8/25/2009

pH meter principles

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pH meter principles

pH Meters
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What is pH and how is it

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by Dr J Floor Anthoni (2005)

www.seafriends.org.nz/dda/ph.htm
This document familiarises you
with the potential of hydrogen
(pH) and how it is measured, in
order to gain most from using a
pH meter.
history: how pH meters came about
how a pH meter works: looking
inside a pH meter - principles and
theory
pH scale: the pH scale and the
acidity of typical substances
seawater composition: more about
pH and salinity of the oceans (4
pages)
periodic table of elements with a
primer on chemistry and essential
elements (6 pages)
ocean acidification: how does it
work and how certain are we? What
knowledge is missing? (25 pages)
the Dark Decay Assay: a new
plankton tool to measure the health
of the sea, lakes and rivers. (large)

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Waterproof pocket pH meter
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20050516,20051025,20060415,20060825,20070716,20070822,

History
The history of measuring the acidity of liquids electrically began in 1906 when Max Cremer in his
studies of liquid interfaces [1] (interactions between liquids and solids) discovered that the interface
between liquids could be studied by blowing a thin bubble of glass and placing one liquid inside it
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pH meter principles

and another outside. It created an electric potential that could be measured.

This idea was taken further by Fritz Haber (who invented the synthesis of ammonia and artificial
fertiliser) and Zygmunt Klemsiewicz [2] who discovered that the glass bulb (which he named glass
electrode) could be used to measure hydrogen ion activity and that this followed a logarithmic
function.
The Danish biochemist Soren Sorensen then invented the pH scale in 1909.
Because the resistance in the wall of the glass is very high, typically between 10 and 100 MegaOhm, the glass electrode voltage could not be measured accurately until electron tubes were
invented. Later still, the invention of field-effect transistors (FETs) and integrated circuits (ICs) with
temperature compensation, made it possible to measure the glass electrode voltage accurately. The
voltage produced by one pH unit (say from pH=7.00 to 8.00) is typically about 60 mV (milli Volt).
Present pH meters contain microprocessors that make the necessary corrections for temperature
and calibration. Even so, modern pH meters still suffer from drift (slow changes), which makes it
necessary to calibrate them frequently.
Improvements have also been made in the chemistry of the glass such that pollution by salt and
halogen ions could be halted. The reference electrode, which traditionally used silver chloride
(AgCl) has been superseded by the kalomel (mercurous chloride, HgCl2) electrode which uses
mercuric chloride (HgCl) in a potassium chloride (KCl) solution as a gel (like gelatine). But
electrodes do not have eternal life and need to be replaced when they drift unacceptably or take
unusually long to settle.
[1] Cremer M (1906): Z. Biol, 47, 562
[2] Haber F and Z Klemensiewicz (1909): Z. Physik. Chem., 67, 385

How a pH meter works

When one metal is brought in contact with another, a voltage difference occurs due to their
differences in electron mobility. When a metal is brought in contact with a solution of salts or acids,
a similar electric potential is caused, which has led to the invention of batteries. Similarly, an electric
potential develops when one liquid is brought in contact with another one, but a membrane is
needed to keep such liquids apart.
A pH meter measures essentially the electro-chemical potential between a known liquid inside the
glass electrode (membrane) and an unknown liquid outside. Because the thin glass bulb allows
mainly the agile and small hydrogen ions to interact with the glass, the glass electrode measures the
electro-chemical potential of hydrogen ions or the potential of hydrogen. To complete the
electrical circuit, also a reference electrode is needed. Note that the instrument does not measure a
current but only an electrical voltage, yet a small leakage of ions from the reference electrode is
needed, forming a conducting bridge to the glass electrode. A pH meter must thus not be used in
moving liquids of low conductivity (thus measuring inside small containers is preferable).
The pH meter measures the
electrical potential (follow the
drawing clock-wise from the
meter) between the mercuric
chloride of the reference
electrode and its potassium
chloride liquid, the unknown
liquid, the solution inside the
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pH meter principles

