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White Paper

Understanding pH in practical terms

Frederick J. Kohlmann

Executive Summary

A paper which describes the theory of pH and how it is measured, looking in detail at the individual components, the
importance of specific items related to the measurement and the proper methods for calibrating, cleaning and general
care of the pH sensor.

About the Author

Fred Kohlmann is Mid-West Business Manager for Analytical Products with Endress+Hauser. Since 1976, he has been
involved in engineering, design service, marketing, and sales of online analytical water quality and process control
instrumentation.

Mr. Kohlmann has taught accredited course work and authored numerous articles relating to pH, ORP and
Conductivity measurements. Past publications include “What Is pH and How Is It Measured?”, a primer on the use
of pH instrumentation, and “Electrical Conductivity Measurements” in the “Process/Industrial Instruments and
Controls Handbook”, Fourth Edition, by McGraw Hill, Douglas M. Consadine Editor.

CP 997C/24/ae/10.08
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US/INDD CS
Understanding pH in practical terms
Why measure pH? Definition of pH Version two:
In everyday life, pH plays an integral part Version one: pH is defined as the negative log of the
of almost everything we eat, drink and for The pH unit is a number set ranged from 0 hydrogen ion concentration in mol/L:
the most part, touch. The determination to 14, where 7 indicates a neutral pH value.
of pH in factories, water and wastewater Increasing values from 7 to 14 pH indicate pH = -log H+
plants and in research laboratories is one increasing alkalinity concentrations, and
of the most common measurements made, decreasing values from 7 to 0 pH indicate The pH unit of measure exactly quantifies
and yet, it remains as somewhat of a increasing acidic concentrations. Simply the degree of acidity or alkalinity
magical or mystical measurement, if not a put, this pH numbering system is used an aqueous solution possesses. pH
frustrating one. Talk to most plant operators as a unit of measurement relating to the measurement is logarithmic, the voltage
or I&E technicians, and their most common acidity or alkalinity of a liquid. A specially output of the sensor is linear in its output.
complaint is one of keeping the pH sensors formulated glass electrode supplies an ECP
up and running. (electrochemical potential) in conjunction So why two versions? Well, each is correct
with a reference element and a voltage – technically speaking, and each describes
The following text will (hopefully) try to measurement device (pH analyzer/ pH from a different yet accurate position.
explain pH theory, practical determination transmitter) to determine the pH value of a Version one describes how pH works and
and proper care and feeding of the friendly liquid. Version two describes what pH is.
beast we call pH.
Note: The pH electrode is temperature Let us put this into practical terms. What
In general, pH is used to determine dependent. As the temperature of the if someone approached you and said “It is
whether: solution and ultimately, the pH measuring really cold outside”. Depending on where
electrode changes, so does the output of you are from, or what climatic conditions
- Municipal drinking water plants are the glass electrode. you are used to, cold has varying meanings.
producing quality drinking water If you lived in Alaska all your life and just
- Municipal wastewater plants are Further, the ECP generated by the glass happened to be vacationing in Florida in
discharging clean water to their receiving measuring electrode is dependent on H+ mid-July and the thermometer showed 60°F,
bodies (lakes, rivers, streams etc.) and/or ions penetrating through the outer layer of the locals might say that is cold. But to you,
the water is not too corrosive and does not the glass, through the hydrated glass layers, your Arctic blood still senses this as warm.
do damage to cement/cement lined pipes then through the internal gel layer of the So without actually feeling the temperature
- Factories, which vary from steel and glass, the electrolyte solution and then to outside or knowing what the temperature
automobile production to food and the silver/silver chloride (Ag/AgCl) internal was in specific degrees, you would never
beverage, are producing product that reference element. really know what the term cold meant.
meets both consistency and quality
specifications Ultimately, this ionic pathway causes pH holds the same analogy. Just saying
- The manufacture of electrical power is a voltage potential difference between something is acidic or alkaline, doesn’t give
optimized for the processes for inlet water the outer glass gel layer and the gel layer a good enough definition of what’s really
treatment, steam cycle, cooling tower existing on the inside of the glass electrode. going on. Some type of number system has
water and any wastewater discharge A voltage is produced from this reaction to be in place to define the degree of acidity
and subtracted from the voltage provided or alkalinity. Hence, the pH scale was
To sum it up, almost every process that by the reference electrode to yield an developed to do just that. It relates a number
contains water and undergoes a chemical overall voltage potential relative to pH. to the ratio of hydrogen ion and hydroxide
reaction probably depends on pH and the A transmitter measures this electrical ion concentrations. This relationship is
more closely the reaction is held to the potential and converts the measured voltage inversely related. That is to say that as the
optimum pH, and the more accurate the into a corresponding pH value based on the (H+) increases the (OH-) decreases.
pH measurement, the better the outcome Nernst equation.
of the process or product. Bottom line: We The pH scale has a range of 0 to 14, where
measure pH because we have to. 7 pH is considered neutral. Anything from
pH 7 to pH 0 is considered acidic and from
7 to 14 pH alkaline. The more acidic the
solution, the more H+ are present, and the
less OH- present. This relationship is always
constant, and so knowing one, we can
determine the other.

H20 = H+ + OH-

In theoretically pure water (7 pH), at


77°F/25°C, the amounts of hydrogen and
Figure 1. pH values of common liquids
hydroxide ions are equal, and their product
is always 10 -14.


The logarithmic nature of pH: Hydrogen Ion Concentration in Moles/Liter @ 77°F (25°C)

