Journal o f Solution Chemistry, Vol. 9, No.

3, 1980

Calibration of Conductance Cells at

Various Temperatures
J. Barthel, 1'= F. Feuerlein, 1 R. Neueder, 1 and
R. W a c h t e r 1
R e c e i v e d February 26, 1979; revised S e p t e m b e r 10, 1979

Precise conductance measurements on aqueous potassium chloride solutions

at O, 10, 18, and 25~ have been made under various conditions over a
concentration range 10 -4 < c < 5 x 10 -2 mole-dm -3, yielding the con-
ductance equations

25~ A = 149.873 - 9 5 . 0 1 ~ / c + 38.48c log c + 183.1c - 176.4c 3j2

18~ A = 129.497 - 8 0 . 3 8 a / c + 32.87c log c + 154.3c - 143.0c 3'2
IO~ A = 107.359 - 6 4 . 9 8 ~ / c + 27.07c log c + 125.4c - 110.3c 312
O~ A = 81.700 - 4 7 . 8 0 ~ / c + 20.60c log c + 93.8c - 79.3c 312

which are p r o p o s e d f o r calibration o f conductance cells.

KEY WORDS: Conductance; temperature dependence; cell constant

calibration ; potassium chloride.

1. I N T R O D U C T I O N

The calibration of conductance cells is based on three methods:

1. determination by direct measurement,
2. use of calibration standards, and
3. use of fitting equations.
Method 1, used first by Kohlrausch (1~and subsequently by Parker, (2~was
recently applied in our laboratory ~3~ using a new type of conductance cell
permitting continuous variation of the cell constant34~
Until now, the calibration standards of Jones and Bradshaw (5~(0.01, 0.1,
and 1.0 normal or demal aqueous potassium chloride solutions which are

1 Chemical Department, University of Regensburg, West Germany.

2 To whom correspondence should be addressed.
209
0095-9782/80/0300-0209503.00/0 9 1980 Plenum Publishing Corporation
210 Barthel, Feuerlein, Neueder, and Wachter

defined by the conductance of mercury) are the standards which have nearly
always been used for method 2 of cell constant evaluation at 25, 18, and
0~ (see also refs. 6-8). Calibrations by method 3 also use these standards in-
directly. A comprehensive survey of calibration methods up to 1977 has been
given by Janz and Tomkins. ~la~
The conductance equations used for method 3 are of the forms
A = A0 - S c 112 + E c l o g c + J l c - J2c al2 (1)
or

A = Ao + A c 112 + B e + Cc al2 + D e z + E c 5j2 (2)

Equation (1) is based on the Fuoss-Onsager theory (9-m of electrolyte
conductance, whereas Eq. (2) is an empirical equation. (12~ However, in spite
of their wide application for determining cell constants, Eqs. (1) and (2) are
known only for aqueous potassium chloride solutions at a single temperature,
25~ The purpose of this contribution is to derive equations of the type of
Eq. (1) for the calibration of cells at 0, 10, 18, and 25~

2. P U R I F I C A T I O N OF C H E M I C A L S
Potassium chloride, KC1 (Merck, suprapur), was recrystallized from
highly purified water (see below), dried at 60-80~ in vacuo (p < 10 -2 Torr),
ground in an agate mortar, and dried once more for two days at 300~
always in presence of P20~. This product, quality A in Table I, was stored in
an atmosphere of pure argon. Part of this sample was melted in a platinum
boat at 770~ and slowly cooled down to room temperature, always under an
atmosphere of flowing argon, yielding a product of quality B (Table I) which
was stored as above.
Demineralized water was distilled three times in a quartz under purified
argon. The final product, specific conductance < 3 x 10-7 f2-1-cm-1, was
distilled into a flask permitting storage and transference of the solvent into
the measuring cell under an atmosphere of argon. The cell had previously
been filled with argon, thus avoiding all contact of the purified solvent with
the atmosphere.
Argon was freed from 02 by reaction with a Cu catalyst (BTS Merck) at
110~ from CO2 (with soda lime), and from water (by desiccation with P205).

