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A high-accuracy, calibration-free technique for measuring the electrical conductivity of liquids

A high-accuracy, calibration-free technique for measuring the electrical conductivity of liquids

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A high-accuracy, calibration-free technique for measuring the electrical conductivity of liquids

A high-accuracy, calibration-free technique for measuring the electrical conductivity of liquids

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Published by: kgrhoads on Feb 04, 2013
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09/17/2013

 
Ahigh-accuracy,calibration-freetechniqueformeasuringtheelectricalconductivityofliquids
Susan L. Schiefelbein,
a)
Naomi A. Fried,
b)
Kevin G. Rhoads, and Donald R. Sadoway
c)
 Department of Materials Science and Engineering, Massachusetts Institute of Technology,Cambridge, Massachusetts 02139-4307 
͑
Received 8 May 1998; accepted for publication 1 July 1998
͒
A high-accuracy, calibration-free technique to measure the electrical conductivity of liquids hasbeen developed — the coaxial cylinders technique. Because the liquid under investigation comes incontact only with metal and not with anything dielectric, this technique enables the measurement of the electrical properties of liquids inaccessible by classical high-accuracy techniques. Two coaxialcylindrical electrodes are immersed in the liquid to an arbitrary initial depth, and ac impedance ismeasured over a wide range of frequency. This process is repeated at many immersions. Theelectrical conductivity is calculated from the change in measured conductance with immersion. Thistechnique was validated in 1.0, 0.1, and 0.01 D KCl
͑
aq
͒
solutions at room temperature. Measuredelectrical conductivities were within
Ϯ
0.5% of the standard reference values. ©
1998 American Institute of Physics.
͓
S0034-6748
͑
98
͒
04909-0
͔
I.INTRODUCTION
In applications ranging from batteries to electrolysiscells, design and optimization can be greatly enhanced withaccurate knowledge of the electrical conductivity of the elec-trolyte, as this property figures prominently in establishingthe thermal balance of the system. Molten oxides have beenidentified as candidate electrolytes for prospective high-temperature electrochemical processes,
1,2
and since all appli-cable classical high-accuracy techniques for measuring elec-trical conductivity rely on the use of dielectric materials, itwas necessary to invent a technique that prevents contactbetween these highly reactive melts and dielectric materials.The result is the coaxial cylinders technique, which uses acell in which only metal contacts the liquid.
3
This articledescribes the technique and offers proof of concept.
II.REVIEWOFAVAILABLETECHNIQUES
Although the electrical conductivities of various moltenoxides have been measured in the past, it is the opinion of the authors that these data are, by and large, inaccurate. Inthis section we review available techniques and explain why,as currently practiced, they are incapable of supplying high-accuracy data, i.e., absolute error
ϽϮ
1.0%, under the ex-treme conditions encountered in such melts. Table I lists 11techniques and classifies them according to accuracy.Electrical conductivity is an intensive property and can-not be measured directly; it must be calculated from a mea-surement of the corresponding extensive property, resistance:
 R
ϭ
␳ 
ͩ
l A
ͪ
ϭ
ͩ
1
␬ 
ͪ ͩ
l A
ͪ
ϭ
G
␬ 
,
͑
1
͒
where
R
is resistance,
␳ 
is electrical resistivity,
␬ 
is the elec-trical conductivity,
l
is the effective length of the currentpath,
A
is the effective cross-sectional area of the currentpath, and
G
is the cell factor. In
all
of the techniques re-viewed, determination of electrical conductivity is a com-parative procedure dependent on calibration in a standardliquid.
25
Calibration is accomplished by measuring the resis-tance of the standard,
R
std
, and calculating the cell factor
G
,by the relationship
G
ϭ
␬ 
std
 R
std
.
26
The conductivity of theliquid of interest,
␬ 
liq
, is then determined by measuring itsresistance and using the measured cell factor,
␬ 
liq
ϭ
G
 / 
 R
liq
.The procedure is valid only when the cell factor is constant,i.e., when the current path is invariant with the electricalproperties of 
all
of the following:
͑
i
͒
the liquid under inves-tigation,
͑
ii
͒
the electrodes, and
͑
iii
͒
the container. High-accuracy techniques satisfy these conditions; low-accuracytechniques do not.
A.Low-accuracytechniques
Seven low-accuracy techniques based on five electrodedesigns were identified. These are depicted schematically inFig. 1.In the two-wire technique, the current path is not con-fined. Current spreads out in all directions to an extent dic-tated by the electrical properties of the liquid
͑
conductivity
␬ 
and dielectric constant
⑀ 
) and the proximity of the electrodesto the container walls and floor. For this reason, calibrationof this type of cell is problematic — the cell factor so deter-mined is in fact not constant, but an unknown function of 
␬ 
and
⑀ 
of the liquid.The four-wire technique suffers from the same current-path problem as the two-wire technique. While some of theeffects of electrode–electrolyte interfacial impedance, con-tact resistance, and spreading resistance are avoided, there isno improvement in accuracy.The four-wire with double immersion technique is an
a
͒
Current address: Corning, Inc., Corning, NY 14831-0002.
b
͒
Current address: Oakland, CA 94602-1413.
c
͒
Author to whom correspondence should be adderessed; electronic mail:dsadoway@mit.eduREVIEW OF SCIENTIFIC INSTRUMENTS VOLUME 69, NUMBER 9 SEPTEMBER 1998
33080034-6748/98/69(9)/3308/6/$15.00 © 1998 American Institute of Physics
Downloaded 01 Nov 2005 to 129.170.26.221. Redistribution subject to AIP license or copyright, see http://rsi.aip.org/rsi/copyright.jsp
 
