a0 vPTERS 33, THE DEBYE-HOCKEL (OR ION-CLOUD) THEORY OF ION-ION INTERACTIONS 3.3.1. A Strategy for a Quantitative Understanding of lonon Interactions ‘The first task in thinking in detail about ion-ion interactions is to evolve & quantitative measure of these interactions." One approach is to follow a procedure similar to that used in the discussion of ion-solvent interactions (Section 2.4) Thus, fone ean weractions. donot exist (are “switched off”) and a final stale in which the interactions are in play (are “switched on"). "Then, the free-energy change in going from the initial state © the final slate can be considered the free energy AG;,,of ion-ion interactions (ig. 33). ‘The final state is obvious; it is ions in solution. ‘The initial state is not 50 straightforward; one cannot take ions in vacuum, because then there will be ion-solvent interactions when these ions enter the solvent. ‘The following approach is therefore adopted. One conceives of a hypothetical situation in which the ions are there in solution but are nevertheless not interacting. Now, if ion-ion interactions. are assumed to be electrostatic in origin, then the imaginary initial state of noninteracting ‘ons implies an assembly of discharged ions. "Thus, the process of going from an initial state of noninteracting ions to a final slate of ion-ion interactions is equivalent (o taking an assembly of discharged ions, charging them up, and setting the electrostatic charging work equal to the free energy AG, of ion-ion interactions (Fig, 34). One point about the above procedure should be borne in mind. Since, in the charging process, both the positively charged and negatively charged ionie species are charged up, one obtains & free-energy change that involves all the ionie species ider an initial stale in which ion-ion "ne queen fw one obtain an experi measur ion-ion traction discus in Seton a remeron | ME Aca] orenacons| Fig. 33. The free energy AG, ,cf fon-ion Interactions is the free-energy change in going from a hypothetical electrolytic eli- ion, in which fon-ion interactions do not operate, to a real solution, in which these intoractone do oporato,JONIONINTERACTIONS 201 \Geonancen tons Fig. 2.4, The free eneray AG, , of ion-ion interactions is the electrestatic work of taking an imaginary assembly of ‘discharged ions and charging ther upto obtain a solution ‘of charged ions, constituting the electrolyte. Generally, however, the desire to isolate the contribution to the free energy of ion-ion interactions arising from one ionic species only. "This partial free-energy change is by definition the chemical-potential change Au, »atising from the interactions of one ionie species with the ionic assembly. ‘To compute this chemical-potential change Aji-p rather than the free-energy change AG,-p one rust adopt an approach similar to that used in the Born theory of solvation, One thinks ofan ion of species i and imagines that this reference ion alone of all the ions in solution is in a state of zero charge (Hig. 3.5). Ione computes the work of charging up the reference ion (of radius 1) from a state of ver charge to its final charge of z¢, then the charging work Wtimes the Avogadio number N, is equal to the partial molar free energy of ion—ion interactions. i. to the chemical potential of ion-ion interactions: TawoLe oF eevenenet aie \ ioe casa ossqancen rere es Tow or rene ¢ ‘ounces Fig. 35, The chemical potential Ay asing trom the interactions of an ionic species i with the electrolytic solfion is equal o the Avagadko number nes the lec. trostatic work of taking an imaginary solution in which one relerence cn alone is discharged and charging this reer fence ion up tos roma charge232 CHAPTERS Mi. NAW BL) ‘Then as the work of charging an electrical conductor is proved to be W= 12 [(Chayye on the conductor) * (conductor's electrostatic potential] (3.2) ‘one obtains 3) an senna Mey a where y is the electrostatic potential of the ion due to the influence on it by the cloctrostatic interactions of the surrounding field, “The essence ofthe task therefore in computing the chemicel-potential change due to the interactions ofthe ionie species é with the ionic solution is the calculation of the lectrostatic potential produced st reference ion by the rest ofthe ions in solution, “Theory must aim at this quantity, Tone knew the time-averaged spatial distribution ofthe ions, then one could find ‘outhow all the other charges are distibuted as a function of distance fromthe reference ion. Atthat stage, one of the fundamental laws ofelectrostaties could be used, namely, the law of the superposition of potentials, according to which the potential ata point due to am assembly of charges is he sum ofthe potentials due « each of the crarges in the assembly. ‘Thus, the problem of calculating the chemical-potential change Buy due to the interactions between one ionic species and the assembly ofall the other ions has been reduced to the following problem: On a time average, how are the ions distributed around any specified ion? IT that distribution became known, it would then be easy to calculate the electrostatic potential ofthe specified ion die to the other ions and then, by Eq, G3), the energy ofthat interaction, ‘Thus, the task is to develop a model that describes the equilibrium spatial distribution ofions inside an electrolyte solution and then to describe that model mathematically. 3.3.2. A Prelude to the lonic-Cloud Theory A spectacular advance in the understanding of the distribution of charges around ‘an ion in solution was achieved in 1923 by Debye and Hiickel Its as signifieant the understanding of ionic solutions as the Maxwell theory of the distribution of ‘velocities isin the understanding of gases. Before going into the delails of their theoty, a moment's reflection on the ‘magnitude ofthe problem will promote appreciation of their achievement. Consider, forexample, a 10-3 M (mol dm) aqueous solution of sodium chloride. ‘There will be 10° 6.023 x 10% sodium ions per cubic centimeter of solution and the same number of chloride ions, together, of course, with the corresponding number of water moke- cles. Nature takes these 2 6.023 x 10" ions em’ and arranges them so that thereICOHION IVTERAGTIONS 298 is a particular time-averaged" spatial distribution of the ions. The number of particles involved is enormous, and the situation appears far oo complex for mathematical treatment, However, there exist conceptual techniques for tackling complex situations. One of them is model building. ‘This involves conceiving @ model that contains only the ‘essential features ofthe real situation, All the thinking ane mathematical analysis is «done on the (relatively simple) model and then the theoretical predictions are compared ‘with the experimental behavior of the real system, A good model simulates nature. If the model yields wrong answers, then one trcs again by changing the imagined model until one arives at a model, the theoretical predictions of which agree well with experimental observations. ‘The genius of Debye and Huckel lay in their formulation of a very simple but powerful moc! for the time-averaged distribution of ons in very dilute solutions of lectrolytes. From this distribution they were able to obtain the electrostatic potential contributed by the surrounding ions to the toll electrostatic potential atthe reference jon and hence the chemical-potential change arising from ion-ion interactions [Eg(3.3)}. Attention will now be focused on their approach, ‘The electrolytic solution consists ef solvated ions and water molecule. ‘The first step in the Debye-Hiickel approach is to select arbitrarily any one ion out of the assembly and call i a reference ion ot central ion. Only the reference ion is given the individuality of a discrete charge. What is done with the water molecules and the remaining ions? ‘The