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J . Chem. SOC.,Faraday Trans. 1, 1988, 84(8), 2609-2618

Influence of Water on Pure Sorbitol Polymorphism

S. Quinquenet, C. Grabielle-Madelmont and M. Ollivon
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Organisation Moleculaire et Macromoleculaire, CNRSI ER286, BP28, 94320 Thiais, France

M. Serpelloni"
Roquette Freres, 62136 Lestrem, France
The behaviour of very pure sorbitol and sorbitol-water mixtures has been examined in relation to water content by both differential scanning calorimetry (d.s.c.) and a new thermal and dielectric analyser operating at microwave frequencies. A new hydrate has been isolated. Four different crystalline forms have been obtained from this hydrate and characterized by d.s.c. and X-ray diffraction. The influence of both temperature and water content on transitions from hydrate to other polymorphs has also been studied. Different types of water interactions have been evidenced from dielectric measurements for sorbitol and glucose, and comparisons of these, according to the physical states of the mixtures and hydrate properties have been made. For both molecules, the influence of water content on dielectric relaxation maximum temperatures has been studied and compared with the viscosity or the entropy. Non-congruency and possible deviation from stoichiometry are suggested for the new sorbitol hydrate. The dielectric properties of mannitol and sorbitol diastereoisomers have been measured at room temperature and compared. The glass transitions of sorbitol and sorbitol solutions have also been investigated down to 170 K by calorimetry measurements. The lowering of Tp with respect to water content is compared with isoviscosity curves.

In the solid state D-sorbitol, which is an acyclic polyol obtained by hydrogenation of D-glucose, exhibits monotropic complex polymorphism. Several polymorphs of sorbitol with different melting points are described in the literature but with neither agreement on number, nomenclature and properties nor purity and origin de~criptionl-~.vitreous A state is also observed.4 Recently, starting from ultrapure sorbitol, we described the evidence for four different crystalline forms characterized by X-ray diffraction, i.r . spectroscopy and d.s.c. m e a s ~ r e m e n t s . ~ The present study is concerned with sorbitol polymorphism and its relationship with water. We briefly describe procedures used to obtain a well defined, new hydrate and four different polymorphs. The relationship with water content was examined by d.s.c. and a new thermodielectric method at a microwave frequency of 2.43 G H z . ~The ,~ behaviour of these various crystalline species, of their metastable melts and aqueous solutions were compared with those observed for glucose and mannitol.

Experimenta1
Ultrapure sorbitol (purity 99.9 YO)was obtained by successive chromatography on Neosorb 70/02 (Roquette) on a simulated fluidized bed Duolite C204-type resin (Roquette, French patent 2 454 830) and by recrystallization from purified aqueous solution (70% by dry weight). The purity of sorbitol was checked by h.p.1.c. (Waters apparatus using a Biorad Q15S-type column and detection by refractive index). It crystallized into thin needles (ca. 1 mm long), the atomic composition of which, determined by microanalysis, corresponded to a non-stoichiometric hydrated form described below.
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Influence of Water on Pure Sorbitol Polymorphism

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Calorimetric measurements were carried out on a DSC4 Perkin-Elmer differential scanning calorimeter equipped with a Cryoson cooling system. The apparatus was calibrated for temperature and enthalpy measurements with lauric and benzoic acids and cyclohexane at rates of 4, 8, 20 and 40 "C mi^--'.^ Transition temperatures (T,) were taken at the onset of the transition. Special thermal treatments including isotherms were achieved either on Perkin-Elmer or Thermanalyse calorimeters. All water-sorbitol compositions are expressed in % water per 100% dry, pure sorbitol (w/w). Dielectric measurements at microwave frequency were measured with a new thermal analyser.' With this apparatus, complex permittivities of sorbitol or glucose were determined as a function of temperature on samples in the form of crystalline powders or melts placed in special Teflon sample-holders and isothermally on aqueous solutions in capillary tubing. With crystalline powders, in which measured values were less precise than with bulk materials since they depend to a small extent on the powder compactness, measured values are given in arbitrary units. With this technique, the dielectric constants E' and E" of water-sorbitol and watermannitol mixtures, melts and crystalline sorbitol or glucose were measured using the small perturbation method5v6of TE 0, 1, 3 (for crystals or melts) and TE 0, 1, 11 (for solutions or vitreous states) rectangular cavities excited at 2.43 GHz. Input power ranged from 6 W to a few mW according to the type of experiment, low power being used for isothermal measurements in the larger cavity. In these last experiments, each value is the average of 20 measurements, obtained by comparison with dielectric standards. The standards, measured at 21 "C, were chosen to maintain similar perturbations of the cavities. They were, respectively, decanol (E', 2.67; E", 0.413) for the small cavity and methanol ( E ' , 21.3; d , 13.8) and water (E', 78.15; E", 10.17) for the ' larger. When required, and especially with mannitol, the preheated capillary tubing was filled with hot and premelted mixtures, then sealed and rapidly cooled prior to measurement in order to keep the rapidly crystallizing mixtures in the metastable undercooled state.

