first term is pK, whose value is responsible for the ‘coarse selection’ of 1st term 2nd term pH. the pl value ofthe acid chosen the [salt/[acid] ratio can shouldbe within about 1 pHunt be adustedtoactiae | |* The second term involves the ratio a the desired pH {[salt[acia] and provides the ‘fine tuning’ ofthe desired pH ® to the final desired pH. -35-me Worked Example 23 om What mass of sodium ethanoate must be added to 1 dm of 1.0 mol dm~ ethanoic acid to produce a buffer of pH 4.5? The pK, of ethanoic acid is 4.8. Solution [CHscoo}) (cHacoon) (Acidic buffer) PH = pKa + Ig ( 45 = 48 + Ig ((CHsCOOV1) [CHCOO] = 198s G50) wal dn o-sl at ‘Amount of CHsCOO-Na' needed = Amount of CHaCOO™= Uden") (0-581 rol do?) Molar mass of CHsCOO-Na’ = 62 g mot" Hence mass of CH;COO"Na’ to be added = (0.501)(¢2) = 41.1 e 12.4 Blood as a biological buffer + The pH of human blood is maintained between 7.35 and 7.45 even though the concentration of carbon dioxide and thus carbonic acid in the blood varies greatly. * The pH of blood must be kept approximately constant so that the enzymes in the blood can function. Enzymes only work over a narrow range of pH. Death may result if the pH falls below 6.8 or rises above 7.8. + The control of pH in the blood is achieved using different buffers: the HsCOJHCOs" buffer, the H,PO.THPO.* buffer, and plasma proteins. ‘The H,CO3/HCOs" buffer in blood ‘© One of the important buffers in human blood is made up of carbonic acid (H2COs) and the hydrogencarbonate ion (HCOs"): H,COs(aq) = HCOz(aq) + H*(aq) The carbonic acid in the blood originates from dissolved carbon dioxide. The latter enters the blood from tissues as the by-product of metabolic reactions: CO,(g) + H:0(l) = HeCOs(aq) * If the concentration of H” ions in the blood increases (e.g. from lactic acid produced from exercise), the HCO; present reacts with the additional H* ions and thus the pH remains virtually unchanged. HCOs(aq) + H'(aq) —> H:CO;(aq) “| Ifthe concentration of OH" ions in the blood increases, H;COs present reacts with the additional OH ions and thus a constant pH is maintained H:CO,(aq) + OH"(aq) —> HCOs(aq) + H20(1) -36-EE Acid-Base Titration and Indicators 413.4 Equivalence point and end-point”? So 13.2. Use of indicators during acid-base titrations fs The aim of any titration is to determine the volumes of two solutions which just react with each other completely. This occurs at the equivalence point and it marks the completion of the titration In an acid-base titration, the equivalence point is the stage reached when the amount of acid needed to react with the amount of base is precisely that required by the stoichiometric equation. In practice, the completion of an acid-base titration can be detected by a distinct colour change brought about by the use of a suitable indicator. The point during titration at which this distinct colour change occurs is called the end-point of the titration. The use of a suitable indicator will ensure that the end-point of the titration is very close to the equivalence point of the titration. During an acid-base titration, there is a change in pH as the base is added to the acid or vice versa. This change in pH! during the course of a titration depends largely upon the strenaths of the acid and base used. As shown in the table below, there are four main types of acid-base titrations but only three of them can employ suitable indicators to help identify the equivalence point. This is essentially because, for the equivalence point of an acid-base titration to be identifiable using an indicator, the pH near the equivalence point must change sharply by several units, This does not occur in the case of a weak acid-weak base titration. Types of acid-base titration Type