water molecules are looked upon as a continuous dielectric medium, ‘The remaining ions ofthe solution (ic. al ions except the central ion) lapse {nto anonymity, their charges being “smeared out” into & continuous spatial distibu- tion of charge (Fig. 36). Whenever the concentration of ions of one sign exceeds that ‘ofthe opposite sign, there will ari a net or excess charge in the particular region ‘under consideration. Obviously, the total charge in the atmosphere must be of opposite sign and exactly equal to the charge on the reference ion. “Thus, the electrolyte solution is considered to consist ofa central ion standing alone in a continuum, Thanks to the water molecules, this continuum acquires a dicleetric constant (taken to be the value for bulk water). The changes of the discrete ions that populate the environment of the central ion are thought of as smoothed out and contribute to the continuum dielectric a net charge density (exoess charge per unit volume). In this way, water enters the analysis inthe guise ofa dielectric constant #: ad the ions, except the specific one chosen as the central ion, inthe form ofan excess charge density @ (Fig. 377). gang camera (wath expose tine ‘fhe ons m an cletdy i ohm. Dae nnybets woul show the as stated decay i the uc containing the sclen, butte seratin falange enough ruber rasta ay, ~10!2) weld permit ne to rscgnize a entainsveageditton erated by average poston ofthe ens; this the dne-avrnged sei dtcunen ofthe oneOTHER 1085 sons wocares UE TO OTHER Tos o Settee Seren Fig. 3. A schematic comparison of (a) the assembly of onS and solvent molecules tral corsltule @ real etectto- Iylic solution and (b) the Debye-Hockel picture in which a reference lon is surrounded by net charge density @ due {o ihe surrounding fons ard dielectric continuurn of the ‘same dielectric constant « as the buk solvent PROMI A. ccecrabur te Fig. 37. The Debye-Huckel model is based upon selecting ‘one ion as a reference ion, replacing the solvent molecules by ‘2. continuous medium of dielectric constant e and the remaining ons by an excess charge density e, (the shading usually used in this book to represent the chargé density is rot indicated in this ture).ICRHION INTERACTIONS. 235, ‘Hence, the complicated problem ofthe time-averaged distribution of ions inside an electrolytic solution reduces, in the Debye- Hiickel model, to the mathematially simpler problem of finding out how the excess charge density @ varies with distance ‘from the central ion. ‘An objection may be raised at this point. The electrolytic solution as a whole is electroneutral ie. the net charge density @ is zero. Then why isnot @=Oeverywherc? So as not to anticipate the detailed discussion, an intuitive answer will first be given. Ifthe central ion is, forexample, positive, it will exert an attraction for negative ions; hence, there should bea greater aggregation of negative ions han of positive ions in the neighborhood of the central pesitive ion, ic, @# 0. An analogous situation, but with achange in sign, obtains nearacentral negative ion, At the same time, the thermal forces are knocking the ions about in all directions and trying (o establish electroneu- trality, ie, the diem motions try « sinovth everyting (0 @= 0. Thus, the time average of the electrosttic forees of ordering and the thermal forces of disordering is a local excess of negative charge near a positive ion andl an excess of positive charge near a negative ion, Of course, the excess positive charge near a negative ion compensates for the excess negative charge near a positive ion, and the overall effect is electroneutrality, ie, a @ of zero for the whole solution. 3.3.3. Charge Density near the Central ion Is Determined by Electrostatics: Poisson's Equation Consider an infinitesimally small volume element V situated al distance r from be arbitrarily seeted central ion, upon which attention is be fixed during the discussion (Fig. 38), and let the net charge density inside the volume element be @,. Fusther, let the average* electrostatic potential in the volume element be y,, The ‘question is: What is the relation between the excess density @, in the volume element and the time-averaged electrostatic potential y,? One relation between @, and w, is given by Poisson's equation (Appendix 3.0. ‘There is no reason to doubt that there is spherically symmetrical distribution of positive sand negative charge and therefore excess charge density around a given central ion, ince, Poisson's equation ean bo writ as 14 (pd Par \" ad here eis the diletrie constant ofthe medium and is taken to be that of bulk: vite an acceptable approximation for dilute solutions. GA) Actually, dere ae diserte chars in the nelgherbond ofthe cxnrl jon and therefore discontinucus ‘ariaions in de pesca. Bu boas in the Dbye-Hickel mode the dares are stocthed ut, the potential is avenged cut26 GMeTERS eutcrrosne roreema vou cuewenr dv re URGE Cena. i N\rerace on Fig, 38. At a distance rfrom the relerence ion, the excess charge density and electrostatic potential in ‘an infiritesimal volume element dV are e, andy, respectively 3.3.4, Excess Charge Density near the Central lon Is Given by a Classical Law for the Distribution of Point Charges in a ‘Coulombic Field ‘The excess charge density in the volume element dVis equal to the otal ion density (otal numberof ions per unit volume) times the charge on these ions, Let there be, per unit volurne, m, ions of type 1, each bearing charge 2y¢q m, of type 2 with charge req and n, of type i with charge Zé where gis the valence ofthe ion and ¢ isthe clectronic charge. Then, the excess chargedensity @, in the volumectement Vis given by = Meio macreot «+z @5) = Tze. 66) In order to proceed further, one must link up the unknown quan yey Myo toknown quantities, Thelinkis made on thehasis ofthe Roltz distribution law of classical statistical mechanics. ‘Thus, one writes an Where [/ can be described either as the change in potential energy of the i particles ‘when their concentration in the volume element dV'is ehanged from the bulk value to n, or as the work that must be done by a hypothetical external agency against the tine average of the cleetrcal and other forces between ions in producing the aboveconcentration change. Since the potential energy U relates tothe time average of the forces hetween ions rather than to the actual forces for # given distribution, it i also known as the potential of average,orce. Ifthere are no ion-ion interactional forecs, U=0; then, n=, which means that the local concentration would be equal to the bulk concentration. Ifthe ferees are attractive, then the potential-energy change U's negative (Le, negative work is done bby the hypothetical external agency) and n,>n?; there is a local accumulation of ions in exces oftheir bulk concentrations. 1 the forces are repulsive, the potential-energy change is pesitive fi dhe work done by the extemal agency is positive) and 1n,< ni there is local depletion of ions. In the first instance, and as a first approximation valid for very dilute solutions, ‘one may ignore all types of ion-ion interactions except those deriving from simple Coulombic" forves. Thus, short-range interactions (e.g. dispersion interuetions) are ‘excluded. ‘This is a fundamental assumption of the Debye-Hiickel theory. ‘Then the potential of average Force U’simply becomes the Coulombic potential energy ofan ion Of charge Zé in the volun: element dV, ie ke charge 2g te io es the ‘electrostatic potential y, in the youme element dV. That is, U=zeey, G8) “The Boltzmann distribution kaw (3.7) thus assures the forma ns re tors0D G9) ‘Now that, the concentration of the onic species inthe volume clement d¥, has ‘been related to its bulk concentration ®, the expression (3.6) for the excess charge density in the volume element AV becomes. = Teveeo= Trg age eor/en G.10) . 