See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/249017754

Temperature and Concentration Dependence of

Heat Capacity of Model Aqueous Solutions

Article in International Journal of Food Properties January 2003

DOI: 10.1081/JFP-120017845

CITATIONS READS

10 4,146

2 authors:

Murat O Balaban Arthur A Teixeira

University of Auckland University of Florida
216 PUBLICATIONS 4,147 CITATIONS 96 PUBLICATIONS 1,280 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Triticale seed properties View project

All content following this page was uploaded by Murat O Balaban on 15 March 2014.

The user has requested enhancement of the downloaded file.

 120017845_JFP6_0_R1_21703

INTERNATIONAL JOURNAL OF FOOD PROPERTIES

Vol. 6, No. 0, pp. 120, 2003

1 Temperature and Concentration Dependence

2 of Heat Capacity of Model
3 Aqueous Solutions

4 Roger Darros-Barbosa,1 Murat O. Balaban,2,* and Arthur A. Teixeira3

1
5 Food Engineering and Technology Department, Unesp-Paulista State University,
6 Sao Jose do Rio Preto, Sao Paulo, Brazil
2
7 Food Science and Human Nutrition Department and 3Agricultural and Biological
8 Engineering Department, University of Florida, Gainesville, Florida, USA

9 ABSTRACT

10 Heat capacities of binary aqueous solutions of different concentrations of sucrose,

11 glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a
12 differential scanning calorimeter in the temperature range from 5
C to 65
C. Heat
13 capacity increased with increasing water content and increasing temperature. At low
14 concentrations, heat capacity approached that of pure water, with a less pronounced
15 effect of temperature, and similar abnormal behavior of pure water with a minimum
16 around 30
C40
C. Literature data, when available agreed relatively well with experi-
17 mental values. A correction factor, based on the assumption of chemical equilibrium
18 between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to
19 correct for the water evaporation due to temperature rise. Experimental data were fitted
20 to predictive models. Excess molar heat capacity was calculated using the Redlich
21 Kister equation to represent the deviation from the additive ideal model.

22 Key Words: Please supply. Q1

*Correspondence: Murat O. Balaban, Food Science and Human Nutrition Department, University of
Florida, Gainesville, Florida 32611-0370, USA. E-mail: mob@gnv.ifas.ufl.edu.

DOI: 10.1081=JFP-120017845 1094-2912 (Print); 1532-2384 (Online)

Copyright # 2003 by Marcel Dekker, Inc. www.dekker.com
 2 Darros-Barbosa, Balaban, and Teixeira

23 NOTATION

24 ai ; bi ; c i Regression coefficients in Eq. (12)

25 ai;0 ; ai;1 ; ai;2 Parameters of Eq. (15)
26 Ai Temperature dependence parameter in Eq. (14)
27 Aw Water activity
28 B Parameter of the Chen model in Eq. (7)
29 Cp Specific heat capacity (J g1
C1)
30 CpE Excess molar heat capacity (J mol1
C1)
31 Cpm Molar heat capacity (J mol1
C1)
32 dH=dt Heat flow (J s1)
33 dT=dt Heating rate (
C min1)
34 m Mass (g)
35 mS Molality of the solution (mol kg-water1)
36 Mww Molecular weight of water, 18.016 (g gmol1)
37 Mwair Average molecular weight of dry air, 29 (g gmol1)
38 n Parameter of the Chen model in Eq. (7)
39 P Total pressure (Pa)
40 P1 ; P2 Total pressure at temperature T1 and T2 respectively (Pa)
41 Pw Water vapor pressure (Pa)
42 S Solute concentration (g solute 100 mL-solution1)
43 T Temperature (
C)
44 X Mol fraction in the liquid phase (mol mol1)
45 Yw Mol fraction of water in the gas phase (mol mol1)

46 Subscripts

47 air Air
48 evap Evaporated
49 ref Reference
50 s Solute
51 sa Sample
52 w Water
53 1, 2 Components 1 or 2 for the binary solutions

54 Superscripts

55 E Excess function
56 o Pure component

57 Greek Letters

58 a; b Parameters of the Norrish and Miyawaki et al. models in Eq. (6)

59 be Parameter of the Chen model in Eq. (7)
 Heat Capacities of Aqueous Solutions 3

60 DT Temperature interval, 0.1
C

61 DHevap Enthalpy carried by water evaporated (J)
62 gw Activity coefficient of water in the liquid phase
63 l Latent heat of water (J g1)