improvement over both the two- and four-wire techniques.The procedure used by Ohta
et al.
13
accounts for the currentthat spreads out below, but fails to account for the currentthat spreads out radially beyond, the four electrodes. Notsurprisingly, measurements were extremely sensitive to theradial position of the electrodes with respect to the cruciblewall. As a result, Ohta
et al.
13
were unable to measure theconductivities of KCl
͑
aq
͒
solutions with great accuracy.The crucible technique is a low-accuracy technique be-cause the current distribution is a function of 
␬ 
and
⑀ 
of boththe liquid and the electrodes. Hence, for the same reasons asthose discussed above, calibration of this type of cell is prob-lematic. By way of example, there are two studies in whichthe electrical conductivity of molten CaF
2
was measured incells of identical geometry but constructed of different ma-terials. Ogino
et al.
18
used crucible cells, one of molybde-num and another of graphite. At 1500 °C, the measured val-ues of 
␬ 
differed by nearly 30%. In contrast, Kim andSadoway
29
used differential capillary cells, one fitted withtungsten electrodes and another with graphite electrodes. Thevalues of 
␬ 
measured in the two cells differed by less than1%. Clearly, the wide variation in the data taken in the cru-cible cells by Ogino
et al.
18
derives from the fact that thecurrent path, and thus the cell factor, is a function of theelectrical properties of the electrodes.In the differential crucible technique, measurements aretaken with the central electrode positioned at several depthsof immersion. The measured resistance
R
meas
is related tothe conductivity by
19
 R
meas
ϭ
G
␬ 
ϩ
 R
leads
,
͑
2
͒
where
G
is the cell factor. However, since the cell factors aredetermined in a single calibration at each depth of immer-sion, this technique suffers from the same current distribu-tion problem as the crucible technique.In the ring technique, the current path is well defined
͑
i.e., strictly radial and invariant with
␬ 
and
⑀ 
of the liquidunder investigation
͒
between the cylindrical electrodes.However, the current is not confined to the space betweenthe electrodes; so-called fringe currents stray above and be-low the interelectrode gap and are dependent on
␬ 
and
⑀ 
of the liquid under investigation. This is a low-accuracy tech-nique because the simple expression used to calculate theelectrical conductivity from the measured resistance does notaccount for these fringe currents.So-called electrodeless conductance measurements havebeen made via the two toroid technique. In this technique,one toroid radiates an ac electric field and the other acts as areceiver to pick up the small current induced by the movingions in a conducting loop of liquid. As applied to date, this is
TABLE I. Available techniques for measuring the electrical conductivity of a liquid.Technique Types of liquids investigated
Low accuracy
͑
1
͒
Two wire Aqueous solutions
͑
Ref. 4
͒
; molten oxides
͑
Refs. 5–11
͒͑
2
͒
Four wire Molten uorides
͑
Ref. 12
͒͑
3
͒
Four wire/double immersion Molten oxides
͑
Refs. 13 and 14
͒͑
4
͒
Crucible Molten oxides
͑
Refs. 15 and 16
͒
; molten fluorides
͑
Refs.17 and 18
͒͑
5
͒
Differential crucible Molten uorides
͑
Refs. 19 and 20
͒͑
6
͒
Ring Aqueous solutions
͑
Ref. 21
͒
; molten oxides
͑
Ref. 22
͒
;molten fluorides
͑
Ref. 23
͒͑
7
͒
Two toroid Aqueous solutions
͑
Ref. 24
͒
High accuracy
͑
1
͒
Interdigitated Cryogenic liquids
͑
Ref. 31
͒͑
2
͒
Capillary Aqueous solutions
͑
Ref. 28
͒
; molten chlorides
͑
Ref. 32
͒
;molten oxides
͑
Refs. 33–36
͒
molten fluorides
͑
Ref. 37
͒
; molten chloride–sulfidesolutions
͑
Ref. 38
͒͑
3
͒
Differential capillary Aqueous solutions
͑
Refs. 39 and 40
͒
; molten fluorides
͑
Refs. 29 and 41
͒͑
4
͒
Meandering winding Aqueous solutions
͑
Ref. 42
͒
FIG. 1. Low-accuracy techniques for measuring electrical conductivity.
3309Rev. Sci. Instrum., Vol. 69, No. 9, September 1998 Schiefelbein
et al.
Downloaded 01 Nov 2005 to 129.170.26.221. Redistribution subject to AIP license or copyright, see http://rsi.aip.org/rsi/copyright.jsp
 
