(Amer «ann Susttuing for Wr Eg (A2.) ad imegrting ee Problem A2.1) lead 0 <7? 323/069 cas) ‘Since f* = 3/(2ni”), the RMS end-to-end distance is given by

smaller than te contour length nf by 8 factor cof nl, The value of being large, this difference is considerable and it indicates the ight coiled ate of flexible polymer chains. A polymer chain in dite solution can thas be picned a col, commonly altering its shape an size duet conformations changes under the action of random thermal moons. The angular brackets of < 72 > denote averaging ove al possible conformational ies evalabe to polymer molecules of the same molecular weight Sie diferences become more sinifian fo polymer samples vii are plydspere and contin chains of wie variety of chain lengths. This eal for ‘nother averaging, Chsin dimensions of polysperse near polymers are thas given bythe teraye RMS endtocnd distance <7? >!, where the bar indicates averaging de to chain polydispersity, whereas !? without bar epresets the RMS end-o-nd distance of & Single chain or monodisperse polymer sampleChapter 3 Polymers in Solution 3.1 Introduction ‘A number of important characteristics of polymers, such as molecular weight, chain length, branching, and chain stiffness, can be explored when the individual ‘molecules are separated from each other. Such studies therefore employ dilute solutions of polymers. However, the dissolution of a polymer also brings with it many new problems. For a correct interpretation of the behavior of polymer solutions it is essential to understand the thermodynamics of polymer-solvent in- teraction, We will therefore explore some of the basic underlying thermodynamic principles of polymer solutions in this chapter. A major part of the chapter will be concerned with methods of studying polymer solutions that deal with equilib- ria and can be fully described by thermodynamic relations. These include vapor “ pressure, osmotic pressure, and phase separation in polymer-solvent systems 3.2 Thermodynamics of Liquid Mixtures ee ee ee ate ae ey ce ee polymer solutions aze partial molar volume V; and partial molar Gibbs fee energy 1G. The later quantity is of special significance since itis identical to te quantity Coe i 1 (Foray Se ee ee ey =G en am12 Chapter 3 {lis evidently equal tothe molar Gibbs free energy G} of pure component iat the same temperature and pressure. ‘The chemical potentials ae the key partial molar quantities. The 4's deter mine reaction and phase equilibrium. Moreover al other partial molar properties and all thermodynamic properties ofthe solution ean be found from the p's if we ‘know the chemical potentials as functions of 7, P, and composition. “The free energy of mixing in the formation of a solution, AGrsix, i given by Ga = G- YG? ea where Gis the free energy characterizing the state of the solution and G7 repre- sents the free energies ofthe individual (pure) components forming the solution. Recognizing that chemical potential is equal to the partial molar Gibbs free energy, as shown by Eq, (31), and that the chemical potential of pure component i, nit is equal to simply the molar Gibbs free energy of pure component i.e, Gf atthe pressure and temperature of the system, itis easy to show from Eq, (3.2) that Ba LS “The partial derivative on the right hand side of Eq. (3.3) is the partial molar Gibbs _free energy change, denoted by BG; (Young and Lovell, 1990). ‘Tt may be noted that all known thermodynamic relations are also valid forthe pattial molar functions. Thus, the relation G =H ~ 7S in terms of partial molar functions is 6) ‘Therefore, from Bq, (3.3) mi = BG, = BA; ~ TAS; G3) For ideal solutions that form with a zero heat effect, BFZ; = 0. Hence for ideal solutions wih = BG, = -THS, (ex) {will be shown late that ideal entropy of mixing of two components, say, | and 2, is given by z Six Where nj and x; ate, respectively, number