5. MOLTEN SALT AND POLYMER SOLUTIONS 5.1. The Temkin Model.

Due to Coulombic forces ionic crystals are ordered in such a way that cations are only surrounded by anions and vice versa. An interchange of an anion and a cation in the lattice is energetically highly unfavourable. We can hence consider an ionic crystal to consist of an anion lattice and a cation lattice with no interchanges between the two. As there is no mixing between the two, the entropy will be given as a sum of a cation and an anion contribution. The Temkin model for molten salt mixtures transfers the ideas for a solid mixed crystal to the liquid, i.e. we assume that we here also have a "cation lattice " and an anion lattice so that S = S+ + S (5.1)

This is the general idea of the Temkin model which first was proposed by Temkin and later applied by Flood, Frland and Grjotheim. The ideal Temkin model then proposes that the mixture can be described by an ideal mixture of anions and an ideal mixture of cations. We define ionic fractions as: xNa+ = (5.2) We have from the previous equations for ideal mixtures
x c ln x c + x a ln x a ) Gmid = -TSmid = RT ( c a
i i j j i j

n Na +
+

xCl- =

nCl

H m = 0 where xci and xai are cation fractions and anion fractions, respectively. Using a mixture of NaCl and KBr as example: Gm = -TSm = RT (xNa+)(ln xNa+) + (xK+) (ln xK+) + (xCl-) (ln xCl-) + (xBr-) (ln xBr-))
o S NaCl = S NaCl S NaCl =

(5.3) (5.4)

S mix S + S = mix + mix = -R(ln xNa+) - R(ln xCl-)=-Rln (xNa+ xCln NaCl n Na + nCl

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RT ln aNaCl

= H T S = 0 + RT ln (xNa+ xCl-) (5.5)

aidNaCl = xNa+ xClGeneral formula:

m n a id Am Bn = x A x B

(5.6) This model is often surprisingly good. As an illustration of the formula let us calculate the activity of NaCl in two mixtures containing NaCl-NaBr and NaCl-KBr, respectively, with xNaCl = 0.9 in both mixtures: 0.90 NaCl - 0.10 NaBr: aNaCl = xNa+ xCl= 10.90 = 0.90

0.90 NaCl

- 0.10 KBr:

aNaCl = xNa+ xCl= 0.900.90 = 0.81

The Temkin model has some resemblance with the activity formulas used for aqueous electrolytes. We will similarly define an activity coefficient as aNaCl = xNa+ xCl- NaCl (5.7)

Deviation from ideality can, however, sometimes also be introduced by redefinition of the ionic species. A classical example is Flood and Urnes interpretation of the freezing point depression of KCl when adding MgCl2. A Temkin model of K+, Mg 2+ and Cl- will give the activity of KCl as aKCl = xK+ xCl- =
nK + n K + + n Mg 2 +

1=

n KCl = xKCl n KCl + n MgCl2

This model did, however, not explain the phase diagram.

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It was, however, assumed that MgCl2 reacted quantitatively with KCl forming the ion MgCl42- which can be defined by Raman spectroscopy MgCl2 + 2Cl- = MgCl42The activity of KCl is then given as:

aKCl

= xK+xCl- = 1

nCl nCl + n MgCl 2

4

x KCl 2 x MgCl2 x KCl x MgCl2

This activity function did explain the freezing point depression.

5.2.

Four-ion system with change in nearest neighbor interaction

Let us assume that we have the four ions Na+, K+, Cl-, Br-. We can assume these to take part in the equilibrium NaCl(l) + KBr(l) = NaBr(l) + KCl(l) and hence
a KCl a NxBr o = K = e-G /RT a NaCl a KBr

Choosing the pure solids as standard states G o is simply: (The Gibbs energy of the pure salts on the right) - (The Gibbs energy of the pure salts on the left) : NaCl(s) + KBr(s) = NaBr(s) + KCl(s) So is close to zero in reactions between solid compounds. The change in nearest neighbour interaction will make Ho and hence Go positive (since small-small and big-big is preferred). Introducing activity coefficients and skipping + and - indexes: aNaBr = xNaxBrNaBr the ion fractions cancel and one obtains:

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 KCl NxBr o = e- G /RT NaCl KBr

(5.8) NaBr KCl < NaCl KBr if Go > 0 for the exchange reaction. NB! We cannot set NaBr = Na+Br- as in aqueous solutions since in the above case the left hand term of Eqn. (5.8) will be identical to one. By only considering changes in nearest neighbour interaction it can be shown that ln NaBr = kNaBr (1 - xNa) (1 - xBr) (5.9)

