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Electrolytic Conductivity and its Measurement

Article  in  Transactions of the Institute of Metal Finishing · February 1992

DOI: 10.1080/00202967.1992.11870940

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Education Topics Number 5

Understanding Electrical and

Electrolytic Conductivity
Gavin Reade, INTRODUCTION waters can be assessed qu ickly from the
The conductance of solutions and so lid conductance measurements.
Gerry Ottewill materials in the metal finishing industry plays Measurements of conductance provide a
an important role in determining the overall
and Frank Walsh po\\er efficiency of electroplating and
\aluable tool for the metal fini sher in
determining the quality of a process.
anodising processes. Poorly conducting Here, we out line the basic princip les of
Applied Electrochc'mistry Group, busbars, electrodes and even electrolytes (i.e., electrical conductance.'conductivity by
University of Portsmouth, plating solutions) can lead to high cell voltages answering a selection of frequently asked
St Michaels Building, which. in turn. lead to energy inefficiencies via questions. Simple worked examples illustrate
White Swan Road, power dissipated as heat (power loss = PR). the concepts.
Portsmouth POI 2DT, UK Figure I shows, schematically, a plating cell
and illustrates the typical conductance
properties of the various components in such COMMON QUESTIONS
a system. Note that the metal components in
the system will usually exhibit a decrease in Question SA) What is Conductance?
conductivity with increasing temperature (i.e .. The electrical conductance (G) is defined as
have a negative temperature coefficient) the reciprocal of the electrical resistance (R)
whereas electrolytes tend to have a positive of the material being considered:
temperature coefficient.
I
The impo11ant points to note from Figure G=- (l)
I are: (i) the range of conductances for the R
metallic materials that are commonly found in
metal finish ing and (ii) the fact that actual The resistance, therefore. decreases as the
plating solution conductances are considerably conductance increases. Si nce resistance is
lower (typically of the order of a million times expressed in units of ohms (Q) the conductance
less) than the electrode and current feeder is expressed in ohm-1 (sometimes written as
materials. The conductance of the electrolyte n-1). Older texts use the term ·mho· to describe
or plating solution may be increased by adding reciprocal ohms but the official SI unit is the
an inert electrolyte, e.g., sodi um hydroxide to Siemens, S. when I S = I n-1 = ohm- 1•
alkaline ti n and alkaline zinc baths or
sulphuric acid in the case of an acid copper Question SB) What is the Difference
sulphate plating solution. Conductance in the between Conductance (G) and
external circuit is kept to a maxi mu m by Conductivity (K)?
ensuring that current feeders (e.g.. bus bars and The resistance is related to resistivity and the
hangers) and electrodes are fabricated from dimensions of the conductor:
conducti1 e materials and that voltage losses
due to poor electrical contacts are minimised. l
R = px- (2)
The quality of 11 ater used to make up A
electrolyte and electroless plating solutions is
easily moni tored by conductance where I is the length of the sample and A is
measurements. A very low conductance value its cross sectional area. The constant (p) is
is desirable indicating low levels of dissolved the resistiv ity of the sample, defined as the
ionic solids. The quality of dragout and rin se resistance of a un it cube (of dimension s:

Symbol Meaning Typical Units

Area mi
Concentration mol m-3
Voltage \'
Conductance S = ohm-1
Current A
Resistance Q=ohm
Cell constant m-'
Conductivity S m- 1
Molar conductivity of electrolyte S 1112 moJ- 1
Molar conductivity at infinite dilution S 1112 moJ- 1
G. Reade, G. Ottewill and F. Walsh, Trans. IMF. Resisth ity ohm m
2000, 78 (2), 89

Trans IMF, 2000, 78(2) 89

 platinum foil electrodes have a finely
divided deposit of platinum on their
surface. This means that the actual
A c surface area is very much greater than the
projected geometrical area and stops the
electrodes polarising.
(iv) The electrodes generally have a small
proj ected area (usually of the order of
I cm2) and are not arranged so as to be
L Ionic -.,._ perfectly planar to each other. This can
'\ transport I
e· lead to edge effects that are difficult to
allow for.