3. E X P E R I M E N T A L
Measurements were carried out with two different measuring assemblies
(I and II in Table I) of identical design, each of them consisting of a cold bath,
a precision thermostat with immersed conductance cell, and a highly precise
 Calibration of Conductance Cells at Various Temperatures 211

Table I. Experimental Results from Conductance Measurements of Aqueous

Potassium Chloride Solutions at Various Concentrations and Temperatures
I

25Oc 18~ I oOc oOc

104 6
A AA A ~A A AA A
~ t ~ n ~A
~- 1aa2mol-1

(I) (2} (3) (4) (51 (6) (7) (8) (91 (10)

9.5203 I a A 147.O15 +O.O11 127.O95 +0.029 105.400 +0.009 80.259 +0.005

10.85OO I a A 146.757 -0,059 126.860 -0.047 105.220 -0.044 80.124 -0.034
15.O443 IIb A 146.337 +0.042 126.525 +0.060 104.967 +0.062 79.946 +0.050
16.7415 IIb A 146.181 +0.075 126.371 +0.065 104.855 +0.078 79.864 +0.064
21.2733 I a A 145.622 -0.029 125.898 -O.O21 104.435 -0.029 79.550 -0.020
21.3033 I a A 145.590 -0,O58 125.864 -0.053 104.407 -0.055 79.530 -0.039
31.2196 I a A 144.785 -0.027 125.175 -0.032 103.856 -0.032 79.119 -0.029
40.6666 I a A 144.105 -0.042 124.596 -0.049 103.388 -0.045 78.769 -0.044
41.7541 IIb A 144.141 +O.O65 124.627 +0.042 103.445 +0.060 78.821 +0.044
42.5721 II b A 143.984 -0.040 124.504 -0.036 103.344 -0.004 78.740 -O.O11
84.4438 II b A 141.805 -0.082 122.663 -0.067 101.847 -0.039 77.648 -0.029
87.8111 IIb A 141.787 +0.040 122.642 +O.O31 101.825 +0.035 77.636 +0.029
99.932 IIb B" 141.290 +O.O21 122.221 +O.O15 - - 77.375 +0.007
99.932 I a B* 141.291 +O.O22 122.225 +O.O19 - - 77.368 +O.OOO
99.932 [ a'B" 141.306 +O.037 122.245 +0.039 - 77.385 +0.O17
99.948 IIb Bi 141.264 -0.005 122.167 -0.038 - - 77.341 -0.027
99.957 IIb B* 141.270 +0.002 122.191 -O,O14 - 77.384 +O.O16
99.962 II ~'B = 141.261 -0.008 122.189 -O.O16 - - 77.358 -0.009
99.962 II a'A = 141.266 -0.002 122.194 -O.O11 - 77.359 -0.008
99.962 I a B" 141.269 +O.OO0 122.207 +0.002 77.371 +0.004
99.962 I b B" 141.274 +0.006 122.197 -0.008 - 77.344 -0.023
99.962 II b B* 141.291 +0.023 122.222 +O.O17 77.369 +O.002
99.963 IIb B* 141.305 +0.037 122.214 +0.009 - - 77.363 -0.004
99.965 IIb B" 141.217 -0.052 122.226 +0.O21 - 77.422 +0.055
99.965 IIb B* 141.264 -0.004 122.197 -0.008 77.306 -O.O61
99.977 I a A* 141.272 +0.004 122.212 +0.008 77.370 +0.003
99.977 IIb A" 141.322 +0.055 122.246 +o.o41 77.397 +0.030
1oo.oo7 I a A= 141.307 +o.041 122.247 +0.043 77.390 +0.024
147.256 II b A 139.625 -0.072 120,811 -0.064 1OO.348 -0.042 76.541 -0.042
147.431 IIb A 139.731 +0.039 120.905 +0.034 100.421 +0.035 76.610 +0.030
216.258 IIb A 137.960 +0.035 119.415 +0.039 99.228 +0.043 75.739 +0.035
231.975 II b A 137.516 -0.062 119.O25 -0.058 98.904 -0.046 75.495 -0.037
297.242 IIb A 136.323 +0.029 118.O41 +0.042 98.121 +0.038 74.932 +0.029
310.226 II b A 136.000 -0.064 117.766 -O,O40 97.903 -0.025 74.764 -0.027
493.992 IIb A 133.452 +0.065 115.607 +0.050 96.183 +0.042 73.540 +0.036
500.916 II b A 133.258 -0.043 115,442 -0.043 96.043 -0.043 73.431 -0.033

conductance bridge. Each temperature of the chosen temperature program,

0, 10, 18, and 25~ was attained within 20 rain with an accuracy of less than
10-a OK. Both short- as well as long-term temperature fluctuations were below
10-3 OK, and no temperature drift beyond this limit could be observed over a
period of six months. Using the precise conductance bridge, the electrolyte
conductance at every temperature was obtained with an accuracy less than
0.01~ Further information on the measuring equipment, temperature
control and calibration, and measuring method is given elsewhere. ~14~
212 Barthel, Feuerlein, Neueder, and Wachter

