Application Bulletin 102/3 e

Conductometry

Branch
Theoretical part
General analytical chemistry; water, wastewater,
environmental protection; pharmaceutical industry; General
petrochemistry, biofuels; food, stimulants, beverages, The following considerations apply exclusively to solutions
flavors; biochemistry, biology; energy, power plants containing ions.
Conductometry concerns the conductivity of electrolytes.
The resistance of a solution is measured by applying an
Keywords
alternating voltage to the measuring cell (if direct current
Conductometry; five-ring conductivity measuring cell;
were applied, electrolytic processes occurring within the
stainless steel cell; USP 645; IP 400; branch 1; branch 2;
solution could alter the resistance). The conductivity of a
branch 4; branch 5; branch 7; branch 8; branch 16;
solution depends on:
6.0915.100; 6.0915.130; 6.0916.040
 the number of ions. The more ions a solution contains,
the higher its electrical conductivity.
Summary  in general on the ionic mobility, which in turn depends
This bulletin contains two parts. The first part gives a short on:
theoretical overview while more details are offered in the o the type of ion: the smaller an ion, the more
Metrohm Monograph Conductometry. The second, practice- mobile it is and the better it conducts.
oriented part deals with the following subjects: Hydronium, hydroxide, potassium and chloride
 Conductivity measurements in general ions are very good conductors. If hydration
 Determination of the cell constant occurs (the ion surrounds itself by water
molecules that make it larger), then the
 Determination of the temperature coefficient
conductivity is reduced.
 Conductivity measurement in water samples
o the solvent: the more polar a solvent, the
 TDS – Total Dissolved Solids easier it is for ionic compounds to dissociate.
 Conductometric titrations Water is an ideal solvent for ionic compounds.
In alcohols, the relative degree of dissociation
decreases as the chain length increases
(methanol > ethanol > propanol). In nonpolar
organic solvents (e.g. chlorinated and non-
chlorinated hydrocarbons) practically no
dissociation occurs.
o the temperature: in contrast to solids, in
solution the conductivity increases as the
temperature increases by 1…9% per °C,
depending on the ion. (Moderately conducting
solutions such as drinking water: 2%/°C).
o the viscosity: as the viscosity increases, the
ionic mobility and therefore also the electrical
conductivity decrease.

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 Application Bulletin 102/3 e
Conductometry

Measuring the electrical conductivity  Measuring temperature: 30 °C

The electrical conductivity is equal to the reciprocal of the Reference temperature: 20 °C
electrical resistance (conductance G) multiplied by the cell Temperature coefficient: 2.2%/°C
constant c: Conducitivty (at Tref) = 20 °C 90.9 μS/cm
The same procedure is applied for the 12.88 mS/cm
1 standard.
= =

–1 –1
Measuring setup
: conductivity (S cm or S m )
The standard measuring setup consists of a conductometer,
R: resistance (Ω (Ohm))
–1 the conductivity cell with an inbuilt temperature sensor and a
G: conductance (1/R), (S (Siemens) = Ω )
magnetic stirrer. For highest precision, a closed vessel that
l: length of measuring path (cm or m)
2 2 can be thermostatted is recommended.
A: cross sectional area (cm or m )
c:
–1 –1
cell constant (l/A), ( cm or m ) A classical conductivity measuring cell has two platinum
electrodes. By selecting the surface area of and the
distance between the two electrodes it is possible to vary
The electrical conductivity is usually expressed in μS/ m or
the cell constant of such measuring cells within wide limits.
mS/cm (e.g. 12.88 mS/ m = 1288 mS/m; 5 μS/ m =
Uncoated, i.e. non-platinized, conductivity measuring cells
500 μS/m).
should only be used for conductivities < 20 μS/ m. For
The electrical conductivity strongly depends on the higher conductivities platinized conductivity measuring cells
temperature. The value measured at a given temperature is or modern sensors like five-ring conductivity measuring cells
therefore often converted to a reference temperature. The – which need no platinization – are used. The conductivity
usual reference temperatures are 20 °C and 25 °C. The measuring cells are characterized by their cell constant c.
conversion is done applying the temperature coefficient α. For low conductivities, cells with a small cell constant (e.g.
stainless steel conductivity measuring cell) are used while
1 25 cells with higher cell constants serve to measure higher
α( 25) = ( ) 100
25 25 conductivities.
The cell constant should match the solution being
25 °C and °C are temperatures at which the electrical measured.
–1
conductivities have been measured. The temperature  ≈ 0.1 m for poorly conducting solutions, such as
coefficient can be given as reciprocal Kelvin or % per °C. fully or partially demineralized water
The temperature coefficient depends mainly on the ions that For organic solvents see Comments
–1
are in the solution but its behavior is seldom linear.  ≈ 1 m for moderately conducting solutions, such as
For entering the data of the standard correctly into the drinking water, surface water, ground water and
software, please proceed as follows: wastewater
–1
 In case no temperature sensor is connected enter the  ≈ 10 m for solutions with good conductivity, such
actual temperature as seawater, rinsing water, physiological solutions, etc.
–1
 Enter temperature coefficient for the actual temperature  ≈ 100 m for solutions with very good conductivity,
depending on the reference temperature (20 or 25) such as brine, acids, alkalis, electroplating baths, etc.