Obtention and Characterization of Sorbitol Polymorphs

A, B and r polymorphic forms? were obtained from the hydrated form of sorbitol by the following thermal treatments. The A-form resulted from 80 days dehydration using phosphorus pentaoxide or from storage at 50 "C for 65 h in a closed sample-holder. B was obtained from the hydrate by dehydration at 50 "C down to 1 YOwater, cooling to room temperature followed by complete melting at 120 "C, then a 72 h crystallization at 62.5 "C. The r form was obtained from the A form after 12 h under vacuum at 85 "C. The maximum water loss reached 6.3 '/o in this last case. The solidified melt was obtained by cooling the undercooled liquid resulting from any stable polymorph melting, down to room temperature and storing the cooled material for a few days. However, the cooling of this undercooled liquid leads to a glass (see below). The calorimetric heating scans of polymorphs of pure and hydrated sorbitol are reported in fig. 1. In order to simplify the results and the presentation, and because of the importance of water in sorbitol crystallization, the hydrate will be reported here as a polymorph. Thermal data, with i.r. and powder X-ray diffraction recordings of the 5 polymorphs3 confirm the existence of several polymorphic species and allow their identification. X-Ray patterns of the I-, A and B forms are identical with those described by Park and Jeffrey.' The hydrated form displays a powder pattern which differs from the other p ~ l y m o r p h s As far as we know, the existence of this species has not been .~ reported in the literature.
t
Notation according to Park.'

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261 1

n
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" I
c v)

(1)

2 0.5-

3
t

O0 4

50

60

70
T/"C

80

90

100

Figure 1. Calorimetric scans of the sorbitol polymorphs (scan rate: 8 "C min-'), 1, solidified melt (1 ); 2, hydrate (1.3); 3, B-form (3); 4,A-form (3); 5, r-form (3); the numbers given in parentheses are y-scale expansion factors.

The structure determination from hydrate monocrystals was underway when this paper was being prepared. Since then, the hydrate structure has been completely determined from X-ray diffraction measurements and will be published elsewhere.' The first results, before any ,refinements,, indicated a, triclinic unit cell, with the following parameters: a = 16.39 A; b = 8 A; c = 4.81 A ; a = 94.14'; p = 95.78"; y = 100.95' l. ! and a unit cell volume of 679.84 A3.The hydrate densities both measured and calculated from the above data are 1.481 and 1.458, respectively. These data, as well as weight losses after thermal treatment (6.3 %), which suggest 2 water molecules are associated with 3 sorbitol molecules per unit cell, are now confirmed.'