Changing pH from 6 pH to 7 pH is pH H+ H-
a difference of only one pH unit but
a 10 fold change in concentration of 0 (100) 1 0.00000000000001 (10 -14)
ions. Changing from 5 pH to 7 pH is a 1 (10 -1) 0.1 0.0000000000001 (10 -13)
difference of two pH units in value, but a 2 (10 -2) 0.01 0.000000000001 (10 -12)
100 fold change in ion concentration. 3 (10 -3) 0.001 0.00000000001 (10 -11)
4 (10 -4) 0.0001 0.0000000001 (10 -10)
Dissociation constant 5 (10 -5) 0.00001 0.000000001 (10 -9)
As long as we introduced the terms 6 (10 -6) 0.000001 0.00000001 (10 -8)
hydrogen ion (H+) and hydroxyl ion 7 (10 -7) 0.0000001 0.0000001 (10 -7)
concentrations, let’s explain what these 8 (10 -8) 0.00000001 0.000001 (10 -6)
mean. 9 (10 -9) 0.000000001 0.00001 (10 -5)
10 (10 -10) 0.0000000001 0.0001 (10 -4)
All solutions have compounds within them 11 (10 -11) 0.00000000001 0.001 (10 -3)
that form ions. Ions are charged particles 12 (10 -12) 0.000000000001 0.01 (10 -2)
that have either gained or lost electrons. 13 (10 -13) 0.0000000000001 0.1 (10 -1)
The rate at which these ions gain or lose 14 (10 -14) 0.00000000000001 1 (10 -0)
electrons is determined by the compounds
in solution. These ions allow electrical Based on the Nernst formula, changes in If the temperature effects of the glass
energy to be passed through the solution temperature, when all other variables are electrode were left uncompensated for
and so the ions act as a conductor. known, will alter the output of the glass within the circuitry of the pH analyzer,
pH electrode. At 77°F (25°C), this output is temperature would cause large errors in the
In mathematical terms, the dissociation calculated as 59.16 mV per pH unit. At 77°F measurement as shown:
constant for water (KW) tells us that in (25°C) and pH 7, the electrode produces 0.0
aqueous solutions the product of (H+) and mV output, the isopotential point, and no @ 77°F (25°C) = 59 mV per pH change
(OH-) (at 77°F/25°C) always equals 10 -14. change with temperature. For every decade @ 32°F (0°C) = 52 mV per pH change
of pH change thereafter, the output changes @ 212°F (100°C) = 74 mV per pH change
KW = (H+) (OH-) by ± 59.16 mV. Since pH has a negative
slope, as the pH increases, the mV potential In a 4 pH solution at 32°F (0°C), the
The Nernst Equation and temperature decreases. indicated pH would be -21 mV in error and
compensation that equates to approximately 0.3 pH units
As stated earlier, the pH sensor output is for a reading of 4.3 pH. In a solution of 11
temperature dependent. As temperature pH and 212°F (100°C),
changes, so does the pH sensor’s millivolt the indicated pH would be
output. Specifically, the electrode produces -45 mV in error and that
more millivolts/pH as the temperature equates to approximately
increases, and as the pH goes further in 0.6 pH units for a reading of
either direction from 7 pH. This change 10.6 pH.
is predictable and linear, and can be
compensated for in the pH analyzer by
using the Nernst equation in the circuit 0 pH = 414.12 mV
design. The Nernst equation is a general 1 pH = 354.96 mV
mathematical equation that describes and 2 pH = 295.8 mV
predicts the pH electrode’s output based
3 pH = 236.64 ACIDIC
on a number of factors, all of which are
constant, with then just one variable, 4 pH = 177.48 mV
temperature. 5 pH = 118.32 mV
6 pH = 59.16 mV
The Nernst equation is stated as:
Vertical shift of ISOPOTENTIAL ERROR in temperature 7 pH = 0.0 mV NEUTRAL
U = U0 - 2.3RT • H+ compensation corrected by standardization 8 pH = -59.16 mV
nf 9 pH = -118.32 mV
Figure 2. Theoretical mV output of a pH sensor @ 77°F (25°C)
10 pH = -177.48 mV
where:
11 pH = -236.64 mV ALKALINE
U = sensor voltage 12 pH = -295.8 mV
U0 = voltage at 7 pH
13 pH = -354.96 mV
R = gas constant
T = absolute temperature (Kelvin) 14 pH = -414.12 mV
n = load of the ion (H+ = 1)
f = Faraday constant
H+ = activity of the ion


Solution temperature compensation a one piece body known as a combination The active electrode is usually constructed
It should be noted here that the Nernst pH electrode or sensor. For very specialized with the tip of the electrode being a pH
compensation factor is for the effects measurements and in the laboratory, sensitive glass (a bulb, dome or flattened
of the pH glass responding differently there does exist separate electrodes or surface) blown onto a stem of more or less,
to temperature changes as temperature electrode pairs for the active, reference and standard type laboratory glass.
effects the glass’s ability of ionic transfer. temperature measurements, but for the
This is not the same principal as solution purposes of this document, we will only be
temperature compensation. Solution detailing the combination pH sensor. Figure
temperature compensation is based on the 3.0 shows a sensor broken down into its
fact that as solutions are changing with active and reference electrode components.
temperature, their pH also changes (changes There are some pH sensors that do not use
of the hydrogen ion (H+) activity). This a glass measuring electrode (ISFET and
change, usually in % / (°C) is solely based Antimony), and those will be discussed in
on the characteristics of the chemistry more detail later on.
of the solution and not that of the glass’
response to temperature change.

pH sensor theory
We can think of a pH sensor in similar
fashion to that of a battery. A battery
(also known as a galvanic cell) converts
chemical energy to electrical energy via two
half cells connected across a conductive
electrolyte. The battery has a positive
electrode (cathode), and a negative electrode
(anode). These electrodes do not touch each
other but are electrically connected via the
electrolyte.

Each half cell produces an electromotive


force (emf). The sum of these forces is the
total voltage output of the battery. As an
example, a fresh AA battery produces about
1.55 volts DC.
Figure 3. pH electrode assembly

Terminology:
The terms sensor and electrode can
be used interchangeably. Some would
When the pH sensor is immersed into the Glass formulation:
argue that a sensor is a completed
solution to be measured, (think of this as
assembly consisting of two or more It is the recipe or formulation of this
the battery’s electrolyte), the circuit loop is
individual electrodes. One usually refers pH sensitive glass that is at the heart of
completed and current is allowed to flow
to the device that measures pH as a pH the measurement. Various components
between the active and reference electrodes,
sensor, but the term pH electrode is also are used for the make-up of the glass.
and thereby generating a small millivolt
acceptable. Predominately silicon dioxide is mixed
potential (combined output emf). When
In theory, two specific isolated pH this signal is connected to a pH analyzer, with other modifiers such as lithium
electrodes, the active electrode and the analyzer measures the overall potential oxide, cesium oxide, barium and
reference electrode, comprise to make a and converts it to a pH reading for display other chemicals to produce a specific
pH sensor. Combination pH sensors are or re-transmission. Because the voltage and formulation to meet the manufacturer’s
a one piece body comprising the active current flow are very small, the reaction of exact specification. Each manufacturer
and reference electrodes, hence the term the electrodes and their chemical balance has its own closely guarded recipes and
sensor, or electrode. Clear as mud? are allowed to continue without adverse feels that theirs is the best formulation for
reaction. a specific measurement need.
The pH sensor operates in a similar fashion
to the common battery as it also produces Active electrode
as a result of an electrochemical reaction A pH sensor’s active electrode, also known
separate emf potentials from its positive as the measuring electrode is the work
and negative electrodes called the active horse of the total assembly called the pH
(+) and reference (-) electrode. Most pH sensor. It is this portion of the sensor that
sensors in use today are comprised of a glass does the real measuring. Without it, the
measuring electrode and varying designs of measurement could not take place, and
a reference electrode both integrated into even with it, the measurement is almost too
fragile to be made.