G C

(c)
I
I

E2
El"~ --

E3
(a

Fig. 1. Assembly of a conductance cell with three-electrode measuring cell (El, E2, Ea:
electrodes), mixing chamber (M) with solvent inlet (I), stirrer (S) and stirrer-motor (SM),
and assembly lid (A) for immersion into the temperature bath of a precision thermostat.
(a) Measuring cell of type " a " (Table I, cell constant B ~ 0.3 c m - I ) ; (b) measuring
cell of type " b " (Table I, cell constant B ~ 4 cm-1); (c) inlet cap for introducing the
electrolyte samples under protective atmosphere (G: gas inlet, W: Weighing bottle, C:
Magnetic switch).
Calibration of Conductance Cells at Various Temperatures 213

[
E

3971
R

397(

0 01 05 10 15 20
-~10 3 ,,--
Fig. 2. Frequency dependence of measured solution resistances at 25~ rh = 84.4438 x
10-4 mole_kg-1.

The conductance cell, shown in Fig. 1, is a three-electrode measuring cell

combined with a mixing chamber M. Two different types (Fig. la, two
versions labeled a and a', and Fig. lb, labeled b, in Table I) of cell constants
have been used (see caption to Fig. 1).
A first series of measurements (Table I, symbol *) was carried out to
provide the cell constants at 0, 18, and 25~ on the basis of the Jones-
Bradshaw standards (5~ for 0.01 D potassium chloride solution. From the cell
constants at 0, 18, and 25~ the value at 10~ can be obtained by interpola-
tion. For this purpose a precise amount of conductance water was transferred
to the mixing chamber M of the cell and the conductance of the solvent was
determined at all temperatures of the program. Then a weighed quantity of
KC1 yielding the 0.01 D solution to a good approximation was added through
the cap (Fig. lc) of the cell, and the temperature program for conductance
measurement was repeated. All operations took place with the solution under
an inert atmosphere of argon which was previously saturated by bubbling
through water at the measuring temperature. All weights were converted to
vacuum. Resistance measurements were made at different frequencies from
which the value R at infinite frequency was obtained by linear extrapola-
tion (1~ (Fig. 2). In summary, in this first step, the conductance of each 0.01 D
solution (which may deviate slightly in concentration from the standard but
which is known with an absolute precision better than 0 . 0 0 3 ~ ) is obtained
with the absolute precision of the a.c. bridge (0.01 ~ ) .
In a second series of measurements the concentration dependence of the
conductance of aqueous potassium chloride solutions was measured at 0, 10,
18, and 25~ using a method of constant r~-values. 3 For this purpose the cell
8 Measurement of the conductance at all temperatures of the program for each concentra-
tion before establishing the following concentration. The advantage of this method when
compared to that of isothermal sections, i.e., measuring all concentrations at one tem-
perature before establishing the next one, is obvious (see refs. 14-16).
214 Barthel, Feuerlein, Neueder, and Wachter

Table II. Physical Properties of Water at

Various Temperatures

Temp. do (g-cm-a)(24) ~7o(cP)(2a) eo(21)

25~ 0.99707 0.8903 78.40

18~ 0.99862 1.053 80.96
lO~ 0.99973 1.306 83.98
o~ 0.99987 1.787 87.92

was filled with a precise amount Gs (g) of pure water and the conductance
was measured as above at all temperatures. Then each concentration at 25~
was established by adding an amount Gj (g) of solid KC1, and the temperature
program was repeated before the next concentration was prepared at 25~
Hence, the concentration c [mole-dm -8] is given by

c = rhd; rh - ~ Gj. 108

Gs + ~Gj ME (3)

d being the density of solution (g-cm-3) and Ms (74.555 g-mole-1) the molar
mass of KC1. Consequently rh is the concentration of solution expressed as
moles per kilogram of solution. The temperature-dependent density function
d = d(T) is given by
d(T) = go(T) + Drh (4)
where do(T) is the density of water at temperature T given in Table II. The
density gradient, D = 0.047 for aqueous KCI is assumed to be independent of
temperature. (17)