glass electrode, and the potential

between that solution and the
silver electrode. But only the
potential between the unknown
liquid and the solution inside the
glass electrode change from
sample to sample. So all other potentials can be calibrated out of the equation.
The calomel reference electrode consists of a glass tube with a potassium chloride (KCl) electrolyte
which is in intimate contact with a mercuric chloride element at the end of a KCL element. It is a
fragile construction, joined by a liquid junction tip made of porous ceramic or similar material. This
kind of electrode is not easily 'poisoned' by heavy metals and sodium.
The glass electrode consists of a sturdy glass tube with a thin glass bulb welded to it. Inside is a
known solution of potassium chloride (KCl) buffered at a pH of 7.0. A silver electrode with a silver
chloride tip makes contact with the inside solution. To minimise electronic interference, the probe is
shielded by a foil shield, often found inside the glass electrode.
Most modern pH meters also have a thermistor temperature probe which allows for automatic
temperature correction, since pH varies somewhat with temperature.
Water is THE most important and miraculous substance on Earth. Its molecules H-O-H form a
boomerang shape with the O- end slightly negative and the H2+ end slightly positively charged.
These charged boomerangs are attracted to one another, forming islands of cohesion, such that
water forms a liquid at temperatures where life thrives, whereas it should really have been a very
volatile gas like hydrogen sulphide (H2S) which has almost twice its molecular weight. At the
surface of Earth, water occurs in solid form (ice), liquid (water) and gaseous form (steam or water
vapour). In cold areas all three phases co-exist.
Water is also unique in that it is both an acid (with H+ ions) and a lye (with OH- ions). It is thus
both acidic and basic (alkaline) at the same time, causing it to be strictly neutral as the number of H+
ions equals that of the OH- ions. Because of its strong cohesion, only few water molecules
dissociate (split) in their constituent ions: hydrogen ions (H+) and hydroxyl ions (OH-). Chemists
would insist that H+ ions are really H3O+ ions or hydronium ions.
Knowing that one molar of water weighs 18 gram (1+1+16), which equals 18ml, and that this
quantity contains a very large number of molecules [1], only 0.1 millionth (10-7 ) mol are dissociated
in one litre of water (pH=7). [2]
The potential difference between the inside of the glass electrode and the outside is caused by the
oxides of silicon in side the glass:
Si.O- + H3.O+ = Si.O.H+ + H2.O
Once the ionic equilibrium is established, the potential difference between the glass wall and the
solution is given by the equation:
E = R x T / ( F x ln( a ))
Where E= electron potential (Volt), R= molar gas constant 8.314 J/mol/K, F= Faraday constant
96485.3 C, T= temperature in Kelvin and a= the activity of the hydrogen ions (hydronium ions).
ln( a )= the natural logarithm which converts to the decimal logarithm = 2.303 x log( a )
The combination R x T / ( 2.303 x F ) is approximately 0.060 V (60 mV) per tenfold increase in
hydrogen ions or one pH unit.
The pH range of 0 to 14 accounts for hydronium activities from 10 to 1E-14 mol/litre. One mol of
water weighs 18 gram. A pH=7 corresponds to hydronium activity of 1E-7 mol/litre (1E-7). Because
log( 10-7 ) = -7, the pH scale leaves the minus sign out.
Even though modern pH glass electrodes have seen major improvements, they still don't like some
substances low in H+ ions, like alkali hydroxides (NaOH and KOH), pure distilled water, etching
substances like fluoride, adsorbing substances like heavy metals and proteins.

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pH meter principles

Most modern pH meters have inbuilt temperature sensors to correct temperature deviation
automatically to give values as if these were taken at a standard temperature of 25C. The readout is
not influenced by temperature at pH=7.00 but outside this by 0.003 per C. Thus a pH taken at 5C
(20 away from 25C), showing 4.00 must be corrected downward by 0.003 x 20 x 3.00 = 0.18. Likewise
a pH value of 10.00 must be corrected upward by this amount.

