Application Data Sheet

ADS 43-002
August 2001
Theory

The Theory of pH Measurement

pH measurement has a wide variety of industrial appli- The concentration of hydrogen and hydroxyl ions can
cations in virtually every industry. These range from vary over 15 orders of magnitude in water solutions.
water conditioning to specific process related mea- Even common household items can reflect this wide
surements to waste treatment. variation (Figure 2).

WHAT IS pH?
pH is a measure of the acidity or alkalinity of a water
solution. The acidity or alkalinity of a water solution is
determined by the relative number of hydrogen ions
(H+) or hydroxyl ions (OH-) present. Acidic solutions
have a higher relative number of hydrogen ions, while
alkaline (also called basic) solutions have a higher rel-
ative number of hydroxyl ions. Acids are substances
which either dissociate (split apart) to release hydro-
gen ions or react with water to form hydrogen ions.
Bases are substances that dissociate to release
hydroxyl ions or react with water to form hydroxyl ions.
In water solutions, the product of the molar concentra- FIGURE 2. pH Values of Acids and Bases
tions1 of hydrogen and hydroxyl ions is equal to a dis-
sociation constant (Kw). Knowing the value of the con- pH is strictly defined as the negative logarithm of the
stant and the concentration of hydrogen ions makes it hydrogen ion activity (aH):
possible to calculate the concentration of hydroxyl
ions, and vice versa. At 25°C, the value of Kw is 10-14
(see Figure 1). pH = -log10 aH

The hydrogen ion activity is defined as the molar con-

centration of hydrogen ions multiplied by an activity
Acids: HA ‘ H+ + A- coefficient, which takes into account the interaction of
hydrogen ions with other chemical species in the solu-
acid hydrogen ion anion
tion.
In practice, pH is often assumed to be the negative
Bases: MOH ‘ OH- + M+ logarithm of the hydrogen ion concentration:
base hydrogen ion cation
pH = - log10 [H+]
(H+) x (OH-) = Kw = 10-14 (25°C)
In this form, the usefulness of pH as a convenient
shorthand for expressing hydrogen ion concentration
FIGURE 1. Acids and Bases can be seen on page 2, Figure 3:

1 Molar concentration is a measurement of the number of atoms, molecules

or ions in a solution.
 The Need for Temperature Measurement
The millivolt signals produced by the pH and reference
electrodes are temperature dependent. However, the
pH and reference electrode combination exhibits an
isopotential point, which is a pH and millivolt potential
at which the potential is constant with temperature
FIGURE 3. Ion Concentration, MOL/L changes. The isopotential point is most frequently
designed to be at 7.0 pH and 0 mV. Using the isopo-
tential point with a theoretical knowledge of electrode
At 25°C, a neutral solution has a pH of 7.0, while solu- behavior makes it possible to compensate (correct)
tions with pH < 7 are acidic and solutions with pH > 7 the pH measurement at any temperature to a refer-
are alkaline. The normal overall pH range is 0 to 14 ence temperature (usually 25°C), using a temperature
pH, although solutions containing non-water solvents signal from the temperature element. This makes the
can have pH values outside this range. pH measurement independent of changes in the elec-
trodes' output with temperature.
THE MEASUREMENT OF pH
pH measurement is based on the use of a pH sensi-
tive electrode (usually glass), a reference electrode,
and a temperature element to provide a temperature
signal to the pH analyzer.
The pH electrode uses a specially formulated, pH sen-
sitive glass in contact with the solution, which devel-
ops a potential (voltage) proportional to the pH of the
solution. The reference electrode is designed to main-
tain a constant potential at any given temperature, and
serves to complete the pH measuring circuit within the
solution. It provides a known reference potential for
the pH electrode. The difference in the potentials of
the pH and reference electrodes provides a millivolt
signal proportional to pH.
Most pH sensors are designed to produce a 0 mV sig- pH MEASUREMENT IN PROCESS SOLUTIONS
nal at 7.0 pH, with a (theoretically ideal) slope (sensi- The potential effects of process solutions on pH sen-
tivity) of -59.16 mV / pH at 25°C. sors will require a more detailed look at the construc-
tion of pH and reference electrodes. But first, some
basic properties of the pH of water solutions need to
be examined.

pH IN AQUEOUS SOLUTIONS
Practical pH Measurement Range
Although the range of pH measurements is defined to
be 0 to 14 pH, solutions with pH values near the
extremes of this range are often better measured
using conductivity.

