Studii şi Cercetări Ştiinţifice 2016, 17(4), pp.

417 – 426
Chimie şi Inginerie Chimică, Biotehnologii, Industrie Alimentară

Scientific Study & Research

Chemistry & Chemical Engineering, Biotechnology, Food Industry ISSN 1582-540X

ORIGINAL RESEARCH PAPER

MATHEMATICAL MODELLING OF CaCl2

AQUEOUS SOLUTIONS THERMOPHYSICAL PROPERTIES

Cristina G. Grigoraş, Gabriela Muntianu, Lucian Gavrilă*

“Vasile Alecsandri” University of Bacău, Faculty of Engineering,

Department of Chemical and Food Engineering,
Calea Mărăşeşti 157, 600115, Bacău, Romania

*Corresponding author: [email protected]

Received: December, 5, 2016

Accepted: December, 15, 2016

Abstract: Calcium chloride is an inorganic salt used in its solid state

or as aqueous solutions in a multitude of research and industrial areas going
from chemical industry to food, cosmetics or drugs production.
This paper was directed to establish mathematical models relating its
density and dynamic viscosity with factors such as temperature and
concentration since it is known that these properties present a high influence
on appropriate transport pipes dimensions and industrial equipment
choosing and / or designing processes.
The assessment and selection of the adequate models were realized by
testing various software’s and equations. The obtained results revealed that
calcium chloride aqueous solutions studied thermodynamic properties can
accurately be expressed by quadratic (density) and respectively by linear
equations (dynamic viscosity) or by more complex equations. Correlation
coefficient, relative error and ANOVA values revealed no significant
differences between experimental and calculated data.

Keywords: calcium chloride, density, mathematical model, viscosity

© 2016 ALMA MATER Publishing House, “VASILE ALECSANDRI” University of Bacău. All rights reserved. 417
 GRIGORAŞ, MUNTIANU and GAVRILĂ

INTRODUCTION

Calcium chloride is a nontoxic inorganic salt which can be easily obtained at accessible
prices. It is characterized by a high hygroscopicity and an important sorption capacity. It
has also a good thermal conductivity, a high fusion latent heat and a low volume
modification in phase transition [1].
Its properties make it suitable for uses in various fields such as chemistry, food
products, cosmetics etc. In chemical industry, pure calcium chloride is used for
producing different compounds such as calcium carbonate, calcium phosphate or
calcium chromate [2, 3]. In food industry, this salt can be incorporated in coating
materials [4 – 7]; it can reduce the non-desirable storage effects (softening,
discoloration etc.) of fruits and vegetable by offering a good protection against enzymes
action [5, 6, 8, 9]; it enhance meat products properties [10, 11] etc. In cosmetic
production processes, calcium chloride, mixed with other ingredients, can be used for
example for bigels manufacturing [12]. In pharmaceutics development, calcium chloride
presents synergic effects on in vitro drugs skin permeation [13] or it can serve to
formulate products aimed to improve oral delivery of low soluble drugs [14]. Due to its
cooling properties, calcium chloride is also used to obtain selective water composite
adsorbents [15, 16], liquid desiccants [17 – 19] or cooling agents [1].
In many of the above mentioned utilizations examples, calcium chloride is often
employed as aqueous solutions whose thermophysical properties (namely density,
dynamic viscosity, thermal conductivity etc.) present high importance in the appropriate
transport pipes dimensions and industrial equipment choosing and / or designing
processes.
As consequence, over the time, several studies were aimed to establish values for the
cited calcium chloride properties and to correlate them with various parameters such as
pressure, temperature, solute concentration different data being nowadays available [20
– 22]. These data are frequently expressed in tabular or graphical form fact that makes
their employment rather complicate. A more elegant, adequate and easy to implement
method consist in transforming the existing data in mathematical equations.
Considered a suitable alternative in different other areas such as juice production [23],
study of flour and dough rheological properties [24], study of dough dynamic viscosity
evolution [25] etc., this data interpretation way was successfully applied also to other
fluids thermodynamic properties studies like aqueous solutions of sodium chloride [26],
glucose [27] or glycerol [28, 29] etc.
Therefore, the present work was focused on the study of the behavior of calcium
chloride aqueous solutions density and dynamic viscosity both known as significant in
characterizing the behavior when passing through pipes as well as in heat and mass
transfer in many processing processes.
Data from existing publications were used for establish mathematical correlations for
these properties when influenced by parameters such as temperature (both in positive
and negative ranges) and solutions concentration.
The obtained equations have a high similarity with the experimental data fact that
confirms the accuracy of the mathematical models.

