E. Obermeier, S. Fischer, and D. Bohne: Thermal Conductivity, Density, Viscosity, and Prandtl-Numbers etc.

805

Thermal Conductivity, Density, Viscosity, and Prandtl-Numbers of Di- and

Triethylene Glycol-Water Mixtures
E. Obermeier, S. Fischer, and D. Bohne
Institut fur Fluid- und Thermodynamik, Universitat - GH Siegen,
Paul-Bonatz-StraDe 9 - 11, 5900 Siegen, Federal Republic of Germany

Density I Liquids Physical Properties Thermal Conductivity Viscosity

Thermal conductivity, density and Prandtl-Numbers of the aqueous solutions of di- and triethylene glycol are reported. Thermal con-
ductivity was measured in the temperature range from -20°C to 20O0C,density in the range from - 10°C to 140°C and viscosity between
- 10°C and 80°C. In addition to the measurements Prandtl-Numbers were calculated using values of specific heat taken from the literature.

Introduction and for triethylene glycol

Aqueous glycol mixtures are extensively used as industrial
solvents. An accurate knowledge of the physical properties
is important to calculate heat transfer problems. Thermal
conductivity, density and viscosity data of some diethylene
glycol-water mixtures (DWM) and triethylene glycol-water
mixtures (TWM) are presented within an extended temper-
ature and concentration range. The properties of mono-
ethylene glycol-water mixtures have been discussed in an
earlier paper [l].
Thermal Conductivity
To measure the thermal conductivity of liquids a hori-
zontal concentric cylinder device has been used. This device
rotates around its horizontal axis to eliminate the effects of
convection. A description of this apparatus is given in Ref.
[2]. The measurements have been carried out with a layer
thickness of 4 mm. The diameter of the inner cylinder was
52 mm.
Because in organic liquids heat transfer by radiation may
occur [3,4], the data of pure glycols had to be corrected.
The method described by Braun et al. [5] has been used to
perform these corrections. To accomplish this calculation,
spectra of Staat [6] and Schrader et al. [7] were used. These
calculations show that the radiation heat flux is 2.4% in
diethylene glycol and 3.0% in triethylene glycol at 200°C
for the 4 mm layer. Because water is a strongly absorbing
fluid, the radiation heat flux in glycol mixtures can be dis-
regarded.
The radiation-free values of the measured thermal con-
ductivities are refering to saturation pressure. They have an
accuracy of k 1 % or less. The purity of the samples was
higher than 98%, the water content less than 0.5%. The
water used in the investigations was redistilled and degassed.
The experimental results of the pure liquids can be approx-
imated by a quadratic equation with a mean deviation of
less than +3%. These equations are for water
Aw = 0.56276 + 1.874. l o w 3 .t - 6.8 - * t2 , (1)
for diethylene glycol
,Itr, = 0.18951 + 1.037. l o p 4 .t - 7.1 . lo-’. t 2 . (3)
In Eqs. (l), (2), and (3) t is the temperature in “C and 1 the
thermal conductivity in W/mK. These equations are valid
in the temperature range from melting temperature to
200°C. To describe the thermal conductivity of mixtures
various equations are given in the Refs. [S - 101. To calcu-
late the thermal conductivity of mixtures the equations given
in [8,9] require thermal conductivity data and physical
properties of the pure components, e.g. the heat of vapor-
isation. These equations correspond with the experimental
results when the thermal conductivities of the pure com-
ponents are similar. The equation proposed by Filippov
[lo] works well even for mixtures with high differences in
thermal conductivity of the pure components. Therefore a
modified form of Filippovs equation was used:
In Eq. (4) AM is the thermal conductivity of the mixture, ,IG
the thermal conductivity of glycol and x the mass fraction
of glycol. In order to describe the experimental values with
this equation within the limits of experimental errors the
factor k was chosen as a function depending on temperature
and concentration. This function is
kdi = 0.4052 + 0.0594. X - 8.4. lop4.t (5)
for (DWM) and
ktri = 0.4085 + 0.1642. x - 9.4. t (6)
for (TWM).
Using these functions the experimental results can be rep-
resented with a mean deviation of f0.3%. The experimental
data are plotted in Fig. 1 as a function of temperature for
different concentrations.
The authors’ data agree within the limits of experimental
error with data given in [ l l - 131.

