pH Measurement

The pH scale is a series of a numbers which express the degree of acidity

(or alkalinity) of a solution as contrasted with the total quantity of acid or base
in some material as found by an alkalimetric (or acidimetric) titration.
As defined by ‘Sorensen’ who introduced the term pH= -log (H+)
Involved is the negative logarithm of the hydrogen ion concentration expressed
in molarity.
A rough indication of pH can be obtained using pH papers or indicators,
which changes colour as the pH level varies. These indicators have limitations
on their accuracy and can be difficult to interpret correctly in coloured samples.
In spite of this, the technique is not applicable to automatic process control.
In order to overcome the problems as indicated above, electronic devices
come into stay so called pH meters, pH Transmitters. pH meters are used at the
laboratory scale just to have the mere indication of pH in the laboratory and the
accurate indication provided by meter are usefully analysed and considered for
the proper manual process control. There are two types of pH meters, analog
and digital type, described in the subsequent discussion. For on line
measurement of pH this technique is updated which mainly consist.
1) Development in pH electrodes considering the appropriate sampling
systems and manual/auto cleaning facility to the pH electrodes to avoid
the scale formation. Because the scale creates an adverse effects on
electrode response.
2) Developments in the pH metering circuits so as to obtain the control
signal in terms of 4 to 20 mA DC which is useful for controlling the end
devices and in turn the process to achieve better quality product.

Dependence & Remedies:

1) The pH electrodes producing minute p.d. proportional to the (H+) of
aqueous solution and having very high output impedance. Therefore it is
essential to have prefect shielding and grounding to the input stage of the
meter.
2) As the pH is very strong function of temp. It is must to have manual/auto
temp. Compensation facility.
3) Due to the face that the asymmetric potential will vary from electrode to
electrode and even for the same electrode from time to time so pH meter
should have asymmetric potential adjustment facility.

Electrode Method:
It permits continuous indication, recording and control of pH process
with 0.01 pH accuracy.
This method consisting of two electrodes:
1) Glass Electrode.
2) Reference Electrode.
There are different type of glass and reference electrodes out of these generally
used are the glass membrane electrode and corresponding reference electrode.

1) Glass Membrane Electrode:

Construction :
It consist of a pH sensitive glass membrane bulb fused to glass
tube. A silver wire whose tip is coated with silver chloride protrude into
the glass membrane bulb. This bulb contains the internal filling solution,
generally it is buffered solution containing chloride ions having constant
pH value.

Working:
To function, both surface of the membrane must be hydrated. Hydration
occurs by absorption of water by the membrane interface in contact with the
process solution. There is also an exchange of univalent cation of glass for H+
ions from the process solution. At both surfaces of the membrane there will be a
boundary potential that will be a function of the hydrogen ion activity in the
solution at the interface. Potential difference across the glass membrane is the
function of hydronium ion activity in the solution at the interface. Because
hydronium ion activity for the internal filling solution is constant, the potential
will be function of the hydronium ion activity of the external solution.
If the hydrogen ion activity is grater in the process solution than inside
solution a positive potential difference will exist across the glass tip.i.e. outside
potential is higher positive than inner potential. Similarly if reverse the case
then negative potential difference will exist.
The relationship between the potential difference and the hydrogen ion
activity follows the Nernst equation.

In the most common type of pH electrode, that an internal buffer solution

of 7 pH, the voltage across the membrane will be zero at 7 pH.
Where E0 includes such factors as the activity of hydronium ion in the
internal solution and the asymmetric potential of the membrane.
Asymmetric potential arises from differences in the characteristics of the
two surfaces of the glass membrane and results from such things as mechanical
stresses, deterioration of the external surface by dissolution of the glass,
chemical attack on the glass membrane, dirty surfaces and so on. Thus the
potential E will not be the same from electrode to electrode or for a given
electrode with relation to time for a constant concentration of active hydrogen
ions. For this and other reasons, a pH system must be standardized or adjusted
periodically for its entire useful life.

Desirable Features of a Glass Electrode:

1) The electrode body should be short and compact so as to resists breakage
and bulk of electrode chamber.
2) Electrode body should have wide diameter to add strength and provide
the lowest possible electrical resistance in the pH sensitive bulb.
3) Electrode cable connecting at electrode top must be fixed by connecting
core to the mail electrode and shield to the inner surface of electrode.