2 Rosemount Analytical
At pH values below 1.0 pH, the glass pH electrode can measure it in the laboratory by noting the pH at vari-
be subject to acid errors, and the sensor can be subject ous temperatures. If the composition of a process
to chemical attack. Solutions with a pH in this range changes, the temperature coefficient can also change;
have an acid concentration at, or approaching the per- therefore, the final product composition should be
cent by weight range, which will have conductivity like- used for determining the solution coefficient.
ly to be large in comparison to other electrolytes in the
solution. A toroidal conductivity measurement, with a
read-out in percent acid, can often be successfully Processes with Mixed Solvents
applied in these cases and will be a far more accurate The conventional pH analyzer and sensor are
measurement of acid concentration than pH. designed to measure the pH in water solutions. When
a non-water solvent is present in appreciable quanti-
ties, the pH reading will be shifted from the expected
value by effects of the non-water solvent on the pH
and reference electrodes, and effects on the activity of
hydrogen ion itself. Since pH sensor components are
designed for use in water, the non-water solvent may
attack seals and O-rings.
There are a few mixed solvent cases that can be con-
sidered:
(1) A solvent that is miscible with (mixes with) water
may cause a shift in the pH reading, but if the solven-
t's concentration is above 15% by weight, it may dry
In the case of high pH, the reason for switching to a the pH electrode, requiring periodic rewetting of the
conductivity measurement is more compelling: highly sensor by water.
alkaline solutions quickly destroy glass pH electrodes. (2) A solvent that is non-miscible with water will likely
If the nominal pH is expected to be above 13 pH, a not have an appreciable concentration of hydrogen
conductivity measurement should be considered. ions; most will be in the water phase. It is better to
make the measurement in a place in the process
where the water and solvent phases separate and
keep the pH sensor in the water phase.
(3) Completely non-water process measurements may
only be possible with periodic rewetting of the pH sen-
sor with water, and may also require a specially
designed reference electrode.
In all of the above cases, pH measurement of the
mixed solvent solution should be studied in the labora-
tory before going on-line, and the study should include
prolonged exposure of the pH sensor to the process
sample.
Solution pH Changes with Temperature
The pH of a solution can change with temperature, PROCESS EFFECTS ON THE GLASS pH
due to the effect of temperature on the dissociation of ELECTRODE
weak acids and bases, and the dissociation of water A glass pH electrode consists of an inert glass tube
itself. In fact, any solution with a pH of 7 or above will with a pH sensitive glass tip, either hemispherical
have some degree of temperature dependence. How (bulb) or flat in shape, blown onto it. The tip contains a
much this will affect the measurement will depend fill solution with a known pH, and it is the influence of
upon the composition of the solution and how high the this solution on the inside of the glass tip versus the
nominal process temperature is above 25°C. This influence of the process solution on the outside that
behavior is frequently the explanation for discrepancies
between laboratory and on-line pH measurements.
Modern pH analyzers allow their temperature compen-
sation routines to be modified to take into account
solution pH changes with temperature as well as
changes in the millivolt output of the electrodes.
Simply entering the temperature coefficient of the
solution (pH change per degree C) into the analyzer
does this. While the temperature coefficient can be
calculated for simple cases, it is often necessary to

