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Conductivity Meter Theory
Conductivity Meter Theory
Conductivity Meter Theory
Part 1: Theory
A Review of Parameters concentration of ions present in the (-1). As discussed above in the con-
Describing Electrolyte solution, the lower R will be. Osten- text of resistance, the measured con-
Solutions sibly molecularly pure water has a ductance for a solution is related to
pH value of 7 and hence contains the distance between the electrodes
When two electrodes are immersed 110-7 Molar OH- ions as well as (d) and the microscopic surface area
in a solution and a potential is ap- 110-7 Molar H+ ions (the latter pre- (geometric area roughness factor)
plied across them, a current will be sent in the form of H3O+, H5O2+, ). of each electrode (A; assumed iden-
produced in the external circuit that If a strong electrolyte (i.e., fully dis- tical for the two electrodes), as well
connects the two electrodes. The sociable salt) like KCl is dissolved in as the ionic concentration. These pa-
mechanism of electrical communi- water, the number of ions per unit rameters are interrelated by (1):
cation between the two electrodes in volume increases and the solution 1 =
S= A
solution is the movement of ions in resistance R is lowered, thus increas- R d
the solution. When no appreciable ing the instantaneous current meas- EQ2
solution electrolysis occurs, the ured fo r a particu lar applied Conductivity
magnitude of the current observed potential. Therefore, current can be The quantity , above, is called
generally obeys Ohms Law: related to the concentration of ions conductivity and it contains all of the
in a particular solution. However, the chemical information available from
E=iR distance between the electrodes, the the measurement (e.g., concentra-
EQ1 surface area of the electrodes, and tions and mobilities of the ions pre-
the identity of the ions also affect R. sent). The ratio d/A is a constant for
where E is the applied potential, i is a particular measurement cell, and is
the current measured, and R is the Solution Conductance hence referred to as the cell constant,
resistance of the solution between The reciprocal of solution resis- (2). Therefore,
the two electrodes. tance is called conductance, symbol-
ized by the letter S (or L). =S
Solution Resistance Conductance is expressed in S.I. EQ3
It is the quantity R (in one form units called siemens (S or -1), al-
or another) that is of interest in the though older literature may refer to The conductivity, , is an intrinsic
present discussion. The higher the an equivalent unit called the mho property of a solution, rather than a
(S-cm2/mol)
measured for a typical
strong electrolyte (KCl) though the values of for solutions
and for a weak electrolyte 90
(CH3COOH). (Adapted
prepared to be 0.1 Molar and 1.0
from reference 3.) Molar in KCl would be different,
60
should be the same in each case,
30 since has effectively been normal-
CH3COOH ized for the difference in concentra-
0 tions. In practice, however, most
0.00 0.02 0.04 0.06 0.08 0.10
compounds that dissolve in water
C (Molar)
and undergo ionization behave dif-
ferently in highly dilute solutions
zi e ( compared to even moderately con-
property of the conductance cell
used. However, for detection pur- (
=Fi zi uiCi= Fi zi
6Ri i
C centrated solutions (3). Compounds
that exhibit molar conductivities that
poses in liquid chromatography or in
determination of equivalence points EQ5 do not change significantly with con-
centration are referred to as strong
during titrations, only relative where F is the Faraday constant
electrolytes, and include salts such as
changes are of interest (rather than (96,485 C/mol), and Ci is the con-
3 KCl. Other compounds such as ace-
absolute values); hence, the conduc- centration of ion i in mol/cm . The
tic acid are nearly completely ion-
tance, S, maybe be reported instead significance of EQ5 is that it shows
ized at low concentrations, but are
of . that conductivity reflects the identity
incompletely ionized at higher con-
(charge and mobility) of all ions pre-
centrations. This class of compounds
Mobility sent in solution, as well as their con-
is known as weak electrolytes. Ex-
It is important to realize that con- centrations. This is the principle that
perimental data (3) for KCl and ace-
ductance (and conductivity) values puts conductivity measurements in
tic acid are plotted in F1 to illustrate
contain more information than sim- the realm of analytical chemistry,
the severity of this effect.
ple ion concentrations. That is, the since there is a linear relationship
measured conductivity for a solution between a measurable quantity ()
Limiting Molar Conductivity
of 1 Molar HCl will be substantially and concentration.
