EXPERIMENT 12:

pH, DISSOLVED OXYGEN AND CONDUCTIVITY MEASUREMENT

12.1 OBJECTIVE OF THE EXPERIMENT

(i) To conduct calibration check on the pH electrode and its amplifier system
(ii) To conduct calibration check on the conductivity electrode and its amplifier system
(iii) Measurement study of the effect of acid-base titration on pH
(iv) Measurement study of the effect of acid-base titration on conductivity
(v) To conduct calibration check on the dissolved oxygen electrode and its amplifier system
(vi) Measurement study of the various gas bubbles on dissolved oxygen

12.2 INTRODUCTION

The starting point for the pH scale is pure water, which is said to be neutral. Water dissociates
into:

+ -
H2O H + OH

Water has equilibrium constant

Kw =
[H ][. OH ] = 10
+ -
-14
[ ] [ ]
or - log K w = pK w = - log H + - log OH - = 14 log10
[H 2O]
+ -
pure water divides to give equal number oh H and OH inos and consequently the concentrations
-7
of ions are 10 so that

pH = pOH = 7

The pH value of pure water is 7. This statement is incomplete since the equilibrium constant
0
depends on the temperature. The definition should be the pH value of water is 7 at 25 C. Some
examples of common solutions with an acid character are

- +
H2SO4 SO4 + 2H

- +
HCl Cl + H
If the concentration of H+ ions in a solution is increased then the solution is said to have a base
character. In this case the pH value of the solution is a number greater than 7.

Figure 12.1 pH value of pure water against temperature

12.2.1 Principles of potentiometer pH measurement

The principles of potentiometer pH measurement can be explained by Nernsts law. Nernst found
that a potential difference occurs between a metal object and a solution containing ions of the
same metal when the object is immersed in the solution.

The potential difference E caused by the exchange of metal ions between metal and liquid was
defined by Nernst as follows:

E = E0 +
RT
Nf
[
In Mn+ ]

which

R = gas constant ( 8.314 J/mol K)

F = Faraday number (96493 C/mol)
n = valency of the metal
+
[Mn ] = metal ion concentration
T = absolute temperature in Kelvin
E0 = normal potential
Since the behaviour of the gas Hydrogen has a certain degree of conformity with a metal (both
have a positive ion formation), Nernsts law can also be applied to a hydrogen electrode
immersed into a solution containing hydrogen ions

The formula can bere-written as follows:

2
E = E0 +
RT
nF
[ ]
In H +

E=
RT
F
[ ]
In H +

Figure 12.2 The hydrogen electrode

Glass can be considered as an undercooled electrolyte consists of an irregular structure (SiO2)

and a number of other components that move in the interspaces. These components commonly
consists of Na+, Ca2+ or Li+ ions and give an electrobalance of the glass membrane.
Figure 12.3 Texture of pH glass

When immersed in aqueous solutions, all type of pH glass has the particular property to
+ +
exchange the metal ions of the glass texture against the H ions in the solution. Since the H ions
are bounded to a H2O molecule and not free, the texture of the siliceous acid will be defound
-1
during the exchange by the bigger H3O ion.

As a result of this reaction a so called gel layer will be developed on the surface of the glass
membrane. This gel layer is the equivalent of the metal in the Nernst theory and is therefore
essential for the functioning of the glass electrode. After one or two days the condition reacshes
equilibrium and the resulting gel layer has a thickness between 10 and 40 nanometers.

This depends on several factors such as the composition of the glass and the temperature in
which the electrode is immersed. The voltage development across the glass membrane is
generally explained by means of the phase limit potential theory. After reaching the equilibrium
the hydrogen concentrations outside the glass and inside the gel layer are equalized and
+
consequently no transport of H ions occur. The voltage across the glass membrane is o volt.

If the concentration of hydrogen ions in the two phase differs from the concentration in the
solution a transport of hydrogen ions takes place. The movement of the ions will effect the
neutrality of the gel layer. As a result a voltage will be developed preventing the further transport
+
of H ions.
The value of the voltage depends on the concentration of the hydrogen ions in the solution. Since
the voltage cannot be measured directly it will be necessary to add a pH independent reference
potential in the measuring circuit. This addition allows measurement of the potential differences
across the glass membrane.

12.2.2 The principles and composition of measuring electrode

Normally the glass electrode has a bulb shaped membrane of specific pH glass that is welded to
the glass tube. The bulb is filled with a buffer solution the composition of which is stable and
accurately known.

