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Conductometry
Conductivity Measurement
Peter A. Bruttel
Table of Contents
4
Foreword
Terms / definitions
21
Measuring instruments
22
23
Calibration
26
Practical applications
41
Literature
42
Tables
Foreword
The measurement of the electrical (electrolytic) conductivity conductometry can look
back on a long tradition. Conductivity measurements were already being made about 125
years ago. For approximately 50 years Metrohm has provided measuring instruments and
accessories for its customers. This monograph is concerned only with the measurement
of conductivity in solutions.
Although conductivity measurements are carried out frequently, they have never achieved
the wide range of application of potentiometry (e.g. pH, ion, redox measurements). The
reason for this may be that in conductometry there is no generally valid equation (such
as, for example, the Nernst equation) that permits the appropriate calculations. On the
contrary, in conductometry experience, experiments and comparative measurements
come to the fore instead of calculations.
This monograph is intended to provide a basic familiarization course in conductometry in
a short time. Help is provided by the alphabetically arranged terms and definitions as well
as the practical examples.
Terms / Definitions
Activity a
In water and polar solvents ionic compounds dissociate into their single ions (e.g. NaCl
Na+ + Cl). At normal concentrations, strong electrolytes (e.g. HCl, K2SO4) are completely
dissociated, but weak electrolytes (e.g. NH3, CH3COOH) are always incompletely dissociated.
However, strong electrolytes behave as if an incomplete dissociation were present. This is
caused by the fact that interactions (associations) occur between the oppositely charged
ions and these reduce the chemical potential. For this reason the electrical conductivity is
not a linear function of the concentration. The effective concentration (c) is known as the
activity a. (Of course, these interactions also occur with weak electrolytes, but can normally
be neglected because of the low ionic concentration.)
Activity coefficient
In real ionic solutions the interaction (association tendency) causes the mass action of
the ions to be smaller than would be expected from the weight present. The stoichiometric
concentration c must therefore be multiplied with a correction factor so that the mass
action law continues to remain valid. This concentration-independent factor is known as
the activity coefficient fi, the effective concentration as the activity a (see above).
Amount-of-substance concentration
c(X) = amount-of-substance concentration of substance X in mol/L, e.g. c(KCl) =
0.01 mol/L.
Ash
The ash content of sugars can be determined by measuring the electrical conductivity. This
method is much more rapid than the ashing process itself and provides usable results.
The theoretical basis is that the majority of the ash components consist of electrolytes,
whereas the sugar itself is a non-electrolyte. This means that the electrical conductivity of
sugar solutions is practically only determined by their ash content.
5.0 g sugar is dissolved in dist. H2O, the solution made up to 100 mL and mixed. The
electrical conductivity is measured at 20 0.1 C K5
The electrical conductivity of the water used is measured at the same temperature KW
K5 = electrical conductivity in S/cm of the 5% sugar solution
20 C
133 S/cm
1.28 mS/cm
11.67 mS/cm
25 C
147 S/cm
1.41 mS/cm
12.90 mS/cm
Cell constant
In principle most instruments for measuring the electrical conductivity are instruments for
measuring the resistance RX or the conductance GX = 1/RX of a measuring cell filled with
the sample.
Conductometry Conductivity Measurement
The relationship to the electrical conductivity , the real subject of interest, is provided by
the cell constant c, which depends on the geometrical dimensions of the measuring cell:
= c/RX = c x GX (S/cm)
In a two-plate measuring cell the cell constant c is obtained from the area F and the
distance d between the plates:
c = d/F (cm/cm2)
[c] = cm1
Because the distribution of the lines of current is not ideal, this calculated value does not
agree exactly with the effective cell constant of the measuring cell. The effective value of c
can only be determined by calibration; see below in the Calibration section.
Charge number
The charge number zi gives the charge of the particular ion including its sign.
Examples:
NaCl Na+ + Cl
CaCl2 Ca
2+
z+ = +1; z = 1
+ 2 Cl
K3PO4 3 K+ + PO43
z+ = +2; z = 1
z+ = +1; z = 3
Conductance
The conductance G is the reciprocal of the electrical resistance (1/R) and has the unit
Siemens (S) = 1. The electrical conductivity is obtained by multiplying it with the cell
constant. Conductivity titrations only require the conductance G.
Conductivity cells
See section on Measuring cells/conductivity cells.
Conductivity standards
See Calibration solutions.
Conductivity titration
See conductometric titration
Conductivity water
Term (introduced by W. Ostwald) for highly pure water with a very small self-conductivity. It
expresses the fact that such a water is suitable for even demanding studies in the field of
electrical conductivity (e.g. preparation of Conductivity standards). The term also applies
to the ultrapure water used in the pharmaceutical industry. USP Monograph 645 defines
the specifications for such a water as <1.3 S/cm at 25 C.
Conductometer
See Instruments section.
Conductometric titrations
In addition to colored indicators, measuring the conductivity is one of the oldest methods
for indicating titration endpoints.
6
Contact-free methods
As the name says, in these methods (for measuring the electrical conductivity) there is
no contact between the measuring cell electrodes and the sample. These methods are
frequently called electrode-free which is, of course, incorrect. Two basic methods are
used:
1. Capacitive method
See under the term High-frequency measurement.
2. Inductive method
In this case the sample forms a coupling loop between two windings of a transformer that
are magnetically shielded from each other. Measuring frequencies of 50 Hz...500 Hz are
used in this case. There is a relationship between the electrical conductivity of the sample
and the voltage transferred from the primary to the secondary winding throughout a very
wide range. This means that it is possible to evaluate the measured values by using the
cell constant.
Contact-free methods have the advantage that the measured values can never be falsified
by polarization. There are also no corrosion or contamination problems with the electrodes.
However, the cost and complexity of the necessary apparatus is considerably higher when
compared with those for normal instruments.
For this reason such methods are used, if at all, for industrial applications.
Convection
One of the three mechanisms (convection, migration, diffusion) by which ion transport
can take place is convection ions travel as a result of liquid flow, e.g. thermal convection
(temperature gradient).
Degree of dissociation
Quantity that describes the extent to which dissociation occurs. It represents the ratio between the free ions and the total molecules present in the solution and is given either relatively or as a percentage (1 or 100% means complete dissociation, 0.5 or 50% means that
only half the molecules are dissociated).
Strong electrolytes such as HCl, HNO3, H2SO4, NaOH, KOH and their salts are always
completely dissociated in aqueous solution.
Dependency of electrical conductivity
The electrical conductivity of a solution depends on:
The number of ions: The more ions a solution contains, the higher its electrical conductivity.
In general on the ionic mobility, which in turn depends on:
The type of ion: The smaller the ion, the more mobile it is and the better it conducts.
H3O+, OH, K+ and Cl are good conductors. If hydration occurs (the ion surrounds
itself with water molecules that make it larger) then the conductivity is reduced.
