Fundamentals of potentiometric pH measuring technology

Fundamentals of potentiometric pH measuring technology

The term pH comes from Latin and means pondus hydrogenii = weight of hydrogen or potentia hydrogenii =
power of hydrogen.

The basics
According to Sörenson, the pH value is defined as the negative decadic logarithm of hydrogen ion activity aH+ :

pH = -lg a H +
where aH+ = f ⋅ [H+]
f = activity coefficient and [H+] = concentration of hydrogen ions

For diluted, aqueous solutions, the activity coefficient approaches 1, so that the pH value directly corresponds to the
hydrogen ion concentration. The pH scale is based on the dissociation of water:

2H2O É H3O+ + OH-

The relationship of the activities of these ions is fixed through the ion product I of the water:

I25°C = (aH+) * (aOH-) = 10-14

The pH scale ranges from pH = 0 (very acidic) through pH =7 (neutral) to pH =14 (very basic). The pH value is thus
a measure of the acidic or alkaline character of a solution.

acid alkaline

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
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Fig. 1: pH scale

The pH value is measured potentiometrically to accurately measure aqueous and non-aqueous solutions. The
electrode system consists of a glass electrode (pH electrode) and a reference electrode. The difference in voltage ∆E
between these two electrodes is measured with high impedance and is a function of the pH value of the solution.

∆E = f(pH) = EGlass - ERef

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Fundamentals of potentiometric pH measuring technology

Electrode structure

Transmitter

pH-electrode Reference electrode

Ag/AgCl-wire Ag/AgCl-wire

KCl-electrolyte KCl-electrolyte

pH-glass membrane Diaphragm

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Fig. 2: pH measuring device

The glass electrode

The glass electrode has a "pH-sensitive" membrane that forms a gel layer in water. The relatively small H+ ions can
nest in this gel layer and the larger negatively charged ions remain in the solution. This creates electrical potential
which depends on the pH value of the outer solution. The glass electrode is filled with a buffer solution, i.e. with a
solution containing H+ ions with a constant pH value (inner buffer with constant pH value). This results in constant
electric charging of the inner gel-like layer. The inner buffer is connected to the instrument via a reference silver
wire. In this way, a voltage can be measured with the glass membrane which is a measure for the difference between
the pH value of the inner buffer and the pH value of the solution.

Glass membrane

Internal buffer pHi

pHo

Gel layer

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Fig. 3: Electrode - gel layer

The reference electrode

The reference electrode provides a stable potential compared to the working electrode. In industrial
instrumentation, only the silver/silver chloride system (Ag/AgCl) with KCl solution is important.
A silver wire coated with silver chloride responds to the chloride ion activity of the surrounding solution. A capillary
connection, known as the diaphragm, separates the electrolyte/solution contact point.

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 Fundamentals of potentiometric pH measuring technology

On the one hand, the diaphragm separates the internal electrolyte of the reference electrode from the solution. On
the other hand, it should electrically connect the two solutions, i.e. make ionic conduction possible. That is why a
range of diaphragms are available for different tasks:
• Ceramic diaphragms are chemically resistant, suitable for oxidizing measuring solutions but tend to clog under
certain circumstances. Areas of application include hygiene applications, lab applications and applications in water
and swimming pools.
• Open ring junctions are particularly suited to applications in the wastewater industry. The construction prevents
clogging taking place to a large extent. Open ring junctions can only be used for gel-filled electrodes.
• Teflon diaphragms made of sintered PTFE are dirt-repellent, almost free from clogging, chemically resistant and
temperature-resistant. Due to the large pores, electrodes with a Teflon diaphragm are generally not hygienic even
though the electrode can be sterilized. Teflon diaphragms have a shorter response time than electrodes with other
diaphragm types.
• Open aperture diaphragms are suitable for applications in contaminated media. The medium is in direct contact
with the gel. For this reason, the electrode has a very rapid response behavior. The open pore structure of the gel
is very stable with regards blocking.
The maintenance effort needed can be reduced by selecting the right reference system and the appropriate
diaphragm.
Combination electrode
To make it more easy to use, the two electrode types are often combined in an electrode system. An electrode system
where the reference silver wires of the glass electrodes and reference electrodes are the same, is called a symmetric
electrode system. If both electrode versions are combined in one model, this is called a combination electrode.
The shaft of the glass electrode is made smaller and it and its reference silver wire are located as a second thin pipe
inside the outer shaft which is 12 mm thick. The resulting intermediate space contains the reference electrolyte and
the reference system. The lower end is sealed apart from the diaphragm. The combination electrode is sealed at the
top with a multi-pole plug-in head. Since the pH value of the electrode system depends on the temperature, a
temperature sensor (usually Pt 100 or Pt 1000) is often integrated in the electrode.