Glass membrane its work. Because the pH electrode is taken out from extremely hot processes
Gel layer: specifically designed to measure hydrogen for calibration only to be submerged into
thickness:
1000 A ion activity, immediately after immersion, cold rinse waters or buffers. This sudden
0.2-0.5 mm
a galvanic potential is formed, based on the temperature change has been known to
Nernst equation, due to charge exchanges fracture or crack the glass. Sometimes the
between a now formed hydrated outer gel cracks or fractures are so small they are
Acid + Internal Alkaline
buffer - solution
layer surface on the glass electrode and its hard to see, other times, the glass may
solution + - pH > 7
inner gel layer surface. shatter completely. Within many processes,
pH < 7 + pH 7 - solids may be present in such magnitude
+ -
+ -
As the inner fill solution is at a pH of 7, any as to not only coat the glass, but break the
difference in the outer solution’s pH will glass from shearing forces or have solids
generate an unequal potential of hydrogen that are big enough (chunks) that when
ions. The hydrogen ions (charges) move the sensor is installed in a pipeline, these
Figure 4. pH glass electrode through the glass layers until they come chunks flow through the piping and impact
to equilibrium). It is this potential that the glass like a bullet.
produces the emf output of this electrode
through the glass, KCl solution and then It is for these reasons that specialty glass
Glass impedance through the silver/silver chloride wire to is constructed and frequent calibrations of
At 77°F (25°C), a glass electrode has very one input of the pH analyzer. The reaction the pH sensor are necessary. Imagine you
high impedance, and varies by manufac- ceases once the charge transfer (difference are in your kitchen preparing the evening
turer, anywhere from 20 to 1000 megohms. in hydrogen ion activity) is enough to cancel meal. You can see everything around you
Ranges between 200 and 800 megohms of out the tendency for the reaction to occur. in vivid color and clarity. Now you pick up
impedance are typical. As mentioned, glass It is at this point that the emf output is an especially juicy, ripe lemon and slice
impedance changes with temperature. As constant. it in half to pour over your flounder. But,
a general rule of thumb, for every 14.4°F just as you cut into it, you get sprayed in
(8°C) change in temperature, the glass Active electrode issues and concerns the eyes. What happens to your vision?
impedance doubles as the temperature Think about what you are asking your Because of the acid in the lemon, for a few
decreases, and glass impedance halves as active electrode to do. Yes, it is to measure seconds, you can’t see, your eyes burn and
the temperature increases. pH. But the pH of what? Drinking water? they immediately start to tear up. This is
– no real problem but what about plant analogous to a pH sensor in the process
Glass Impedance Temperature effluent from a hazardous chemical waste - think of the pH sensor as your eye ball.
(Megohms) °F (°C) disposal company? These are two extremes, Depending on the process, it may take a
but two very real measurement needs. while for the sensor to come to equilibrium
The drinking water application is fairly and adapt to its surroundings.
1000 64.4 (18) benign. It is usually around 7 pH, so the
500 77 (25) electrode is not working very hard since its Hydrofluoric Acid (HF):
250 91.4 (33) isopotential is also at 7 pH. The temperature
is usually ambient, more towards the colder Hydrofluoric acid (HF) is a common acid
side 50°F (10°C) to maybe 75°F (23.9°C), in the process industry and is either
In terms of pH error on uncompensated used as a reagent or is the by-product of
temperature changes, the error is fairly and pressures are usually well within the
sensor’s range, so no real issues. a process. HF will attack the measuring
consistent at 0.003 pH / (°C) / pH. This is glass electrode and over time, etch
to say that if the pH sensor were calibrated away layers of glass, making the glass
at 77°F (25°C) and the sample to be As for the chemical waste disposal
application, the pH could be anything thinner, more brittle and more subject
measured were at a pH of 4, and 73.4°F to breakage. Glass electrodes should not
(23°C) and not compensated, the error from very acidic, 0-2 pH to something very
alkaline, 11 pH or higher. Temperatures be used where HF acid is present and the
would be 0.018 pH (0.003 x (2°C) x 3 pH pH value is less than 6.5 pH. Specialty
units). At or near 7 pH, the error is fairly could be very hot, perhaps 200°F (93°C)
or more, and if the sensor is in a pipeline, sensors using Antimony electrodes can be
insignificant. Let’s examine the error with used in some of these applications. Above
the following conditions: the pressures could be at 100 psi or greater.
Imagine what is happening to the glass 6.5 pH, the HF acid content is not strong
when exposed to these extremes. In order enough to do damage to the glass.
- Calibrate the sensor in 7 buffer at 77°F
(25°C) for the glass to do its job, it must be clean
and allow the migration of hydrogen If the measuring glass is exposed to grease,
- Measure the process pH with active oils or fats, the glass will become coated and
temperature compensation (=3 pH) ions across its geometry. If the glass
becomes coated, or the gel layer becomes can’t see the process to be measured. The
- Actual process temperature = 131°F (55°C) glass needs to be cleaned to once again be
- In an uncompensated reading, we would disturbed or is eliminated, this migration
is impeded and the signal is not accurate. able to see properly. But what if your process
see a fairly significant error of 0.36 pH and a is continually coating the glass? Well, you
reading of 2.64 pH on the display If the temperature is too cold or too hot,
or fluctuates widely, the ability of the need to continually clean the glass. It’s
(0.003 x (30°C) x 4 pH units) = .36 pH error just the way it is. That’s why pH has been
glass to do its job also changes, and if the
temperature gets too hot, the internal fill described as one of the most maintenance
Active electrode gel layer intensive and difficult measurements one
When immersed into the solution to be solution undergoes changes and may even
come to a boil. Many times sensors are can make.
measured, the active electrode starts


