14th International Conference on the Properties of Water and Steam in Kyoto

The Equations for Thermophysical Properties of Aqueous

Solutions of Sodium Hydroxide
Alexey A. Alexandrov*

Department of Theoretical Principles of Thermotechnics, Moscow Power

Engineering Institute (Technical University), Moscow Krasnokazarmennaya 14,
Russia
*
E-mail: [email protected]

The survey of experimental data on isobaric heat capacity, viscosity and thermal
conductivity of aqueous solutions of sodium hydroxide is presented. The equations
for these properties are obtained on base of experimental data. The equation for
isobaric heat capacity is obtained for the region of pressures up to 7 MPa and
temperatures up to 523 K. It is valid for solutions at concentrations up to 4 mol/kg
water. The equation for viscosity is valid for boiling solutions at temperatures up to
550 K at concentrations up to 3 mol/kg water. The equation for thermal
conductivity is obtained for region of temperatures up to 400 K at pressures up to
15 MPa for solutions at concentrations up to 5 mol/kg water.

1. Introduction diapason from 276 to 362 K was fulfilled by

Beretetti and McCabe [6] for solutions at
The aqueous solutions of sodium hydroxide are concentrations 4-51%. In region of high
applied in various branches of industry such as concentrations from 50 to 76% measurement of
power engineering, chemical technology and so on. heat capacity was fulfilled by Wilson and McCabe
In spite of this there is a little equations for [7] in range of temperatures 301-396 K. At
thermophysical properties of these solutions which saturation pressures for temperatures from 273 to
would be suitable for using in industrial 403 K Ackermann [8] carried out an investigation
calculations. The aim of this report is to present for solutions at molality 0.5-2 mol/kg. Puchkov,
equations for some of these properties based on Barinova and Matveeva [9] carried out the
experimental data valid in region of parameters and measurement of average heat capacity in interval
concentrations most important for power temperatures 25 K for solutions at concentrations
engineering and ones convenient for users. from 5 to 50% in region of temperatures 293-673 K
at pressures near to saturation one. These
2. Isobaric heat capacity experimental values were described by equations
which transformed form gives the possibility to
First experimental measurements of isobaric heat calculate a true heat capacity. Allred and Woolley
capacity were carried out at atmospheric pressures [10] published a results of investigation of diluted
and in narrow temperature interval. Thomsen [1] solutions at concentrations 0.04-0.4% in
fulfilled measurement of heat capacity of solutions temperature interval from 288 to 313 K as values of
at concentrations 1.1-23% (wt) at temperature 291 apparent molar heat capacity using data for heat
K. For more concentrated solutions at 16.5-47.4% capacity of pure water from [11]. Roux, Perron and
values of heat capacity were obtained by Takker [2] Desnoyers [12] presented the results of
in interval 292-297 K. In more wide temperature measurement also as apparent molar heat capacity
diapason 273-307 K investigation was carried out values for solutions at molality 0.02-10.9 and at
by Pratt [3] for solutions with content 0.6-16% of temperatures277-328 K. They accepted values from
sodium hydroxide. Richards and Hall [4] measured [13] for heat capacity of water. The only
heat capacity of solutions at concentrations 0.14- measurements of heat capacity of sodium
27.8% at temperatures from 288 to 293 K. Gucker hydroxide aqueous solutions in region of elevated
and Schminke [5] obtained heat capacity values for pressures up to 7 MPa was carried out by Simonson
solutions at concentrations 0.16-8.2% at one and Mesmer [14] in diapason temperatures from
temperature 288 K. Investigation in temperature 323 to 523 K. These authors investigated solutions

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14th International Conference on the Properties of Water and Steam in Kyoto

