(RINCIPLES OF PHYSICAL CHOMSTRY O= teats) J he aig rf uo sete ob ge 1296 = s46ci04 ig st If we asume ht the meu i perc, then Gyo, Lew rt ee oneal suing bat it aera, ice M=OL 5g ma and x= 0-75 en? Va = (64500 g ea) 75:10 wg) = O18 wP mot! Mor volume, Volume per moe Yq, _0-0¢8nP WOE _ 7.57 «10m? ane er ee, ty = He = ONT = 797 x10 se mole is steel, - va = D8 | atau) £1610 «107m tom exe, ‘fp = ban = 6 6116 COI5HI0? be wT ) ATO 9) = sosxtom test L-Series netics iy fo SREY or ‘Siwe f/f Sec to ity, te buemogbia moll Dawes as 2 sphere i agen ein Conformations and Configurations of Macromoleue in Suton. Ii convenient 1 wea Of conleuinons sud covomatons of macromokes i sun, The term confisratin pies conf cruture et can be changed ony by being bonds ad reforming new nes WA He ato vction ofa polymer chain refers tthe spat arrangement ofthe dierent parts of ie cer coaiormle Thus, whereas the chaifeA~B—C™ has 2 configuration diferent rom rnc conformation ofa chain ean be wansormed ato another simply by rotating port of te cain round the bond jig it 1 aoe at. It posible 10 determine he ass of randomly coiled polymer chain in solution. “The simplest model ofa randomly coiled polymer chain is freely-jointed chan where any bond is free to make any angle with respect to the one (ig. 3). This model is the exact analogue of the ttyee-dimenstional random walk model in which etch bond represents a step taken in a random direction. ‘The contour length, Re, is the, length of the macromolecule measured along its backboxe from ftom to atom (Whe maximum distance that the random ‘walker could walk). For a polymer of N monomer tits each of length f, the contour length Re=NL Te is know thatthe probability ofthe ends of the chain (een the net distance travelled by a random walker) lying in where Kesay Fig 3. A ely jotted polymer cn the range R to R+AR is given by ARR -()atetes &- 95 109 «(App aatetts Poa 5) vtere i the numberof bonds (the mami f yes and 1s te ond length (te lneth of each pe). ‘Using the function defn in Eq. 95 ne eam sean square end-to-end distance of = hai, Rw calculate three important quantities, vz, the rot the mean end-to-end distance ofthe chain, R MACROMOLECULES * 197 and the most probable end-to-end distance, Rey 8 illustrated below o i ( free] 69 vewwea [nmin «(fo firertae o ‘The integral on the righthand side canbe evalu using the standard img [Crewe 00On-0( a)" , eerste rt eG ) sivng [rreerer - 08) (5 7 _ 3x 0 Bela) “sae 2 ‘Thus, = My fe Ras = HL i » B= [rsa = (-2,) ca (eM [Prion =() eo [Pan fa Using the standard integral, i fF oe (1s) nana [Pecan K «009 4 so tat 22 (8)? any (it) To obtain Rp, we diferente AR) with respect wo R and set the derivative equal oz. GR) (2 y pd)? HE) - (-£) syar-2atahyee = 0 «006, Rap = (2/3)? MA (107) From Eg, 101 we see tat rt = It we ean square et--end dine fo a comply fexle payer it ol ese ot fe ie te, pret cir eigthe bod lng 1 Howetes, fractal polymer tole, Rg sears Ths dit1298 PRINCIPLES OF PHYSICAL CHEMISTRY to the following reasons : : @ There isa fixed bond angle @ between the bonds forming the backbone ofthe chain, (There aie restictions'to free rotons about bonds. ~ (Gi) Chain segments occupy volume and this volume is exchuded to other chain segments. ramp 16. Braate Ri, std Pu ty led anual ead polymer ttn 8400 andthe be dat bp aad Solio: N= 4.000; 1 18 pn - = Isto Rene = M71 = C0! (54x30 