In addi tion. if a direct current is used to

measure the solution resistance or
conductance, the electrodes. or the solution or
Componcnl Anode reeder Anode Eleclrolyle Cathode Cathode feeder both may undergo electrolysis. Therefore. the
conductivity meter uses a high frequency
Charge c.:i rricrs e e ions e e· alternating current to perform the
t-· measurement.
K/ S m·• 2 xJO' (Ti) lo 67 x 10' (Ag) 5 to 50 2 x 10' (Ti) to 67 x 10' (Ag)
In order to overcome the limitations
imposed by points (i) and (ii) above it is more
Figure I Schemaric represenrario11 of a plaring cell, il/11s1rali11g the various componen/s and rheir convenient to consider a ce ll constant (s).
conductivily. From equation (6). we may replace the factor
/'A with the cell constant giving:

K= G x s (7)
1 m x 1 m x I m). Resisti vity has units of with electrodes of constant area at a
ohm m. Equation (2) shows that the constant temperature. The electrodes The dip cell is calibrated with a solution of
resistance of the sample increases with its known conductivi ty e.g. 0. 1M KC! then
shou ld, therefore. be clean and rinsed
length and decreases as the cross sectional thoroughly with distilled \\ater between conduct ivity readings are obtained from the
area increases. The conductivity of a sample measurements. conductance readings on the conductivit)
is defined as the in verse of its res isti vi ty: meter multiplied by the cell constant.
(ii) The measuring compartment of the di p
1 cell has an air or breathing hole. This
K= - Question SD) What are Typical Values of
(3) hel ps to ensure that th e measuring
p
compartment is fully immersed in the Conductivity?
where K is the conducth ity expressed in solution to be measured. The dip cell Table I illustrates the conductivities of a number
S m-1 or. more conveniently in practical should, therefore, be agitated gently to of very different materials. The conductivities
situations, S cm-1• ensure there are no air bubbles trapped in of the metal materials are of the order of l 06 S
1
Combining equations (2) and (3) \\ e may the compartment that would decrease the 111- while those of strong electrolyte solutions
write: effective area of either or both electrodes. are of the order of tens of S m- 1• The
1 l (iii) The electrodes are fab ricated from conductivity values of most polymer materials
R=-X- (4) platin ised platinum. In other words the are very many orders of magnitude smaller.
K A

or
I
K =-- (5)
RA (• )

Substituting equation ( 1) into (5) gives;

GI conduclivity meter
K =- (6)
A di;:iul ditpl::ay or oplional ou1put
device
copper wire conduc:unct. G::: J..1E
- - ) -·-· <•·C··'""""'°'d«
So conductance and conductivity are related or microcomputer)

by the geometric factor (//A).

While conductance is simply the reciprocal
of resistance. the conductivity takes into
account the distance the electrical current has
to travel.

Question SC) How do we Measure plalinised platinum conductivity t hermometer

foil elec:lrodcs
Electrical Conductivity? all (probt:)

The electrical conductivity of so lutions is

measured with a conductivity probe or dip cell c:lectr°'11e:samp•ev1•ssor pla$1ictube
(see Figure 2A) connected to a conductivity
meter (see Fi gure 2B). An optional output
lb) 1 dtclrolylt
(sample}
[Link] (e.c. bt:•kcr)

plalinised Jurract pl::uinum foil

device such as a chart recorder or a
microcomputer may be used to record the data. A B
(1) Secuon1I 1i1tew, (b) plan rn:w from below. A "'d1p·Ctlr' is sh...,..1t1n.
A number of important points can be noted:
(i) The experimental arrangement measures Figure 2 Sche111a1ic represe11/ation of A) a dip cell for the 111eas11re111en1 of rhe electrical conducrivity of
the steady state conductance of a fixed solulions and. B) a typical experimental arrangeme111 for the meas11remen1 of electrical conduc/ivity of
volume of electrolyte. using a dip cell solutions.

90 Trans IMF, 2000, 78(2)

Table I Conductivity data (IC) for various different materials, illustrating the wide variation in Table II Experimental conductance data for
commonly encountered materials three different aqueous solutions and distilled
water
Material Conductivity KIS m- 1 Material Conductivity KIS m- 1
Solution Conductance, G
Silver (Ag) 66.7 x 10 · 10 M H:SO, 60.4
Copper (Cu) 64. 1 x 106 I ~1 H:SO, 24.6 Distilled H,O 2.4 µS
Aluminium (Al) 40.8 x 106 0. 1 :.i H,so, 4.8 [Link] KCI 10.85 ms
Zinc (Zn) 18.2 x 10'' JO~ CH,COOH 0.04 0.100M H,so, 46.6 ms
Nickel (Ni) 16.4 x 10'' I M CH,COOH 0.04 [Link] H:S04 24.4 ms
Iron (Fe) I 1.2 x 10'' Dem ineralised water Io-• to 10-s J.00M CH3COOH 128 µS
Tin (Sn) 8.7 x 106 Polymethylmethacrylate (perspex) ~ 10-"
Titanium (Ti) 2.3 x 10'' Polypropylene 10-" to 10-s
Brass (Cu-Zn alloy) (8- 10) x 10• Polytetranuoroelhylene (PTFE) 10- 1 to lO-"

