Acta Chim. Slov.

2006, 53, 391–395 391

Technical Paper

Modern Advances in Electrical Conductivity

Measurements of Solutions†
Marija Bešter-Rogač1*, Dušan Habe2
1
Faculty of Chemistry and Chemical Technology, University of Ljubljana, SI-1000 Ljubljana, Slovenia.
2
Test and Measurement Technique, Tribuče4/b, SI-8340 Črnomelj, Slovenia,
http://www.tm-measurement.com.
Received 15-06-2006
†
Dedicated to the memory of Prof. Dr. Davorin Dolar

Abstract
The temperature and concentration dependence of the electrolyte conductance is one of the most appropriate
methods for studying ion-ion, ion-solvent and solvent-solvent interactions in solutions and can be widely applied
in diverse ionic systems. In this work an improved method for determining the precise temperature-dependent
electric conductivity data in a more user-friendly way is described.

Key words: electrical conductivity measurements, electrolyte solution

1. Introduction excellent characteristics needed for high accuracy

measurements. They have been described in detail in
The temperature and concentration dependence literature2 but are still not commercially available.
of the electrolyte conductance has been proved as one The conductivity measurement in the measuring
of the most appropriate methods for studying ion-ion, cell has been accomplished by using an electrode
ion-solvent and solvent-solvent interactions in solutions. assembly in the arm of an a.c. bridge, built on the
Evaluating the conductivity within the framework of classical lines of Jones3 and Shedlovsky.4 Using the
present electrolyte theories requires high accuracy precise conductance bridge, the electrolyte conductance
in measurements which is difficult to achieve over a at every temperature was obtained with accuracy better
sufficiently large temperature range. In order to obtain than 0.01%. More information on this measuring
the sufficiently accurate conductance data which could equipment, temperature control and measuring method
be used in conductance equations, it is necessary to is given elsewhere.1 This equipment has been used by
have an equipment which allows reasonably quick and the Institute of Physical and Theoretical Chemistry,
accurate measurement at different temperature values. University of Regensburg, Germany for more than
Temperatures need to be accurate within 0.001-0.005 K 30 years. The evidence of its excellence is reported in
to achieve the required reproducibility of data. There is more than 100 papers on high precision conductance
a thermostat assembly which meets these requirements data of (mainly) non-aqueous electrolyte solutions.
and has been described in detail in literature.1 It is necessary to stress that the described equipment
The concentration dependence of conductance (conductivity cells, temperature bath, a.c. bridge) was
can be determined in different ways. Usually, solutions entirely developed in the laboratories and workshops
are prepared by mixing the solvent and electrolyte of the University of Regensburg and is therefore
compounds by weight. A method, which allows stepwise unavailable commercially. Nevertheless, this equipment
concentration by successive additions of weight samples is a master piece of work and means actually the borders
of the electrolyte compound (pure or in solution), of feasibility in conductivity measurements.
starting from the pure solvent, has proved to be very With the kind help of Professor Barthel and
useful. Dipl. Ing. Herbert Hilbinger from the Institute of
Every method requires appropriate measuring cell, Physical and Theoretical Chemistry, University of
built according to the requirements of the electrolyte Regensburg, similar equipment has been built at the
solution and the desired concentration range to be Chair of Physical Chemistry, Faculty of Chemistry and
studied. At the University of Regensburg different Chemical Technology, University of Ljubljana, Slovenia,
conductance cells were developed which showed allowing measurements between 5 and 45 °C. In our

Bešter-Rogač and Habe Modern Advances in Electrical Conductivity Measurements of Solutions