64 INTRODUCTION

65 Heat capacity plays an important role in thermal processes and refrigeration. Heat
66 loads, processing times, and equipment size are influenced by the products heat capacity.
67 Heat capacity is affected by temperature, pressure, and composition.
68 The accurate prediction of thermal properties of non-electrolyte (sugars and pectin),
69 weak electrolyte (organic acids), and electrolyte (inorganic salts) solutions and their
70 combinations is important to a number of food engineering, processing, and quality
71 control applications in the sugar and syrup industry, juice and beverage industry, and
72 related areas. However, such data are scarce in the literature and restricted to a few discrete
73 temperatures and concentrations. Predictive models often do not consider molecular
74 interactions.
75 Heat capacity is a useful thermodynamic property because its change may be directly
76 related to the watersolute interactions. Different solutes behave differently in response to
77 temperature and concentration depending on their chemical structure and electrolyte or
78 non-electrolyte behavior.
79 Reliable estimation of the effect of temperature, concentration, and the type of solute
80 on specific heat are important for accurate predictions in food systems with complex
81 composition.
82 Adiabatic calorimeter, method of mixtures, comparison calorimeter, and differential
83 scanning calorimeter (DSC) are common techniques to measure specific heat of food
84 materials. Measurement by DSC is suitable for temperature dependence studies. Tem-
85 perature is scanned in a preset range at a fixed rate. The difference of heats required for
86 the sample and the reference is measured and recorded. Sources of error may include
87 sample size, since it assumes uniform temperature in the sample, and heating rate in terms
88 of the response of the system to the temperature rise. In addition, proper sealing of the
89 capsule and the effect of temperature might be a problem. Temperature rise during testing
90 increases vapor pressure within the capsule and therefore, volatile compounds, such as
91 water, may escape from the sample in the form of vapor. When the vapor pressure of the
92 sample, even in a hermetically sealed capsule, reaches a significant level, the enthalpy of
93 evaporation even a small amount of sample into the headspace of the sealed capsule will
94 significantly increase the apparent heat capacity of the sample. The magnitude of the error
95 will depend on the properties of the sample, as well as on the ratio of sample volume to
96 headspace volume in the capsule. For many substances, the magnitude of the error in a
97 0.01 cm3 sample in a 0.03 cm3 capsule approaches 1% as the vapor pressure reaches 50
98 100 kPa. Because of the gradual onset of this error, it can often go unnoticed until errors
99 far greater than 1% have been reached. It should be mentioned also that the accuracy of
100 DSC measurement on heat capacity is considered around 3%. Therefore, heat capacity
101 measurements using DSC for a sample, which generates a vapor, should be terminated
 4 Darros-Barbosa, Balaban, and Teixeira

102 below a temperature for significant vaporization, or viewed with extreme caution. Reports
103 of any mathematical correction to address this issue have not been found in the literature.
104 Our eventual objective is to develop predictive correlations for heat capacity as a
105 function of pressure, temperature, and composition. Therefore, this work is an initial step
106 towards this objective. A better understanding of the pressure effects on food and food
107 constituents is dependent on its influence on thermodynamic properties, which are scarce
108 in the literature. This area is intended to be the continuation of the present work.
109 The objective of this study was to investigate the temperature and concentration
110 dependence of the heat capacity of model solutions, and to fit experimental data into
111 predictive equations. The aqueous solutions investigated were binary solutions and
112 combinations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts of
113 potassium chloride, calcium chloride, magnesium chloride, and potassium phosphate
114 monobasic. A method to calculate a correction factor is proposed to accommodate for the
115 effect of water that evaporates into the headspace of the sample holder due to increase of
116 water vapor pressure with temperature. Coefficients of mathematical equations were
117 determined by fitting the experimental data providing predictive models. In addition,
118 excess molar heat capacity expressions using the RedlichKister equation were used to
119 represent the deviation from the additive model.