Water Interactions in Crystalline or Molten Sorbitol

Interactions of water with crystalline or molten sorbitol have been examined at low water concentration (0-1 2 Yo) by measuring the complex permittivity dependence on temperature at 2.43 GHz. For simple dipolar relaxation, measurements during heating at fixed frequency are equivalent to frequency-sweeping at constant temperature. Anhydrous crystalline (whichever the polymorph considered) and hydrate sorbitol samples display very low losses and therefore were only examined at room temperature. Thin layers of hydrate samples maintained in 90 O/O RH adsorb 6-10 O h water in a few hours. Water adsorption was controlled both by weight increase and d.s.c. melting measurements. In these conditions, dielectric losses (e.g. E" 0.16) sometimes occur, resulting in self-heating to above the hydrate melting temperature. The dielectric behaviour is dependent on the adsorption rate. Slow adsorption leads to super-hydrated crystals with low dielectric losses (e.g. E" 0.002). Although hydration homogeneity is difficult to establish, it is thought that these samples were equilibrated. Pure hydrate samples kept under a dry atmosphere in order to remove part of their constituent water, whatever their final content also display low dielectric losses (e.g. E" 0.003). Therefore, the hydrate seems to accept positive or negative non-stoichiometry and only unequilibrated adsorbed water is responsible for dielectric losses (e.g. E" 0.98). This dielectric behaviour, which will be compared with dextrose monohydrate below, and the
86

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Influence of Water on Pure Sorbitol Polymorphism

30

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20
E M (0)

10

0
1
sorbitol (%)

30

20
El)

(0)

1 0

20

LO

60

80

100

mannitol (%)

Figure 2. Dielectric constant variations at 22 "C and 2.43 GHz: (a) sorbitol-water mixtures as a function of sorbitol content; (b) mannitol-water mixtures as a function of mannitol content.

thermal properties previously recorded3 (fig. 2) indicate that this hydrate is noncongruent and stoichiometric, with possible non-stoichiometry. In the melted state hydrated (6.3%) or anhydrous sorbitol has more important dielectric losses, resulting in dielectric heating and indicating that sorbitol molecules interact relatively more weakly in the molten than in the crystalline state, whatever the water content. The variations in dielectric constant us. temperature are presented in fig. 3. No water losses were observed when the samples were heated. Maximum dielectric losses were observed for anhydrous (E" 0.31) and hydrated (E" 0.27) samples at 85 and 65 "C, respectively.

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261 3

4
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f

...

.......... .......... .......... ..........

...............................
T

- 140
(2)- 120
0

3
El

- 100% - 80

......
1

1..

.............. ......-........ - E" -...

(3)- 6o - 40

- 20
0
01
I

'

(bl

-1

4 -

e' 3

0 '

/---Ell

- 0.5

el1

2/ '

//

1-

-0

Figure 3. ( a ) Kinetics of heating of anhydrous () and hydrated (.....) (6.3 YOwater) molten sorbitol at 2.43 GHz; (b) dependence of dielectric constant on temperature for anhydrous () and hydrated (6.3 YOwater content) (----) molten sorbitol samples at 2.43 GHz.

Although the temperature dependence of dielectric losses are often considered as more difficult to interpret than frequency plots, both determinations are c~mplementary.~. lo Moreover, for simple relaxations, maxima are observed by both techniques (frequency and temperature scanning) at the same values, provided no thermal event occurs in the explored temperature range. As multiple relaxations are expected for sorbitol," temperature spectrum deconvolution is not possible. However, the relative position of the two maxima can be compared together and with those of the sorbitol-water mixtures (see below). The strong negative temperature dependence of these maxima on the increased water content has already been observed for viscosity and dielectric relaxation of polyols near their glass-transition temperature" and can be related to changes induced by water insertion in the hydrogen bond distribution and to the associated decrease in viscosity. Therefore, water insertion in the undercooled liquid 'structure' can be considered either as plasticization or loss of structure of sorbitol.
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Influence of' Water on Pure Sorbitol Polymorphism

In their careful analysis of carbohydrate dielectric relaxations, Tait et a1.l' separated three relaxation times for glucose solutions which were linearly dependent on solution viscosity. The relaxation times (7) of these substances cs. temperature ( T ) obey simple Vogel-Tammann-Fulcher (VTF) equations where A and B are constants and T, is a temperature close to the temperature at which the liquid entropy curve extrapolated below Tg would intersect the crystal entropy curve. BIT, can be approximated to 12.7.1 The 85 "C value observed for pure sorbitol at 2.43 GHz is ca. 20 "C above the expected value deduced from VTF equation. The 0.6 YOwater retained by sorbitol used in ref. (10) cannot account for such a difference since T = 65 "C was found for the relaxation maximum of the 6.3% water sample. Nevertheless, addition of the value obtained in the microwave region to those previously reported at lower frequencies keeps the same good correlation coefficient ( r = 0.986), showing no excessive departure from VTF law at high temperature and frequency.