of tration Acie Base Regonctmatiod | sutabe indicator methyl orange screened methyl orange strong acid - strong base | HCi(aq)_‘| NaOH(aq) 4-10 thymol blue thymolphthalein phenolphthalein ‘methyl orange strong acid-weak base | HCi(aq)_ | NHs(aq) 35-65 erred roti ngs thymol blue weak acid ~ strong base | CHsCOOH(aq) | NaOH(aq) | —7.5-10.5 __| thymolphthalein phenolphthalein weak acid ~ weak base | CHsCOOH(aq) | _NHs(aq)_| no marked change | no suitable indicator A3iS"Acid-base indicators’ ee ELGG Sas Acid-base indicators such as thymolphthalein and methyl orange are substances which change colour according to the hydrogen jon concentration of the solution to which they are added. Consequently, they are used to test for acidity and alkalinity. They are also used to detect the end point in acid-base titrations. Acid-base indicators are usually weak acids or weak bases. When dissolved in water, they dissociate slightly forming ions. eat(a) Indicators as weak acids + Consider an indicator which is a weak acid with the general formula Hin. In aqueous solution, the following equilibrium is established: + The equilibrium constant expression for the reaction is HIn(aq) = H*(aq) + In-(aq) given in the left-hand box below. ~ acid conjugate base |* It can be used to derive the equation which shows the f ts Ct relationship between pH and (and Tin} _ Him) tin] Kin = pH = pKin + Ig ( {Hin} (Hin} * When the indicator is added to an acidic solution, the relatively high [H’] in the solution causes the equilibrium position of the above reaction to shift to the left. = Colour A will be observed since [HIn] > [In"]. = When the indicator is added to an alkaline solution, the OH" ions in the solution react with the H" ions from HIn and this causes the equilibrium position to shift to the right. = Colour B will be observed since [In"] > [HIn] * Hence the indicator colour that is observed depends on the relative proportions of HIn and In”. The relative proportions of Hin and In” in turn is affected by the [H'] in the solution (b) The pH range of an acid-base indicator + Each acid-base indicator has a pH range over which it changes colour. The colour change of an indicator is due to the change from one coloured form to another. + Typically, the human eye sees [Hin} Un] ty 2 1° colour B when icy colour A when 210 * Consider a titration experiment in which an indicator HIn(aq) is added to an acid solution in a conical flask and this solution is then titrated against a base placed in the burette. In this case, the indicator will be changing from colour A to colour B during the titration. This colour change can be summarised as follows: (Hinytin-] Remark pH [Hinytin-]> 10 | Cotour A is observed. [Hiny{in7] = 10 | Change of colour starts though colour A still dominates. pH=pKin—1 [Hiny[in-]= 1 _ | Mic-point of colour change. Observed colour: colour A+ colour B | pH = pKin [Hinytin-] = 0.1. | Change of colour ends and colour B now dominates. pH = pKin+ 1 [Hiny{in-] < 0.1 | Colour B is observed. + From the above table, the colour-change interval is accordingly from PH=pKn-1 to pH=pKin+1 (ie. over approximately two pH units) pH range of an indicator = pKin +1 -38-* The pH ranges of selected indicators are shown in the table below: a PKin approximate | _ colourin colour in colour at a at25°C_| pHrange_| ‘acid’ solution | ‘basic’ solution |~ __ end-point methyl orange 37 34-44 red yellow orange soreened methyl a - i Serene 34-44 Violet green grey bromothymol biue | 7.0 60-76 yellow blue green thymol blue 89 80-96 yellow blue green light blue (i tirant is alkall) thymolphthalein 89 | 93-105 | colourless blue ioutocs ities nan light pink Gi trant i akall) sy - ink henolphthalein 92 83-100 | colourless pin are Giearees (c) The pH at the end-point of a titration + For the titration experiment described in (b), the end-point of the titration is reached when the indicator used gives a distinct colour change, i.e. from colour A to a colour that results from the combination of colour A and colour B. + This end-point is reached when the indicator colour observed is a combination of the two extreme colours and this occurs when: fin} {HIn(aq)] = [In-(aq)] => pH= pKin + Ig (- Trin) ) = pKin +19 1= pKin + Hence at the end-point of the titration, [pH = Kin] The pH at the end-point is generally the centre of the pH range of the indicator used. + Note: The end-point is a property of the indicator and does not necessarily show that the reaction between acid and base is complete. (d) Choice of indicators + Essential characteristics of a suitable indicator: © The colour change of the indicator must occur when the correct volume of fitrant is added from the burette, i.e. the pH range over which the colour change takes place must be such as to indicate when the reaction (as shown by the equation) is complete © The indicator must give a sharp end-point in the titration, ie. it must change colour distinctly upon the addition of one drop of the titrant from the burette. + The choice of an indicator for an acid-base titration depends on the * type of titration carried out and + pH range of the indicator + The ideal situation would be to choose an indicator such that the end-point of the titration coincides exactly with the equivalence point of the titration. This occurs if the chosen indicator has a pKin value which is identical to the pH of the resulting solution at the equivalence point. In other words, A suitable indicator is one where its pH range coincides with the region of rapid pH change in the titration curve (i.e. the pH range of the indicator must fall on the vertical portion of the titration curve), -39-EEZY Acid-Base Titration Curves 414.1 Types of titration curves * A titration curve is a graph of pH against volume of an acid or base. = It shows how the pH of an acid (or base) solution in a conical flask changes as it is neutralised by the addition of a base (or acid) from a burette. = There are 4 main types of titration curves based on the 4 types of acid-base titration. Strong acid ~ Strong base Titration shan 7 < ‘| “| syrmnan | | i om | al : TET E TET TSS | eemBoore asst on Ae ‘vans ethaohfed estefan? Stoscarrt Strong acid - Weak base Titration on Twaterct Ga molamsnaana) = | meeMORNe Thraton of 259 em? of 040 mold HK) ashe 010 mol dies Hi Voter ot sag) ate? | iy melon Weak acid ~ Strong base Titration suusie neater TWrtion of 25.0. ot 810 mot aescHxcOoHaa) | Ho sale mda, seemed “ons 8 10 mol an Hoon) LG 2 ~ Weak acid — Weak base Titration "ton 25.9 of 10 mot am cnscoong) ‘oma mel amo) ‘+ Important parts of a titration curve 1 initial pH 2. (for SA-WB and WA-SB titrations only) region where solution is a buffer solution * pH of solution at maximum buffering capacity 3. region near the equivalence point (ie. region of drastic pH change) * pH of solution at equivalence point 4 region after the equivalence point «final pH of solution Weak base — Strong acid Titration Note: The base ic inthe conical flask. Votume of HcXaq) add fr? -40-14.2. Titration curve of a strong acid-strong base titration The graph below shows the change in pH of the reaction mixture when 0.100 mol dm-? of NaOH was Added to 26.0 em? of 0.100 mol dm? HCl ey « Aus nh ded rape of indiudey hd on ke wed Strong Acid — Strong Base Titration Suitable indicator: methyl orange thymolphthalein ® 15 20 25 30 35 40 45 50 Vol ofaq NaOH em * © The initial pH is low because the acid used is a strong acid, pH remains low from 0.00 to 25.00 om? as the