Sodium ion error, Na+ (alkaline error) Because it always changes. Maybe not in the Reference electrodes use salt bridges/
Sodium ion error (Na+) is common laboratory under ideal conditions, but in the junctions that are constructed of Teflon®,
and is only present as the pH rises over real world, when the sensor is in the process ceramic, wood, sintered glass or various
approximately 11 pH. Values of less than and under temperature, pressure and fibers. The salt bridges, being porous,
11 pH have very little sodium ion present. chemical attack, it almost never remains as contain an amalgam of solution. This
Sodium ion error exists because the pH a stable signal, and after all, if the reference solution is a mixture of the liquid fill
glass becomes confused. The confusion portion of the pH sensor is not stable, the solution in the reference, usually KCl and
occurs as the glass electrode responds to total output of the pH sensor changes the process that is being measured. Best
and takes into account (or measures) the and then one does not know if this signal case scenario, the fill solution is the only
addition/concentration of sodium ions and change is due to the fact that the actual thing that occupies the spaces in the salt
hydrogen ions within the process. These pH process is changing or the reference bridge/junction. Worst case scenario,
sodium ions are similar in size to hydrogen potential is changing. the spaces in the salt bridge/junction
ions and can be interpreted by the glass become filled with the process which
electrode as an excess of hydrogen ions, The reference electrode is usually adds unwanted potential to this part of
thereby artificially lowering the pH. (The constructed of a glass or plastic stem, an the measurement leg. The varying of the
higher the H+ concentration, the lower the internal fill solution of a buffered 3.0 or 3.5 porosity of the junction allows for varying
pH). Sodium ions penetrate the molecular molar KCl solution, either a liquid or gel, leakage rates of the filling solution into the
structure of the glass electrode’s silicon- and a silver/silver chloride wire. process being measured. Some reference
oxygen amalgam, and form an asymmetry electrodes also use an open junction or
potential difference (the difference in open aperture. As the name implies, this is
potential) between the inner and outer a junction that has only a small weep hole
layers of the glass, causing an offset error. Reference which allows the reference solution or gel
Potential EREF
to gradually leak out, and in theory does
As sodium ion error only occurs at the high not allow process to back into the reference
end of the pH scale, above 11 pH, most and cause contamination. The site at which
general purpose electrodes function well at the reference solution and process meet is
this level. Above 11 pH, one should consult then the junction. This style of reference
the sensor manufacturer for a specific type Liquid system is deployed when the process to be
of pH sensor that uses low sodium ion error Junction measured is heavily soiled, or in the case of
glass. This glass is specially designed and Potential ultra-pure water applications.
Ej
has little sodium ion error at or above 11
pH. Process When electrically connected to the
measuring electrode through the process
Be aware that even Na+ resistant pH solution (electrolyte), this reference
glass may be compromised by exposure E = EpH - EREF + E j produces its own emf. This output is
to amounts of 1-4% caustic. This will also dependent on the chloride concentration
depend on the temperature of the process. and the ability of the salt bridge/junction
Figure 5. pH reference electrode
At ambient temperatures one might expect to remain neutral (in resistance) to the flow
the reference electrode to be the limiting of electrons and ions. Remember, we don’t
This is the same setup as the active
factor (junction potential error), but at want this reference electrode to change, so
electrode with one exception. Instead of
elevated temperatures (>150°F /66°C) the if we used another pH sensitive glass in the
a pH sensitive glass bulb blown onto the
glass itself becomes the limiting factor. place of the junction, it would change as the
end, the reference uses a porous junction,
process changed. Instead, the porous liquid
also known as a salt bridge or diaphragm,
To summarize, glass electrodes are junction provides electrical contact with
to achieve electrical contact with the
influenced and affected by: the process and at the same time, keeps the
measuring solution. The junction’s sole
process outside of the internal reference
job is to keep the reference electrolyte in
1. Coating assembly. Process can not be allowed
the reference, keep the process out, and
2. Excessive temperatures, either low or to disturb the reference electrode as its
maintain a constant and stable flow of
high and/or large temperature swings chemical reaction must remain constant and
electrons. The typical impedance of the
3. Excessive pressure provide a reliable unchanging output. The
reference system varies from 1000 to 5000
4. Extreme pH values either low or high reference electrode’s output is not affected
ohms as opposed to the active electrode
5. Solids present in the process by changes in process temperature since it
(previously discussed) which varies from 20
6. HF acid uses no glass.
to 800 megohms.
Reference electrode assembly There are various styles of reference
The majority of pH sensor errors and
The active electrode couldn’t do its job electrodes. Some involve gels or liquids
problems can be traced directly back to
if it were not for the reference electrode. and some are internally pressurized, while
the reference electrode. These errors come
Remember, we need two halves to this others use a reservoir with tubing to
from one or all of the following: junction
pH battery, and the reference provides our provide constant flow through the junction.
plugging, junction coating, (liquid junction
other half. The name reference is really There exists a wide variety of reference
potential errors – more on this later on),
a misnomer however. Whoever named electrode filling solution and junction
contaminated fill solution and damage/
this the “reference” should be shot. Why? combinations. Here is a case where one size
attack of the silver/silver chloride reference
does not fit all.
wire.


Junction potential PTFE junction (double junction)

A very common ailment in the electrolyte electrolyte chamber


measurement of pH is the potential (error) chamber
filled with KCl
filled with KNO3
Pt 100
that develops at the reference junction.
This error is the result of dissimilar ions
in the reference electrode fill solution
(usually KCl) and the process. If one were
measuring a process of KCl similar to the
PTFE
reference fill solution, theoretically no ionic Fixed cable Reference lead junction
error would be present. As this is usually
pH-sensitive
not the case in real world applications, glass membrane
a potential develops across the junction
caused by the differences in diffusion rates Figure 6. Double junction pH sensor -
construction model CPF81
of the chemistries across and through the
junction. This results in an error or voltage
offset of the reference electrode, which is
part of the overall signal and is measured Other types of pH sensors 2) is formed, i.e. a drain current (ID) is
by the pH analyzer. This offset can look to induced.
the pH analyzer as a drift in pH readings, ISFET
or sometimes it can be a steady state signal. Ion-selective, or more generally ion- With the ISFET, the medium is in direct
Either way, it is an error. sensitive field effect transistors (ISFET) were contact with the gate isolator layer.
developed in the 1970s as an alternative to Therefore, H+ ions available in the medium,
Methods to correct this problem are varied the glass electrode for pH measurement. which are located in the medium/gate
and are usually able to be overcome once Since no glass measuring electrode is used isolator boundary layer, create the electric
there is an understanding of the chemistries in this type of sensor, it is a perfect fit for field (gate potential). Depending on the
involved. Each manufacturer may have processes where glass breakage would be a effect described above, an N-conducting
their own solution(s) to this issue ranging hazardous condition such as in the food and channel is formed and a current between
from a different type of junction material, beverage industry, or where solids in the “Source” and “Drain” is induced. Suitable
to the use of a double junction or triple process wreak havoc with glass breakage in sensor circuits use the dependence on the
junction reference assembly or a pressurized heavily soiled industrial applications. ion-selective gate potential to create an
free flowing reference/junction assembly. output signal proportional to the
The latter version helps to eliminate the concentration of the ion type.
possibility that process works its way back
up the reference junction (salt bridge) and pH selective ISFET: The gate
contaminates the inner fill solution. isolator serves as an ion-selective
layer for H+ ions. The gate isolator
A typical and known problem of reference is impermeable to the ions as
error or poisoning is one of sulfides in the well (isolator effect) but allows
process. Sulfides react with KCl (the fill reversible surface reactions with
solution in a typical reference electrode), the H+ ions.
and forms a precipitate in and on the salt
bridge, thereby clogging the salt bridge, Depending on the acidic or alkaline
changing its potential (resistance) and Figure 7. ISFET pH electrode
character of the measurement
providing false data (voltage) back to the pH solutions, functional groups in the isolator
analyzer. A cure to this ailment is a sensor surface accept or reject H+ ions (amphoteric
with a double junction reference electrode Ion-selective field effect transistors use a character of the functional groups). This
that uses a potassium nitrate (KN03) fill transistor arrangement where the metallic leads to a positive (H+ acceptance in the
solution (this solution will not react with gate is not a control electrode. Instead, the acidic medium) or negative (H+ rejection
the sulfides and cause a precipitate) and a medium in the ISFET is in direct contact in the alkaline medium) charging of the
Teflon junction at the sample interface, and with the gate isolator layer. Two strong isolator surface. Depending on the pH
then transitions to a second junction and N-conducting areas are diffused in the P- value, a defined surface charge can be used
then finally to the KCl solution as shown in conducting substrate of the semiconductor to control the field effect in the channel
the following figure. material (Si). These N-conducting areas between “Source” and “Drain”. The
are a current supplying “Source”, S) and processes which leads to the creation of a
current accepting (“Drain”, D) electrodes. charge potential and therefore to a control
The metallic gate electrode (in case of the voltage UGS between “Gate” and “Source”
MOSFET) resp. the medium (in case of the are described with the Nernst equation:
ISFET) forms a capacitor with the substrate
below. A potential difference between UGS =UO + 2.3 x RT x lg a ion
gate and substrate (UGS) causes a higher F
electron density between “Source” and
“Drain”. An N-conducting channel (pos.


