Ph. Principles and Measurement
Ph. Principles and Measurement
Ph. Principles and Measurement
Definition and Basics and F is the Faraday constant. It follows that the potential of
such a pH-sensitive electrode is a linear function of the pH
pH Basics and Notional Definition
when the latter is defined in terms of activity.
The acidity and alkalinity of aqueous media, where most According to the international standard ISO 31-8, the
reactions in nature occur, depend (according to the Arrhenius standard methodology for pH measurements involves the con-
definition of acids and bases) on the concentration of the hydro- struction of a liquid junction-free galvanic cell where the
nium (H3Oþ) and hydroxyl (OH) ions. The former is quanti- pH-sensitive electrode is the hydrogen electrode (Pt/H2/Hþ:
fied by the more general concept of pH, initially proposed by the H2 gas bubbled at 1 atm through a Hþ-containing solution in
Danish chemist Søren Peder Lauritz Sørensen in 1909 and contact with a high surface area Pt electrode) and the reference
revised in 1924 to adjust definitions in relation to the electro- electrode is a Ag/AgCl in a KCl solution. The following nota-
chemical cells used for its measurement. The pH is notionally tion refers to such a cell:
defined for any medium as the decimal logarithm of the recip-
AgjAgCljconcentrated solution of KCl,
rocal of the hydrogen ion activity, aHþ , in that medium:
test solutionjH2 ðg, 1 atmÞjPt
1
pH ¼ log 10 aHþ ¼ log 10 [1] where vertical lines denote the interface between two different
aHþ
phases. The cell is filled with a standard solution of known pH/
It is only for very dilute solutions that the pH can be directly hydrogen ion activity, pHs, and its electromotive force (emf),
related to proton concentration: ES, is measured. Then, the test solution is replaced by the
pH ¼ log 10 cHþ [2] sample solution of unknown pHx and the new emf of the
cell, EX, is measured. It follows (applying eqn [3] twice and
This approximation holds for pure water where, due to its taking into account that the same reference electrode is used)
self-dissociation constant being Kw ¼ 1014 at 25 C, proton that the pH of the unknown solution is a linear function of the
and hydroxyl concentrations are as low as 107. Thus, pure difference between the two measured emf values:
water at 25 C has a pH value very close to 7; therefore, a value
of pH ¼ 7 defines a ‘neutral’ medium where the proton and its pHX ¼ pHs þ ðES EX Þ=ð2:303RT=F Þ [4]
hydroxyl counterion are present in equal concentrations. Equation [4] describes the operational definition of pH.
Media with pH < 7 are characterized as acidic, whereas those The pH values of the standard solutions (of both primary
with pH > 7 as alkaline. The common pH range is between and secondary/operational standards), used in the operational
0 and 14 since cases with Hþ or OH concentrations higher definition of the pH of unknown solutions, are estimated by
than 1 M are not often encountered. It should be stressed that a direct measurements of the emf of cells similar to the one
standard pH reference value has been set by IUPAC with described earlier, following the methodology adopted by
respect to which primary and operational standard solutions IUPAC Recommendations 2002.
are further defined; this is the value of pH ¼ 4.21 for a
0.05 mol kg1 potassium hydrogen phthalate aqueous
solution.
Buffer Solutions
A (pH) buffer solution refers to an aqueous solution contain-
Operational pH Definition ing a mixture of a weak acid and its conjugate base or vice
The notional definition of pH according to hydrogen ion versa. The most outstanding characteristic of a buffer solution
activity (eqn [1]) is based on the fact that pH is accurately is its ability to keep its pH almost constant with the addition of
determined by pH-sensitive ion-selective electrodes, which, a small amount of strong acid or base. This is the reason that
strictly speaking, respond to activity rather to concentration buffer solutions are applicable in a variety of chemical pro-
changes. Ideally, the electrode potential, E, of a pH-sensitive cedures where the prevention of changes in the pH of a solu-
electrode follows the Nernst equation, which, for the hydrogen tion is needed. Many living organisms grow in a relatively
ion, can be written as small pH range, and in order to keep the pH constant, they
utilize a buffer solution (e.g., blood). This remarkable property
0 RT 0 2:303RT of buffer solutions is attributed to the presence of equilibrium
E¼E þ ln ðaHþ Þ ¼ E pH [3]
F F between the acid HA and its conjugate base A:
where E is the measured potential, E0 is a formal electrode
HA ⇄ Hþ þ A - [5]
potential (i.e., the constant value of the electrode potential
for aHþ ¼1 and the specific electrode/solution conditions for According to Le Chatelier’s principle, the addition of a
each case), R is the gas constant, T is the temperature in Kelvin, small amount of strong acid to this equilibrium mixture will
Table 1 Standard buffer solutions at 25 C concentration. Glass electrodes are the main components
of potentiometric sensors and are used in the determination
pH of univalent cations. The glass electrode used in pH
Buffer solution composition value
measurements has a glass bulb membrane with a typical
Potassium tetraoxalate (0.05 m) 1.68 three-component composition of 72% SiO2–22% Na2O–6%
Potassium hydrogen tartrate (saturated) 3.56 CaO (or 80% SiO2–10% Li2O–10% CaO for highly alkaline
Potassium hydrogen phthalate (0.05 m) 4.01 media).
