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Calibration of pH meters, glass electrodes

and conductometers at INPL


Dr. Elena Kardash, Supervisor of the Project

Address: The National Physical


Laboratory of Israel (INPL),
Givat Ram, Jerusalem 91904, Israel
tel.: +972-2-6536-534
fax: +972-2-6520-797
e-mail: lena.ka@moital.gov.il

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

pH is defined as the negative decimal logarithm of the


hydrogen ion activity aH.
pH scale is based on the pH values of a series of standard
buffer solutions determined by the potentiometric
technique.
Routine potentiometric measurements of pH are carried
out by means of a pH meter equipped by a pH-indicator
glass electrode, a reference electrode and an automatic
temperature compensator.
compensator
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

The following cell is required for the pH measurements:


glass electrodetest solutionbridge solutionref. electrode, (1)

where is the electrode-solution interface, and is the


liquid junction denoting an interface between the test
solution and the salt bridge solution.
pH meter is a high impedance voltmeter. Direct pH
readings are possible after adjustment of a pH meter.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

If emf corresponding to two buffer solutions S1 and S2


with pHS1 and pHS2 are E1 and E2, respectively, the pH
value of the unknown (test) solution can be calculated
from its measured emf value E by the following formula:
pH pH S + (E E1 )
1

pH S
E E1
2
1
pH S
,
E2 E1
k'
1

pH S

(2)

where k' is the practical slope of the glass electrode.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

The practical slope k' usually differs from the theoretical


slope - Nernst coefficient - k = 2.3026 RT/F (R is the
universal gas constant 8.31451 Jmol-1K-1, T is the
Kelvin temperature, F is the Faraday constant, 96485.309
Coulombsmol-1).
The pH value to be determined should lie between the
pH values of the two adjacent buffer solutions.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

Some factors lead to systematic errors in pH


measurement results, which can not be compensated by
the adjustment procedure:
asymmetry potential of glass electrode,
liquid junction potential of cell (1),
clogging of glass electrode diaphragm etc.
This problem can be solved by a calibration of the pH
meterelectrodes assembly.
assembly
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

The IUPAC recommendations of the year 2002 require at


establishing a traceability chain of the pH measurement
results from the national metrological institution level
down to field, laboratory and industry measurements.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

The national primary standard of pH value developed


at INPL

consists of a precise pH/ion-meter and the

following electrochemical cell:


Ag/AgCl3M KCl3M KClTest sol-nH2,Pt/Pt.

(3)

The emf of cell (3) depends on the activity of hydrogen


ions according to the Nernst equation:
E = EAg/AgCl - klg aH
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

(4)
8

Calibration of cell (3) is carried out using six primary


pH buffers at 25C. These buffers are prepared from the
NIST standard reference materials with expanded
uncertainties of 0.005 pH.
The national pH value standard have participated
successfully in two interlaboratory international key
comparisons in the years 2002 and 2004 organized by
the CCQM.
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

Calibration of a pH-meter (as a voltmeter).


Calibration of an automatic temperature
compensator (as a thermometer).
Calibration of a glass electrode.
electrode
Certification of buffers for pH- measurements.
These calibrations assure the shortest unbroken
traceability chain to the national measurement
standards of Israel.
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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Electrolytic conductivity ( ) is the measure of a solutions


ability

to

conduct

measurements

require

current.

Reliable

traceability

to

conductivity
national

or

international measurement standards.


INPL has developed the such Israeli standard.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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The standard is developed using the direct current


method and includes conductivity cell. This standard
allows to determine values from 510-4 up to 10 Sm-1.
Calibration of the conductivity cell at fixed temperature
is carried out using five standard conductivity
solutions from NIST.

Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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Conductometer calibration is based on the comparison


of the measuring results obtained by

the tested

conductometer and by INPL electrolytic conductivity


standard.
In the year 2003 INPL took part in the interlaboratory
key comparison organized by the CCQM for solutions
with low conductivity levels. 0.005 Sm-1. The results
obtained

were in good agreement with the assigned

values.
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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Calibration of a conductometer.
Calibration of a conductivity cell.
cell
These calibrations assure the shortest unbroken
traceability chain

to

the

national

measurement

standards of Israel.

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The national standards of pH and electrolytic


conductivity values have been developed and passed
successfully interlaboratory key comparisons.
INPL proposes calibration of corresponding
equipment based on these standards.

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Calibration
Calibration of
of aa glass
glass electrode
electrode isis performed
performed by
by
measuring
measuring of
of emf
emf values
values with
with this
this electrode
electrode
simultaneously
simultaneously with
with the
the reference
reference hydrogen
hydrogen electrode
electrode in
in
the
the same
same cell
cell and
and buffer
buffer solutions.
solutions.
The
of the linear calibration
The experimental
experimental slope
slope Sl
SlHE
HE of the linear calibration
curve
curve E-pH,
E-pH, measured
measured with
with hydrogen
hydrogen electrode,
electrode, and
and
the
of the
the similar
similar slope
slope Sl
SlGE
the tested
tested glass
glass electrode
electrode
GE of
should
should be
be not
not less
less than
than 53
53 mV/pH
mV/pH and
and not
not greater
greater
than
/ Sl HE))100,
than 59.5
59.5 mV/pH
mV/pH at
at 25
25ooC.
C. The
The ratio
ratio (Sl
(SlGE
100, %
%
GE / SlHE
should
should be
be not
not less
less than
than 90%.
90%.
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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In order to make a pH meter calibration independent of


the vagaries of electrode performance, the calibration is
conducted by the pH meter comparison with known d.c.
potentiometer traceable to the national standard of volt.
Calibration of a automatic temperature compensator
is done by comparison of temperature values measured
using this compensator with simultaneous readings of the
reference glass thermometer, traceable to the national
temperature standard.
Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL

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