of moles and mole fractions of com- ‘ponent i. Partial ideal entropies of mixing can be obtained by differentiating Eq. (G7), Thus for component i, in general, =-R(mlnx: + malnm) en BS eee? Rinx, G8) Substituting in Eq. 6.6), ena = Ring, 6%Polymers in Soltion 13 “Thus, the change in chemical potential of the th component in n ideal solution depends only onthe mole fraction ofthat component in solution Inthe case ofa real solution, : » sh = Rind 6.10) where py and pf ae the pata vapor pressures ofthe ith component above the solution and above the pure component, respectively. Since fora themodynam cally stable solution p< pit follows fom Ea, (3.10) that pz < 0 oF j= ic. the chemical potential of ech component inthe solution i salle than that of the pure component Comparing Eqs. (39) and (3.10) we obtain, fran ies solution, pildh = 3 Gay Relation (3.11) was obtained empirically by Raoult and is called Raoult's law. Hence in idea solutions Raoult’ law hold ovr the entice range of compositions, this being represented by a straight line inthe vapor pressure composition curve (Fig. 3.1). In reality, most solutions do not obey Eqs. (3.9) and (3.11). Such solutions ae called nonideal or rea. Polymer solutions charactristiely display Sharp negative deviations from ideality, a canbe seen in Fig. 3. 'A method of estimating the deviation of solutions from ideality, suggested by Lewis, consists in substituting a certain function elled activity forthe mole fractions in all thermodynamic equations which are not valid fr real solutions. ‘Thus, instead of Eqs. (3.9) and (3.11) we may write ‘i wen = Su = RT Ina; G.12) = pip = a G13), ‘Theoretical procedures for deriving expressions for AGruix usually start with the construction of a model of the mixture. The most popular Flory-Hugeins theory, which was developed in the early 1940s, is based on the pseudolattice ‘model and many approximations (Flory, 1953). Though extremely simple, the theory explains correctly (atleast qualitatively) a large number of experimental ‘observations, and serves asa basis for other more sophisticated theories. Flory-Huggins theory is based.on splitting AGaix into an enthalpy term and an entropy term according to Eq. (3.14) and evaluating these two terms separately AGniz = AHpix ~ TASaix G14) ‘The entropy of mixing ASqiz is computed from the number of possible ar- rangements of the molecules on a lattice, while the enthalpy of mixing, Anis, is calculated from the change in interaction energies among molecular surfaces uring the process of mixing. Before turning to Flory-Huggins theory, itis con- venient to develop firs the theory for mixtures of low molecular weight solvents to gota better grasp of the principles involved.4a Chapter 3 Figure 3.1 Dependence of vapor pres- sure over a polymer solution on mote {action of components. 3.2.1 Low-Molecular-Weight Mixtures: van Laar Model Letus considera mixture of to substances A and B satisfying the conditions that molecules of A and B are identical n size and shape and (i) the energies of ike Ge, A-A or B-B) and unlike (.e., A-B) molecular interactions are equal. Such mixtures form deal solutions. Condition i leads to athermal mixing (i. AH (0), which also means that there are no changes in the rotational, vibrational, and vansatonal entropies and in the entropy of intermolecular interetions ofthe Components upon mixing. Thus, MSaix depends only upon the configurational (er combinatorial entropy change, ASant, whichis positive because the mimber odstngushable spatial arangements ofthe molecules increases when they are mixed. Hence SGux of Eq, (14) is negative and formation ofan ideal solution is favorable. “The methods of statistical mechanics can be used to derive an equation for Swat by assuming tha the molecules are placed randomly into eels that are of molecular size and are arranged inte form of