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Electrical conductivity of aqueous sodium hydroxide

solutions at high temperatures

Article  in  Journal of Solution Chemistry · November 1994

DOI: 10.1007/BF00974030

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Journal of Solution Chemistry, Vol. 23, No. 11, 1994

Electrical Conductivity of Aqueous Sodium

Hydroxide Solutions at High Temperatures
H. Bianchi, 1 H. R. Corti, 1,2 and
R. Fern&ndez-PrinF 2
Received May 2, 1994; Revised August 19, 1994

Electrical conductivities o f dilute sodium hydroxide aqueous solutions

have been determined at 75, 100 and 150~ at 1.6 MPa using a recently
developed DC-measuring technique especially suited for the study of
aqueous solutions above room temperature. The data were analyzed with
modern theories to obtain the infinite dilution conductivity and the associa-
tion constant at the three temperatures.

KEY WORDS: DC conductivity; sodium hydroxide; high tempera-

tures; association constants,

1. INTRODUCTION
Electric conductivity is a classical experimental technique which
has proved to be a very precise and flexible tool for the determination of
the transport and thermodynamic properties of dilute electrolyte solu-
tions. Its success also depends on the fact that the available theoretical
treatments for symmetric electrolytes are able to describe precisely the
concentration dependence of the dilute solutions. (1) More recently the
theory of electrolytic conductivity has been extended (2~) to unsymmetri-
cal electrolytes and mixtures of electrolytes; its performance for mix-
tures of electrolytes containing unsymmetrical electrolytes has been
tested at room temperature. (4) Thus, electrolytic conductivity can be an
important tool for the study of the behavior of aqueous electrolytes at
high temperature. This field was explored many years ago by Noyes, (s)

1Departamento QuLmica de Reactores, Comisi6n Nacional de Energfa At6micr Av.

Libertador 8250, 1429-Capital Federal, Argentina.
2Member, Carrera del Investigador CONICET.
1203
0095-9782/94/I1G0-1203507.00/09 t 994 PIenmnPublishingCorporation
1204 Bianchl, Corti, and Ferndndez-Prini

after that there were important contributions from the schools of E.U.
Franck, C6)of S. W. Benson, ~ W. L. Marshall (g) and W. Lindsay. (9~These
pioneering studies were devoted essentially to the study of associated
electrolytes and since they were previous to many of the more m o d e m
theories, they were not able to extract information on the association
constants of slightly associated electrolytes.
To get the full advantage of the conductivity measurements it is
necessary to have an overall precision better than 0.1 percent. With this
purpose we have designed and built a DC conductivity apparatus and air
oven which enabled us to accomplish such a goal) 1~ Here we report the
results obtained for NaOH dilute aqueous solutions up to 150~ The
limitation in the upper temperature that could be studied in this work
was the result of the materials used for the gaskets which prevent leaks
and electrically insulate the electrodes.

2. EXPERIMENTAL
In order to study aqueous systems at high temperature, it is con-
venient to use metal vessels to contain the solutions, but this is likely to
introduce spurious components in the equivalent circuit of an AC
measuring system thus complicating the determination of the electrical
resistance o f the solutions. For this reason we favored the use of the DC
conductivity technique which had been introduced by Gunning and
Gordon ~ to study solutions at room temperature and shown to be a
good alternative to the standard AC measuring method in terms of the
attainable precision. A drawback of this technique is that it requires the
use of reversible electrodes, so that the measured electric resistance is
only related to the ohmic component and no faradaic resistances con-
tribute to it. In our case we decided to employ as the measuring revers-
ible electrodes, platinum disks covered with platinum black, the solu-
tions were saturated with gaseous hydrogen to guarantee reversibility of
the electrochemical reaction leading to charge transfer at the electrodes.
Only a brief account of the conductivity setup is given here since
it has been described in detail elsewhere. (12) The cell consists o f five
platinum disk electrodes insulated with teflon gaskets and pressed be-
tween anodized zircalloy rings. The resistance of the passivation layer
on the surface of the zircalloy was more than a thousand times bigger
than the highest resistance measured in the solutions. Each of the five
platinized platinum electrodes were sandwiched between two teflon gas-
kets and introduced between two zircalloy cylinders, thus forming the
conductivity cell illustrated in Fig. 1. The two extreme electrodes were
used to introduce a DC-electfic pulse in the cell; the three intermediate
NaOH Conductivities 1205