For comparison of conductivi-
different than for 1 Molar KCl. This
fact arises because protons are much ties of dissimilar compounds, the
Molar Conductivity
more mobile in solution than potas- most useful quantity to consider is
Since conductivity is concentra-
the limiting molar conductivity, 0.
sium ions. Such differences may be tion dependent, measured values for
quantified by considering the pa- This parameter represents the molar
different solutions are not easy to
rameter called the mobility (u) of an conductivity for a compound that
compare directly. For this reason, a
would hypothetically be measured in
ion. The mobility is essentially that quantity called the molar conductiv-
part of the conductivity that is inde- the limit of infinite dilution (i.e., the
ity (or sometimes equivalent con-
pendent of concentration. In an ideal y-axis intercepts of plots like those
ductivity) is used (2,3). The molar
in F1). In practice, such values are
case, the mobility of an ion i de- conductivity is symbolized by ,
pends on the charge on the ion (zi), obtained by fitting experimental data
and it is defined as the solution con-
to an equation known as
its solvated radius (Ri), the viscosity ductivity () normalized by the total
Kohlrauschs Law (3):
of the solvent () and the elementary ionic concentration (C):
charge constant (e) according to (3):
= =0KC
zi e C EQ7
ui= EQ6
6Ri
EQ4 The coefficient K depends pri-
In this context, total ionic con- marily on the type of the electrolyte
Conductivity and Concentration
centration means Molar concentra- (e.g., 1:1 or MA, 2:1 or M2A, etc.),
The experimentally determined tion of positive charges (or negative
conductivity reflects contributions rather than its specific chemical
charges) in solution, expressed in identity (3). In any event, experimen-
from all ions present in solution that units of mol/cm3.
are mobile and can support the cur- tal values of have been carefully
rent. Conductivity can be written in determined for many salts as a func-
Strong vs. Weak Electrolytes
terms of the mobilities of all of the tion of concentration in very dilute
In an ideal case, the molar con- solutions, and the intercept values of
ions present (3): ductivity experimentally determined the resulting plots obtained. In ex-
for a compound would be the same, amining such data, it was discovered
Measured Conductivity
Example of a
conductometric 2
titration curve 852.6 S-cm /mole contacts they make are shown as Cc
for the titration and Rc, respectively. The double-
of a strong acid
with a strong base. Comparison of 0 for KOH, HCl layer capacitances of the two elec-
(Adapted from and KCl. Last, we can compare val- trodes (Cd) are assumed to be equal,
reference 1.)
ues of 0 for three electrolytes of since the electrodes are constructed
interest in acid/base titrations. Cal- to have identical microscopic sur-
Equivalence
culated values for these 3 com- face areas. The resistance of the so-
Point p ou nds are: 272.6 S-cm2/mol lution between the two electrodes is
(KOH), 425.95 S-cm2/mol (HCl) symbolized by Rs. An interelectrode
Volume of Base (Titrant) Added and 149.85 S-cm2/mol (KCl). Now capacitance term, Ci, is included to
consider how the measured conduc- account for the dielectric properties
F3 tivity will change during the course (9) of the bulk solvent (outside the
Cc Cc
General equivalent of a titration in which HCl is the diffuse layer). Last, a frequency-de-
circuit for a
two-electrode
analyte and KOH is the titrant. In- pendent Faradaic impedance, Zf,
conductance cell. Rc Cd Rs Cd Rc itially, the measured conductivity which includes both charge-transfer
(Redrawn from
reference 8.)
will have a relatively high value (un- resistance and Warburg impedance,
Zf Zf doubtedly not 425.95 S-cm2/mol in is shown for each electrode.
Ci any real-life example, but high
nonetheless). As KOH titrant is A Simplifed Equivalent Circuit
added, the conductivity decreases, By making low impedance con-
F4
since HCl is converted to KCl and nections to the cell it is usually valid
Simplified equivalent
circuit for a Cs Rs water. At the equivalence point in the to ignore the influence of Cc and Rc.
two-electrode titration, all of the HCl has been neu- (However, for very low solution re-
conductance cell.
(Adapted from tralized to form KCl, and the conduc- sistances, Rc may become important,
reference 8.)
Cp
tivity will be at its lowest value. As since it is in series with Rs.) The
KOH is added after reaching the complications imposed by the
equivalence point, the conductivity Faradaic impedance are minimized
using EQ8 and data from the table. will begin to rise again, since KCl through experimental design. As we
Both the cation (H+) and anion and unreacted KOH are both ionized will see below, conductance meas-
(CH3COO-) are singly charged; thus, in solution. The shape of the titration urements are often made by impos-
+ = - = 1. From T1, +0 = 349.6 curve obtained is shown in F2. Ex- ing a potential excursion (pulse or
S-cm2/mol and -0 = 40.9 S-cm2/mol. amples of curves for other types of sinusoid) and measuring the result-
Therefore, 0 = (349.6 + 40.9) = titrations are given in reference 1. ing current. By using short pulse
390.5 S-cm2/mol. It is interesting to widths or high frequencies, the
compare this calculated value to the Conductance Measurements: branch of the circuit containing Zf
data plotted in F1. For milliMolar (or Theory can be neglected (Zf varies as the
greater) concentrations of acetic reciprocal square-root of frequency,
acid, the experimental value of 0 is The section above dealt with the (3)). Therefore, the circuit shown in
less than 30 S-cm2/mol. This indi- chemical aspects of conductance and F3 can be simplified to the three-
cates that acetic acid is incompletely conductivity. In this section, we will component model drawn in F4.