thee-cimensional tice (rep- fesented in two dimensions in Fig. 32(a). The entropy $ of an‘assembly of Inolecues andthe total mmber {1 of distinguishable degenerate (ie. of equal nergy arrangements of the molecules are related by the well-known Boltzmann uation: = S = kind ei ‘where kis the Boltzmann constant. Since ASaix is equal to ASzo. applying Fa (3.15) the formation ofan ideal soltion one obtains AScost = KIN mig ~ Cn + InMs)] G16) where M4, 0g, and Opis are, respectively, the total numbers of distinguishable spatial arrangements ofthe molecules in the pure substance A, pure substance B, and the ideal mixture. All the molecules ofa pure substance being identical, there ccan be only one distinguishable spatial arrangement of them, thats, of placing NVPolymers in Solution ns eo[o[e[se[oje] + [OJoyo 3] ofefelofofofefo] —|ofojo| ) ofojolofefe|oje| joletet oO} e@[ole[ojojolelo} [olelo o ofelolelefolojo| folete alo e[ololojofe|ole| | fojofeojojetelo olole|e|o[o|o} ololeterete|6o olelololefofelo| —[ojofojojojofojo @ © Figure 32 Schematic representation of quasicystalline latice model for salutons. (2) Simple solution: mixture of molecules of equa siz, white circles representing the solvent ‘molecules and filed ctces the solute molecules. It is assume that solvent molecules can ‘exchange sites with solute molecules. Tis results in an increas in the number of Ways they ‘canbe arranged, and hence in an increase in entopy, £0) Polymer solution: mixture of solvent molecules (unfilled cirles) wit a polymer molecule composed of chain segments {ach segment represented by a filled circle) tied with chemical bons. Its assumed that solvent molecules can exchange sites with polymer chain segments, This results in an increase in entropy. (After Flory, 1953) indistinguishable molecules in a latice containing N cells. Thus 4 = 1 and Og and Eq, G16) reduces Swot = EnDnis Gun) The total number of distinguishable spatial arrangements of Ng molecules of and Ny molecules of B in a lattice of (Na +Np) cells is equal to the number of permutations of (V4 +Na) objects consisting of Na identical objects oftype A and Np identical object of type B, thet is, ia Na So = Na Substitution of a, (18) into Bg, 3.17) gives ae ‘(Na + Np)! A = Hn tA on) Applying Siting’ approximation lant = wiaw = 9 220 (Gor large N), Eq. G.19) leads to sa = nla Seg) + eine }] oan6 Chapter 3 Itis more convenient to deal with equations in terms of numbers of moles, m, and mole fractions, x. Inthe present case, these are given by na = MalNav, mp = NaiNay, m= m4 + Mw 822) xa = naling +a), 2p = malta + na) 623) “where Nay is Avogadro's number, Thus, Eq. (3.21) takes a simple form AScost = —RUnalnzy + nalnzs] 24) in which R(= KNay) is the universal gas constant. (It may be noted that since the configurational entopy of unmixed components is 270, Sais infact exeal to San ofthe mix) Since forthe formation of nidealslition, Six = ASwut and Hix = 0, 4, 6.14) becomes Gis = RT toalnsy + plas) 25) uation (3.25) provides the bass for deivation of standard thermodynamic relationships for del solution (©, Raoult lav). To make it more genealy “pleas this equation has to be andi for nonidealty of solution when tuning is nonathermal (Le. Aff # 9) de to nonequivalent intermolecular in- teractions caused by the socalled dispersion forces. The decrease in eneay due to imeractions is called the interaction energy. This energy 8 larger for poet molecules than for nonpolar mlecules Inthe liquid late defied above, each molecule as z contact points, 2 being the coordination number ofthe lates, In «mixture of A and B there are three ‘oper of contact namely, A-A. B-Band A-B ith interaction energies xa 55 fit a, respectively. (The tmodel implies that all contact points ofa molecule areequivalent) The enthalpy of mixing is ven by Adis = H - Ha - He 326) where H, Ha, and Hy represent the contributions of the contact energy to the ‘enthalpies ofthe mixture, pure component A, and pure component B, respectively Hand Hp can be calculated (Munk, 1989) from Hy = wNaernal 2 Hy = Waess/? 