Teflon Insulation

Zircalloy Rings

Fig. 1. Sketchof the injectionsystemand conductivitycell describedin the text.

electrodes formed two independent conductivity cells and the dif-
ferences of electric potentials between pairs of electrodes were
monitored.
The conductivity cell was thermostatted within +0.01~ (~z) in a
high performance air oven and the pressure of the system was fixed with
a back pressure regulator (BP). The operation of the conductivity setup
and the oven used as thermostat was carried out through a digital con-
trolling and data-acquisition unit. DC pulses not exceeding 300 mV and
lasting 1 s were produced by the controlling unit; the pulses were used
to determine the electric resistance of the cell comparing the electric
potential differences produced in the conductivity cells with that ob-
served in a standard resistor (RR). The DC pulse was controlled by a
personal computer (PC) which monitored the ceils using a digital
voltmeter (DVM) and an analog signal scanner (SC).
To guarantee a low level of contamination of the working solu-
tion, the cell was designed to allow solutions to flow through them. Be-
fore entering the actual cell, the working solution was only in contact
with stainless steel, teflon and sapphire. The hydrogenated solution was
injected into the system through a high pressure liquid chromatography
pump (HPLC). To avoid boiling of the solutions, all measurements
1206 Bianchi, Corti, and Ferndndez-Prini

were carried out at 1.6 MPa; the pressure was monitored downstream
with a calibrated pressure transducer (T).
Sodium hydroxide solutions were prepared by decomposition of
sodium mercury amalgam in water under an inert atmosphere. The mer-
cury employed to prepare the amalgam was purified using standard
procedures involving a nitric acid treatment, an alkaline oxidation and
finally vacuum distillation. The amalgam was prepared by electrolysis
of an aqueous solution having 40 wt. percent of NaOH (Mallinckrodt
pro analysi) using the purified mercury as cathode and a platinum foil
anode. An approximately 0.1 molar sodium hydroxide stock solution
was obtained after the amalgam was completely decomposed in water.
This stock solution was weight titrated with 0.1 molar potassium
biphthalate using a digital analytical balance, weighing burettes and a
pHmeter. The titrations were carded out in a closed cell flushed with
CO2-free nitrogen. The solutions which were studied were carefully
prepared by weighing the appropriate amount of stock solution under a
controlled atmosphere. The solutions were hydrogenated before they
were injected into the conductivity cell to reduce the bias potential be-
tween the measuring (reversible) electrodes.
Table I. Solvent Properties at 1.6 MPa

~C p~ (g-cm "3) lqa (P) eb

50 0.98868 0.0054730 69.94

75 0.97553 0.0037825 62.27
100 0.95910 0.0028223 55.44
150 0.91770 0.0018279 43.96

aRef. 16. bRef.18.

The conductivity data for NaOH at 50 and 75~ obtained by

Marsh and Stokes (13) were used to determine the cell constants at these
temperatures. At higher temperatures the cell constants were corrected
for the thermal expansion of the zircalloy rings a*) which did not con-
tribute more than 0.1 percent to the cell constant between 50 and 200~
The density of the solutions were calculated from the partial molal
volumes of the electrolyte(~s) and water densities (~) at the experimental
temperature. The values of viscosity, density and dielectric constant of
water used are summarized in Table I.
NaOH Conductivities 1207

Table H. NaOH Conductivity Data at 1.6 MPa

75~ 100~ 150~

103C= Ab 103C~ Ab 103C = Ab

1.6757 472.70 1.6475 588.63 1.8463 799.47

1.9627 471.67 1.9296 588.11 1.8463 799.56
1.9627 471.77 1.9296 588.35 1.8463 799.47
1.9627 471.67 1.9296 587.98 2.4198 795.19
4.1421 467.58 3.7589 579.74 2.4198 795.85
4.1421 467.41 3.9835 580.20 3.8117 785.90
4.1421 467.11 3.9835 580.04 3.8117 786.36
5.2894 464.66 4.0023 579.42 6.8955 772.91
5.7577 464.29 4.8217 576.53 6.8955 772.47
7.3296 462.10 5.4554 575.98 7.9816 770.41
7.3296 462~ 5.4554 575.83 8.6977 767.52
8.4841 460.15 5.4554 575.85 10.231 762.64
9.2452 459.02 5.4554 575.68 14.594 752.39
10.875 457.81 7.9076 570.29
15.512 452.32 7.9076 570.27
15.512 452.41 8.3413 569.14
15.512 452.40 10.692 567.80
15.251 561.27
15.251 561.40
a
mol-dm-3 . b
S-cm2-mo1-1.