7 3.35. A Vital Step in the Debye-Hiickel Theory of the Charge Distribution around lons: Linearization of the Boltzmann Equation AL this point of the theory, Debye and Hiickel made a move that was not only _mathematically expedient but also turned out to be wise. They decided to carry out the “Inthis book, tbe term Cankombic is restricted to forces (with ## dependence on distance) Which are based diet en Canker a. Mee compli as whi vary as cr? yeeros al fore from the combination of several different Coulombic interactions. Nevertheless, such more complex salle py fd Conlon Kase nl Fe call no Condon228 CHAPTERS analysis only forsystems in which the average electrostaticpotential y, would bemuch smaller than the thermal energy 7. ‘Then: eu) Ws sey kT oe BME Based on this assumption, one can expand the exponential of Eg. @.10) in a Taylor series, ie, oy ete 0D, and neglect afl except the first two terms. Thus, in Bq. (3.10), ox) e=Bita[! : (.14) “The frsttorm Sab gives the charge on the cleetroytic slution as a whole. This is zero because the solution as a whole must be electrically neutral. The loc: charge densities nar ions cancel out becase the exces postive charge density near ‘negative fon is compensated fr by an excess native charge density near apositive jon. Hence, Yrizeo=0 G15) sand one is left with @.16) 3.3.6. The Linearized Poisson-Boltzmann Equation “The stage is now set forthe calculation of the potential y, and the charge density ¢; in tems of known parameters ofthe solution,YONON INTERACTIONS 799 Notice that one has ebtained two expressions for the charge density @, in. the volume element dV at a distanee r from the central ion. One has the Poisson equation Fg. (3.4)] efi d( a “al 2e(%] G17) and one also has the “linearized” Boltzmann distribution G.18) ‘where J; refers to the summation overall species of ions typified by i. Ione equates these two expressions, one ean obtain the linearized Poisson— Boltzmann (PB) expression 34 ? os } (a Ted G19) “The constant inthe right-hand parentheses can all be luraped together and called anew constant x”, ic, are Enlde @20) AL this point, the symbol ws used! only to reduve the tedium of writ out later, however, that wis not only a shorthand symbols it contains information concerning several fundamental aspects ofthe distribution of ions around aa ion in solution. In Chapter 6 it will be shown that it also contains information conceming the distribution of charges near a metal surface in contact with an ionic solution, In terms ‘off, the linearized P-B expression (3,19) is 1d (2.4, G21) Bale " 2.37. Solution of the Linearized P-B Equation ‘The rather messy-locking linearized P-B equation (3.21) ean be tidied up by a ‘mathematical trick. Introducing a new variable pr defined by240 cHuPTERS 32) cone has and therefore, 3.23) Hence, the Adu _jak G2) rape or eu. 25) ane ‘To solve this differential equation, itis recalled that the differentiation of sn ‘exponential function results in the multiplication of that function by the constant in the exponent, For example, der ayer @.26) Baim ) and ft eBamrJON-ION INTERACTIONS 241 Hence, if is an exponential function of r, one will obtain a differential equation of the form of Fg, 325). In other words, the “primitive” or “origin” of the differential equation must have had an expenential in xr. ‘Two possible exponential functions, however, would lead to the same final differential equation; one of them would have a positive exponent and the otber @ negative one [Fq. (3.26). The general solution of the Finearized P-B equation can therefore be written as Ae" + Be” 27 where A and B are constants to be evaluated. Or, from Bg. (3.22), 5 ae (328) rte 1 the boundary condition that far enough from ‘central ion situated at r= 0, the thermal frees completely dominate the Coulombic Torves, which decrease as A, and there is electroncutrality (ie., the electrostatic potential y, vanishes at distances sufficiently far from such an ion, y,—>O as 1r-+-), This condition would be satisfied only if 2 = 0. Thus, if B had a finite value, Fg, (328) shows that the electrostatic potential would shoot up to infinity (ic, y, > eas r+), a physically unreasenable proposition, Henec, 8.29) “Toevaluate the integration constant A, a hypothetical condition will be considered in which the solution is so dilute andl on the average the ions are so far apart that there is anegligible interionic field, Further, the central ion is assumed to be apoint charge, ice, to have aradius negligible compared with the distances otherwise tobe considered. Hence, the potential near the central ion is, inthis special case, simply that due to an isolated point charge of value x This is given directly from Coulomb's law as 0 30) er Y, At the same time, for this hypothetical solution in which the concentration tends to zero, ic. m?—> 0, it is seen from Eg. (3.20) that +0. Thus, in Eq. 3.29), 71, and one has A G31)Pore, [USTANCE FROM CENTRAL fon 46174 TRS Fig. 39. The vatation ofthe electro- sfatic potential y as a function ofdis- tance trem the cartral on expressed in unitsof rx. Hence, by combining Eqs. (3.30) and 331), Ani 32) € By introducing this expression for A into Eq, (3.29), the result is Boe" a3) er Here then is the appropriate solution of the linearized PD equation (3.21). It shows how the electrostatic potential varies with distance y from an arbitrarily chosen reference ion (Fig. 3.9). 3.3.8. The lonic Cloud around a Central lon In the imaginative DebyeHuckel model of « dilute electrolytic solution, « reference ion sitting atthe origin ofthe spherical coordinate system is surrounded by the smoothed-out charge ofthe other ions. Further, heeause ofthe local inequalities in the concentrations of the positive and negative ions, the smooihed-out change of one sign does not (locally) cancel out the smoothed-out charge of the opposite sign; there isa local excess charge density of one sign opposite to that ofthe entra ion Now, as explained in Section 33.2 the principal objective ofthe Debye-Huckel ‘theory is tocalculate the time-averaged spatial distribution ofthe excess charge density around a reterenee ion, How is this objective attained? ‘The Poisson equation (24) relates the potential at from the sample ion to the charge density at rte.lotion nerenacnions 248 G4) 1d(pdv, sa(r | Purther, one has the linearized P-B equation 21) From these two equations, one has the linear relation between excess charge density and potential, ic, e2 (334) and by inserting the solution (3.33) for the linearized P-B equation, the result is 2 2% G38) Oa ST Here then isthe desired expression forthe spatial distribution ofthe charge density ‘with distance rfrom the central ion (Fig. 3.10). Since the exoess charge density results from an unequal distribution of positive and negative ions, Fg. (3.35) also describes the distribution ofions around! a reference or sample ion, “Tounderstand this distribution of ions, however, one must be sufficiently attuned {to mathematical language to read the physical significance of Fg (3.35). The physical ‘deas implicit in the distribution will therefore be stated in pictorial terms. One ean say that the central reference ion is surrounded by acloud, or atmosphere, oFexcess charge (Fig. 3.11). This ionic cloud extends into the sofution (ic, r increases), and the excess Fig. 3.10. The vatiation of the excess charge density @ as afunction of dstance from the central ion.244 CHAPTERS Fig. 3.11. The dstibution of excess charge density arcund a creiral ion, ‘can be pictured as a coud, or atmos- Phere, of net charge around the c2n- ‘ralion charge density @ decays with distance r in an exponential way. The excess change residing on the ion cloud is opposite in sign to that ofthe central ion. Thus, a positively charged reference ion has a negatively charged ion atmosphere, and vice versa (Fig. 3.12), Up to now, the change density at a given distanee has heen discussed. ‘The total excess change contained in the ionic atmosphere that surrounds the central ion ean, however, easily he computed, Consider a spherical shell of thickness dr ata distance r from the origin, ie, from the center of the reference ion (Fig. 3.13), The ebarge dg in this thin shell is equal to the charge density e imes the volume 4nd ofthe shell, ie, dy = e,tnedr 036, The total charge d4qy Contained in the ion atmosphere is obtained by suming the charges dg contained in all the infinitesimally thick spherical shells. In other words, the total excess charge surrounding the reference ion is computed by integrating dg (which is « function of the distance r from the central ion) from » lower limit corresponding to the distance from the central ion at which the cloud is taken t0 ‘commence to the point where the cloud ends, Now, the ion atmosphere begins a the surface of te ion, s0 the lower limit depends upon the model ofthe ion ‘The first meet Fig. 3.12. A posiively charged ion has a nega- tively charged ionic cloud, and vice versa,JONON INTERACTIONS. 