smply the reciprocal 0.63 = 1.5. 0.20 aonnalized), in question, 2.28 iS S be instantaneous aypsumn dissolved, role of dissolving sted with respect sraction between rolecule and a B shown by statis- ‘equal their con- sits aro used). In ions are not met. "= generally sur- ‘e different from ing of the water he ideal solution concentrations, ivity of water is issolved CO; or charged species vity of a species vooetfficients of in-concentrated involved in the xd species. The by the equation of reference, the Activity Concentration Relstionships 27 Activities of Ionic Species From a purely thermodynamic point of view, there is ao way in which the activity coefficient of single ion can be measured without introducing non-thermodynamic (and non-veriiable) assumptions. In principle, to measure the activity coefficient of, for example, Na’ in solution, ‘we would have to measure how much the free energy of a solution varied asthe concentration cof Na* vacied. The problem is that itis impossible to vary the concentration of Na* without also varying the concentration of some anioa or some other cation. Itis therefore impossible, in principle, to say how much of the free-energy change should be attributed to Na* and how much to the other ion. The themodynamically correct way to treat activity coefficients of ionic species is not in terms of ionic components (Na*, K*, CT, SOF, etc), but in terms of uncharged components (NeCl, K,SO, etc), For ile solutions, hoxeves, iL convenient to use single-ion activity ts even though they are not rigorously defined thermody ‘hainigally” For concenirated brines, it may be advantageous to consider uncharged species ‘ater than joa. The covicepival approach that ip used to relate activities to concentrations is called a solution model. We shali generally use the single-ion activity coefficiention pair model in this text. The mosel is expiained in the following sections. Debye-Hiickel Theory, The Debye-Hilckel theory is a model that allows activity coefficients for single ions to be caleulated on the basis ofthe effect ionic interactions should have on free energy. In an ionie solution, positive ions will tend to have a cloud of negative ions around them, and negative ions a cloud of positive ions. This wil result ina system with lower free energy than would be the ease ifthe distribution of ions were completely random, and hence an activity for the solutes lower than it would be for the random (ideal) case, Activity coefficients for ions in solution shoul thus be fess than 1. If i is assumed that the fons ae Pott charges, the interactions are entirely electtostalic, and the ions eround any par- ticular ion follow a Boltzmann distribution, itis possible to derive the equation logy, = “AZT a9) where A is a constant depending only on P and T, 2 is the charge on the particular ion, and T is the ionic strength of the solution. Ionic strength is given by Lime Tonic strength (m, i the concentration of the ith fon; the summation sign means that the contribu tions from all jons in solution must be summed) is a quanity that oceurs frequently in sofution chemistry. It differs from total concentration in that it takes account of the greater electrostatic effectiveness of polyvalent ions. Thus the ionic strengih of a { m solution of NaCLis 1, of a1 m solution of Na,SO, is 3, and of a 1 m solution of MgSO, is 4. Ea. (2-9), the original form of the Debye-Hiickel equation, holds reasonably well up to ionic strengths of about 10° At higher fonie strengths the simple model fails because it requires an impossibly high concentration of anions around each cation, and vice versa. The equation can be modified to take account of the finite size of the ions, giving the extended Debye-Hiickel equation: es = That 2-10)2a Chemical Beckground — Chapter 2 Bisa constant depending only on P afd T, and ag is, in theory, the hydrated radius of the par- ticular ion, In practice, the value of ay is chosen to give the best fit to experimental data. Some values for the parameters in the Debye-Hckel equation (Eq. (2~10)} are given in ‘Table 2-1. Equation (2-10) is reasonably accurate up to ionic strengths of about 10”, ‘Note in Table 2-1 that the product Bay has a numerical value of about 1. A commonly used alternative form of Eq, 2-10) ean Bg. (2-11) is commonly called the Guntelberg equation. For higher ionic strengths, Eq. (2-10) and (2-11) can be modified by adding a further tert 12) 3) where b may be a general constant (Davies, 1962), or may be & constant specific to the indi- ‘vidual ion £ (Parktusst, 1990), Bq, (2~13) with 6 set equal to 0.3 is called the Davies equation ‘The additional term cap be justified on theoretical grounds, or it can be justified as an empir- ical fit to experimental data. An important consequence of the additional term is that it pre diets that activity coefficients should incvease with increasing ionic strength at high ionic strengibs, in accord with experimental observations (Fig: 2-2). ‘There are many jong for which a, values have not been measured experimentally, The Giintelberg or Davies equation rather than the Debye-Hlckel equation must TABLE 2-1 Perametars for the Debye Hoke! Equation at 7 Atmasphore Pressure (Adaptod from Teuoedell and Janes, 1874; Bal ans Nordserom, 1891} a bon apo") ’ oases 0541 o 50 016s ose omy we 55 020 04960 03288 Ne 40 ons 03000 one Kcr 3s nts oso ons sor 50 0.06 2s ose 03281 1005, c0% sa 00 20 0.5130 0.3290 Na 25 *° osm 03305 SoBe 50 80 ossis 03321 Be Me Li 60 @ osas 038 EAI, 50 Activity-Concer FIGURE. Va Example $ ‘The Rio(