 Enter conductivity of standard at reference temperature

(not actual one!)
The following two examples illustrate this for a 100 μS/cm
standard with an actual temperature of 30 °C, and with
reference temperatures of 20 °C and 25 °C, respectively:
 Measuring temperature: 30 °C
Reference temperature: 25 °C
Temperature coefficient: 2.0%/°C
Conductivity (at Tref) = 25 °C 100 μS/cm

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 Application Bulletin 102/3 e
Conductometry

Performing the measurement

Practical part  Only use clean measuring cells. It is best to rinse them,
1. General remarks concerning conductivity prior to measuring, with the solution to be measured.
measurements The lateral openings of the conductivity measuring cell
must be fully immersed. Immerse and withdraw the
Preparing /handling the conductivity measuring cell
measuring cell a few times (e.g. three) in the measuring
 The measuring cell must be well conditioned/prepared. solution to remove adhering air bubbles. Wait for the
Platinized measuring cells stored dry must be placed in measuring cell and solution to reach a constant
acetone for 30 min. They are rinsed with ultrapure temperature
water and allowed to stand in this water for at least 2 h,
but preferably overnight. Frequently used measuring
cells are stored in ultrapure water or 20% ethanol (to 2. Determination of the cell constant c
prevent the growth of microorganisms). Measuring cells Use of the conductivity measuring cells may cause the cell
that are used only occasionally should be stored dry. constant to change. Therefore, for high-precision
 Stainless-steel or five-ring measuring cells are measurements, the cell constant must be checked or
generally stored dry. redetermined from time to time. KCl solutions of a known
 Contaminated measuring cells cannot be used for concentration are used for these determinations.
conductivity measurements and must be cleaned. After Instruments
cleaning they should be rinsed thoroughly with ultrapure
 Conductometer
water.
 Magnetic stirrer
Possible sources of contamination and recommended
cleaning:  Titration vessel with thermostat jacket

o Deposits of calcium carbonate or barium  Thermostat (third party provider)

sulfate: Rinse with HCl. In the case of BaSO4 Electrodes
immerse the cell overnight in a stirred solution
 Conductivity measuring cell
of w(Na2EDTA) = 10% in c(NaOH) = 0.1 mol/L.
o Fat and oil residues: Rinse with acetone. In Reagents
severe cases, saponify with ethanolic c(NaOH)  Ultrapure water
= 1 mol/L at approx. 40 °C.
Standards
o Proteins: Place in w(pepsin) = 5% in c(HCl) =
Conductivity standard 100 μS/cm 6.2324.x10
0.1 mol/L for 1...2 h.
or
Preparing the instrument
Conductivity standard 12.88 mS/cm 6.2301.060
 Temperature coefficient: If known, enter it into software
configuration, otherwise determine it with tiamo .
TM Procedure
Another possibility is to use a thermostat and to perform The measuring cell is rinsed with ultrapure water. The
the measurement at the reference temperature, which titration vessel is first rinsed with conductivity standard and
means that this setting is not necessary. then filled up with the standard. The measuring cell is also
 Temperature: It is best to use a measuring cell with an rinsed with conductivity standard and inserted into the
integral temperature sensor. Otherwise, connect a titration vessel. With the help of the thermostat, the standard
separate temperature sensor or use a thermometer – in in the titration vessel is brought to 25.0 °C with gentle
the latter case the measuring temperature must be stirring. Care must be taken to ensure that there are no air
entered on the instrument. bubbles inside the measuring cell. Therefore, the
conductivity measuring cell is dipped three times into the
 Cell constant: Enter the cell constant indicated on the
solution prior to measurement to remove adhering air
packaging or, preferably, redetermine the cell constant
bubbles. A calibration method is created in the control
by way of calibration.
software of the conductometer. Here the measuring
 Reference temperature: This is normally 25.0 °C; for
temperature and reference temperature are entered as
some applications 20.0 °C is stipulated or preferred.
25 °C and the temperature compensation is switched off.
Any reference temperatures can be entered on the After that, the calibration is started.
conductometer.