120 MATERIALS AND METHODS

121 The heat capacity measurements were performed using a differential scanning
122 calorimeter DSC-2920 from TA Instruments (New Castle, DE) with cooling system.
123 This system measured the differential heat flow between a sample and an inert reference.
124 The sample and reference were subjected to controlled heating or cooling in a controlled
125 atmosphere. The purge gas was helium with a flow rate of 93 mL min1. By using the
126 sample-encapsulating press, the liquid sample was prepared within a hermetic sample
127 capsule. The sample mass was in the range 1214 mg. Sealed capsules containing samples
128 were weighed before and after every run to assure capsule integrity. Based upon a series of
129 preliminary runs, a method was created that held the sample isothermally at 12
C for
130 5 min without freezing the sample (to account for the transient period to reach the desired
131 starting temperature, 5
C), and then heated at a rate of 7
C min1 to 70
C.
132 The DSC calibrations consisted of the baseline slope (heating an empty cell through
133 the entire temperature range of the experiments), the cell constant and the temperature
134 calibrations (from the run of a calibration material, in this case pure water, through its
135 melting point). To obtain accurate results, the calibrations had to be checked and repeated
136 periodically.
137 The specific heat of a given sample was then determined by creating a baseline profile,
138 a standard substance (pure sapphire-Al2O3) profile, and a sample profile using the same
139 method described above. From the thermograms (resulting heat flow vs. time or
140 temperature recorded at 0.2 sec intervals), the heat capacity was calculated by using
141 ONeills method.[1] The samples were run in duplicates. The accuracy of the Cp
142 measurements was estimated to be 3% on the basis of the measurement of the Cp of
143 pure water.
 Heat Capacities of Aqueous Solutions 5

144 Solutions were prepared with analytical grade reagents from Synth (>99% purity,
145 Diadema, SP) using double distilled water, on a weight by volume of the solution basis,
146 with 0.1 mg accuracy for mass. Chemicals were not submitted to further purification or
147 dehydration. The concentrations were in the range from 1% to 65% (w=v) for sugar
148 solutions, from 0.1% to 10% (w=v) for acid solutions, and 0.05% to 5% (w=v) for
149 inorganic salt solutions. Binary aqueous solutions of sucrose, glucose, fructose, citric acid,
150 malic acid, KCl, CaCl2, MgCl2, and KH2PO4 were prepared. Other combinations were
151 tested for component interaction and predictive analysis.

152 DATA ANALYSIS

153 The Cp measured with the DSC was derived from the heat flow measured using
154 Eq. (1), in the temperature range from 5
C to 65
C, calculated at each 0.1
C temperature
155 interval, with a total of 615 data points for each sample, even though the sampling rate
156 used allowed for a shorter temperature interval. The Cp values were further averaged for
157 two replication runs.

Cpsa mref dH=dtsa

1
Cpref msa dH=dtref

159 A correction factor has been proposed to account for the effect of water that
159 evaporates into the headspace of the sample capsule due to the exponential increase of
160
water vapor pressure with temperature. By assuming equilibrium between liquid phase and
161
162
the gas phase (headspace) inside the DSC-capsule, the equilibrium relationship derived
163 from Clapeyron and ClausiusClapeyron equations for a binary system could be used.
164 Assumptions:

165  The liquid phase consists of a non-ideal binary solution (solute water) and the
166 gas phase consists of an ideal mixture of dry air and water vapor, with the
167 equilibrium given by:

Yw P Xw gw Pw 0 Aw Pw 0 2

169  Water activity of solution was considered a function of solute and water
169 concentrations and activity coefficient, using selected models according to the
170
component;[24]
171
172
 The driving force for water to evaporate was given by the temperature increase,
173 and was computed for each temperature interval;
174  The volume of gas phase present inside the capsule was determined by means of
175 an air comparison pycnometer (Multi-Pycnometer, model MVP-5DC, Quanta-
176 Chrome, Boynton Beach, Fl);
177  The amount of solution (liquid phase) changed over time (as temperature
178 increases) in direct proportion to the amount of water evaporated;
 6 Darros-Barbosa, Balaban, and Teixeira

179  Enthalpy changes of the liquid solution (as measured by DSC in terms of specific
180 heat flow) were determined by the latent heat of water in proportion to the water
181 evaporated (going to the gas phase);
182  Vapor pressure and latent heat of water were functions of temperature;
183  There was negligible effect of sensible heat of the evaporated water in the gas
184 phase. Simulation has shown a deviation of less than 0.007% on Cp values.

185 The correction term that was applied for heat capacity followed Eq. (3) below:
! !  
1 dH 1 dH moriginal DHevap dT 1
 3
msample dt moriginal dt msample msample dt DT
corrected DSC

187 The changing in sample mass due to evaporation is given by:

187

msample moriginal  mevap 4

189 Mass of water evaporated by using water molar fraction Yw calculated using Eq. (2), was
189 computed with the following expression:
190

Yw Mww
mevap mair 5
1  Yw Mwair

192 Water activity of solution as a function of composition in Eq. (2) was calculated using
192 models from Norrish[2] and Miyawaki et al.[3] both given by Eq. (6), and Chen[4] given by
193
Eq. (7). Note that Norrishs model differs from that of Miyawaki by the absence of the b
194
195
term in Eq. (6).