Antimony • Coating of glass Calibration is accomplished when
Antimony pH sensors are identical to glass • Plugging of liquid junction after immersion into buffers the sensor
pH sensors with the exception that the • Flow velocity consistently reads less than ± 0.1 pH
active or measuring electrode, instead of • Conductivity of solution difference in the given buffers. Some users
being made from pH sensitive glass, it is – Flow velocity may expect the sensor to have greater
made from a noble metal, antimony. The – Static Electricity accuracy in buffers, and it may, but this
antimony electrode has and creates a similar – Ion cloud will require considerably more care and
output to glass electrodes as it relates to • pH sensitive glass membrane (gel) attention to the calibration procedures as
hydrogen ion concentration. That is to say – Abrasion well as the overall accuracy of the buffers.
that an antimony electrode responds to – Drying
changes in hydrogen ion activity, but within – Aging The first step in calibration is to determine
a defined linear range, from about 4 to 9 • Poisoning of reference the isopotential point (also known as the
pH, and with a somewhat slower speed of • High impedance cable issues zero point) of the sensor. This is the point
response. If measuring a pH value outside • Sensor placement/orientation at which theoretically, the sensor produces
the 4 to 9 pH range, the sensor appears non- • Cable length a 0.0 mV output at 7 pH. Since this is rarely
linear and may in fact never reach the actual • Preamp location the case, an isopotential point needs to
reading. Within the linear measuring range, • Analyzer location Hazardous area be established. The sensor is placed in a 7
antimony sensors may be used when a high classifications (if any) pH buffer and its signal output is allowed
degree of accuracy or speed is not needed. • Location of sensor for ease of to come to equilibrium (both the pH/mV
maintenance/calibration output, as well as the temperature output).
Antimony is used where there exists in the Once the pH reading has stabilized,
process fluid to be measured, significant Calibration using buffers the voltage output is entered into the
concentrations of hydrofluoric acid In theory, the output of a pH sensor is only pH analyzer and an “offset” number is
(HF). As HF is used in the manufacture dependent on the concentration of the H+. established.
of glass, it has a very adverse effect on In the real world however, there are many
glass; it consumes it, actually eating away factors which impact the output of the pH The second step is to rinse off the pH sensor
the various layers of conventional glass sensor. Differences in potentials between in deionized, distilled, or tap water and dab
measuring electrodes. In processes where the measuring electrode and the reference it dry.
HF may be present in both cumulative time electrode, asymmetry potential across the
and significant concentrations (below 6.5 measuring glass, temperature changes,
Note: Never “wipe” the measuring
pH), an antimony sensor may be an alternate reference junction potentials and reference
electrode using a towel or cloth. Instead,
choice to a glass measuring electrode. electrode contamination. So, how does
dab or blot the electrode as wiping the
Note however that antimony pH electrodes one know what the actual pH is when
glass may create a static charge and make
should not be used, in any case, in food the sensor is in the process? The sensor
the measurement unreliable until the
or beverage applications as antimony is a must first be calibrated and then properly
charge dissipates.
poisonous material and considerable care maintained and calibrated over its lifetime.
must be taken in handling of and disposing
The third step is to place the sensor in the
of antimony electrodes for health matters. Calibration is accomplished by using
second buffer to establish the slope (span)
a set of calibration buffers which are
of the sensor. This second buffer is a matter
General issues concerning the sensor traceable to a governing body for accuracy
of debate however. This buffer should be
The combination pH sensor is expected to purposes. Buffers exhibit the quality of
at least two units of difference from the
be fast responding (90% step change in 10 being accurate and stable over time and
standardization buffer, if not three, and be
seconds or less), accurate, repeatable and are resistant to contamination by other
a buffer that is not subject to contamination
long lasting. It relies on the premise that its chemicals. Typically, a 7 pH and then
by C02. The user may also want the second
reference is stable and free flowing and that either a 4 pH and/or a 10 pH buffer are
buffer to be in close proximity of the actual
the glass remains hydrated. Since the sensor the buffers of choice. Other buffers are
solution to be measured. Typically, a 4 pH
has a lot of work to do, and in a precise way, available, for instance 6.98 pH or 9.75 pH
buffer is the buffer of choice as it does not
it stands to reason that it must be well cared and others, depending on the supplier
have the ability to be readily contaminated
for. Also, the application for the intended one chooses. Calibrations should be done
by C02 intrusion as 10 pH buffer does, and
use of the sensor must be well understood at or near 77°F (25°C) for best accuracy.
the pH output of the sensor (in terms of
as well as the dynamics surrounding the Since most pH analyzers and sensors are
work or absolute mV output) in 4 pH buffer
sensor’s health and well being. Here are temperature compensated, this is not a
equals that of 10 pH buffer.
just a few, although major items one must huge issue as the instrument will measure
consider and take into account before the temperature of the buffers and do an
Some users may be operating in the higher
delving into a pH measurement: internal correction. But for best accuracy,
pH ranges (above 7-9 pH) and may feel that
and since the pH of the buffer does change
the calibration/span of the pH sensor in 7
with temperature, and most bottles of buffer
and 4 pH buffers is not sufficiently accurate.
have a temperature correlation table printed
If so, a simple calibration check in 10 pH
on them, the exact pH value should be
buffer may be an option. The ultimate
entered into the pH analyzer based on the
sensor reading in the 10 pH buffer (± X.XX
buffer temperature.


