chemical princdples revisited Edited by MunIe_ Bov0 BISHOP ‘Comson Ueloraty hen, 6 29831 Chemical Equilibrium IV. Weak Acids and Bases ‘Adon A. Gordus ‘The University of Michigan, Ann Arbor, Mi 48708 In this article in the series' on chemical equilibrium we ‘examine wook acide and bases and the various aasumptions ‘that are Implied by the simplified equations given iv most introductory texts. Ta article Il of this sories! we derived a completely general expression for a mixture of a weak triproticacid, HX, with ¢ tweak base, ROH. Te expression reduced to a cubic equa- tion in [F1'] for a single solution of 2 monoprotic acid, HA. “The purpose af this article is to discuss the conditions for which various approximations, valid to within 1% result in ‘even simplor equations, ‘We use a method of inequalities? similar to that wed in icle TIT" to define the pH ranges over which the water ‘equilibrium ean be neglected. Here, we define regions on a lot of C, (the concentration of the acid) versus K; (the acid iqnization constant) over which various assumptions are val id to within 16. "Tha previous aricies in this serles are: Gordss, A.A “I The ‘Thermoadyneric Equllorum Constant" «Cham Edie. 1891, 66, 438-140; "Deriving an Exaot Equllevium Equation’, J. Chem. Egue. 1981, 08, 295," A Fow Math Tice", J. Cherm. Zc. 1994, 68,291 Tha algebra can become tather complicated. A supplement to ‘he and the sith paper In this series is avalebe ier the author. hows the complete derivation for woek acid 22 well as forth fll Uiraton range. "The walorequllorum can be negiected wien he pHs less than £6.00 or groser than 8.00 98 was shown in article Il of the series (xe feosnete 1 “Fron a maximum anor of 19% she maximum H* that can be added so hat the pi remairs at 7.00 willegual 1% of 1.00 X 10-Yor 1.00 % SO". Srrlery, he maxrnum aaded OF that wal permit tre oH to bbe 7.00 wil also be 1.00 X 10-” MOF”. (There is anaemste way ot dething the maxireum arrr Ie tarms of he sit inthe wat equi ‘his ca the meximam added concertration of Hor OH Ie? aM 2The derivations of these equations are gven In: Gordus, A. A Schaum's Quine of Analtical Chemistry: MeGraw-Hil: New York, 1985: Onepto 5 To smelly tho notation, wo ute Ky, Ky, ad Key to eignty the quiltrum constants. he slut i Soa, thn these Kvalues are the thermogyramic equlibrum constanes. If the solalon Is nonideal, then these K values are he hermodynenic constants dvi by Ki Mihioh Ie the actviy-coaffician! “constant” as discussed in artce | (G00 foornate 1) This gat i sila, but nt dential fo that gv hy Burk, J. J. Chom. Ease. 1876, 53, 78-80 and by King, E. Chemisty, Panter Horkine: Sousatto, CA, 1979; p 661, except that ner graphs are Dbasad en amaxcnum arr inte calculated [H"] rather than i tho ‘asourptione. Algoorlealy, ite much easior fo dosh the conditions needed to doling the areas of the graph Hf the maximury oro Is Imposed on the assumotions. ‘Thereare only four porsible assumptions tha: can eppy to solution of a C, M solution of an acid HA. They are: 2. The water equilibrium con be neglected Phere is at roost 1% iomlnsion of HA: this is the weak acid approrimetion. The [H'] produced by dssosition of HA is Tess than 10~* M. ‘This reults in the appreximation’ thatthe pH = 7.00; it corr 1onds toa eolution thi iseithers very very dilute and/or that Fvelvegan acid that ie a0 very, very wenk thet the A from the tid is peligible compared with the It” fiom the water. 4. The acid HA 's more than $99 folzed, This is the strong acid approrinstion. ‘The equstions that result from the introduction of the various asstmptione# aro given in Teble 1, The regions" on a plot of ~log Ka = pK, versus ~Icg O, = pC, over which the various simplifying assumptions and the resulting equa- tions" are valid to within 1% aro shown in the figure. PCa 14 40 6 20 10 4 4 1 5 ° 104 Ke 108 7 1072] 1078! . 16 1 oe eee Ce Aoglone wor vrousermpPod equations given In Ta are als ora Volume 68 NumberS May 1991 387‘Tobe 1. Simpitied Equaltons for a G, M Ack with Ky Region Aesumeion| Equation envigrs Nore LHP + HY Gag + I~ Ry = 0 1 ab i= sex 2 : BP me] = oun 0 a oe (i= 9 4 ¢ WP = atte] y= 0 5 ° pel 8 e Wt] = Moco" 7 ‘The equation usually givon in introductory toxte for the hhydrogen-ion. concentration of a C, M weak acid with an ionization constant K, involves the implied assumptions a and b. Under these conditions, [H*] = (A-] and [HA] ~ Cy ‘This results in Ky = [H"][A [HA] = [F*]*/C, so that [A] CK, which spplies only in region 2 of the fleure, Fert nately, a number of C, = 9.100 M acids have K, values that fall in this region of the graph, and most texts limit their discussion of weak acid calculations to these acids. However, ‘acids can range from the very strong (HCI) to the very, very weak (HON, K, = G17 