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A-157

J. Chem. Thermodynamics 1981, 13, 8 9 ~ 8

H e a t - c a p a c i t y m e a s u r e m e n t s of
aqueous solutions of m o n o - , di-,
and tri-saccharides using an
isoperibol t w i n c a l o r i m e t e r
F. KAWAIZUMI, N. NISHIO, H. NOMURA, and
Y. MIYAHARA
Department of Chemical Engineering, Faculty of Engineering,
Nagoya University, Chikusa-ku, Nagoya 464, Japan

(Received 1 May 1979; in revised form 23 July 1980)

An isoperibol twin calorimeter of dry-shield type was constructed and the specific heat capacities
of D ( - )-fructose, D ( + )-glucose, D ( + )-galactose, D ( + )-mannose, D ( + )-lactose, D ( + )-
maltose, and D ( + )-raffinose in aqueous solution have been determined at about 303 K. The
partial molar heat capacity at infinite dilution C~,2 = C~,+ was determined by the least-squares
application of the relation: mCp,, = bm + cm2. The specific heat capacities of the solutes (except
raffinose) in the solid state have also been measured from 270 to 325 K using an adiabatic
scanning calorimeter. C~,2 and (AC~,2 = C~.E- C*,2) are positive for all compounds and increase
from mono- to tri-saccharides. The additivity parameters for C~,2 of saccharides are different
from those for other organic solutes. The results are discussed in relations to other properties
such as hydration number and diffusion constant.

1. Introduction
During the past few years much progress has been achieved in the determination of the
partial molar heat capacity of solute at infinite dilution, Cp,~ 2" Measurements have
been accumulated and are now accurate. The assignment of the contribution of ionic
or non-ionic groups in a molecule to the partial molar heat capacity of the molecule
as a solute has been discussed. (1-3) In spite of the rapid development of solution
calorimetry, measurements of partial molar heat capacities of saccharides are scarce.
They are desirable from chemical and biological points of view. In addition, a notable
deviation has been observed between observed and calculated values of partial molar
heat capacity in the application of additivity parameters to sucrose, a representative
saccharide.(2) In the present paper, values of partial molar heat capacities for the
monosaceharides: D ( - )-fructose, D( + )-glucose, D(+)-galactose, and D(+)-
mannose, the disaccharides: D ( + )-lactose and D ( + )-maltose, and the trisaccharide :
D(+ )-raffinose, will be presented. The determination of the specific heat capacity of
these aqueous solutions has been carried out using a laboratory-constructed
isoperibol twin calorimeter of the dry-shield type.
To allow speculations about the structural change of water caused by the addition
of solute, the intrinsic contribution of the solute, C~.2, must be subtracted. A search of

0021-9614/81/010089 + 10 $01.00/0 © 1981 Academic Press Inc. (London) Ltd.


6
90 F. KAWAIZUMI, N. NISHIO, H. NOMURA, AND Y. MIYAHARA

the literature for specific heat capacities of saccharides in the solid state was in vain.
Thus the determination of this quantity was also done as a supplement to the present
work.
Prior to the present work, the authors have made measurements of the specific heat
capacities of several kinds of non-electrolytes in aqueous solution34' 5)

2. Experimental
MATERIALS
All saccharides used were extra-pure grade reagents supplied from Nakarai Chemical
Co., Ltd. The water contents of reagent were determined from the decrease of mass
caused by drying for 24 h in a vacuum electric oven held at about 365 K. Maltose and
raffinose, which contain respectively 1 and 5 hydration water molecules per
saccharide molecule in the crystalline hydrate, had respectively 0.3 and 0.06 mass per
cent of water in the anhydrous samples. As will be seen by the results of the
calorimetry of solids, the relations between cp* of the saccharides and temperature can
be represented by smooth curves, and an abrupt change which would be ascribed to
the dehydration process was not observed. The water contents of the other samples
were similar to or less than those for raffinose. For the study of the heat capacities in
the anhydrous solid state, the specimens were dried and kept in a desiccator. For the
solution calorimetry, the undried chemicals were used and the molality of the solution
was corrected taking account of the water contents of the samples.