Ber. Bunsenges. Phys. Chem. 89, 805-809 (1985) - 0VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1985.
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806 E. Obermeier, S. Fischer, and D. Bohne: Thermal Conductivity, Density, Viscosity, and Prandtl-Numbers etc.

0,80 Density
Density measurements were performed with a digital den-
sity meter. The measuring principle is based on the variation
w
- of natural frequency of a hollow oscillator filled with liquid
mK
or gas [14]. The temperatures ranged between -10°C and
140°C and were checked by a calibrated platinum resistance
0,60 1.1 5

I0,50
g
-
h cm3
0,40

11.05
0,30
P

0,20
1.00

0,lO 0.95
-25 0 50 100 150 "C 200
t-

Fig. l a
Thermal conductivity of diethylene glycol-water mixtures 0.90
0 40 80 120 "C 160
t -
0,80 r
- Fig. 2a
A 100% trig Iy col Density of diethylene glycol-water mixtures
0 75% t r i g l y c o l
0 50% t r i g l y c o l
w
- 0 25 % t r i g l y c o l
mK VlOO % w a t e r

0,60

1
h
oso

0,40

0,30

0.20

0,l 0
-25 0 50 100 150 "C 200
t--- t -
Fig. l b Fig. 2b
Thermal conductivity of triethylene glycol-water mixtures Density of triethylene glycol-water mixtures
 E. Obermeier, S . Fischer, and D. Bohne: Thermal Conductivity, Density, Viscosity, and Prandtl-Numbers etc. 807

thermometer with an accuracy of 0.2 K. Using a thermostat
the temperature was kept constant within k0.01 K. The
accuracy of measured density is about k 1.0. lop4 g/cm3.
The experimental data for (DWM) and for (TWM) are well
represented by the quadratic equation
correlates measured data with an accuracy of f5%. The
constants ai have to be calculated with Eq. (10) using the
empirical constants given in Table 4. Eq. (9) fits (DWM)
data within +4%. Fig. 3 graphically shows the viscosity
data for (DWM) and (TWM).

Prandtl-Number
The Prandtl-Number is frequently used to describe char-
where Q is the density in kg/m3 and acteristic physical properties. The Prandtl-Number

The empirical constants A,,j are given in Table 1 (DWM)

was calculated using the authors’ experimental data for ther-
and in Table 2 (TWM). Eq. (7) approximates the data with
mal conductivity and viscosity using Eqs. (4), (9), (10) and
an accuracy of f0.5%. In Fig. 2 the density of (DWM) and
literature values for the specific heat at constant pressure cp
(TWM) is plotted against temperature for various concen-
given in Ref. [17]. Calculated values of Prandtl-Numbers
trations.
are correlated in the temperature range from -20°C to
Table 1 110°C with an equation similar to that of viscosity for
Coefficients A, of Eq. (7)- (DWM) (DWM)
-

j = l j = 2 j=3 In P r = (all2.’ - (a2)0.5.

t + t2
(a3)0.4. (13)

i-1 9.9880’lo2 2.0729 lo2 -7.2103 ’ 10’ and for (TWM)

i =2 - 1.0357.lo-.‘ - 1.0797 4.2904.lo-’
i = 3 -3.2251 3.432O.lO-” -4.5246. 1nPr = (a1)9.9- (a2)1.2s.t+ (a3)04.t 2 (14)
where ai has to be calculated with Eq. (10) using the empir-
ical constants given in Table 5 (DWM) and Table 6 (TWM).
Table 2
Coefficients A,,J of Eq. (7) - (TWM)

j - 1 j = 2 j=3

i = l 9.9823.10’ 2.2137.10’ -7.6034.101

i =2 -9.6366.10--’ - 1.0982 3.5935 ’ 10-1
i =3 -3.2626.10-3 3.3568.lo-? -1.6939.

