Monograph: Conductometry - Conductivity Measurement

Monograph
Conductometry – Conductivity Measurement

Peter Bruttel
Conductometry –
Conductivity Measurement
Peter A. Bruttel
All rights reserved, including those of translation.

Printed by Metrohm Ltd., CH-9101 Herisau, Switzerland
8.028.5003 – 2004-11
Conductometry – Conductivity Measurement 1

2 Metrohm Monograph 8.028.5003
Table of Contents
4 Foreword
4 Terms / definitions
21 Measuring instruments
22 Conductivity measuring cells
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 µS/cm of the 5% sugar solution
% ash = K5 – (0.9 x KW) x 0.0018
Calibrated Reference (767)

With the 2.767.0010 Calibrated Reference, Metrohm can provide users of conductivity
meters with a handy solar-cell-powered device for checking their instruments. The built-in
resistors are certified. This means that it is possible to check the conductometer displays
for electrical conductivity as well as the temperature (Pt 100 or Pt 1000 temperature
sensor) and validate the instruments in this way.
The same instrument is also suitable for checking pH/
mV meters, potentiometric and Karl Fischer titrators.
See also the Calibration section.
Calibration
See the Calibration section.
Calibration solutions
These solutions are used for calibrating conductivity cells, i.e. for determining the cell
constant. See also the Calibration section.
Calibration solutions are solutions whose electrical conductivity γ is known exactly. It is
best to use so-called secondary standards. These are certified and can be directly traced
to standard reference materials (e.g. National Institute of Standards and Technology
– NIST, USA – www.nist.gov).
Of course, you can also make up your own calibration solutions by dissolving the
corresponding salts in ultrapure water or by diluting concentrated solutions (e.g. c(KCl) =
0.1000 mol/L – Metrohm no. 6.2301.060). However, for electrical conductivities <100 µS/cm
we recommend that you purchase these standards (they are extremely difficult to prepare
by ordinary means). Sources are, for example:
– Hamilton (5 µS/cm...100 µS/cm, accuracy ±1%)
– Reagecon, Shannon (Ireland) – www.reagecon.com – (1 µS/cm…100 µS/cm).
The following table shows the electrical conductivity of KCl solutions at two different
temperatures:
c(KCl) 20 °C 25 °C
0.001 mol/L 133 µS/cm 147 µS/cm
0.010 mol/L 1.28 mS/cm 1.41 mS/cm
0.100 mol/L 11.67 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.

The relationship to the electrical conductivity γ, the real subject of interest, is provided by
the cell constant c, which depends on the geometrical dimensions of the measuring cell:
γ = 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] = cm–1
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– z+ = +1; z– = –1
CaCl2 → Ca 2+
+ 2 Cl –
z+ = +2; z– = –1
K3PO4 → 3 K+ + PO43– z+ = +1; z– = –3
Conductance
The conductance G is the reciprocal of the electrical resistance (1/R) and has the unit
Siemens (S) = Ω–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 µS/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.

As at each point in the titration, all
the ions present contribute to the
conductivity, typical V-shaped titration
curves are obtained.
Example: Titration of HCl with NaOH

H+ + Cl– + Na+ + OH– =
H2O + Cl– + Na+
Thin lines
contributions of the individual ions to the
conductivity
Bold lines
total conductivity (produces titration curve)
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 be-
tween the free ions and the total molecules present in the solution and is given either rela-
tively 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 conduc-
tivity.
• 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 con-
tains can ionize. Water is an ideal solvent for ionic compounds. In alcohols ionization
decreases as the chain length increases (methanol > ethanol > propanol). In non-
polar organic solvents (e.g. chlorinated and non-chlorinated hydrocarbons) practi-
cally no ionization occurs.
– The temperature: In contrast to solids, in solutions the electrical conductivity increas-
es 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 Fick’s 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 γ is equal to the reciprocal of the electrical resistance (conduc-
tance G) multiplied by the cell constant c:
γ = conductivity unit: S cm–1 (S m–1)
R = resistance unit: Ω
G = 1/R conductance unit: S (Siemens) = Ω–1
l = length of measuring path unit: cm (m)
A = cross sectional area unit: cm2 (m2)
c = l/A cell constant unit: cm–1 (m–1)

The electrical conductivity is normally given in µS/cm or mS/cm (12.88 mS/cm = 1288
mS/m; 5 µS/cm = 500 µS/m). In American usage the terms mhos and µhos 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 Coehn’s 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. 223–228
Equivalent conductivity
The equivalent conductivity Λ* is a quantity that is primarily used in theoretical studies. It
can be obtained from the molar conductivity Λ and the electrochemical valency ne:
Λ* = Λ / ne
The electrochemical valency ne can be calculated for a molecule that dissociates into
ν– anions and ν+ cations with the corresponding valencies z– und z+ as follows:
ne = ν– x z– = ν+ x z+
Examples:
NaCl → Na+ + Cl– ν+ = ν– ne = 1
AlCl3 → Al 3+
+ 3 Cl –
ν+ = 1 and z+ = 3 ne = 3
Four-electrode measuring technique