SOLUTION CALORIMETRY
The specific heat capacities of aqueous solutions of the saccharides were determined
with a new laboratory-constructed isoperibol twin calorimeter. Figure 1 shows the
schematic representation of this solution calorimeter. The aluminium block of the
calorimeter, with dimensions 30 c m x 30 cm × 30 cm, was supplied from Sumitomo
Light Metal Indhstrials. The firm contact between cap D and Dewar vessel E of
figure 1 makes impossible the passage of air or vapour from and to the inner part of the
Dewar vessel during the measurements. Into one of the Dewar vessels, 100 g of the
solution to be examined is introduced, while the other contains always 100 g of pure
water as a reference liquid. The heaters in the two Dewar vessels are connected in
series. The temperature differences between the two solutions in the Dewar vessels are
detected by the thermistor, amplifed by a laboratory-made thermistor bridge, and
then recorded on a strip-chart recorder. The measurements were carried out under
the following experimental conditions: (i), the aluminium block, kept at
(303+0.1) K, was placed in an air-bath whose temperature was controlled to be
lower than that of aluminium block by about 1.5 K ; this was done so as to establish a
small temperature gradient between calorimeter and the environment; (ii), the e.m.f.
applied to the terminals of the heating circuit was 20.00 V ; the electric power to the
heating circuit was supplied from a stabilized source, Hewlett Packard Model 6266B ;
(iii), the temperature rise due to the heating in the Dewar vessel was 1 to 2 K ; (iv), the
difference of the temperature rises in the two Dewar vessels in 5 min was examined;
HEAT CAPACITY OF_AQUEOUS SOLUTIONS OF SACCHARIDES 91
A

C ~

[ _
1 '

M ~ - t

FIGURE 1. Isoperibol twin calorimeter. A, Cover made of bakelite; B, urethane foam ; C, heater wire in
a rubber tube; D, cap of the Dewar vessel made of Derlin (polyacetal); E, Dewar vessel; F, glass tube
containing heater; G, glass tube containing thermistor; H, magnetic stirrer chip; I, magnet; J, bakelite
plate to reduce the conduction of heat generated in motor; K, aluminium block;L, motor; M, support
made of wood.

the time of 5 min was read off on the recorder chart from the instance of the sudden
change of electric potential ; it was found that the values of the potential change AV in
5 min, obtained directly in the experiments, depend on the slope of the base-line in
the period prior to the measurements. F o r each solution, measurements were
repeated six times and the values of AV under the condition that the slope of the base-
line is zero were estimated.
The calibration of the calorimeter was carried out with the aid of suitable standard
solutions. F o r this purpose aqueous solutions of NaCl and urea were chosen because
they have been used as standards in solution calorimetry and their specific heat
capacities are known precisely, t6) A mass of 100 g of solution was weighed. The
calibration curve of the calorimeter obtained as a relation between the potential
difference and the specific heat capacity of the solution is illustrated in figure 2. The
heat capacities are estimated by interpolation of values found in the literature/6) The
results for two different solutes are in excellent agreement. The curve in figure 2 can be
represented as a quadratic form:
cp = A + B ( A V ) + C ( A V ) 2, (1)

Using a pair of heaters having resistances of 45.45 and 45.42 f~ we obtained the
values: A = (4.1293+0.0011) J K -1 g - l , B = (-0.06561+_0.00073) J K -1 g - 1 V - ~ ,
and C -- (0.00115 +_0.00013) J K - ~ g - 1 V - 2. The contribution of the second-order
term is very small. The r a n d o m errors in c v amount to +_0.004 J K -~ g-1.
92 F. KAWAIZUMI, N. NISHIO, H. NOMURA, AND Y. MIYAHARA
' i |

4.]

7~ 4£
e~O

7
V.
~ 3.9

3.8

0 1 2 3 4 5 6 7
Av/v

FIGURE 2. Calibration curve of the twin calorimeter using aqueous solutions of CO(NH2)2 and of
NaC1. AVis the change of potential of the thermistor bridge during 5 min. ©, Urea; Q, sodium chloride;
@, water.