at molality 0.1-4 mol/kg and represented the results with standard deviations equal ı =0.032% for data
as values of ratio of heat capacities of solution and [13], ı =0.015% for [10] and ı =0.074% for [12].
that of water. Latter were determined with the help Values from [8] not used as input ones have the
of equation of state from [15]. The uncertainty in scatter from –0.87 to +1.4%
heat capacity ratio is estimated as (2-3)×10-4 It is known that the temperature dependence of
Besides data of experimental works there are water isobaric heat capacity at low temperatures has
values of heat capacity calculated by Akerlof and anomalous character. At atmospheric pressure it has
Kegeles [16] on base of measurements of a minimum at temperature equals 307.34 K [18].
electromotive force for solutions at molality 0.1-12 The aqueous solutions of sodium hydroxide have
mol/kg in temperature interval 273-343 K. analogues type of dependence for heat capacity at
After preliminary comparison of experimental low concentrations (Fig.1) with minimum
data of different works as input values for equation temperature decreasing when concentration is
were accepted the data of works [10, 12, 14] and increasing. Minimum of dependence reaches
part of calculated values from [9] for parameters temperature equals 0ºC at molality of solution
where another data are absent. The experimental m=0.455 mol/kg. For more concentrated solutions
values of apparent and relative heat capacities of minimum of heat capacity is absent.
solutions were recalculated into values of specific
heat capacity using water heat capacity values used 2. Dynamic viscosity
in each work.
Equation for isobaric heat capacity of aqueous The experimental investigations of dynamic
hydroxide solutions has a form viscosity of aqueous sodium hydroxide solutions
are carried out mainly at atmospheric pressure also.
j 5 i 5 Hitchcock and McIlhennny [19] measured viscosity
cp c p ,w  ¦¦ aijW i m j (1) of solutions at molality 1.1-8.3 mol/kg in
j 1 i 0
temperature diapason 293-313 K. Krings [20]
investigated solutions at concentrations 12.6-70%
where cp-isobaric heat capacity of solution, in range of temperatures from 295 to 343 K. For
kJ/(kg·K); cp,w- isobaric heat capacity of water, solutions at molality from 1.005 to 28.7 mol/kg
kJ/(kg·K); IJ =T/T0; T0 =273.15 K; m –molality of measurement of viscosity was fulfilled by Kobus
solution, mol/kg. The values of coefficients aij are [21] in temperature diapason 298-353 K. Klochko
presented in Table 1. The data for heat capacity of and Godneva [22] carried out measurements for
water are calculated from the equation of state for solutions at concentrations from 6.21 to 71.5% in
water liquid phase from IAPWS Formulation IF – range of temperatures 273-398 K. Baron and
97 [17]. Matveeva [23] measured viscosity of solutions at
Equation (1) is valid for solutions in the region concentrations from 3 to 47.6% in temperature
of concentrations up to 4 mol/kg at pressures up to range 298-363 K and then Baron and Tscherba [24]
7 MPa in range of temperatures from 273 to 523 K. extended the measurements in region of more low
In this region it describes the experimental values temperatures from 246 to 288 K for the solutions at

Table 1. Values of coefficients aij of equation (1) 4.23

4.21
a01=9.8555259×10 a03=1.9791083 4.19
Cp, kJ/(kg*K)

a11=-3.4501318×102 a13=-5.3828966 4.17

a21=4.8180532×102 a23=5.5124212 4.15
a31=-3.3440616×102 a33=-2.5430046 4.13
4.11
a41=1.1516735×102 a43=4.5943595×10-1 4.09
,

a51=-1.5708814×10 a04=-5.6191575×10-2 4.07

a02=-3.4357815×10 a14=8.5936388×10-2 4.05
a12=1.1674552×102 a24=-1.6966718×10-2 273 293 313 333 353 373
a22=-1.5776854×102 a34=-1.4864492×10-2 T, K
a32=1.0577045×102 a05=7.9944152×10-3 Fig. 1. Temperature dependence of heat capacity of
a42=-3.5099188×10 a15=-1.5444457×10-2 solutions: i - water, Ÿ - m=0.1, Ŷ - m=0.2, Ŷ -
a52=4.5935013 a25=7.5030322×10-3 m=0.3, Ŷ - m=0.4

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14th International Conference on the Properties of Water and Steam in Kyoto

concentrations 5.2-24%. Table 3. Values of coefficients ci, di of equation (3)

Most extensive investigation of viscosity of
aqueous sodium hydroxide solutions was carried I ci di
out by Mashovets, Puchkov, Sergaev and Fedorov 0 - -3.18833435×10-1
[25]. They measured the viscosity of solutions at 1 5.17341030 -1.07314454×10
molality 0.5-20 mol/kg in range of temperatures 2 9.81838817 -8.61347656×10
from 273 to 548 K and at pressures a little higher 3 2.83021985×10 -6.50268842×102
than saturation ones. This work is only one where 4 7.02071954×10 -6.06767730×103
measurements fulfilled at elevated pressures. The 5 -9.92041252×102 -4.07022741×104
uncertainty in its results is estimated by authors as 6 -1.13267055×104 -1.59650983×105
1-1.5%. 7 -5.10988292×104 -3.53438962×105
The data of works [20 –24] were used as input 8 -1.18863488×105 -4.11357235×105
values for elaboration of equation for viscosity of 9 -1.41053273×105 -1.96118714×105
solutions with moderate concentrations. Values of 10 -6.78490604×104 -
saturation pressures for work [25] were calculated
from equation [26] used as input data during the preparation of
The equation for viscosity of solutions was equation (3). It describes viscosity of water on
obtained in a form saturation line with standard deviation equals ı
=0.052% and describes viscosity of liquid under
j 3 i 4
i pressures higher than saturation ones with standard
ln K / K w  ¦¦ b T ij 0 /T m j (2) deviation equals ı =0.151%. The region of validity
j 1 i 1
of equation (3) includes temperatures up to 623 K
and pressures up to 30 MPa.
where K -viscosity of solution; K w -viscosity of Equation (2) describes the viscosity of solutions
water at the same pressure and temperature; at molality up to 3 mol/kg in temperature range
T0=293.15 K; values of coefficients bij are from 273 to 548 K and under pressures up to 6
presented in Table 2. MPa. In this region the standard deviations of
The viscosity of water can be calculated from values of experimental works are as follows: for
equation given in [27]. But the viscosity in this [25] ı =2.05%, for [23] ı =2.23%, for [24] ı
document is presented in dependence on =2.17%, for [21] ı =1.88% and for [22] ı =3.37%.
temperature and density. For industrial calculations These deviations are rather big and engendered by
it is more suitable often to have this property as great scatter of experimental values.
function of temperature and pressure. Therefore an In Fig. 2 the temperature dependence of relative
additional equation is prepared for viscosity of viscosity Ș/Șw is shown for solutions at different
water concentrations. It is known that different aqueous
solutions of electrolytes have different types of this
ªi 10 º i 9 dependence. For some solutions relative viscosity
Kw 1001.6(W  1) 2 exp « ¦ ciW i »  S ¦ d iW i (3) increases when temperature increases, for others it
¬i 1 ¼ i 0 decreases. It is clear from Fig. 2 that relative