This equation reminds a little of the equation for regular solution. It is an important difference, however, If we have a mixture of NaBr and KBr then xBr = 1 and In NaBr = 0, ): NaBr = 1. We do not have a change in nearest neighbour interactions since we have only Cl- ions, and we are back to the Temkin ideal mixture. Combining the two above equations: kNaBrxKxCl + kKClxNaxBr - kNaClxKxBr - kKBrxNaxCl = -Go /RT As this equation will be valid for all x it will also be valid for pure KCl, xK = 1, xCl = 1, xNa = 0, xBr = 0. Hence: k NaBr = -Go /RT Similarly: kNaBr = kKCl = - kNaCl = - kKBr = -Go /RT ln NaBr = -[Go /RT](1 - xNa) (1 - xBr) = -[Go /RT](xKxCl) (5.13) (5.12) (5.11) (5.10)

We can also introduce more complicated excess functions, but this will not be done in this text.

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5.3. Illustrating Problems The example illustrate that simple ionic phase diagram can be calculated from fundamental data with reasonable accuracy. NaF and KCl do not form any compounds, and there is no solid solubility in the system NaF-KCl. a) Assume the liquids to form regular Temkin mixtures, and, on the basis of the data below, calculate the liquidus temperatures for the liquid mixtures in equilibrium with solid NaF. (Use the Flood, Frland and Grjotheim's 1st approximation formula for calculation of activity). We find from JANAF Tables: NaF(l) + KCl(l) = NaCl(l) + KF(l), Go 800C = 5.5 kcal fus.H (NaF) = 7.8 kcal/mole Melting point of NaF: 996C. b) The following liquidus temperatures have been measured in the system NaF-KCl: Mole % NaF 90 80 70 60 50 Liquidus temp.C 900 841 814 785 754

Do these data fit the Temkin model for regular solution, used in problem a)? Solution to problem I: To calculate the liquidus temperature of a melt of NaF-KCl in equilibrium with solid NaF we have to calculate the activity of NaF in the melt. According to Flood, Frland and Grjotheim's I. approximation equation, the activity of NaF in the regular Temkin mixture is given by
o ln aNaF = ln (xNa+ xF-) + xK+ xCl- G

RT

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where xNa+ and xF- are the cation and anion fractions, respectively, and G o is the Gibbs energy of exchange for the given reaction at the melting point. xK+ = xCl- = (1 - xNa+) = (1 xF-) since only pure NaF and KCl are mixed. Combined with the cryoscopy formula we have:

ln aNaF = -

fus H ( NaF ) R

(1 / T 1 / T fus ( NaF ))

Putting in data we get T = 1195K or 922oC for T = 1139 K or 866C for T = 1098 K or 825C for

xNaF = 0.9 xNaF = 0.8

xNaF = 0.7 T = 1062 K or 789C for xNaF = 0.6 T = 1028 K or 755C for xNaF = 0.5

b) The calculated melting points fit the experimental results quite well at concentrations of KCl. 5.4.

higher

Polymer solutions We will now discuss solution properties of polymers in a solvent, the solvent usually having considerably smaller size and molecular weight. For solutions of polymers in a solvent the entropy usually differs from the ideal one, and becomes larger than corresponding to ideal solution. This is easily understood by considering the polymer in a low-molecular solvent. There are many more ways of arranging the polymers than if they are considered globular. The so-called athermal mixture model has been a useful approximation especially for polymer mixtures. One assumes
Hmix

=0

Gmix

= -TSmix

(5.14)

On a purely configurational basis without arbitrary assumption one is able to calculate the entropy of mixing from a lattice model. (See Guggenheim: Mixtures). The formula is involved but by using some approximations one arrives for one mole of mixture at the simple formula:
Gmix

= -TSmix

= RT(x1 ln 1+ x2 In 2)

(5.15)

(Florys approximation). 2 is the volume fraction of the polymer and x2 the mole fraction. The entropy of mixing for an arbitrary number of moles:
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n1V1o n2V2o n ln + n ln ) 2 Smix = -R( 1 n1V1o + n 2V2o n1V1o + n 2V2o

when neglecting volume changes. Partial quantities (
S mix ) n2 = S1 S1o = n1

(5.16)

n1V1o n1 (n1V1o + n 2V2o )((n1V1o + n 2V2o )V1o n1V1o 2 + - R[ ln n1V1o + n 2V2o n1V1o (n1V1o + n 2V2o ) 2
(5.17) + n2

(n1V1o + n2V2o )(n2V1oV2o ) ] n2V2o (n1V1o + n2V2o ) 2

S mix V1o o ( ) n2 = S1 S1 = - R [ ln1 + 2(1 - o )] n1 V2

(5.18)

og aktiviteten til 1
V1o RT lna1 = 1-1o = -T( ( S S o ) = RT [ ln1 + 2(1 - o )] 1 1 V2