Caring for a pH meter depends on the types of electrode in use. Study the manufacturer's
recommendations. When used frequently, it is better to keep the electrode moist, since moisturising
a dry electrode takes a long time, accompanied by signal drift. However, modern pH meters do not
mind their electrodes drying out provided they have been rinsed thoroughly in tap water or
potassium chloride. When on expedition, measuring sea water, the pH meter can be left moist with
sea water. However for prolonged periods, it is recommended to moist it with a solution of
potassium chloride at pH=4 or in the pH=4.01 acidic calibration buffer. pH meters do not like to be
left in distilled water.
Note that a pH probe kept moist in an acidic solution, can influence results when not rinsed before
inserting it into the test vial. Remember that a liquid of pH=4 has 10,0000 more hydrogen ions than
a liquid of pH=8. Thus a single drop of pH=4 in a vial measuring 400 drops of pH=8 really upsets
measurements! Remember also that the calibration solutions consist of chemical buffers that 'try' to
keep pH levels constant, so contamination of your test vial with a buffer is really serious.
[1] Avogadro's constant is 602,213,670,000,000,000,000,000 (602.214 billion trillion) or 6.02E23, named in honour of
Amedeo Avogadro. One mole of a chemical substance contains this number of molecules. Amedeo Avogadro
(1776-1856) was an Italian physicist. He proposed in 1811 his famous hypothesis, now known as Avogadro's
law. The law stated that equal volumes of all gases at the same temperature and pressure contain the same
number of molecules. Avogadro also distinguished between an atom and a molecule, and made it possible to
determine a correct table of atomic weights.
[2] On the Seafriends web site we frequently use the exponential notation E, such that 2.34E-4 means 2.34 x 10-4 .

The pH scale
The values for pH make more sense when compared with that of known substances. Note that the
pH scale is logarithmic and that each next value contains ten times less hydrogen ions. A pH=0
contains the most, and is highly acidic.
0 5% Sulphuric acid, H2SO4, battery acid.
1 0.1 N HCl, hydrochloric acid (1.1)
2 Lemon juice. Vinegar (2.4-3.4)
3 wine (3.5-3.7)
4 Orange juice. Apple juice (3.8). Beer. Tomatoes.
5 Cottage cheese. Black coffee. Rain water 5.6.
6 Milk. Fish (6.7-7). chicken (6.4-6.6).
7

Neutral: equal numbers of hydrogen and hydroxyl ions. Blood (7.1-7.4). Distilled
water without CO2, after boiling.

8 Sea water (8.1). Egg white.

9 Borax. baking soda.
10 Milk of magnesia
11 Household ammonia
12 Photographic developer
13 Oven cleaner
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pH meter principles

14 Sodium lye NaOH, 1 mol/litre.

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26.2 How do pH electrodes work?

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26.2 How do pH electrodes work?

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Description
This article is from the Chemistry FAQ, by Bruce Hamilton
B.Hamilton@irl.cri.nz with numerous contributions by others.

26.2 How do pH electrodes work?

Contributed by Paul Willems <Paul.Willems@rug.ac.be>, and slightly
modified
by Bruce Hamilton.
The most common type of pH electrodes are the "glass" electrodes.
They
consist of a special glass membrane that is sensitive to variations in
pH,
as pH variation also changes the electrical potential across the glass.
In
order to be able to measure this potential, a second electrode, the
"reference" electrode, is required. Both electrodes can be present in a

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26.2 How do pH electrodes work?