392 Acta Chim. Slov. 2006, 53, 391–395

case some parts of the equipment have been replaced However, the advantages is that the precise
by commercially available apparatus: Lauda WK1400 temperature-dependent electric conductivity
which serves as a cold bath and Lauda UB40 functioning measurement can be widely applied in ionic systems
as a precise measurement thermostat. The temperature (electrolyte and polyelectrolyte aqueous and nonaqueous
of the measurement thermostat is controlled by solutions, ionic surfactants, microemulsions containing
precision platinum resistance thermometer Pt 100 ionic surfactants…). We belive that a lot of challenging
(MPMI 1004/300 Merz) attached to a HP 3458A work still remains in the field of theoretical work,
Multimeter. Resistance thermometer is calibrated especially studying concentrated electrolyte solutions,
regularly at the National laboratory, authorized for non-symmetrical electrolytes and higher-charged
thermometer calibration. electrolytes, which needs to be supported by reliable
Each temperature value of the chosen temperature and precise experimental data.
program was attained within 15 minutes with an accuracy To eliminate some of the deficiencies of the system
of better than 0.005 K. It was closely monitored that both we tried to make the temperature-dependent electric
short, as well as long-term temperature fluctuations conductivity measurements more »user friendly«
were below 0.005 K, and no considerable temperature and attractive for contemporary students by using
drift beyond this limit could be observed. However, modern technology, and still not to lose precision
this accuracy is still five times lower than the accuracy requirements.
reported by the University Regensburg for its specially The weaknesses of the existing system in our
designed equipment. Nevertheless it turned out that this laboratory can be summarised as the following:
accuracy in the temperature setting and reproducibility i. Manual measuring.
still allows the accuracy in the measurement of data
ii. Long measuring times giving small number of
required for the evaluation within the framework of
results.
current electrolyte theory.
Using a three-electrode conductivity cell for dilute iii. Very narrow impedance measurement range in
solutions and a set of nine capillary cells, which we limited frequency range, limiting measurement
obtained as a gift from Professor Alexander Apelbat possibilities, consequently leading to larger number
(Ben Gurion University of the Negev, Beer-Sheva, of measuring cells with adopted impedance.
Israel) and Professor Josef Barthel (University of iv. The system is not “user friendly”. It demands
Regensburg, Germany), the resistance of the electrolyte permanent presence of a laboratory worker
solutions in the cells was measured, using a highly to record the resistance values and adjust the
precise conductance bridge (LEEDS & NORTHRUP). temperature at a desired value.
At 25 °C and relative humidity not exceeding 50%, the
precision of the bridge at 0.02 % is decleared in its To avoid the above mentioned weaknesses it has
technical specification. been decided to replace and/or upgrade some system
The measuring equipment described above has components. The scheme of the upgraded system is
proved successful in some investigations carried out shown in Figure 1, followed by detailed explanation.
in aqueous 5-8 and also in non-aqueous electrolyte The control of the measuring instruments and
solutions.9 process is entered with the computer, which gathers
Despite the high precision which has been measurement results (Figure 2). The laboratory worker
achieved for the temperature-dependent electric needs only to
conductivity measurements the method is not widely i. select a temperature range and define the allowed
used. Moreover, it has been labelled as an »old temperature deviation for the beginning of the
fashioned« procedure compared to other »modern« temperature stabilization (A),
methods (spectroscopy, scattering techniques...). ii. choose the time of the temperature stabilization of
One reason for this opinion certainly may be that the the sample (B),
precise temperature-dependent electric conductivity
measurement is a very time consuming method. It iii. enter the number of measured cells (C),
demands a person to carefully monitor the temperature iv. specify the file, where the data are stored (D) and
cycle and record the frequency-dependent electric v. the desired range and frequency step (E).
resistance for each temperature of the program. For
this reason this procedure is not particularly attractive All this data can also be written in the “setup file”
for modern generations who are used to computer and (F) and confirmed by “load setup” (G). At this point
quick solutions. This attitude can be observed with our the measurement is started (H). The cold bath and the
students who see the conductivity bridge for the first measurement thermostat are set at the first temperature
time and look upon it as something out-of-date. value of the program. After reaching the desired

Bešter-Rogač and Habe Modern Advances in Electrical Conductivity Measurements of Solutions

 Acta Chim. Slov. 2006, 53, 391–395 393

PERSONAL COMPUTER

SWITCHING UNIT
DMM AGILENT 3458A LCR AGILENT 4284A

Pt 100

ULTRA THERMOSTAT CIRCULAR COOLER

LAUDA UB40 LAUDA WK1400

Figure 1. Thermostat assembly with a cold bath (Lauda WK1400), a measurement thermostat (Lauda UB40) with an immersed conductivity
cell, attached to the new measuring equipment. The weaknesses in impedance measurements of the system were eliminated by purchasing
an Agilent Technologies 4284A automatic electronic impedance analyzer of highest measuring accuracy. This instrument allows accurate
measurements disregarding the resistance of the sample. The adaptation of the expected resistance with the cell constant, which enables
the measurement by the resistance bridge, is not needed. In terms of automation of the system the general requirement was that all system
components should have a suitable interface to connect to a computer. This required the replacement of some system components. Finally,
by adapting the switching unit the system allows selection of a single cell or a set of cells (up to 9) for measurements.

I
A

K
B E J
C F
D G
H
Figure 2. An example of the display with graphical user interface showing the measurement process. For explanation see the text.

Bešter-Rogač and Habe Modern Advances in Electrical Conductivity Measurements of Solutions

394 Acta Chim. Slov. 2006, 53, 391–395

temperature with defined precision, the program will of measurements on aqueous solutions of saccharine
procede with thermostating the sample (stabilization (c = 7.317⋅10-4 mol dm-3) at 35 °C. The extrapolation
time) which is followed by measuring the resistance in values were 2638.7 Ω and 2640.3 Ω measured by LEEDS
the desired range of the frequencies (usually between & NORTHRUP conductivity bridge and a precision
200 and 6000 Hz in steps of 200 Hz). The measured LCR meter Agilent 4284 A respecitively. The obtained
resistance values are shown on the display (I) in difference is still within the declared precision of the
relation to the frequency. Finally, the temperature bridge and the LCR meter. For this reason the new
in the measurement thermostat is controlled (Pt 100, upgraded equipment could be regarded as an excellent
Agilent 3458A, Figure 1) and displayed (J). In case of substitute for the old one.
a single cell measurement the system is switched to
another temperature of the program and the procedure 2648
is repeated. If the set of cells is being measured, the R/ Ω
program will measure the resistance of all samples at 2646
the set temperature, and only then the temperature is
changed. 2644
Thus the graphical user interface keeps the
experimentator updated on the measurement process 2642
status (K) and displays measured results. The remote
control of the entire measurement process is possible 2640
either through local area network or from the internet.
The results (temperature and the frequency dependent 2638
0 2 4 6
resistance) are saved in a file (D) and available for 1/ ν *1000/Hz
-1