Rosemount Analytical 3
gives rise to its millivolt potential. Ideally, the pH elec- upset conditions) and the total concentration of fluo-
trode will have a slope (response) of -59.16 mV/pH, ride in the solution to determine what the maximum
but in practice, a new electrode may only have a slope concentration of HF will be.
of -57 to -58 mV/pH. As the electrode ages, its slope
decreases.
PROCESS EFFECTS ON REFERENCE
ELECTRODES
Temperature Effects The common reference electrode used in pH mea-
In addition to changing millivolt output of the pH elec- surements consists of a silver wire coated with silver
trode, elevated temperatures accelerate the aging of chloride in a fill solution of potassium chloride. The
the electrode. Extremely high or low temperatures can purpose of the potassium chloride is to maintain a
alternatively boil the fill solution or freeze it, causing reproducible concentration of silver ions in the fill solu-
the electrode tip to break or crack. Elevated tempera- tion, which in turn, results in a reproducible potential
tures can also affect the interior and exterior of the pH (voltage) on the silver-silver chloride wire. For the ref-
electrode differently, giving rise to asymmetry poten- erence electrode to maintain a reproducible potential,
tial, which shifts the zero point of the pH electrode and the fill solution must remain relatively uncontaminated
changes its temperature behavior, which leads to tem- by certain components in the process solution.
perature compensation errors. At the same time, the reference electrode must be in
electrical contact with the pH electrode through the
Sodium Error process solution. A porous liquid junction of ceramic,
wood, or plastic, which allows ions to pass between
More correctly called alkali ion error, sodium ion error the fill solution and the process, typically does this.
occurs at high pH, where hydrogen ion concentration This passage of ions between the reference electrode
is very low in comparison to sodium ion concentration. and the process is necessary to maintain electrical
The sodium ion concentration can be so high relative contact, but also creates the potential for contamina-
to hydrogen ion contration that the electrode begins to tion of the reference fill solution by components in the
respond to the sodium ion. This results in a reading process solution.
that is lower than the actual pH. Depending on the pH
glass formulation, this can occur as low as 10 pH.
Where accurate high pH readings are required, the
upper pH limit of the pH electrode should be checked
and a specially formulated, high pH electrode used if
necessary. Compared to sodium, lithium ions will pro-
duce a larger error, while the effect of potassium ions
is negligible.

Components Attacking pH Electrodes Caustic

As noted earlier, high concentrations of hydroxyl ions
shorten the life of pH electrodes. Solutions, that reach
a pH in excess of 14 pH (equivalent to 4% caustic
soda) can destroy a pH electrode in a matter of hours.
There is nothing that can be done to prevent this,
short of simply avoiding pH measurements in these Reference Poisoning
solutions and using conductivity instead. The mechanism of reference poisoning is a conver-
sion of the reference from a silver-silver chloride
Hydrofluoric Acid based electrode to an electrode based on a different
silver compound. The ions, which typically cause this
Hydrofluoric acid (HF) also dissolves pH glass, but form less soluble salt with silver than does chloride.
there are pH glass formulations designed to resist These ions include bromide, iodide, and sulfide ions.
destruction by HF, which when used within their limits When these ions enter the fill solution, they form insol-
can give satisfactory electrode life. uble precipitates with the silver ions in the fill solution.
It is important to note that, while only hydrofluoric acid But there is no initial effect on the potential of the ref-
(HF) attacks glass and not fluoride ion (F-), hydrofluo- erence, because the silver ions lost to precipitation are
ric acid is a weak acid. Therefore, a solution can con- replenished by silver ions dissolving off the silver chlo-
tain a relatively high concentration of fluoride ion at a ride coating of the silver wire. It is not until the silver
high pH and do no damage to the electrode. But if the chloride coating is completely lost that a large change
pH of the solution decreases, the fluoride ion will com- in the potential (and temperature behavior) of the ref-
bine with hydrogen ion to form HF, which will damage erence occurs. At this point, the reference electrode
the electrode. So, it is important to look at the must be replaced.
extremes of the pH measurement (even in process