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Comparison with Glucose and Glucose-Water Mixtures

Since the properties of glucose are well known4, 11-14 and because it forms a hydrate, the dielectrical properties of glucose and glucose-water mixtures were studied. Glucose samples were submitted to the same treatments and examined under the same experimental conditions for comparison with the results observed for sorbitol and its new hydrate. Both pure anhydrous glucose and glucose monohydrate undergo very slight losses at 2.43 GHz as observed for sorbitol and sorbitol hydrate. However, monohydrated or anhydrous glucose in the molten state, as previously observed for sorbitol, are subject to substantial dielectric losses. Fig. 4 (a) and 4(b) represent, variations in dielectric constant during dielectric heating as a function of time and temperature, respectively. This similarity between the properties of the two substances is also observed in the hydration of the monohydrate beyond its stoichiometry as shown in table 1. These results show that water exerts a similar effect on both sorbitol and glucose. At room temperature, these dielectric effects of water on glucose have previously been observed by Abadie et al.14The very weak losses observed for glucose monohydrate, as well as for the new sorbitol hydrate, show that this water must be considered as a constituent. This type of water is easily distinguished from the sorbed water which displays higher losses. Note also that the maximum relaxation frequency of glucose melts are observed at higher temperatures than for sorbitol. This could be related to stronger hydrogen bonds between glucose molecules. Thus, the thermodielectric analyser used in this study for sorbitol and glucose, although less informative than frequency measurements, can be considered as an alternative method for rapidly obtaining essential information about states of water.

Dielectric Behaviour of Sorbitol and Mannitol Solutions

Dielectric properties of sorbitol and mannitol solutions have been examined at 22 "C and 2.43 GHz and the measured dielectric constants us. sorbitol and mannitol concentration are reported fig. 2(a) and 2(b). For both, the permittivity decreases as the polyol concentration increases. The corresponding losses initially increase up to ca. 50 % polyol then decrease sharply at ca. 65 %. This behaviour is similar to that of solutions of glucose or sucrose, but different from that of glycerol measured at 1 and 3 GHz.13The high E" values observed for ca. 1 : 1 mixtures have been explained by water hydrogenbond stabilization by the polyol hydroxy groups.13 These correspond to the relaxation frequency maxima, since 2.43 GHz is intermediate between pure water (17 GHz) and

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5.0

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4.0 -

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3.0 -

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8
(b)
*

1.0

//

. 0.8

//
3.0 .
El

.0.6
fl)

2.0 .

. 0.4

1.0.

- 0.2
50 100 150

O20

Figure 4. (a) Kinetics of heating of anhydrous (----) and monohydrated () molten glucose at 2.43 GHz; (6) dependence of dielectric constant on temperature for anhydrous (----) and molten glucose at 2.43 GHz. monohydrated (--)

sorbitol (1 KHz) or mannitol relaxations. Moreover, the E maximum value of ca. 22, corresponds to an average of the free water and sorbitol or mannitol loss maximum values. Finally, despite marked physico-chemical differences, such as in the respective mannitol and sorbitol solubilities (sorbitol is 3.5 times more soluble in water than niannitol), and in the less marked differences, e.g. the hydrodynamic volumes, solution viscosity and hydration,15-16 solution dielectric behaviour of these diastereoisomers the is similar.

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Influence o Water on Pure Sorbitol Polymorphism f

Table 1. Qualitative comparison of the dielectric properties of sorbitol and glucose in the microwave domain (2.43 GHz)."
molten product
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hydrate slow hydration rapid hydration