A reference pin is fitted and protrudes into this liquid. The complete reference system is
completely separated from the outer parts of the electrode and is connected to the plug of the
electrode via a platinum wire welded in glass.

Consequently it is impossible for the buffer liquid to penetrate the other parts of the electrode. As
the glass membrane has a high ohmic resistance an integral metal screen which also carries a
printed code denoting applications is fitted to prevent pick up of electrical interfrence.
Figure 12.4 The glass electrode

12.2.3 The principles and composition of the reference electrode

Nernst found that the composition of a metal and insoluble salt of that metal and a salt solution
have constant potential. This potential is temperature dependent. When such a combination is
immersed directly in a process liquid variations may occur as a result of other ions which may be
present in the liquid.

Furthermore the reference system may be poisoned by the penentration of unwanted ions in the
salt solution. To overcome this problem an electrolyte and diaphragm is used to connect the
metal/metal salt with the process liquid.
Figure 12.5 The reference electrode

12.2.4 The measuring circuit with a glass and a reference electrode

Figure 12.6a and 12.6b shows a pH measuring circuit. The diagrams show the potentials which
effect the final potential difference (Et) between the glass electrode and the reference electrode.

The following potentials are the most significant:

E1 = potential difference between the pH sensitive glass membrane and the liquid to
be measured
E2 = potential difference between the electrolyte in the glass electrode and the inner
face of the glass

E3 = potential difference between the electrode pin and the electrolyte in the glass
electrode
E4 = potential difference between the electrolyte and the electrode pin in the
reference
electrode
E5 = potential difference that occurs at the interface of two liquids with different
concentrations namely the electrolyte and the process liquid.

Figure 12.6 a and 12.6 b The measuring circuit.

The sum total of these potential differences is measured by the signal converter is

Et = E1 + E2 + E3 + E4 + E5

As we are only interested in the potential difference between the glass membrane and the liquid
to be measured the remaining potentials must be compensated for so that they do not affect the
true measurement . Re-examination of the potentials generated shows that if the reference
systems in the glass and reference electrode are identical and at the same temperature the
potentials generated by each are equal but opposite.

E3 = -E4

The potentials E3 and E4 are defined as follows:

RT [ Lmz ]
E = ENe + IN
F Cz

Lmz = solubility product of sparingly soluble salt

Cz = concentration of the salt solution
The equation will then be simplified to

Et = E1 + E2 + E5

With correct selection of the electrolyte used in the reference electrode and a good flow through
the diaphragm the potential difference E5 can be neglected so that

Et = E1 + E2

E = E0H +
RT
F
[ ]
In H + outer

E1 = E 0 H - 0.05916. pH outer

In the same way E2 can be defined as

E2 = E 0 H - 0.05916. pH inner

Since E1 and E2 in the pH measuring loop are opposite polarities the equation becomes

Et = E2 E1

Et = 0.05916( pH inner - pH outer )

RT
The potential pH inner is kept constant by filling the glass electrode with an electrolyte with
F
good buffer properties and consequently the measured E1 now only depends on the potential
difference may exists when the glass and the reference electrode are both immersed in a liquid of
similar properties and pH value to the electrode.

Et = 0.05916( pH inner - pH outer ) + Easy

The potential difference is called the asymmetric potential of the measuring system. The
asymmetric potential Easy may be caused by
The liquid diffusion potential. The potential difference is the result of concentration differences
across the flow diaphragm and is called the diffusion potential differences.

The inner and the outer faces of the pH sensitive membrane vary because of differences in glass
texture which occur during the glass blowing. The correct selection of a glass electrode for a
particular application can only be made if details of the component of the measuring loop and
their significant properties are known.

The following points will be considered in details:

- selection of the glass membrane

- sensitivity of the glass electrode (mV/pH)
- alkaline error
- acid error
- chemical resistance of the glass membrane
- electrical resistance of the glass membrane

12.2.5 Selection of the glass membrane

The glass membrane is the most important part of the complete pH measuring loop. pH sensitive
glass has the particular property that alkali metal ions present in the texture of the glass are
+
exchanged with H ions of the liquid.

To facilities this process it is necessary for the pH sensitive glass membrane to be conditioned by
allowing it to absorb a film of water or gel film. Conditioning is achieved by soaking the electrode
in distilled water for a minimum of 24 hours. This is also necessary if the electrode has been
stored dry.