pH) will then have to be determined by sensor. If after inspection you find no debris The frequency of cleaning and the best
the user. If further refinement/accuracy or fouling with the naked eye, rinse the methodology for cleaning can only be
is needed, a sometimes long and tedious sensor off in distilled water and perform a determined by the operator. This frequency
routine may have to be implemented to get buffer check. That is to put the sensor in is best adjusted by checking the sensor after
the pH sensor to agree, or at least be close in the calibration buffers you typically use and an initial operating time in the process,
all three buffers. note the readings. If they are close to the perhaps 12, 24 or even 48 hours – again
calibration numbers your procedures call experience is the key. Keep an eye on the
Note: pH 10 buffer is not a long-term for, let us use ± 0.2 pH as an example, leave pH value the sensor is providing and how
stable buffer. Left exposed to the the sensor as is and re-install it. Repeat this value relates to what the theoretical pH
atmosphere, 10 pH buffer can be easily this exercise every few days until you see a is supposed to be.
contaminated by the absorption of C02 change in either the level of debris/foulant
(lowers the actual pH value) and therefore on the pH sensor, more than the ± 0.2 pH Remove the sensor from the process and
yields an inaccurate result during as in the example above or a step change in rinse it in warm tap water. Check the
calibration. Over time, C02 molecules will the zero or slope numbers. probe in calibration buffers and determine
also diffuse through the sealed plastic whether the values are consistent with
containers that the 10 pH buffer is stored To a certain extent, this sets the benchmark the initial calibration or your company’s
in. Your calibration is only as accurate as for time between cleaning/calibration. standards and guidelines for good
your buffers and techniques. Now you need to determine whether the manufacturing practices. If the readings
sensor needs just a cleaning or a cleaning are within acceptable limits, re-install the
Once the sensor’s signal outputs are and re-calibration. This is done easily by sensor and repeat these steps in another
stabilized, these values are entered into first making sure the sensor is clean. (Refer 12 or 24 hours. Once you have found a
the pH analyzer, and then the sensor’s to the section on Cleaning pH sensors). time base which relates to the shift in the
slope is calculated. This number, as well It may be as easy as rinsing the sensor in calibration numbers that deviate from your
as the offset number, are now the official water or as complicated as using acid or standards and guidelines, you have set your
calibration values of the sensor and are caustic solutions to remove the particular cleaning/calibration frequency.
the benchmark for all future measurement contaminate build-up that has occurred.
values, until the next calibration. In general, the following is the
Cleaning pH sensors recommended cleaning agent vs.
In practical terms, the average usable output For your pH sensor to maintain an accurate contaminant:
of a pH sensor in the zero point buffer of reading of the process pH it is supposed to
7 pH should be between ± 30 mV and be measuring, the pH sensor must remain CONTAMINANT CLEANING SOLUTION
have a slope value (in a standard buffer clean. Specifically, the glass measuring
Alkaline or Scale 5% hydrochloric acid or
solution at least three pH units from the electrode can not become coated and
vinegar
standardization/zero point buffer) of not reference electrode assembly must not
become coated, plugged or otherwise Acidic Coatings Weak caustic (less than
less than 52 mV/pH. Numbers outside these
contaminated by the process solution. 4% NaOH)
ranges indicate a dirty, contaminated, or
worn out pH sensor. Herein lies the paradox however; if one Oil, Grease, Detergent or if coating
subjects the pH sensor to the process and Organic is tenacious, an organic
Calibration – Calibration check the process is coating the electrode, how solvent compatible with
– Cleaning can one expect the sensor to do its job? sensor material
Once your pH sensor is installed in the Well the answer is simple, do what it takes
process and operating, how do you know to keep the sensor clean. The following steps are typical of a general
when it is time to take it out of the process cleaning procedure:
and do a cleaning, or a calibration? Do you In general terms, if the pH sensor has a
perform both a cleaning and a calibration or slight coating or scaling, this might be • Keep sensor as reasonably clean as
just a cleaning, or just a calibration, or do removed using a water jet from a faucet possible. Time intervals between
you just make a calibration check in buffers or spray bottle. The author has seen cleaning are process dependent and are
or…..? successful use of an electronic spray jet determined by experience
originally intended for oral hygiene use. • Remove the bulk of contaminant by
This is something that can be quite More entrenched coatings may require the carefully blotting/wiping away debris.
confusing, especially when the operational use of a gentle acid brush or tooth brush to Be careful not to rub too vigorously as
practices and procedures laid out for you carefully remove the coating. Depending on this may cause static charge
by your company’s QC or environmental the nature of the scale or coating, you may • Rinse the sensor in warm tap water or
department may not be specific enough, or find it necessary to dip the brush in a 2% distilled water
inversely, too specific, outlining far more HCl acid solution and then lightly scrub the • Prepare a cleaning solution containing
procedural than actually required. electrode for a few seconds or so to facilitate a soap and water mixture. Use
cleaning. Immediately after one of these dishwashing detergent and warm water.
In practical terms, users must develop steps, one should let the pH sensor soak in Use only soaps that do not contain
their own maintenance and calibration tap water or a 7 pH buffer solution to allow abrasives or lanolin. Some choices may
schedules. This is accomplished by taking the pH sensor to stabilize. be Alkanox® lab glass cleaner, Joy ® or
the pH sensor out of the process after a day Dawn® dishwashing detergent
or two and make a visual inspection of the


• Soak the sensor in this solution for up as they will not remove the soap (or The optimum storage environment for pH
to five minutes and then gently or while any alkaline cleaner for that matter). If sensors is a temperature of ~10 to 30°C
soaking, use a soft bristle brush to gently your tap water is soft, you may have to (50 to 85°F) and some type of hydrating
scrub the bulb and reference area of the neutralize the soap with an acid, or take solution. Most manufacturers of pH sensors
sensor it off with a soft cloth or towel (see note ship the sensors with protective caps
• Rinse the pH sensor in warm tap water on using cloths and soft brushes to clean containing a hydrating liquid. Keep such
and standardize the sensor in buffer ISFET sensors). caps intact with an adequate amount of fill
solutions 2. To remove alkaline or hardness solution as the manufacturer recommends.
scales use a weak acid. White vinegar Some users prefer to use a large storage
Should these steps not produce adequate (acetic acid) works well as does weak vessel (large plastic pail) to house numerous
results: hydrochloric (HCl) or phosphoric (H3PO4) sensors for a central location and fast turn-
acid. Let the sensor soak in the solution around time. The pH sensors are immersed
• Soak the sensor in a 5% to 10% HCl acid while periodically swishing the sensor in into the liquid and it should be easy to see
(or similar dilute acid) solution for a few the solution. that the liquid level is at height needed
- less than five - minutes. Do not use this 3. To remove proteins, add a bit of an to keep the wetted end of the pH sensor
procedure if the sensor has been used in enzyme like Pepsin to a 1M HCl solution submerged.
a solution containing cyanide as this may (about 3.6% by weight). Let the sensor
produce poisonous cyanide gas. Always soak while periodically swishing the Recommended pH sensor storage solutions:
consult a chemist if you are unsure of sensor in the solution
chemical reactions that may cause harm 4. For oils and greases put the sensor in 1. 3 to 3.5 molar KCl solution
to your person Methanol (methyl alcohol) or Isopropyl 2. pH 4 buffer
• Rinse the sensor in warm tap water and Alcohol (isopropanol) and let it soak for 3. Distilled water
then place the sensor into a mild soap a few minutes. You may need to use a 4. pH 7 buffer
solution for a minute or two to neutralize soft cloth or brush to loosen and remove 5. Tap water (softened)
any remaining acid and let the sensor heavy deposits (see note on using cloths
come to equilibrium and soft brushes to clean ISFET sensors). De-ionized water should never be used as a
• Rinse in warm tap water and standardize storage solution for pH sensors. A pH sensor
the sensor in buffer solutions AFTER CLEANING: Put the sensor back stored in this solution will be continuously
in a buffer or the process to let it recover leaching out ionic species to the greater
Consult a chemist to be sure you are using from the cleaning. It will take at least 5 and volume of de-ionized water. In essence, it
the proper chemicals for cleaning and not perhaps as many as 15 minutes to recover, will be drained of its life blood, H+ from the
generating hazardous chemical reactions. especially if a cleaning brush or cloth was glass electrode and KCl and Ag/AgCl from
used. the reference electrode.
Caution: NEVER clean a sensor that was
used in a cyanide destruct system using Note: On using cloth or soft brushes: Should your pH sensor be found to have
acid. Dangerous and lethal hydrogen Sometimes you need to use some elbow- been left dry for a period of time, it may
cyanide gas may be produced causing grease to clean things. With an ISFET be rejuvenated by soaking it in one of the
serious injury or death. Consult a chemist sensor elbow grease is not advised. solutions mentioned above for a few minutes
to be sure you are using the proper However, you can gently clean the ISFET to a few hours or perhaps overnight,
chemicals for cleaning and not generating area with a soft toothbrush or cloth. Do depending on the amount of time the sensor
hazardous chemical reactions. not get too vigorous with the cloth or has been left to dry out.
brush as you do not want to scratch the
Cleaning ISFET sensors ISFET. Rinse thoroughly and give the Transporting a pH sensor
Cleaning pH sensors is a necessity. The sensor at least 5 minutes of recovery time. Do not allow pH sensors to freeze. When pH
difficulty in writing instructions on how sensors freeze, the solution inside them also
to clean a pH sensor is that there is no Sensor Storage freezes causing the glass to crack. Whether
universal cleaning agent, nor is there a pH sensors need to remain hydrated. The you are taking a pH sensor from its storage
universal procedure. How a sensor should glass electrode, if left to become dehydrated, facility to its ultimate measurement point
be or needs to be cleaned (as stated above, will show higher electrical impedance from within your facility, storing it overnight
there is a difference between should be and the norm and will react much slower to pH for the next day’s use or sending a sensor
needs to be…) it depends on what foulant is changes. It may take from a few minutes to another location, caution should be
on the sensor. Here are some guidelines: to hours or even days for the sensor to observed. Make sure the pH sensor is
regain its original operational performance, always subjected to a climate controlled
1. A good general cleaning agent is if ever. Repeated cycles of hydration and environment, even when shipping it cross-
dishwashing soap, one with good grease dehydration will significantly shorten country. Confirm that any third party
cutting ability (Dawn and Joy work the pH sensor’s useful life. The reference shipper uses climate controlled vehicles and
well). Dilute the soap with water per electrode is also affected by dehydration. storage facilities.
normal use and let the sensor soak in the If left dry, salt from the internal KCl fill
solution for a few minutes. Agitate the solution will form salt crystals on the outer Caution: Do not allow pH sensors to
sensor in the solution periodically. Then surface of the junction and thus cake the freeze. When pH sensors freeze, the
rinse the sensor thoroughly to remove junction and ultimately the junction may solution inside them also freezes causing
the soap. Do not use DI, RO or soft water siphon out all its fill solution. the glass to crack.