"combined" pH electrode, or two physically-separate electrodes can
be used.
The glass electrode consists of a glass shaft on which a bulb of a
special
glass is mounted. The inner is usually filled with 3 Mol/Litre aqueous
KCl
and sealed. Electrical contact is provided by a silver wire immersed in
the
KCl.
For "combined" electrodes, the glass electrode is surrounded by a
concentric
reference electrode. The reference electrode consists of a silver wire
in
contact with the almost-insoluble AgCl. The electrical contact with the
meter
is through the silver wire. Contact with the solution being measured is
via
a KCl filling solution. To minimise mixing of the solution to be
measured and
the filling solution, a porous seal, the diaphragm, is used. This is
usually
a small glass sinter, however other methods which allow a slow
mixing contact
can also be used, especially for samples with low ionic strength.
Besides the
"normal" KCl solutions, often solutions with an increased viscosity,
and
hence lower mixing rate are used. A gel filling can also be used,
which
eliminates the necessity for slow mixing devices.
In contact with different pH solutions a typical glass electrode gives,
when
compared to the reference electrode, a voltage of about 0 mV at pH 7,
increasing by 59 mV per pH unit above 7, or decreasing by 59 mV per
pH unit
below 7. Both the slope, and the intercept of the curve between pH
and
generated potential, are temperature dependent. The potential of the
electrode is approximated by the Nernst equation :
E = E0 - RT log [H+] = E0 + RT pH
Where E is the generated potential, E0 is a constant, R is universal
gas constant and T is the temperature in degrees Kelvin.
All pH-sensitive glasses are also susceptible to other ions, such as
Na or K.
This requires a correction in the above equation, so the relationship
between
pH and generated voltage becomes nonlinear at high pH values. The
slope tends
to diminish both as the electrode ages, and at high pH. As the
electrode has
a very high impedance, typically 250 Megohms to 1 Gigohm, it is
necessary to
use a very high impedance measuring instrument.
The reference electrode has a fairly constant potential, but it is
temperature dependent, and also varies with activity of the silver ions
in
the reference electrode. This occurs if a contaminant enters the
reference
electrode.
Calibration
From the preceding, it is obvious that frequent calibration and
adjustment of
pH meters are necessary. To check the pH meter, at least two
standard buffer
solutions are used to cover the range of interest. The pH meter should
be
on for at least 30 minutes prior to calibration to ensure that all

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26.2 How do pH electrodes work?

components
are at thermal equilibrium, and calibration solutions should be
immersed for
at least a minute to ensure equilibrium.
First use the buffer at pH 7, and adjust the zero (or the intercept).
Then, after thorough rinsing with water, use the other buffer to adjust
the
slope. This cycle in repeated at least once, or until no further
adjustments
are necessary. Many modern pH meters have an automatic
calibration feature,
which requires each buffer only once.
Errors
People assume pH measurements are accurate, however many
potential errors
exist. There can be errors caused by the pH-sensitive glass, reference
electrode, electrical components, as well as externally generated
errors.
Glass Electrode Errors
The pH-sensitive glass can be damaged. Major cracks are obvious,
but minor
damage can be difficult to detect. If the internal liquid of the pHmeasuring
electrode and the external environment are connected, a pH value
close to 7
will be obtained. It will not change when the electrode is immersed in
a
known solution of different pH. The electrical resistance of the glass
membrane will also be low, often below 1 megohm, and it must be
replaced.
Similar results occur if the glass wall between the inner and outer part
of
a combined electrode breaks. This may occur if the outer part is
plastic.
The inner part can crack without any external signs. The electrical
resistivity over the glass electrode is intact, but actual measuring
between
both electrodes reveals a low resistivity. The electrode must be
replaced.
The glass can wear out. This gives slow response times, as well as a
lower
slope for the mV versus pH curve. To rejuvenate, immerse the
electrode in a
3 Molar KCl solution at 55 degrees Celsius for 5 hours. If this does
not
solve the problem, try removing a thin layer of the glass by immersion
for
two minutes in a mixture of HCl and KF (be careful, do not breathe the
fumes,
and wear gloves). The electrode is then immersed for two more
minutes in HCl,
and rinsed thoroughly. As an outer layer of glass has been removed,
the new
surface will be like a new electrode, however the thinner glass will
result
in a shorter electrode life. Frequent recalibration will be required for
several days.
The glass can be dirty. A deposit on the glass will slow the response
time,
make the response sensitive to agitation and ionic strength, and also
give
the pH of the film, not the sample solution. If the deposit is known,
use a
appropriate solvent to remove it, and rehydrate the electrode in 3M
KCl.
If the deposit is not known, first immerse the electrode for a few
minutes