further analysis.
Figure 3. Frequency dependence of measured solution resistance
Basic specifications of the improved measurement at 35 °C (aqueous solutions of saccharine; c = 7.317⋅10-4 mol
system are: dm-3); () LEEDS & NORTHRUP conductivity bridge, (O)
i. Temperature range 0-45 °C, stability ±0.005 K. Agilent 4284A.

ii. Measurement uncertainty for resistance measu-

rement: > 0.05 %.
We may conclude that the improved method is
iii. Measuring frequency range: 20 Hz - 1 MHz. a useful and reliable technique for determining the
iv. Simultaneous measurement up to 9 conductivity precise temperature-dependent electric conductivity
cell with automatic switch between them. data in a more user-friendly way which makes made
this method more interesting and appealing for many
However, the temperature range is still limited by laboratories and even companies.
the characteristics of the cooler and the thermostat in We would like to emphasize that the conductivity
our equipment. In the future it needs be improved by cells play an important role but are not commercially
their replacement. It should also be mentioned that the available. Making a cell requires a highly skilled
temperature of the cooler and thermostat should be set glassblower. Last but not least, it should be stressed
appropriately (see A in Figure 2) to obtain the desired that while modern technologies make measurements
temperature with sufficient accuracy. So far these values easier, the high precision, which has been achived by
have been obtained by introducing of some additional the apparatus developed by the Institute of Physical and
measurements following the temperature oscillations Theoretical Chemistry at University of Regensburg2 still
in the measurement thermostat. Consequently, the remains inaccessible for general use.
actual temperature is also controlled separately by the
help of the calibrated Pt 100 resistant thermometer 2. Acknowledgment
(Figure 1).
In order to check the reliability of this upgraded This work was supported by the Slovenian
equipment some paralel measurements were carried Research Agency through Grants No. P1-0201 and J1-
out using the same solutions. Firstly, the resistance 6653. M. B. R. is grateful to Prof. Josef Barthel, Prof.
was obtained by the help of LEEDS & NORTHRUP Werner Kunz, Dipl. Ing. Herbert Hilbinger (University
conductivity bridge, followed by measurement using of Regensburg, Germany) and Prof. Alexander Apelblat
LCR meter Agilent 4284 A. As usually, the resistance (Ben Gurion University of the Negev, Beer-Sheva,
measurements were made at different frequencies from Israel) for providing the conductivity cells.
which the value R at infinite frequency was obtained by
linear extrapolation.1 Figure 3 shows the comparison

Bešter-Rogač and Habe Modern Advances in Electrical Conductivity Measurements of Solutions

 Acta Chim. Slov. 2006, 53, 391–395 395

3. References 5. M. Tomšič, M. Bešter-Rogač, A. Jamnik, R. Neueder, J.

Barthel, J. Solution Chem. 2002, 31, 19–31.
1. R. Wachter, J. Barthel, Ber. Bunsenges. Phys. Chem. 1979, 6. M. Bešter-Rogač, V. Babič, T. M. Perger, R. Neueder, J.
83, 634–642. Barthel J. Mol. Liq. 2005, 118, 111–118.
2. J. Barthel, R. Wachter, H.-J. Gores, in : B. E. Conway, J. 7. D. Rudan Tasič, T. Župec, C. Klofutar, M. Bešter-Rogač,
O´M. Bockris (Ed.): Modern Aspects of electrochemitry J. Solution Chem. 2005, 34, 631–644.
No. 13, Plenum Press, New York, 1979, pp. 1–79. 8. A. Apelblat, M. Bešter-Rogač, J. Barthel, R. Neueder,
3. G. Jones R. C. Josephs, J. Am. Chem. Soc. 1928, 50, J. Phys. Chem. B 2006, 110 (17), 8893–8906.
1049–1092. 9. M. Bešter-Rogač, N. Hauptman, J. Barthel, J. Mol. Liq.
4. T. Shedlovsky, J. Am. Chem. Soc. 1930, 52, 1793–10805. accepted for publication.

Povzetek
Temperaturna odvisnost električne prevodnosti raztopin je ena izmed najbolj primernih metod za študij interakcij
v raztopinah različnih ionskih sistemov. V tem delu smo opisali posodobitev metode merjenja temperaturne
odvisnosti električne prevodnosti.

Bešter-Rogač and Habe Modern Advances in Electrical Conductivity Measurements of Solutions