In particular when materials other than platinized platinum (e.g. steel) are used for
electrodes, interference occurs and incorrect measured values are obtained because of
polarization.
The four-electrode measuring technique was introduced to prevent this. It is somewhere in
the middle between the classical two-electrode method and contact-free methods.
It uses two current and two voltage electrodes. The resistance RX between the two voltage
electrodes, which is proportional to the conductance G, and the voltage drop resulting
from RX are measured (high-impedance), amplified and compared against a reference
voltage Uref in a controller. If there is a difference between the two voltages then this is

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

refers to 25 °C and an infinite dilution (measurement series extrapolated to ci = 0). Some
examples:
Cation I+ Anion I–
(cm2 / Ω) (cm2 / Ω)
H+ 350 OH– 199
Li +
39 Cl– 76
Na +
50 NO 3
–
71
K+ 74 CH3COO– 41
1⁄2 Mg2+ 53 1⁄2 SO42– 80
1⁄2 Ca 2+
60 1⁄2 CO 3
2–
69
Ionic product of water

Water undergoes a self-dissociation known as autoprotolysis:
2 H2O → H3O+ + OH–
As a result of this self-dissociation, pure water has an electrical conductivity of 0.055
µS/cm at 25 °C or 0.039 µS/cm at 20 °C. Please note the high temperature coefficient of
5.8% per °C!
Ionic strength
The ionic strength is a measure of the interionic interaction occurring in the solution of an
electrolyte. It is determined solely by the concentration ci and charge zi of the ions, and not
by their characteristic features. The following applies for the ionic strength:
J = (1/2) Σci x zi2
The calculation of the ionic strength J of a known molar concentration ci of a particular
electrolyte is simplified by the fact that there is a multiplication factor for each type of
electrolyte. It is calculated for 1-molar solutions and can then be used generally:
Type of salt Example Factor

1,1 KCl 1
1,2 K2SO4 3
2,2 MgSO4 4
1,3 K3PO4 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).

In dilute solutions anions and cations migrate independently without any interactions in
an electric field.
Kohlrausch cells
See section on Measuring cells/conductivity cells.
Kohlrausch’s square-root law

This law for strong electrolytes links the molar conductivity ΛC with the square root of the
concentration c according to:
ΛC = Λ0 – 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
Λ0 is the limiting equivalent conductivity or limiting conductivity for short. Λ0 is the sum of
the limiting conductivities of the cations (λ0+) and anions (λ0–) (law of independent ionic
migration).
For Λ see the definition under equivalent conductivity.
Limiting conductivities of some ions in water at 25 °C
Cations Limiting Anions Limiting

conductivity conductivity
(S x cm2 x mol–1) (S x cm2 x mol–1)
H3O+ 349.8 OH– 197.0
NH4+ 73.7 SO42– 80.8
K +
73.5 Br –
78.4
Ba2+ 63.2 I– 76.5
Ag +
62.2 Cl –
76.4
Ca2+ 59.8 NO3– 71.5
Mg2+ 53.1 ClO4– 68.0
Na +
50.1 F –
55.4
Li+ 38.6 CH3COO– 40.9
Mass fraction
w(X) mass fraction of the substance X in %, e.g. w(NaOH) = 25%
Mass concentration
ρ(X) mass concentration of the substance X in g/L, e.g. ρ(NaCl) = 2.5 g/L
Measuring cell See section on Measuring cells/conductivity cells.
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

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 frequen-
cy of 300 Hz.
– At high conductances measurements are made at a frequency of 2.4 kHz (712 Conduc-
tometer).
Measuring range
The usable measuring range depends on the type of conductivity cell (platinized/non-
platinized), 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 cm–1 0.1 µS/cm...20 µS/cm
1 cm–1 1 µS/cm...10 mS/cm
10 cm–1 10 µS/cm...100 mS/cm
100 cm–1 100 µS/cm...10 S/cm
Solution Measuring cell Cell constant Measuring

frequency
<20 µS/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 (Coulomb’s law). On the other hand,
the friction Ri depends on the ionic radius ri and the viscosity η 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 6π x η 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

Typical values for ui are about 10–4 cm/s.
If ui is multiplied by the Faraday constant F we obtain the ionic mobility Ii.
The sum of the ionic mobilities of the anions and cations of an electrolyte produces the
molar conductivity Λ.
Molar conductivity
The molar conductivity Λ is defined as the quotient of the specific conductivity γ and the
concentration c (mol/L) of the dissolved substance:
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.
Ostwald’s dilution law

This law applies for strong electrolytes and links the molar conductivity ΛC with the square
root of the concentration c as follows:
ΛC = Λ0 – 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 Kohlrausch’s 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