The most important requirement in any electrode system for pH measurement is that the actual
mV/pH ratio generated is as close as possible to the thereotical value. The potential generated by
a glass electrode is given by equations

RT
E= .2303( pH inner - pH outer )mV
nF

At a temperature of 250C the equation becomes

 273 + 25
E = 5916.. ( pH inner - pH outer )mV
298

In the equation pH outer is the pH value of the liquid at the outer face of the glass membrane and
pH inner is the value of the electrolyte at the inner face of the membrane. The mV/pH ratio is
called the sensitivity or slope of the electrode. The quality of the glass membrane is the most
important factor in achieving correct electrode sensitivity. Reduction in sensitivity of glass
electrode may be compensated for by adjustment of the mV/pH ratio of slope at the signal
converter.

The decrease in sensitivity is usually caused by fouling of the glass membrane. It is of the
greatest importance that electrode is properly cleaned before buffering and adjustment of
sensitivity is made. If the electrode has been stored dry for a long period the sensitivity will not
reach an optimal value until the electrode has been conditioned for a number of hours.

12.2.6 More information about the reference electrodes

The accuracy of measurement also depends on the properties of the reference electrode used. It
is important therefore to describe the different properties of reference electrodes so that a correct
selection can be made.

A good reference electrode satisfies the following requirements, the output voltage is determined
by Nernsts law and the output voltage is stable. In the description below the different types of
reference system, the flow diaphragms and the electrolytes used in reference electrodes are all
discussed.

12.2.7 Reference system

Generally the reference system used in the reference electrodes is silver/silver chloride-
potassium chloride (Ag/AgCl-KCl). This reference system consists of a silver wire electrolytically
coated with silver chloride. This metal-metal salt combination is dipped ina potassium chloride
(KCl) solution.

A second type of construction for this system consists of a silver wire dipped in a paste of silver
chloride, silver and potassium chloride. This paste is sealed into a tube by means of a plug
wadding soaked in KCl. This reference assembly is similarly dipped in a KCl solution.
When selecting the correct junction consideration has to be given to ensure that the process
liquid does not penetrate into the electrode causing poisoning a consequential unstable liquid
junction potential.

With the first two types of junction listed above the KCl solution flows slowly into the process. The
flow rate is dependent on the over-pressure in the electrode and on the process temperature. The
electrolyte flow rate increases with increasing temperature.

12.2.8 Electrolyte in the reference electrode

The electrolyte in the reference electrode must satisfy the following requirements:
- chemically inert and neutral
- no reaction with the process liquid
- equitransferent the ions of the electrolyte must pass the diaphragm at equal speed
- having a constant activity ions
- having a low electrical resistance

The electrolytes in most common use for the reference electrodes are:
- I molal KCl solution with or without gel
- 3.3 molal KCl solution
- saturated KCl solution

1 molal KCL solution

Electrodes with the note Ag (1.0 m) shown on the type plate must be refilled with a 1 molal KCl
solution. This solution is obtained by dissolving 74.56 gram of KCl in 1000 gram of demineralised
water.
1 molal KCl solution (gel)
Non flowing reference electrodes with PTFE junction have a gel ingredient added to the KCl
solution. For operating temperatures up to 800C this gel ingredient maintains the electrolyte at a
higher viscosity and prevents an excessive flow rate.

3.3 molal KCl solutions

Electrodes with the note 3.3m shown on the type plate must be refilled with a 3.3 molal KCl
solution. This solution is obtained by dissolving 3.3 X 7456 g of KCl in 1000 g
Saturated KCl solution
The solubility and consequently the saturation of KCl increases with increasing of temperature.
Therefore when refilling electrodes with saturated KCl solution, due allowances should be made
for the maximum expected process temperature.

12.2.9 The combined electrode

As an alternative to the normal configuration with separate glass and reference electrodes a
combined system may be used which combines the glass and reference electrode into one unit.
With this construction the high ohmic glass electrode is screened by the electrolyte of the
reference electrode and the metal foil screen can be omitted.

The reference systems of both the glass and the reference electrode consists of an Ag/AgCl with
I molal KCl solution. The advantage of a combined electrode is ease of service and the ability to
measure in very small quantities of liquid.

A major disadvantages is that due to the construction of the electrode it is not possible to provide
the selection of glass types or design variations required for many applications. Consequently for
all but the least stringent applications separate glass and reference electrodes are recommended.
Figure 12.7 The combined electrode

12.2.10 The effect of temperature

pH measurement are temperature dependent from two different effects:

a) By the variations with temperature on the contact potentials in the glass and the
reference system
b) By the temperature variations of the liquid being measured

As the glass and the reference electrode have a number of temperature dependent contact
potentials it will be obvious that the voltage supplied by the measuring system is temperature
dependent.

