1585 SIMPLE MIXTURES Intercept = KN Slope = -K Intercept = W MAL Number of binding sites, v 4.820 A Scatchard plot of {Al agains vetheslopeisK andthe intercept a BEN. [bag Peotone fatlowing a wil give you an idea of bow graphical analysis an distinguish between systems with thesame values of Kor N. is, splay om the sme graph several Scatchard plots with varying K values but five Then peat the proces, time sarying Nbut fixing K. ‘This expression isthe Scatchard equation, It implies that a plot of VI[A]aq against v should be straight line of slope ~K and intercept KNV at V= 0 (see Fig. $30). From ‘these two quantities, we can find the equilibrium constant for binding and the nam- ber of binding sites on each macromolecule. Ifa straight line is not obtained we can conclude that the binding sites are not equivalent or independent. Activities [Now we se how to adjust the expressions developed earlier in the chapter to take into account deviations from ides! behaviour. In Chapter 3 (specifically, Further informa tion 3.2) we remarked thata quantity called “fugacity” takes into account the eects of gas imperfections in a manner that resulted in the least upset of the form of equations. Here we see how the expressions encountered in the treatment of ideal solutions ean alsobe preserved almost intact by introducing the concept of activity’. Itisimportant to be aware of the diferent definitions of standard states and activities, and they are summarized in Table 5.3, We shall put them to work inthe next few chapters, when ‘we shall see that using them is much easier than defining them, 56 The solvent activi ‘The general form of the chemical potential of a real or ideal solvent is given by a straightforward modification of eqn 5.23 (that sl,= [4% +RT In(p,/pf)swhere p isthe vapour pressure of pure A and p, i the vapour pressure of A when it sa component of a solution. For an ideal solution, as we have seen, the solvent obeys Raoult’ law atall concentrations and we can express this relation as eqn 5.25 (that is as y= 4 + RT'In x). The form of the this relation can be preserved when the solution does not obey Raoult’s law by writing y= HRT log saz] ‘The quantity ag is the activity of A, a kind of ‘effective’ mole fraction, just as the fugacity isan effective pressure. Because eqn 5.23 i true for both real and ideal solutions (the only approximation being the use of pressures rather than fugacities), we ean conclude by comparing it with eqn 5.42 that Pa 7 (5.43) m Table 5.3 Standard tates ‘Component ‘Basis _—_Slandard tate ‘Activiy Limite Solid orliguid ure Solvent Raoult Pureschent re=re ya wx1 {pure solvent) Solute Henry (1)Abypothetclsweof —a=pikia=yx yr Las 30 the puresste ()Abypotheticalstateof a =i” yortaeb40 The soit a laityWe sce that there is nothing mysterious about the activity of a solvent: it can be determined experimentally simply by measuring che vapour pressure and then using eqn 53, Ilustration 8.3 Calculating the solvent activity {The vapour pressure of 0.500 a KNO,(aq) at 100°C is 99.95 kPa, so the activity of water in the solution at this temperature is 99.95 kPa Because all solvents ubey Raoult’s law (that pylp = x4) increasingly closely ay the concentration of solute approaches zero, the activity of the solvent approaches the mole faction as x, 98, 88 X71 44) A convenient way of expressing this convergence is to introduce the activity coefficient, 7, by the definition =I Te XII (5.45) atall temperatures and pressures. The chemical potential of the solvent is then Ha= HAART Inxy+ RT In I (5.46) ‘The standard state of the solvent; the pure liquid solvent at 1 bar, is established when el 57 The solute activity ‘The problem with defining activity coefficients and standard states for solutes is that, they approach jdeal-dilute (Henry's law) behaviour as.xp -> 0, not a8 xp 1 (corres ponding to pure solute). We shall show how to setup the definitions for a solute