3. RESULTS
The cell constants had values of 4.0045 and 4.0020 cm -x with an
uncertainty of 0.05 percent. The bias potentials between pairs of
electrodes, which were monitored before and after each determination of
the difference in their electric potentials, were about 0.5 mV and were
determined within 10 percent. Table II reports the measured conduc-
tivities of NaOH at 75, 100 and 150~ The performance of the conduc-
tivity cell improved at temperatures higher than 75~ mainly due to
smaller bias potentials.
In order to fit the experimental data we have used the well proven
expansion of the Fuoss-Hsia equation (FHFP) (17) and also the Lee and
Wheaton complete equation (LW) c2~which is the most successful of the
available equations for the general case of dilute electrolyte mixtures/4~
Ion association cannot be neglected for NaOH at temperatures above
1208 Bianchi, Corti, and Ferndndez-Prini

ambient, an incipient ionic association is observed when analyzing the

results of Marsh and Stokes for 75~ (1~ Ionic association corresponds
to the process,

Na+(aq) + 0H-(aq) <__--->Na0H(aq) (1)

and the association constant KA is
(1 - a)C
KA - (2)

where a is the degree of dissociation of the electrolyte and y• its mean

activity coefficient.
In the calculation of the association constant from the conduc-
tivity data, we have used the Debye-Htickel expression for the activity
coefficients of the free ions and the distance of closest approach of free
ions d was fixed at the value of the Bjerrum distance q. According to
the FHFP equation, the conductivity of NaOH is given by,
a-lA = A ~ - Sq"aC + E a C l n (aC) - J , ( d ) a C + J2(d)(aC) 3n (3)
For the LW equation we have,
$ S

)~j= ~j ( 1 + zjEZE tv%pj [A~(~d)(13~:)+BvPOcd)(~) 2 + CvP(r.d)(~x:)'])

p=2 v=l
IzjbceF
-6~q(1 + r,d)( 1 + ~')(r,d)(~c) + ~2)(r,d)(~l~:)2 + 1-l~5)rd/6) (4)

where 1~ is e2/e&T and the other symbols are described in the original
paper. (2) The conductivity of the NaOH solutions were calculated from
the ionic conductivities using

A = ct[~,(Na+) + ~.(OtV)] (5)

The values of the dielectric constant and viscosity of pure water at dif-
ferent temperatures were taken from reliable sources, t16'ls)
Table III gives the least-square best-fit parameters obtained with
the two theoretical expressions for the data reported in the present work
and those reported by Marsh and Stokes (13) for 4 lower temperatures.
Figure 2 illustrates the deviation of the points as function of the con-
centration. In the case of NaOH at 75~ we have also included the
deviations of the data obtained by Marsh and Stokes (13) which are about
five times more precise than the ones obtained with our high tempera-
NaOH Conductivities 1209

0,5 h -- I I ' I

75 ~
0.0 O

-0.5
1

100 ~
</ 0.0 ,b " ~

-0.5
0.5 - - " ~ ' - I J L

150 ~
e._ @
0.0 8 - v

-0.5 1 t

0 5 10 15 20 25

C/mmolar

Fig. 2. Scatter of the conductivity data of NaOH at different temperatures

and 1.6 MPa: o, Marsh and Stokes, Ref.13; o, this work.

ture conductivity setup at the same temperature. It should be mentioned

that in Figure 2 only the deviations of FHFP equation are shown since
the performances of Eqs (3,4) were found to be almost indistinguish-
able. Consequently, the standard deviations are almost the same for
both equations as indicated in Table II, Also the differences between
the values of the parameters with both theories are within the ex-
perimental uncertainty.