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 MATHEMATICAL MODELLING OF CaCl2 AQUEOUS SOLUTIONS THERMOPHYSICAL PROPERTIES

MATERIALS AND METHODS

Data shown on Tables 1 – 3 provided by different scientific publications [30] on density

and dynamic viscosity evolution of aqueous calcium chloride solutions with their
concentration and temperature were introduced in various software’s in order to establish
accurate mathematical equation.

Table 1. Variation of CaCl2 aqueous solutions density with temperature and concentration [30]
Concentration,

Density, ρ [kg·m-3]
C% [%, w/w]

Temperature, T [K]

268.15 273.15 293.15 303.15 313.15 333.15 353.15 373.15 393.15 413.15
2 - 1017.1 1014.8 1012 1008.4 999.4 988.1 974.8 959.6 942.8
4 - 1034.6 1031.6 1028.6 1024.9 1015.8 1004.6 991.5 976.5 960.1
8 1070.8 1070.3 1065.9 1062.6 1058.6 1049.2 1038.2 1025.7 1011.1 995.4
12 1108.3 1107.2 1101.5 1097.8 1093.7 1084.0 1073.0 1061.0 1046.6 1031.7
16 1147.1 1145.4 1138.6 1134.5 1130.1 1120.2 1109.2 1097.3 1083.5 1069.1
20 1187.4 1185.3 1177.5 1173.0 1168.4 1158.1 1147.1 1135.2 1121.9 1108.0
25 - 1237.6 1228.4 1223.6 1218.6 1207.9 1196.5 1184.6 - -
30 - 1292.2 1281.6 1276.4 1270.9 1259.7 1247.8 1235.9 - -
35 - - 1337.3 1331.6 1325.5 1313.7 1301.3 1289.3 - -
40 - - 1395.7 1389.5 1382.6 1370 1357.1 1345 - -

Table 2. Variation of CaCl2 aqueous solutions density with temperature and concentration [30]
Density, ρ [kg·m-3]
Concentration,
Temperature, T [K]
C% [%, w/w]
288.15 273.15 263.15 253.15 243.15 233.15
15 1132 1137 1140 - - -
16 1142 1147 1150 - - -
17 1151 1157 1160 - - -
18 1161 1167 1170 - - -
19 1171 1177 1180 - - -
20 1181 1187 1190 - - -
21 1191 1197 1201 1205 - -
22 1201 1207 1211 1215 - -
23 1211 1218 1222 1226 - -
24 1222 1228 1233 1237 - -
25 1232 1239 1244 1248 - -
26 1243 1250 1254 1259 1263 -
27 1252 1261 1266 1270 1275 -
28 1264 1272 1277 1282 1287 -
29 1275 1283 1288 1293 1298 1303
30 1286 1294 1298 1304 1310 1315

Microsoft Excel™ 2013, CurveExpert® and TableCurve 3D® v.4 software’s were
employed for mathematical models development and for data 2D and 3D plotting.

St. Cerc. St. CICBIA 2016 17 (4) 419

 GRIGORAŞ, MUNTIANU and GAVRILĂ

Table 3. Variation of CaCl2 aqueous solutions dynamic viscosity with temperature and
concentration [30]
Concentration,

Dynamic viscosity, μ [mPa·s]

C% [%, w/w]

Temperature, T [K]

293.15 283.15 273.15 268.15 263.15 258.15 253.15 248.15 243.15 238.15 233.15 228.15 223.15
9.4 12.36 15.49 21.58 25.48 - - - - - - - - -
14.7 14.91 18.63 25.6 30.4 40.6 - - - - - - - -
18.9 18.04 22.36 29.91 34.32 46.68 61.49 - - - - - - -
20.9 20.01 24.52 32.75 38.25 50.7 65.9 - - - - - - -
23.8 23.54 28.73 38.15 44.13 59.23 75.51 94.73 115.72 - - - - -
25.7 26.28 32.17 42.56 - 66.78 83.65 105.62 129.15 148.08 - - - -
27.5 29.32 36.09 48.05 - 75.22 - 118.66 147.1 171.61 215.74 - - -
28.4 31.38 - 51.19 - 80.22 - 126.51 159.85 188.29 245.17 304.01 - -
29.4 34.03 - 54.92 - 86.3 - 138.27 - 212.8 254.97 323.62 402.07 490.33
29.9 35.11 - 56.88 - 90.43 - 144.16 - 225.55 284.39 353.04 431.49 509.95

RESULTS AND DISCUSSION

Density

10 different second order polynomial simple correlations (Equation 1) have been

developed on Microsoft Excel software by representing density ρ [kg·m-3] values as
temperature T [K] functions at constant calcium chloride concentrations C% [% w/w].
  A1  A2T  A3T 2 (1)
The A1, A2 and A3 coefficients values are presented in Table 4. For all of them, the
regression coefficients R2 are superior of 0.999 indicating a good correlation of variables.