Limitations:-
1) It gives accurate results up to 9pH solution.
2) Above 9pH it gives alkali error and it is very large for 12 to 13 pH
solution, because the glass is composed of sodium and silicate ions which
are capable of taking up a number of ions such as potassium and silver if
they are present in the solution. Alkali error depends on temperature type
of glass, the composition of solution and so many other factors.
 3) Highly acid solutions, concentrated alcoholic solutions, high temperature
and the presence of ionised colloidal particles introduce errors when glass
electrode is used.

2) Reference Electrode:
The potential inside the glass is the output of the measuring electrode. It
must be compared with the potential in the solution out-side the glass electrode
to determine potential difference (pH). The sensing of the potential in the
solution must be independent of change in solution composition. A reference
electrode is the answer.

Basically there are two

i) Non-Flowing reference electrode.- Less accurate and sensitive requires
reactivation periodically.
ii) Flowing reference electrode- More accurate and sensitive

i) Non-Flowing reference electrode

It consist of a glass tube filled with a1N, Kcl. (saturated kcl) solution, in
which silver electrode whose tip is coated with silver chloride material
chloride material protrude (immersed) at the bottom of the tube there is a
fine bore in which asbestos fibre is fitted for minimal flow of kcl. Solution
into process solution, because of minimal flowing of kcl. Solution form a
typical salt bridge, which makes a typical electrical contact through a liquid
junction between internal kcl. Solution and the process solution hence the
electrical circuit with the glass membrane electrode, which provides stable
potential.
 Combination Electrode:

Effect of Temperature on pH Measurement:

Hydrogen ion concentration generally increase as temperature increases,
but the relation is not linear. The pH temperature coefficient varies with the
material. Acid solution and normally have small temperature coefficient and
Alkaline solution normally have large pH temperature coefficient since the H+
ion of alkaline solution come from water has a relatively high pH temperature
coefficient.

For particular solution this E only varies as temperature varies. This

potential variation corresponding to temperature variation can be calculated,
that is 0.188 mV/oC. From various experiments it has been observed that the
slop mV/pH for several temperature can be determined. The table for the slop
mV/pH for several temperature is given below:

Temp. oC 0 25 50 75 100
mV/pH 54.20 59.14 64.08 69.02 74.00

pH Meters:
Modern pH meter usually utilize the glass electrode and corresponding
reference electrode or the combination electrode. A typical modern pH meteris
illustrated here. Because the conductivity of glassis very low, even a thin
membrane exhibits very high resistance (10 ohms), it is necessary to amplify the
potential difference across the two electrodes and to measure the voltage
directly with a calibrated galvanometer/digital display.
The overall potential developed by the complete electrode assembly is of
the form
E= E0 + KpH
Where E= Overall measured potential.
E0= Asymmetric potential.
K= A thermodynamic constant varying with temperature.
Considering the above mathematical expression of pH, Ph meter is
divided in to various block as shown in schematic block diagram.
The potential drop across the electrodes is connected through a shielded
coaxial cable to the input of pre amplifier (i.e. Instrumentation amplifier). This
pre- amplifier transmits the signal without loss, as one input to the pH amplifier
circuit. Another input to pH amplifier is from standardization knob as shown in
fig. This is because of the fact that asymmetric potential will vary from
electrode to electrode and even for the same electrode from time to time, a pH
amplifier must be standardized before adjusting the gain (for any gain from
minimum to maximum value) i.e. the offset adjustment of pH meter, by
adjusting the standardization knob when pH electrode immersed into the 7 pH
buffer solution. Then after by immersing pH electrode in the 9.2 pH suffer
solution adjust the span knob so as to adjust the gain or slope of the pH
amplifier to fit for pH/mV relation. During carrying out the above procedure
temperature knob must be kept on the buffer solution temperature reading so as
to get temperature compensated pH readings.
Precautions:
1) Before switching on the pH meter, make sure that the electrodes are
properly connected, and selector switch must be in stand by mode.
2) Before using the ph meter for pH measurement it must be standardize.
3) Rinse the pH electrodes with distilled water & clean dry with filter
paper(Tissue paper) only before every measurement.
4) When the electrode not in use, store the electrode in distilled water. In the
event of prolonged storage the electrode can remain dry, then it must be
reactivated before use.
5) See the range of pH specified before use otherwise permanent damage
will happen to electrode, if used out side the range.
6) See the useable range of temperature before use. The electrode will loose
the response if used beyond operating temperature range.
7) Do not handle the glass membrane or subject it to abrasion of any kind as
this may cause sluggishness or span error.