1280 PRINCIPLES OF PHYSICAL CHEMISTRY dimensions of reciprocal density and hence its units are em? g°1, Typical values of K and a are summarized ff Table TABLE 1 Parameters for the Mark-Kuha-Hoawink-Sakurada Equation Palmer Soret Temperature °C) J RXIO 2 Polarene Benzene 3 om Polysyeene: Arace “olsen » on soactic | Toluene 0 on Polysesionivle Dinetty! ormamide 2s oa, Palyabuyene yetoberane x” on Beazese ra 051 Polysoprene Cyelohexae n on Narre abter ‘Tkcne cS oe Polyvinyl alcool Waee 3 076 Polyvinyt eboride Texalitiin ow os Polyetyene Declin 3s o70 Pyisobarylene Beezene % os Toluene o oo yctoberane x» 09 Polymetyl metaerlxe | Toluene Ea on Taking los of th sides of Eq 13, we ve lon) =k + gin Mae 08) Ea. 14 shows tat log-log pot of fn} vers Me gives a straight ine wid slope equal t 0 nd interept equa ola KT, the coats a and canbe easily termite owing the valieso a and, the visiy-average molar mass Hic can be denned from sie veo measurements Example 3. The ftrinic viscosity of mycin i217 x? g. Calculate the apprsinate concentration of ‘myosin water which would havea relate vicy of 1° in Slaton + From a, 7, as = 15 (ge) It 9 a) = arn! See mi de ee 6 Ha pen a ee a Aa SN SL sshog= ‘Solution : En] = 3-107 (He « 160) £! = 30x10 ae Fach 5 OE 559 sex07 Taking ops 0-66 Ree = a 60x10» Biv = 60 gett MACROMOLECULES * 201 Example $. The following data were obtained forthe fatrinsc vissity of popfaobaslee fn CCl, solos at 30°C asa Tunconof the vediy-nerage mar mas, : {nh a? gt Hoes 8 008 nh cm? gt Bhai 8 mot 0 120000 : a 3.000 206 463000 : 1st 19.000 Bs 2850 us 1080, K(Fiae)*- Deering the contacts K 331 1 ne cpt fle Hl a lige = = 0 t= = = 8265 tm web gs = bol ‘We sal now comment on te vissy-rerage moar mass We, Ith exponent in 3 ash a= ed 0, hen the vse mar a canbe Wen Hvac = (VK = (ar WKe * Ais) ‘The (Mra!) values of the individual factions can thei be added to yield the total (ny). © (t= Dr + (Met D2. (eet~ Ds + KoiMy + Key + KeMs + Therefore, the vscosity-average molar mass canbe writen as Wie = KOM + OM + ls +) yyy Rata tae) ieee = Thy te.) 06) ‘We see that when the constant a=, the viscosity average molar mass yields the mass-average solar mass. Wael, then, according to Eqs: 13 an 15, ic) = (nea DIRE Att K@Mi + QMi + qM$ + Ka + arg +) Hence, Wise = Want ay" 49) co EoMt Ee ap Ie flows from E19 ao tat Fle —> Ts when a —> 1 2. Osmometty Osmotic pressure measurements are used for studying macromolecules because osmotic changes se larger than the changes in boiling point elevation, freezing point depression and vapour pressure lowering, For instance, an order-of-magaitule calculation shows that for an aqueous solution containing 10 g de? of polymer having molar mass 20,000, the bolling point elevation and teezing1262 PRINCIPLES OF PHYSICAL CHEMISTRY int depresion are (025°C and 0-00095°, respectively. Evidently, these values are ao lw tobe 16 Tis the osmotic pressure of a solution in which the mole fraction of the solvent ix, thea, the condition for eqlirum for he chemical potential of the solvent on bah side ‘semipermeable membrane gives inate ca Rr ings 40% 0) here she cv coe ofthe sve! nd Ys the pata mala volume of sole in the solution. Fora ditt soliton, sy» 1 and Vie Wf, the moar volume of the pu seat rey (a) nse ke st et ete, pi en nif = ara + 20 Gia 6 mr) 2 Fora polymer cain of comet 3 aes by em” ie : myo 2M, ME tr tite tion, ecw Me : =) Hee Mi th mola mas of eye. Sing Eq. 22 n By. 21, we ia, fr ane oan, ar] af) fe ya x haf oi( Jes. 2 ‘hich is the virial expression ofthe form es Ba Has aecat 4, 24 is often writen ithe form + a Saat ps eet ae 105) it Bi By ee mnt inkl ein, 25 we Ha fore ero se in ep ai en: 25 Bal eas ete one ple cart are cate oe Sa eeu al Sere ite hs St ee oe) From the intercept, the molar mass M can be easily calculated. Example 6. The i ae AEEBPE GT flowing dua were aed nthe smal pres of sans of yeh i O15 gat 927 ns so Mmm WO 483 3 12 Clete the molar ase ofthe poner. Salon + 100 sil = O- ice = 04 da? Bee seo oF wee) 0) 1203 Macromoucus Comin he lig le eg dw) 7 53 et Ie tm HO dog) 235 ae ” et Ue vers ¢ to obtain sight He. wil be sen from the plot that oy (1) = 196 nn HO de? = RM fa ar. op tama TRO) * Wom 0 ane 64.15 (* 05006 de? mK! ot) = 0082067601556 om HO dn? K mo! 1 am = 76) mH; tm Hg = 19-56 HHO 4567 wn 10 da? Kot! (665-S emt, 040? Kw SIOK) — 149,08 g wt! om Deore sureneat leads to oumber-average molar mass because osmotic estas kn caliguve pope) whic pets von the ruber of molecules of the omer and wo UB hele mass and all molecules wher eavy of ight make equal contribution is can 1 taal remembering tat the oat pes Tl comiss ae a att oc pres yy or he lees of ies dees of polymerization, 1, 2,3, et. Thus, < u The osmotic pressure mea RT, GRT | GRT. Pati r ofleg Rien a nize, a) T= m+ +My Me iy My Ltatat ‘phe same holds for the total concentration : “Tis, the osmotc-average molar mass can be writen ag a. , bate pat DRE co Mosse) = TE Tip + Tg . G@tqrat— et = RIG IM, + G/B, + IMs + ” Ze, — ra 0) * Eq/EM, ‘Molar Mass of Charged Macromolecules : Donnan Membrane Equilibrivs: eee ee ee vec ae ora ft, ey sc cee a a re Ca et ee si en a, a ee ee Ir inc NF emenin mpi pet sof nc Se scene ei) en me ee fein on a i