The temperature effects obtained by immersing the electrodes in different standard solutions and
then by varying the temperature of these standard solutions are shown in the graphs of Figure
14.8
Figure 12.8 The temperature effect on the MV/pH ratio

This graph shows that

a. The mV/pH ratio increases as the temperature of the measuring system increases. AT
0 0
25 C, the mV/pH ratio is 59, 16 and at 200C this ratio is 58, 16 mV/pH. At the 80 C the
mV voltage per pH unit is increases to 70,08 mV.
b. The various isothermal lines intersect at one point S (the isothermal point of intersection)
c. This intersection point dependent on the pH of the buffer solution used in the glass
electrode is at pH 7. It is of the greatest importance that the isothermal lines intersect at
one point as only if this is achieved by good electrode design and manufacture will it be
possible to make accurate temperature correction within the electronic amplifier.
In general when a pH measurement is made in a process at widely fluctuating pH and
temperature levels automatic temperature compensation is necessary. To achieve this the
electrode system is completed with a temperature sensing element, packaged in a similar
construction to an electrode that compensates for slope variations of the mV/pH ratio of the
electrode system.

The temperature effect on the measuring system and its correction has been considered. In
addition there is however a temperature effect on the chemical balance of a process itself. It has
 0 0
been previously stated that the pH value of water at 0 C differs from the pH value at 100 C. This
is caused by a change of the chemical balance.

For accurate comparison of pH values made by different techniques it is necessary to state at

what temperature the measurement was made. As the effect of temperature on any process
liquid is highly dependent on it composition it is not possible to accurately compensate for this
effect automatically.

12.2.11 Temperature effect on the application range of the glass electrode

Process temperature is a major factor in selection of the type of glass electrode to be used for a
particularly application. Different reference system are used for high or low process temperatures.
Furthermore the chemical resistance of the membrane is temperature dependent and correct
selection is important.

12.2.12 The resistance thermometer

To provide automatic compensation for the effect of temperature variations on the measuring
system it is necessary to include a temperature compensator in the system. These compensators
are made in the same form as the electrodes to enable them to be mounted in any electrode
position in all pH fittings. The temperature compensator consists of a platinum resistance element
mounted in a glass tube. The tube is completely filled with white silicon grease the thermal
conducting properties of which ensure fast temperature response.

As an alternative to automatic temperatures compensation it is possible to manually compensate

for temperature variations by means of a potentiometer. The temperature of the liquid is
measured with a thermometer and the corresponding resistance is set on the temperature
compensation potentiometer. This latter method is often used for laboratory measurements.

12.2.13 Isolation resistance

In view of the relatively high resistance of the pH sensitive glass membrane, it is necessary to
use a signal converter with high input impedance. This impedance must be at least a factor of
1000 higher than the membrane resistance ( the resistance electrode is much lower and can be
neglected )
Insulation and screening of all cables and connections between the measuring electrode and the
signal converter must be of the highest order. In industrial applications the signal converter
should be installed as near to the electrode as possible. At all times the connections between the
electrodes and transmitter should be kept dry. The insulation resistance decreases considerably
when any moisture is present.

The insulation resistance of the reference electrode is less critical, as its resistance with respect
to the measuring liquid is much lower. Generally an insulation resistance of 107 ohm is adequate.
0
The resistance between electrode and liquid is usually between 1 and 10 kohms at 25 C
depending on the type of junction. At higher resistance values the sensitivity of the measuring
system will be reduced and may cause instability of measurement.

12.2.14 Conductivity

What is the conductivity of a solution? The term conductivity is derived from Ohms law which is
defined as follows: E = IR

Whenthe voltage E is connected across an electric conductor then an electric current I will follow
which is dependent on the resistance R of the conductor. Conductivity is defined as the reciprocal
of resistance, therefore its value can be written:
Conductivity G = 1/R

Figure 12.9 Resistance measurement of fixed solutions and in solution

When a DC voltage E is connected across the two metal electrode being mounted parallel to
each other and immersed in a liquid then an electric current, I will flow between the two plates.
This will be analogue to the current through a metal conductor.