245 CHARGE SHELLY de Silane Fig. 3.13, A spherical shell of thickness drat a distance rfrom the center of the reference ion, chosen by Debye and Hlckel was that of pointelirge ions, in wh limit is r= 0."The upper limit for the integration is r» 9 because the cherge of the joni cloud decays exponentially into the solution and becomes zero only in the limit roe, ‘Thus, oe (337) tou Jda=Jeamtir ‘and by substituting for @, from Fa. @.35), the result is dow | 812 one ar a - (3.38) 269 J er) ar) 0 “The integration can be done by parts (Appendix 32), leading tothe result Facus=260 (39) ‘which means that central ion of charge +2¢p is enveloped by a cloud containing a total charge of ~2¢9 (Fig. 3.14). Thus, the total charge on the surrounding volume is {just equal and opposite to that on the reference ion, This is of course precisely how ‘hings should be so that there ean be eleetroneutrality forthe Zone solution taken as & whole; «given ion, together with its cloud, has a zee net charge246 CHAPTERS SECON ( see onanoe 2 Fig. 2.14. The total charge ~2@g0n the ionic loud [sjust equal and opposite to the charge +2/¢, onthe ccentral ion. How is this equal and oppesite charge of the jon atmosphere distributed in the space around the central ion’ tis seen from Eqs. (3.38) and (36) thatthe net charge in a spherical shell of thickness dr and at « distance r from the origin is| dg =-cege "Crd 3.40) ‘Thus, the excess charge on a spherical shell varies for a Value ofr piven by rand hes « maximum value on a = Seen deem ee er gee" — re) G41) Since (zegX’) is finite, Eq. (341) can be true only when O= 6 re 8.42)ONION INTERACTIONS 247 we ae a ai am mes our Fig. 3.18. The dctance variation (n+ uit) of the charge dg enclosed ina dthick spherical shel showing that dis a meximum at r= x". Hence, the maximum value of the charge cont a spherical shell (of infinitesimal thickness dr) is atained when the spherical shel is at adistance from the reference ion (Fig. 3.15). For this reason (but see also Section 3.3.9), Tis Known as the thickness, or radius, of the ionic eload that surrounds a reference fon. ‘An clementary dimensional analysis [eg., of Eg. (843)] will indeod reveal that xt has the dimensions of length. Consequently, x7 is sometimes referred to as the Debye-Hiiekel length. may be recalled that xs given [ftom Bg. (3.20)) by -1_(ekT_1 \" Lil ree (3.43) Cd ; Asthe concentration tends toward zero, the cloud tends to spread out increasingly (Fig. 3.16). Values ofthe thickness of the ion atmosphcte for various concentrations ofthe electrolyte are presented in Table 3.2. 3.3.9. Contribution of the lonic Cloud to the Electrostatic Potential w,, ata Distance r from the Central lon ‘An improved feel for the effects of ionic clouds emerges from considering the following inferesting problem. Imagine, in a thought experiment, that the charge on the ionic cloud does not exist. There is only one charge now, that on the central ion, Whatis the potential atdistance rfrom the central on? Itis simply given by the familiar formula for the potential ata distance rfrom a single charge, namely,ame GWPTERS 320 200) 240 _, to) 4 (inky 120) +0 ooo oi oe Fig. 3.16. The varaton inthe thicmess 1 ofthe ionic oud as a function of electrolyte concentration (1A =0.1 mm. 20 (3.44) ae ‘Then ket the charge on the clonsd he switched on, ‘The potential y, atthe distance 1rfrom the central ion is no Tenger given by the central ion only. Itis given by the law of superposition of petentials (Fig. 3.17) ie. y, isthe sum ofthe potential due to the ‘central ion and that due to the ienie eleud (3.45) TABLES2 ‘Thickness of lonic Atmosphere (nm) at Various Concentrations and for Various Types of Salts: Concerartion Type of Salt oe (mold) a a a a 304 16 52 128 ae 555 ant 393 308 176 82 124 96 033 oas 039ION-ON BVTERACTIONS 240 Fig, 3.17. The superposition ofthe potential yr due to the on and the potertial Vagus due to the cloud yields the total potential ata distance r from the central ion. ‘Thecontribution Varga €20 thus be easily found, One rearranges Fy, (345) toread Yess = Yr ~ Yon 6.46) and substitute for Ypg With Eq. (3.44) Leg. (6.33) Then, ul for y, with the Debye-Hckel expres Ls! sey Vet = oor er 2a ne Gan mae D ‘The value of «| ef. Eg.(3.20)]is proportional to Enfzje9, Insufliciently dilute solutions, Znbcie4 can be taken as sufficiently small to make xr << 1, eM Lal xr 3.48) and based! on this approximation, G49) By introducing the expressions (3.44) and (3.49) into the expression (345) forthe total potential y, al a distanee r from the central ion, it follows that @.50)280 CHAPTERS “The second! term, which aries from the cloud, reduces the value ofthe potential to value less than that ifthere were no cloud, ‘This is consistent with the model; the cloud has « charge opposite to that cn the central ion and must therefore alter the n a sense opposite to that due to the central fon. The expression 20 G49) Ye leads to another, and helpful, way of looking atthe quantity 1°" It is seen that Yea is independent o'r, and therefore the contribution ofthe eloud tothe potential ar the site ofthe point-charge central ion ean be considered to be given by Eg. 3.49). But, ifthe eutive chaage of the fouie stucsphere [whicl is ~zey as xoyulsed by elecuoneu- trality—Eq. (3.39)] were placed al adistance “from the central ion, then the potential predhiced at ihereference ion would bo ~2¢9/(EX"). It is seen therefore from Eq. 349) thatthe effect ofthe ion cloud, namely, Wigaye #8 equivalent to that of single charge, equal in magnitude but epposite in sigh to that ofthe central ica, placed at a distance 2" from the reference ion (Fig. 3.18). Thisis an alded and more important reason that the quantity x is termed the effective thickness or radius of the ion atmosphere surrounding acentral ion (see Section 3.38) 3.3.10. The ionic Cloud and the Chemical-Potential Change Arising from lon-on Interactions It will be recalled (see Section 3.3.1) that it was the potential atthe surface of the reference ion which needed to be known in omer to calculate the cbemical-potential change dy, , arising from the Interactions between a particular fonie spedes fan the rest of the ions of the solution, i, one needed LOKHOW Yigg it Eq 33), Fig. 3.18, The contribution veg Of the ionic loud to the potential at the central ion is ‘equivalent to the potential due to a single ‘charge, equal in magnitude and opposite sign to that ofthe central ion, placed ata distance "from the central ionJON-ON INTERACTIONS 251 @3) Tt was to obtain this potential y that Debye ancl Hiickel conceived their miedel of an ionic solution. ‘The analysis presented the picture of an ion being enveloped in an ionic cloud. Whats the origin ofthe ionic cloud? Itis bor of the interactions