2 3
Aw 1  XS eaXS bXS 6
1
Aw 7
1 0:018be BmS n mS

197 Enthalpy carried by water evaporated was determined by multiplying it by the latent heat
197 of water as a function of temperature using Wagners expression:[5]
198

DHevap mevap l 8
2
l 2500:8  2:3293T  0:0008T 9

200 The effect of the variation of the total pressure of the biphasic system along a DSC run, as
200 a function of temperature at constant volume, was computed using:
201
 
T2 273:15
P2 P1 10
T1 273:15
 Heat Capacities of Aqueous Solutions 7

203 Antoine equation was used to determine water vapor pressure as a function of temperature:
203
 
3816:44
Pw o mm Hg exp 18:3036  11
T 273:15  46:13

205 An example of an outcome by applying the proposed approach for one particular DSC
205 run (heating rate of 7
C=min, temperature range of 5 to 65
C, for approx. sample mass of
206
12.000 mg) for 1%-sucrose solution, the calculated amount of water evaporated over the
207
208
entire run was 0.0115 mg. For this particular run, the calculated amount of water
209 evaporated over each 0.1
C temperature increase was in the range from 2.4 106 to
210 3.7 105 mg. This represents about 0.1% of water being evaporated for the entire run
211 relative to the initial sample mass. After applying Eq. (3), the difference in the heat
212 capacity calculated using Eq. (1) ranged approximately from 1 to 3% depending on the
213 solute, concentration, and temperature. The greater the concentration of the solution
214 the smaller the deviation due to the effect of solute, which causes a decrease in vapor
215 pressure of the solution as would be expected. All heat capacity data presented in this
216 report include the above correction.
217 Heat capacity data for each binary solution as a function of temperature and
218 concentration were fitted to the following model:

Cp a1 b1 S c1 S 2 T a2 b2 S c2 S 2 T 2 a3 b3 S c3 S 2 12

220 An expression using the RedlichKister[6] equation for the concentration and
220 temperature dependence was applied to represent the measured Cp data of the binary
221
solutions. The excess molar heat capacity for a binary mixture is defined as.[7]
222

Cp E Cp m  X1 Cp1 mO X2 Cp2 mO 13

224 Molar heat capacities of the pure components were taken from literature data.[8,9] A
224 two- or three-term RedlichKister equation was applied to represent the compositional
225
dependence of the excess molar heat capacity as follows:
226

X
3
Cp E X1 X2 Ai X1  X2 i1 14
i1

228 The temperature dependence of Ai is assumed to follow the equation:

228

Ai ai;0 ai;1 T ai;2 T 2 15

230 The parameters ai,0, ai,1, and ai,2 were determined by fitting excess molar heat capacity
230 data calculated with Eq. (13).
 8 Darros-Barbosa, Balaban, and Teixeira

231 RESULTS AND DISCUSSION

232

233 Experimental results of heat capacity of binary solutions of sucrose, glucose, fructose,
234 citric acid, malic acid, KCl, CaCl2, MgCl2, KH2PO4, as a function of temperature and
235 concentration, together with the heat capacity of pure water, are presented in Figs. 13. F1; 2; 3
236 Heat capacity increased with increasing water content and increasing temperature for all
237 compounds, with more pronounced effect of temperature for the more concentrated
238 solutions. The effect of temperature in the behavior of inorganic salt solutions should
239 be viewed with caution because of the relatively lower concentrations investigated. In some
240 cases, the small concentration difference falls within experimental error. This effect can be
241 more clearly distinguished for the higher concentration range examined for sugar
242 solutions. At low concentrations, heat capacity approached that of pure water, with less
243 pronounced effect of temperature, and similar abnormal behavior of pure water with a
244 minimum around 30
C40
C.

Figure 1. Experimental heat capacity of binary aqueous solutions of sucrose, glucose, and fructose
as a function of temperature and concentration.
 Heat Capacities of Aqueous Solutions

Figure 2. Experimental heat capacity of aqueous binary solutions of citric and malic acid as a function of temperature
and concentration.
9
 10 Darros-Barbosa, Balaban, and Teixeira

Figure 3. Experimental heat capacity of aqueous binary solutions of potassium chloride, calcium
chloride, potassium phosphate monobasic, and magnesium chloride as function of temperature and
concentration.

