PRINOPLES OF PHYSICAL CHOMBTRY Ea ts To me pace he nr pres lve, te blag pit cao andthe ema $l comet oo you sf lien (iy = 504 kgm a lune (> Saige Sra OO YH ra 2; fr ee Kym DENK man he per pres eee "The mule tation ofthe plyme soe by 5 E0300 10g wat) FOGGE-Ox 10g wor) + 99-0 5901S gmarh ~ HOKI0S ‘Aig he cocnatin © of te pl nly m, cut -0 «10? g mot o . te 2a ite ee, rai res eigen by oe = ph = (86105370) = 699x102 Pa ‘The boiting point elevation ‘8 given by. : . {P= k= OK mr! emrKtot smote pese phen by T 104K rr © aD 10 wt ea) (0-088 da am K mot) 8 K)xC-O12108 Pa we = 00x09 Py e notice that the vapour apes depression ae except PESUE lovey, Biing point elevation (and alo freeing pin extremely smal for po i experimental mely iymer solutions and it would be difficlt to measure them rere Osmotic presi are, however, sfcienly large fo eagerness e sample 21. tthe 128 studied ws sfc, raceatitgation set is traentcegaone-up he edie aplacemeat (rn) of bovis scum slbumia he RencHK RCH,CHX + CHy=CHX —» R-(CHlyCHX), and so on, ‘The rate of the disappearance ofthe monomer M is given by 9 np Lae ‘These chain propagation steps are of the steond order and very rapid 3. Chain termination is achieved by the recombination of two free radicals, vi, 5 R{CH;—CHX), + (XCH—CH)-R- —?— R-(CH,—CHX0,-(KCH—CH,),-RPRINGPLES OF PHYSICAL CHEMISTRY r tow concato,we cin reasonably asume of prouton ie ti at of sapere Ge seal state pasa a, oe Att) = (RP (t4) Hone, RI = Gey? ye i (ui ‘Substituting for (R] into Eq. 113, we obtain ee aM] 7 09 «4 (4) wane 9 oe We die te Kinetic hain egy he she ra of oe atte of nat ‘9. Kean also be det a he amber opening natal ne ne y= calle. ae . ll eae ‘Also the probability p for the addition of ’ 'YP for the addition of another monomer to the growing chain radical i given - ht) AIM KER) ayy “a aM) {a vnyt polymerization, piso he order of 0559, 4 Kinetics of Condensation Polymerization, Coaer the reaction Ma + My —¥ Maia where m, mate integers greater thas one. The monomer My may be removed by reaction wi ne enon ceo he mag tt el a with any ober mae pre aM) y a HUMP + [MyJMQ) + ~ i) a A119) The net rate of proton ofthe dime is give by AM) Lange 5 a Say HD (em The firs erm on the right hand side of to monomers We coy ie tan sie f a. 120 ses he rate of formation ofthe diner fm Crag nears ny HOW Ot tee rae of fematn of tener, ey eye att) dt ‘Adding these equations, we obtain aS) 1° Mg) o]- Mg SM) «a = ot ” {S| e 22) MACROMOLECULES IC [MJ is the total concentration ofthe moaomers inthe beginning and (Mx) that of al the molecules at time f, the Fraction fof the reaction that has ocurred at time ¢ 1= [os Bo nity (2) 2 Heme, om Ey. 12 and 13, We ain ofa = MMA? -) . (Moe Iegraion els, I = a The concentration ofthe n-ne i gen by IM = Mb HD? ad “Matar Mass Distribution In Step-Growth (Condensation) Polymerization es Consider linear polymer tht might be produced by the condensation of a hydroxy acid HO-{CH)--COOH to produce a poet. Lethe monet be represented as AB to symbolize the two fimetonl groups. Then, if we cosier a polymer ie tams ARAB AB— the bond (—) indicates that the end-group B (a COOH group) is attached through an ester linkage to the end-goup A (ie OH) on another molecule. Nex we ask wha isthe probability hat the polymer contains units ? Let p be te probability tht the end-group B is esterified and let us assumed ths prbubity oes not depend on how many AB uns ae atached tothe AB ni of interest, Thea the probaly of an ester linkage at postion |i p, the probably ofan ester linkage at positon 2 {balsa p. The probably that both linkages are preset is given By te product ofthe independent probabilities or p®. If there are £ units in the polymer, there are k-I ester linkages and the Frobabilty ip, However, the probability tht enf-roup Bis not Linked is ~ p. Thus, ifthe Flecule i termina fe F-1 nk, the probability mast be (I~) PF. This probably must be qual NIN where isthe numer of maecols hata Kos Vig and Wis the otal umber of molecules. The, the moe actin, x of mes, is given by a= ppt an 128) Sut te value of Ni fom Bq. 127, Ba. 128 becomes =0-p)Eih 0)