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Absolutemeasurementofthethermalconductivityofelectricallyconductingliquidsbythe
transienthotwiremethod
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J.Phys.E:Sci.Instrum.,Vol.14,1981.PrintedinGreatBritain
AbsolutemeasurementoftheofthermalelectricalI
conductivity
yconductingliquidsbythetransient
hotwiremethod
YNagasakatandANagashimaDepartmentofMechanicalEngineering,KeioUniversity,Hiyoshi,YokohamaJapan
Received9March1981,infinalform10June1981
AbstractAnapparatusforpreciseandabsolutemeasurementofthethermalconductivityofelectricallyconducting
liquidsusingthetransienthotwiremethodhasbeendeveloped.Inthepresentapparatus,ametallicwirecoatedwith
athinelectricalinsulationlayerhasbeenusedasaheatingelementandaresistancethermometerinsteadofabare
metallicwire.Theeffectsonthethermalconductivitymeasurementcausedbythethininsulationlayerhasbeen
analysed.Intheanalysis,itwasfoundthattheeffectscanbenegligiblysmalliftheinstrumentisadequately
designed.Theusabilityofthemethodforelectricallyconductingliquidshasbeentestedtomeasurethethermal
conductivityofanaqueousNaClsolutioninthetemperaturerange0to45Catatmosphericpressure.Theaccuracy
ofthepresentmeasurementwasestimatedtobe&OS%.
1IntroductionThetransienthotwiremethodhasbeenwidelyusedfordeterminingthethermalconductivityoffluids
withahighdegreeofaccuracy(Pittman1968,Haarman1969,Mani1971,deGrooteta11974,Castroeta11976and
NagasakaandNagashima1981).Themostadvantageousfeatureofthemethodappliedtofluidsisitscapabilityof
experimentallyeliminatingconvectiveerrorandthedataobtainedwiththismethodisgenerallymorereliablethan
thoseusingthesteadystatemethod.However,itisnotpossibletomeasurethethermalconductivityofelectrically
conductingfluidsusingthismethod,sinceabarethinmetallicwireisusedasanelectricalheatingelementanda
resistancethermometer.Themeasuredsubstancesobtainedwiththismethodhavebeenrestrictedtoelectrically
nonconductingfluidssuchasnoblegasesandorganicliquids.
There have been only a few attempts to expand the transient hotwire method to measure the electrically
conducting liquids. Van der Held and van Drunen (1949) measured the thermal conductivity of some inorganic acids
withalacqueredwireandthethermocoupletogetherinanarrowglasscapillary
?Present address (15 March 198114 March 1982) c/o Professor J Kestin, Division of Engineering, Brown University,
Providence,RhodeIsland,RI02912USA.
Electricallyconductingliquid
Cell
Metallicwire
Figure1Electricalcombinationofthemeasuringsystem.(Inthecasewhentheordinarytransienthotwiremethodis
appliedtotheelectricallyconductingliquids.)
Our past experience has shown that the last problem produces the most serious influence on the thermal con
ductivity measurements. In many cases, there is a trend towards recording the higher value of the slope of voltage
change against Int. Such an example of this type of measurement is found in the report by Korosi and Fabuss (1968),
who meas ured the thermal conductivity of aqueous NaCl solutions using the ordinary transient hotwire method.
Theirdatashowthatavariationfromotherdataofuptoabout30%.
In the present paper an attempt has been made to overcome the abovementioned problems by using a metallic wire
coated with a thin electrical insulation layer instead of just the bare metallic wire. The effects on the measurement
caused by the thin insulation layer, (i.e. a temperature rise in the metallic wire and that on the surface of the
insulation) have been analysed. A new instrument, which has been designed as a result of our analysis, has been
developed. The use of this method for electrically conducting liquids is tested by measuring the thermal conductivity
ofanaqueousNaCl
00223735/81/121435+06801.50
tube instead of a bare metallic wire, but the influence of an air layer and glass capillary on the temperature change
were not analysed. Turnbull (1961) used a bare platinum wire for molten salts at elevated temperature (3OO2C),
concluding that the current through the salts would be negligible under the experimental conditions. It seems
insufficient that the con clusion of Turnbull was based on Smythes analysis (1955) which gives only the ratio of
total current to the wire current. Baruel (1972) carried out measurements with an electrically uninsulated wire for acids
and salt solutions by arranging the experiment in such a way that a balance was quickly established between the
counterelectromotive force from polarisation and voltage applied to the cell. Baruel also considered the theoretical
foundation of the modification in detail. Recently, Dietz et al (1980) modified the method for heating a bare metallic
wireusingalternatingcurrentinordertoavoidthepolarisationeffectsonsurfaceofthewire.Theusabilityofthe
AC
methodhasbeendemonstratedwiththemeasurementsofwaterathighpressure.