The solvent: The more polar a solvent is, the better the dissolved compounds it contains can ionize. Water is an ideal solvent for ionic compounds. In alcohols ionization
decreases as the chain length increases (methanol > ethanol > propanol). In nonpolar organic solvents (e.g. chlorinated and non-chlorinated hydrocarbons) practically no ionization occurs.
The temperature: In contrast to solids, in solutions the electrical conductivity increases as the temperature increases by 1...9% per K, depending on the ion.
The viscosity: As the viscosity increases, the ionic mobility and therefore the electrical
conductivity decreases.
Dielectric constant D
In electrochemistry the dielectric constant is important wherever opposite charges act on
each other. Examples are dissociation or ionic interaction. The larger the relative dielectric
constant (Dvacuum = 1), the better the ionic compounds dissociate in the particular solvent.
A few examples:
Solvent
D (20 C)
Formamide
110
Water
80
Methanol
34
Ethanol
25
Acetone
21
Propanol
19
Chloroform
4.8
Hexane
1.9
Diffusion
One of the three mechanisms (convection, migration, diffusion) by which ion transport
can take place is diffusion ions travel as a result of differences in chemical potential
(concentration gradients).
Diffusion is described quantitatively by Ficks law.
Dissociation
In solvents with a high dielectric constant (polar solvents) ionic compounds break down
into freely mobile single ions, e.g.
KCl K+ + Cl
A different type of dissociation occurs when a chemical compound with a heteropolar
bond is dissolved in a protic solvent, e.g.
CH3COOH + H2O CH3COO + H3O+
The most important solvent for dissociation is water. It has a high dielectric constant and
is polar.
Ionic solutions are electrically conductive and decompose when a direct current is applied
(electrolysis).
Ionic solutions are also known as electrolytes. Both strong and weak electrolytes occur;
these are differentiated by their degree of dissociation.
Dissociation constant
This quantity is used to describe the ionic equilibrium in aqueous solutions of weak
electrolytes and is defined by the following equation:
K = (CA x CC) / CCA
CA and CC are the concentrations of the anions and cations formed by dissociation, CCA is
the concentration of the molecules that remain undissociated.
K increases as the degree of dissociation increases and therefore represents a usable
quantity for describing the strength of a weak acid or weak base.
The negative common logarithm of K is also known as the pK value; pK = log K. As all
dissociation equilibria are temperature-dependent this also applies to K and pK.
Dosimat
Metrohm term for motor-powered piston burets. Dosimats are high-precision universal
dosing devices that can be controlled manually or remotely. Dosimats are equipped with
so-called Exchange Units.
Dosino
Metrohm term for a stepper-motor-controlled drive for precise dosing in small spaces.
Dosing Units are attached to the dosing drive by a quick-action coupling and screwed
directly onto the reagent bottle.
Electrical conductivity
The electrical conductivity is equal to the reciprocal of the electrical resistance (conductance G) multiplied by the cell constant c:
R
G
l
A
c
=
=
= 1/R
=
=
= l/A
conductivity
resistance
conductance
length of measuring path
cross sectional area
cell constant
The electrical conductivity is normally given in S/cm or mS/cm (12.88 mS/cm = 1288
mS/m; 5 S/cm = 500 S/m). In American usage the terms mhos and hos are frequently
encountered.
Definitions according to EN 27888 (1993) or ISO 7888.
Electrolytes
Electrolytes are substances that, in solutions or melts, undergo heterolytic dissociation
into ions that conduct the electrical current. Electrolytes include acids, bases and salts.
Strong electrolytes dissociate completely, weak electrolytes only partially.
Emulsions
Emulsions (water in oil or oil in water) normally belong to the group of non-electrolytes.
Migration of ions in an electric field and the resulting electrical conductivity do not occur.
However, a technical effect can be used for measurement this is charge transport in an
electric field. According to Coehns law, two phases that are immiscible are characterized
by the occurrence of surface charges. The phase with the higher dielectric constant
(water) assumes a positive charge, that with the lower one (oil) a negative charge. At
maximum viscosity the stability of the emulsion is also at its maximum, but also has the
lowest electrical conductivity. This means that under defined measuring conditions
conclusions can be drawn about the stability of emulsions.
Reference:
Dahms, G.H., Jung, A., Seidel, H.
Predicting emulsion stability with focus on conductivity analysis
Cosmetics & Toiletries Manufacture Worldwide 2003, p. 223228
Equivalent conductivity
The equivalent conductivity * is a quantity that is primarily used in theoretical studies. It
can be obtained from the molar conductivity and the electrochemical valency ne:
* = / ne
The electrochemical valency ne can be calculated for a molecule that dissociates into
anions and + cations with the corresponding valencies z und z+ as follows:
ne = x z = + x z+
Examples:
NaCl Na+ + Cl
AlCl3 Al
3+
+ = ne = 1
+ 3 Cl
+ = 1 and z+ = 3 ne = 3
compensated by the controller altering the oscillator potential Uvar. The current J flowing
in the sensor area is then a measure of the required resistance RX or the conductance G,
respectively:
J = Uref/RX = Uref x GX
Thanks to advances made in the fields of measuring and electrode technology we have
been able to establish that, despite its advantages, this method with its extra costs for
apparatus cannot replace the classical two-electrode measuring technique and that the
extra costs involved for laboratory applications are not justified.
High-frequency measurement
This term is used in connection with capacitive, contact-free methods for measuring the
electrical conductivity. It refers in particular to the relatively high frequencies (3 MHz...100
MHz) used for this type of measurement.
The special measuring cells are constructed so that two ring-shaped metal electrodes are
attached to the outer sides of a non-metallic cell body (e.g. glass beaker).
The electric field penetrates the cell body and is influenced by the properties of the sample
that it contains.
A major component of all instruments used for measuring the high-frequency conductivity
is an oscillating circuit. The contact-free measuring cell is located parallel to the rotary
condenser of the oscillating circuit. If resonance tuning is carried out during the
measurement (maximum value of voltage U), then evaluation is carried out by the reactive
component method. In contrast, if after resonance tuning has been carried out the value
of U is divided by the conductance G, the evaluation takes place according to the active
component method. Both types of evaluation require calibration with different conductance
standards and also produce different calibration curves.
In comparison to the classical method, high-frequency measurement has practically no
advantages this is why it has never been able to establish itself on the market.
Hydration
In an aqueous solution all the ions are surrounded by a sheath of oriented water dipoles
(hydration sheath). This phenomenon is known as hydration.
Interionic interaction
In infinitely dilute solutions no electrostatic attraction can occur between the oppositely
charged anions and cations of a dissolved electrolyte. This condition would occur for an ion
i at the hypothetical concentration ci = 0, which can only be achieved by extrapolation.