4 Rosemount Analytical
Poisoning can also occur by reducing agent (bisulfite) tive ions tend to move together and maintain a net
or complexing agents (ammonia), which reduce the zero charge at all points within the liquid junction.
concentration of silver ion in the fill solution by reduc- However, not all solutions are equitransferent, and
ing it to silver metal or complexing it. when the process solution is not, a liquid junction
To counter this effect, multiple junction reference elec- potential can result. When a positive ion diffuses
trodes are used, which consist of two or more liquid through the liquid junction faster than a negative ion,
junctions and fill solutions to slow the progress of the or vice versa, a charge imbalance will result. This
poisoning ions. Gelling of the reference fill solution is gives rise to an opposing potential, which is liquid
also used to prevent the transport of poisoning ions by junction potential. The magnitude of this potential
convection. depends upon the composition and concentrations in
the process solution and the design of the liquid junction.
This potential gets added to the potentials of the pH
and reference electrodes and causes an offset to the
pH measurement of typically a few tenths of a pH.
This phenomenon normally takes 15 to 20 minutes to
develop after the pH sensor is put on line. pH buffer
solutions, used to calibrate pH measurements, are by
and large equitransferent, so returning a freshly
buffer-calibrated pH sensor to a buffer solution from
the process will show an offset in the buffer until the
liquid junction potential subsides.
The remedy for liquid junction potential is to standard-
ize the pH measurement after the sensor has been
put on-line and has stabilized.
A new approach is the use of a reference with a long
tortuous path to the silver-silver chloride wire, along
with gelling of the fill solution.

Plugging of the Liquid Junction

To maintain electrical contact between the reference
electrode and the pH electrode, there must be a rela-
tively free diffusion of ions between the reference fill
solution and the process solution. In some cases,
large concentrations of an ion that forms an insoluble
precipitate with silver ion (most notably sulfide ion) will
precipitate within the liquid junction and plug it. Metal
ions that form insoluble salts with chloride ion (typical-
ly the heavy metals: silver, lead, and mercury) will also
precipitate in the liquid junction.
When the liquid junction is closed to migration, the pH pH SENSOR COATING AND CLEANING
reading will drift aimlessly.
Undissolved solids and liquids in a process can coat a
To counter these effects, multiple junction reference pH sensor, drastically increasing its response time or
electrodes have been used with the outermost fill solu- even plugging the liquid junction of the reference elec-
tion containing potassium nitrate, rather than potassi- trode. Depending upon rate of fouling, the sensor can
um chloride.This lowers the concentration of chloride either be cleaned manually or on-line.
available for precipitation by heavy metals, as well as
lowers the concentration of free silver ion, which can Manually cleaning the sensor should be done with the
precipitate with sulfide. mildest effective cleaning solution possible. Alkaline
deposits can be removed with weak acid solutions
(5% HCl or vinegar), while acid deposits may be
Liquid Junction Potential removed with mild caustic (1% caustic soda). Organic
Potassium chloride is chosen for the fill solution not deposits (oil and grease) can often be removed with a
only for its ability to solubilize silver ion, but also detergent solution, but a more tenacious coating may
because it is equitransferent. Equitransferent means require the use of a solvent. The solvent used should
that the positive potassium ion and the negative chlo- be carefully chosen to avoid attack on the sensor's O-
ride ion diffuse through a water solution at nearly the rings and seals.
same rate. When diffusing through the liquid junction In all cases, the exposure to the cleaning solution
of a reference electrode, both the positive and nega- should be minimized to limit the amount of cleaning