When the ordinary transient hotwire method is applied to the electrically conducting liquids, the following
problemsmayoccur.
(i)Thecurrentflowsthroughtheliquidandtheheatgenerationofthewirebecomesambiguous.
(ii)Polarisationoccursonsurfaceofthewire.(iii)Theelectricalsystemcombineswiththemetalliccellthroughthe
liquidsandsmallvoltagesignalsaredistorted(figure1).
I
/
01981TheInstituteofPhysics1435

YNagasakaandANagashima
solutioninthetemperaturerange0to45Catatmosphericpressure.
2EffectsofaninsulationlayeronthemeasurementIntheordinarytransienthotwiremethod,therehasbeenanumberofstudies
concerningthistheory(Healyeta11976andCastroeta11976)andtheprincipleofthemeasurementiswellknown.Inthis
section,wehavediscussedonlytheproblemswhichariseduetotheuseofinsulatedwire.
2.1EfectsofaninsulationlayeronthetemperatiireriseofmetallicwireThecoordinatesystemwhichdescribestheinsulatedwire
isshowninfigure2.ThebasicproblemsaregovernedbythefollowingFourierequations:
auT1a+
1
aarl
1
ahrlrar
K~
__rl
O<r<ri(1)
3
Figure2Thecoordinatesystemofaninsulatedwire.1,Metallicwire2,insulator3,sampleliquid.
whereC=expy=1.781
..
.,
yisEulersconstant.Theaboveapproximatesolutionisvalidforlargevaluesof
K3f/Y2,
using the expansion method outlined by Carslaw and Jaeger (1959).
These equations, of course, include the solution without an insulation layer. In equation (lo), substituting ro by ri, suffix 2 by 3
andtakinganintegralaveragegives:
whichisthesamesolutionasHealyeta1(1976).
TheactualtemperaturemeasurementistakenastheresistanceofthewirecorrespondingtoanintegralaverageofhTl(r,t).
(13)
The above equation is rewritten using A, B and C, which become constant fixing the insulated wire and measured substance as
AT1=follows:
4nh3
[Int+A+(Blnt+C)
1
Ifl/tterminequation(14)issmallenough,constanttermAshiftsthehTIagainstIn
t
relationshipwithoutchangingtheslopefromwhichthermalconductivity
A3
iscalculated.Thenthethermalconductivityisdeterminedby
1436
atnri2X1
Wherehisthethermalconductivity,
K
the thermal diffusivity, r the radial coordinate measured from the centre of the wire, q
theheatgenerationperunitlengthofthewire,
Yi
the radius of the metallic wire and ro the radius of the insulated wire. The
suffixesdenoteeachmaterialaccordingtofigure2.Theinitialconditionandboundaryconditionsare:
hTi
=
hTz
=
AT3
hl__he__
t<OahTl
ahrzarar
Y=Yi
ATi=ATzr=riaraAT2
A3
aAT3ar
r=ro
hTz=AT3r=roAT3=0r+w.
Thesolutionfortheproblemisexpressedas:
hTl(r,t)
q
A2
__

4nh3[
Inro2C
+In4~3t2h3A2
ro
h(rZri2)
hTz(r,
t)
r1ri2hl

ThermalConductivityofconductingliquid7
2.2 Effects of an insulation layer on the reference temperature When the initial temperature of the liquid is Th, the
temperaturetowhichthemeasuredthermalconductivityrefersTrisdefinedas(Pittman1968):
indicateWhere
t1
the times at the start and end of the run, respectively. In the case of an insulated wire, AT in
equation(16)isreplacedbyatemperatureriseonthesurfaceoftheinsulation.
AT2(r0,t)
2.3EffectsofthermalcontactresistancebetweenthemetallicwireandinsulationlayerThethermalcontactresistance
betweenthemetallicwireandinsulationlayer,owingtodifferenceofthethermalexpansioncoefficientineachlayer,
existstosomeextent.Inthiscase,boundaryconditionequation(5)isreplacedbythefollowingequation:
4[In4K3t+l
{!i2('
Equation(17)isalsorewrittenusingconstantsDandE:
Here, R indicates the thermal contact resistance per unit length. An approximate solution can be obtained, in a
mannersimilartoderivingequation(I3),toyield
ATI=~~?[Int+A+
ridKZ
(20) where A, B and C represent the same constants in
equation(14),andh=27rriR.