between the central ion and the ions of the environment, If there were no interactions (e.. Coulombic forees between ions), thermal forces would prevail, distribute the ions randomly (@=0), and wash out the ionic atmosphere. It appears therefore that the imple ionic eloud picture has uot only led to success in describing the distribution of jons but also given the electrostatic potential Yjayy athe surface of & reference fon due tothe interactions between this reference ict and the rest te ions inthe solution (the quantity required for reasons explained in Section 3.3.1). ‘Thus, the expression (3.49) for Wagga be substituted for yin Ey. (3.3) with, the result that est The Debye Htickel ionie-cloud model for the distribution ofions in an electro Iytie solution has permed the theoretical ealculation of the chemical-potential change arising from ion-ion interactions. How is this theoretical expression to bo checked, ie, connected with & messured quantity? It is to this testing of the Debye-Hiickel theory that attention will now be turned, 34. ACTIVITY COEFFICIENTS AND ION-ION INTERACTIONS 3.4.1. Evolution of the Concept of an Activity Coefficient "The existence of ions in solution, of internetions chemical-potentil change Ay, ising from ion—ion interact to be self-evident inthe treatment hitherto presented here. This, however, is & moder point of view. The thinking about electrolytic solutions actually developed along & lifferent path, Tonic solutions were a frst treated in the same way as nonelectrolytic solutions, though the latter do net eontain (interacting) charged species, ‘The starting point was the classical thermiedynamic formula forthe chetnical potential 4, ofa nonelectrolyte sole ween these ions, and of 1214 RTIn x, 57In this expression, x; is the concentration? of the solute in mole fraction units, and 2 is its chemical potential in the slandued state, ie, when x, assumes standard ot normalized value of unity HEH when ¥, 53) Since the solute particles in a solution of @ nonelectrolyte are uncharged they do not engage in long-range Coulombic interactions. The short-range interactions arising from dipole-dipole of dispersion forces become significant only when the mean we between the solute particles is small, i, When the concentration ofthe solute h. Thus, one ean to a good approximation say that there are no interactions ‘between solute particles in dilute nonelectrolyte solutions. Hence, if Eq. (352) forthe ctiemical potenti! of a solute in a nonelectrolyte selution (with nonimeracting parti- les) is used for the chemical potential of an ionie species ‘in an electrolytic solution, then it s tantamount to ignoring the long-range Coulombic interéctions between ions. In an actual electrolytic solution, however, ion-ion interactions operate whether one jgnores them ornct.Itis obvious therefore that measurements ofthe chemical potential 14, fn ionie species—or, rather, measurements of any property that depends on the chetnieal potential —would reveal the error in Eg, (3.52), which is blind to ion-ion interactions. In other words, experiments show that even in dilute solutions, aya #RTINS, In this content, a frankly empirical appreach was aopted by earlier workers not yet blessed by Debye and Hiickel's light. Solutions that obeyed Kg. (3.52) were characterized as idea! solutions since this equation applies tosystems ofnoninterseting solute particles, i, ideal particles. Electrolyte solutions that do not obey the equation wert said to be nonideal. In order to use an equation of the form of Eq. (352) to treat nonideal electrolytic solutions, an empirical correction factor f was introduced by Lewis as ¢ modifier ofthe concentration ter’ MH =RT In Xf, 3.54) The value of inthe case of an elevlye derives fom he numberof moles of ons especie actually ‘seo in scltion, This mumber mea no b equa tothe nunber of es of expecta of distro tet; if for insta, the eetote a pct om en only traction the electrolyte may react with th solvent o farm ions, i, he eletoyte way te incompletely issoviatd, The standardcerieal poeta hos the same sgnicnc here sin F.C.) frida soltons. Tus, ‘ca be defined eer the chemical ptemal fan kal solution ni tes te y= 1 OF {he emial potential ofa soltion im its state = Land f= "No el slation can have i= Vwhen 1, 50 the tana state pein tothe same hypotesial selon asthe standard tae of ‘neat ottionJON-ON INTERACTIONS 259 1 was argued! tha, in nonideal solutions, it was not just the aualytical concentration 4, of spocies f, hut its effective concentration xf, which determined the chemi tential change gy — 4°, This effective concentration x, was also known ws the activity 4a, of the species i ie, =f G55) ‘and the correction factor fy as the activity coefficient. For ideal solutions, the activity coefficient is unity, and the activity a, becomes identical to the concentration ai, =x, when fy G56) “Thus, the chemical-ptestial change in ing from the stand tte to the final state can be written as by-WP = RTI 3+ RT Inf, esp Equation @.57) summarizes the empirical or formal treatment of the behavior of electrolytic solutions. Such a treatment catnnot furnish a theoretical expression for the activity coefficient f, Il merely recognizes that expressions such as (3.52) must be ‘modified ifsignificant interaction forces exist between solute particles. 3.42. The Physical Significance of Activity Coefficients For ahypothetical system of ideal (1 tial has been stated to be given by iterating) particles, the chemical poten (ideal) = 9 + RT In x, 52) or areal system of interacting puaticles, the chemical potential has been expressed in de form 4 (teal) = p+ RT In, + RT Inf, esp Hence, to analy2e the physical significance of the ativity coefficient term in Eq. 57), itis necessary to compare this equation with Eg. (2.52). Its obvious that when Fy. G 52) is sublracted from Fg, (357), the difference fie, a, (rel) ~ 4, (ideal) is he chemical-potential change 44, arising [rom interactions between the solute particles (ions in the case of electrolyte solutions). That i, s{veal) ~ 1, (deal) = 4,4 6.58) and therefor,24 CHPTERS Ay, ,=RTInf, G59) "Thus, the activity coefficient is « measure of the chemical-potential change arising from ion-ion interactions. ‘There are several well-established methods of experimen tally determining activity coefficients, and these methods are treated in adequate detail in standard treatises (sev Further Reaing at the end of this sectien). Now, according to the Debye-Hickel theory, the chemical-potential change ‘yt, atising from ion-ion interactions has been shown to be given by Nalse? @s1 Dax" ae Hence, by combining Fs. (3.51) and (3.58), the result is LAC 00) a RT Inf, Thus, the DebyeHicke! ionic-cloud mode for ion-ion intraetions bias permite d a theoretical calculation of activity coefficients resulting in Eq. 3.60). “The activity coefficient in Eq, (3.59) arises from the formula (3.57) for the chemical potential, in which the concentration of the specie iis expressed in mole fraction nits x Ove ean also express the concentration in moles per Titer (I liter = 1 dm’) of solution (molarity) or in moles per kilogram of solvent (molality). ‘Thus, alternative formulas for the chemical potential of a species i in an ideal solution read Hime) +RT Ing and 1H, = 18m) + RT In m, 62) ‘where ¢, und m, are the molarity and molality of the species i, respectively, and 4i%(e) and yf(m) are the corresponding standard chemical potentials, When the concentration of the ionie species in areal solution is expressed as @ molarity ¢, ora molality m, there are correspending activity coefficients 7, snd y, end corresponding expressions For py m= nXo4RTIng + RT In, 66) U9) + RT In m, + RT In y,, G.64)HONON INTERACTIONS 255 3.4.3. The Activity Coefficient of a Single lonic Species Cannot Be Measured Before the activity ecefficients calculated on the basis of the Debye-Hiickel mexdel can be compared with experiment, there arises a problem similar to one faced in the discussion of ion-solvent interactions (Chapter 2). There, it was realized the heat of hydration of an individual ionic species could not be measured because such ‘4 measurement would involve the transfer of fons of only one species into a solvent instead! ofions oftwo species with equal and eppesite charges. Even ifsuch a transfer were physically possible, it wenld result in acharged solution? and therefere an extra, undesired interaction between the ins and the electrified solution. The only way out was to transfer @ neutral electrolyte (an equal number of positive and negative ions) into de selyent, but this meant that one could only measure the beat of interactions of «salt With the solvent and this experimental quantity could not be separated into the individual ionic heats of hydration. Her, in the case of ion-ion interactions, the desired quantity is the activity coefficient, which depends through Eq. 3.57)an ~ n°. This means that one secks te free-energy change of an ionic solution per mole of ions of a single species i. 