As the concentration increases the ions move closer together. This causes an interaction
between the ions in which each cation is surrounded by a cloud of oppositely charged
anions. In the same way each anion is surrounded by a cloud of cations. Interionic
interaction is particularly important for strong electrolytes.
Ionic mobility Ii
The product of the migration speed ui and the Faraday constant F is the ionic mobility. ui
refers to a uniform field with a field strength of 1 V/cm. The distance covered by an ion i is
given in cm. The ionic mobility depends on the temperature and the concentration. It usually
Conductometry Conductivity Measurement
11
I+
(cm2 / )
Anion
I
(cm2 / )
H+
350
OH
199
Li
39
Cl
76
50
NO
71
Na
K+
74
CH3COO
41
12 Mg2+
53
12 SO42
80
12 Ca
60
12 CO
69
2+
2
3
Example
KCl
K2SO4
MgSO4
K3PO4
Factor
1
3
4
6
The ionic strength is obtained by multiplying the particular molar salt concentration by this
factor. Example:
c(MgSO4) = 0.0025 mol/L
J = 4 x 0.0025 mol/L = 0.01 mol/L
Ions
are positively or negatively charged atoms or molecules that are formed by dissociation
from compounds with ionogenic or heteropolar bonds. In an electric field the positively
charged ions (cations) migrate to the cathode (negative pole), negatively charged ions
(anions) to the anode (positive pole).
12
In dilute solutions anions and cations migrate independently without any interactions in
an electric field.
Kohlrausch cells
See section on Measuring cells/conductivity cells.
Kohlrauschs square-root law
This law for strong electrolytes links the molar conductivity C with the square root of the
concentration c according to:
C = 0 A
The equation states that the molar conductivity extrapolated to infinite dilution decreases as
the square root of the concentration. The constant A depends on the type of electrolyte.
Limiting conductivity
0 is the limiting equivalent conductivity or limiting conductivity for short. 0 is the sum of
the limiting conductivities of the cations (0+) and anions (0) (law of independent ionic
migration).
For see the definition under equivalent conductivity.
Limiting conductivities of some ions in water at 25 C
Cations
Limiting
conductivity
(S x cm2 x mol1)
Anions
Limiting
conductivity
(S x cm2 x mol1)
H3O+
349.8
OH
197.0
NH4+
73.7
SO42
80.8
78.4
73.5
Br
Ba2+
63.2
Ag
62.2
Cl
76.4
Ca2+
59.8
NO3
71.5
Mg2+
53.1
ClO4
68.0
Na
50.1
55.4
38.6
CH3COO
Li+
76.5
40.9
Mass fraction
w(X) mass fraction of the substance X in %, e.g. w(NaOH) = 25%
Mass concentration
(X) mass concentration of the substance X in g/L, e.g. (NaCl) = 2.5 g/L
Measuring cell
Measuring frequency
For conductivities the measuring frequency has a decisive influence on the correctness
of the measured conductance G. Interfering polarization effects can be eliminated by
Conductometry Conductivity Measurement
13
increasing the measuring frequency. At the same time the usable measuring range
is extended. On the other hand, it must also be taken into consideration that at high
frequencies a cable error could occur as a result of capacitive shunting. The following
time-proven compromises apply:
At low conductances (not electrical conductivity) measurements are made at a frequency of 300 Hz.
At high conductances measurements are made at a frequency of 2.4 kHz (712 Conductometer).
Measuring range
The usable measuring range depends on the type of conductivity cell (platinized/nonplatinized), the cell constant and the measuring frequency. Unfortunately no universal
measuring cell exists for the whole usable range. This is why Metrohm offers measuring
cells with different cell constants. The following tables should make your choice easier:
Cell constant
Measuring range
0.1 cm1
1 cm1
1 S/cm...10 mS/cm
10 cm1
10 S/cm...100 mS/cm
100 cm1
Solution
Measuring cell
Cell constant
Measuring
frequency
<20 S/cm
non-platinized
small
300 Hz
<1 mS/cm
platinized
medium
300 Hz
>1 mS/cm
platinized
large
2.4 kHz
Migration
One of the three mechanisms (convection, migration, diffusion) by which ion transport can
take place ions travel (or are transported) in an electric field (field gradient).
Migration speed
Electrical conductivity in aqueous solutions takes place by the charge transport of the ions.
This means that anions and cations can be differentiated by their direction of movement
(in a direct current field). The migration speed wi of an ion is obtained from the force Ki
acting on the ion and the friction Ri inhibiting the migration.
The force Ki is produced by electrostatic attraction (Coulombs law). On the other hand,
the friction Ri depends on the ionic radius ri and the viscosity of the solution.
If E is the field strength and if the ion zi carries one electron charge e0, then the following
applies for the migration speed wi:
wi = Ki/Ri = (zi x e0 x E) / 300 x 6 x x ri)
If wi is divided by the field strength E, then for a field of 1 volt/cm we obtain for the migration
speed ui:
ui = wi/E
14
Non-electrolyte
In contrast to electrolytes, non-electrolytes release no freely mobile anions and cations
and therefore make no contribution to the electrical conductivity in aqueous solutions.
Typical representatives of this group are e.g. alcohols, urea, sugar (raw sugar), nonionic
surfactants and emulsions.
Electrolytic contaminations may contribute to the electrical conductivity see Ash.
However, higher concentrations of non-electrolytes may influence the viscosity of the
solution, which also affects the ionic mobility.
Oscillometry
See under high-frequency measurement.
Ostwalds dilution law
This law applies for strong electrolytes and links the molar conductivity C with the square
root of the concentration c as follows:
C = 0 A
The equation states that the molar conductivity extrapolated to infinite dilution decreases
as the square root of the concentration.
The constant A depends on the type of electrolyte. See also Kohlrauschs square-root
law.
Platinization
Platinization is the deposition of finely dispersed platinum (platinum black) on smooth
platinum electrodes. It is an important feature of all classical conductivity cells and is
used to avoid polarization effects (and the measuring errors they cause), particularly at
high electrical conductivities. Platinized measuring cells are not suitable for industrial
applications. Application Bulletin no. 64 provides information about the pretreatment and
platinization of measuring cells (the 712 Conductometer has a built-in 20 mA DC source).
Polarization
In the measurement of the electrical conductivity a number of technical measurement
effects that produce incorrect measured values are grouped together under polarization.
Their source lies at the electrode/solution boundary. Of chief interest here are the
Conductometry Conductivity Measurement
15
polarization resistance, which is in series with RX (resistance of the solution), and the
polarization capacity, which is also in series. Interference by polarization usually results in
too low electrical conductivities being measured.
Polarization depends mainly on the current density at the electrode. This current density
can be kept negligibly small if platinized measuring cells are used together with a suitable,
not too low measuring frequency.
Reference temperature
The electrical conductivity measured at a given temperature is converted to a reference
temperature. The conversion is carried out (usually automatically) by using the temperature
coefficient.