Question SF) How do we use Conductivity

Calculations to Find the Minimum Cross
Section of a Solid Conductor?
Question SE) What is the Difference electrolyte. The molar conductivity is defined
between Stro ng and Weak Electrolytes? as: An example calculation is h.:!lpful:
This question may be answered with the help K During the installation of a plating bath it is
of data in Table I. Notice the difference in A,.=- (8) necessa1y to connect a busbar, approximately
c
conductivity behaviour between the sulphuric 3.5 m long between the power supply and the
( H 2 SO,) and ethanoic (CH 3 COOH) acid cathode bar. If the maximum current passing
where c is the concentration of the electrolyte
electrolytes. Th e conductivity data for the through the 'at is 750 A and the maximum
solution. A has units of S m 2 mo1- 1• Plots of
su lphuric acid show marked differences over permissible voltage drop over the length of the
A versus tl~e square root of concentration for
a one hundred fold change in concentration busbar is 0.4 V, what is the minimum cross
v~ rious different electrolytes produce
0

whereas the ethanoic acid solutions show no sectional area required for a copper or an
(typically) the results shown in Figure 3. This
difference in conducti v ity over a tenfold aluminium b usbar?
clearly illu strates the differences between
change in concentration. Sulphuric acid is a (Assume the electrical conductivities of the
strong electrolytes that show a linear p lot of
s trong e lectro lyte whi le ethanoic acid is a copper and aluminium are 64 x I 06 S m- 1 and
Amvs. c 112• and weak electrolytes that do not.
weak electro lyte, i.e. the sulphuric acid 41 x I 06 S m- 1, respectively, at room
This behaviour is described by the Kohlrausch
dissociates completely into its constituent ions temperature.)
law:
while the ethanoic acid electrolyte is We will assume that the busbar is a pure
incompletely dissociated. Indeed, the data in Am = A 0 - b c 1 : (9) homogeneous material of uniform cross
Table I show that ethanoic acid solution s sectional area, that the system remains at room
where A 0 is the extrapolated value of Am at
between I M and I 0 M produce few additional temperature and that all contact resistances
zero concentration and b is a proportionality
ions in solution. may be ignored.
constant. The Kohlrausch law breaks down at
To examine the concept of weak and strong From Ohm ·s law, the resistance of the
high concentrations due to interactions among
electrolytes it is useful to consider a quantity busbar is the voltage drop across it divided by
ions and the solvent that are not considered by
known as the molar conductivity (Am) which the current fl owing through it;
equation (9).
is directly related to the ionisation of an
LIB
R=-
/\IS m 1 m-01 · 1
I
c I mol dm' 3

0.10
0.001 0.01
~--..------.------------.-------,
0.1 R =0.40V
750A
R =5.3x10-'Q

0.08 Using equation (4):

l
K=-
H,so. RA
Rearranging to give an expression for the
0.06 cross sectional area, A:

A=-l-
xR
For a copper busbar:
0_04 F _______ HCI '
_:,~-,:::.....,_=-=-=---___:~

' ', - -- - A = ([Link])

' cu (64xl06 Sm- 1)x(5.3xlO-•ohm)
Na OH ''
',
-- - - - - -~ - -- A Cu = 1.0 x 10..... m 2
0.02 '' ' Ac.= 1.0 cm2
NaCl ''
and for an aluminium busbar:

(3.5 m)
0
0 O.t 0.2 0.3 OA (41xl06 s m -1 }x(5.3xl0..J ohm)
j,...c-l_m_u_I -dm--.,.·)
AA
1
= 1.6 x l0- 1 m 2
Figure 3 Plors of molar conducrivity (A) versus the square roor of e/ecrrolyte concenrrarion (c).
il/ustraring rhe difference bef\Veen srrong (eg. H: SO,. HCI. NaOH. 1 ·ac I) and weak (eg. CH, COOH) AA,= 1.6 cm2
e/ecrrolyres.