Table 4. Coefficients for equation no. 1

Concentration, Equation 1 coefficients
C% [%, w/w] A1 A2 A3 R2
2 839.99 1.4414 -0.0029 0.9994
4 879.7 1.3054 -0.0027 0.9996
8 950.78 1.084 -0.0024 0.9997
12 1034.3 0.8028 -0.002 0.9999
16 1116.6 0.5376 -0.0016 1
20 1196 0.3018 -0.0012 1
25 1291.6 0.0461 -0.0009 1
30 1393.9 -0.2327 -0.0005 1
35 1494.9 -0.4864 -0.0002 1
40 1616.8 -0.846 0.0003 0.9999

A1, A2 and A3 coefficients were associated with concentrations C% [% w/w] by using

CurveExpert® software. Quadratic equation for A1 (Equation 2) and linear equation
420 St. Cerc. St. CICBIA 2016 17 (4)
 MATHEMATICAL MODELLING OF CaCl2 AQUEOUS SOLUTIONS THERMOPHYSICAL PROPERTIES

(Equation 2) for A2 and A3 coefficients with good regression coefficients (Table 5) have
been established.
Coefficient  a1  a 2 C %  a 3 C %2 (2)
Coefficient  a1  a 2 C % (3)

Table 5. Coefficients for equations no. 2 and 3

Equations 2 and 3 coefficients
Equation 1 coefficient
a1 a2 a3 R2
A1 803.55498 18.65180 0.03781 0.99971
A2 -0.05916 1.53134 - 0.99827
A3 - 0.00301 0.00008 - 0.99571

Equations 1, 2 and 3 were combined in order to obtain the general model expressed by
Equation 4:
  ( a1  a2  C%  a3  C% 2 ) A ( a1  a2  C% ) A T  ( a1  a2  C% )A  T 2
1 2 3
(4)
A parallel between data calculated with the mathematical model and the experimental
ones was realized by the mean of relative error equation (5).
Dataexperimental  Datacalculated
  100[%] (5)
Datacalculated
An average of 0.630% (in absolute value) was obtained. The regression coefficient R2 of
the proposed model was 0.9946 for densities values presented in Table 1 and higher
(0.9999) for those given in Table 2. In both cases the absolute value of the relative error
was of 0.524%.
The ANOVA (Two-Factor with Replication) test was used also to compare tabular and
calculated density values. The results revealed sample P-values of 0.900567 and
0.941336, greater than the targeted alpha 0.05, and Fcrit values of 3.89364 superior to
F-test values (0.015655 and 0.005431) for calcium chloride aqueous solutions density
values variation in positive (Table 1) and negative (Table 2) temperature ranges. In this
case, the null hypothesis cannot be rejected and no statistical difference between tabular
and calculated data was registered.
Density data were introduced in TableCurve 3D® v.4 software which served to generate
two different polynomial equations (6 and 7): one classified Rank 49 (Eqn. 313) with a
precision of R2 = 0.9999966601, FitSdErr = 0.2326931809, Fstat. = 2.46181E+06 for
values shown in Table 1 and one of Rank 16 (Eqn. 310) with R2 = 0.9999560422,
FitSdErr = 0.3701979907, Fstat. = 139015.96133 for values exposed in Table 2.
  b1  b2  C%  b3  ln(T )  b4  C%2  b5  (ln T ) 2 b 6 C%  ln(T )  b7  T 3 
2
(6)
 b8  (ln T ) 3  b9  C %  (ln T ) 2  b10  C %  ln T
  b1  b2  C%  b3  T  b4  C%2  b5  T 2  b6  C%  T b 7 C% 3  b8  T 3 
2
(7)
 b9  C %  T 2 b10  C %  T
Coefficients of the equations 6 and 7 are presented in Tables 9 and 10.

St. Cerc. St. CICBIA 2016 17 (4) 421

 GRIGORAŞ, MUNTIANU and GAVRILĂ

Table 9. Coefficients for equation 6

Coefficient Value Coefficient Value
b1 10406.05291 b6 -109.516623
b2 325.6324771 b7 6.15222E-05
b3 -7007.51748 b8 -116.551335
b4 0.203129712 b9 9.436791193
b5 1604.133205 b10 -0.02778971

Table 10. Coefficients for equation 7

Coefficient Value Coefficient Value
b1 810.4786129 b6 -0.09129409
b2 22.6640109 b7 -0.00028682
b3 1.070837953 b8 -5.4388E-06
b4 0.05461806 b9 0.000134079
b5 0.000191949 b10 5.71015E-05

The graphical representation of the equations 6 and 7 is presented in Figure 1.