solution still contains strong acid that has not yet been neutralised, - © This is the region of rapid pH change. * There is a sudden increase in pH over the equivalence point (pH 4 to pH 10) when one or two drops of base are added from the burette. "At the equivalence point E, the pH of the ‘resultant solution containing NaCi(aq) is 7. puxhd of U5 @ After E, excess NaOH is added. The titration curve flattens out at a high pH value since the base used isa strong base. (pH<13 due to dilution by titrant added) int be the mid the two inte Note: The equivalence point E is found by extrapolating the linear portions of the titration curve (0, @ & ©) and taking Calculation of pH at various parts of the titration curve: (0 Initial pH= pH of strong acid Solution is an aqueous solution of strong acid [H+] = [HCKaq)] 410 mol dm Wg [H*] = -Ig (0.10) = 1.00 pH (il) pH af equivalence point (point E) At equivalence point, HC/ has been neutralised by NaOH) ‘The resultant solution is NaCi(aq). Since Nat and Civ do not hydrolyse in water, the resultant solution is neutral ‘At25 °C, pH of a neutral solution is 7. exactly | (ii) pH of mixture when 8.00 cm? of NaOH(aq) 1s added, (Before equivalence point E) H*(aq) + OH (aq) > H-0()) n(OH") = 0.008 x 0.10 = 0.0008 mol (H*)reactes = 0.0008 mol 1(H*)ewa = 0.025 x 0.10 = 0.0025 mol = His in excess, A(H*) left = n(Hiskal ~ n(H*)eactes = 0.0025 - 0.0008 = 0.0017 mot Volume of reaction mixture = 25.0 + 8.00 em? = 33.0 cm? [Hr] = SH = 90087 9.05152 mol dm Vv > 0033 PH = ~ Ig [H"] = -Ig (0.05152) = 1.29 (iv) pH of mixture when 32.00 om? of NaOH{aq) is added. (After equivalence point E) H*(aq) + OH (aq) -> H20(1) n(OH*) = 0.032 x 0.1 n(H*}es = 0.025 x 0.10 = 0.0025 mol = OH" is in excess, OH") — n(n 0.0032 ~ 0.0025 = 0.0007 mot Volume of reaction mixture = 25.0 + 32.00 cm? 57.0 em? = 0.01228 mol dm? 0007 POH = ~Ig [OH pH = 14-pOH = 12.1 me Exercise 5 @m [N2012/I/11] ‘A 1dm? solution was made by mixing 0.0040mol of Hi What was the pH of the resulting solution? A 219 B 240 © 260 (Cl(aq) and 0.0025 mol of NaOH(aq). He ly Coan) ae14.3 Titration curve of a weak acid-strong base titration The graph below shows the change in pH of the reaction mixture when 0.100 mol dm-* of NaOH was. added to 25.0 cm? of 0.100 mol dm-* CHsCOOH (Kz of CHsCOOH = 1.8 x 10° mol dm © The initial pH is not very low (1 < pH < 7) since a weak acid is used. (pH may be calculated using the formula (H'] = JK,Co) ‘Weak Acid ~ Strong Base Titration © Change in pH is fairly constant due to the formation eee of an effective buffer when large amounts of the ‘weak acid and its salt are present. pH at % equiv pt (M) (where [HAJ=[4") = pKs © The region of rapid pH change is shorter and occurs ata higher pH range than that for a SA-SB titration. ‘At equivalence point E, + CHsCOOH is exactly neutralised by NaOH + The resultant solution is CHsCOO-Na*(aq). + pH > 7 as CHsCOO™ hydrolyses in water to give 0 10 15 20 25 30 35 40 45 50 OH" @ After E, the base is in excess. The titration curve flattens’ out at a high alkaline pH value (e.g. pH 12.5) since the excess base present is a strong base. Calculation of pH at various parts of the titration curve: (i) Initial pH = pH of weak acid (iii) pH at haltequivalence point (point M) Solution is an aqueous solution of weak acid Half-equivalence point isthe point at which haf the wok : of NaOHiaa) needed for neutralisation is added HY = Cp = V7.8 10% «0.10 At this point, CHsCOOH is halt-neutralised, mice omc n(CHsCOOH) = n(CHsCOO>) pH = —Ig [H"] Hence, [CHsCOOH] = [CHsCOO] = Hig (1.942 x 10) | {cH,c001 : oe PH = pk + liner cso = PKe + 1g (1) = pKa = 4.74 (Note: pH at half-equivalence point = pK.) (i) pH of mixture when &00 cm? of NaOH{aq) is | (iv) pH at equivalence