where Șw –viscosity, µPa·s, W =(T0/T –1); T0

2,2
=293.15 K; S =(p –psw); p-pressure, MPa; psw –
saturation pressure of water; the values of
Ș/Șw

1,9
coefficients ci and di are given in Table 3. The
values calculated from equation given in [28] were 1,6

1,3
Table 2. Values of coefficients bij of equation (2)
1
b11 =5.7070102×10-1 b22 =3.7957782×10-1 273 373 473
b21 =4.9395013×10-1 b32 =-7.423751×10-2 T, K
b31 =-2.0417183 b13 =4.9815412×10-2
b41 =1.1654862 b23 =-4.8332728×10-2 Fig. 2. Relative viscosity of solutions: i - m =0.1,
b12 =-2.9922166×10-1 - Ŷ - m =1.0, ɯ - m =2.0, ǻ – m =3.0.

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14th International Conference on the Properties of Water and Steam in Kyoto

viscosity of low concentrated aqueous solutions of Table 5. Values of coefficients of equation (5)
sodium hydroxide increases and it decreases for
more concentrated ones. i gi qi
0 5.99454842×10-1 5.31492446×10-4
3. Thermal conductivity 1 -4.82554378×10-1 3.46658996×10-4
2 -4.31229616×10-1 1.23050434×10-2
The experimental investigations of thermal 3 -8.62555022×10-1 1.27873471×10-1
conductivity of aqueous solutions of sodium 4 -3.80050418×10-1 -7.40820487×10-1
hydroxide are scant and carried out mainly at 5 4.85828450×10 -1.93072528×10
atmospheric pressure also. Ridel [29] measured the 6 3.35400696×102 -1.22835056×102
thermal conductivity of solutions at concentration 7 1.08007806×103 -3.66150909×102
10.5-60% in temperature range from 274 to 353 K. 8 1.67727081×103 -5.31321978×102
Vargaftik and Osminin [30] measured the thermal 9 1.04225629×103 -3.03153185×102
conductivity at one temperature 293 K in range of
concentrations from 0 to 40%. Also at one where Ȝw –thermal conductivity, W/(m K); IJ=
temperature 311 K the thermal conductivity of (T0/T–1), T0 =293.15 K; ʌ =p –ps, p-pressure, MPa;
solutions with molality 1.36-16.4 mol/kg was ps -saturation pressure, MPa; coefficients gi and qi
measured by Losenicky [31]. The only are presented in Table 5. The equation (5) describes
investigation of thermal conductivity under thermal conductivity of water in region of pressures
elevated pressures up to 15 MPa was fulfilled by up to 30 MPa and temperatures up to 623 K. Values
Guseinov [32] in temperature range from 298 to of [33] were used as basis for this equation and it
401 K for solutions with concentrations up to 20%. describes these data with average square deviations
The experimental data of works [29-32] were equal ı =0.007% on saturation line and ı =0.198%
used as input values for elaboration of equation. for liquid under other pressures.
The equation obtained has a form Equation (4) is valid in region of pressures up to
15 MPa and temperatures from 273 to 405 K for
j 3 i 3
solutions with concentration up to 5 mol/kg. In this
O Ow  ¦¦ eij T / T0 i m j (4) region it describes the experimental data with
j 1 i 0
average square deviations equal ı =0.45% for [29],
ı =0.43% for [30], ı =1.0% for [31] and ı =0.52%
where O -thermal conductivity of solution, W/(m for [32]
K); Ow - thermal conductivity of water at the same The character of change of thermal conductivity
pressure and temperature; T0 =403.0 K; m –molality of solutions along saturation line is shown in Fig. 3.
of solution, mol/kg; values of coefficients eij are It is known that this dependence for water has
given in Table 4. The equations from [33] may be anomalous behaviour. Aqueous solutions of sodium
used for calculation of thermal conductivity of hydroxide remain that type of dependence. It can
water where it is given as functions of temperature note also that heat conductivity of these solutions
and density. Some times it is more suitable to increases when concentration increases in
calculate the thermal conductivity of water in contradiction to aqueous solutions of many others
dependence of temperature and pressure from electrolytes.
additional equation
750
i 9 i 9
i
Ow ¦gW i  S ¦ qiW i (5) 700
lamda