'To ‘measure this quantity, one would have @ problem similar to that experienced with jon-solvent interactions, namely, the measurement of the change in free energy of a solution resulting from a change in the couveutration of ene icnie species only. ‘This change in free energy associated! with the addition efcne ionie species only ‘would include an undesired work term representing the electrical work of interaction between the ionie species being aided and the charped solution. To avoid free-energy chauges associated with interacting with a solution, it is necessary that after a change in the ccncentratien of the fenie species, the electrolytic sotution should end up uncharged and electroneutral. ‘This aim is easily accomplished by adding an elec- troncutrl electrolyte containing the ienie species i ‘Thus, the concentration of sodium ions can by altered by aiding sextiunt chloride, The solvent, water, naintains its eectroneutrlity when the uncharged ionie lattice (containing two ionic species of opposite charge) is dissolved in it, ‘When ionic latices, ic, salts, are dissolved instead of individual ionic species, ‘one climinates the problem ofending up with charged solutions but another problem ‘emerges. If ene increases the cencentraticn of sodium ions by adding the salt seaium chloride, one has perforce to produce « simultaneous inerease in the concentration of chloride ions. This means, however, that there are two contributions o the change in “ie stition may not be nts charged but wil eeome eo once an one pies i ded 10 re ene Ue sol Fre stint cece en eer expressed in ie std ‘nels should be ned. Wien he concentration is expres a moe action f has been used here. For dilute solutions, he numerical values of cetivity cowie for Use different systems cf units ae moat the sare286 CHAPTERS: fice energy associated with a change in salt concentration: (1) the contribution of the ons. and (2) the contribution of the negative ions. Since neither the positive nor the negative tons can be added separately, the individual contributions of the ionic species 10 the fiee energy of the system are difficult w determine. Noumally, one can only measure the activity coefficient of he net electrolyte, ic. of at least two ionic species together, It is. necessary therefore to establish a conceptual link between the activity coefficient ofan clectrofyte in solution (that quantity directly accessihe to experiment) and thatof only one of is ionic species [not accessible to experiment, but calculable theoretically from Eq. 3.60)). 3.4.4. The Mean lonic Activity Coefficient Consider a uni-univaent electrolyte MA (eg., NaC). The chemical poten the M* ions is [F, 59] ng = He + RT nag + RTI fg 8.65) and the chemical potential of the A~ ions is Mig =u + RT In xy + RTI fy, 3.66) Adding the two expressions, one obtains Byatt 1g = Rye + WD) + RT In (Hype) ERT Ine h) G67 ‘What has been obtained here is the change in the free energy ofthe system due to the addition of 2 moles of ions—1 mole of M” ions and 1 mole of A” tons—which are containes! in | mole of electroneutral salt MA. Now, suppose that one is only interested in the average contribution to the free energy ofthe system from 1 moleof both M* and A~ions. One has to divide Eq. (367) by2 ° ~ ey - (3.68) era HEI area) + RT neh)!” oe Athi stage, on ean define several new quantities bye tig 69) 2 sea 67 pani= (age)? em) and a= Guta? G72) ‘What is the significance of these quantities 1.9. 1. and f,? Itis obvious they are all, average quaniies—the mean chemical potential ji, the mean standard chemical Potential 4, the mean ionie mole tration xj and the mean fone-nctiity eoetFiciet fe Tn the case of xyane 22, the arithmetic mean (halfthe sum) is taken because free ‘energies are additive, but in the case of x, and J the geometric mean (the square root of the product) i taken because the effects of mole fraction and activity coefficient on frve energy are multiplicative. In this notation, Eg. G.68) for the average contribution ofa mole of ions to the free energy of the system becomes 21+ RTInx, + RTI f, 73) Sinceamole offens is preuced by thedisslten of hala mele oft. In ether words, ‘is half the chemical potential pyq of the salt? Mlygn= Me =HS+ RTIN x, +RT Inf 74) “Thus, a clear connection has been set up between observed free-energy changes ‘yaa consequent upon the change from state in which the two ionie species of a salt concentration and ts mean ie-ctivity eceflicient f,. Hence the value of fis experimentally measurable, What ‘can be obiained from fis the product of the individual ionie-ctvity coefficients [Eg G72). The theoretical approsch must be o calculate the activity coefficients f, and for the positive and negative ions [Fq. (3.60)] and combine them through Eq, (@.72) into a mean jonic-cetivity ecefficient f which can be compared with the easily experimentally derived mean ionie-actvity coefficient, 3.4.5. Conversion of Theoretical Activity-Coefficient Expressions into a Testable Form Individual ionic-activity coefficients are expetimentally inaccessible (Section 3.4.3); hence, it is necessary to relate the theoretical individual activity coefficient f, “Te gual shld notte ken tora molecules MA cxistin escton: yy ecb fescencrgy dang ef he sytem relng from the dselton ef ale cect.28 CHAPTERS Eg, (3.60) to the experimentally accessible mean ionic-activity coefficient f, so that the Debye-Hlickel model can be tested, “The procedure is to make use ofthe relation (3.72) f= Guy? 72) ‘of which the general form for an electrolyte that dissolves to give v, zevalent positive ions and ¥_z -valent negative ions can be shown to be (Appendix 3.3) fea CG" 75) where f, and f_ are the activity coefficients of the positive amd negative ions, and. vey ty, 6.76) By taking logarithms of both sides of Eg, (3:75), the result is Ing= be, ing, +vmp) em Atthis stage, the Debye-Hiickel expressions (2.60) for f, and f_canbeintroduced into Eq. (8.77) to give ingz-t [ noon] 78) Since the solution as a whole is electroneutral, v,z, must be equell to v2. and therefore vgeudevertyzr BEY, AV) ev G79) Using this relation in Fg. (2.78), one obtains MeeX G0) he err Now, one ean substitute For» from Bg. (343)IONON INTERACTIONS 250 ee att (Ee) os) but before this substitution is made, Kean be expressed in a different form. Since: oN, @81 7000 where cis the concentration in mice per Tite, it follows that Stade MEY of 8 Prior to the Debye—Hiickel theory, 124,27 had been empirically introduced by Lewis ass quantity of importance in the treatment of ionie solutions. Since it quantifies the charge in an electrolytic solution, it was known a8 the ionic strength and given the symbol 1 miDed os In terms ofthe ionie strength 4, «an be waitten as [Fgs. (3.43), 3.82) and .83)) eal 88)" 10008KT | (3.84) oss wa Be (3.85) where Bae 5 (aed 8.86) Values of B for water at various temperatures are given in Table 33. ‘On the basis ofthe expression (285) for, Fa. 2.80) becomes oS gyn Gan200 CHAPTERS TABLES Values of the Parameter B for Water at Various Temperatures “Temperature °O) on ° ose 10 0.3264 20 ome 25 03291 30 03001 3 oar » o3ms 30 o3m6 o3m 0 oa26 100 03488 1 Me Mn les he=—a3g5 Bp! 2.88) For greater compaciness, one can define a constant A given by 3%) and write Fg. (3.88) in the form logh, =-A@z 1? 