ionized under these solution condi- examine the theory of conductance In F4, Rs signifies the solution
tions; i.e., it is a weak acid. measurements from an electro- resistance, and the Cs and Cp denote
0 for KCl. Better agreement be- chemical perspective. combined series and parallel capaci-
tween the calculated limiting and tances, respectively. Occasionally,
measured values for 0 could be ex- A General Equivalent Circuit of a other treatments of the above prob-
pected in the case of the strong elec- Conductance Cell lem omit Cp and use a single resistor
trolyte KCl. Again using EQ8 as Most conductance measure- and capacitor in series. While valid
above, we calculate 0 to be 149.85 ments are made using two electrodes for a range of experimental condi-
S-cm2/mol. The experimental data of the same geometric surface area. tions, this assumption tends to break
in F1 are within about 10% to 13% These electrodes are positioned par- down for large solution resistances
agreement with the calculated value allel to and facing one another, sepa- or when high frequencies are used in
for dilute solutions. rated by a gap of fixed dimensions. a.c. measurements (8,9).
0 fo r Ferric Oxalate. For this common configuration, the
Fe2(C2O4)3 is an example of a 2:3 equivalent circuit drawn in F3 ap-
electrolyte. In this case, plies (7,8).
( ( ( (
ods). Each of these broad categories
may be further subdivided into fre-
1 Q
sQ(s)-Q(0)+
RsCs
1
(s)= E
s Rs ( )
S t
ln(i)=ln(ES)-
Cs
quency domain (a.c.) and time do- EQ13 EQ18
main (pulse) experiments. Readers
interested in frequency domain po- In EQ13, s is the Laplace vari- The advantage of the single-
tentiostatic techniques should refer able (not conductance!). A boundary pulse technique is its simplicity. The
to a paper by Bott on a.c. impedance condition for this experiment is that disadvantage is that linearity in
experiments (10) and to the informa- the charge accumulated on capacitor EQ18 will only be obtained when
tion on the BAS-Zahner IM6/6e in- Cs = 0 until the potential is applied; the conductance cell can accurately
struments available on our website i.e., Q(0) = 0. Making this substitu- be represented by an equivalent cir-
(11). Controlled current techniques tion into EQ13 and rearranging cuit with only two components (Rs
are discussed in several texts (3,9) gives: and Cs) connected in series. As men-
and in the patent literature (12). E
tioned above, this assumption breaks
BAS offers three instruments with
Q(s)=
Rs down when the solution resistance is
galvanostatic capabilities: the IM6 ( 1
s s+
( large and/or data are acquired at
RsCs short times (high frequencies).
(11), the IM6e (11) and the LG-50
EQ14
(13). The remainder of this paper
will focus on the theory of time do- Taking the inverse Laplace trans- Bipolar Pulse Methods
main potentiostatic techniques. The form (s t) of EQ14 yields: A more robust approach is pro-
experimental implementation of vided by the technique called bipolar
[ t
]
-(
(
these techniques for determining
RC
s s pulse conductance (7-9). In this ex-
Q(t)= (ECs) 1-e
conductivity will be addressed in periment, a potential pulse of magni-
EQ15 tude +E is applied for a period t1,
Part 2 of this paper, as will a planned
series of BAS products named ep- followed by a pulse of opposite po-
Thus, the magnitude of the
silon. larity, -E, for a period t2. There are
charge that has accumulated at a
two constraints placed on the pulse
given time, Q(t), is given by EQ15.
Single-Pulse Measurements widths. First, t1 should be suffi-
The corresponding current observed
When a potential pulse is applied ciently short such that no greater
at any point in the circuit can be
to a conductance cell, the equivalent than 1% charging of the series ca-
obtained by differentiating EQ15
circuit drawn in F4 can be simplifed pacitance (Cs) shown in F4 occurs.
with respect to t:
to a single capacitor (Cs) and a single Second, t1 and t2 should differ in
resistor (Rs) placed in series for mil- t ( duration by no more than 1% (i.e.,
E e -( R C
()
dQ =
i= s s
they should be identical). No as-
lisecond time scales (and longer). In dt Rs
this case, the applied potential (E) sumptions need to be made about the
EQ16
drops across the two circuit elements absence of a parallel capacitance in
according to (3): this case.
The above equation is identical
A single current measurement is
in form to equation (1.2.6) in refer-
Q made at time t2, when the current
Eapp= EC+ER= + iRs ence 3. However, Cs in EQ16 is a
Cs represents solely the resistive com-
function of the capacitances of both
EQ11 ponent of the cell impedance. That
electrodes in the conductance cell,
is, immediately after application of
rather than the double-layer capaci-
the first pulse, any parallel capaci-
tance at a single (working) electrode.
tance present charges quite rapidly.