Rosemount Analytical 5
solution entering the liquid junction. Cleaning solution Another type of calibration error can be caused by
that enters the liquid junction can create a liquid junc- buffer calibrations done in haste, which may not allow
tion potential, which will persist until the cleaning solu- the pH sensor to fully respond to the buffer solution.
tion components diffuse out of the liquid junction. This will cause errors, especially in the case of a warm
On-line cleaning reduces maintenance in processes pH sensor not being given enough time to cool down
that quickly foul the sensor. Ultrasonic cleaning was to the temperature of the buffer solution. Current pH
the first approach to on-line cleaning, but was ineffec- analyzers have a " buffer stabilization" feature, which
tive on soft or gelatinous coating, and only marginally prevents the analyzer from accepting a buffer pH
effective with hard crystalline coatings, which it was reading that has not reached a prescribed level of sta-
designed to address. It has, for the most part, been bilization.
abandoned as a cleaning method.
One of the most fruitful methods for on-line cleaning Grab Sample Standardization of pH
has been the jet spray cleaner. This method directs a Standardization is a simple zero adjustment of a pH
spray of water or cleaning solution at the face of the analyzer to match the reading of a sample of the pro-
pH sensor at timed intervals or based on a high refer- cess solution made using a laboratory or portable pH
ence impedance alarm (see Reference Electrode analyzer. It is most useful for zeroing out a liquid junc-
Impedance [next page]). tion potential, but some caution should be used when
A new liquid junction design, the hydrolysis reference using the zero adjustment. A simple standardization
junction (TUpH™), has proved effective in avoiding the does not demonstrate that the pH sensor is respond-
effects of severe coating. The TUpH junction uses ing to pH, as does a buffer calibration. In some cases,
extremely small pores, difficult to penetrate by most a broken pH electrode can result in a believable pH
particulates and suspensions, over a relatively wide reading, which can then be standardized to a grab
area. Use of this junction can drastically reduce the sample value.
required frequency of manual cleaning and, in most A sample can be prone to contamination from the
cases, eliminates the need for on-line cleaning. sample container or even exposure to air; high purity
water is a prime example. A reaction occurring in the
CALIBRATION sample may not have reached completion when the
sample was taken, but will have completed by the time
Buffer Calibration it reaches the lab. Discrepancies between the labora-
Buffers are standard solutions formulated to maintain tory measurement and an on-line measurement at an
a known pH in spite of small amounts of contamina- elevated temperature may be due to the solution pH
tion. Buffer calibrations use two buffer solutions, usu- being temperature dependent; adjusting the analyzer's
ally at least 3 pH units apart, which allows the pH ana- temperature compensation (not a zero adjustment) is
lyzer to calculate a new slope and zero value to be the proper course of action. Finally, it must be remem-
used for deriving pH from the millivolt and temperature bered that the laboratory or portable analyzer used to
signals. adjust the on-line measurement is not a primary pH
The slope and zero value derived from a buffer cali- standard, as is a buffer solution, and while it is almost
bration provide an indication of the condition of the always assumed that the laboratory is right, this is not
glass electrode from the magnitude of its slope, while always the case.
the zero value gives an indication of reference poison-
ing or asymmetry potential. Overall, the buffer calibra- pH Diagnostics
tion can demonstrate how well the pH sensor
responds to pH. The most straightforward way to validate the accuracy
of a pH analyzer and sensor is by a buffer calibration.
This is not possible during on-line operation, and, in
Buffer Calibration Errors general, the only clue to an on-line problem is a pH
Buffer solutions have a stated pH value at 25°C, but reading that is clearly impossible, given what is known
when that value is 7 pH or above, the actual pH of the about the process.
buffer will change with temperature. The values of the Over the years, on-line pH diagnostics came into use
buffer solution at temperatures other than 25°C are with the advent of the microprocessor driven analyz-
usually listed on the bottle. The pH value at the cali- ers. But these early diagnostics were restricted to the
bration temperature should be used or errors in the pH analyzer only. They provided self-checking of the
slope and zero values, calculated by the calibration, analyzer and detection of electrode and temperature
will result. An alternative is to use the "buffer recogni- sensor inputs that were out of range due to shorts or
tion" feature on modern pH analyzers, which automati- open circuits.
cally corrects the buffer value used by the analyzer for
the temperature.

™ TUpH is registered trademark of Rosemount Analytical, Uniloc Division.

