‘Reprinted from Journal of Chemical Education, Vol. 72, Pago 1099-1105, December 1995. Copyright ® 1995 by the Division of Chemical Education of the American Chemical Society, and reprinted by permission of ‘the copyright owner. Predominance-Zone Diagrams Solution Chemistry Dismutation Processes in Two-Component Systems (M-L) ‘A. Rojas-Hernénde2, M. T. Ramirez, and |. Gonizélez Universidad Auténoma Metropolitana-iztapalapa, Departmento de Quimice, Apartado Postal 55-534, 08340 México, DF. Mexico J.G. Ibanez Universidad Iberoamericana, Departmento Ingenieria y Ciencias Lomas de Santa Fe, 01210 México, D. F. Mexico The concept of disproportionation or dismutation has been frequently used to analyze the stability of intermedi- ate oxidation states of different elements; nevertheless, it has only been used sporadically (usually in a relatively nonsystematic fashion) in processes without electron ex- change. A recent paper in this Journal explains the con- struction of predominance-zone diagrams (P2D's) as an important aid for the comprehension of aqueous solution chemistry by using a general donor/acceptoriparticle treat ment (1), However, the dismutation concept is not dealt with in this reference. In this paper we show the application of the concept of dismutation in nonredox processes and its relationship to the corresponding chemical-species distribution diagrams and P2Ds. During the past few years, we have used this approach in analytical chemistry courses for students ma- Joring in chemical engineering, chemistry, pharmacy, and biochemistry with gratifying results at the Universidad Nacional Auténoma de México as well as at the Universi- dad Auténoma Metropolitana-Ietapalapa. Distribution Diagrams and the Predominance of Chemical Species ‘Systems of the Type Mly/.../MUMIL In aqueous solutions containing two components, Mand L, the chemical species, ML, ML, Ml, on MLy can be produced by the following formation equilibria, Quimicas, Prolongacién Reforma 880, with an associated equilibrium constant, en) t= aL ° 46 10,1,2).4§—Dh fe UL, Q nl ‘This notation includes successive and overall equilibria (2), Other formation equilibria that are useful in some cases are also included. ‘Taking logs on both sides of this equation and solving for pl Gefined as pL. = -log (L), one obtains the following Henderson-Hasselbalch type of equation. ohn AB) ed In Charlot's nomenclature (3), MLx is the polydonor spe- can he speom Mis he pgaceptor Ml, Mla Siar Ge ampboe’ andi he fart Ao ‘mon, well-known graphical representation for this type of Soloms ss te tetas Paco tho posi oe ine be pu Theale a shemtapecte tab Sndagam (48 Molar Fractions of the Species ‘The equations of the molar fractions of the species of M depend on the concentration of L as follows. i] __ A" DTD) Mg) + + OME, @ 1 Mi, +G-0L=Mj o Ti mor | Table 1. Overall Formation Equlibria and log Values of their Equilibrium Constants for the Systems Used ‘System Equilibrium og Bh Ret | ‘System Equilibrium jogB Ref Gann, GP TNH, = Gung 106 | Brl-NAy Zn? SNH = ZN) 20 6 Cu + 2NHy = CuNH 7.60 Zn 4 2NHy = Zn(NH)3* 2.30 Cur + 3NHy= CuNH,S" 10.50 Zn? 4 NH, = Zn(NHS)3" 2.60 Cu + ANH = CuNHS# 1250 22nt* 4 4NHy = Zn¢NHg 210 Proton-phosphates pos +H" = HPO 1234 6 | Mnjl-oxalates Mn? Ox = MnOx 2407, Por +2H* 10.54 Mn + 20x = Mn(Oxs - POS +H" = HPO, 21.68 MnP + 30x = MincOx 6.00 ‘Ag(i)-NHy ‘Ag’ + NH3 = Ag(NHa)” 3.30 6 | Fe(lt-(o-phen) Fe® + ophen = Fe(o-phen)* 5a4 7 ‘Ag’ +2NHy= AgiNH)3 720 Fe «20ghen = Felopheng 11.20 P+ Sopher elophen)g _ 21.90 Volume 72 Number 12 December 195 1099cant capa ewan” | cane cor ear ss ea pt, g £ eS p @ : pm, e) Figure 1. Chemical-speciescitribution diagrams fr some metal cat Jom systems as a function of pNH,, (2) CulI-NHs.(b) Znl}-NHs,(), ‘AQ()-NH. (fraction of M, 2 faction of ML, x fraction of ML, O {racton of Mg and a fraction of ML,. The PZ0's above each distr. bution eiagram are obtained by projecting the intersection points of the greatest fractions over the pNH, scale.) and ral ee ay DO. | MLE oI fe 1,2, .0n1 ‘These functions are monotonic with respect to {L} (or to pL) for the polyacceptor as well as for the polydonor be- cause the functions in their denominators are polynomials, containing only integer exponentials (positive for M, nega- tive for MLq). However, the functions for the ampholytes present a maximum because here each polynomial pre- sents integer exponents that are both positive and nega- tive when the expression is simplified with the numerator. 