X 10-9. Thetr concentrations can also range from very high to very low values. The use of the figure allows one to dotermine, for any specified C, and K, values, which assumptions are valid and which equation arplies "The figure shows that there must be a smocth transition {rom strong to weak tovery weak acidity. Forinstance, begin in region 2 where assumptions a and b apply, and consider ‘whet happens as tho acid being considered is made stronger. This corresponds to larger Ky values and requires moving upward on the graph. Eventually region 3 is reached where the degree of ionization of the acid caa ne longer bo neglect: ed, At this point the degree of ionization is greater then 1%, and a quadratic equation is required to solve for the hydro- fon-ion concontration. For even stronger acids (a further Uipward movement on the graph) the point is reached at which the acid is more than $9% ionized and region 4 is tntered. This isthe strong-acid region and [Kt] = Cy. We stillare able toneglectthe water equilibrium. However it we now move to the left in rein 4, corresponding to lower concentrations of the strong acid, the strong-acid solution ‘eventually isso dilute and the [1] from the acid Is sosmall that we must begin including the water equilibrium: a cua- dratic equation for [H] is now required. As we cross into region 8, where the water equilibrium musi be included, we are ina pH range >6.00. Further dilution (movement tothe Jef€) eventually results in a solution that igs a pH = 7.00 which is region 7; the strong acid contribates « negligible amount to the pH: the water equilibrium predominates, "Agein startin rogion 2, and aak what happone.as tho acidia nace weaker. This involves moving downward on the graph. ‘Theslation becomes les acaicand when inrepion 6 the HH jin 3800. At thin atago, the water equilibrium ean no longor Denegleciel and [Ht] = (CuK, FR For even weaker acids (corresponding to a further downward movement) or for moro dilute solutions (corresponding to a leftward movo- rent) the acid contributes even less to the [FI+] end eventa- ally the pH = 7.00 (region 7) because the water equilibriam will predominate. Tshould also be noted that for eny two adjecent regions in the figure the more complicated equation (ie., less restric- tivoin tara of axourptions) wil alzo be valid in an adjacont region where the simpler equation isalso valid, For example, the equations for regions 6 and 3 are also valid in region 2 ‘Similarly, the equations for regions 9 and & are also valid in, region 4. The general cubic equation, used in region 1, & of| course valid throughout the full grab, 04 Journal of Chernical Education Tabla 2. Equations for Linas on Graph of Fgure for C,> 10-4 Fogle sper Equation fom 3 e210, Strom? tote, ton? Solutions of Although the figures beled in term of O, and K, for use with solutions of colds, an idontial graph reculte for sok Hons of aC, Maolutin of a base with y- And, asia set of exuations also applies. The only differences will bein the notation, where a is replaced by b in the subsexipte forthe equations in Tables 1 end >and inthelebelsof the igureand {H*] is replaced by [OH] in the equations, Tha equstion for region 2, For example, becomes: (OH-] expression tha is derived inmost texsfor use artheequiva- lence point inthe titration of an acid HA. Tn this cae, atthe equivalores point, there exiets « Cy M eolution of the eon base, A, which uncergoes hydrolysis: A+ Ha0 “> HA, + OH The equilibrium constant for this reaction of the conjugate base, A" i Ky, where K; = Key/K,- If we assure at Tess than 1% of A~ hydrolyzes and that the water equi- librium ean be neglected (which is usually what is assumed in mont texta and here ozreaponda to pH >6.00) then [HA] = [OH] and [A-] = Cy v0 tut Ky = PHAI[OH 1A] = [OH-}46,, This leads to [OH] = VOR. Equatione for Lines on Graph ‘As anexempleof the method of inequalities used to define the lines that ssparate regions in tho figure, we ean. exat region 2 where the applicable equation is [H'] = yC,K,. The first assumption is that the water equilibriam can be na- lected, ie, [H*] > 10-8. Therefore, \C,K, > 10° or, equar- Ing both side, CyX, > 10°. This isthe samne as pC, + Be < 12.0 and is the equation for the line separating regions 2 and 6. The lino that soparatos rogions 2 and 3 reaults from the requirement that the degree of dissoclation be <1% so that [H*] < 001 C,. Thus, {C.K < 10-%C, or, sauaring both sides, cancalling Cy, and takeing —loge: pK, > pC, + 40. ‘These two inequalities define the boundaries for region 2. ‘Thus, for the region 2 equation to be valid, the acid must have C.K, > 1074 and Ky < 10-IC,, For inetance, if O, = 0.1 ‘M, then X, must be between 10~*and 10". The conditions for the equivalent weak base, where