hydrate stoichiometry

anhydrous

anhydrous

hydrated

sorbitold glucosed
a

+-b

+ +

+ +

+, dielectric losses are high enough to allow self-heating (see fig. 3 and 4); -, low dielectric losses, self-heating is less than 10 "C. * Depending on the extent of hydration and the presence or absence of sorbed water (see text). 'Weak with evaporation. Dextrose monohydrate is a Roquette Co. industrial product with traces of impurity; sorbitol hydrate is pure with a 3:2 sorbitol : water stoichiometry.
Influence of Water on Sorbitol Glass Transition The influence of water on the glass transition temperature (T,) of sorbitol which has been investigated down to 170 K by d.s.c., is shown fig. 5. T, depression as a function of water
content was expected since water reduces glass viscosity and acts as a plasticizer of sorbitol17 by increasing the free volume and hydrogen-bond exchange possibilities. Moreover, the decrease in Tp agrees with that expected for binary mixtures,18assuming the Tg for pure water is probably close to - 140 OC.19 It can be considered here as the 'copolymer ' of a water-sorbitol 'ideal mixture'. At the glass transition point, water-sorbitol mixtures, whatever their water concentrations, reach the same critical vis~osity.~' Thus, it is not surprising that the curve in fig. 5 is similar to the isoviscosity curve observed by Angel1 et aL4 Levine and Slade20 have found, by extrapolation of the water crystallization peak enthalpies to zero, T and W; values, which are the glass-transition temperature and L concentration limits of the glassy domain, respectively, at -43.5 "C for 0.23 g incongealable water per g sorbitol. These values are in good agreement with our data (AT = 12 "C) taking into account the different methods of determination and sorbitol purities. T, determinations for pure sorbitol vary within ca. 10 "C depending on the method and conditions chosen along with, often unknown, variations in the effective water content of the sorbit01.~ Delayed water crystallization has also been observed for sorbitol-water mixtures. This well known phenomenon, which is generally considered as a devitrification process2' and which has already been observed for glucose,21 glycerol22and other sugar solutions, occurs for sorbitol on heating at a few tens of degrees above the glass-transition temperature with water-rich mixtures, over WL, e.g. for >, 70% water. Over the domain in which water crystallization is possible and below the hydrate water concentration there is a zone in which water is rendered incapable of freezing by the high sorbitol concentration, often referred to as 'unfreezable or unfrozen water ' . 1 7 This water is often wrongly called 'bound water',23 despite the lifetimes of the water-substrate bonds being shorter than in bulk water (in the ps range). Conversely, the high water concentration cannot be considered as inhibiting sorbitol crystallization, since sorbitol self-inhibits its own crystallization (it exhibits an ' undercooling ' temperature of ca. 100 "C3and, by lowering the mixture viscosities, water favours the crystallization of sorbitol hydrate and polymorphs. However, both water and sorbitol act as 'structure breakers' to each other since strong hydrogen bonds inhibit their respective separations and crystallizations and thus do not permit phase separation. Indeed at low temperature, close to q,supersaturated solutions become so viscous that

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J
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10

20

30

40

50

60

water (YO)

Figure 5. Effect of water content on the glass transition temperature Tg of pure sorbitol. N is the average number of water molecules per sorbitol molecules in aqueous mixtures.

any crystallization is inhibited. In this domain, the glass transition must correspond to a blocking of sorbitol and water molecules leading to a glassy, metastable structure exhibiting only very short-range order.20 Thus, the relaxation peaks following glass transitions (data not shown) were attributed to the melting of this weakly organized part of the glass.3 Continuous depression observed as a function of increased water content indicates, as well as the dielectric behaviour of water-sorbitol mixtures shown before, that water and sorbitol are co-participating in the glassy state (fig. 5 ) . Therefore, both this co-participation of sorbitol and water in the glassy state and in the undercooled liquid mixture, along with high viscosity and the existence of a maximum dielectric relaxation for pure molten sorbitol indicate that a complete analysis of the dielectric relaxations of water-sorbitol mixtures, which is not possible with data determined us. temperature, should not only take into account possible water relaxations but also possible sorbitol relaxations. At high sorbitol concentrations (0-70 % water in sorbitol-water mixtures), three kinds of crystallization are possible depending on the relative proportions, temperature and pressure,24namely water, hydrate and pure sorbitol polymorph crystallizations. Water crystallization may occur at high water content and low temperature. The polymorphs crystallize only at very low water concentration and high temperature. Hydrate crystallization occurs for intermediate values. Therefore, influence of medium viscosity on crystallization is evident, and in this respect sorbitol behaves exactly as other sugars and polyols. However, the influence of water on viscosity is variable : increase in water concentration leads to decreased viscosity, when its influence on crystallization processes is different and depends on whether water or sorbitol is crystallizing. Other parameters influence crystallizations, such as the purity and thermal properties of the constituents, but these have not been studied to any great extent. From the investigation of solid-state sorbitol using a variety of techniques, the occurrence of four different crystalline forms has been confirmed, including a hydrate a n d at low temperature, a vitreous state which leads to a particularly complex polymorphism. The characterization of the hydrate, its two water and three sorbitol