4. R E S U L T S

4.1. Cell C o n s t a n t s
The standard values of Jones and Bradshaw for the specific conductance
of the 0.01 D aqueous potassium chloride solution (0.745263 g KCl/kg
solution) at 25~ (K~ = 0.00140877 f l - l - c m - 1 ) , 18~ (~0 = 0.00122052 ~-1_
era-1), and 0~ (K~ = 0.00077364 ~ - L c m - 1 ) were used as follows to deter-
mine the first approximation of the cell constants. ~ The specific conductances
~(T) of our approximately 0.01 D solutions were calculated from
~(r) = K~ ~ (5)
4 Differences of the temperature scale used in our investigations (see refs. 14, 18), i.e.,
the International Practical Temperature Scale of 1968 (IPTS 68) (see ref. 19), and that
used by Jones and Bradshaw (see ref. 5) can be neglected (el. also ref. 3).
Calibration of Conductance Cells at Various Temperatures 21 5

with e ~ calculated from the above-quoted concentration of Jones and Brad-

shaw. The appropriate cell constants taking into account solvent correction

A(T) = •(T)/(1/R - 1/R~2o ) (6)

were used for calculating preliminary equivalent conductances of all solutions,
yielding preliminary equations of the type of Eq. (1) at the different tempera-
tures. Based on this first set of equations, shifts ~A corresponding to our
deviations from Jones-Bradshaw concentrations, 3c -- c - c ~ are obtained
and yield, after transformation into 8K values, the final cell constants A ( T ) .
The cell constants of the first and second approximation differ by less than
0.003%

4.2. Experimental Results

All rh values and the appropriate molar conductances as obtained with

the final cell constants are summarized in Table I. Column 2 lists the informa-
tion about measuring equipment, type of cell, and treatment of KC1. The
quantities AA are the deviations of the measured conductances from those
obtained by the use of equations of the type of Eq. (1) (coefficients in Table
III). In spite of a maximum deviation of 0.06~o for a single value, the agree-
ment in Table I is satisfactory if one takes into account the fact that the results
were obtained with different equipment and cells and varying qualities of
products, and were determined by different workers. The results were used
together to provide a single data set for which the data analysis was applied.
Obviously, if only measurements of the same series are used to evaluate an
equation of the type of Eq. (1), the margins of error would correspond to the
usual standard of high precision determinations, i.e., < 0.01 70.

Table I I I . Coefficients for Equation (1) for Aqueous Potassium Chloride

Solutions at Various Temperatures

Author Temp. Ao S E J1 J2

LZF 25~ 149.93 94.65 58.74 198.4 --

FH 25~ 149.936 94.88 58.67 221.0 229
J 25~ 149.89 94.87 58.63 229.0 264.3

This work 25~ 149.873 95.01 38.48 183.1 176.4

(149.90) (94.87) (58.65) (228.4) (267.0)
18~ 129.497 80.38 32.87 154.3 143.0
10~ 107.359 64.98 27.07 125.4 110.3
0~ 81.700 47.80 20.60 93.8 79.3
216 Barthel, Feuerlein, Neueder, and Wachter

4.3. C o n d u c t a n c e Equations
F r o m the values o f T a b l e I, c o n d u c t a n c e equations o f the type o f Eq. (1)
are o b t a i n e d b y d e t e r m i n i n g A0, J1, a n d -/2 b y a least-squares method51~,2~
T h e n u m e r i c a l values o f the solvent p r o p e r t i e s which were used are s u m m a r i z e d
in T a b l e II. T a b l e I I I c o n t a i n s the resulting coefficients.
The difference between o u r S values a n d those o f F u o s s e t al. (9,~~ or
Justice (1~ results f r o m the use o f different values for the relative p e r m i t t i v i t y
o f p u r e water w h i c h we have r e d e t e r m i n e d and f o u n d to be in c o m p l e t e agree-
m e n t with the values o f K a y e t al. ( ~ The larger difference in the E values is
due to o u r t a k i n g a c c o u n t o f the Chen effect (22~ in this coefficient. The co-
efficients o b t a i n e d f r o m o u r d a t a with the relative p e r m i t t i v i t y eo = 78.54 as
used b y Justice, a n d o m i t t i n g the Chen effect, are q u o t e d for 25~ in brackets.