245 The proposed correction factor in DSC measurements to account for the effect of
246 evaporation of water at higher temperatures appeared to be a reasonable approach for
247 applications on high moisture content samples, such as most food systems. At tempera-
248 tures above 35
C40
C, the deviation becomes significantly greater, as a consequence of
249 the exponential increase in the water vapor pressure. As stated before, at higher
250 concentrations the deviation becomes smaller due to the effect of solutes lowering the
251 vapor pressure of the solution.
252 Heat capacity of all solutions showed a quadratic dependence with concentration and
253 temperature. Table 1 shows the parameters for the predictive equations obtained by T1
254 regression analysis by fitting experimental data to the mathematical model [Eq. (12)]. The
255 fitted surfaces are shown along experimental results in Figs. 13. Binary aqueous solutions
256 of all compounds investigated fitted well into the proposed model with correlation
257 coefficients greater than 0.9, except for magnesium chloride aqueous solution with a
258 slightly lower correlation coefficient. The standard errors of all fitted equations were from
 Heat Capacities of Aqueous Solutions 11

Table 1. Heat capacity predictive equation parameters for binary aqueous solutions.

Aqueous a1 b1 c1 a2 b2
solution (J g1
C1) (J m3
C1 g2) (J m3
C1 g3) (J g1
C2) (J m3
C2 g2)
Sucrose 4.17674 0.02573e4 0.723e8 0.00123 2.179e8
Glucose 4.15263 0.03271e4 1.994e8 0.00107 1.999e8
Fructose 4.18252 0.03103e4 1.565e8 7.622e4 3.627e8
Citric acid 4.19429 0.05887e4 0.00247e4 0.00112 1.849e8
Malic acid 4.16103 0.03255e4 0.00106e4 0.00146 5.606e8
KCl 4.16032 0.06198e4 0.00265e4 0.00150 8.589e8
CaCl2 4.16550 0.14796e4 0.01543e4 0.00128 5.870e8
KH2PO4 4.18626 0.08562e4 0.00285e4 0.00103 3.887e8
MgCl2 4.13424 0.19298e4 0.02462e4 0.00147 5.208e8

Table 1. Continued.

c2 a3 b3 c3
(J m6
C2 g3) (J g1
C3) (J m3
C3 g2) (J m6
C3 g3) r2
0.017e12 0.203e4 0.012e8 0.0010e13 0.994
0.014e12 0.174e4 0.013e8 0.0013e13 0.996
0.031e12 0.212e4 0.021e8 0.0033e13 0.990
0.657e12 0.190e4 0.041e8 0.0166e13 0.979
0.367e12 0.212e4 0.037e8 0.0169e13 0.963
1.078e12 0.162e4 0.084e8 0.0979e13 0.941
0.204e12 0.145e4 0.066e8 0.0441e13 0.912
0.213e12 0.171e4 0.064e8 0.0316e13 0.988
0.017e12 0.150e4 0.099e8 0.1112e13 0.771

259 0.034 to 0.117, with p-values less than 0.01, and the residual analysis showed adequacy of
260 the models. The largest deviations from the model occur at lower concentrations, where
261 the uncertainties in experimental measurements of heat capacity with DSC are greater.
262 This corresponds to smaller differences between the heat capacity of pure water and that of
263 the solution. The relatively high experimental error intrinsic to DSC measurement on heat
264 capacity, is because of the notably small changes in heat flow associated with changes in
265 sensible heat as temperature scanning proceeds in contrast with higher heat flow
266 experienced in phase transition studies.
267 Comparison of predicted values with available literature values are presented
268 in Tables 24. An additional difficulty in making this comparison was the variation in T2; 3; 4
269 concentration and temperature range (sometimes only few data points) as well as the
270 differences in units (g 100-cm3 solution, g 100-g1 solution, mole kg1 water, molar
271 fraction, mole-of-water mole-solute1, and so on) to express these concentrations by
272 different authors.
273 Figures 46 show the calculated excess heat capacity by applying RedlichKister F4; 5; 6
274 model along with the fitted equations. Table 5 presents the results for the parameters of T5
275 RedlichKister equation for the excess heat capacity.
 12

Table 2. Comparison of predicted values with literature data for binary aqueous systems of sucrose, glucose, and fructose.