the equation is [OH] 1GpKy are similar: CK, > 10-1? and Ki, <10-1G,, ‘The equations for the straight lines of the figure that apply toC, > 10™ Mare given in Table 2. These expressions an be used to determine if a particalar simplified equation {a valid for values of C, and X, end, thus, could be useful when creating homework or exam problems to ensure that the selected simplified equation can be used, For instance, if wwe want to consider anacid with K, = 2.6 x 10-4 (which can. {all in either rogion 2.or 6), the equation separating these tworegions ie CaK, 010385 M. If we choose & ‘value of C, lightly greater than 0,0366M, then the equation for region 7 will apply, but, if We choose a value of C, slightly lees than 0.0385 M, then the equation for region 6 will apply. "The curve in the figure that separates regions 4-9-2 from regions 5-1-6 corresponds to pH = 6.00 because the ware? Cauilibsiurs must be inckided im tho region to the left of regions 4-9-2, The equation® for the curve is: “, 04+ WK, a Similarly, the curve that eeparates 5-1-6 from region 7 ‘corresponds to DH = 7.00 because an acid at these low con- ‘centrations and/or with these very smnallK, values has neali gible effect on the pH to the left of regions 6-1-6. The equation’ for this curve is: ox, 10K, + 1077) o fH at Start and End of Titration of an Acid ‘The Henderson-Hasselbalch equation is often used in texis to calculate the pH in the buffer region of the titration of a weal acid with 4 strong base, ae will be discussed in article VI. Students sometimes ask if there is an equivalent. equation that oan be used at the start or at the end of the titration. The answer ia yeo. The start of the titration is simplya C, Msolution ofa weak acid, and the equation that, ‘most texistuse for ealealation of the hydrogen-ion concentza- tion ofa solution of a weak acid isthe expreseion for region 2 [HT = \CiK, which implies assumptions a and b, Teking the negative log of thia equation results in: =H oe, 0ky forthe pH at the start of the titration. "Tha equivalence point in the titration of a weal acid HA. sritha strong baroiea C, Msolution ofthe conjugate hase A~ witha Ky, = Ke/K,. As discussed above, if itis assumed thet there is less than 1% hydrolysis of A“, and, if the water equilibrium can be neglected, which is what most texts a sume, then [OH-] = yCoKs, Taking the negative log of this ‘equation rosults in: porte ac, + 959 a for the pOH at the equivalence point. Because pOH = pK. — pH and because DK, = PKw— PKs, eq4.can be converted to: pl = 3 (0K, + pK, —pCy 6) for the pH at the equivalence point. ‘As was done in the figure, aga 3-5 can be converted for use in the titration of a hase by substituting b for a, a for b, pH for pOH, and pOH for pH. Tfa.C, MH,X polyprotie weak acid i titrated with NaOH, cq 3 will apply" to the start of the titration with Kj, subst tuted for K,. For the same titration of H,X, eqs 4 and 5 will, apply to the last aquivalence point (which is a salutioa of CiM Ne,X) with Ky, substituted for Ky and Kny = Ke/Kuy substituted for Ky. * The equation te derived as follows: A Gy M solution of HA iontzes| to the extent of a meles/iter producing a roles/Iter of H" and the curt of A. Whan px = 6.000. we can neglec: the water ‘Seuilrium ao that [H¥] = 1.00% 10-PM = a= [A]. Thus, K, (i9-*y10"*)(c, — 10->. Raerrangerrort lade t 09 4 The equation cane Gerwvedina rarner srs to that dascaibod intootrots 8. inthis case, a= [A"] = 1.00 X 10? M, out, because the H fom the acid can bo naglacted, [H"] = 1.00 10°" Ms0that Ke= (10-"K10-94(0, ~ 10°, Rearrangement leads 1.69 2. "0 n adctlon to the essurptions of a than 19% reaction and neglect of the water equloriim, there 'S another assumption, 2. that G/X Is greater than about 10*Ter fe start ote tration nc that Kon ya greater than about 10* or the last equivalence poi. Pedagogical Symposium on Graph Theory in Chemistry | ‘A.spexil pedagogical symposium on graph theory in chemisiry will beheld August 27,1961, atthe 202nd National AGS Hecting in New York Clty. The symposium will have e unique tatorial format se fonck ‘may want to plan te ‘ltend the enlive days cesions, The mocping seston will be cnnddclod by ME Rancic aad N. Trinajstic and will cover the Graph Theoretieal Anpreach toStucture/Droperts/Aetivity Relationships. It will star: witha review offundsroent Fallowed by an hour in which participants are given four representative problems to solve, ‘The last hour willbe # Gioeusoion ef Ube celutions to those probleme. The nfcnoen session will cover the Graph Theoretical Apprcach to Conjugsted Motocalar Systems ind wil be conducted by J, Das end DJ, Klein, The format will parallel hemaming easton, Participants wil receive handouts st both sessions. Volume 68 Number§ May 1991 399