Potassium dihydrogen phosphate (0.025 m) þ disodium 6.87 The interaction of the protons in solution with the surface
hydrogen phosphate (0.025 m) of the glass membrane is based on the ion exchange property
Potassium dihydrogen phosphate (0.08695 m) þ disodium 7.41 of the latter since, when its main silica component comes in
hydrogen phosphate (0.03043 m) contact with water, it is hydrated and dissociates to Si–O– and
Borax (0.01 m) 9.18
this in turn can be partially protonated:
Calcium hydroxide (saturated) 12.45
Si O þ H3 Oþ ⇆ Si O H þ H2 O [6]
Source: Bates, R. G. (1964). Determination of pH: theory and practice (1st ed.), p. 123.
London: Wiley; Westcott, C. C. (1978). pH measurements, p. 81. Michigan: Academic The name of the glass electrode may be misleading to the
Press. nonspecialist operator in that two misconceptions may sus-
tain: that a pH meter contains a single electrode and that the
electrode material is made of glass. Both of these are obviously
force the equilibrium to shift to the left side of reaction [5]. In not true: glass is an ion conductor and not an electronic one
this way, the concentration of the hydrogen ion increases by (hence, it is not an electrode material) and a potential differ-
less than the amount expected for the quantity of strong acid ence can only be measured between two points (hence, there
added. On the other hand, if a portion of strong alkali is added are two electrodes in a pH meter). In reality, the voltage
to the mixture, the hydrogen ion concentration decreases by between the two sides of the glass membrane is measured
less than the amount expected for the quantity of alkali added, with the help of two electrodes immersed in the solutions on
since more protons are produced as reaction [5] is shifted either side of the membrane. In Figure 1, where (a) a simple
to the right. glass electrode coupled with a reference electrode and (b) a
Table 1 gives the characteristics of seven standard buffer combined system of them are shown.
solutions that cover the usually encountered pH range The glass electrode is made of a plain glass or plastic tube
(between 2 and 12). with the pH-sensitive specialty glass membrane (0.1 mm
thick) blown from its melt and sealed at the end of the tube.
The latter contains an internal standard acidity solution (typi-
cally 0.1 N HCl, sometimes with the addition of a AgCl satu-
Measurement rated solution too) and an internal reference electrode, REin
pH Meters (typically a Ag/AgCl salt-covered wire electrode). The glass
membrane is in contact with the test/sample solution, and in
pH is a measurable parameter and the electronic device that is
the plain configuration of Figure 1(a), the second external
used for measuring the pH of a liquid (or in special cases of
reference electrode, REext (again a Ag/AgCl electrode), is also
semisolid compounds) is called a pH meter. The most impor-
immersed in the test solution. Alternatively, the external elec-
tant component of a typical pH meter is its special measuring
trode can be placed in an external tube, concentric to the glass
probe (a glass electrode or, for special applications, an ion-
electrode tube and containing a KCl solution, which is in
selective field-effect transistor (ISFET)), which is connected to
contact with the test/sample solution via a porous ceramic
an electronic meter that measures and displays the pH read-
frit (Figure 1(b)); in that case, the system is termed as a
ing. All pH meters are calibrated against buffer solutions of
combination pH electrode. Hence, a pH meter consists of an
known hydrogen ion activity. The use of a set of buffer solu-
electrochemical cell that, in the case of a combinatorial system,
tions (operational pH standards) has been proposed by
can be denoted as
IUPAC.
A crude estimate of pH in laboratories can also be per- Ag=AgCl ðREin Þj0:1 N HCljglass membranejsample
formed by pH indicators and sometimes in connection with
solution ðHþ s ÞjjKCl solutionjAg=AgCl ðREext Þ
holographic pH sensors, which allow the measurement of pH
colorimetrically. with vertical lines signifying the interface between two different
phases and the double vertical line an electrolytic junction. The
measured potential, E, between the two cell terminals can then
Glass Electrode be written as
Construction and principle E ¼ Ein DEm DElj Eext [7]
.The most widely used pH meter is based on the glass electrode,
which belongs to the large family of ion-selective electrodes, where Ein and Eext are the potentials of the reference electrodes,
that is, electrodes that contain a material sensitive to changes DEm the potential drop between the two sides of the glass
with respect to the concentration of ions in the test solution, membrane, and DElj the liquid junction potential drop at the
in such a way that the potential drop between the electrode electrolytic junction. Since Ein, Eext, and DElj are expected to be
and the outer surface of the material depends on this constant, eqn [7] becomes
pH: Principles and Measurement 335
Ein Eext E
E Ein Eext
KCl solution
0.1 N HCl
KCl solution
0.1 N HCl internal solution
Porous diaphragm
internal solution ([H+]in) ΔElj
([H+]in)
Figure 1 Schematic representation of a pH meter comprised of (a) a glass electrode coupled with a separate reference electrode and (b) a
combined system.
E ¼ Econst DEm [8] Specialty glasses, rich in Li, partially alleviate this problem.
Other problems encountered include attack by high F levels,
The DEm potential drop is due to the development of dif-
noble metal deposition, protein deposition, and debris fouling
ferent surface concentrations of chemisorbed Hþ at opposite
of the ceramic frit. Cleaning the surface of a fouled glass
glass surfaces, as a result of the establishment of different
electrode can be done by brief immersion in HF, but
equilibriums for reaction [6], due to different bulk solution
nowadays, replaceable affordable glass membrane tips have
concentrations in the internal and sample solutions.
appeared in the market too.
This potential drop may be given by the Nernst equation for
the potential of a concentration cell:
– + – +
VG VG
– + – +
Substrate
(a) (b)
Figure 2 Schematic representation of (a) a MOSFET device and (b) of a SiO2-based ISFET used for pH measurements.
See also: Acids: Natural Acids and Acidulants; Acids: Properties and
Determination; Biosensors; Fatty Acids: Determination and
Requirements; Fatty Acids: Fatty Acids; Nucleic Acids.