Heat capacity of binary aqueous solution (J g1
C1)

Conditions Sucrose Glucose Fructose

T (oC) S (% w=v) This study Ref.[11] This study Ref.[8] Ref.[12] This study Ref.[8]
10 10.41 3.926 3.936
10 21.69 3.680 3.684
10 33.95 3.428 3.475
10 61.84 2.918 2.973
20 10.39 3.938 3.936
20 21.63 3.707 3.726
20 33.86 3.469 3.475
20 61.80 2.971 3.014
25 3.53 4.038 4.1007
25 10.20 3.864 3.9565
25 16.92 3.703 3.8187
25 23.54 3.560 3.6890
30 4.45a 3.69b 4.015 4.071 4.097 4.091
30 8.55 8.69 3.910 3.983 3.983 4.001
30 10.05 10.91 3.873 3.964 3.932 3.959
30 13.19 12.90 3.797 3.896 3.886 3.936
30 15.38 14.99 3.747 3.866 3.837 3.893
Darros-Barbosa, Balaban, and Teixeira

30 17.76 17.53 3.694 3.808 3.777 3.870

34.15 3.45 4.044 4.1029
34.15 10.24 3.873 3.9633
34.15 16.15 3.737 3.8458
34.15 23.64 3.581 3.7052
40 10.32 3.967 3.977
40 21.47 3.763 3.726
40 33.60 3.547 3.517
40 61.40 3.074
45.56 3.58 3.098 4.048 4.1045
45.56 10.32 3.885 3.9722
45.56 16.12 3.757 3.8646
45.56 22.50 3.629 3.7523
Heat Capacities of Aqueous Solutions

53.86 4.30 4.038 4.0987

53.86 10.55 3.891 4.0401
53.86 16.09 3.772 3.8881
53.86 22.55 3.646 3.7781
60 10.22 4.003 3.977
60 21.26 3.818 3.768
60 33.24 3.619 3.559
60 60.59 3.171 3.140
a,b
Concentrations for glucose and fructose respectively at 30
C.
13
 14
Table 3. Comparison of selected predicted values with literature data for aqueous binary systems of KCl, CaCl2, and MgCl2.

Heat capacity of binary aqueous solution (J g1
C1)

KCl CaCl2 MgCl2

T (
C) S (% w=v) This study Ref.[13] S (% w=v) This study Ref.[13] S (% w=v) This study Ref.[13]
10 2.023 4.022 4.070 2.034 3.927 4.071 2.037 3.840 4.065
10 4.100 3.863 3.960 4.134 3.825 3.951 4.140 3.766 3.939
15 2.022 4.022 4.072 2.032 3.927 4.064
15 4.098 3.864 3.965 4.129 3.828 3.945
20 2.021 4.021 4.072 2.029 3.926 4.058 2.032 3.837 4.065
20 4.094 3.865 3.965 4.123 3.831 3.94 4.130 3.774 3.939
25 2.019 4.021 4.073 2.026 3.926 4.057
25 4.090 3.866 3.969 4.116 3.834 3.938
30 2.017 4.021 4.073 2.023 3.927 4.055 2.020 3.834 4.065
30 4.084 3.867 3.969 4.109 3.837 3.937 4.117 3.780 3.939
35 2.014 4.021 4.073 2.019 3.927 4.055
35 4.078 3.868 3.973 4.102 3.839 3.939
40 2.010 4.022 4.073 2.015 3.927 4.056 2.017 3.830 4.069
40 4.070 3.869 3.973 4.094 3.841 3.939 4.102 3.784 3.948
45 2.006 4.022 4.077 2.011 3.928 4.057
45 4.061 3.870 3.977 4.085 3.843 3.942
50 2.001 4.023 4.077 2.007 3.929 4.059 2.009 3.827 4.069
50 4.052 3.871 3.977 4.076 3.844 3.944 4.084 3.787 3.948
55 1.996 4.024 4.077 2.002 3.930 4.062
55 4.041 3.872 3.977 4.067 3.845 3.948
60 1.990 4.025 4.077 1.997 3.931 4.065 2.000 3.824 4.073
60 4.029 3.873 3.981 4.057 3.846 3.951 4.060 3.788 3.952
65 1.984 4.027 4.082 1.992 3.932 4.069
65 4.016 3.874 3.985 4.046 3.847 3.956
Darros-Barbosa, Balaban, and Teixeira
 Heat Capacities of Aqueous Solutions 15

Table 4. Comparison of selected predicted values with literature data for

aqueous binary system of citric acid.