10
Some larger plants store their gear, such location to optimize process control, but Insertion – A sensor or hardware assembly
as tools and spare parts in maintenance mechanically, this location may not allow that is intended to be pipe mounted as
vehicles that are driven on site. Storing of adequate conditions for the pH sensor to above, but with the added capability of
pH sensors in these vehicles is not a good do its job. Even though the sensor may being able to insert and remove the sensor
idea because in northern climates, these be installed in its correct orientation, the while the pipe is under full operating
sensors may freeze and break. piping layout may cause other problems conditions. This is typically accomplished
such as: using a ball valve or retractable assembly
Sensor mounting and installation which effectively isolates the process when
- The fluid flow may be too fast. Flow rates the sensor is pulled out for inspection,
ORIENTATION - There are certain should be less than 10 ft per second and cleaning, calibration or replacement.
guidelines one must follow to insure that much less so for viscous and/or abrasive
the pH sensor is installed into the process fluids Submersion – A sensor or hardware
connection properly in order for the pH - The mounting hardware isn’t sized assembly that is intended for mounting a
sensor to do its job. In many instances, the correctly. The mechanical mounting sensor directly into (submersion) a tank,
only problem associated with a particular hardware for the sensor may be keeping trough, pond or other non pressurized
pH measurement point is the way in which the sensor tip too far out of the process volume of fluid. Typically a sensor in this
the sensor has been installed. flow and it may be sitting in a void within configuration is suspended into the process
the hardware itself via rigid or flexible piping, or suspended
As described earlier, pH sensors are - The pipe isn’t full. The sensor may be with lanyard wires or cable supports.
comprised of two electrodes, an active and installed vertically in a horizontal pipe
a reference. Most often, these electrodes use run but the pipe and flow through it, has Connectors, cables and preamplifiers
liquid fill solutions. When manufacturing no back pressure, it is not full of solution, Because the impedance of the pH sensor
these electrodes, an air gap/bubble is and the sensor is reading in air. is very high, make sure the sensor you use
incorporated to allow for expansion of has cables and connectors of the highest
the electrolyte fill solution under high In general, pH sensors should be installed quality. Why? Because any degradation
temperatures. However, if the pH sensor with the following recommendations: in a connector or cable, adds resistance
is installed incorrectly, the air bubble and capacitance errors to the measuring
may migrate into the tip of the measuring - Process flow is moving up through the loop and this equates to errors in the pH
electrode, between the internal silver/silver pipe, not downward reading. Gold plated connectors are best,
chloride wire and the inner surface of the - There is sufficient back pressure within and wiring/cable assemblies must have
glass bulb where an open circuit will exist. the piping system to insure that where low signal loss and low EMI/RFI ingress
If this happens, no current will flow and the pH sensor is mounted, that portion of characteristics. Follow the manufacturer’s
any reading displayed on the analyzer is the pipe is always full of solution and no recommendations and instructions for
not meaningful. It is for this reason that air gaps exist proper grounding connections. Never run
pH sensors should be mounted vertically, - The best practice is to mount the sensor the sensor’s signal wire/cable in the same
with the electrode end (tip) facing down. In in a piping goose-neck configuration as conduit as other signals, especially AC
this position, any air bubbles within the pH shown below. signals.
sensor will migrate to the back end, where
they have no interfering effects. Sensor Styles Any moisture that finds its way across the
pH sensors have widely varying styles and sensor’s connections is a recipe for disaster.
If a sensor can not be mounted vertically hardware assemblies depending on the Therefore the use of junction boxes should
and must be mounted at an angle, for specific nature of the intended application. be avoided and make sure to keep all cable
instance mounting the pH sensor into Here are a few common industry terms and glands and connections water tight. Inspect
the side of a tank, it is recommended that their associated definitions: the sensor and any associated interconnect
this angle be not less than 15° from the cable regularly for any tears or gouges in
horizontal. Flow-thru - A sensor or hardware assembly its protective coating. Replace worn or
that is intended for pipe mounting such that broken cables immediately. If junction
PIPING CONFIGURATION – The other the pipe has an opening in it to allow for the boxes are used, make sure they are dry
consideration in pH sensor mounting sensor to be threaded or otherwise mounted and not installed where there is a potential
is where to install the sensor in the in the pipe and into the flow stream. for the junction box to be subjected to
piping run. Users may need to see a process splashing or hose down by cleaning
pH measurement made in a particular personnel.