3.90) For I:l-valent electrolytes, z,=2.= 1 and J =c, and therefore log, =—Acl® G91) Values of the constant A for water at various temperatures are given InFgs. (3.90) aud G91), the theoretical mean ionic-activity coefficients are in a form directly comparable with experiment. How are such experiments earied out? 3.46. Experimental Determination of Activity Coefficients A reasonably informative account has now been given as to how—alheit in very low concentrations —theoretical developments concerning interionic interaction give tise to theoretical values of the quantity (activity coetficient) hy which the realYON-ION INTERACTIONS 261 TABLES. Jues of Constant A for Water at Various Temperatures “Temperature (°C) A 0 ‘04918 10 04989 20 0.3070 25 Osis 50 05161 0 05262 50 03373 6 05498 80 05767 100 0.6086 (©bserved) behavior of electrolytes in solution can be linked to the behavior expected if there were zero electrostatic interactions between ions in solution, During this presentation, the experimental mean activity coefficients showing up in the deductions have been taken for granted—nothing has been said about how they have been oblained, Obviously, one must be sure when dealing with theory that the experimental values with which the theory is compared are soundly based. ‘is time then that some account be given about the means by which experimental 1s are known. Only two methods will be presented because the material contains no new ideas and is only presented so the reader is assured that the ground is fim, values of activity coeffi 3.4.7. How to Obtain Solute Activities from Data on Solvent Activities ‘A characteristic of an ionic solution is that any vapor pressure due to the dissolved electrolyte itself'is effectively zero. ‘The vapor pressure of the solvent in the solution therefore falls with increesing concentration of the electrolyte in the solution, ‘Thus, the solvent vapor pressure in the solution will be less than the vapor pressure ofthe pure solvent because the nonvolatile fons block out part of the surface from which, in the pure solvent, solvent molecules would evaporate. Now, there is nothing mysterious about a solvent activity, Iti determined by G92) i where Piste vapor presurof pure solventand Pi the vapor pressure ofthe solvent when it is a component of a solution, ‘The relation of P, to Py in the ideal condition will governed ty Raoul’ tv, thats282 CHAPTERS HP 93) where x, is the mole fraction of the solvent. One allows for the nonideal behavior of the solvent in respect to its vapor pressure by writing Ahr 94) Asx 1, f; 1 Thus, the “standard state” is the pure solvent. ‘AL this point, one calls into play the Gibbs-Duhem equation of thermodyn: according to which!” Yndy=0 95) Or, fora two-component system (solvent and electrolyte) ny day +g djng=0 96) here the subscript 1 represents the solvent and the subscript 2 represents the electrolyte sotute, It follows from p=? + R7In ay that a9 or 3.98) ‘Thus, if one measures a number of values of the vapor pressure of the solvent P, at acoresponding number of solute concentrations, x, (Wo whieh there are matching solvent concentrations 2r),one can plot the In ayvalues against the n/n, ratios. Then the area ofthat plot will give In a thea being the solute activity corresponding to the Himit of the integral ata, (this a, being the measured solvent activity for a solution containing a solute, the activity of which is a). ‘The left-hand side of Eg. 3.98) came from "ny inal impression tthe somxttng uncon aur the Gibbs-Daster eytion sea be intanly que. 1 mer tells ove dl (era ts-compynent syste) when an incase in my ayes, it causes a decrease in my dey of equal magnitude atypically powerful and genral result of hemody amie rsening,FONLION INTERACTIONS 269 4 Jaina, “ and dy > 0 is simply ¢ because when the solute concentration (hence also activity) tends to 7er its activity becomes equal to its concentration, “This solvent vapor pressure method for measuring the activity of electrolytes has the advantage that the actual experiments one has to do are simple." The method can be applied to any concentration (e.g. 15 M solution!) The difficulty comes at low concentrations when the difference of the vapor pressure between the solution and that ofthe solvent becomes limitingly small. A huge amount of data (see Table 3.5) have been determined by this methed, particularly in the 1950s by a long-term Australian— New Zealand collaboration between professors Stokes and Robinson. 3.4.8. A Second Method by Which One May Obtain Solute Activities: From Data on Concentration Cells and Transport Numbers “Vhermedynamies treats electrochemical culls in equilibrium and indeed such hoary material, going back to the work of the great German physical chemist Nernst," is apart of lassicel electrochemistry thats still being taught in uiversites to students as iF were representative of modern electrochemistry! Consider then the etiemical potential ofa metal as peg in the solid electrode. “The chemicel potential ofthe ion is that of a solute in a solution ancl hence is given ty My = Hee FAT IN aye 99) "hee soften no need for an absolute dination of vapor presre The seve vapor presure can be determined simply by seting up closed sytem that contains ¢scution of large volume having an lady known scent activity. The unknov solution will ehange is concertos (al Benes its ‘wcighs) unis cleat atv isthe same as that th referace sytem, whichis know Great aocuney in te weighing is esta ane cno should use platinum veses to minimize possible dsoltin, Wale Nem was peofessr of chemistry in Pelion dhe early yeas ofthe venti entry. He epitomized te professor es a “Great Man” Ameng his ray achievements ws the work het (vite ‘Nera heat orem) to de hind Jaf thermodynamis. e was active no cly in chemistry but also made significant contributions tothe theory of the expanding nivers, Nernst was famous net ely for his rea (many and gest) contributions to physical eletechemisry but also for the cola ig discipline be demanted from tse who aspired wo be bis eollabxaors. Were ene ofthese to ave at his vweeplace fer the scbeduled hour ef7.0 am, he mig ind a note Fm the profs reminding bien ‘ft numberof applicants who were wating to cecupy it (One such exlorater (er ime a famous pyical chemi) is known ty have reed that, in smaking the minture for Ners, the Her Creator had put in an extra doe ofthe intellectual but let cat the uma24 CHAPTERS TABLES Experimental Activity Coefficients of NaCl at 298 K. ~e fy cor) experimental Valves) 0.000997 ootss 0.001994 oo 0.000985 00327 0.009969 0.0446 01993 0.0599 0.049891, 0.0859 0.09953, 107 0.1987 0.130% 04940 0.1593 9788 ogni 1921 01453 3.606 corr 5305 007s Source Reprinted for RA, RobnsonasdKH, Stk, Becht Solus, 2nd ev -Puenworth Condon, 16h ‘where ay," is the metal ion’s activity in solution, Now the reaction that goes on at an clectrede when an ion in sotution exchanges electrons with the electrode can be writen as M4g=M 0.100) Cleary, one has to make an allowance forthe electron in the Nemst-type theories — “whitch ae thermodynamically valid (model free) and therefore ean he used today. ‘This was done by a term Beg (potential x the electronic charge = energy in electrostatics). ‘The E was thought ofby Nernst as the potential between the metal and the solution