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 Application Bulletin 102/3 e
Conductometry

If no thermostat is available, the following procedure can be The method MEAS TC Cond is loaded and adapted.
used: The stirrer is switched on and the solution is heated to
The measuring cell and the solutions used are prepared in approx. 45 °C with the help of the thermostat. The automatic
exactly the same way as described above. The determination is started and the solution is allowed to cool
measurements are also performed in a closed down slowly (not faster than 1 °C/min) or, starting at room
measuring/titration vessel. Instead of thermostatting, a temperature, it is heated up slowly. Before starting the
Pt1000 temperature sensor is connected, if a cell with method, ensure that the temperature of the solution is
integral Pt1000 is not being used. The parameters in the outside the heating range.
conductometer software also remain the same with the
exception of the temperature coefficient, which is entered as
described in the theoretical part. 4. Conductivity measurement in water

Calculation Instruments

The cell constant is calculated automatically by the  Conductometer

conductometer software, as follows:  Magnetic stirrer
 Titration vessel with thermostat jacket
h or i on i i  Thermostat (third party provider)
=
m r on n
Electrodes
 Conductivity measuring cell with temperature sensor
3. Determination of the temperature coefficient (TC) α of
c(Na2SO4) = 0.05 mol/L Wastewater, ground water, mineral water, surface water
and drinking water
As explained in the theoretical section, the conductivity of
ionic solutions is extremely temperature-dependent and this The reference temperature is normally 25.0 °C. In order to
dependency is rarely linear. This is why we recommend that avoid errors due to incorrect selection of the temperature
the TC in the temperature range of interest is recorded coefficient (TC), it is either recommended or stipulated that
automatically with the 856 Conductivity Module with the sample solution is thermostatted at 25.0 °C. If this is not
tiamo™. desired, a TC can be entered or in the case of water the
«DIN» template can be selected. It is suitable for water that
Instruments contains mainly calcium and hydrogen carbonate ions as

TM
856 Conductivity Module with tiamo well as small amounts of magnesium, sulfate, chloride and
 Magnetic stirrer nitrate ions.
 Titration vessel with thermostat jacket Demineralized water
 Thermostat (third party provider) Because of possible interferences, a special procedure must
b for w r wi h on i i of < 5 μS/ m. Thi
Electrodes
pp i o w r wi h on i i < 1 μS/ m in p r i r!
 Conductivity measuring cell with temperature sensor
The main interferences are:
Reagents
 entrainment of CO2 (or other «conducting» gases) from
 Ultrapure water the atmosphere;
Solutions  leaching of traces of Na and Ca from the glassware
used.
c(Na2SO4) = 7.10 g Na2SO4 or 16.11 g
0.05 mol/L Na2SO410 H2O are dissolved in Both interferences cause the settings to drift and
ultrapure water and made up to excessively high conductivities are obtained. We
1000 mL. recommend the following procedures to eliminate such
interferences as far as possible:
Procedure
Version 1
The conditioned measuring cell is rinsed with ultrapure
Perform flow-through measurements. Because of the small
water and with Na2SO4 solution. Sufficient Na2SO4 solution
volume of the measuring setup we recommend using the
is filled into the measuring vessel and the measuring cell
stainless steel conductivity measuring cell (integral Pt1000
inserted with no air bubbles.
temperature sensor) screwed into flow-through vessel