that ‘obeys Heney’s law exactly, and then show how to allow for deviations. (e) ldeal-dilute solutions A solute B that satisfies Henry's la has vapour pressure given by py Kis an empirical constant. In this cas, the chemical potential of Bis Kgs, where Ky ig+RTIn 84 RTInxy 7 Both Ky and pare characteristics ofthe solute, so the second term may be combined with the firs 0 give a now standard chemical potential: Ks i nce RT In {s7) 5 It then follows that the chemical potential of a solute in an ideal-dilute solution is related to its mole fraction by My = HG + RT in x (5.48)° Ifthe solution is ideal, Ky= p3 and eqn 5.47 reduces to 4g= pj, 2s we should expect, 5.7 THE SOLUTE ACTIVITY 159160 5 SIMPLE MIXTURES (b) Real solutes ‘We now permit deviations from ideal-dilute, Henry’ law behaviour. For the solute, wwe introduce ay in place of xin eqn 5.48, and obtain Hy= H+ RT In ay 5.49] ‘The standard state remains unchanged in this last stage, and al the devistions from ideality are captured in the activity dp. The value of the activity at any concentration «an be obtained in the same way as forthe solvent, but in place of ean 543 we use Pn 5 a= 8 5.30) ra (630) AAs forthe solvent, itis sensible to introduce an activity coefficient through y= oh [551] Nowall the deviations from ideality are captured in the activity coefficient 7p, Because the solute obeys Henry's law as its concentration goes to zero, it follows that dx, and Yeo] as x90 652) tall temperatures and pressures. Deviations of the solute from ideality disappear as zero concentration is approached. Example 5.5 Measuring actly Use the information in Example 5.3 to calculate the activity and activity coeficient of chloroform in acetone at 25°, treating it first asa solvent and then as a solute. For convenience, the data are repeated here: xe 0 020 «0400600 PokPs 0478838 pukPa 463 333° 233123849 ‘Method Tor the activity ofchloroform asa solvent (the Raouil’s lw activity), form Jpg and Y= acl. For it activity asa solute (the Heenry’s law activity), Re and Ye ele “Answer Because p=360 kPa and Ki-= 22.0 kPa, we can construct the following tables. For instance, at x= 0.20 in the Raoul’ law case we find ay = (4.7 kPa) (364 kPa) = 0.13 and %= 0.13/0.20 = 0.65; likewise, inthe Henry's law case = (4.7 KPa) 22.0 KPa) = 0.21 and 7e=0.21/0.20= 1.05. From Raoult’s law (chloroform regarded as the solvent): a 0 (013 030 052 073 1.00 % 065 075 087 0911.00 From Henry's aw (chloroform regarded as the solute) a 9 021 050 086 121165 % 1 OS 125 SL. ‘These values are plotted in Fig. 5.31. Notice that o> 1 as xg Tin the Raoult’s lav case, but that 71 asx¢—> On the Henry's law case. Softtest 6.7 Calculate the activities and activity coefficients for acetone according tothe two conventions. [At = 0.60, forinstance ag = 0.505% i y= 1.00, y= 1.67]© & Activity, a and activity coetficie 0 8 02 04 0608 1 02 04 06 08 1 ‘Mole fraction, x ‘Mole fraction, x (6) Activities in terms of molalities ‘The selection ofa standard state is entirely arbitrary so we are free to choose one that best suits our purpose and the description of the composition of the system. In chem: istry, compositions are often expressed as molalites, in place of mote fractions. It therefore proves convenient to write y= G+ RT In by 5.53)" where 1° has different value from the standard values introduced earlier, According, to this definition, the chemical potential ofthe solute has its standard value f° when the molality of Bis equal to b* (that is, at 1 mo! kg). Note that as by —* 0, fy —>—95 that is, as the solution becomes difuted, so the solute becomes increasingly stabilize. ‘The practical consequence of this result is that itis very difficult to remove the last traces of «solute from a solution. Now, as before, we incorporate deviations from ideality by introducing a dimen- sionless activity a, a dimensionless activity coefficient yg end writing where 791 as by >0 [554] at