Now, the thermodynamic equilibrium for Eg. 3.100)" sg Eey 1a 101 Substituting py? from Eg. (39), phot kTIN ayy — Beg= He (8.102) or "The negative sign ares Doeauw tbe magninde of he charge cn the ecto, bars a negative ign.JON-JON INTERACTIONS 265 emi ew |] vie tow Fig. 3.19. Determina- tion of indhvidual ionic activity from the col potential. ME Tg cae a ing. Baa Tinga B+ TE nay 103) where £*is the standard potential of the electrode reaction, at 25 °C and a unit activity ‘of the ion in solution; N,k=R; Ny¢o=F, the Faraday, or cage on 1 gram ion. follows that ifone has twe electrodes, each in contact with the same ions but at lifferent setvites, and the reactions are in thermodynamic equilibrium, then neglect- ing for armoment any potential that mightexist af the contact hetween the two solutions, ie, any liguid-junction potential, from Eg, @.103), (3.104) ‘and a schematic representation of this idea is shown in Fig. 3.19. Thus, one could argue as follows: if one of the solutions in the cell has a sufficiently low concentration, eg, <5% 10" mol dm for I:1 electrolyte, then the Debye-Hickel limiting law applies excellently. Hence, if one of the solutions has concentration of <5 % 10 mol dm”, we know a;,,the activity of the ion é in that cel, 0 that Eq. G10) would give at once dj, the activity of species fin the more concentrated cell. ‘Morcover—and still keeping the question of the Liquid junction rigidly suppressed in one’s mind—the answer would have one big advantage, it would give an individual ionic activity coefficient, f. ‘A method of such Virtue must indeed have a compensating complication, end the truth is that the neglected liquid junction potential (LIP) may not be negligible at all.!* "Fr wars out het Ezy Eg = Cy where fy ale ws wapectnaly, te alone adenine onpent rurnbers. There are cases, frjunctins cf sttions of KC where 4, and are almest the same aa hence the Ep =O si the corection duct the iuidjumetion ie negigile. a seme esses the diference tot may be quite considerable268 CHAPTERS 01 O31 10 173 223 268 3.00 3.08 se Fig. 320. Plot of log 74" ¥s.1e al dilerent temperatures for (CF,SO3H. (Reprinted from B.C. Bhardival, M.A. Enayetullah, and 4. OM. Bock, J. Electrochem. Soc. 137: 2070, 1990.) Finding an equation for Eysp is surprisingly difficult, but itis finally shown that [¢f. the deduction of the Planck-Henderson equation, Fi. (4.291)] = (2t,— 1) EE jp Seem (4.291: Fue = (1, - DT neat (4291) Using Bs. 104) and (4.291), the cell potential withthe liquidljunction potential Sra sain _ 9, RT yo, Sit'sot (3.105) Sram Fa stat fone knows f, atthe concentration at which itis desired to know dy ggg One can find the later Value by using the limiting law for dyqjqqy- Compared Wilh the first method (Section 3.4.7), the advantage of being able to aim for an individual ion’s suctvity coefficient is significant However, there are penalties to pay if one uses the electrochemical cell method, Fics, there is the question of the value of ¢,—it should be known as a Function of concentration, and such values are offen not available and imply the need for ascparte determination. Further, there is « nasty experimentel point. One talks of “the liguid- {junction potential” as though it were clear and definite entity. ‘The thermedynamic ‘equation [g. (4.291)] assumes that there is a sharp boundary with linear change of concentration across a small distance (see Section 4.5.9), ‘These conditions assumed in the deduetion only last for short time after the two solutions have been broughtFONON INTERACTIONS 267 TABLE 36 Experimental Values of Activity Coefficients of Various Electrolytes. at Different Concentrations at 258 K 11 electolyte, HCL ‘Concentration, mala ©0001 9.0002 Ges 0.001.—_0.002 Mea acivity cefliciert 0.9891 0.9842 09752 0.9656 0.9521, 2:1 eleeuolyte, CaCl, Cancentsation (moles dex') 0.0018 00061 0,009 Mem activity coefficient OS388 7745 0.7361 22 electrolyte. CASO, Concentration, mola cos p00) .00S Mean activity coefficient 0.740097 0.476 into contact, even when the boundary is made very carefully.!* Hence, the conditions ‘under which Fg. (3.104) is valid are subtle and difficult to achieve. Nevertheless, the method has been used—with guarded admissions about the dangers of using it—when infcrmation on single ion activities is desirable, eg. inthe stay of O, reduetion(O, 44H 44.69 21,0). Some results the latter stucly— al very high concentra. tions—are given in Fig. 320. Note the extremely high values of the proton rneasured in the concentrated acid. Further Reading Seminal LP. Debye and E Hckel, “Ihe Inerionic Auraction ‘Theory of Devi Behavior in Solution,” Z Phys. 2& 120 (1923). 2. H. S. Hamed and B. B. Owen, The Physical Chemisry of Electrolwie Soluions, 31d ed, Reinbold Publishing, New York (1958). 3. HL. Fricdanan, “Electrolyte Solutions,” in Mader Aspecte of Electrochoniciry, Na. 8, 4.0™M, Bocksis and B. B. Conway, os, Plenum, New York (1971). jons from Ideal Reviews |. TL. Friedman, “Thecry of Ionic Solutions in Equilibrium.” in Physical Chemistry of Aqueous onic Solutions, M-C. Bellisent-Fund and G, W. Nielson, eds, NATO ASTSevies C205: 61 (1986). Ther ase echnigues for making an unditurhed boundary nearin ely oa impli assed in thethecey (Sotion 567.2. nthe one most usually used, two soho cf fferent concentrations ere eld epat ya ges aide hati skoly remove, allowing contact Belwecn the cltons with minimal coereveness. Inandhr, he to sctiens ee beld apart ina he tbe one on tp being rstrined aginst ‘rovity hy means of reduced prosurs. Very slow release ofthis pressure allows the gradual descent of the top solution to make a gente jmtion withthe lower one. ‘Ihe sim ef ech mod is to acid ddstuanoe ofthe ssn aed ext bound.2. J.C. Rasaiah, “Dhearis of Eectelyle Solutions.” in The Liguid State and lis Electrical Properis, FF. Kunhard, LG. Christophorou, and. H. Luesen ets, NATO AST Series B19 135 (1987, Papers L. CLP. Baes, Jr, EJ. Reardon, snd B. A. Bloyer, J Pls. Chem, 97:12343 (1993), 2. HP. Diogo, M. E. Minas da Piedaée, and J. J. Moura Ramos, J. Chem. Ed. We A227 (1993. 3. Hi Sehnert, J. Phys. Chem, 9: 643 (199, 4, HL Seliinert J. Phys. Chem. 98: 654 (199), 5. B. Honig and A. Michols, Science 268: 1144 (1995). 6 B.B.Laird and A. D. J. Haymet, J. Chen Phys. 10 3775 (1996). 3.5, THE TRIUMPHS AND LIMITATIONS OF THE DEBYE-HUCKEL, THEORY OF ACTIVITY COEFFICIENTS 35.1. How Well Does the Debye-Hiickel Theoretical Expression for Activity Coefficients Predict Experimental Values? “The approximate theoretical equation log f, =-AC,2 1? @.90) indicates that tbe logarithm of the activity coefficient must decrease linearly with the square rool of the ionic strength or, in the case of 1:1-valent electrolytes, with <2, Funher, the slope of the log fy versus 1 straight line ean be unambiguously evaluated from fundamental physical constants and from (2,2). Finally, the slope does not depend on the particular electrolyte (i.e, whether it is NaCI or KBr, ete) but only ‘0 its valence type, Le, om the charges borne by the ions ofthe electrolyte, whether it isa I:L-valent or 2:2-valent electrolyte, et. ‘These are clear-cut predictions. Even before any detailed eomparisen with experiment, one can use an elementary spot check: AL infinite dilution, where the interionic forces are negligible, does the theory yield the aetivity coefficient that one would expect from experiment, te, unity? Alinfinitedilution, coe 0, which meuns that log fy > Ocrf, > 1.'The proper of an extremely dilute solution of ions should be the same as those of a solution ‘containing nonclectrlyte paticles. Thus, the Debye-Hickel theory emenges success fully from the infinite dilution tes. Furthermore, ifone takes the experimental values ofthe activity coefficient (Table 36) al extremely low electrolyte concentration and plets log f, versus 1'7? curves, it Thats, P= Sad. Fra LL electlte, =e? G 79. As