Heat capacity of binary

aqueous solution of
Conditions citric acid (J g1
C1)

T (
C) S (% w=v) This study Ref.[14]

18 4.96 3.963 4.03
18 9.29 3.880 3.90

276 Excess molar heat capacity is a good indicator of non-ideality and for solutesolvent
277 interactions. Results indicated that at higher concentrations, as well as at higher tempe-
278 ratures, all compounds deviated strongly from ideal behavior. While non-electrolyte
279 compounds showed positive deviations especially at higher concentrations, electrolytes
280 had negative deviations. This can be interpreted by means of the structure-forming

Figure 4. Excess molar heat capacity as a function of solute molar fraction and temperature for
aqueous solutions of sucrose, glucose, and fructose.
 16

Figure 5. Excess molar heat capacity as a function of solute molar fraction and temperature for aqueous solutions of
citric and malic acid.
Darros-Barbosa, Balaban, and Teixeira
 Heat Capacities of Aqueous Solutions 17

Figure 6. Excess molar heat capacity as a function of solute molar fraction and temperature for
aqueous solutions of KCl, CaCl2, KH2PO4, and MgCl2.

281 (sugars) or structure-breaking (salts) ability of the solute in causing structural changes
282 accompanying its dissolution in water. Significant positive excess heat capacity values
283 suggest that the overall structural order is enhanced in aqueous sugar solutions, which is
284 apparently caused by the competitive gain of the hydrophilic interactions over the
285 hydrophobic ones, causing an increasing in hydrogen bonds. In the case of ionic solutes,
286 the negative excess heat capacity was attributed to the breaking of the hydrogen bonds of
287 water in aqueous solutions by the influence of solute molecules, the so-called electro-
288 striction effect.
289 Among sugars investigated in this study, fructose had the strongest deviation at higher
290 temperatures and concentrations. This might be related to the difference of the equilibrium
291 isomeric composition in aqueous solution of monosaccharides. Moreover, Galema and
292 Hiland,[10] based on compressibility studies on the stereochemical aspects of hydration of
293 sugars, suggested that fructose is less compatible with water structure, and consequently
294 the hydration layer is more disturbed than glucose. The authors attributed such behavior to
295 differences in the conformational molecular structure of these carbohydrates.
 18 Darros-Barbosa, Balaban, and Teixeira

Table 5. Excess heat capacity parameters of the RedlichKister equation.

Aqueous a1,0 a1,1 a1,2 a2,0 a2,1

solutions (J mol1
C1) (J mol1
C2) (J mol1
C3) (J mol1
C1) (J mol1
C2)
Sucrose 5836.3 103.59 13,223 235.67
Glucose 2696.3 40.263 7265.7 93.045
Fructose 5899.6 43.965 14,171 95.406
Citric acid 7786.5 115,790 1942.5 10,154 234,770
Malic acid 9502.7 140,730 2069.5 19,042 287,000
KCl 20,599 340,050 3967.3 45,563 692,110
CaCl2 23,768 873,430 10,665 116,630 17667e2
KH2PO4 15,148 181.40 1.6200 15,983 189.32
MgCl2 16353e3 10,646 485.41 33224e3 21,647

Table 5. Continued.

a2,2 a3,0 a3,1 a3,2

(J mol1
C3) (J mol1
C1) (J mol1
C2) (J mol1
C3) r2
73,125 136.94 0.989
4702.9 55.289 0.980
8407.8 56.463 0.985
3937.9 18,592 118,990 1995.6 0.707
4222.4 9915.8 146,310 2153.6 0.825
8073.4 25,475 352,140 4107.1 0.928
21,569 94,548 8933e2 10,905 0.795
1.7117 0.909
988.93 16875e3 10,998 503.72 0.756

296 Malic acid showed more negative deviations than citric acid. This can be explained by
297 the stronger electrolyte behavior of malic acid, and the greater ability of citric acid to form
298 hydrophobic interactions in water.
299 The effect of temperature in the excess heat capacity can be explained by the fact that
300 the bound water decreases as the temperature rises. In addition, since the interaction effects
301 are not taken into consideration in the ideal additive model, the magnitude of the solute
302 solvent interactions is greater than that of the bulk water at higher temperatures. Sugar
303 aqueous solutions showed linear temperature dependence, while citric and malic acids and
304 aqueous salt solutions exhibited quadratic temperature dependence regarding excess heat
305 capacity.
306 One factor that makes the analysis of the excess function more difficult is the lack of
307 heat capacities of pure compounds as a function of temperature. Some data were obtained
308 by regression analysis from literature data at few discrete temperatures.
309 Overall, excess heat capacity of majority of the aqueous solutions investigated could be
310 modeled well with a three-term RedlichKister equation, only potassium phosphate
311 monobasic aqueous solution was better modeled with a two-term RedlichKister equation.
 Heat Capacities of Aqueous Solutions 19