all tamperarures and pressures. The standard state remains unchanged in this last stage and, as before, all the deviations from ideality are captured in the activity coelfcient 7. We then arrive atthe following succinct expression forthe chemical potential of areal solute at any molality w=ur+RTIna (5.55) {d) The biological standard state Oneimportantilastration of he ability to choose standard stat to suit the circum= stances arises in biologicel applications. The conventional standard state of hydrogen ions (unit activity, corresponding to pH = 0)° is not appropriate to normal biological conditions. Therefore, in biochemistry it is common to adopt the biological stand- ard state, in which pH = 7 (an activity of 10”, neutral solution) and to label the corresponding standard thermodynamic funetionsas G®, H®,u®,and S® some texts use Xs * Recall from introductory chemistry courses that pH= ge 5.7 THESOLUTEACTIVITY 161 Fig.8:21 The variation of activity and activity coelicient of chloroform (eichloromethane) and acetone (propanone) with composition according 10 2) Kaoul’s law, (b) Henry’ law.162 5 SIMPLEMIXTURES pe.saz The vapour pressure ofa mixture bused oma model in which the excess enthalpy is proportional o iy. A dea Solution corresponds to B=0and gvesa Straight Tine, in accord wi Raoul’ aw Positive values of Byive vapour pressures higher than deal. Negative vale of give lower vapour presse. [bag Bouton Moco ssi with fi=2.5 by sing eqn 5.24 and them oqn 539. Above what value of do the values of pp given by these equations aifler by more than 10 er cent? ‘To find the relation between the thermodynamic and biological standard values of the chemical potential of hydrogen ions we need to note from eqn 5.55 that Hye = fh + RT Ua ay = 19. ~ (RT In 10) x pH Iefollows that HG. = Mj. -7RT In 10 (556) At 298 K, 7RT In 10 = 39.95 ky mol, so the two standard values differ by about 40 kJ mol}. 58 The acti “The material on regular solutions presented in Section 5.4 gives further insight into the origin of deviations from Raoult’ law and its relation to activity coeficints. The starting point is the expression for the Gibbs energy of mixing for a regular solution {qn 5.31). We show in the following Justification that eqn 5.31 implies thatthe activ ity coeficients ae given by expressions of the form In y= Be In y= Bi (5.57) ‘These relations are called the Margules equations. ities of regular solutions Justification 8.4 The Magus equations The dibbs energy of mixing to forma nonideal solution is AgaG= mR) Ina +59 In ay) This ration follows from the derivation of eqn 5.31 with activities in plice of mole fractions. Ifeach activity i replaced by 7, this expression becomes pad MRT by + 5 In gp +84 In Y +84 I IL [Now we introduce the two expressions in «qn 5.57, and use.xy +4 L. which gives Sg G= MR Tag I x, +3 In p+ Bred + Bad) RT| Ina b+ 08%) EnRThxg In 3, 435 5+ Begg) as required by eqn 3.31. Note, moreover, thatthe activity cneficients behave cor: rectly for dilute solutions: 7, > 1 a8 4; > O and > 1 as.x, 0. [At this point we can use the Margules equations to write the activity oF A as a4= Hea eam 658) with similar expression foray, The activity ofA, though isjustthe ratio of the vapour pressureof Ain the solution othe vapour pressure of pure A (eqn 5.43), wecan write a= base py 9) ‘This function is plotted in Pig. 5.32. We see that 8=0, corresponding to an ideal solu- tion, gives straight linen accord with Raoult’s Iw (indeed, when B= 0, eqn 3.59 becomes py = x, whichis Raoul’s law). Positive values of (endothermic mixing, unfavourable solute-solvent interactions) give vapour pressures higher than ideal Negative values of (exothermic mixing, favourable solute-solvent interactions) give 2 lower vapour pressure. All the curves approach linearity and coincide with the Raoult’s law line as x, —> | and the exponential function in eqn 5.59 approaches 1 When x, «,eqn5.59 approaches