6.28) Where the factor 2 accounts for the fact that each contact involves two contact points. ‘Assuming that the number of heterogeneous contacts is Nag, we can thus write (Munk, 1989) for H = Napwas + (Na ~ Nasbona/2 + (Na ~ Nan )ons/2 (3-28) Substtation of Hy, Hp, and H from Eqs. (3.27)-(3.29) into Eg. (3.26) then yields Adlnix = Naslwas ~ (4a + nn)/2] = Nason -° (3.30)Polymers in Solution 7 where Awxe = Was — (waa + wap), representing the change in energy for the formation of an AB contact, is the excess contact energy of an AB contact. ‘The numberof heterogeneous contacts Nap can be easly estimated. I is equal to the number of contact points associated with A molecules multiplied by the probability pp that a neighbor of molecule A is molecule B (Munk, 1989), that is, Nap = Napa 63) For simplicity, pg is assumed to be the probability that any molecule (not necessarily a neighbor of molecule A) in the solution is a molecule B. This letter probability is equal to the mole fraction of component B in the mixture. Its use is justified only when the arrangement of molecules on the lattice is completely random, Combining Eqs. (3.30) and (3.31) and replacing pe by the mole fraction x5 of component B, which is equal to Np/(Na + Np), one obtains Adaix = Naxezhuns 632) Substitution of Nj from Eq, (3.22) then yield, AHinix = xanaNwzhons 633) ‘The product Nqy2Aw,p has a physical meaning. It represents an enthalpy change for the transfer of 1 mol of A (or B) from its pure state to an infinitely dilute solution in B (or A). Combining Eqs. (3.14), (3.24), and (3.33), and noting that Swix one obtains ao Scant RY (nly + mplnzg + nqxpNayzhenss/RT) (3.34) ‘The last term in this expression is commonly simplified by introducing the interaction parameter Xap, defined (Munk, 1989) as Yaa = Navchwgg/RT = Beogy/hT 635) According to the model, 4p is thus inversely proportionalto temperature, whereas ‘Awan is assumed to be independent of temperature, Note that Aus, and hence _xAp, can be either postive or negative, Combination of Eq. (3.34) with Bq. (3.35) yields Gig = RE (nglnay + mplnxy + naxayas) 3:36) Equation (3.36) describes the vn Laar model of solvent mixtures and i appli- cable only to mixtures of low-molecular-weight components with approximately the same molar volume. ‘The van Laar model fails to give realistic predictions of the thermodynamic properties of polymer solutions. This arises from the assumption made in this ‘model that the solvent and solute molecules ate identical in size. Flory (1942) and. Huggins (1942) proposed, independently, a modified lattice theory that takes into account the large differences in size between solvent and polymer molecules, in addition to intermolecular interactions.us Chapter 3 3.2.2 Polymer-Solvent Mixtures: Flory-Huggins Model In order to place both the solvent molecules and polymer molecules onto the same pseudolattice, it becomes necessary to consider the polymer molecules to be ‘chains of segments, each segment being equal in size to a solvent molecule. Tae ‘umber, ofthese segments in the chain defines the size of a polymer molecule and is given by the ratio of molar volumes V/V; (from now on we will assign the Subscript Ito the solvent and 2 tothe polymer solute). Hence o is not necessarily ‘equal tothe degree of polymerization, ‘The model assumes that each lattice cell is occupied by either a solvent molecule or a chain segment, and each polymer ‘molecule is placed in the latice so that its chain segments occupy a continuous sequence of cells (as indicated in Fig. 3.2(b). ——————eE Problem 31 Calulte, in terms of the ltce model ofthe Flo-Huggins theory. the umber of segments per polysiyrene motel of molecular