The normal reference temperatures are 20 C and 25 C.
Salinity
Applications exist in which it is not the electrical conductivity that is of interest, but rather
the total content of the dissolved salts. Separation into the individual ions cannot be
achieved by measuring the conductivity, as each type of ion makes a different contribution
to the total conductivity. This is why when the salinity is measured it is the electrical
conductivity of the sample solution which is compared with those of pure NaCl solutions
and the corresponding NaCl concentration is given. The salinity is given in mg/L or g/L
NaCl as the TDS (Total Dissolved Solids).
Solvents, non-polar
Non-polar (also known as aprotic) solvents have no self-dissociation. Molecules with ionic
bonding only decompose in them to form ions on rare occasions.
Examples of acidic non-polar solvents are:
pyridine, dimethylformamide (DMF), dimethylsulfoxide (DMSO)
Examples of neutral polar solvents are:
acetone, methyl isobutyl ketone (MIBK), acetonitrile, nitrobenzene, ethers, hydrocarbons
and chlorinated hydrocarbons.
Normal conductometers are not suitable for non-polar solvents such as chlorinated
and non-chlorinated hydrocarbons, insulation oils or petrochemical products. In order
to measure the electrical conductivity (insulation properties) of such products, special
instruments are required. These work with voltages in the kV range and with special
measuring cells.
Solvents, polar
Polar (also known as amphiprotic) solvents have an appreciable self-dissociation. In such
solvents molecules with ionic bonding decompose by dissociation to form ions (the higher
the dielectric constant, the better). The most polar solvent is water:
2 H2O
H3O+ + OH
CH3OH2+ + CH3O
Metrohm Monograph 8.028.5003
25 and
17
Titrando
Metrohm name for the most modern titration system on the market. The Titrando provides
flexibility at the user interface and dosing system. The basic unit can be extended to form
a fully automated supertitrator.
Titrino
Metrohm name for a whole range of titrators. The range of titrators covers everything from
a simple endpoint titrator up to potentiometric and Karl Fischer titrators for universal use.
Transference number
The transference numbers n+ und n describe the current fraction transported by the
cation and anion respectively.
n+ = +/ = u+ / (u+ + u)
n = / = u / (u+ + u)
Experimental determination of the transference numbers allows the calculation of the ionic
conductivities and ionic mobilities.
Validation
Validation is the systematic checking of analysis procedures and/or measuring devices
with the aim of ensuring that if defined SOPs (= Standard Operating Procedures) are
observed then reliable and reproducible measurements and results will be obtained.
See also the Calibration section.
Viscosity
The (dynamic) viscosity is the property of a liquid to resist (by internal friction) the
mutual laminar displacement of two neighboring layers. For Newtonian liquids at a given
temperature, is a material constant with the SI unit Pascal per second (Pa s1).
In connection with the measurement of conductivity there is the fact that, as the viscosity
increases, the ionic mobility and therefore the electrical conductivity decreases and vice
versa. See also Waldens rule.
Waldens rule
In its general form this rule states that the product of the ionic mobility Ii of an ion and the
viscosity of a solvent is constant:
Ii x = K
An increase in the viscosity results in a reduction of the ionic mobility (and therefore the
electrical conductivity) and vice versa.
Water, self-conductivity
Kohlrausch already recognized about 150 years ago that even the most overdone
purification of the water by distillation resulted in a self-conductivity that could not be
lowered any further. The cause is the self-dissociation of the water, which is also known as
autoprotolysis:
2 H2O
18
H3O+ + OH
Metrohm Monograph 8.028.5003
This self-dissociation depends very strongly on the temperature. Examples are shown in
the following table:
C
S/cm
0.010
18
0.038
25
0.060
34
0.090
50
0.170
19
Instruments
Instruments for measuring the electrical conductivity are called conductometers. They are
instruments for measuring complex resistances with changing potentials. (In contrast to
the measurement of purely ohmic resistances of metallic conductors, in liquids together
with the measuring cell a whole network of resistances and capacitances exist.) It makes
sense to have at least two frequencies available for the applied alternating potentials
(see under Measuring frequency and Polarization). However, by the correct choice of
the measuring frequency, the cell constant and the material of the measuring cell, purely
ohmic relationships can be achieved. Under these conditions the electrical conductivity
can be determined from the measured resistance.
This means that an instrument for measuring the conductivity must be able to measure the
electrical conductivity of liquids. The demands placed on such instruments for laboratory
use have increased year by year. With the 712 Conductometer Metrohm provides the
user with an instrument of the highest performance class that leaves nothing to be desired.
The possibilities of this instrument are listed below:
Types of measurement
Electrical conductivity
Standard (calibration solutions)
TDS (Total Dissolved Solids), expressed
as mg/L NaCl or g/L NaCl salinity
Titration (conductivity titration)
Temperature (of solution)
Sensor connections
One input each for conductivity measuring
cell and temperature sensor (Pt 100 or Pt
1000)
Measuring ranges
Electrical conductivity (automatic range
switching):
0...2000 S/cm and 0...20000 mS/cm.
Resolution: max. 412 digits are shown.
Temperature: 170.0...500.0 C.
Resolution: 0.1 C.
Compensation ranges, e.g. for titrations, background suppression
Electrical conductivity: 0...2000 S/cm and
0...2000 mS/cm (0...2 S/cm)
Temperature: 170.0500.0 C
Measuring frequencies
300 Hz or 2.4 kHz; automatic switching to the
most suitable frequency or manual setting.
Temperature coefficient
Automatic determination with connected
temperature sensor; TC = f(T) is calculated
as a polynomial. Can also be entered manually. Range 0.00...9.99% per C.
20
Reference temperature
For automatic temperature compensation.
Freely selectable, 20 C or 25 C are normal.
Cell constant
Automatic via determination dialog-guided
with automatic calculation, or manual input.
Range 0.001...500/cm.
Platinization
DC output for platinizing conductivity cells.
I = 20 mA.
Interface RS 232
For connection to printer or PC.
Remote I/O lines
For connecting a sample changer or laboratory robot or for triggering any type of alarm.
Analog output for electrical conductivity
Connection of a lab recorder or titrator. Output signal 0...2000 mV with a resolution of 0.5
mV (12 bit).
Analog output for temperature
E.g. for connection of a lab recorder. Output
signal 0...2000 mV with a resolution of 0.5 mV
(12 bit).
Instrument diagnosis
The instruments carries out a self-diagnosis
when switched on. The built-in diagnosis program allows the user to localize or exclude instrument faults.
21
Calibration
GLP (Good Laboratory Practice) requires, among other things, that the accuracy and
precision of analytical instruments are checked regularly by using SOPs (Standard
Operating Procedures).
Calibration is used to validate the whole system that is used for making the measurements.