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26.2 How do pH electrodes work?

in a strongly alkaline solution, rinse thoroughly, and immerse it in a
strong acid (HCl) solution for several minutes. If this does not help, try
using pepsin in HCl. If still unsuccessful, use the above HCl/KF
method.
Reference Electrode Errors
The diaphragm of the reference can become blocked. This is seen as
unstable
or wrong pH measurements. If the electrical resistivity of the
diaphragm is
measured, high values are reported (Most multimeters will give an
over-range
error). The most common reason is that AgS formed a precipitate in
the
diaphragm. The diaphragm will be black in this case. The electrode
should be
immersed in a solution of acidic thiourea until the diaphragm is white,
and
then replace the internal filling liquid of the reference electrode
There is no contact across the diaphragm, due to air bubbles. This
appears
as if the diaphragm were blocked, except that the diaphragm is white.
Ensure
that the filling solution level in the reference electrode is always well
above the sample, so that liquid is always slowly flowing from the
reference
electrode towards the sample.
The electrode filling solution is contaminated. This appears as
unstable or
wrong pH measurements. Often the 0mV pH differs considerably from
pH 7. The
diaphragm has its normal colour and the electrical resistivity is
normal.
However, the solution often becomes contaminated due to low filling
solution
levels, and air bubbles may also appear in the diaphragm, which
obviously
affects electrical resistivity. Replacing the reference filling solution
several times should solve the problem, but the electrode may have
been
permanently damaged. The problem can be avoided by choosing gelfilled
reference electrodes, double-junction electrodes, or ensuring there is
an
outflow of reference filling solution towards the sample.
The electrode was filled with the wrong reference solution. This
appears as
as displaced pH measurements. Flush and replace the reference
liquid.
Electrical errors
Condensation or sample contamination of the electrode connecting
cable. This
appears as an almost-constant measurement of about pH 7, even
when the pH
electrode is disconnected from the cable, or as a pH which changes
less than
it should, when tested with two standard solutions. If the cable is
disconnected from the meter, the pH will start to drift.
There is a short circuit in the cable. The symptoms are similar to the
above
case, except that bending the cable may create sharp, spurious
readings. In
most pH cables, between the two copper conductors there are two
layers which
appear to be insulators. The inner layer is an insulator, whereas the
outer
layer is a conductor to avoid trace electrical effects. If this outer layer
does contact the inner conductor, there will be a short circuit.

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26.2 How do pH electrodes work?

Replace
suspect cables.
The input stage of the meter is contaminated with conducting liquid.
The
symptoms are the same as above, except that removing the cable
has no
effect. Closely examine the input stage of the meter for liquid or
deposits.
If present, rinse with distilled water, then ethanol, and dry thoroughly.
The input stage of the meter is faulty. This gives random
measurements.
Shorting both input wires does not make any difference. Repair the
meter.
The input stage appears faulty. Shorting both input wires gives a
stable
pH measurement of about 7. The meter may be faulty, but probably
the problem
is elsewhere in the electrical circuit.
Externally-generated Errors
If a significant flow of liquid passes the electrode, then there can
be a minor electrical effect. This generates a potential on the glass
membrane, which is superimposed on the actual pH measurement.
This effect
becomes negligible for highly-conducting liquids. It is seldom
observed.
If the trace electric effect does influence pH measurements, the
addition
of a little salt to increase the conductivity, or changing the flux of
liquid around the electrode, should solve the problem.
Ground loops and spurious electrical currents may generate
unexpected
electrical signals. Such signals can strongly influence pH
measurements.
A pH reading in the range of -15 to +20 is possible, even if the pH is
7.
Ground loops can be eliminated by grounding the system according
to the
manufacturer's instructions, and ensuring insulation is in good
condition.
Often these problems can be extremely difficult to detect and remedy.
Low ionic strength samples can be affected by electrolyte from the
electrode,
and special electrodes are available.

Continue to:
prev: 26.1 What is pH?
Index
next: 26.3 What are ion-selective electrodes?

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