weight 290,00 solved in {a)taluene and () metyl ety ketone (MEK) at 25°C, (Data: polymer density = 1.083 fem fa tolvene and L091 glem? in MK, calculated onthe assumption of aivity of Solumes toluene density = 0.861 gem; MEK density =0.799 glen all a 25°C] Answer: (@ Polysyrenatoluene Mz _ 290x108 got! n 085 80 Vi = (2gmoty(0:861 gear) Ye _ 2678x108 en? mo = 2.678% 10% cm? mot % 106,852 em? mot” 4) e gx 0% ca) Hi * “068s2@n8 mor = 78 (Pye MEK: : aa010% gmat ee pp = 290210 mY 9.6510 en! ma A ae ad rpm = sot ent matt 079960) (2.658108 cm? mol!) (0.1 ex? mor) In comparison, the degre of polymerization ofthe polymer = (2.90%10° g ma-"V(Q04 g = 7950 Inthe first stage, the Flory-Huggins theory derives an expression for ASzix ‘when AMfaix = 0. This involves the application of Eq. (3.16), but this time withPolymers in Solution ug ‘M > | because each molecule can adopt many different conformations (ue. dis- tinguishable spatial arangements of the sequence of segments). Hence for poly ‘mer solutions (considering the configurational entropy change ASyeq to be the only source of AS) one can write ASpie = kla(O2/ 02) 37) ‘The evaluation of 2, 92, and AS of Eq. (3:37) is rather complex. The cal- culations, considered in outline below, are based on the formation of a polymer solution by mixing N2 polymer molecules, each comprising segments in the chain, with Nj solvent molecules in a lattice containing N, + o> (= N) cals, ‘The polymer molecules are added tothe lattice one-by-one before adding the sol- vent molecules. ‘When adding a polymer molecule tis assumed, using s mean feld approxima ‘fon, that the segments ofthe previously added polymer molecule are distributed uniformly in the latice. The N; solvent molecules are added to the lattice after the addition of Np polymer molecules. However, since the solvent molecules are identical, there is only one distinguishable spatial arrangement of them obtained by placing one solvent molecule in each of the remaining empty cells. Consider- ing further the fact thatthe Np polymer molecules are identical, the total number ‘of distinguishable spatil arrangements of the mixture is given by On = WMD TEY we 338) ‘here 1 is the total number of possible conformations of the polymer molecule i and [Tis the symbol for a continuous product, which inthis ease is uy up us x ug ++ ay. The expression for yp given in 2 useful form by Flory is ao = for EPI al] 0m ‘The product of the quantities in the frst two pair of square brackets of Eq, (3.39) represents Mand s0 Eq. (3.37) takes the form ee ke Sux = ~K{Ni In) + NoIngo) Gan where ) and gare the volume fractions of solvent and polymer given by the fractions of the total number of lattice points occupied by solvent molecules and polymer segments, respectively OL = MIM +O) and gy = eNA/N +02) 3.42)120 Chapter 3 Tn terms of number of moles, Eq. (3.41) becomes Snax = ~Rfn Ing + n2lnds) (3.43) ‘This expression for polymer solutions is seen to be very similar to the comrespond- ing expression for ideal mixing of small molecules, ie., Eq. (3.24). The only difference is that in place of the mole fractions in Eq. (3.24) we now use the cor- responding volume fractions. It should be noted that Eq. (3.43) reduces to Eq (3.24) when Problem 3.2 Using te entropy change equation ofthe lattice model, calculate the change inentropy when equal amounts (100 g) of two components are mixed foreach ofthe fol- Towing systems: (a) toluene and meth] ethyl ketone (MEK); (0) toluene and polystyrene ‘of molecular weight 1.210%; and (2) polystyrene and poly(methy! methacrylate) each of molecular weight 10,000. Take the density ofeach component as 1.0 gem. Comment on the comparative entropy changes of mixing forthe thee systems. Answer: (@) Tose Bq, (2.24) let A and B cepresent toluene and MEK, respectively, Molar masses of A and B: Ma (CyHs)=92 gmol"!; Mp (C4Hg0)=72 g mot? (200 =) 400 @) Moles of AsndB: nq = 108) 1.087 mol, np = 0°08 — = 1.389 mol Sgmor} emo} 561 ‘Mole factions of A and B: x4 = 1.087(.087 1.389) = 0.439, x5 = 1-0.439) Spc = —(8314 J mol! K-"((.087 mol) in0.439 + (1.389 mot) In0.561) 4K (0) Ea, (643) is used for calculating Sais of polymer solution. 