In our case this means that instrument and the measuring cell(s) used must be calibrated
from time to time.
The following test procedures should be considered as guidelines. The limits they contain
are merely examples. Depending on the accuracy required for the measuring system it
may be necessary to redefine these limits in your own SOPs.
Literature: Application Bulletin no. 272
1.000 / cm
meas. temp.
25.0 C
ref. temp.
25.0 C
TC selection:
const.
TC const.
0.00% / C
frequency:
auto
meas. type:
standard
At the 767 Calibrated Reference the cover over the solar cells is closed. The two banana
plugs of the electrode cable are inserted into the input sockets (measuring cell) of the
conductometer and the electrode plug screwed onto socket 5 or socket 6 of the 767. The
two 6.2106.020 cables are now used to connect the two input sockets of the 712 with
sockets 1 and 2, or 2 and 3, respectively, of the 767.
22
Actual value
S/cm
Theoretical value
S/cm
Difference
S/cm
Error tolerance
(0.5%)
S/cm
70.07
70.01
0.06
0.35
2.168
2.17
0.002
0.011
1&2
10010
10008
50
2&3
999.2
999
0.2
Actual value
C
Theoretical value
C
Difference
C
Error tolerance
C
1&2
0.2
0.20
00
0.1
2&3
00.1
00.17
0.07
0.1
23
Wait until the temperature is constant and then read off the measured value. If the KCl
calibration solution from Metrohm (6.2301.060) is used then the electrical conductivity
must be 12.90 0.15 mS/cm.
New cell constant = theoretical conductivity / measured conductance
Example c(KCl) = 0.1000 mol/L, 25 C
Electrical conductivity
= 12.90 mS/cm
Displayed conductance
= 16.13 mS
24
Practical applications
1. Determination of the cell constant c
Metrohm conductivity cells are supplied with the cell constant printed on them. The
use of the cells may cause the cell constant to change. This is why, if high-precision
measurements are to be made, the cell constant must be checked or redetermined from
time to time. KCl solutions of a known concentration are used for these determinations.
For reasons of precision (weighing errors) a stock solution with c(KCl) = 0.1000 mol/L is
either prepared or purchased and lower concentrations are prepared from it by dilution
with conductivity water.
The electrical conductivity of conductivity water is 1 S/cm.
c(KCl) = 0.1000 mol/L (Metrohm no. 6.2301.060)
KCl reagent grade (e.g. Merck no. 104936) is dried at 105 C for 2 h and allowed to cool
down in a desiccator. 7.456 g is dissolved in conductivity water and made up to 1000 mL.
The conductivity of this solution is:
at 20 C: 11.67 mS/cm
at 25 C: 12.88 mS/cm
c(KCl) = 0.010 mol/L
10.0 mL c(KCl) = 0.1 mol/L is diluted to 100 mL with conductivity water.
The conductivity of this solution is:
at 20 C: 1.28 mS/cm
at 25 C: 1.41 mS/cm
c(KCl) = 0.001 mol/L
This solution should only be prepared immediately before use. It cannot be stored. The
conductivity water must be freed from carbon dioxide before use by passing nitrogen
through it. 10.0 mL c(KCl) = 0.01 mol/L is diluted to 100 mL with degassed conductivity
water.
The conductivity of this solution is:
at 20 C: 133 S/cm
at 25 C: 147 S/cm
Certified conductivity standards with a wide range (1 S/cm...100 mS/cm) are sold,
e.g., by Messrs Reagecon, Chemical Measurement Specialists, in Shannon Free Zone,
Shannon, Co. Clare, Ireland; www.reagecon.com
25
Reagents:
c(KCl) = 0.0100 mol/L
Acetone and conductivity water
Procedure
The measuring cell is placed in acetone for 30 min. It is rinsed with conductivity water
and then allowed to stand in it for at least 2 h, preferably overnight. The titration vessel is
first rinsed with c(KCl) = 0.01 mol/L and then filled with this solution. The measuring cell
is also rinsed with c(KCl) = 0.01 mol/L and inserted in the titration vessel. The thermostat
is used to bring the liquid in the titration vessel to 20.0 C under stirring while nitrogen is
bubbled through the solution for at least 10 min. The nitrogen is then allowed to blanket
the solution. Care must be taken that there are no gas bubbles inside the measuring cell.
The following settings are made on the 712 Conductometer (see also parameter report):
Cell constant
Measuring temperature
Reference temperature
TC selection:
TC const.
Frequency
Meas. type:
Range limit:
Standard
1.0 / cm
20.0 C
20.0 C
const.
0.0% / C
auto
Standard
off
1.278 mS/cm
40.0 C
15.0 C
20.0 C
auto
0.00%
actual value
The stirrer is switched on and the solution is brought to approx. 45 C by using the
thermostat. The automatic determination is started and the solution is allowed to cool
down slowly (not faster than 1 C / min).
Example:
Measured value; TC = 2.35 0.09% / C (n = 8)
3. General remarks concerning conductivity measurements
The measuring cell
The cell constant should match the liquid to be measured. Low conductivities require
the use of a small cell constant, high conductivities a high one:
c 0.1 cm1
c 1 cm1
c 10 cm1
27
c 100 cm1
for solutions with very good conductivity such as brine, acids, alkalis,
electroplating baths, etc.
The measuring cell must be well conditioned/prepared. Measuring cells stored dry
must be placed in acetone for 30 min. They are then rinsed in conductivity water and
allowed to stand in it for at least 2 h, preferably overnight. Frequently used measuring
cells are stored in conductivity water or 20% ethanol (to prevent the growth of microorganisms). Measuring cells that are only used occasionally should be stored dry.
Contaminated measuring cells cannot be used for conductivity measurements and
must be cleaned. After cleaning they should be thoroughly rinsed with conductivity water. Possible sources of contamination:
Deposits of calcium carbonate or barium sulfate: Rinse with HCl. For BaSO4 immerse
the cell overnight in a solution of w(Na2EDTA) = 10% in c(NaOH) = 0.1 mol/L under
stirring.
Fat and oil residues: Rinse with acetone. If this does not help, saponify with ethanolic
c(NaOH) = 1 mol/L at approx. 40 C.
Algae or bacterial growth: Place in hot chromosulfuric acid.
Protein: Place in w(pepsin) = 5% in c(HCl) = 0.1 mol/L for 1...2 h.
The instrument
Set the measuring frequency to auto this ensures that the measurement is made at
the optimal measuring frequency. Generally: Measure low conductivity at a low measuring frequency and high conductivity at a high one.
Temperature coefficient: If known then set on instrument, otherwise determine it. A further possibility is to use a thermostat and to perform the measurement at the reference
temperature, which means that this setting is not necessary.
Temperature: It is best to use a measuring cell with a built-in temperature sensor. Otherwise connect a separate temperature sensor or use a thermometer in the latter case
the measuring temperature must be entered at the instrument.