5. D I S C U S S I O N
M e a s u r e m e n t s were p e r f o r m e d up to c o n c e n t r a t i o n s o f 0.05 m o l e - d m - a
a n d limiting the use o f o u r equations, T a b l e III, to c o n c e n t r a t i o n s o f this o r d e r
of magnitude.
T a b l e I I I also c o n t a i n s a c o m p a r i s o n with o t h e r e q u a t i o n s o f the t y p e o f
Eq. (1) at 25~ The c o n c e n t r a t i o n limits for each e q u a t i o n are

L i n d - Z w o l e n i k - F u o s s ( L Z F ) (m: c < 0.012 m o l e - d m -a

F u o s s - H s i a (FH)(10): c < 0.1 m o l e - d m - a
Justice (J) (11 ~: c < 0.05 m o l e - d m -3

U s i n g Eq. (2) S~indig, Feistel, G r 6 s c h , a n d Einfeldt ( S F G E ) o b t a i n e d (12~

A = 150.000 - 99.282~cc + 135.798c - 120.788c a/2

+ 57.89Ic 2 - I 1.725c s/2

a n d a c o n c e n t r a t i o n limit c < 1.0 m o l e - d m - 3 .

Table IV. Percent D e v i a t i o n between the Results f r o m

This W o r k a n d T h a t o f Others at 25~ at V a r i o u s Con-
centrations

Concentration, mole-dm - 3

Equation 10 -a 5 x 10 a 10-2 5 x 10 -2

LZF + 0.02 - 0.01 + 0.01 --

FH + 0.03 + 0.01 0.00 + 0.07
J 0.00 0.00 0.00 +0.04
SFGE + 0.04 + 0.04 + 0.04 + 0.05
Calibration of Conductance Cells at Various Temperatures 217

Table V. Percent Deviation of All Equations from

the Standard Value of Jones and Bradshaw for
0.01 D Aqueous Potassium Chloride Solution

Temperature

Equation 25~ 18~ 0~

LZF - 0.005
FH + 0.008
J + 0.008 m B

SFGE - 0.034

This work +0.007 -0.001 0.000

Table IV shows the difference between the values predicted by our equa-
tion and those of the others at four concentrations. Table V illustrates the
deviations of all of them from the Jones-Bradshaw values for the 0.01 D
solution. The agreement of all equations at 25~ is satisfactory.
Taking into account the procedure by which the results at 0, 10, and
18~ have been obtained in this investigation, it can be assumed that they are
of the same reliability as are the values at 25~ Every solution was prepared
at 25~ and its conductance measured at 25~ after passing through the
temperature cycle, and no change could be observed. The temperature control
guarantees absolute temperatures with a certainty of 0.01~ when compared
to the IPTS 68 scale and a reproducibility and stability better than 0.001~
at every temperature of the program (cf. ref. 14). Finally, resistance measure-
ments are exact within 0.01 ~ irrespective of the resistance range covered by
the change of conductance as a function of temperature of solutions.
The temperature dependence of the cell constant is usually represented
by the formula~2~

A(T)=A29s[1+ A--~98
1 dA
0--~) (T - 298.
16)]
2
(7)

On the basis of a geometric definition of the cell constants as A = L/S,

where
L is the length of the electrolyte conductor and S its cross section, the rela-
tionship

~ =~ ~ --~ ~ (8)

is obtained. Two limiting situations can be considered :