1400 1350 1350

1400
1350 1350
1300
Density,  [kg.m-3 ]

1300
Density,  [kg.m-3]

1300

Density,  [kg.m-3 ]
Density,  [kg.m-3]

1300
1250 1250
1200 1250 1250
1200
1150 1150
1100 1200 1200
1100
1050 1050
1000 1150
1000 1150
950 950
900 1100
900 1100
Co 35 0 27 .5 5 24
n ce 3 5 30 Co 2 25 0
2 0 nce
nt r
atio 20 5 35 ntr 22 .5 0 26 0
0 ] atio 2 0 [K ]
n, C 1 T [K n, C 17 .
5 27 0 re ,
T
% 10 40 r e, 28 at u
[% 5 0 atu % 15 0 pe r
,w 0 450 p er [%
,w .5 29 m
/w] T em /w ] 12 0 Te

Figure 1. CaCl2 aqueous solutions density values plotted in TableCurve 3D and fitted
with polynomial type (Equations 6 and 7) and its residuals

Dynamic viscosity

The same calculus algorithm was followed for calcium chloride aqueous solutions
dynamic viscosity data. In this case, 10 quadratic correlations expressed by equation 8
have been established by plotting the logarithmic values of dynamic viscosity μ [mPa·s]
vs temperature T [K] at fixed CaCl2 concentrations.
log(  )  A1  A2T  A3T (8)
Table 10 depicts A1, A2 and A3 coefficients values.
A1, A2 and A3 coefficients were correlated with CaCl2 concentrations C% [% w/w], and
various mathematical models (1st, 2nd and 3rd degree polynomial equations, “vapour
pressure” model, “heat capacity” model etc.) were generated.
Among them the best fit was given by the quadratic equation 9 whose coefficients values
are shown in Table 11.
Coefficien t  a1  a 2 C %  a 3 C %2 (9)

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 MATHEMATICAL MODELLING OF CaCl2 AQUEOUS SOLUTIONS THERMOPHYSICAL PROPERTIES

Table 10. Coefficients for equation 8

Concentration, Equation 8 coefficients
C% [%, w/w] A1 A2 A3 R2
9.4 0.000165 0.10509 17.75579 0.9992
14.7 0.000152 0.09875 17.01874 0.9974
18.9 0.000137 0.09013 15.87924 0.9993
20.9 0.000135 0.08849 15.65616 0.9971
23.8 0.000113 0.07694 14.16871 0.9978
25.7 0.000094 0.06653 12.79728 0.9966
27.5 0.000076 0.05687 11.56793 0.9968
28.4 0.000066 0.05173 10.98032 0.9972
29.4 0.000054 0.04563 10.18695 0.9948
29.9 0.000048 0.0423 9.79841 0.9955

Table 11. Coefficients for equation 9

Equation 9 coefficients
Equation 8 coefficient
a1 a2 a3 R2
A1 0.0001293054 0.0000063231 -0.0000003008 0.9940
A2 0.0869560277 0.0032994350 -0.0001596278 0.9956
A3 -0.0203417811 0.4191380278 15.4856071276 0.9962

The last mentioned two equations (8 and 9) were combined leading to the following final model:
log(  )  ( a1  a2  C%  a3  C% ) A1 ( a1  a2  C%  a3  C% ) A2 T 
2 2

2
(10)
 ( a1  a2  C%  a3  C% )A3  T 2
The error of this model was of 0.897% (2.488% in absolute value) and its regression
coefficient was of 0.996.
The ANOVA test revealed a sample P-value of 0.9647 (superior to targeted alpha of
0.05) and an Fcrit value of 3.881505 (larger than the F-test value of 0.001956). The
same conclusion as for density values analysis was drawn, namely that there is no
statistical difference between tabular and calculated data.
Multiple equations were generated also with TableCurve 3D® v.4 software but only one
was selected due to its high precision (Rank 33, Eqn. 254122972). This equation has a
correlation coefficient of 0.9990438298 and its FitSdErr and Fstat. values were
6922.0578888 and 3.2745062671 respectively. The established equation (11) has the
coefficients presented in Table 14 and the graphical form pictured in Figure 2.
ln(  )  b1  b2  C%2  ln( C% )  b3  C%  b4  C%  b5  T b6 T 0.5  ln( T ) 
2.5 3