Cell constant: Enter the cell constant marked on the measuring cell or determine the
cell constant again.
Reference temperature: This is normally 20.0 C; for some applications 25.0 C is stipulated or preferred (water samples or, e.g., measurements in tropical countries). Any reference temperature can be entered at the 712 Conductometer.
The measurement
Only use well-conditioned measuring cells. It is best to rinse them with the solution to
be measured before the measurement. Immerse the measuring cell in the measuring
solution to an adequate depth and make sure it is bubble-free. The lateral openings must
be fully immersed. Remove and re-immerse the measuring cell a few times. Wait until the
temperature of the measuring cell and solution become constant.
28
TC in % / C
5...10 C
2.62
10...15 C
2.41
15...20 C
2.23
20...25 C
2.08
25...30 C
1.94
30...35 C
1.79
Examples:
Tap water in Herisau, 25 C
Mineral water, 25 C
B) Deionized water
Because of possible interferences, a special procedure must be selected for water with a
conductivity of <5 S/cm. This applies to water with a conductivity <1 S/cm in particular!
The most important interferences result from:
Absorption of CO2 (or other conducting gases) from the atmosphere.
Leaching of traces of Na and Ca from the glassware used.
Both interferences cause the settings to drift and finally high-bias conductivities are
measured. We recommend the following procedures to eliminate such interferences to as
great an extent as possible:
Version 1
Perform flow-through measurements. Because of the small volume of the measuring
setup we recommend to use the 6.0912.110 conductivity cell (PP shaft, built-in Pt 1000
temperature sensor) screwed into the 6.1420.100 flow-through vessel. The water is allowed to flow through the measuring setup and the conductivity is determined in the
usual way.
Version 2
The measurement is carried out in as large a volume as possible. Nitrogen or argon
should be passed through and over the solution, which should also be stirred. If possible, use a closed or covered setup.
Please note the high TC (approx. 5.8% / C) of such water samples!!
29
5. Salinity
Applications exist in which it is not the electrical conductivity that is of interest, but rather
the total content of the dissolved salts. Separation into the individual ions cannot be
achieved by measuring the conductivity, as each type of ion makes a different contribution
to the total conductivity. For this reason, when the salinity is measured it is the electrical
conductivity of the sample solution that is compared with that of pure NaCl solutions and
the corresponding NaCl concentration is given. The 712 Conductometer carries out this
conversion automatically if the measuring mode TDS (Total Dissolved Solids) is selected.
TDS appears on the 712 as mg/L or g/L NaCl in the dialog display instead of the cell
constant.
Examples:
Tap water Herisau, 25 C
Mineral water, 25 C
6. Conductometric titrations
For conductometric titrations the cell constant does not normally need to be known. A
double platinum sheet electrode is used for the measuring electrode as the titration is
usually carried out in a beaker. This electrode is easy to clean. Thermostatting is not
required for simple titrations room temperature is adequate. Alterations in conductivity
caused by temperature variations are of virtually no consequence.
Instruments and accessories:
2.712.0010 Conductometer
Titrino with 2.728.0040 Magnetic Stirrer
6.3026.220 Exchange Unit
6.0309.100 double Pt-sheet electrode with 6.2104.080 electrode cable
6.2116.000 connecting cable 712 Titrino
PC with connecting cable for Titrino, printer and printer cable
E.g. Metrodata VESUV 3.0 Light for the manual evaluation of L- or V-shaped titration
curves (VESUV = Metrodata Application software; Verification Support for Validation).
Reagents:
c(AgNO3) = 0.01 mol/L as titrant (in Exchange Unit)
c(KCl) = 0.1000 mol/L, e.g. Metrohm no. 6.2301.060
Conductivity water and acetone
Procedure
The instruments are connected together as described in the 712 Instructions for Use.
0.25 mL c(KCl) = 0.1 mol/L and 30 mL each of acetone and conductivity water are placed
in a beaker. The electrode and buret tip are immersed and the titration with c(AgNO3) =
0.01 mol/L is started after the following instrument parameters have been set:
30
712 Conductometer
>cond/parameters
cell constant
1.0/cm
meas. temp.
20.0 C
ref. temp.
20.0 C
TC selection:
const.
TC const.
0.0% / C
frequency:
auto
meas. type:
Titration
limits:
off
>cond/analog output
status:
on
polarity
+
1 V range:
1 mS/cm
0 V at:
0 S/cm
offset:
0 mV
>cond/limits
status:
off
>cond/plot margins
left:
0 S/cm
right:
1000 S/cm
799 Titrino
MET U
Cond. titr.
>titration parameters
V step
0.10 mL
dos. rate
max. mL/min
signal drift
50 mV/min
equilibr. time
26 s
start V:
off
pause
0s
>stop conditions
stop V:
abs.
stop V
4.0 mL
filling rate
max. mL/min
>evaluation
EP criterion
30 mV
EP recognition
all
Evaluation
L- and V-shaped titration curves are evaluated as follows:
Tangents are applied to the two legs of the curve. The titration endpoint is defined as
the intercept of the tangents. In the Metrodata VESUV 3.0 program this is carried out as
follows:
Move Tangent 1 along the curve with the <CTRL> key and the left-hand mouse key,
Tangent 2 with the <Shift> key and the left-hand mouse key.
Conductometry Conductivity Measurement
31
2.712.0010
6.1420.100
2.767.0010
2.728.0010
6.1418.250
6.1414.010
2.683.0010
6.2125.060
6.2125.010
6.6008.140
32
0.0 C
33
2002-03-07
time
15:28:15
dialog:
english
device label
program
712.0015
9600
data bit:
stop bit:
parity:
none
handshake:
HWs
RS control:
ON
---------------------------------------Sample preparation
Water is taken from the Nanopure unit. The first 500 mL is rejected. 1 Liter is then filled
into an amber glass bottle (thoroughly rinsed) and the bottle placed in a thermostat bath
for 1 h at 25 C.
Preparing the measuring setup
The 712 Conductometer is validated with the 767 Calibrated Reference as described in
Application Bulletin No. 272. The protocols shown below provide an overview:
712 Conductometer: protocol of measuring amplifier check
Instrument: 1.712.0010
Serial/Fabr.-No: 16162
Test agent:
Serial/Fabr.-No: 01102
Calibrator (master)
Type .......................................................
2.767.0010
Yes
x
Signature:..........................................................
Decision:
Place Calibrated Reference on bench near sensor. The cover remains always closed and therefore the light is
not of importance.
The electrode cap must not necessarily be firmly screwed onto sockets (4), (5), (6) of the 767; plugging it in is
sufficient.
34
............... /cm
1.0 /cm
<enter>
meas. temp.
............... C
20C
<enter>
ref. temp.
............... C
20C
<enter>
TC selection:
............... <select>
const.