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Influence of Water on Pure Sorbitol Polymorphism

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molecules per the unit cell, complicates the study of its relationship with water. However, the general behaviour observed for sugar and polyol solutions, melts and vitreous states, which is mainly the dependence of properties on the viscosity of the system, is also observed for sorbitol. It has been shown that the use of our new thermal and dielectric method helps in this respect. The examination of water-sorbitol mixtures, by the way of calorimetry and dipolar relaxation in the microwave domain, proves the existence of different types of water-sorbitol interactions depending mainly on the physical and thermodynamic state of the system i.e. whether crystallized, in solution (stable), melted or vitreous (metastable).

S. Q. was supported by a joint grant CNRS-Roquette Freres Company. We thank Mrs Gillier and Mrs Neuman (Universite Paris-Nord) for the determination of the hydrate structure, and Mr Comini (Roquette Freres) for i.r. spectra.
References
1 Y. J. Park and G. A. Jeffrey, Acta Crystallogr., Sect. B, 1971, 27, 2393. 2 J. Sztatisz, S. Gal, L. Fodor and E. Pungor, J . Therm. Anal., 1977, 12, 351. 3 S. Quinquenet, M. Ollivon, C. Grabielle-Madelmont and M. Serpelloni, Thermochim. Acta, 1988, 125, 125. 4 C. A. Angell, R. C. Stell and Z . Sichina, J . Phys. Chem., 1982, 86, 1540. 5 M . Ollivon, IEEE-Microwaves Theory and Techniques Int. Symp. (St Louis, USA, 1985), p. 645. 6 M. Ollivon, S. Quinquenet, M. Seras, M. Delmotte and C. More, Thermochim. Acta, 1988, 125, 141. 7 M. Ollivon and R. Perron, Thermochim. Acta, 1982, 53, 183. 8 H. Gillier and S. Quinquenet, in preparation. 9 P. Sixou, P. Dansas and D. Gillot, J . Chern. Phys., 1967, 64, 834. 10 C. A. Angell and D. L. Smith, J . Phys. Chern., 1982, 86, 3845. 11 M. J. Tait, A. Suggett, F. Franks, S. Ablett and P. A. Quickenden, J . Solution Chem., 1972, I , 131. 12 J. B. Hasted, in Aqueous Dielectrics (Chapman and Hall, London 1973). 13 B. D . Roebuck and S. A. Goldblith, J . Food Sci., 1972, 37, 199. 14 P. Abadie, R. Charbonniere, A. Gidel, P. Girard and A. Guilbot, J . Chim. Phys., 1953, 50, 46. 15 A. Mayaffre, R. Bury and M. Chemla, J . Chim. Phys., 1976, 83, 637. 16 J. R. Grigera, J . Chern. SOC.,Faraday Trans. I , 1988, 84, 2603. 17 F. Franks, Properties of Water in Food.y, ed. D. Simatos and J. L. Multon (NATO Asi Series, 1985), p. 497. 18 A. J. Kovacs, Fortschr. Hochpolym. Forsch., 1963, 3, 394. 19 D. R. Macfarlane, Cryo-letters, 1986, 7, 136. 20 H. Levine and L. Slade, Water Science Rez;ieu.s,ed. F. Franks (Cambridge University Press, 1987), vol. 3, pp. 79-185. 21 Water, A Comprehensive Treatise, ed. F. Franks (Plenum Press, New York, 1982), vol. 7. 22 D. Simatos and M. Faure, in Water Relations of Foods, ed. R. B. Duckworth (Academic Press, New York, 1975), p. 193. 23 F. Franks, Cryo-letters, 1983, 4, 73. 24 T. Atake and C. A. Angell, J . Phys. Chem., 1979, 83, 3218.

Paper 712077; Received 23rd November, 1987