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Conductance Measurements Part 1: Theory: A Review of Parameters Describing Electrolyte Solutions
Conductance Measurements Part 1: Theory: A Review of Parameters Describing Electrolyte Solutions
Part 1: Theory
Measurement of solution conductance is a classical electroanalytical technique
that finds application in a variety of chemical and biochemical studies. For
example, conductance can be used to assess solvent purity, determine relative
ionic strengths of solutions (including functioning as a detector for ion
chromatography), monitor dissolution kinetics and the approach to equilibrium
for partially soluble salts, determine critical micelle concentrations, follow the
course of some enzymatic reactions, as well as to provide basic thermodynamic
data for electrolyte solutions. The first installment in this two-part article
reviews the basic physicochemical concepts underlying ionic conductivity in
solution and discusses the principles of two different approaches to the
determination of conductance. Part 2 will present experimental details of
conductance measurements and discuss a few representative applications of
conductance measurements in chemical analysis.
A Review of Parameters
Describing Electrolyte
Solutions
When two electrodes are immersed
in a solution and a potential is applied across them, a current will be
produced in the external circuit that
connects the two electrodes. The
mechanism of electrical communication between the two electrodes in
solution is the movement of ions in
the solution. When no appreciable
solution electrolysis occurs, the
magnitude of the current observed
generally obeys Ohms Law:
E=iR
EQ1
where E is the applied potential, i is
the current measured, and R is the
resistance of the solution between
the two electrodes.
Solution Resistance
91
The reciprocal of solution resistance is called conductance, symbolized by the letter S (or L).
Conductance is expressed in S.I.
units called siemens (S or -1), although older literature may refer to
an equivalent unit called the mho
(-1). As discussed above in the context of resistance, the measured conductance for a solution is related to
the distance between the electrodes
(d) and the microscopic surface area
(geometric area roughness factor)
of each electrode (A; assumed identical for the two electrodes), as well
as the ionic concentration. These parameters are interrelated by (1):
1 =
A
S=
R
d
EQ2
Conductivity
EQ3
The conductivity, , is an intrinsic
property of a solution, rather than a
F1
150
KCl
(S-cm2/mol)
120
90
60
30
CH3COOH
0
0.00 0.02
0.04
0.06
0.08 0.10
C (Molar)
Mobility
zi e
ui=
6Ri
EQ5
where F is the Faraday constant
(96,485 C/mol), and Ci is the con3
centration of ion i in mol/cm . The
significance of EQ5 is that it shows
that conductivity reflects the identity
(charge and mobility) of all ions present in solution, as well as their concentrations. This is the principle that
puts conductivity measurements in
the realm of analytical chemistry,
since there is a linear relationship
between a measurable quantity ()
and concentration.
Molar Conductivity
=
C
EQ4
zi e
=Fi zi uiCi= Fi zi
C
6Ri i
EQ7
EQ6
In this context, total ionic concentration means Molar concentration of positive charges (or negative
charges) in solution, expressed in
units of mol/cm3.
Strong vs. Weak Electrolytes
92
0+ (S-cm2/mol)
Cation
H+
349.6
Li+
38.7
Na
K
50.10
73.50
Rb
Cs
Ag
NH4
77.8
77.2
61.9
+
73.5
Ethylammonium
47.2
Diethylammonium
42.0
Triethylammonium
34.3
Tetraethylammonium
Tetra-n-butylammonium
Dimethylammonium
Trimethylammonium
FCl
55.4
-
76.35
78.1
Br
I
76.8
NO2
NO3
71.8
71.46
ClO3
64.6
ClO4
67.3
IO4
54.5
HCO3
19.5
HSO3
HSO4
44.9
Piperidinium
199.1
H2PO4
47.2
Tetramethylammonium
OH-
32.6
51.8
37.2
0- (S-cm2/mol)
Anion
44.5
-
HC2O4
57
50
50
HCOO
40.2
CH3COO
54.6
-
C6H5COO
Be
2+
90
2+
106.0
Mg
Ca
Sr
2+
2+
119.0
HPO4
118.9
2-
SO4
32.4
138.6
2-
2-
66
160.0
2+
127.2
2+
108.0
Cu2+
107.2
PO43-
Zn2+
105.6
Fe(CN)63-
302.7
Pb2+
142.0
Fe(CN)64-
442.0
Ba
Fe
UO22+
64
Al3+
183
Fe3+
204
La3+
209.1
Ce3+
209.4
that
for any electrolyte can be
expressed as the sum of independent
contributions from the constituent
cations and anions present. This fact
is now known as Kohlrauschs Law
of the Independent Migration of Ions
(3):
0
= + + + -
0
-
EQ8
93
CO32-
40.9
-
C 2O 4
148.2
207
T1
0
1
di ~
-1
=
= 0.02 deg
0
i
dT
EQ9
= 0
i,T i,25C
[1+(T-25C)]
EQ10
Measured Conductivity
Example of a
conductometric
titration curve
for the titration
of a strong acid
with a strong base.
(Adapted from
reference 1.)
Equivalence
Point
= + + + - (2204)+(3148.2)=
2
852.6 S-cm /mole
F2
Cc
Rc
Cc
Rs
Cd
Zf
Cd
Rc
Zf
Ci
F4
Simplified equivalent
circuit for a
two-electrode
conductance cell.
(Adapted from
reference 8.)
Rs
Cs
Cp
Conductance Measurements:
Theory
The section above dealt with the
chemical aspects of conductance and
conductivity. In this section, we will
examine the theory of conductance
measurements from an electrochemical perspective.
A General Equivalent Circuit of a
Conductance Cell
In F3, the capacitance and resistance of the cell connectors and the
contacts they make are shown as Cc
and Rc, respectively. The doublelayer capacitances of the two electrodes (Cd) are assumed to be equal,
since the electrodes are constructed
to have identical microscopic surface areas. The resistance of the solution between the two electrodes is
symbolized by Rs. An interelectrode
capacitance term, Ci, is included to
account for the dielectric properties
(9) of the bulk solvent (outside the
diffuse layer). Last, a frequency-dependent Faradaic impedance, Zf,
which includes both charge-transfer
resistance and Warburg impedance,
is shown for each electrode.
A Simplifed Equivalent Circuit
94
1 Q
1
E
sQ(s)-Q(0)+
(s)=
RsCs
s Rs
( )[ ]
t
E -
ln(i)=ln
Rs
RsCs
( )
S t
ln(i)=ln(ES)-
Cs
EQ18
EQ13
In EQ13, s is the Laplace variable (not conductance!). A boundary
condition for this experiment is that
the charge accumulated on capacitor
Cs = 0 until the potential is applied;
i.e., Q(0) = 0. Making this substitution into EQ13 and rearranging
gives:
E
Rs
Q(s)=
1
s s+
RsCs
EQ14
t
-(
RC
s
]
EQ15
dQ =
E e -( R C
i=
Rs
dt
()
95
EQ11
EQ17
Q
Eapp= EC+ER= + iRs
Cs
EQ12
1 Q=
E
Q'+
RsCs
Rs
Single-Pulse Measurements
where Q is the charge that accumulates on the capacitor, and i is the cell
current. Since i is the time rate-ofchange of charge (Q), the above
equation can be rewritten as:
Interrogation Waveforms
EQ16
A Look Ahead
References
1.
2.
3.
i2
S=
E
EQ19
4.
5.
6.
7.
96