i 0 i 0
650

Table 4. Values of coefficients eij of equation (4) 600

E01 =3.2900544×10-1 e12=5.9100989×10-2 550

250 300 350 400 450
e11=-1.1048583 e22=-4.4407173×10-2 T, K
e21=1.2503803 e03=1.5069324×10-3
e31=-4.4228179×10-1 e13=-4.3273501×10-3 Fig. 3. Thermal conductivity of solutions on
e02=-2.1990820×10-2 e23=3.3763248×10-3 saturation line: i - water, Ŷ - m=1.0, Ŷ - m=5.0.

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14th International Conference on the Properties of Water and Steam in Kyoto

[14] J.M. Simonson and R.E. Mesmer, J. Chem.

14
Thermodyn., 21, 561 (1889).
11 [15] L. Haar, J.S. Gallagher and G.S. Kell, NBS/NRC
Delta, %

Steam Tables. Hemisphere, Washington, DC. (1984).

8 [16] G. Akerlof and G. Kegeles, J. Am. Chem. Soc., 52,
5 620 (1940)
[17] Release on the IAPWS Industrial Formulation 1997
2 for the Thermodynamic Properties of Water and
273 323 373 Steam, International Association for the Properties of
T, K Water and Steam, Executive Secretary R.B. Dooley,
Electric Power Research Institute, Palo Alto, Ca
Fig. 4. Deviations of viscosity values from [34] and 94304, USA
our once: i - m=1.0, Ŷ - m=2.0, ǻ – m=3.0 [18] A.A. Alexandrov and M.S. Trakhtengerts,
Thermophysical Properties of Water at Atmospheric
4. Discussion Pressure, Izdatelstvo Standartov, Moscow (1977)
[19] L.B. Hitchcock and McIlhenny, Ind. Eng. Chem.,
Extensive information about properties of 27, 461 (1935)
[20] W. Krings, Zeit. anorg. Chem., 255, 294 (1948)
aqueous solutions of electrolytes is given in
[21] G.L. Kobus, Proceed. Hydrometeorolog. Institute,
reference book [34]. But it concerns mainly to 7, Odessa (1955), 113
solutions at atmospheric pressure and at [22] M.A. Klochko and M.M. Godneva, Z. Neorg. Chem.
temperatures up to 100ºC. Values of heat capacity (Rus), 4, 2127 (1959)
and heat conductivity from [34] agree with our ones [23] N.M. Baron and R.P. Matveeva, Z. Priklad. Chem.,
within ±1.5%. The divergences of viscosity values 40, 673 (1967)
are bigger and are shown in Fig. 4. New equations [24] N.M. Baron and M.U. Tscherba, Z. Priklad.
presented in this work expand analytical Chem.,42, 2128 (1969)
representation of properties of sodium hydroxide [25] V.P. Mashovets, L.V. Puchkov, P.M. Sergaev and
solutions in region of higher temperatures and M.K. Fedorov, Z. Priklad. Chem., 46, 992 (1973)
[26] Draft release on vapor pressure of aqueous
pressures.
solutions (273–623 K), V.M. Valyashko, L.V.
Puchkov, M.U. Matyushenko, V.M. Giljarov, N.V.
Acknowledgment
Milovidova, R.P. Matveeva, N.A. Giljariva,
This work is supported by Scientific Council of Leningrad Technology Institute (1986), 3
President Program for Support of Scientific [27] Revised Release on the IAPS Formulation 1985 for
Schools. Grant 1414.8.2003 the Viscosity of Ordinary Water Substance,
International Association for the Properties of Water
References and Steam, Executive Secretary R.B. Dooley, Electric
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1013 (1933). [31] Z. Losenicky, J. Phys. Chem, 73, 451 (1969)
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[9] L.V. Puchkov, T.A. Baranova and R.P. Matveeva, Substance, International Association for the
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