<enter>
TC const
............... %/C
1.0 %/C
<enter>
frequency:
............... <select>
auto
<enter>
meas.type:
............... <select>
standard
<enter>
range limit
............... <select>
OFF
<enter>
20.0
1.000 /cm
C
1.00%/C
Conductivity
Carry out on 712 or on sensor
Remarks
Carry out on
767
Difference2
Permitted
Difference
1.
Close cover
Sensor cable
to socket (6)
2.
(Cover
remains
closed)
S value 6:
2.167S
2.169 S
0.2 S
0.04 S
Sensor cable
to socket (5)
S value 5:
69.86 S
69.881 S
0.0281 S
0.77 S
Sensor cable
to sockets
(2) and (3)
(Pt 1000)
S value 2)/(3):
Sensor cable
to sockets
(2) and (1)
(Pt 100)
S value 1)/(2):
3.
4.
5.
999.80 S
9990.1S
OK
999.842 S
0.042 S
11 S
9995.202 S
2.202 S
70 S
6.
<auto zero>
Display 0
7.
<az off>
Display
as before
35
Remarks
Enter actual
alue from
712 display
Difference2
Permitted
difference
OK
1.
2.
Measuring (mode) C
on the main
display
there
appears:
X.X C
3.
On 767.0010:
C value:
0.1 C
0.2 C
0.1 C
0.4 C
0.0 C
0.0 C
0.0 C
0.4 C
25.7 C
25.8 C
0.1 C
0.4 C
During pH checks the two Pt 100/Pt 1000 resistances at sockets (1)...(3) can be used at the same time. However,
it must be clear that the measuring temperature assumed by the 712 Conductometer being tested will then be
approx. 0 C, while the information in the table refers to 25 C. This must be taken into account.
1
The given permitted difference applies for normal room temperatures (2030 C) and warmed-up instruments.
Otherwise this should be determined from the technical specifications of the 767 and 712 Conductometer.
The cell constants of the conductivity cells are measured at 25 C with 100 mL conductivity
standard (Hamilton 5 S/cm) in a closed, thermostatted titration vessel. When the
conductivity standard has reached the stipulated temperature of 25.0 C the cell constant
is determined as described in Method 1 above. The temperature compensation is switched
off at the 712 during the measurement. The newly determined cell constant is entered at
the 712 Conductometer or taken over by it. Result reports for two conductivity cells are
shown below:
Conductivity cell PP
Subject
Requirement
Achieved
Conductometer validation
yes
yes
Cell constant
2%
0%
c displayed: 0.091 cm
0.091 cm1
, limit at 25 C
<1.3 S / cm
<0.08 S / cm
Temperature measurement
1 C
0.1 C
36
Requirement
Achieved
Conductometer validation
yes
yes
Cell constant
2%
0%
0.082 cm1
, limit at 25 C
<1.3 S / cm
<0.08 S / cm
Temperature measurement
1 C
0.1 C
Remarks
USP Guideline 645 sets standards for the quality control of ultrapure waters using
electrochemical conductivity measurements. The conductivity test according to USP 645
is a three-step test. The requirements have been met when the conductivity of the
tested water is <1.3 S /cm at 25 C. If this value is exceeded or if no online measurement
is possible, this leads to the second step.
In this case the water is thermostatted in an open vessel at 25 C under stirring and
the CO2 absorption from the atmosphere is allowed to reach equilibrium. The electrical
conductivity of the solution is measured and the temperature is compensated. If >2.1
S/cm then the third step must be carried out.
The water sample from step two is treated with a small amount of KCl in order to ensure a
stable pH value.
The measured electrical conductivity must be less than a value laid down in a table. If the
value in the table is exceeded then the conditions of the USP test have not been fulfilled.
The cell constant (c) can be determined by two methods:
directly with a conductivity standard, or
indirectly by comparison with a conductivity cell with a known, validated cell constant
(precision 2%).
37
Summary / Procedure
In practice the electrical conductivity of water from ultrapure water units is determined
according to the USP Guidelines 645 for conductivity measurements as follows:
1. The conductometer (712) is calibrated using the 767 Calibrated Reference.
2. The cell constant of the conductivity cell is determined at 20 C according to Application
Bulletin no. 272. The value given on the conductivity cell should be in agreement with
the value measured to 2%.
3. The 6.1420.100 flow-through cell is connected to the outlet valve of the ultrapure water
unit (inlet at bottom, outlet on top) and the conductivity cell is inserted.
4. The water now flows through the cell into the outlet (a pump can also be used to transport it through the cell).
5. Temperature compensation is switched off at the conductometer (712).
6. The measuring setup is rinsed with 200...500 mL water (from the unit).
7. The electrical conductivity of the water is now measured at the temperature at which
it leaves the unit (to 1 C) and the value is accepted after a flow-through time of
15 min.
8. The value is compared with the following table (USP requirements):
USP 645 Requirements Ultrapure water (without temperature compensation)
Temp. C
S / cm
Temp. C
S / cm
0.6
55
2.1
0.8
60
2.2
10
0.9
65
2.4
15
1.0
70
2.5
20
1.1
75
2.7
25
1.3
80
2.7
30
1.4
85
2.7
35
1.5
90
2.7
40
1.7
95
2.9
45
1.8
100
3.1
50
1.9
9. If the electrical conductivity (at the corresponding temperature) is not greater than the
value given in the table then the USP requirements have been fulfilled. However, if the
measured electrical conductivity is larger than the corresponding table value then step
two given under Remarks is carried out.
38
Literature
Metrohm Application Bulletin no. 102
Conductometry
Metrohm Application Bulletin no. 272
Validation of Metrohm conductometers
United States Pharmacopeia Convention, Inc.
USP 26 / NF 21 (2003) Water conductivity (645)
Kunze, U.R., Schwedt, G.
Grundlagen der quantitativen und qualitativen Analyse
Wiley-VCH, Weinheim 2002. ISBN 3-527-30858-X
Donald T. Sawyer et al.
Electrochemistry for chemists
John Wiley & Sons, New York 1995 ISBN 0-471-59468-7
hme, F., Bnninger, R.