Introduction of 100 g of pure water in each Dewar vessel does not produce the result
that AV = 0. This phenomenon o f residual heat-capacity difference might be mainly
ascribed to the inequality of the masses of the two Dewar vessels; one is 207 g, while
the other 191 g.

CALORIMETRY OF SOLIDS

The determination of the specific heat capacity of the saccharides was done in the
temperature range 270 to 325 K in Professor Naito's laboratory of N a g o y a
University. An adiabatic scanning calorimeter was used. Mr Takahasi, a co-worker of
Professor Naito, performed the measurements. The details of the calorimeter and the
experimental procedures are to be found elsewhereF )

3. Results
SOLUTION CALORIMETRY
The values of the specific heat capacities of the aqueous solutions of saccharides
obtained in the present work are listed in table 1. The limiting partial molar heat
capacity of the solute, Coo
,,2 = Cp,¢,
°O can be directly estimated by the extrapolation of
apparent molar heat capacity Cp,, against molality m. However, the present authors
HEAT CAPACITY OF AQUEOUS SOLUTIONS OF SACCHARIDES 93

TABLE 1. Specific heat capacities cp and calculated values of apparent molar heat capacity Cp. ~, of aqueous
solutions of saccharides as functions of molality m

m cv Cp,, m cv Cp,, m cp Cp,,


molkg -1 J K t g ~ j K - l m o l - X molkg - 1 J K - ~ g - l J K lmo1-1 molkg - 1 J K - l g - l J K - l m o l - 1

glucose, C6H1206, M = 180.16 g mol 1


0.2552 4.071 313 0.5517 3.978 352 0.8729 3.883 361
0.3420 4.041 327 0.5972 3.964 355 0.9467 3.866 367
0.3985 4.028 348 0.7064 3.926 350 1.0976 3.820 362
0.5028 3.983 330 0.8002 3.896 349 1.1111 3.808 352
mannose, C6H1206, M = 180.16 g mol -~
0.3504 4.048 357 0.7469 3.907 341 1.1409 3.798 350
0.4768 3.996 336 0.8658 3.875 348
0.6036 3.955 343 1.0085 3.830 344
galactose, C6HxzO6, M = 180.16 gmo1-1
0.3487 4.039 330 0.7288 3.915 344 1.0991 3.829 372
0.4725 3.999 340 0.8612 3.883 356
0.5869 3.975 361 0.9820 3.850 362
~uctose, C6H1206, M = 180.16 gmo1-1
0.2102 4.091 324 0.5773 3.989 390 0.8504 3.930 415
0.3251 4.056 353 0.6516 3.969 393 0.9202 3.893 391
0.4518 4.022 378 0.7085 3.959 404 0.9966 3.885 405
0.5117 4.001 375 0.7811 3.936 398 1.0954 3.870 416
lactose, C12H2201~,M= 342.30 gmo1-1
0.2221 4.011 617 0.3748 3.917 643 0.5241 3.827 639
0.2849 3.968 618 0.4230 3.894 662
0.3249 3.949 646 0.4692 3.863 650
maltose, C12Hz2Oll, M = 342.30 g mol -~
0.2474 3.991 611 0.3852 3.916 659 0.5411 3.816 638
0.2886 3.965 617 0.4315 3.873 619
0.3411 3.934 627 0.4864 3.848 637
raffinose, C18H32Ot6.5H20, M = 594.5 gmo1-1
0.0345 4.136 870 0.1344 4.032 945 0.2310 3.940 952
0.0674 4.102 934 0.1665 4.001 949 0.2648 3.908 947
0.1009 4.066 937 0.1996 3.967 942

have calculated the values o f C p,


°~2 by least-squares fitting to the relation :

mCp,, = bm+cm 2. (3)

T h e i n t e n t i o n in e m p l o y i n g this m e t h o d is to a v o i d the o v e r e m p h a s i s o f the results


o b t a i n e d in the dilute region where the uncertainties of Cp will increase. F i g u r e 3
shows the relation b e t w e e n m C p , 4, a n d m for m o n o s a c c h a r i d e . The curve for fructose
differs f r o m those o f o t h e r m o n o s a c c h a r i d e s .