my) = 974x109 m= 9.74 wm Re (Ev (SY cepa x10-2m) 97 2 Vi a - fy o(3) 01-2) com nest ton «ran Aber oti of nee i he rai again ec a be ee : Ged te rag rt Sauaredistence of e as rom te cenafan Oy te equa = , sHfiee] = here R isthe distance from the cea of mass ofeach c ¢ from the cea. of mass emeot my in he polymer molec Note tat fy haste dimensions of eth and is roughly he rads fe plymer cel ps ibe dems of shes polymer mos fof en wea, ZT MOE Is wt Glox unter (ESS) Br Gr ar coil polymer chain, iti Fouad tat 1 Renk, eo agh (U1) le 17.-Caenlate fora Uneae i 2 acute Ry aad R, for 4 nee polymere chain cotaaing 250 monomeric nis, ech Solution: Accatig 10 Bg, 101, Rang ME = OSAKA A = THES A Aone BU fee = MA 3 Deen ee, ee “eli toto eat we as aan in i te pati non a a ed tere el iain en ce dat cmd ee ceca i a ‘Theoretical calculations show that the values of Rime, R, nate a es of RF, oie shove pied bya tor = (“cs 6) cr 8). aed nd force 10952 1209 MACROMOKECUUES so that cas 0 = - 1B and F = VE. Hence, Reve = QM ad Ry = (63) i may be mentioned tat he dissolution ofa polymer ina solvent is often & very slow paces this is particularly the case with th highly crosinked network polymers. As the solven pemnetes the polymer network, considerable swelling ous. In some cases, after the inal swelling, the polymer dissolves inthe solvent aftr a coasiderable period of time. In polymer solution chemistry, ‘re often speak of ‘good solvents and ‘poor solvents’. In a good solvent, there is stronger Interaction between Qe solvent and the polfmer an betwen the solvent and the solvent or between the various segments of the polymer. On the ober hand, in a poor solvent, there is stonger interaction between the various segment of the palmer tan between the polymer andthe solvent ‘Thus, while in a good solvent, the polymer sretes ou, ie, ancols, in solution, in & poor salvent the polymer col upon ite ‘Let ws remark in passing thal the effectiveness of a solvent can also be measured by the value of the second virial coefficient B. Foran idea saan of two components 1 and 2 (I designating he solvent and 2th slut), Bae = V2? au Assume tat My=10* g mot, Since Vi for water is 18 cu? mot, hence, Bunt = 910" em? aol 72 Solvents for which B > Bj ae called good solvents fr that polymer and solvents for which <0 ate ealed poor solvents. For god solvents, Bis inthe range of 10° to 10° which is moch Inger than the ideal vale. "The polymer canbe preipated relatively easly from poo solvents, [MISCELLANEOUS SOLVED EXAMPLES ample 18. A protein sample cosas of on equimolar mixture of haemoglobin (M=15'S ky mot), tonuclese (Ml = 137 hg mol) and myoglobin (= 172 kg mat), Calculate the number-average aod tease average mans. Which greater Salton: Acentig 10g. 1, . Fy = OSB AAS) + 6385. x13-) 40-30 7 2ypAE wat we 0-5 + 05134035 = 18S hg mot 1550 g mt ' Acconig a, 2, 0:38 x t5-5) 40-333 03-7 40.383 «(17-2 (O35 x 155) 6 Vx 1ST) + (OD 9 17) th 56 bg mel Ta Teg > He xmgpe 1. Cae the ain vcsty pee i lene from the flowing rate vicsty doa hed aC C00 ke mw} 0002 ome 0006 008 ooo » 10 1208 1307 430 188 ‘Ate cacoate He ifthe Matk-Kube-Houwink Sharada constants are @=009 and K=1-7X10° mk" Soluion + fal = Klee? {Mark-Kut-Houwik-Sslorafa ote} ere Tle the vcosiy-average molar mss of the poles Inn vcs fq» the interept of the plat of =e vers cs found tat Inj = S010? a ag! in = (9) =e] = ag