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–

Alcohols also belong to the protic solvents,
e.g. 2 CH3OH CH3OH2+ + CH3O–

Examples of acidic polar solvents are:
formic acid, glacial acetic acid, cresols, phenol
Examples of basic polar solvents are:

ethylenediamine, benzylamine, butylamine
Examples of neutral polar solvents are:

methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether
Specific conductivity
Earlier term for the electrical conductivity γ (EN and ISO standard). It was known as κ and
had the same units, i.e. S/cm (from conductance G x cell constant c).
Specific resistance
The specific resistance ρ is the reciprocal of the specific conductivity κ – electrical
conductivity γ – with the unit Ω x cm.
In earlier days it was usual in water purification plants to give the water quality in these
units. 1 µS/cm corresponds to a specific resistance of 1 MΩ x cm.
Temperature coefficient
25 and °C are temperatures at which the electrical conductivities have been measured.
The temperature coefficient can be given as reciprocal Kelvin or % per °C.
The temperature coefficient depends primarily on the ions contained in the solution and
shows seldom a linear behavior. We recommend that it is determined automatically by the
712 Conductometer.
Temperature compensation
See under the term Reference temperature.
Temperature dependency
The temperature dependency of the electrical conductivity can be explained by
observations concerning the migration speed of the ions in an electric field. See also
Walden’s rule. This can be used to explain at least the positive temperature coefficient.
However, the quantitative relationships are complicated and calculations are therefore
practically impossible.
Even with uniform substances (e.g. KCl solutions) the temperature coefficient changes
with the concentration. In mixtures all the ions contribute to a new, mixed temperature
coefficient.
If high accuracy is required the temperature coefficient must therefore be determined
experimentally.
See also under the terms Reference temperature, Temperature coefficient and Temperature
compensation.
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+ = λ+/Λ = u+ / (u+ + u–)
n– = λ–/Λ = 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 η 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, η is a material constant with the SI unit Pascal per second (Pa s–1).
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 Walden’s rule.
Walden’s rule
In its general form this rule states that the product of the ionic mobility Ii of an ion and the
viscosity η of a solvent is constant:
Ii x η = 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 H3O+ + OH–

This self-dissociation depends very strongly on the temperature. Examples are shown in
the following table:
°C µS/cm
0 0.010
18 0.038
25 0.060
34 0.090
50 0.170
The very large temperature coefficient is conspicuous. Between 18 °C and 25 °C it is 8.3%

per °C!

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 Reference temperature

– Electrical conductivity For automatic temperature compensation.
– Standard (calibration solutions) Freely selectable, 20 °C or 25 °C are normal.
– TDS (Total Dissolved Solids), expressed
Cell constant
as mg/L NaCl or g/L NaCl – salinity
– Titration (conductivity titration) Automatic via determination – dialog-guided
– Temperature (of solution) with automatic calculation, or manual input.
Range 0.001...500/cm.
Sensor connections
Platinization
One input each for conductivity measuring
cell and temperature sensor (Pt 100 or Pt DC output for platinizing conductivity cells.
1000) I = 20 mA.
Measuring ranges Interface RS 232

– Electrical conductivity (automatic range For connection to printer or PC.
switching): «Remote» I/O lines
0...2000 µS/cm and 0...20’000 mS/cm.
Resolution: max. 41⁄2 digits are shown. For connecting a sample changer or labora-
– Temperature: –170.0...500.0 °C. tory robot or for triggering any type of alarm.
Resolution: 0.1 °C. Analog output for electrical conductivity
Compensation ranges, e.g. for titrations, back- Connection of a lab recorder or titrator. Out-
ground suppression put signal 0...2000 mV with a resolution of 0.5
– Electrical conductivity: 0...2000 µS/cm and mV (12 bit).
0...2000 mS/cm (0...2 S/cm) Analog output for temperature
– Temperature: –170.0…500.0 °C
E.g. for connection of a lab recorder. Output
Measuring frequencies signal 0...2000 mV with a resolution of 0.5 mV
300 Hz or 2.4 kHz; automatic switching to the (12 bit).
most suitable frequency or manual setting. Instrument diagnosis
Temperature coefficient The instruments carries out a self-diagnosis
Automatic determination with connected when switched on. The built-in diagnosis pro-
temperature sensor; TC = f(T) is calculated gram allows the user to localize or exclude in-
as a polynomial. Can also be entered manu- strument faults.
ally. Range 0.00...9.99% per °C.