312 CONCLUSIONS

313 The heat capacities of aqueous solutions of sucrose, glucose, fructose, citric, and
314 malic acids, potassium chloride, calcium chloride, magnesium chloride, and potassium
315 phosphate monobasic were measured from 5
C to 65
C with a differential scanning
316 calorimeter. The concentrations of the solutions studied were in the range from 1% to 65%
317 (w=v) for sugar solutions, from 0.1% to 10% (w=v) for acid solutions, and 0.05% to 5%
318 (w=v) for inorganic salt solutions. These experimental data fitted well into predictive
319 equations. The thermodynamic approach to account for the effect of evaporation of water,
320 within the hermetic sealed pans, at higher temperatures, assuming equilibrium between
321 liquid and gas phase, appeared to be a reasonable approach for applications on high
322 moisture content samples in DSC measurements.
323 An excess molar heat capacity expression using RedlichKister equation for the
324 composition and temperature dependence was used to represent the deviation of the
325 measured Cp from the additive ideal model.
326 For a total of 1230 data points for each solution, the results showed an average standard
327 deviation of 1.12 and 0.058 for excess molar heat capacity and heat capacity, respectively.

328 ACKNOWLEDGMENTS

329 The authors gratefully acknowledge Dr. Miriam D. Hubinger and Dr. Florencia C.
330 Menegalli for allowing us to use the TA Instruments DSC-2920 and facilities in their
331 laboratory at the Department of Food Engineering, State University of Campinas, SP,
332 Brazil, and to FAPESP (The State of Sao Paulo Research Foundation-97=7546-4) for
333 financial support.

334 REFERENCES

335 1. ONeill, M.J. Measurement of specific heat functions by differential scanning Q2

336 calorimetry. Anal. Chem. 38 (10), 13311336.
337 2. Norrish, R.S. An equation for the activity coefficients and equilibrium relative
338 humidities of water on confectionery syrups. J. Food Technol. 1966, 1, 2539.
339 3. Miyawaki, O.; Saito, A.; Marsuo, T.; Nakamura, K. Activity and activity coefficient of
340 water in aqueous solutions and their relationships with solution structure parameters.
341 Biosci. Biotech. Bioch. 1997, 61 (3), 466469.
342 4. Chen, C.S. Water activityconcentration models for solutions of sugars, salts, and
343 acids. J. Food Sci. 1989, 54 (5), 13181321.
344 5. Wagner, W.; Pruss, A. International equations for the saturation properties of ordinary
345 water substance. Revised according to the International Temperature Scale of 1990. J.
346 Phys. Chem. Ref. Data 1993, 22 (3), 783787.
347 6. Redlich, O.; Kister, A.T. Thermodynamics of non-electrolyte solutions. Ind. Eng.
348 Chem. 1948, 40 (2), 341348.
349 7. Lide, D.R.; Kehiaian, H.V. CRC Handbook of Thermophysical and Thermochemical
350 Data; CRC Press: Boca Raton, FL.
 20 Darros-Barbosa, Balaban, and Teixeira

351 8. Kawaizumi, F.; Nishio, N.; Nomura, H.; Miyahara, Y. Heat capacity measurements of
352 aqueous solutions of mono-, di-, and tri-saccharides using an isoperibol twin
353 calorimeter. J. Chem. Thermodyn. 1981, 13, 8998.
354 9. Barin, I. Thermochemical Data of Pure Substances, 3rd Ed.; VCH Pub.: Weinheim,
355 426 pp.
356 10. Galema, S.A.; Hiland, H.J. Stereochemical aspects of hydration of carbohydrates in
357 aqueous solutions. 3. Density and ultrasound measurements. J. Phys. Chem. 1991, 95,
358 53215326.
359 11. Lyle, O. Technology for Sugar Refinery Workers; Chapman & Hall Pub.: London, UK,
360 629 pp.
361 12. Kishore, N.; Goldberg, R.N.; Tewari, Y.B. Apparent molar heat capacities and
362 apparent molar volumes of aqueous glucose at temperatures from 298.15 K to
363 327.01 K. J. Chem. Thermodyn. 1993, 25, 847859.
364 13. Zaytsev, I.D.; Aseyev, G.G. Properties of aqueous solutions of Electrolytes; CRC
365 Press: Boca Raton (translated by Lazarev & Sorochenko, V.A.).
366 14. Washburn, E.W. Ed. International Critical Tables of Numerical Data, Physics,
367 Chemistry and Technology; McGraw-Hill Book Co.: New York, 1929; Vol. 1, 125 pp.

368 Received March 25, 2002

369 Accepted September 22, 2002

View publication stats