What is pH?

Acidic and basic are two extremes that describe chemicals, just like hot and cold are two
extremes that describe temperature. Mixing acids and bases can cancel out their extreme effects;
much like mixing hot and cold water can even out the water temperature. A substance that is
neither acidic nor basic is neutral.
The pH scale measures how acidic or basic a substance is. It ranges from 0 to 14. A pH of 7 is
neutral. A pH less than 7 is acidic, and a pH greater than 7 is basic. Each whole pH value below
7 is ten times more acidic than the next higher value. For example, a pH of 4 is ten times more
acidic than a pH of 5 and 100 times (10 times 10) more acidic than a pH of 6. The same holds
true for pH values above 7, each of which is ten times more alkalineanother way to say
basicthan the next lower whole value. For example, a pH of 10 is ten times more alkaline than
a pH of 9.
Pure water is neutral, with a pH of 7.0. When chemicals are mixed with water, the mixture can
become either acidic or basic. Vinegar and lemon juice are acidic substances, while laundry
detergents and ammonia are basic.
Chemicals that are very basic or very acidic are called reactive. These chemicals can cause
severe burns. Automobile battery acid is an acidic chemical that is reactive. Automobile batteries
contain a stronger form of some of the same acid that is in acid rain. Household drain cleaners
often contain lye, a very alkaline chemical that is reactive.
The following diagram shows the pH scale and the pH of some common items:

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 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 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.
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 10,000 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 web site we frequently use the exponential notation E, such that 2.34E-4 means 2.34 x 10-4.