Trans IMF, 2000, 78(2) 91

The calculations show that a smaller cross Thus. for the 0.1 M H2SO,: conductor by comparison with 0.1 M H2SO,.
section of copper busbar would be required. The sulphuric acid exhibits a conductivity over
However. note that the copper wou ld be I( = (46.6 x 10-3 S)x( f03 m 1) 3500 t imes that of the organic acid. On the
considerably heavier and more expensive than /( = 4.80 S ni-1 other hand, increasing the Zoncentration of the
the aluminium. sulphuric acid by ten times decreases molar
conductivity by approximately 20 times. The
0.1 M H SO has a higher molar conductivity
Question 5G) How do we Calculate the
K= (24.4 x 10 3 S)x(l03 m- 1) value indicating a higher degree of dissociation.
Conductivity of an Electrolyte Solution?
The molar conductivity val ue fo r the ethanoic
A conductivity cell was used to obtain the K = 2.509 S ni-1
acid illustrates that the substance is a weak
conductances of the solutions shown in Table
electrolyte. while the sulphuric acid shows the
I! at a temperature of25°C. The values can be And for the 1.0 M CH3COOH:
characteristics of a strong electrolyte.
used to cany out a useful calculation.
K= (127 x JO-<> S) (103 m-1)
FURTHER READING
Using the Observed Conductance of the K= 0.0131 S m-1 I. Frank C. Walsh, .. Electrolytic
0.100 M KC! Solution, Calculate the Cell
Conductivity and its Measurement,
Constant and Hence Obtain the The molar conductivities are calculated using Tutorial Series'' Paper 5. Trans. Inst.
Conductivities and Molar Conductivities of equation (8): Metal Finish .. 1992. 70. 45.
the Remaining Solutions. 2. Frank C. Walsh and Brian Perry.
The value of the \\ ater sample is a background /(

conductance. The conductance value obtained

A=
m
-C "Fundamental Defi nitions and Concepts,
Tutorial Note I ". Trans. Inst. Metal
for the KC! solution is very much greater than
For 0.1 M H2SO,: Finish.. 1992. 70. 87.
the hackground conductance so, the
3. Frank C. Walsh and Brian Perry. "Units
conductance of the water may be ignored. The
(4.80sm- 1) and Conversions. Tutorial Note 2". Ti-ans.
conductivity of 0.100 :vi KC! is known to be A=--'-----'-- Inst. Metal Finish., 1992, 70. 90.
1.119 S m- 1 at 25°C (this may be obtained '" ([Link]-3)
4. David Hulse. "Electrolytes and Their
from tables of physical data or from a
Am = 4.80 x I 0-2 S m2 moI-1 Properties. Tutorial Note 9", Trans. Inst.
handbook supplied with the conductivity
Metal Finish .. I 993. 71. 4 1.
meter).
5. ·'Physical Chemistry". P. W. Atkins. 5•h
The ce ll constant. is calculated from a
Edn .. Oxford University Press, New York,
rearranged equation (7): (2.509Sm·1)
A = -"'-----'-7'- 1995, ISBN 0-1 9-855 -730-2. pp 834-839.
m (Ix 1000 mo] m-') 6. ·'Chemistrv in Action". Michael
S = /( KCJ Freemantl~. 2•d Edn., Macmillan Press
GKCI
Am = 2.51 x 10-3 S m 2 mo! 1 Ltd, Hants, UK, 1995. ISBN 0-333-
(I.I 19 S m -1 ) 565 15-0, pp 289-293.
s= For 1.0 M CHpOH: 7. ..CRC Handbook of Chemistry and
(10.85xl0 -3 S) Physics". D. R. Lide Ed .. 79'h Edn .. CRC
(0.0131Sm -')
s = 103 m- 1 A=-'----"-:- Press LLC. Florida. USA. 1998- 1999,
'" ( l x lOOOmolm -') ISBN 0-8493-0479-2/98.
8. F. ~·alsh and B. Perry. ·'Electrochemistry
To calculate the electrolytic conductivity of the 1.31 x I 0 ~ S m 2 mol-1 for Surface Finishers: Distance Learn ing
remaining samples, ' ' e use equation (7) again:
Course MF3a, The Institu te of Metal
The resu lts of the conductivity calculations Finishing. Exeter H ouse, 48 Holloway
K= G x s show that 1.0 M ethanoic acid is a poor Head. Birmingham. BI INQ. UK.

92 Trans IMF, 2000, 78(2)

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