point (point E) added. (region 2) At equivalence point, the mixture present is a solution CHsCOOH + OH" > CHsCOO-+ H20 of CHsCOO"Na*. n(CHsCOO>) = n(OH") = 0.008 x0.10 = 0.0008 mol | CHsCOO-+ HzO = CHsCOOH + OH- n(CHsCOOH races = 0.0008 mol n(CHsCOO*) = 0.025 x 0.10 = 0.0025 mot (CHCOOH)on = n(CHsCOOH)nas ~ n(CHsCOOH)osaes_ | Volume of reaction mixture = 25,0 + 25.0 om? = (0.025)(0.10) - (0.008)(0.10) = 0.0017 mol = 0.050 dm? The resultant mixture is @ buffer containing 1002 _ CHsCOOH and CHsCOO [CRsCOO7 = y= 2-060 mol ar (chico. ng 22008 a= xc - [= , PH= PKs Wicsiccoon PX* * (ora LOHT= fag *Co= asso *0-080 4g (1.8 x 10°) + 1g (0.4706) 270 x 10-* mol dm? = 4,748 - 0.3272 = 4.42 POH = -Ig [OH] = 5.278, pH = 14 pOH = 8.72 (v) pH of mixture when 32.00 cm? of NaOH(aq) is added, (region @) n(OH") added = 0.032 x 0.10 = 0.00320 mol, n(CHsCOOH) present initially = 0.025 x 0.10 = 0.0025 mol 1n(OH*) in excess = 0.0032 ~ 0.0025 = 0.0007 mol, [OH] = aera POH = ~Ig [OH] = 1.911, pH = 14-pOH = 12.4 01228 mol dm? 42.me Worked Example 24 om The graphs on the right show the change in 4g PH of the reaction mixture when 0.10 mol dm? NaOH(aq) is gradually added separately to 5 25.0 cm® of 0.10 mol dm CHsCH2COOH(aq) 8 and 25.0 cm® of 0.10 mol dm HCi(aq). (a) State two reasons why the dotted graph is ott due to HCL Propanoie acial (b) Determine the Ks of propanoic acid using 4 relevant data from the graph. [Hydrochloric ac Solution D te i (a) Firstly, HCi(aq) is a strong acid and ’ . 0 15 20 a= 30 ionises completely in aqueous solution. Volume of NaOH added / em Thus its initial pH = -Ig (0.10) = 1.0 Secondly, HCI reacts with NaOH to form NaCI which contains ions that do not hydrolyse in water. Thus, for the titration involving HCI, pH at equivalence point = 7 which corresponds to the dotted graph. (b) Method 1: pH at half-equivalence px = pKa For a weak acid-strong base titration, pH at % equivalence (or neutralisation) point = pKy. Hence pK can be found by finding the pH at % equivalence point which is the point when % the volume of titrant needed for equivalence point'is added. Since volume needed for complete neutralisation is 25.00 cm’, half-equivalence point is the Point at which 12.50 cm? of aq NaOH is added. From graph, pH when 12.50 cm? of aq NaOH is added = #80 Thus pKs = pH at % equivalence poin 480 Ke= 10° = 19 2 LST x 0% poldan? Method 2: Initial pH of weak acid Ha OH oA Let HA represents propanoic acid. From the graph, initial pH of HA = 2.40 Initia He] = 107"? eg 901255 mel de? T= BT = 0.00255 nde? and [HA]= O-lo ~ 0.691254 = 0.848 TH pol dm? a Ltt x107 pala”14.4 Titration Curve of Weak Base — Strong Acid Reaction The graph below shows the change in pH of the reaction mixture when 0.100 mol dm? of HCI was added to 25.0 cm* of 0.100 mol dm-* NHa (Ke of NHs = 1.74 x 10° mol dm), Weak Base ~ Strong Acid Titration Suitable indicator: methyl orange © 8 10 15 20 25 30 96 40 45 50 © The initial pH is not very high (7 < pH < 13) since a weak base is used. (DOH may be calculated using the formula [OH] = /KyCo). Change in pH is fairly constant due to the formation of an effective buffer when large amounts of weak base and its salt are present. POH at % Equiv (pt M) (where [Bj=[BH")) = pK» © The region of rapid pH change is shorter and occurs at lower pH ranae than that for a SA-SB titration, At equivalence point E, + Nis is exactly neutralised by HCI ‘+ The resultant solution is NH«Ci(aq) + pH<7 as NH« hydrolyses in water to give H*. © After E, the acid is in excess. The titration curve flattens out at a low acidic pH value since the excess acid present is a strong acid, Calculation of pH at various parts of the titration curve: Initial pH = pH of weak base Solution is an aqueous solution of weak base. [OH] = YRC, = V1.74x 10% «0.100 = 1.319 x 10° mol dev? POH = -Ig [OH] = ~Ig (1.319 10-4) = 2.88 pH = 14-pOH = 11.12 PH at half-equivalence point (point M) Half-equivatence point isthe point at which half the volume of |HCifaq) neetied for neutralisation is added. Atthis point, NH is half-neutralised (Ns) = n(NH) PH et bell oe gost = pe Ny Hence, [NH] = [NH.