Conductivity measuring cells
These measuring cells, which are also known as Kohlrausch cells, normally have two
platinized platinum electrodes. By selecting the area of and the distance between the two
electrodes it is possible to vary the cell constant of such electrodes throughout a wide
range. Platinizing the electrodes greatly reduces the risk of obtaining incorrect measured
values because of polarization. This also has a favorable effect on the usable measuring
range. This means that a conductivity cell with a cell constant of c = 1 cm–1 can be used at
a measuring frequency of 1 kHz from 10 µS/cm to 100 mS/cm. Smooth, i.e. non-platinized
measuring cells should only be used for low electrical conductivities (<20 µS/cm).
However, platinization also has its disadvantages. Platinized measuring cells are
susceptible to encrustation, inclusion and also growth of algae, bacteria or mold. They
also dry out during long storage or the platinization slowly breaks down. As a result of
these effects the cell constant changes and has to be redetermined from time to time (and,
of course, after every replatinization process).
Some suggestions for treating and preparing the conductivity cells:
– Place measuring cells that have been stored dry in acetone for approx. 30 min. Then
thoroughly rinse with dist. H2O and place in dist. H2O for 2...3 h.
– Frequently used measuring cells should be stored in dist. H2O.
– Less frequently used measuring cells should be stored in 70% ethanol or stored dry
(prevents biological growth).
– Always thoroughly rinse the measuring cell with dist. H2O after use.
Examples of measuring cells
Flow-through measuring vessel:

The illustration shows the
6.1420.100 flow-through meas-
uring vessel. Together with
Measuring cell with built-in Immersion measuring cell the 6.0912.110 conductivity
Pt 1000 temperature sensor in (c = 0.1...20 cm–1) cell (screwed into the lid) a
PP shaft flow-through measuring cell is
obtained

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
A) Checking the instrument (using the 712 Conductometer as an example)

Required accessories:
– 2.767.0010 Calibrated Reference
– 2 x 6.2106.020 cable (2 x plug B)
– 1 x 6.2104.080 electrode cable (with plug B)
Parameter settings at the Conductometer (712) for the two following tests:
> cond/parameters
cell constant 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
The following equation applies:
γ=Gxc
γ = electrical conductivity (µS cm–1)
G = conductance (µS)
c = cell constant (cm–1)
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.

Examples of measured value
Socket(s) Actual value Theoretical value Difference Error tolerance

µS/cm µS/cm µS/cm (±0.5%)
µS/cm
5 70.07 70.01 0.06 ±0.35
6 2.168 2.17 –0.002 ±0.011
1&2 10010 10008 2 ±50
2&3 999.2 999 0.2 ±5
Evaluation: The checked instrument is OK.
In order to check the temperature display, the two 6.2106.020 cables are used to connect
both red input sockets of the des 712 with sockets 1 and 2 (Pt 100) or 2 and 3 (Pt 1000)
of the 767.
Examples of measured value
Socket(s) Actual value Theoretical value Difference Error tolerance

°C °C °C °C
1&2 –0.2 –0.20 00 ±0.1
2&3 00.1 00.17 –0.07 ±0.1
Evaluation: The checked instrument is OK.
B) Checking the conductivity cell with calibration solution

It is assumed that the conductivity cell is in a well-conditioned state.
The measuring vessel is thoroughly rinsed, first with ultrapure water and then with the
calibration solution. It is then filled with the calibration standard and thermostatted at
25 °C.
The measuring cell is first immersed several times in the calibration solution and then
positioned so that the upper openings at the sides are completely immersed in the liquid.
Any air bubbles that are present inside the measuring cell can be removed by swirling and
tapping.
The Conductometer is switched on and the corresponding value for the cell constant
(printed on the measuring cell) is entered in the 712. The measuring and reference
temperatures are also entered in the 712.
712 parameters:
> cond/parameters
cell constant value printed on electrode (e.g. 0.78 / cm)
meas. temp. 25.0 °C
ref. temp. 25.0 °C
frequency: auto
meas. type: standard

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 γ = 12.90 mS/cm
Displayed conductance G = 16.13 mS
New cell constant c = 12.90 mS/cm / 16.13 mS = 0.80 cm–1

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 µS/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.
– 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.
– at 20 °C: 133 µS/cm
– at 25 °C: 147 µS/cm
Certified conductivity standards with a wide range (1 µS/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

Example of a determination at 20 °C, 712 Conductometer
Instruments and accessories:
– 2.712.0010 Conductometer, 2.728.002X Magnetic Stirrer
– Conductivity cell, e.g. 6.0907.110
– Printer and printer cable, thermostat, nitrogen from gas cylinder
– 6.1414.010 titration vessel lid, 6.1418.250 titration vessel with thermostat jacket and
6.1440.010 gas inlet and overflow tube
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 1.0 / cm
Measuring temperature 20.0 °C
Reference temperature 20.0 °C
Frequency auto
Meas. type: Standard
Range limit: off
Standard 1.278 mS/cm
The automatic determination is now started at the 712.
If no thermostat is available then the following procedure can be used:
The measuring cell and the solutions are prepared in exactly the same way. The use of
nitrogen in the closed measuring cell and titration vessel is also identical. However, instead
of a thermostat a Pt 1000 or Pt 100 temperature sensor (6.1110.100 and 6.1103.000
respectively) is connected. All the 712 Conductometer settings remain the same with the
exception of the temperature coefficient, which is entered as 2.11% / °C.
Calculation:
New cell constant = theoretical conductivity / measured conductance
Example:
Theoretical conductivity = 1.28 mS/cm (0.010 mol/L KCl, 20 °C)
Measured conductance = 1.533 mS
1.28 mS/cm / 1.533 mS = c = 0.835 cm–1
Example with 6.0907.110 conductivity cell:

c = 0.8195 ±0.007 cm–1 (n = 10)

