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: [email protected]

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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
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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 The following cell is required for the pH measurements:
 

glass electrode│test solution║bridge solution│ref. 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.

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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 S  pH S E  E1
2 1 (2)
pH  pH S + (E  E1 )  pH S  ,
1 E2  E1 1 k'

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

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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 J·mol-1·K-1, T is the
Kelvin temperature, F is the Faraday constant, 96485.309
Coulombs·mol-1).

The pH value to be determined should lie between the

pH values of the two adjacent buffer solutions.

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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
meter–electrodes assembly.
assembly
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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.

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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/AgCl│3M KCl║3M KCl║Test sol-n│H2,Pt/Pt. (3)

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

ions according to the Nernst equation:

E = EAg/AgCl - k·lg aH (4)

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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 Calibration of cell (3) is carried out using six primary
pH buffers at 25°C. 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.
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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.
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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 Electrolytic conductivity () is the measure of a solution’s
ability to conduct current. Reliable conductivity
measurements require traceability to national or
international measurement standards.

INPL has developed the such Israeli standard.

 

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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 The standard is developed using the direct current
method and includes conductivity cell. This standard
allows to determine  values from 5ּ10-4 up to 10 S·m-1.

Calibration of the conductivity cell at fixed temperature

is carried out using five standard conductivity
solutions from NIST.

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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 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 S·m-1. The results
obtained were in good agreement with the assigned
values.
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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 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
The experimental
experimental slope
slope SlSlHE of the linear calibration
HE of the linear calibration
curve
curve “E-pH”,
“E-pH”, measured
measured with with hydrogen
hydrogen electrode,
electrode, andand
the
the similar
similar slope
slope SlSlGE of the
GE of the tested
tested glass
glass electrode
electrode
should
should be be not
not less
less than
than 53 53 mV/pH
mV/pH and and not
not greater
greater
than
than 59.5
59.5 mV/pH
mV/pH at at 25
25ooC.
C. The
The ratio
ratio (Sl
(SlGE / Sl HE))100,
GE / SlHE 100, %%
should
should bebe not
not less
less than
than 90%.
90%.
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Dr. Elena Kardash - Calibration of pH meters, glass electrodes and conductometers at INPL
 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.

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