HEAT CAPACITIES O F SACCHARIDES IN T H E SOLID STATE

The results o f the d e t e r m i n a t i o n o f the specific h e a t capacities of the saccharides in the


solid state o b t a i n e d o n the same samples used in the present w o r k are s u m m a r i z e d in
94 F. KAWAIZUMI, N. NISHIO, H. N O M U R A , AND Y. M I Y A H A R A

400

3OO
7

-e- 200
d-

100

0 ~
0 0.5 1.0
m/mol kg -1

FIGURE 3. Relation between apparent molar heat capacities and molality for the monosaccharides.
O, Fructose; 0 , glucose; O , galactose; O , mannose.

TABLE 2. Specific heat capacities of saccharides in the solid state as a function of temperature

c*/J K - 1 g- 1

T/K fructose glucose galactose mannose lactose maltose

265 1.09
270 1.15 1.11 1.06 1.10
275 1.18 1.14 1.10 1.08 1.10 1.15
280 1.20 1.16 1.12 1.11 1.13 1.17
285 1.22 1.20 1.15 1.13 1.16 1.20
290 1.24 1.20 1.16 1.15 1.19 1.22
295 1.26 1.22 1.18 1.17 1.20 1.25
300 1.28 1.23 1.20 1.19 1.22 1.27
305 1.30 1.26 1.21 1.20 1.24 1.29
310 1.31 1.29 1.25 1.22 1.25 1.32
315 1.33 1.31 1.27 1.24 1.27 1.33
320 1.35 1.33 1.26 1.28
325 1.36 1.36 1.29 1.32
HEAT C A P A C I T Y OF A Q U E O U S SOLUTIONS OF SACCHARIDES 95
table 2. No measurements were made on raffinose because of troubles in the
apparatus.

ESTIMATION OF THE HEAT CAPACITIES OF SACCHARIDES IN THE


SOLID STATE
The specific heat capacity of raffinose was estimated. The starting point is the method
proposed by Dobratz t8~ for gaseous organic materials: to the heat capacities arising
from the stretching and bending vibrations of C-C, C - O , C - H , and O - H bonds, are
added the contribution of internal free rotations of C - C and C - O H bonds, and the
translational and rotational heat capacities 4R. The calculation for a monosaccharide
is as follows. The numbers of bonds taken for the calculation of the stretching and
bending vibrations are for C-C, C-O, C - H , and O H bonds: 5, 7, 7, and 5,
respectively, and that taken for the internal rotation is 6 as a whole. The values
calculated in this method are, 222, 409, and 600 J K - 1 m o l - 1 at 303 K, respectively
for mono-, di-, and tri-saccharides. The agreement between experimental and
estimated values is good. This value of 600 J K - 1 m o l - ~ was, therefore, adopted as a
value of the molar heat capacity of solid raffinose. Obviously the estimation
procedure lacks theoretical rigour.

4. Discussion
Final results of the present work, Cp~,2 and C*, 2, are presented in table 3, where AC~,2
is defined as
oo ,
AC22 : Cp, 2 - Up, 2. (4)
In table 3 are shown the values for sucrose at 303 K, CT. obtained from the data of
Gucker et al. (9) and Cp,2
,
from the data of Anderson et v,~
al. (i0) The values of Cp,2
oo
for

TABLE 3. Limiting partial molar heat capacities C~,2 of saccharides in aqueous solution at about 303 K,
and increments AC~,2 = (Cp. ~ 2- Cp.
* 2)

C.~2 C~2 AC2:


j K -1 mol-1 J K -1 mol-1 J K -1 mol-1

fructose 352_+ 8 232_ 3 120


galactose 324-+ 10 217 + 3 107
glucose 331 + 7 224--+3 107
322.6"
mannose 337-+ 5 216-+3 121
lactose 619 ___16 420-t- 6 198
maltose 614 -+ 20 438 -+ 6 176
sucrose 655 b 433.8 c 221
raffinose 931-+ 7 600a 331