2. Determination of the temperature coefficient α of c(Na2SO4) = 0.05 mol/L
As explained in the theoretical section, the conductivity of ionic solutions is extremely
temperature-dependent and this dependency is rarely linear. This is why we recommend that
the TC in the temperature range of interest is recorded automatically at the Conductometer.

– 2.712.0010 Conductometer and 2.728.002X Magnetic Stirrer
– e.g. 6.0912.110 conductivity cell with built-in temperature sensor (Pt 1000)
– Printer and printer cable, thermostat
– 6.1414.010 titration vessel lid, 6.1418.250 titration vessel with thermostat jacket
Reagents:
– c(Na2SO4) = 0.05 mol/L. 7.10 g Na2SO4 or 16.11 g Na2SO4 x 10 H2O is dissolved in con-
ductivity water and made up to 1000 mL.
– Conductivity water
Procedure
The conditioned measuring cell is rinsed with conductivity water and then with Na2SO4
solution. Sufficient Na2SO4 solution is filled into the measuring vessel and the measuring
cell inserted and made bubble-free.
The following settings are made on the 712 Conductometer (see also parameter report):
Start temperature 40.0 °C
Stop temperature 15.0 °C
Reference temperature 20.0 °C
Frequency auto
Temperature coefficient 0.00%
Cell constant 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 cm–1 for poorly conducting solutions such as fully or partially deionized wa-
ter
c ≈ 1 cm–1 for moderately conducting solutions such as drinking water, surface
water, ground water and wastewater
c ≈ 10 cm–1 for solutions with good conductivity such as seawater, rinsing water,
physiological solutions, etc.

c ≈ 100 cm–1 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 microor-
ganisms). 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 wa-
ter. 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 measur-
ing frequency and high conductivity at a high one.
– Temperature coefficient: If known then set on instrument, otherwise determine it. A fur-
ther 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. Other-
wise 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 stipu-
lated or preferred (water samples or, e.g., measurements in tropical countries). Any ref-
erence 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.

4. Conductivity measurements in water
A) Wastewater, ground, mineral, surface and drinking water
The reference temperature is normally 25.0 °C. In order to avoid errors by incorrectly
selecting the temperature coefficient (TC) it is either recommended or stipulated that the
sample solution is thermostatted at 25.0 °C. If this is not required then a TC can be entered
as given in the table below, or TC Ident: «DIN» can be selected. The latter setting is suitable
for water that contains mainly calcium and bicarbonate ions as well as small amounts of
magnesium, sulfate, chloride and nitrate ions.
Sample temperature 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 γ = 512.5 ±8.3 µS/cm (n= 10)
Mineral water, 25 °C γ = 1.813 ±0.013 mS/cm (n= 10)
B) Deionized water
Because of possible interferences, a special procedure must be selected for water with a
conductivity of <5 µS/cm. This applies to water with a conductivity <1 µS/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 al-
lowed 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 pos-
sible, use a closed or covered setup.
Please note the high TC (approx. 5.8% / °C) of such water samples!!

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 TDS = 245.6 ±4.2 mg/L NaCl (n = 10)
Mineral water, 25 °C TDS = 894.8 ±6.7 mg/L NaCl (n = 10)
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.

– 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:

712 Conductometer 799 Titrino
>cond/parameters MET U Cond. titr.
cell constant 1.0/cm >titration parameters
meas. temp. 20.0 °C V step 0.10 mL
ref. temp. 20.0 °C dos. rate max. mL/min
TC selection: const. signal drift 50 mV/min
TC const. 0.0% / °C equilibr. time 26 s
frequency: auto start V: off
meas. type: Titration pause 0s
limits: off >stop conditions
>cond/analog output stop V: abs.
status: on stop V 4.0 mL
polarity + filling rate max. mL/min
1 V range: 1 mS/cm >evaluation
0 V at: 0 µS/cm EP criterion 30 mV
offset: 0 mV EP recognition all
>cond/limits
status: off
>cond/plot margins
left: 0 µS/cm
right: 1000 µS/cm
Example of a titration (VESUV 3.0):
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.