Dynamic Viscosity
Viscosity was determined by means of a Hoeppler Falling
Body viscosimeter [lS] and an Ubbelohde capillary viscosi-
meter [16]. Both viscosimeters were calibrated with two
standard solutions. The accuracy of this methods is better
than f 2 % .
Experimental results are obtained in the range from
-10°C to 80°C for (DWM) and (TWM). Temperature
measurements were made as described above. The following
equation correlates the viscosity data with temperature and
concentration for (DWM):

In 4 = (a1)1,3514 + a 2 .t + (u3)06803.
t2 (9)

where q represents the viscosity in mPas and

a, = A,J + A,,2 * x + A,,3 * x2. (10)

with the empirical constants A,,, given in Table 3. A similar 110 0 10 20 30 40 50 60 “ C 80

equation for (TWM) t-
Fig. 3a
lnq = (a1)2,0833 - (a2)164.t + (a3)04425.t 2 (11) Viscosity of diethylene glycol-water mixtures
808 E. Obermeier, S . Fischer. and D. Bohne: Thermal Conductivity, Density, Viscosity, and Prandtl-Numbers etc.
-__)

30 1000

mPas 500
300
25

100
20

1 ;:
t
rl
15
Pr

10

10 5
3

5
1
-25 0 50 100 "C 150
t-
0 Fig. 4b
-10 0 I0 20 30 40 50 60 "C 80 Prandtl-Number of triethylenc glycol-water mixturcs
t-
Fig. 3b
Viscosity of tricthylene glycol-water mixtures The accuracy of calculated Prandtl-Numbers (Eqs. (13), (14))
is better than +3%. Fig. 4 shows the Prandtl-Numbers as
1000 a function of temperature.
Table 3
500 Coefficients A,J of Eq. (9) - (DWM)

3 00 j = l j = 2 j = 3

i = l 6.3513, lo-' 3.0176 - 4.9609. lo-'

i =2 -2.9276.10-* -4.0815 lo-' 9.9051. lo-'
100 i = 3 1.8238. 5.7651 -2.6245.10-6

1: Table 4
CoefficientsA,,, of Eq. (11) - (TWM)

Pr j = l j = 2 j = 3

10 i = 1 7.4560.10-' 2.1797 -7.2795.10-'

i =2 1.1473.10W' 9.7489. -2.3061
i =3 1.3345, lo-'' 5.8019. 2.3392.
5
3
Table 5
coefficients A,,, of Eq.(13) - (DWM)

j = l j = 2 j = 3
1
-25 0 50 100 "C 150
t- i = 1 1.4539 9.5616.10-' -2.1388.10-'
i =2 1.0111~10-~ 2.8728. lo-' -3.6635.
Fig. 4a i =3 1.6878.10-'0 1.4891. - 6.7294.10- "
Prandtl-Number of diethylene glycol-water mixtures
 A. Lainez, J.-P. E. Grolier, and E. Wilhelm: Excess Molar Heat Capacity of (1,2-Dichloroethane + Benzene) Revisited 809

Table 6 [5] R. Braun, S. Fischer, and A. Schaber, Warme Stoffubertrag.