1100 Joumal of Chemical Education a + +e » ) “0, ™ 7 £ ry pee, fe Froure 2. Distibuton diagrams and PZD's for systems of the type MUgMLIML, (a) Limiting ease, where legKtES << log Kor og Katy <<0. (2) Case where log AE =logKi orton Hin 0. (6) Limiting case where og Kifct >> log Kit or log Kit >> 0. (Bt fraction of M, 2 ration of ML, and acon of ML) ‘When the fraction of ML, is larger than that of all the other species that contain M, then ML, is said to predomi- nate in the system. The chemical-species distribution dia- ‘grams shown throughout this paper can be easily con- structed by introducing eqs 4 and 5 in a spreadsheet (eg, Excel 4.0, Mierosoft) and using equilibrium constants re- ported in the literature (6, 7). Table 1 shows the values of, the equilibrium constants of the systems discussed in this paper.Table 2. Dismutation Equilibria of the Ampholytes, In the Systems Poe Poe aa Proton-Phosphates, Manganese()-Oxalates (Ox) ‘and lron(l)ortho-Phenanthroline (phen) with Corresponding Values ofthe log ofthe Equilibrium Constants Amphotee ‘Dismutaton Equiibum eg K HOF apo} = HPO; + POF 51 SHPOE = HPO, + 2PO -159 HiPOT —2H,PO=H:PO,+ HPO ao 3H,PO;=2H,P0, + PO -183 Minox 2htnOx = MnOxd + Me? os “12 Moox 19 “60 Fetophen® are(opnen)® “05 Fe(ophenj*=Felopheni’ «2Fe® 978 ‘2Fe(o-pheniz* = Felophen)s” aa ++ Fo(ophen? 90 Felopheniz” sFe(ophenié" = Fe(ophene"+ Fe® In Figure 1 some distribution diagrams of metallic cat- ions (Cu(II), Zn(ID, and Ag(1)) with ammonia are shown. In the case of copper, all of the species can predominate in a given pNHs interval. On the contrary, in the cases of silver ‘and zine the species monoamminesilver and diamminezine ‘cannot predominate anywhere even though they are pro- sent in the system; thus it eannot be said that they do not exist. ‘Although this type of system (where not all the existing species have a predominance zone in the pL scale) is not ‘considered in the paper mentioned above (1), PZD's can be ‘constructed for them. Suffice it to observe the pL interval for which the fraction of one species is larger than any ‘other in order to construct the PZD of M-containing species in the system. The Points of intersection ‘The points of intersection of the fractions of the species ‘ML; and ML; are given by the values of, Jor according othe Henderson-Hasselbalch ype of equation ‘The upper part of Figure 1 also shows how the. PZD’s of the Gul, ABCD, and Eat) systems can be obtained a2 preiseuions of the interestion points of tho Ingest frac tions on the pNHs scale. At these points, the molar frac- tions of the predominant species become equal. Vale et al. {Peal theoe punts ancoptance potentials they mark the predominance boundaries ofthe chemical species. AT though PZD's can be constructed this way, this method des a show why some ampholytes eannt predominate in the system. Diomutation Equilibria and Ampholyte Stability Ampholytes can react both as particle donors and ac- ceptors; this enables them to react with themselves under some circumstances. Charlot (3) has pointed out that it is, ‘useful to include the dismutation of ampholytes to simplify fA Pere te) Figure 8. Sample distribution and PZD's for systems of the type MUyMLIMLIWIL (a) proton-phosphates, (6) Mall-Ox, (c) Felt (ophen).(W fraction of M, 2 rection of ML, x traction of ML, and Cracton of ML) the analysis of polydonor/ampholyte(s)/polyacceptor/parti- cle systems. This is shown below. TworParticle Donors (ML2/MLIM/L) Here, there is only one ampholyte (ML) with one dismu- ‘tation equilibrium. 2ML = Mla + M © and with an associated equilibrium constant given by i, <0 a = IML ‘Two possibilities arse from this: Bither the ampholyte can predominate in the system (Fig. 2a), or it eannot pre- dominate (Figs. 2 and 2c). This information can be ob- tained from the value ofthe dismatation constant of the Volume 72 Number 12 December 1995 1101