1m, = mq = 1.087 mal; mz = (100 g)/(1-2x10° g mol!) = 833%10-* mol “The polymer consists of segments, cdch of which can displace a single solvent molecule fron alatice sit. Thus, = Ms /(exV4), where Ma isthe molecular weight ofthe polymer that would have density pp in the coresponding amorphous state at the solution tempers- ture and V9 isthe molar volume ofthe solvent Using aproprite data the calculated values are (4.2%10° gmat!) 0x10? (O2gme) gens) EBC) coven | tore] (1.087 mot) = 1 = TroeTmoh + 130x105 eI IO man] ~ °° 62 = 10-050 = 050 Sn = ~(8.314 Jmol“! °K (1.087 mol) In 0.50 + (8.33%10~ mol in'0.50]Polymers in Solution oy (6) Ba, (343) applies also if ewe polymers are being mixed. In this cas, the number of segmens inte th component ofthe mixture is eleulated from a; = M/piV- where Y; is now a reference volume equal to the molar volume ofthe smallest polymer repeating ‘unit in the mixture. The corresponding volume fraction is = mi! Zr, For the given problem, my = np = (100 (10000 ¢ mol!) = 001 mol. The mola volume cof metiyl methacrylate repeating Unit ( = CsHy02) i aken a the reference volume (V). ‘Thus, yy = MCstaO "= Dens (10000 g mot!) an (1.0 gem-)(100 em® mot) 01% 100 * = Goretoo-+oorxiag “0% #2 = 25 Six = ~(8:314 J mol“ *K-Y[(0.01 mol) 205 + (0.01 mol) in0.5] ork ” ‘Comment: The entropy of mixing of polymers with solvent is small compared to that of micromolecules because there are fewer possible arrangements of solvent molecules and polymer segments than there would be ifthe segments were nos connected to each oer The entropy gain per unit of mixture is futher reduced drastically if two polymers are ‘mixed than if one of the component is #low-mmolecular-weight solvent, beeause both m and mare very small inthe former case. Having obtained an expression for AS, the second stage inthe development . of Flory-Huggins theory is to derive an expression for the enthalpy change, AFfnix. {or the polymer solution. This follows almost exactly the outline depicted for low. ‘molecular-weight mixtures in Eas. (3.26)-(3.33). The only difference now is in probability pz {ie., pa in Eq. (3.31)) that a given lattice point is occupied by 4 polymer segment. In this case, the probability must be approximated by the volume fraction go, instead of mole fraction ra. Thus, for a polymer solution the expression for AFigix reads [ef. Eqs, (3.33) and (3.35)] Alinix = midaNavzher = RTmérx ra G44) where x2 is the Flory-Huggins interaction parameter defined by Eq. (3.38). The interaction parameter y plays a very important role inthe theory of polymer solu- tions. Ifollows from Bq, (3.44) that y12 isa dimensionless parameter equal the ratio of the energy of interaction of the polymer with the solvent molecules to the kinetic energy RT, which should not depend on the concentration of a solution, ‘However, a more rigorous derivation reveals that y2 should be concentration de- ‘pendent. This dependence is a slowly varying function and the absolute value of 1x12 increases with increasing é,m2 Chapter 5 ‘A combination ofthe entropy term of Eq, (3.43) and the enthalpy term of Ea. (3.44) according to Eq, (3-14) gives the following expression for AGaix Gmix = RT (mynd + malng2 + mgzxia) G45) “This remarkably simple expression is the famous Flory-Huggins equation forthe Gibbs free energy of mixing, It has remained as the comerstone of polymer ther- ‘modynamics for more than six decades, Using Flory-Huggins theory its possible to account for the equilibrium thermodynamic properties of polymer solutions. However, the theory is only able to predict general