(11)
b7  ln( T )2 b8 T 0.5 b9  ln( T )

Table 14. Coefficients for equation 11

Coefficient Value Coefficient Value
b1 -1.3076e+06 b6 -76142.224
b2 0.028660749 b7 -142669.246
b3 -0.02505711 b8 716967.2378
b4 0.001365614 b9 117931.3782
b5 1268.065255

St. Cerc. St. CICBIA 2016 17 (4) 423

 GRIGORAŞ, MUNTIANU and GAVRILĂ

500

Dynamic viscosity,  [mPa.s]

500

Dynamic viscosity,  [mPa.s]

450 450
400 400
350 350
300 300
250 250
200 200
150 150
100 100
50 50
0
0
Co 25 23
nce 24 0
nt r 20 25 0
atio 26 0 ]
n, C 15 27
0
0
T [K
% 10
28 r e,
[% 29 0 atu
,w 5 300 0 per
/w] T em

Figure 2. CaCl2 aqueous solutions dynamic viscosity values plotted in TableCurve 3D

and fitted with linear type (Equation 11) and its residuals

Kinematic viscosity

Using the data obtained for density and dynamic viscosity of calcium chloride aqueous
solutions, with the help of equation 12, one can calculate also the kinematic viscosity (ν).

  [m2·s-1] (12)

Compared to results presented in other studies on the same thematic [20, 21], the
mathematical models developed in this work present a higher degree of accuracy. In
some cases, they are also simpler and therefore easier to use.

CONCLUSION

This paper was able to establish mathematical models relating density and dynamic
viscosity of calcium chloride aqueous solutions with their temperature and concentration.
The results released with the help of Excel Microsoft software showed that a second
order polynomial equation can be considered a suitable mathematical expression of
density while the dynamic viscosity can be presented as a linear model. More complex
equations were obtained with CurveExpert and TableCurve 3D softwares. Correlation
coefficient, relative error and ANOVA values revealed no significant differences
between the experimental and calculated data. The high degree of accuracy registered
for all the mathematical models developed in this study recommends their use for data
base enrichment but also for equipment and processes sizing and optimization.

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23. Simion, A.I., Dobrovici, P.E., Rusu, L., Gavrilă, L.: Modelling of the Thermo-Physical Properties
of Grapes Juice III. Viscosity and Heat Capacity, Scientific Study and Research: Chemistry and
Chemical Engineering, Biotechnology, Food Industry, 2011, 12 (4), 409-420;
24. Temea (Moroi), A.M., Pircu (Vartolomei), N., Simion, A.I., Grigoraş, C.-G., Ungureanu
(Cărbune), R.E., Alexe, P.: Improvement of Flour and Dough Rheological Properties by
Maturation Process, Romanian Biotechnological Letters, 2016, 21 (2), 11381-11392;
25. Simion, A.I., Grigoraş, C.-G., Moroi, A., Vartolomei, N.: Mathematical Modelling of Pasta Dough
Dynamic Viscosity. Thermal Conductivity and Diffusivity, The Annals of the University Dunărea
de Jos of Gala i, 2015, 39 (1), 81-92;
26. Simion, A.I., Grigoraş, C.-G., Roşu, A.M., Gavrilă, L.: Mathematical Modelling of Density and
Viscosity of NaCl Aqueous Solutions, Journal of Agroalimentary Processing and Technologies,
2015, 21 (1), 41-52;
27. Simion, A.I., Grigoraş, C.-G., Rusu, L., Gavrilă, L.: Modelling of the Thermophysical Properties
of Liquids Involved in Food Processing, Environmental Engineering and Management Journal,
2012, 11 (11), 2035-2045;
28. Simion, A.I., Grigoraş, C.-G., Gavrilă, L.: Modeling Thermodynamic Properties of Glycerol
Involved in Cosmetic and Pharmaceutical Industries. Boiling Point, Heat Capacity and Thermal
Conductivity, The 5th IEEE International Conference on E-Health and Bioengineering – EHB
2015, Grigore T. Popa University of Medicine and Pharmacy, Iaşi, Romania, November 19-21,
2015, DOI: 10.1109/EHB.2015.7391366;
29. Simion, A.I., Grigoraş, C.-G., Gavrilă, L.: Mathematical Modeling of Glycerol Aqueous Solutions
Thermophysical Properties. Case Study of Density and Viscosity, Journal of Agroalimentary
Processing and Technologies, 2015, 21 (2), 125-135;
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