Coefficients A,,, of Eq. (14) - (TWM) 17, 121 (1983).
[6] H. Staat, Personal Communication.
j = l j = 2 j = 3 [7] B. Schrader and W. Meier, DMS Raman/IR Atlas, Verlag
Chemie, Weinheim 1974.
i = 1 1.0987 1.9693.10- ' -6.8200.10-* [8] L. P. Filippov, Int. J. Heat Mass Transfer 11, 331 (1965).
i =2 6.3369.10-' 6.2862. -1.4260.10-2 [9] G. Latini and M. Pacetti, The Thermal Conductivity of Liq-
i =3 1.7246.10-'0 9.2259. lo-'' 2.6197.10-'0 uids - a critical survey. Thermal Conductivity 15, Plenum
Press, New York.
[lo] J. E. S. Venart, The Thermal Conductivity of Binary Organic
Liquid Mixtures. Proceedings of 4th Symposium on Ther-
The authors are grateful to Dr. H. Staat of the Institut fur Spek- mophysical Properties, 292 pp., ASME, New York 1968.
trochemie und angewandte Spektroskopie for supplying the ab- [ll] M. A. Gazdiev and Yu. L. Rastorguev, Russ. J. Phys. Chem.
sorption spectra. Thanks are due to Mr. J. Burt and Mr. G. Schons
45, 383 (1971).
who conducted the experiments.
[12] Yu. L. Rastorguev and Yu. A. Ganiev, J. Phys. Chem. 40,869
(1966).
[13] I. S. Bogacheva, K. B. Zendikhanov, G. Kh. Mukhamed-
References zyanov, A. Kh. Sadykov, and A. G. Usmanov, Russ. J. Phys.
D. Bohne, S . Fischer, and E. Obermeier, Ber. Bunsenges. Phys. Chem. 54, 838 (1980).
Chem. 88, 739 (1984). [14] PAAR Digital Density Meter, Instruction Manual, Graz, Aus-
S. Fischer and E. Obermeier, Influence of Thermal Radiation tria 1984.
Heat Transfer on Effective Liquid Thermal Conductivities; [15] DIN 53015, Viscometry; Measurement of Viscosity Using the
Experimental and Theoretical Investigation. Proceedings of Hoeppler Falling-Ball Viscometer, Beuth Verlag, Berlin 1978.
9th European Conference on Thermophysical Properties, Sept. [16] DIN 51562, Viscometry; Measurements of Kinematic Viscos-
1984, Manchester, to be published in High Temperatures, ity Using the Ubbelohde Viscometer, Beuth Verlag, Berlin
High Pressures. 1983.
H. Poltz and R. Jugel, Int. J. Heat Mass Transfer 10, 1075 [17] R. W. Gallant, Physical Properties of Hydrocarbons, Gulf
(1967). Publishing, Houston 1970.
G. Schodel and U. Grigull, Kombinierte Warmeleitung und
Warmestrahlung in Fliissigkeiten. Proc. 4th Int. Heat Transfer (Eingegangen am 24. Januar 1985, 5939
Conference Paris 1979. Vol. 111, R2. endgultige Fassung am 27. Marz 1985)

Excess Molar Heat Capacity of (1,2-Dichloroethane + Benzene) Revisited

A. Lainez
Departamento de Quimica Fisica, Universidad Complutense, Madrid, Spain

J.-P. E. Grolier
Laboratoire de Thermodynamique et Cinbtique Chimique, Universiti: de Clermont-Ferrand 2, F-63170 Aubiire, France

Emmerich Wilhelm
Institut fur Physikalische Chemie, Universitat Wien, WahringerstraDe 42, A-1090 Wien, Austria

Excess Heat Capacities Liquid Mixtures Thermodynamics

Excess molar heat capacities C," at constant pressure were measured, as a function of mole fraction x1 at 298.15 K, for {xl 1,2-C2H&
+ x2CsHs}. Determinations in the regions x1 < 0.1 and x1 > 0.9 were emphasized. The instrument used was a Picker flow calorimeter.
The new data corroborate our results of 1977 [2]: CpE shows only one minimum at about xlSmin= 0.4595, and C,"(xl,min)= -1.162
J K-' mol-'. The "inverted" W-shaped composition dependence of CF, as inferred by Baiios et al. [9] from their measurements of excess
enthalpies between 288.15 and 318.15 K, is thus shown to be untenable.

1. Introduction
1,2-Dihaloethanes are classical examples of molecules
showing rotational isomerism (trans-gauche conformational
equilibrium) [I]. In particular, 1,2-dichloroethane (1,2-
DCE) - either in the pure liquid state or in mixtures with
various hydrocarbons - has been well investigated, the fo-
cus being on thermodynamic and acoustic properties (see
for instance Refs. [2-41). Perhaps one of the most inter-
esting results obtained recently is the highly unusual com-
position dependence of the excess molar heat capacity C,",
at 298.15 K, in the series (1,2-DCE + an n-alkane) [S]. In
mixtures with the lower n-alkanes, say n-hexane, the curve
CpE vs. mole fraction x1 of 1,2-DCE is almost W-shaped.
This behavior is remarkably similar to that found in the
series (1P-dioxane + an n-alkane) [6]. At present, only a

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