tends and fails to achieve precise agreement with experimental data Tn dilute polymer solutions, the polymer molecules are isolated from each other by regions of pure solvent, ie, the polymer segments are not uniformly tistibuted in the lattice, Tn view ofthis, he Flory-Huggins theory is least satis factory for dilute polymer solutions and only applies to concentrated solutions or mixtures, Furthermore, the interaction parameter introduced to account for the f- fects of polymer-solvent contact interactions is nota simple parameter and should contain both enthalpy and entropy contributions, Additionally, as noted carir, it hhas also been shown to be dependent on the solution concentration, 3.2.2.1 Plory-Huggins Expressions for Thermodynamic Functions Once the analytical expression for AGnix is known, the calculation of chemi- cal potentials and other thermodynamic functions (activities, activity coefficients, vVrial coefficients, et.) is straightforward. For polymer solutions, we must apply Eq, (3.3) to Flory-Huggins equation (3.45), keeping in mind that volume fractions (are functions of the number of moles, as given by 6 = mln +072) 3.46) 2 = om|(m + o7m2) Gan [These relations result from Eqs. (3.42) by dividing numerator and denominator by the Avogadro number Nay.] Thus partial differentiation of Eq. (3.45) with respect to ny (note that both g and gz are functions of m) leads to the following relation for the solvent (see Problem 3.3): 1 : mii = BG, = RT lings + (1-5 be + x0 48) and partial differentiation of Eq, (3.45) with respect to ny similarly leads to the following relation for the polymer o-18, = BO, = RT (ing +(l-oi+ox’G] G49) A= x Gxn/3bder (350) X= xn + Oxn/dbder GSI) wherePolymers in Salation 13 Problem 33 Stating from Flory Hugains equation (3.45) show that forthe formation ofa soltion from a monodisperse polymer the partial molar Cibbs free energy of mixing ‘BG, forthe solvent is given by Ea, (3.48). Answer: ‘The Flory-Huggins equation (3.45) Gag = RT (nm ln6 + myIngs + migoxiad /ASGen) em Sins = mil, +m) ad 8 = hy + om andfrom Ea. G0: BG = = a BG, = er (sr tectnmy ~ mtaem + omy) a + pp alam ~ manny + m)) RG _ om my an ae any — In(rr + om) rom m =H 1 eee om GS ome ay + omy) + mma dee be Gi tomy des dn, Simplifying and substiating for da/dny, Ra 14D, yy [tt mt om Br tA Geaay tome gmm_ den _-om Gert oma) dey tas + om Rg pM EOM=M gy alt Ge 7 be + ESM oa — 68( 2) ts + [I +e (2 3 = wre where x 41 (0x12/6))mm Chapter 3 tn the simplest form ofthe Flory-Huggins theory, te parameter yi is inde- pendent of concentration, and doesnt depend onda Consequently, te Perefone vine ada equal and they are usually represented by the same Symbol. Frter replacing be factor by a = Vuh 52) where Vand V are the molar volumes of solvent and slut (polyme) respec Uvely Eqs, O48) and G49) are rewsiten as . vi 7 mi = Rtgs + (1B) +0] @s3) arlnes+(t-Z2}u «(pel 059 ree pains e ie wit Fy (12) 9 btn fe corresponding activities ofthe components. For example, the activity of the sol vent is given by ob mah er te can be shown hain the limit of extremely small volume fictions, the sighthand side of Eq, (35) sequal fo hy and Eq. (58) dhs reduces to the aon va for ideal solutions with actives aegul to ol fractions w na, = tc +(I- Pe tx G59) 3.222. Colligative Properties and Interaction Parameter x “Thermodynamic equations relating yy and ay to various colligative properties are found in any textbook on thermodynamics. The following relationships are ob tained on using the expression for wet Hatt = na 56 wat Ds om ee a os my na ox Inthese equations, AA; and AH are the latent heats of freezing and vaporization; Ty and Ty are the boiling and freezing points of the solution; 7s and 7 are the boiling and freezing points of the pure solvent; AT, (= Tp 7s) is the elevation inthe boiling point; AT (= 1j~T3) isthe depression in the freezing point; 1 is