Situations to avoid

Figure 8. Sensor mounting

11
It is not recommended that the sensor’s of the automobile. Two cars coming off - an offset from the actual pH reading
electrical cable is used for mechanical the same assembly line may appear to be - a drift of the actual pH reading. This
mounting purposes. For example, identical, but sometimes one will exhibit could be an increasing or decreasing drift,
suspending the sensor into a sump or tank problems the other one never sees. and
via the electrical cable puts undue stress on - Isolate the problem sensor(s) and describe can start and stop at any time
the connection at the cable/sensor interface, to the manufacturer what you see. Even - Saturation of the signal to a high or low
and over time any turbulence of the process if it was a “one off” failure, describe level, or to a level anywhere within this
adds cumulatively to the wear and tear what the sensor looks like, is there range
at this connection point. Over time the discoloration in the reference gel? If so,
connection may become loose, and allow describe it in detail, from the color to how You can tell if you have a ground loop by
moisture to get into the connection, making far the discoloration has gone into the placing the pH sensor in a plastic or glass
for a measurement error. There is also the reference. If it is a gelled reference, is the beaker of the process sample and then
added consideration of UV light degrading reference body completely filled with gel ground the solution in the beaker to the
the cable as well as chemical attack of the or are there gaps? process piping. If the pH changes by more
cable by the process itself. All such types of - What does the area look like around the than ± 0.1 pH, a ground loop is present.
mounting methods, should use a secondary reference junction? This is either the
lanyard or piping system to suspend the small ‘hole’ in the side of the glass, a frit, For analog sensor systems, the fix might
pH sensor such that no stress is put on the or annular ring. Is it discolored or is the be as simple as removing any output wires
electrical cable, and keeping the cable out of hole filled with debris? Describe anything from the transmitter (for example the 4-20
harms way from chemical attack. you think is abnormal. mA output) and then determine if the pH
- Does the glass electrode look discolored, value returns to its proper reading. If so,
Preamplifiers are used when the signal coated, or etched? Does it have a crack? a simple current isolator on the 4-20 mA
from the pH sensor to the analyzer exceeds Sometimes cracks develop that can output line will likely fix the problem.
the normal length that the sensor/analyzer only be seen under a microscope. Many
system can withstand (dependent on the times, especially when the glass is wet, If the pH system is running in the single
manufacturer’s specifications). Usually it looks fine. Let the liquid on the glass ended mode (asymmetrical), the reference
this is no more than 33 ft. (10 meters). air dry and then describe it. There will electrode is connected to the ground
Preamplifiers are either mounted in the almost always be deposits on the glass potential of the pH transmitter. A ground
head of the pH sensor, in a termination/ after it dries. If these deposits come off loop will in this example, go straight to the
junction box, or mounted remotely from easily with a finger wipe (or similar light grounded side of the transmitter and present
the sensor, also in a termination/junction physical cleaning) the glass may not be an offset. The fix in this situation would be
box. Here too, it is important to make sure the problem. to configure the transmitter to a floating
moisture is not coming into contact with the - Is there a ground loop? input mode. In this mode, the reference is
sensor connections, or worse, the exposed not grounded to the transmitter’s ground,
electrical components of the preamplifier Ground loops and any potential would be seen equally on
itself. Keep the preamplifier in a clean dry Might your pH system be experiencing both the measuring electrode and reference
environment. a ground loop? Have you ever set up electrode, effectively cancelling out the
a stereophonic sound system using an potential. However, sometimes there may
Troubleshooting pH sensors: amplifier, preamplifier and a turntable? not be a “fix” to the ground loop problem in
Here are a series of questions/thoughts to (Today’s version would be a surround sound the traditional analog pH system.
consider when troubleshooting a pH sensor system comprising an integrated amplifier
or a pH application: and a separate CD/DVD player. This Memosens technology
comparison is for those of you too young to Endress+Hauser has a unique solution to the
- Have there been other pH sensors know what an LP is). If so, that buzz you ground loop dilemma, and most all other
installed in this application and have they might have heard through your speakers analog pH sensor ailments, and that is the
exhibited the same problems, or is this was a ground loop. It is hard to say why it Memosens line of digital pH sensor systems.
the first time a pH sensor is being used? occurred or where it emanated from, but it
If repeated failures of the measurement was there. Data safety through digital data
are occurring, perhaps the application transfer
is the problem, or the particular sensor So what is a ground loop – in simplistic The Memosens technology digitalizes
configuration or mounting is causing the terms, a ground loop is two electrically the measured value in the pH sensor
problem. grounded points with two different and transfers it to the transmitter via a
- If this (these) are “one-off” failures, try a electrical potentials. In the case of pH, the contactless inductive connection. This
second sensor. In theory, all sensors with ground of the solution you are measuring results in automatic error messages being
the same model number are the same, but is at a different level than the ground of generated should the sensor fail or the
the manufacturing of pH sensors is still your pH transmitter’s circuitry, and these connection between sensor and transmitter
considered an art, and not all pH sensors two differing potentials are fighting for become interrupted. The availability of the
are created equal. Every once in a while superiority. This mismatch in ground measuring point is dramatically increased
a pH sensor may check out fine not only potential starts at the pH electrode’s by immediate error detection and the digital
at the manufacturer, but at the customer’s measuring tip and travels down the signals are suitable for applications in
site as well but they only live a short life. cable assembly and finally into the pH hazardous areas; the integrated electronics
The reasons are myriad and tough to transmitter’s input circuitry. A ground loop are intrinsically safe.
figure out if ever. Consider the analogy can cause:

12
Bibliography
Arthur, Robert M. 1982. Application of On-
line Analytical Instrumentation to Process
Control

Bates, Roger G. 1973. Determination of pH,


Theory and Practice

Beckman 1983. The Beckman Handbook


of Applied Electrochemistry. Beckman
Instruments, Inc

Chemtrix. pH in Plain Language

Gray, David M. 1994. On-line High Purity


Figure 9. Memosens
pH Measurement. Leeds and Northrup

data in the sensor allows for calibration Kohlmann, Frederick J. What is pH and
Maximum process safety How is it Measured? GLI International, A
The inductive and non-contacting measured and adjustment away from the measuring
point. pH sensors can be calibrated under Hach Company Brand. Hach Company
value transfer of Memosens guarantees
maximum process safety and offers the optimum external conditions in the
measuring lab. Wind and weather affect McMillan, Gregory K. 1994. pH
benefits of eliminating all problems caused Measurement and Control; Second Edition.
by moisture such as corrosion of the neither the calibration quality nor the
operator. The measuring point availability Instrument Society of America
plug-in connection, loss of signal due to
moisture at the connections (the plug- is dramatically increased by the quick
in system can even be connected under and easy replacement of pre-calibrated
water) and the transmitter is galvanically sensors. The transmitter does not need to
decoupled from the medium thereby be installed close to the measuring point
eliminating ground loops. There is no need but can be placed in the control room.
to specify “symmetrically high-impedance” Maintenance intervals can be defined
or “unsymmetrical” or an impedance based on all stored sensor loaded data and
converter. The cable does not act like an calibration and predictive maintenance
antenna. Thus, EMC safety is guaranteed. is possible. The sensor’s history can be
documented on external data carriers and
Easy handling evaluation programs at any time. Thus, the
Sensors with Memosens technology have current application of the sensors can be
integrated electronics that allow for saving made to depend on their previous history.
calibration data and further information
such as total hours of operation and Communication with the transmitter
operating hours at very low or very high pH Memosens pH sensors must always be
values. When the sensor is mounted, the connected to an appropriate Endress+Hauser
calibration data is automatically transferred transmitter with Memosens technology.
to the transmitter and used to calculate the Connecting a Memosens pH sensor to a
current pH value. Storing the calibration standard transmitter is not possible.

13
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