Buffer solution, pH 7

pH potential wire
(Ag/AgCl-element)
Reference potential wire
(Reference-Ag/AgCl-element)
Medium

Reference electrolyte, KCl

Reference diaphragm

pH glass membrane

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Fig. 4: Combination electrode

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Fundamentals of potentiometric pH measuring technology

The electrode voltage of the glass electrode follows the Nernst equation:

R×T . ×
U = U 0+ ln aH+
n×F

U = Voltage
U0 = Voltage at pH = 7.00
R = Gas constant
T = Temperature in Kelvin
F = Faraday constant
a H+ = Ion activity
n = Ionic charge at H+ = 1

The following applies for the voltage at the glass electrode:

U = 0.0592 (lg[H+]a - lg[H+]i)

U = s(pHi - pHa) = s(7 -pHa)
U = Electrode system voltage
s = 59.2 mV/pH (NERNST-slope)
pHi = pH value of the inner buffer = 7
pHa = pH value of the measuring solution

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 Fundamentals of potentiometric pH measuring technology

pH value and temperature

The electrode slope (mV/pH) depends on the temperature. At a solution temperature of 25 °C, the electrode returns
a voltage of 59.16 mV per pH difference between the inner buffer and the solution. The theoretical slopes at various
temperatures are:

Temperature Slope

0 °C 54.2 mV/pH

20 °C 58.2 mV/pH

25 °C 59.2 mV/pH

50 °C 64.1 mV/pH

75 °C 69.1 mV/pH

mV
600 100°C (74.04 mV/pH)
500

400 25°C (59.16 mV/pH)

300

200

100
8 9 10 11 12 13 14
0 pH
1 2 3 4 5 6 7
-100
0°C (54.2 mV/pH)
-200

-300

-400

-500

-600
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Fig. 5: Nernst voltage dependence on temperature

This effect is corrected with automatic or manual temperature compensation in the transmitter.
Ideally, the various Nernst lines (isotherms) of different temperatures cut at one point which is known the isotherm
intersection point. This is at 0 mV = pH 7 for electrodes with inner buffer pH 7. However, since the individual
potentials of an electrode system have different temperature dependencies in real-case scenarios, the real isotherm
intersection point deviates from the ideal value.
Every measuring solution has its own temperature/pH behavior (temperature coefficient). This temperature
coefficient results in different pH values at different temperatures for the same measuring solution. This
phenomenon is a real pH change and cannot be compensated or corrected with measuring devices (in contrast to
conductivity measurement). It can only be compensated for µP-driven devices (during calibration) if the
temperature coefficient is known (e.g. buffer solutions). Thus, you can only compare pH values that were also
measured at the same temperature.

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Fundamentals of potentiometric pH measuring technology

Measuring problems
Errors in industrial pH measurement can often be traced back to reference electrode errors and are mostly caused
by the diaphragm. High diaphragm potential occurs with:
• Very acidic solutions
• Very alkaline solutions
• Low-conductivity samples (aqua dest.)
• Solutions with high salt concentrations
• Part-aqueous and non-aqueous solutions
• Suspensions and emulsions
• Solutions that contaminate the diaphragm. This can cause the electrolyte contact to the measuring solution to be
interrupted partly or completely. Chemical or mechanical cleaning can help.

Acid and alkaline errors

In alkaline solutions, the H+ ions of the gel-like layer are largely replaced by sodium or lithium ions. The resulting
decrease in H+ ionic activity in the gel-like layer results in smaller membrane voltages. The pH values are
understated. The resulting error is only significant, however, with pH values > pH 12. This error is known as an
alkaline error. Glass types are available with particularly small alkaline errors. The alkaline error depends on the
following:
• pH value
• Alkaline concentration
• Temperature
• Membrane glass type
• Electrode age
At very low pH values, the gel-like layer can absorb acid molecules. This increases the H+ ionic activity in the layer.
The membrane voltage is reduced and, as a result, a higher pH value is measured. This measuring error is known
as the acid error. Generally, electrodes with a low alkaline error also have a low acid error. With increasing glass
membrane age, and depending on the operating conditions, changes in the gel-like layer can be linked to an increase
in the internal resistance with a simultaneous decrease in the electrode slope. However, acid errors practically no
longer occur among modern membrane glasses.