ABC der Konduktometrie
Reprint Chemische Rundschau, 1979 (out of print)
EN 27888: 1993
Water quality Determination of electrical conductivity
AOAC, Method 973.40 (1990)
Specific conductance of water
DIN 38404, Part 8 (1982)
German standard methods for the examination of water, waste water and sludge; physical and physicochemical parameters. Determination of the electrical conductivity
39
Tables
Electrical conductivity of organic acids at 25 C
% formic acid
mS/cm
% acetic acid
mS/cm
6.22
1.36
10
8.26
10
1.76
15
9.86
15
1.82
20
11.1
20
1.82
25
11.4
25
1.71
30
11.8
30
1.58
40
11.1
40
1.23
50
9.78
50
0.840
60
7.92
60
0.521
70
5.92
70
0.270
80
3.92
80
0.093
90
1.95
100
0.32
mS/cm
% HCl
mS/cm
5.09
239
2.03
202
9.16
409
6.00
506
15.3
603
10.0
698
20.4
706
15.2
821
25.3
787
19.0
849
30.5
828
20.3
844
32.5
833
24.8
809
35.5
833
29.9
737
37.5
825
33.0
688
40.7
801
36.0
638
40
mS/cm
% HNO3
mS/cm
3.06
4.89
8.99
14.0
18.1
24.0
28.0
33.1
36.3
40.0
176
270
454
631
741
830
852
859
844
819
45.1
49.9
55.0
60.0
70.1
80.1
88.5
92.6
99.5
775
719
659
597
442
239
80.0
70.6
48.8
mS/cm
31
61
91
122
152
180
204
% H3PO4
40
45
50
55
60
70
80
mS/cm
222
232
233
224
210
169
98
mS/cm
177
308
426
586
717
798
825
819
781
714
640
% H2SO4 (SO3)
53.5
58.4
63.1
72.3
85.9
95.4
98.0
100.0
101.5
103.8
105.1
mS/cm
555
471
380
223
124
124
94.7
10.46
32.05
34.50
28.84
41
mS/cm
% NaOH
mS/cm
225
197
10
360
10
353
15
407
15
478
20
395
20
567
25
342
25
618
30
266
30
624
35
209
35
595
40
169
40
525
mS/cm
% NH3
mS/cm
1.04
0.821
15.2
0.810
3.73
1.176
18.6
0.625
5.26
1.275
23.2
0.419
7.46
1.236
27.3
0.286
9.52
1.142
31.0
0.197
11.5
1.035
mS/cm
% LiCl in ethanol
mS/cm
2.5
45.4
2.5
3.648
5.0
82.6
5.0
4.565
7.5
112.5
7.5
6.565
10.0
135.6
10.0
4.035
12.5
142.6
12.5
3.139
15.0
148.6
15.0
2.541
42
mS/cm
% NaCl
mS/cm
68.9
70.3
10
134.0
10
118.8
15
197.8
15
164.2
20
250.2
20
196.8
25
299.6
25
220.2
mS/cm
g/L NaNO3
mS/cm
1.01
1.236
0.85
1.025
2.02
2.405
1.70
2.00
5.05
5.745
4.25
4.775
10.1
10.94
8.50
9.11
20.2
20.62
17.0
17.19
50.5
46.6
42.5
38.7
mS/cm
g/L MgCl2
mS/cm
0.555
1.085
0.476
1.030
1.11
2.088
0.952
1.982
2.77
4.90
2.38
4.64
5.55
9.26
4.76
8.76
11.1
17.39
9.52
16.38
27.7
39.35
23.8
36.55
43
mS/cm
g/L Na2SO4
mS/cm
0.602
0.798
0.71
1.015
1.204
1.42
1.42
1.925
3.010
2.98
3.55
4.39
6.020
5.20
7.10
8.22
12.04
12.04
14.2
14.97
35.5
31.3
mS/cm
g/L Na2CO3
mS/cm
0.535
1.275
0.53
1.010
1.07
2.50
1.06
1.883
2.675
6.02
2.65
4.220
5.35
11.57
5.30
7.670
10.7
22.25
10.6
13.81
26.75
52.9
26.5
28.70
in mS/cm
c(H3PO4) in mol/L
in mS/cm
65
0.05
7.5
10
113
0.10
10.2
15
148
0.50
32
20
175
1.00
57
25
191
2.00
110
3.00
165
4.00
190
5.00
210
44
S/cm at 20 C
S/cm at 25 C
0.0005
67
74
0.001
133
147
0.005
654
720
0.010
1280
1410
0.020
2510
2770
0.050
6060
6700
0.100
11670
12900
0.200
22440
24800
mS/cm
0.1 mol/L
TK () in % per C
0.1 mol/L
mS/cm
0.01 mol/L
TK () in % per C
0.01 mol/L
18
11.19
2.06
1.225
2.07
19
11.34
2.06
1.251
2.11
20
11.67
----
1.278
----
21
11.91
2.06
1.305
2.11
22
12.15
2.06
1.332
2.11
23
12.39
2.06
1.359
2.11
24
12.64
2.07
1.386
2.11
25
12.88
2.07
1.413
2.11
TK () in % per C
05...10
2.62
10...15
2.41
15...20
2.23
20...25
2.08
25...30
1.94
30...35
1.79
45
TC at 5%
TC at 10%
TC at 15%
TC at 20%
TC at 25%
NH4Cl
1.98
1.86
1.71
1.61
1.54
NH4NO3
2.03
1.94
----
1.79
----
(NH4)2SO4
2.15
2.03
----
1.93
----
BaCl2
2.14
2.06
2.00
1.95
----
CaCl2
2.13
2.06
2.02
2.00
2.04
Ca(NO3)2
2.18
2.17
----
----
2.18
KBr
2.06
1.94
----
1.77
----
KCl
2.01
1.88
1.68
1.66
----
KNO3
2.08
2.05
2.02
1.97
----
K2SO4
2.16
2.03
----
----
----
LiCl
2.23
2.18
----
2.20
----
MgCl2
2.22
2.20
----
2.37
----
MgSO4
2.26
2.41
2.52
2.69
2.88
Na acetate
2.51
2.59
----
2.93
----
Na2CO3
2.52
2.71
2.94
----
----
NaCl
2.17
2.14
2.12
2.16
2.27
NaNO3
2.21
2.17
----
2.15
----
Na2SO4
2.36
2.49
2.56
----
----
AgNO3
2.18
2.17
----
2.12
----
ZnSO4
2.25
2.23
2.28
2.41
2.58
TC () in % per C, at 18 C
46
S/cm
Temp. C
S/cm
0.6
55
2.1
0.8
60
2.2
10
0.9
65
2.4
15
1.0
70
2.5
20
1.1
75
2.7
25
1.3
80
2.7
30
1.4
85
2.7
35
1.5
90
2.7
40
1.7
95
2.9
45
1.8
100
3.1
50
1.9
2.73%
20...40 C
3.24%
40...60 C
3.86%
60...80 C
4.07%
80...100 C
4.35%
Dependency of the electrical conductivity of dist. H2O and KCl solutions on the
measuring frequency (at 25 C and c = approx. 1 cm1)
(own measurements)
Solution
300 Hz
2.4 kHz
dist. H2O
1.12 S/cm
1.59 S/cm
147 S/cm
151 S/cm
1.35 mS/cm
1.41 mS/cm
11.03 mS/cm
12.90 mS/cm
KCl, c = 1 mol/L
45.37 mS/cm
96.18 mS/cm
47
48