" Calculated from data in reference 11 at 298.15 K.


b Calculated from data in reference 9.
c Reference 10.
d Estimated by the method shown in the text.
96 F. K A W A I Z U M I , N. N I S H I O , H. N O M U R A , A N D Y. M I Y A H A R A

glucose determined in the present work seem compatible with one found in
literature.t11)
The first thing to be noted in table 3 is that both Cp~2 and AC~,2 are all positive,
increasing with the dimensions of the saccharides. Cp~2 can be used to make guesses
about structural changes accompanying the dissolution of a solute. (4) In this sense, all
of the saccharides studied in the present work would be classified as "structure-
forming" in water, and the "structure-forming" ability seems to become greater with
the degree of polymerization. Positive values observed for AC~,2 ( - C H 2 - ) for organic
molecules have been interpreted in terms of the hydrophobic interaction of a - C H z -
group with solvent water. (4' 5) However, positive values of AC~,2 for the saccharides
and the increase of this quantity from mono- to tri-saccharides observed in the
present study can not be expressed simply as hydrophobic interaction, as six - O H
groups are contained in a monomer unit of saccharide.
Among the monosaccharide, the value of Coo p, 2 for fructose is larger than those of
others. According to an n.m.r, study, the equilibrium configurations of glucose,
galactose, and mannose in heavy water are substantially pyranose. (12) Fructose
dissolved in water is considered to be in equilibrium among five- and six-membered
rings, and ~- and 13- forms, while in the solid state, it takes only the 13-fructopyranose
form. One might consider that the deviation observed for the C p,OO2 value of fructose
from those of the others is due to the difference of the isomeric composition in the
aqueous solutions of monosaccharides. This kind of discussion, however, must be
deferred until sufficient information concerning the equilibrium compositions of the
saccharides in the aqueous media is available. As for the variation of Cp~2 in
stereoisomers of other saccharides, sorbitol and mannitol attract our attention. A
calculation based on the reported measurements on aqueous solutions of these two
samples(11) leads to 413 and 441 J K - 1 m o l - 1, respectively for the values of C~,2 tbr
sorbitol and mannitol at 298.15 K.
Among the disaccharides, sucrose, which has a fructose unit, shows the largest
values of Coop,2 and AC~. 2. This might be related to the results observed for
monosaccharides.

COMPARISON OF THE ADDITIVITY PARAMETER OF SACCHARIDES


WITH THOSE OBTAINED FROM OTHER ORGANIC SOLUTES
Nichols et al. (2) have estimated the group contribution to the partial molar heat
capacities on the basis of their measurements on the mono- and di-functional
compounds of the type H-(CH2)n-X and X (CH2)n-X, where X is OH, NH2,
C O O H , etc. The application of the additivity parameters to saccharides without
taking account of the cyclization effect of - 30 J K - 1 m o l - 1 gives rise to the results :
C p,~°2 for mono-saccharide: 193, for di-saccharide: 311, and for tri-saccharide,
429 J K - 1 m o l - 1. The estimated values for tri-saccharide amount to less than half of
the values determined by experiments. On the other hand the numerical values shown
in table 3 indicate that the average differences in C~,2 between di- and mono-
saccharide, and tri- and di-saccharides are 293 and 302 J K - 1 m o l - 1, respectively.
Therefore it is concluded that, with regard to C~,2, the additivity parameters of
HEAT CAPACITY OF AQUEOUS SOLUTIONS OF SACCHARIDES 97

saccharides differ from those of other organic molecules. This difference is possibly
because the g r o u p - c o n t r i b u t i o n values have been derived for the cases where polar
functional groups o n a molecule are isolated, while in saccharide, two or more
functional groups are in close proximity.