4. DISCUSSION
It is highly rewarding to verify ( cf Fig. 2 and Table II) that the
conductivity parameters of the equations corresponding to two different
theoretical treatments agree so closely. This is in contrast with the usual
discrepancies that have been reported to exist among different theoreti-
cal treatments,m It is clear from Table III that the data for NaOH at
75~ may be considered to correspond either to a dissociated electrolyte
or to a slightly associated electrolyte.
Figure 3 shows the Walden product as a function of temperature
for sodium hydroxide. We have also included the data previously
reported by other authors(s'9~ at higher temperatures. The Walden
products for NaOH are compared in the same figure to the HC1~176
and NaC1(9) data. As expected, the Walden product for NaOH has a
1210 Bianchi, Corti, and Ferndndez-Prini

Table HI. Data Analysis of NaOH Aqueous Solutions

103C A~ d KA c5 Ref.
oC Molar S-cm2-mol"1 nm dm3-mol S-cmZ-molq

Fuoss-Hsia-Fem~ndez-Prini
15 1.3-18.0 205.68 +-0.02 0.358 a 0.08 12
25 1.3-18.0 249.32+-0.02 0.354 a 0.06 12
50 0.8-17.6 364.58+-0.03 0.356 a 0.11 12
75 1.0-19.2 484.01+-0.07 (0.384) 0.30+-0.02 0.09 12
b
1.7-15.5 484.42+0.2 (0.384) 0.5+-0.1 0.45
b
100 1.6-15.3 603.57+-0.5 (0.404) 0.8+-0.2 0.91
b
150 1.8-14.6 827.03+ 0.4 (0.449) 2.9 + 0.2 0.65
Lee-Wheaton
15 1.3-18.0 205.65:1:0.02 0.403 a 0.07 12
25 1.3-18.0 249.29+0.01 0.388 a 0.05 12
50 0.8-17.6 364.55+_0.03 0.370 a 0.I0 12
75 1.0-19.2 483.93+-0.06 (0.384) 0.22 + 0.02 0.09 12
b
1.7-15.5 483.46+-0.2 (0.384) a 0.64
b
1.7-15.5 484.37+-0.2 (0.384) 0.4+-0.1 0.43
b
100 1.6-15.3 603.49+-0.3 (0.404) 0.8-+0.2 0.94
b
150 1.8-14.6 826.90+ 0.4 (0.449) 2.8 +-0.1 0.69

a Completely dissociated electrolyte, b This work. c Values of d in parenthesis indicated

that it was fixed at the value of q.

temperature dependence which is between that of HC1 and that of NaC1;

this is due to the contribution of the proton transfer mechanism to ionic
mobility.
Figure 4 shows the dependence of lnKa on the reciprocal tem-
perature for the data reported in the present work, including the datum
for 75~ of Marsh and Stokes. ta3)
In terms of the Bjerrum model, the association constant is deter-
mined by the value of the distance a between cation and anion in the ion
pair according to o)
4gNn a 2d
KA - ~ f r 2 e x p ( r ) dr
Ja (6)

For NaOH association, the distance between ions in the ion pair
was found to be 0.32+0.02 nm at 100~ and 0.23+0.02 nm at 150~
The value for 100~ is somewhat larger than the sum of the crystal-
lographic ionic radii (0.235 nm). Thus, as expected, the NaOH(aq) ion-
pair does not appear to be a solvent separated ion-pair.
NaOH Conductivities 1211

4.5 "

|
4.0
0
3.5
O
3.0
|
~:: 2.5
%
2.0 O A
@
[]
1.5 ~TA
[]
T
1.0 V ~, y

I I -i mL
0.5
0 5O 100 150 200 250
T~ ~
Fig. 3. Walden product for different salts as function of the temperature. NaOH: o,
Marsh and Stokes Ref. 13; m, Quist and Marshall Ref. 8; A from Ref. 9; V, this work;
NaC1; le, from Ref. 9; HC1; o, Strong, Ref. 19; A, Frantz and Marshall, Ref. 20, l , from
Ref. 9.

~2

-2

- - I t I
1.5 2.0 2.5 3.0
]o~ K/T

Fig. 4. Ion pair formation constant at different temperatures:

n Izatt et al, Ref. 21; T, Marsh and Stokes, Ref. 13,., this work

In Figure 4 we have also plotted the values calculated by Izatt et

al. (21) from heat of dilution data for higher temperatures. Although the
temperature ranges of both sets of data do not overlap it appears that the
values of KA obtained in the two laboratories do not agree. We consider
that the association constants reported by Izatt et al. are too low since
they correspond to a = 0.57nm at 250~ according to the Bjerrum
 1212 Bianchi, Corti, and Ferndndez-Prini

model, a value considered too large since it would imply an ion pair
separated by more than one solvent molecule.
The high temperature cell is now being modified so as to replace
with ceramics the teflon gaskets which have seriously limited the
highest temperature at which our cell may be used.

REFERENCES
1. R. Fern~adez-Prirti, in Physical Chemistry of Organic Solvent Systems, A.K.
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