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 Application Bulletin 102/3 e
Conductometry

6.1420.100. The water is allowed to flow through the As example the TBN titration of motor oil according to IP400
measuring setup and the conductivity is determined in the is presented here (see also AB 405).
usual way.
Instruments
Version 2

TM
856 Conductivity Module with tiamo
The measurement is carried out in as large a volume as
 Magnetic stirrer
possible. Nitrogen or argon should be passed through and
over the solution, which should also be stirred. If possible,  10 mL buret
use a closed or covered setup. Electrodes
Please note the high TC (approx. 5.8%/°C) of such water  Conductivity measuring cell with temperature sensor
samples!!
Reagents
 Toluene
5. Total dissolved solids (TDS)
 2-propanol (IPA)
Applications exist in which it is not the conductivity that is of
 Ultrapure water
interest, but rather the total content of the dissolved salts.
Separation into the individual ions cannot be achieved by Solutions
measuring the conductivity, as each type of ion makes a Titrant HCl in IPA; c(HCl) = 0.1 mol/L, if
different contribution to the total conductivity. For this possible this solution should be
reason, in this determination, the conductivity of the sample bought from a distributor.
solution is compared with that of pure salt solutions
Solvent 500 mL toluene + 495 mL IPA +
(normally NaCl) and the corresponding salt concentration is
5 mL ultrapure water.
stated. The conductivity is converted by means of a factor,
which depends on the way in which the result is to be Procedure
expressed.  Weigh out sample into a clean and dry tared beaker.
 Add 75 mL solvent.
T S=  Immerse conductivity measuring cell into the titration
m
h o vessel, activate stirrer and wait 30 s. Then start the
titration with 0.1 mol/L alcoholic HCl. Parameters: 10 s
TDS: Total dissolved solids in mg (salt)/L intervals, volume increment of 0.1 mL.
: Mass concentration of the corresponding salt  After titration rinse the buret tip and sensor with solvent
concentration in mg/L until no oil is visible. Then rinse the sensor with
ultrapure water followed, again, by solvent. (Parameters
theo: Theoretical conductivity of the corresponding salt
can be found in the Application Bulletin 405.)
concentration in μS/cm
meas: Measured conductivity of the sample solution in Example determination
μS/cm

If, for example, TDS is expressed as c(NaCl) = 0.01 mol/L,

the factor is 0.51, as quotient of the concentration of (NaCl)
= 584 mg/L and its theoretical conductivity of 1156 μS/cm.

6. Conductometric titrations
For conductometric titrations, the cell constant does not
normally need to be known. A conductivity measuring cell is
used as measuring electrode. Thermostatting is not required
for simple titrations. Alterations in conductivity caused by
temperature variations are of virtually no consequence.
Room temperature is adequate as long as sample and Conductometric determination of TBN (blue = measured
curve, red = extrapolation)
titrant are having the same temperature.

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 Application Bulletin 102/3 e
Conductometry

Calculation
1 f
T =
m

TBN Total base number in mg KOH/g sample

VEP1: Titrant consumption in mL to reach the first
equivalence point.
cHCl: Concentration of titrant in mol/L; here
c(HCl) = 0.1 mol/L
f: Correction factor (titer) without unit
MA: Molar mass of KOH; 56.106 g/mol
ms: Sample weight in g

Comments
 Measurement according to DIN 51627-4 in ethanol is
possible using the stainless steel cell.
 For samples in the pS/cm range (e.g. organic solvents)
standard laboratory conductometer cannot be used. For
such applications special instruments are available on
the market from third party suppliers.

References
 DIN EN 27888: 1993
Water quality – determination of electrical conductivity
 DIN 51627-4
Electrical conductivity in ethanol and ethanol fuel
 AOAC, Method 973.10 (1990)
Specific conductance of water
 IP 400/01
Determination of base number of petroleum products –
conductometric titration method
 USP Monograph 645
Water conductivity
 Metrohm Monograph
Conductometry – Conductivity measurement
 Metrohm Application Bulletin 405
Determination of the total base number in petroleum
products
 Donald T. Sawyer et al., Electrochemistry for Chemists,
John Wiley & Sons, New York, 1995
ISBN: 0-471-59468-7

Author
Competence Center Titration
Metrohm International Headquarters

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