7. Conductivity measurements in deionized water according to USP guidelines
Summary
The electrical conductivity of ultrapure water is measured according to USP Method
645 (US Pharmacopeia; USP 23, Vol. 5) in a flow-through cell with a cell constant of c =
0.1 cm–1.
Sample
Ultrapure water from a «Barnstead Nanopure» unit, Application Lab, Herisau.
Reagents
Hamilton conductivity standard. 5 µS/cm ±5%; WO 1197985, P/N 238926
Instruments and accessories

712 Conductometer 2.712.0010
Conductivity cell PP, c = 0.091 cm–1
Conductivity cell glass, c = 0.082 cm–1
Flow-through cell 6.1420.100
767 Calibrated Reference 2.767.0010
728 Magnetic Stirrer 2.728.0010
Titration vessel 6.1418.250
Titration vessel lid 6.1414.010
683 Pump 2.683.0010
Thermostat bath
Cable 712 – PC (RS 232) 6.2125.060
Cable 712 – PC (RS 232) 6.2125.010
Metrodata VESUV 3.0 6.6008.140
The schematic shows the connections.

Fig. 2 Parameter settings at the 712
712 Conductometer OP1/106 712.0015
date 2001-03-07 time 15:28:11
conductivity
>cond/parameters
cell constant 0.091 / cm
meas.temp. 25.0 °C
ref.temp. 25.0 °C
TC const. 0.0 %/°C
frequency: auto
meas.type: standard
range limit: OFF
> cond/analog output
status: OFF
> cond/limits
status: OFF
> cond/plot margins
left: 0 µS / cm
right: 0 µS / cm
----------------------------------------
config
> config / print
id. 1
id. 2
print header: always
date & time ON
send to: IBM
> config / print meas. values
print crit.: time
time interval 300.0 s
stop time 12000 s
date & time ON
> config / report type
orig. cal. Report: OFF
cal. Report format: short
> config / Pt sensor
Pt id
Pt correction 0.0 °C

> config / auxiliaries
run number
date 2002-03-07
time 15:28:15
dialog: english
device label
program 712.0015
> config / RS 232 settings
baud rate: 9600
data bit: 8
stop bit: 1
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 ID-No (if available): ...................

Test agent: 2.767.0010 Serial/Fabr.-No: 01102 ID-No (if available): ...................
Cal. date: 12/2001 checked by: S. Jung ..........................................
Calibrator (master) Type .......................................................
SCS Cal. Serv. Reg. No. Certificate No 8.767.3003 ......................
Check carried out on: 2002.02.25 Name: Christian Haider Signature:..........................................................
Checked instrument meets Yes no Decision:

requirements: x
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.

Prepare the 712 Conductometer:
Remove all cables except the mains cable. Switch on instrument.
<cond param>, LCD display: conductivity
>cond/parameters
<enter>:
Note down the following parameters (see LCD display) in list below and then enter the following standard
values:
cell constant ............... /cm → 1.0 /cm <enter>
meas. temp. ............... °C → 20°C <enter>
ref. temp. ............... °C → 20°C <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>
<quit>, <quit>, LCD display: 20.0 °C

1.000 /cm 1.00%/°C
Conductivity
Carry out on 712 or on sensor Remarks Carry out on Enter theo- Enter actual Difference2 Permitted OK
767 retical value value from Difference
from 767 cover 712 display1 ü
1. Screw off cable at the plug-in head Close cover
of the sensor (if no sensor or sensor Sensor cable
without plug-in head is connected: to socket (6)
use 6.2150.020 cable from
accessories in 767 case, insert into
‘Cond. Cell’ socket)
2. Main display: µS/cm (Cover µS value 6: ü
LCD display: conductivity remains 2.167µS 2.169 µS –0.2 µS ±0.04 µS
closed)
3. Sensor cable µS value 5: ü
to socket (5) 69.86 µS 69.881 µS –0.0281 µS ±0.77 µS
4. Remove sensor cable from Cond Cell Sensor cable µS value 2)/(3): ü
input and use 2x 6.2150.000 instead to sockets
(2) and (3) 999.80 µS 999.842 µS –0.042 µS ±11 µS
(Pt 1000)
5. Sensor cable µS value 1)/(2): ü
to sockets
(2) and (1) 9990.1µS 9995.202 µS –2.202 µS ±70 µS
(Pt 100)
6. <auto zero> Display 0 ü
→
7. <az off> Display ü
as before
→

