pH meter principles

What is pH and how is it measured?

by Dr J Floor Anthoni (2005)

Reference: http://www.seafriends.org.nz/dda/ph.htm
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 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
Mega-Ohm, 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chloride (AgCl) has been superseded by the kalomel (mercurous chloride, HgCl
2
) 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).

Fig.: Schematic pH electrodes
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 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 H
2
+
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 (H
2
S) 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 H
3
O
+
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
) mole
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 inside the glass:
Si.O- + H
3
.O
+
= Si.O.H
+
+ H
2
.O

Once the ionic equilibrium is established, the potential difference between the glass wall
and the solution is given by the equation:
E = R T / (F ln( a ))
Where E= electron potential (Volt), R= molar gas constant 8.314 J/mole/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 log(a)
The combination R T / (2.303 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 mole/litre. One
mole of water weighs 18 gram. A pH=7 corresponds to hydronium activity of 1E-7
mole/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.
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 20 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 10,000 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 website we frequently use the exponential notation E, such that 2.34E-4
means 2.34 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, H
2
SO
4
, 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 CO
2
, after boiling.
8 Sea water (8.1), egg white.
9 Borax, baking soda.
10 Milk of magnesia
11 Household ammonia
12 Photographic developer, household bleach
13 Oven cleaner
14 Sodium lye NaOH, 1 mol/litre.