~] tH at hell ext poh = pk of MH, OH = pk + ight «ps + 1g (1) = pk = 4.759 pH= 14~ pOH = 9.24 i) pH of mixture when 14.00 om? of HCI(aq) is added. (region @) Nib+ HY > NHe (NH) = n(H") added = 0.014 x0.10 = 0.0014 mol (NH) = (Hs) 0H") = (0.025)(0.10) ~ (0.014)(0.10) = 0.0011 mo! “The resultant mixture isa buffer containing NHs and Nie OH = pki Pho + g( poor, Ig (1.74 x10-) + 1g (1.272) = 4.759+0.1047 = 4.864 pH=14~pOH=9.14 (iv) pH al equivalence point (point E) lence point, the mixture present is a solution of, NHe + H2O <2 NHa + Hs0° n(NHe") = 0.025 x 0.10 = 0.0025 mol Volume of reaction mixture = 25.0 + 25.0. cm? .050 dm? 050 mol dmv? - fae 1742 68 * 0-050 361 x 10-* mol dm? INHe*] pH = -Ig (H"] = 5.27 (v) pH of mixture when 35.00 cm? of HCi(aq) is added. (region @) n(H*) added = 0.035 x 0.10 = 0.00350 mol, n(NHs) present initially = 0.025 x 0.10 = (Ht) in excess = 0.0035 - 0.0025 = 0.001 mol, {H pH = -Ig (H'] = 1.78 .0025 mol 001 Tins + 0088 01667 mol dav? -A4-4.5 Titration Curve of Weak Acid — Weak Base Reaction The graph below shows the change in pH of the reaction mixture when 0.100 mol dm-* of NHs was added-to 25.0 cm? of 0.100 mol dm-® CHsCOOH: © Since the acid is weak, the starting pH is a fairly Tigh value. Weak Acid ~ Weak Base © There is no straight, vertical section on the graph. This shows that the change in pH at the equivalence point is not as sharp as any of the previous titrations. + pate <7, if Ke of WA> Koof WB 3 + pH atE>7, if Ke of WA < Ko of WB aR? @ Soon after the equivalence point E has been 5 Passed, the titration curve flattens out at a 4 fairly low alkaline pH value since the excess 2 base present is a weak base. 6 Note: There is no suitable indicator for a weak acid— weak base titration as the region of rapid pH change is absent. © 5 10 15 20 25 30 95 40 45 50 Volume of ag ammonia/ em? 14.6. Titration curve of a carbonate-strong a Sodium carbonate is a diacidic base. — 12] coe COs*(aq)"+ He) = HGOs(aq) +OH-(@q) [Kor] 2 | HCOs (aq) + H0() = HCOs(aq) FOH(aq) | Kea 10 Heo pH * The figure on the right shows how the pH changes ‘ during the titration of 25.0 om? of 0.10 mol dm= Na2CO;(aq) with 0.10 mol dm~ HCi(aq). There are a ‘wo equivalence points in the titration curve. e °o 46 20 86 a5 60 GO + The reaction of NasCOs(aq) with HCi(aq) can be ‘olurio of 0:10 moter Wcwoq) acd represented in two stages: 5 indicator to indicate Stage coon completion of reaction (a) NagCOs(aq) + HCi(aq) —> NaHCOs(aq) + NaCi(aq) thymolphthalein (b) _ NaHCOs(aq) + HCi(aq) —> NaCi(aq) + CO2xg) + H20(1) methyl orange Overall NazCOs(aq) + 2HCi(aq) —> 2NaCi(aq) + CO.(g) + HzO(I) + If thymolphthalein is used as the indicator, it changes colour from blue to colourless when reaction (a) is completed, i.e. when NaxCOs is only half-neutralised to form NaHCOs, + If methyl orange is used as the indicator, it changes colour from yellow to orange when reaction (b) is completed, i.e. when NazCOs is completely neutralised to give CO2 and H.0. -45-+ From the stoichiometry of the two reactions, it can be seen that + if volume of HCI required for reaction (a) = x cm®, + then volume of HCI required for reaction (b) = x cm* and * volume of HCY required when using thymolphthalein as indicator = x cm? — | + volume of HC/ required when using methyl orange as indicator = 2x cm* * The double indicator method makes use of this two-stage titration to estimate the NasCOs in = a mixture of NagCOs and NaOH or * amixture of NagCOs and NaHCOs 14,7 Titration curve of a polyprotic acid-strong base titration * Phosphoric acid, HsPO,, is a triprotic acid. Dissociation | Equilibrium in aqueous solution | Kymoldm® | pk, First | HsPO«(aq) = H'(aq)+H:POr(aq) | 7.5x10° | 24 Second | H.POr(aq) = H'(aq)+HPO.