Temperature (Pt 100 / Pt 1000)
Carry out on 712 or on Remarks Carry out on 767 Enter theo- Enter actual Difference2 Permitted OK
sensor retical value alue from difference
ü
from 767 712 display
cover
1. Remove banana cables Leave banana cables
from the sockets ‘Cond Cell’ at the sockets (1)
and connect them to the - (2) (Cover does
temperature measuring input not matter whether
of 712. open or closed)
2. Measuring (mode) °C on the main
display
there
appears:
X.X °C
3. Insert banana cables to On 767.0010: °C value:
the sockets of 2.767.0010
Sockets (1) and (2) (Pt 100) → 0.1 °C 0.2 °C 0.1 °C ±0.4 °C ü
according to the table at the
right and always depress Sockets (2) and (3) (Pt 1000) → 0.0 °C 0.0 °C 0.0 °C ±0.4 °C ü
<mode>.
Sockets (1) and (3) (Pt 1000) → 25.7 °C 25.8 °C 0.1 °C ±0.4 °C ü
Temp. value sockets
(1) and (3) see certificate
Remove cable and re-enter the parameters noted above.
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
Wait until display remains stable
2
The given permitted difference applies for normal room temperatures (20…30 °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 µS/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 –1
0.091 cm–1
γ, limit at 25 °C <1.3 µS / cm <0.08 µS / cm
Temperature measurement ±1 °C ±0.1 °C

Conductivity cell glass
Subject Requirement Achieved

Conductometer validation yes yes
Cell constant ±2% ±0%
c displayed: 0.082 cm–1 0.082 cm–1
γ, limit at 25 °C <1.3 µS / cm <0.08 µS / cm
Temperature measurement ±1 °C ±0.1 °C
Measuring with the flow-through cell

The measuring system is first rinsed with 500 mL «sample». Further sample is pumped
through the closed system, the electrical conductivity is measured and transmitted to
VESUV 3.0 by pressing the «PRINT» key at the 712 Conductometer after the pumping
process has been started.
Calculations
cnew [cm–1] = γtheor. [µS/cm] / G [µS]
c = cell constant
γ = electrical conductivity
G = conductance
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 µS /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 γ >2.1
µS/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%).

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 trans-
port 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 µS / cm Temp. °C µS / cm
0 0.6 55 2.1
5 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.

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
– Öhme, F., Bänninger, 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; physi-
cal and physicochemical parameters. Determination of the electrical conductivity

Tables
Electrical conductivity of organic acids at 25 °C
% formic acid mS/cm % acetic acid mS/cm

5 6.22 5 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
M(HCOOH) = 46.026 g/mol

M(CH3COOH) = 60.052 g/mol
Electrical conductivity of hydrogen bromide and hydrogen chloride at 25 °C
% HBr 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
M(HBr) = 80.912 g/mol

M(HCl) = 36.461 g/mol

Electrical conductivity of nitric acid at 25 °C
% HNO3 mS/cm % HNO3 mS/cm
3.06 176 45.1 775
4.89 270 49.9 719
8.99 454 55.0 659
14.0 631 60.0 597
18.1 741 70.1 442
24.0 830 80.1 239
28.0 852 88.5 80.0
33.1 859 92.6 70.6
36.3 844 99.5 48.8
40.0 819
M(HNO3) = 63.013 g/mol
Electrical conductivity of phosphoric acid at 25 °C

% H3PO4 mS/cm % H3PO4 mS/cm
5 31 40 222
10 61 45 232
15 91 50 233
20 122 55 224
25 152 60 210
30 180 70 169
35 204 80 98
M(H3PO4) = 97.995 g/mol
Electrical conductivity of sulfuric acid (and oleum) at 25 °C

% H2SO4 mS/cm % H2SO4 (SO3) mS/cm
3.93 177 53.5 555
7.00 308 58.4 471
10.0 426 63.1 380
14.6 586 72.3 223
19.8 717 85.9 124
25.3 798 95.4 124
29.4 825 98.0 94.7
34.3 819 100.0 10.46
39.1 781 101.5 32.05
43.9 714 103.8 34.50
48.7 640 105.1 28.84
M(H2SO4) = 98.07 g/mol
M(SO3) = 80.06 g/mol

Electrical conductivity of potassium and sodium hydroxide at 25 °C
% KOH mS/cm % NaOH mS/cm

5 225 5 197
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
M(KOH) = 56.106 g/mol
M(NaOH) = 39.997 g/mol
Electrical conductivity of ammonia solutions at 25 °C
% NH3 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
M(NH3) = 17.030 g/mol
Electrical conductivity of lithium chloride at 25 °C
% LiCl in H2O 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
M(LiCl) = 42.394 g/mol

Electrical conductivity of potassium and sodium chloride at 25 °C
(own measurements)
% KCl mS/cm % NaCl mS/cm

5 68.9 5 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
M(KCl) = 74.551 g/mol
M(NaCl) = 58.443 g/mol
Electrical conductivity of potassium and sodium nitrate at 20 °C
g/L KNO3 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
M(KNO3) = 101.103 g/mol
M(NaNO3) = 84.995 g/mol
Electrical conductivity of calcium and magnesium chloride at 20 °C
g/L CaCl2 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
M(CaCl2) = 110.99 g/mol
M(MgCl2) = 95.211 g/mol