COMPARISON O F AC~,2 VALUES WITH THE RESULTS O F HYDRATION


NUMBER AND THE D I F F U S I O N C O E F F I C I E N T

I n table 4 are s h o w n the values of AC~, 2 d e t e r m i n e d in the present work, the


h y d r a t i o n n u m b e r h, a n d the diffusion coefficient D in a q u e o u s solutions. As the term
" h y d r a t i o n n u m b e r " is defined according to the m e t h o d of m e a s u r e m e n t , a n y
discussion of h y d r a t i o n n u m b e r s should be d o n e a m o n g values o b t a i n e d by the same
method. T h e h y d r a t i o n n u m b e r s s h o w n in the third c o l u m n of table 4 are those

TABLE 4. Comparison of AC~,2 with hydration numbers h, and diffusion coefficientsD

AC~.2 h(298.15 K)a D(298.15 K)


J K -1 mol-1 10-~ cm2 s-2

fructose 120 3.8 b 7.00 d


galactose 107 4.30 c
glucose 107 3.5,b 3.67 c 6.75,d 6.728 e
mannose 121 3.30 c
lactose 198 6.28 c
maltose 176 4.2,b 4.89 c
sucrose 222 3.8 b 5.23,d 5.209 e

raffinose 331 6.2 b 4.339 e

aHydration water is defined as water moleculesbonded to solute which have the same compressibilityas
that of ice.
b Reference 13.
c Calculated using data in reference 14.
d Reference 15.
e Reference 16.

d e t e r m i n e d from the compressibilities of the solutions, a n d they c o r r e s p o n d to the


n u m b e r of water molecules a r o u n d a solute molecule of which the compressibility is
a s s u m e d to be equal to that of ice.(13~I" The v a r i a t i o n of h from m o n o - a n d di-
saccharide is n o t so large as that of AC~. 2, which changes nearly p r o p o r t i o n a l l y with
the degree of p o l y m e r i z a t i o n of saccharide. Shiio ° 3~ explained the observed variation
of h as follows. The effects o f - O H groups are d o m i n a n t in h y d r a t i o n . The m o l e c u l a r
c o n f i g u r a t i o n of a di- or tri-saccharide is considered to decrease the n u m b e r of free
- O H g r o u p s because of i n t r a m o l e c u l a r h y d r o g e n b o n d i n g or steric h i n d r a n c e a m o n g
two m o n o m e r s . O n the other h a n d , as m e n t i o n e d above, AC~, 2 m a y reflect the degree

t Corresponding t o AC~,2, a parameter, AK~ {=/(~-K2(pure state)}, where/(~ is the partial molar
compressibilityof solute, may be adopted for the discussion. However, K2(pure state) does not change so
much with the specimensas does K~. It follows that the comparison of the quantity AC~,2with K~ in place
of AK~ is on a sound ground. Although the compressibility is one of the bulk properties of a solution,
compressibility measurements and therefore the hydration number calculated from them can reflect the
solvent structure in the vicinity of solute molecules3TM
98 F. KAWAIZUMI, N. NISHIO, H. NOMURA, AND Y. MIYAHARA

of the structural change of water originating from the dissolution o f solute. A n d the
effects induced b y the addition of solute are proportional to the molecular size of
saccharides as suggested by the variation o f AC~, 2.
The smaller values of AC~, 2 might c o r r e s p o n d to a more disordered state in
solution, in which the solute can m o v e m o r e freely and the diffusion coefficient
becomes larger. It might be possible to consider the interpretation of the smaller
values of D observed for sucrose and raffinose in terms o f the larger volumes ofdi- and
tri-saccharides, as illustrated by partial m o l a r volumes. °4)

The authors wish to express their thanks to H. Ohgashi, chief of N a g o y a works of


S u m i t o m o Light Metal Industrials. They are also grateful to M r S. Takahashi for the
measurements of the heat capacities of saccharides in the solid state. This w o r k has
been supported by grants given to Y.M. from Asahi Glass F o u n d a t i o n for Industrial
Technology.

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8. Dobratz, C. J. Ind. Eng. Chem. 1941, 33, 759.
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10. Anderson, G. L. Jr.; Higbie, H.; Stegeman, G. J. Am. Chem. Soc. 1950, 72, 3798.
11. Bonner, O. D.; Cerutti, P. L. J. Chem. Thermodynamics 1976, 8, 105.
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