*(aq) | 62x10% | 7.2 Third | HPOW*(aq) = H’(aq) + POL(aq) 42x10 | 124 ‘= The following three equations represent the step-wise reactions of HsPO, with NaOH, HaPO.(aq) + OH (aq) —> H2PO¥(aq) + HzO(1) HPO.-(aq) + OH(aq) —> HPO.*(aq) + H20(1) HPO.*(aq) + OH(aq) —> PO.*(aq) + H20(|) (ty (2) (3) + When a solution of phosphoric acid is titrated against sodium hydroxide, the titration curve shows three eauivalence points corresponding to the completion of each of the above reactions: pi Blenne eee en eee 30 o volume of NSOH (em) HW, 30, 50 um? (Lae 44s poh), THe phe. ;EEE Summary HA(aa) + Blaq) = Ar(aq) + Heteq) acid base2 base acid? | ny ‘Avis the conjugate baso ofthe acid HA. Hs the conjugate acie'of he base 6 For a conjugate acid-base pai, Kix Ky = k= 1.0 10" mo? dm? PK.+ pk = pk = 14 (at 296 K) K acidic solution: (H'] > [OH] alkaline solution: (H'] < [OH] HOM) = Haq) + OFF (aq); Ke = [HLH] = 1.0% 10-" mot dv? pK. ‘Arienlus theory | Bronstediowy theory [Lewis theony ThO™ youn on | Woe: Far spicy acii_| releases H'(aq) ‘a proton donor ‘an electron pair acceptor et hydroxonium ion | we wrte H(aq) bese | leases OH(20)_| —aproton acceptor —|—-anelectonpairdonor —] [eroxonumion "| wsteadet Gag Conjugate acibase pars meen a degree of ionisation pow=igiony WW. | or ogroe of eesociation ral solation: [1] = [OH] nic product of water aH>o pH + pOH= 14 (at 298 K) «can be expressed in faction or percentage ‘= ‘facon of molecuesonsed at equ For a weak acid, HA(aa) = H'(aq) + A-(aq) wy Tat Wa <4 such that (1-2) = 0, Ky ‘Strong acid + cornplete dissociation in aqueous solution + degree of dissociation, a = 4 + HX(aq) — (aq) + Xfaq) “+ Note: for monobasic acd, (T= [Ge and pH =—lo 0) ‘Sirong baso + complete ionisation in aqueous solution + degree of ionisation, « = 4 + NaOH(2q)—+ Nafaq) + O1-(aq) + Note: for monoacdic base (e 9, NaOH), [OH1 = [NaOH] and pOH=~Ig (0H Weak acid * partial dissociation in aqueous solution socal + HAlag) « HY(aq) + A-(aq) oe} thay + Kuis the acid dissociation constant of HA. + The larger the K, ofan acid, the greater is the strength ofthe acid kK units: mat dm Weak base + partial fonisation in aqueous solution scat + Beeg) + H.0() # BH"(aq) + OFFYaq) *] for ie + Kois the base dissociation constant of B + The larger the K ofa base, the greateris the strength of te base. we nits: mo de ’H Calculations When solutions are mixed, always consider whether a reaction has taken place. Then take note of what specie are present in the resutant solution at equilorium before calculating the pH of the eoltion + strong ac or stong base? + weak acid or weak base? hhycolysis of san? cide butter? alkaline butler? ‘misture of strong acid and ‘weak acid (ignore weak acid) {mixture of strong base and weak base (ignore weak base) [ Calculating pH of aweak aciat HA(aq) = H'(aq) + Ata) 1 = Ja pH=-lg( Calculating pH of salt of weak aca: (0g) + H:0() = HA(aq) + OH (aq) pare torre eee IA”) POH = -g(0H1] pit= 14=p0H Calculating pH of a woak bas: Bag) + H.O() = BH(aq) + OH (aq) (OHI = JR] pOH = ig [0H] pH = 14~poH Calculating pH of salt of weak base: BH"(aq) = H'(aq) + B(eq) [ Buffer solution + defintion and composition + actions of buffer upon adding H" OH" ions ‘Rela butter — ‘+ a midure of weak acid and its sat + E.g. midure of CHsCOOH and CH,COONs* = ke + 1p (ate PH = pe + 1a Sa) + maximum utr capac when 8 and hence pH = pK + effective buflor range: pH = pk 1 ‘Alkaline butter + 8misture of weak base and its sat + E.g. midure of NH, and NHCI ‘Salt hydralysis 1. salt ofa strong acid and a strong base eg. NaCllaq) ~ neutral salt ofa stiong acid and a weak base e.g. NH.Clfaq) ~ acidic NHe'(aa) + H0() = NHfaq) + Hs0"(aq) ‘alt of a weak acid and a strong base 1.9. CH:COO-Na'(aq)~ alkaline (CHCOO-(aq) + H20() «¢ CHSCOOHag) + OF (aq) 4. salt of weak acid and a weak base 9. CHCOO-NH(aq) ~ vory weakly actic 2 3 Note: lons that are conjugate acids of weak bases or conjugate bases of weak acids wil Under hydrotyis, POH = pkey + iy (Say + maximum buffer capacity when ‘and hence pOH = pk ibasey + effective buffer range: pOH = pk 1 ‘Acld-base indicator Note: A suitable indicator is one where its pH range coincides with the region of rapid pH change inthe tration curve (1. the pH range of the indicator must fll on the vertical portion of ‘Acid:-base Titvation Curves 1. strong acid — strong base titration 2. strong acid — weak base titration 3. weak acid strong base thration 4. weak acid — weak base titration the titration curve) -47-Ei Appendix (1) Calculation of pH after a small amount of H'/ OH" to an acidic/ alkaline buffer (Consider an aii bulerinally containing au? mol of HA and ac mol ofA Initial pH = pk + 1g l= pa + ig SAH (@) After adding a small amount of am Te mol (b) After adding of a small amt of OH, now. mol A (aq) + Haq) > HA(aQ) HA(aq) + OFF (aq) > Ar(aq) + H20() (Avis used up while HA is formed) (Ac is formed while HA is used up) a= M2 = ae a = MA No un roa? + a= in? ~ now pH = pKa + Ig 41 = pk + ig “1s pKa (way Hayy Pes ‘9G (aay = PK oe nna nact= mie ae aoa '9 aot mae [ead "Soa Non- Since nis® and na are large, pH of buffer is similar | Since nx® and na-° are large, pH of buffer is similar to its inital pH if niwis small to its initial pH if nox-is small (i) Consider an alkaline buffer initially containing ne® mol of B ae ‘mol of BH = pKa+ ig ttl = pry tg MEM = ong Initial POH = pk + Ig EE = pK + Ig “BHET = pk Ig (@ After adding a smal amount Of HF, re mal | (b) After adding of @ small amt of OFF, now mol B (aq) + H* (aq) > BH* (aq) BH* (aq) + OH” (aq) — B (aq) + H20 (i) (Bis used up while BH* is formed) « (B is formed while BH’ is used up) one = Nw? + Fa Pane = Ray? = Non e= ne? — rie ne ne? + now | OH = pk +g tl = pg LEE POH = p+ Ig Hl py + 1g MEHL | = pk + ig Baus? teae = py + bg tame Mone Since ne? and navw° are large, POH and hence pH | Since ne? and nsis® are large, pOH and hence pH of buffer is similar to its intial pH if nie is small of buffer is similar to its initial pH if nox-is small (2) Buffer solution made of a salt of weak acid and base ‘A buffer solution is able to resist changes in pH when a small amount of H’ or OH” is added to it. Hence it must contain species that are able to react with both H’ and OH". Besides the common acidic buffer (made of weak acid and its salt) and alkaline buffer (made of weak base and its salt), a solution containing salt of a weak acid and weak base can also function as a buffer as it contains species which react with both H* and OH” Consider a solution of ammonium ethanoate, CHSCOO-NH.": When a small amount of H" is added, CHsCOO-(aq) + H"(aq) > CHsCOOH(aq) H’ added is removed by CHsCOO™. Hence pH is maintained. When a small amount of OH" is added, NH4*(aq) + OH"(aq) > NH;(aq) + H2O() OF added is removed by NH,*. Hence pH is maintained. Large reservoir of CHsCOO- and NH«* helps the buffer cope with small amount of H’ and OH” added. ‘An aqueous solution of amino acid such as H:NCH:COOH is also able to act as a buffer as it is able to react with both H* and OH" as shown by the following equations: H:NCH2COOH(aq) + H'(aq) > *HsNCH2COOH(aq) H.NCH2COOH{(aq) + OH"(aq) > HzNCH:COO (aq) + H-0(1) -48-