2.4EffectsoffinitelengthofthewireItisnotpossibletopredicttheerrorduetothefinitelengthofthewire
analytically.So,itisadoptedpracticallytocompensatefortheeffectsexperimentally.Therearetwosuchmethods:
theshortandlongwiremethod,andthepotentialleadsmethod.Inusingtheinsulatedwire,itseemsverydifficult
technicallytoadoptthelatermethod.Therefore,inthepresentapparatus,theshortandlongwiremethodhasbeen
employed.AdetailedanalysisexplainingthispointisdescribedinthereportproducedbyKestinandWakeham
(1978).
3Experimentalapparatus3.1InsulatedwireThecrosssectionoftheinsulatedwireinthepresentapparatus,which
wasoriginallyusedasaresistancethermometer,is
4rA3ro2Ct4
~2KI,
ri2
A2
AIro1
8
ATdro,t)=
47rA3
"
and
12
In+2A2
(K2KI)
rf+2/\3
x
[.I2(K2Kl)
+
'02(K3K2)
27rAlr=(ATiAT2)
+
BInt+C+
(+&+:)I)II
7t2
[..(If2KI)
+Tr=TI)
+[A
T(t1)
+
AT(t2)I.(16)
A2A1A3A2
aATi1
arR
2A3
d
K<
[
Inro2C+t(DInt+E)].4K3fI
t,.rf(
K3
1
K2
I)
rih
h
dG
]
In
23
z)j'
r=ri.(19)
(17)
(18)
Figure3Crosssectionoftheinsulatedwire.1,Platinumwire2,polyesterlayer.
shown in figure 3. Thin platinum wire, 40 pm in diameter 1, is coated with a polyester 2 electrical insulation layer 7.5
pm in thickness. As shown in figure 3, the platinum wire almost makes a concentric circle with the insulation layer and
the change in the diameter of the wire and the thickness of the polyester along the longitudinal direction is 40 pm f 1.5
% and 7.5 pm k 20%, respectively. The polyester insulation has good resistance against many chemical reagents and
solvents, and also, has good physical and electrical properties (electrical resistivity of IOl7 !2 mm at 25C). This
insulatedwirecanbeusedtotemperaturesupto150C.
3.2HotwirecellFigure4showsthehotwirecellassembly.Thecellisdesignedforhighpressuremeasurement
operatingupto50MPa,withthetemperaturerangeupto150C.Twocellsofthistype,differingonlyintheirlength,
havebeenconstructedthelengthsofthewiresareabout200"(resistanceisabout15
s2 at OOC) and 100 mm respectively. In constructing the cell the polyester layer of each end of wire 5 is melted
away with HzS04 and connected to platinum pins with a diameter of 500 pm. The pins are soldered to copper rod 9
insulated with a silicon tube. The soldered pins and inside portion of terminal 1 are painted with thin silicon rubber
for insulation. These vessels were immersed in a liquid thermostatic bath at a stable controlled temperature of k 0.05
K.Thetemperatureofthebathwasmeasuredwithastandardthermometer.
3.3ElectricalsystemAblockdiagramoftheelectricalsystemisshowninfigure5.Inthisdiagram,RIandRs
representtheresistanceoflongandshortwire,respectively.Thetemperatureriseofthewire,theendeffectsare
compensatedusinglongandshortwire,isconvertedintovoltagechangewithabridgecircuit.Thevoltagechangeis
measuredbyanintegratingdigitalvoltmeter(Yokogawatype2501),whichisexternallytriggeredbyapulsegenerator
witharepetitionrateofsixpersecond.These
1437

YNagasakaandANagashima
0X
012345TimeIs)Figure6Magnitudeofl/tterminequation(13).
Firstly, the deviation from the linear relationship of A TI In t, owing to the heat capacity of the wire and the
insulation layer, is calculated from equation (13). An example of this calculation, in the case of measuring the aqueous
NaClsolutionat45"C,isshowninfigure6.ThepropertiesofeachlayerusedinthecalculationareAI
=71.5(Wm1Kl),
KI=2.5x105(m2s1)(estimatederrorf5%)(Touloukianet
a11970),hz=0.141,~2=8.32xlo*,(estimatederrorf10%)(BrandrupandImmergut1967),=0.619,
K3=
1.57xlo'(estimatederrorf1%)(densityfromRoweandChou1970andspecificheatfromWashburn1928).As
showninfigure6,thel/ttermofequation(13)decreaseswithtimeandafterFigure4Thehotwirecellassembly,1,
terminal2,Cupacking3,teflonpacking4,pressurevessel5,insulated
acertainperiodoftime,thevariationofthistermbecomessmallenoughsothatthethermalconductivity
A3
c
anbePtwire6,susrod7,
ABS
disc8,grandretainingring9,insulatedCurod.