(5.19) Mixing of a monomer and a r-mer 2 =

rx r x1 + rx r

1 =

x1 x1 + rx r

(5.20)

V2o r= o V1
RT ln a1 = RT [ ln1 + 2(1 - 1/r)] The activity coefficient, 1, is obtained as follows: a1 = x11 ln a1 = ln x1 + ln 1 = ln (1 - 2) + (1 - 1/r) 2

(5.21)

(5.22)

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ln 1 = ln

1 2 + (1 - 1/r) 2 x1 n1 + n 2 n + n2 2 1 ) + (1 - 1/r)2 n1 n1

ln 1 = ln (

ln 1 = ln (1 2 +

n 2V1o ) + (1-1/r) 2 n1V1o + n2V2o

(5.23)

ln 1 = ln (1 - (1 -1/r) 2) + (1 -1/r) 2 In Fig. 5.1 ln 1 is plotted versus 2 for different values of r.

Fig. 5.1. Solvent activity coefficient in an athermal polymer solution according to the equation of Flory and Huggins. Parameter r gives the number of segments in the polymer molecule. From eqn.5.19 we can see that for dilute solutions will n 2V2o V1o 1 ( )+ (1 o ) n 2V2o n1V1o V2 ln a1 ln 1+ o n1V1 since n2V2o/n1V1o 0

n 2V2o n2V2o V1o + (1 o ) = - x2 ln a1 n1V1o n1V1o V2

and a1 = e x2 x1

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Raoults law is approached in very dilute solution as expected. Remember, however, that for polymer solutions it is necessary that the volume fraction is small, not only n2/n1. For solutions of a high-polymer Eqn. 5.19 can often be simplified further. We assume

V1o V2o
and we obtain

<< 1

RT In a1 = RT(ln 1 + 2) ln a1 = ln 1 + 2, ln(a1/1) = 2 a1 = p1/p1o = (1 - 2) exp 2

(5.24)

(5.25)

The formula for S may also be valid if H mix 0, but then RT ln a 1 are no longer equal to T

( S1 S1o ) .
We will demonstrate the use of this formula. Gee and collaborators measured the vapour pressure of benzene in benzene rubber solution. Fig. 5.2 shows the vapour pressure as function of volume fraction 2 of rubber. We will first try a usual ideal model. Rubber do not have a clearly defined molecular weight but let V2o V2o us assume the values: o = 100 and o = 1000. V1 V1 From Raoults law: p1/p1o= x1 As p1/p1o in Fig. 5.2 is expressed in volume fraction we have to convert:

V2o (1 2 ) o o n V V 1 1 1 1 = = p1/p1o = n1 + n2 1V1o + 2V2o V2o 2 + o (1 2 ) V1

Examples: At 2 = 0.8 we obtain;

V2o V2o o o o = 100 gives p1/p1 = 0.96 and o = 1000 gives p1/p1 = 0.999 V1 V1
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The curves for varying values of 2 are given as a and b and the discrepancy gets larger the larger molecular weight is assumed. We will then try Flory's approximation in its simplest form (5.25). p1/p1o = (1 -2) e 2 For 2 = 0.8, p1/p1o = (1 - 0.8) e0.8 = 0.445

The full curve is given as c in Fig. 5.2

Fig. 5.2.

Dependence of the vapour pressure of the solvent in polymer solutions on the volume fraction of polymer. a; Raoult's law for r = 100. b; Raoult's law for r = 1000. c; Flory's formula (Eqn. 5.25). e; Eqn.5.29 b/RT = 0.43. : Experimental data of Gee and his collaborators for rubber/benzene.

We see that Flory's formula overestimates the vapour pressure depression but it is substantially better than any other Raoult or regular solution model. It is possible to obtain a still better fit by also introducing H different from zero and by a similar reasoning as for regular mixtures we arrive at the formulas (Guggenheim: Mixture) :
Hmix

= N1/N22 wN0 = x12b

(5.26)

Gmix

= RT(x1 ln 1 + x2ln 2)+ x12b

(5.27)

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By differentiation the activity of the solvent is obtained. This is often a measurable quantity: ln a1 ln a1

V1o ) + 22b/RT V2o ~ ln(1 - 2) +2+ 22b/RT

= ln(1 - 2) + 2 (1 -

(5.28) (5.29)

From Eqns. (5.23 and 5.26) an equation for ln 1 may be obtained ln 1 = ln (1 - (1 -1/r) 2) + (1 -1/r) 2 + 22b/RT (5.30)

In Fig. 5.3 activity coefficients of heptane in a binary mixture is compared with data calculated using Eqn. (5.30).

Fig. 5.3. Activity coefficients of heptane in the n-heptane(1)/polyethylene(2) system at 109C.

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