Electrical conductivity of magnesium and sodium sulfate at 20 °C
g/L MgSO4 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
M(MgSO4) = 120.36 g/mol
M(Na2SO4) = 142.04 g/mol
Electrical conductivity of ammonium chloride and sodium carbonate at 20 °C
g/L NH4Cl 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
M(NH4Cl) = 53.491 g/mol
M(Na2CO3) = 105.989 g/mol
Electrical conductivity of NaCl and H3PO4 solutions at 20 °C
% G/V NaCl γ in mS/cm c(H3PO4) in mol/L γ in mS/cm

5 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
M(NaCl) = 58.443 g/mol
M(H3PO4) = 97.995 g/mol

Electrical conductivity of potassium chloride solutions at 20 °C and 25 °C
c(KCl) in mol/L µS/cm at 20 °C µS/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
M(KCl) = 74.551 g/mol
1 mS/cm = 1000 µS/cm
1 µS/cm = 0.001 mS/cm
Electrical conductivity and temperature coefficient (TC) of potassium chloride
solutions at various temperatures
°C mS/cm TK (α) in % per °C mS/cm TK (α) in % per °C

0.1 mol/L 0.1 mol/L 0.01 mol/L 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
M(KCl) = 74.551 g/mol
Electrical conductivity of water – temperature coefficient (TC) as a function of sample
temperature
Sample temperature in °C TK (α) 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
– The reference temperature for water samples is normally 25 °C.
– The above values refer to water samples containing mainly calcium hydrogen carbon-
ate ions and small amounts of magnesium, sulfate, chloride and nitrate ions.

Electrical conductivity of salt solutions –
temperature coefficient (TC) as a function of the salt content
Salt 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 (α) in % per °C, at 18 °C

Requirements of USP 645 for ultrapure water
(without temperature compensation)
Temp. °C µS/cm Temp. °C µS/cm

0 0.6 55 2.1
5 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
TC (% per °C) calculated from the above values:

0...20 °C 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 cm–1)
(own measurements)
Solution 300 Hz 2.4 kHz

dist. H2O 1.12 µS/cm 1.59 µS/cm
KCl, c = 0.001 mol/L 147 µS/cm 151 µS/cm
KCl, c = 0.01 mol/L 1.35 mS/cm 1.41 mS/cm
KCl, c = 0.1 mol/L 11.03 mS/cm 12.90 mS/cm
KCl, c = 1 mol/L 45.37 mS/cm 96.18 mS/cm


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Monograph

Conductometry – Conductivity Measurement

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Conductometry – Conductivity Measurement 1

22 Conductivity measuring cells

Conductometry – Conductivity Measurement 3

4 Metrohm Monograph 8.028.5003

% ash = K5 – (0.9 x KW) x 0.0018

Calibrated Reference (767)

Conductometry – Conductivity Measurement 5

6 Metrohm Monograph 8.028.5003

Example: Titration of HCl with NaOH

Conductometry – Conductivity Measurement 7

Dependency of electrical conductivity

Solvent D (20 °C)

8 Metrohm Monograph 8.028.5003

Conductometry – Conductivity Measurement 9

Four-electrode measuring technique

10 Metrohm Monograph 8.028.5003

Conductometry – Conductivity Measurement 11

Ionic product of water

Type of salt Example Factor

12 Metrohm Monograph 8.028.5003

Kohlrausch’s square-root law

Cations Limiting Anions Limiting

Measuring cell See section on Measuring cells/conductivity cells.

Conductometry – Conductivity Measurement 13

Cell constant Measuring range

Solution Measuring cell Cell constant Measuring

14 Metrohm Monograph 8.028.5003

Ostwald’s dilution law

Conductometry – Conductivity Measurement 15

Examples of acidic non-polar solvents are:

Examples of neutral polar solvents are:

2 H2O H3O+ + OH–

e.g. 2 CH3OH CH3OH2+ + CH3O–

16 Metrohm Monograph 8.028.5003

Examples of basic polar solvents are:

Examples of neutral polar solvents are:

2 H2O H3O+ + OH–

18 Metrohm Monograph 8.028.5003

The very large temperature coefficient is conspicuous. Between 18 °C and 25 °C it is 8.3%

Conductometry – Conductivity Measurement 19

Types of measurement Reference temperature

Measuring ranges Interface RS 232

20 Metrohm Monograph 8.028.5003

Examples of measuring cells

Flow-through measuring vessel:

Conductometry – Conductivity Measurement 21

A) Checking the instrument (using the 712 Conductometer as an example)

22 Metrohm Monograph 8.028.5003

Socket(s) Actual value Theoretical value Difference Error tolerance

Examples of measured value

Socket(s) Actual value Theoretical value Difference Error tolerance

B) Checking the conductivity cell with calibration solution

Conductometry – Conductivity Measurement 23

Example c(KCl) = 0.1000 mol/L, 25 °C