Ideterminedbyequation(15).Thisconclusionisvalidforthe
measurementofliquidsinwhichthermalconductivitiesandthermaldiffusivitiesdonotdifferdrasticallycompared
with
Digitalvoltmeter
b
I
thesampleliquidinthepresentmeasurement.
It is very difficult to measure the magnitudes of the thermal contact resistance between the metallic wire and
insulation layer in situ. However, according to the correlation of Veziroglu (1967) h is roughly estimated to be in the
order of 106 (m2 K W1) thus the relative magnitudes of the term involving h compared with (B In t+ C) can be
calculatedtoabout10%.ThiscausesonlynegligibleeffecttohT1htrelation.
r
PulsegeneratorInordertodemonstratethattheinstrumentoperatesinaccordancewiththemathematicaldescription
ofit,figure7,
represents deviations of the measured AT1 from the fitted straight line for a typical run. As shown in this figure
devia tions 15 s. never The average exceed deviations 0.15 % during from the linearity available is about time 0.05
duration
%.Theaccuracyofthethermalconductivityvalueinthepresentmeasurementisestimatedasfollows.The
temperatureComputer
Figure5Blockdiagramofelectricalsystem.
Imeasured
voltagechangesarerecordedanddeducedtother
010mal
conductivityvaluesusingadesktopcomputer(HP85).R2isa10standardresistorandthecurrentthroughthewire
ismeasuredbythevoltageacrossit.RDisusedforstabilisingthecurrentthroughthewirebeforeinitiatingthe
measurement.
4EstimationofaccuracyInthefollowing,theapplicabilityoftheinstrumenttoelectricallyconductingliquids,an
aqueousNaClsolutioninthepresentwork,isanalysedusingtheresultsin82andtheoverallaccuracyisestimated.
I
&p
01
c00
0
,
IO
Q,02
I
I
I
I
0051015InfFigure7DeviationsofmeasuredATIfromfittedstraightline.
1438

Thermalconductiaityofconductingliquids
Table1
ThermalconductivityofanaqueousNaClsolution(3.027molality).
Referencetemperatureqh("C)(Wm1)(Wm1K1)
0.960.89060,550815.340.89590.576430.890.92040.600045.820.94050.6218
coefficient of the wire resistance was determined by the calibration carried out in the temperature range 0 to 45C
during the course of the measurement and its accuracy was 0.17%. The uncertainty of dATl/d In t was 0.16% which is
estimated by the deviations from linearity and a number of available ATl(ti) plots. The heat generation per unit length
ofwireqisaccurateto0.1%.Includingalltheothersmallestimatedfactors,thetobeoverallI0.5accuracy%.
ofthepresentmeasurementis
5SampleofmeasurementInthepresentwork,theapparatusdescribedherehasbeenemployedtomeasurethe
thermalconductivityofanaqueousNaClsolutionwithaconcentrationof15.03wt%(3.027molality)asasampleof
electricallyconductingliquidsinatemperaturerange0to45Catatmosphericpressure.Theaqueoussolutionused
forthesemeasurementsweremadebyweightwithreagentgradeNaClstatedpurityof99.9%(withoutfurther
purification)andionexchanged,twicedistilledwater.Table1containsthemeanvaluesofthethermalconductivity
obtainedinthesemeasurements.Themeasurementswereperformedunderthesameconditionssixtotentimesand
thereproducibilitywas+0.1%to+0.2%,astandarddeviationwhichisconsistentwiththeestimatedaccuracy.The
temperatureriseofthesurfaceoftheinsulationlayerduringthemeasurementwaslessthan1Kandaperiodofabout
30minwasallowedbetweenruns,
1020304050
TemperatureI
OC
I
Figure8ThermalconductivityofanaqueousNaClsolution(3.027molality).D,Riedel(1950),Riedel(1951)0,
presentwork.
In figure 8, the present experimental data are compared with those of earlier works. As far as this concentration of
an aqueous NaCl solution, only the works of Riedel (1950, 1951) who measured the thermal conductivities of many
kinds of aqueous salt solutions, are available. The figure shows that agreement with the present data and those of
Riedelarewithintheaccuracyclaimed.
This method has the possibility of being applied to measure ments for electrically conducting liquids at high
temperaturesusingaceramiccoatedwire.
AcknowledgmentsWewouldliketothankDrKTanishitaofTokyoWomen'sMedicalCollegeforhisvaluableadvice
inhandlingofthiswireandMrTItoandMrHOkada,studentsofKeioUniversityatthattime,fortheirassistancein
carryingouttheseexperiments.
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1439

YNagasakaandANagashima
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1440