6 Rosemount Analytical
pH Sensor Impedance Diagnostics Reference Electrode Impedance
The pH sensor is the most maintenance intensive part The overall impedance of a reference electrode is a
of the pH measurement, and with the widespread use sum of the resistances of its components with the
of disposable pH sensors, it is likely to fail after 6 to 12 largest being the liquid junction. This is due to the lim-
months of use, or even sooner in severe applications. ited volume of current carrying electrolyte within the
Failures can occur slowly, such as the gradual loss of liquid junction. Coating or blockage of the liquid junc-
pH electrode slope or poisoning of the reference elec- tion further increases the impedance of the liquid junc-
trode. Or they can occur suddenly or catastrophically, tion. Detection of coating or blockage involves setting
as in the case of pH electrode breakage or coating a high reference impedance alarm.
and plugging of a reference electrode. In either case,
failure might go undetected until the next routine buffer
calibration. The purpose of impedance diagnostics is SUMMARY
to detect these problems in real time. pH measurements are based on the response of a pH
sensor to the logarithmic concentration of hydrogen
ions in solution and are a measure of the acidity or
Glass pH Electrode Impedance alkalinity of a solution. There are a number of factors
Glass pH electrode impedance is in the range of 10's that should be considered for on-line pH measure-
to 100's of megOhms and is strongly temperature ments. These involve the temperature behavior of the
dependent. A crack or break in the glass electrode solution pH, the composition of the process solution,
creates a short, which results in an impedance of 1 and the potential for fouling of the sensor by undis-
megOhm or less. Detecting broken or cracked pH solved material in the process. Contemporary pH ana-
electrodes requires impedance measurement circuitry lyzers offer the user calibration routines to improve the
with temperature compensation and the simple setting accuracy of calibrations, as well as diagnostics to
of a low impedance alarm. detect pH sensor failure on-line.

Emerson’s Asset Management Solutions software is an excellent tool for tracking changes in the condition of the
pH sensor. The Windows-based software can continuously display live values of sensor diagnostic variables
when used with a compatible HART device. For more information, see Application Data Sheet 43-017.

Rosemount Analytical 7
INSTRUMENTATION

Model 54e pH Model 396P pH/ORP

Microprocessor Analyzer TUpH Sensor
• NEMA 4X (IP65) weatherproof, • Patented1 polypropylene refer-
corrosion-resistant enclosure. ence junction and patented heli-
cal pathway mean longer sensor
• Comprehensive pH glass and
life in process solutions contain-
reference diagnostics.
ing heavy solids.
• Fully descriptive diagnostic messages.
• Disposable, one-piece construction is convenient and
• Two independent outputs. economical where minimal troubleshooting and mainte-
• Back-lit dot-matrix display. nance downtime are of prime importance.

• HART and AMS aware. • Versatile. Can be used in numerous loop configurations
with all Rosemount Analytical and other manufacturers’
• Optional TPC relays and PID current outputs. instruments.
1 U.S. Patent No. 5,152,882, Foreign Patent Pending.

Model 3081 pH/ORP

Smart Two-Wire Transmitter
• Hand-held infrared remote control Model 396R Retractable
link to activate all the transmitter pH/ORP TUpH Sensor
functions. • Rugged titanium and polypropy-
• Large custom LCD display. lene construction for maximum
chemical resistance.
• NEMA 4X (IP65) weatherproof, corrosion-resistant
enclosure. • Longer sensor life and reduced
maintenance.
• Comprehensive pH glass and reference diagnostics.
• Retractable version for greater insertion depths.
• Non-volatile EEPROM memory to hold data in event of
power failure.
• Compatible with HART SMART communication protocol
and AMS software.

The right people,

the right answers,
right now.

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Rosemount Analytical Inc.
2400 Barranca Parkway
Irvine, CA 92606 USA
Tel: (949) 757-8500
Fax: (949) 474-7250
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© Rosemount Analytical Inc. 2001