Calibration

The operating life of a pH electrode is limited. One reason for this is aging of the pH-sensitive membrane glass. This
aging is linked to a change in the gel-like layer which becomes thicker over time. Symptoms of this include:
• Increased membrane resistance
• Slow response behavior
• Reduction in slope
A change in the reference system (e.g. through toxication, i.e. undesired redox reactions at the reference electrode)
or electrolyte solution bleeding in the reference half cell can result in a change in the reference potential which leads
to a zero point shift of the measuring electrode.
To ensure a high degree of accuracy, the pH sensors have to be recalibrated at given intervals. The calibration
interval depends heavily on the area of application of the sensor and can vary between daily and every few months.
Two-point calibration is common here:
In zero-point calibration, the slope lines are "shifted" to the real zero point (electronic or computational). In slope
calibration, the system adjusts to the real electrode slope by "turning" in the zero point (electronic or computational).

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 Fundamentals of potentiometric pH measuring technology

Digital sensors
Digital sensors with Memosens® functionality are conventional pH glass sensors with additional electronics in the
electrode plug-in head. The high-impedance pH signal is increased and the pH value is digitized. The signal is
transmitted to the transmitter inductively.

C07-GRUNDLxx-15-06-00-xx-015.jpg

Fig. 6: Inductive data and energy transmission

The following problems do not play a role due to the inductive transmission of data:
• Corrosion
• Contact problems
• Salt bridges
• Moisture
• Crack formation
• Non high-impedance connection
• Earth circuits
A digital memory also integrated saves the current calibration data and other information useful for predictive
maintenance such as hours of operation, maximum and minimum pH values, maximum and minimum
temperature. This additional intelligence in the sensor makes the unit easier to use:
• Easy sensor replacement with precalibrated sensors
• No field calibration but rather exact calibration in the lab
• Easy installation with greater distance between sensor and transmitter

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Fundamentals of potentiometric pH measuring technology

ISFET sensors
In contrast to glass electrodes, ISFET sensors use a pH-sensitive semi-conductor to determine the pH value.
Ion-sensitive field effect transistors are based on an MOS transistor arrangement where there is no gate as the control
electrode. Instead, an electrolytic liquid is used to achieve control effects on the drain current of the ISFET by means
of induced surface charges at the gate insulating layer. Charging at the gate (the H+ ions) achieves a current flow
between the source and drain in the simplest of cases. This area is an insulator when not charged. Induced by the
charge at the gate, the negative charge occurs at the mirror side of the gate causing the area between the source and
drain to be conductive. This conductivity is directly proportional to the pH value of the medium.

H+ Gate
H+
H+

Source Drain

- - - C07-GRUNDLxx-16-05-00-xx-015.eps

Fig. 7: Structure of the ISFET sensor

However, all types of charge affect the gate (e.g. also static charge ). Temperature, drift and the influence of light
would also affect the result. For this reason, a reference electrode is also used here to compensate for such effects.

Transmitter
The transmitter has to meet the following requirements:
• The transmitter must be able to measure the electrode potential without current flow as far as possible, i.e. it must
have very high input impedance. This is specified in DIN 19265 to a minimum of 5 x 1011 Ohm.
• It needs configuration options to adjust the transmitter to the individual properties of an electrode system, i.e.
slope adjustment and zero point adjustment.
• It must compensate the temperature dependency of the electrode system:
– By being able to enter the temperature of the material being measured at the transmitter
– Through automatic compensation using a platinum resistance thermometer
The insulation of the connecting line between the glass electrode system and the transmitter has to meet strict
requirements. Due to the high-impedance nature of the measuring circuit, special measures must be taken against
electrical interference signals, i.e. the measuring line must be screened. In addition, there must also be
high-impedance measuring line insulation towards earth.
Measuring and controller units are often linked to process control systems. There are two ways of doing so:
• Analog: current output 0/4 - 20 mA
• Digital: fieldbus systems such as Profibus, Fieldbus or Hart

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 Fundamentals of potentiometric pH measuring technology

Symmetrical or asymmetrical electrode connection

Static charging can be caused by high-impedance media or strongly flowing media in plastic pipes or poorly
grounded metal pipes. The influence of static charge can be minimized by symmetrical measurement with a
potential matching pin.
With a symmetrical connection, the line to the potential matching pin (PML) must be connectred to the potential
matching terminal of the instrument. The PML must always be in contact with the medium, i.e. immersed in the
buffer solution during calibration.
If the instrument input is asymmetrical, pH measuring chains connected to assemblies can be connected without
an additional potential matching pin. If necessary, connect the available potential matching pin to terminal PE.

Advantages of symmetrical vs. asymmetrical

• Symmetrical measurement
– No leak current since the reference and the pH/redox electrode is connected with high resistance
– Safe measurement under difficult process conditions (strong flowing and high-resistance media, partially soiled
diaphragm)
• Asymmetrical measurement
– Use of assemblies without potential matching possible