21 8 Barthel, Feuerlein, Neueder, and Wachter

(1) I n a m e a s u r i n g cell o f the t y p e shown in Fig. l a , S is d e t e r m i n e d

a p p r o x i m a t e l y , b y the surface area o f the circular p l a t i n u m electrodes.
Then S = rrr 2, a n d hence S - I ( d S / d T ) = 2 r - l ( d r / d T ) = 2c~pt, where
ch,t = 9 x 10 -6 ~ -1 is the coefficient o f linear e x p a n s i o n o f p l a t i n u m .
O n the o t h e r hand, L - ~ ( d L / d T ) = ~py = 3.5 x 10 -6 ~ -1 (coefficient
o f linear e x p a n s i o n o f Pyrex). F r o m this a p p r o x i m a t i o n , a value
A-I(dA/dT) =-15 x 1 0 - 6 ~ -1 is o b t a i n e d . T h e e x p e r i m e n t a l
m e a n value o f the cells l a a n d l a ' , the type shown in Fig. la, is f o u n d
tobe(-17 + 5) x 1 0 - 6 ~ -1.
(2) F o r a c a p i l l a r y cell with infinitely large p l a t i n u m electrodes, S is
d e t e r m i n e d b y the cross section o f the c a p i l l a r y a n d S - ~(dS/dT) =
2~ey, yielding A - I ( d A / d T ) = - a p y = - 3 . 5 x 1 0 - 6 ~ -~. F o r o u r
cell b shown in Fig. l b , which is an i n t e r m e d i a t e t y p e between the
t y p e shown in N g . l a a n d a c a p i l l a r y cell, a value o f ( - 8 _+ 5) x
10- GoK - ~ is f o u n d experimentally.

ACKNOWLEDGMENT

W e are grateful to the Deutsche F o r s c h u n g s g e m e i n s c h a f t for a g r a n t

e n a b l i n g us to c o n d u c t these investigations.

REFERENCES
1. F. Kohlrausch, IVied. Ann. Phys. 60, 315 (1897).
2. H. C. Parker, J. Am. Chem. Soc. 45, 2017 (1923).
3. P. Saulnier and J. Barthel, J. Solution Chem. 8, 847 (1979).
4. P. Saulnier, J. Solution Chem. 8, 835 (1979); Th6se de Doctorat 6s Sciences, Stras-
bourg (1978).
5. G. Jones and C. Bradshaw, J. Am. Chem. Soe. 55, 1780 (1933).
6. F. Kohlrausch, L. Holborn, and H. Diesselhorst, IVied. Ann. Phys. 64, 417 (1898).
7. G. Jones and R. C. Josephs, J. Am. Chem. Soc. 50, 1049 (1928).
8. G. Jones and J. Prendergast, J. Am. Chem. Soe. 59, 731 (1937).
9. J. F. Lind, Jr., J. J. Zwolenik, and R. M. Fuoss, J. Am. Chem. Soe. 81, 1557 (t959).
10. R. M. Fuoss and K. L. Hsia, Proe. Natl. Aead. Sei. U.S.A. 57, 1550 (I967).
11. J.-C. Justice, J. Chim. Phys. 65, 353 (1968).
12. R. S/indig, R. Feistel, A. Gr6sch, and J. Einfeldt, cited in ref. 13.
13. G. J. 3anz and R. P. T. Tomkins, J. Eleetroehem. Soe. 124, 55C (1977).
14. R. Wachter and J. Barthel, Ber. Bunsenges. Phys. Chem. 83, 634 (1979).
15. R. Wachter and J. Barthel, Eleetroehim. Aeta 16, 713 (1971).
16. J. Barthel, Ionen in nieht-wdflrigen L6sungen, Dr. Dietrich Steinkopff-Verlag,
Darmstadt (1976).
17. G. Jones and S. K. Talley, J. Am. Chem. Soe. 55, 624 (1933).
18. R. Wachter, Habilitationsschrift, Regensburg (1973); H. Hammer, Diplomarbeit,
Saarbrticken (1970).
19. International Practical Temperature Scale of 1968, Metrologica 5, 35 (1969).
Calibration of Conductance Cells at Various Temperatures 219

20. J. Barthel, R. Wachter, and H. J. Gores in Modern Aspects of Electrochemistry,

B. E. Conway and J. O'M. Bockis, eds., Vol. 13 (Plenum Press, New York, 1979).
21. R. L. Kay, G. A. Vidulich, and K. S. Pribadi, J. Phys. Chem. 73, 445 (1969).
22. M. S. Chen, Ph.D. Thesis, Yale University (1969).
23. R. A. Robinson and R. H. Stokes, Electrolyte Solutions, 2nd edn. (Butterworth,
London, 1970).
24. International Critical Tables, Vol. III, E. W. Washburn, ed. (M cGraw-Hill, New York,
1928), pp. 25-26.