a low-accuracy technique because the current distribution isa function of 
␬ 
and
⑀ 
of the liquid under investigation.In closing, it is important to point out that if appropriatemeasures are taken, e.g., modifying the experimental proce-dure along with the data reduction method, it may be pos-sible to make high-accuracy measurements using cell designscited in this section. For example, recent work in this labo-ratory has demonstrated how to get high-accuracy data witha two-wire cell.
30
B.High-accuracytechniques
Four high-accuracy techniques based on three electrodedesigns were identified. These are depicted schematically inFig. 2. Factors to consider in choosing one of these tech-niques for a specific application include
͑
i
͒
the range limitsof the available impedance measuring instrument,
͑
ii
͒
theconductance of the liquid under investigation
͑
i.e., the con-ductivity as seen through the cell factor of the particularelectrode configuration
͒
, and
͑
iii
͒
chemical compatibility be-tween the liquid under investigation and cell materials. Theinterdigitated electrode design, featuring relatively short andwide current paths, is best suited for use in highly resistiveliquids
͑
e.g., transformer oil
͒
, while the capillary design, fea-turing relatively long and narrow current paths, is best suitedfor use in highly conductive liquids
͑
e.g., molten NaCl
͒
. Themeandering winding method, which has been used for mea-suring the electrical conductivity of solid metals, is, in prin-ciple, suitable for use with highly conductive liquids. As forthe molten oxides of interest, their high conductivity ex-cludes the interdigitated design while their incompatibilitywith dielectric materials excludes both the capillary tech-niques and the meandering winding method.
III.THECOAXIALCYLINDERSTECHNIQUE
The coaxial cylinders technique employs cylindricalelectrodes: the inner electrode is a rod situated coaxially in-side the outer tube electrode
͑
see Fig. 3
͒
. The two electrodesare positioned by dielectric separators that never contact theliquid under investigation. The electrodes are immersed inthe liquid to an arbitrary initial depth, and ac impedance ismeasured over a wide frequency range. This process is re-peated at many immersions, and the electrical conductivity iscalculated from the change in measured conductance withdepth of immersion.
A.Theory
The electrical conductivity of the liquid is derived fromits impedance,
˜ 
liq
,
͑
the tilde denotes a complex number
͒
. Inthe present investigation, impedance was measured by elec-trochemical impedance spectroscopy.
43–45
An impedancemeasurement
˜ 
meas
necessarily contains contributions fromother sources, i.e., electrodes, leadwires, etc., so that
˜ 
meas
 Z 
˜ 
liq
. The primary goal of the technique is extraction of 
␬ 
from
˜ 
meas
.The equivalent circuit for the measurement is shown inFig. 4.
46
Summing series impedances give:
˜ 
meas
ϭ
 Z 
˜ 
leads
ϩ
 Z 
˜ 
electrode
ϩ
 Z 
˜ 
liq
, where
˜ 
leads
is the impedance of the lead-wires from the impedance measuring instrument,
˜ 
electrode
isthe impedance of the electrodes, and
˜ 
liq
is the impedance of the liquid under investigation.Since
␬ 
derives solely from
˜ 
liq
,
˜ 
leads
and
˜ 
electrode
mustbe eliminated from
˜ 
meas
. This is done by measuring theimpedance of the system with the electrodes shorted, thensubtracting this from
˜ 
meas
.
48
As
␬ 
influences only resistance
͑
not capacitance or in-ductance
͒
, it is necessary to isolate the
purely resistive
partof 
˜ 
liq
, denoted here as (
 Z 
liqreal
)
*
. (
 Z 
liqreal
)
*
contains radial andfringe resistances related as follows:1
͑
 Z 
liqreal
͒
*
ϭ
1
 R
liqradial
ϩ
1
 R
liqfringe
,
͑
3
͒
where 1/ 
 R
liqradial
is the radial contribution to the liquid conduc-
FIG. 2. High-accuracy techniques for measuring electrical conductivity.FIG. 3. Schematic illustration of coaxial cylinder electrodes as deployed inmeasuring the electrical conductivity of a liquid.
3310 Rev. Sci. Instrum., Vol. 69, No. 9, September 1998 Schiefelbein
et al.
Downloaded 01 Nov 2005 to 129.170.26.221. Redistribution subject to AIP license or copyright, see http://rsi.aip.org/rsi/copyright.jsp

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