It appears that the liquid will conduct the electric current in the same manner as a fixed meta
conductor. Whilst the type of material used in a fixed conductor is a measure of its ability to
conduct in a liquid it is the electric conductivity of the solution that is considered.

In addition in fixed conductors the electric current flows by transport of electrons in liquid
conduction it flows by ion transport. It will clear that an increasing amount of ions present in the
liquid the transport of the number of changes per unit time will be greater. The liquid then has a
higher conductivity.

By combining the equations from the values of E and I the conductivity of a solution can be stated
as

Conductivity, G = 1/R = 1/E

-1
The unit for the conductivity G is the Siemens, which equals to 1/Ohm or Ohm .

12.2.15 Factors influence the conductivity of a solution

Examination of a given electrolyte indicates that electrolyte conductivity depends on the nature as
well as the concentration and the charge of the ions in the solution. The conductivity of the
solution increases as the amount of ions present in the solution increases. Since each ions has
its own characteristics mobility the following formula for the conductivity can be noted:

G = C.n.F.(I+ +I-)

C = concentration of the liquid

n = valency of the ion
F = Faraday constant
I+ = mobility of the positive ion
I- = mobility of the negative ion
The conductivity of the electrolyte that are not completely dissociated will be lower and will be a
function of the degree of dissociation. Then the formula will then be G = a. C. n.F .(I+ +I-)
a is the degree of dissociation.

If the electrolyte are present in the solution the total conductivity then will dependent on the sum
of above equations for each electrolyte.

12.2.16 The influence of concentration changes on conductivity

Depending on the nature of the dissolved solution (the influence of valency as well as mobility of
the ions and the degree of dissociation are important factors) the conductivity will increase
proportional to an increase in concentration providing the mobility of ions is not influenced by this
increase.

With strong electrolyte with a high degree of dissociation a decrease of the mobility of ions
occurs. An equal increase in the number of ions will then give a smaller increase at a certain
concentration. This can be explained by the decrease of the mobility and dissociation of the ions.
There is also a relationship between conductivity and concentration for weak electrolyte with a
low degree of dissociation.

12.2.17 The influence of temperature on conductivity

Electrolytic conductivity not only depends on the nature and the concentration of the solution but
also on its temperature. The mobility of the ions is strong dependent on the temperature. The
temperature behaviour of an electrolyte is expressed as the temperature coefficient. Further
information about this item is given in later part of the courseware.
Figure 12.10 Conductivity values of common electrolyte at various concentrations

12.2.18 Specific conductivity

As describe before we consider an electrolyte arrangement formed by two metal plates being
placed in a solution and having an area O with a distance L apart.

Figure 12.11 Dispersion area

It is self evident that if the area of the plates is increased the total number of ions between the
plates will increase and consequently the conductivity will increase. Conversely if we increase the
distance between the two plates the strength of the electric field between them is reduced and a
fewer number of ions will reach the plates per unit time.

Hence a greater electrode area results in a higher conductivity with the same voltage applied. A
greater distance between the electrode results in a lower conductivity with the same voltage
applied. Resulting in the measured conductivity G depends on the both the dimensions of and the
distance between the electrodes.

Naturally this leads to considerable complications for comparative measurements. To avoid this
problem the concept specific conductivity has been introduced. This is defined as the conductivity
2
of a liquid column having a length of 1 m and cross section of 1m . The relationship between
measured and specific conductivity is given by:

O
G=K
L

where G = conductivity in Siemens

K = specific conductivity in S/m
2
O = Area of the electrode in m
L = Distance between electrode in m

12.2.19 Specific conductivity measurement using the two electrode principle

The current I through a conductivity cell of the two electrode principle is direct proportion to the
resistance of the cell at a constant voltage across the cell.

Icell = Gcell .Vcell

Vcell is the applied AC voltage across the measuring cell at a frequency dependent on the
conductivity value of the liquid to be measured. The value of the current I through the measuring
cell determines the output of a connected signal converter. The construction of the two-electrode
conductivity measuring cell used depends on the cell constant required, and the process
condition involved like temperature and pressure. In practice elelctrodes are seldom plate shaped
but are rings,cylinders or pins depending on the design of the cell.

12.2.20 The cell constant of the conductivity measuring cell

From the formula K = G.L/O

It can be seen that the specific conductivity can be determined from the measured conductivity G
and L. The factor L/O is solely determined by the design and construction of the electrode system
and is called the cell constant of the measuring cell (with symbol C).

The unit of the cell constant C is determined by the equation:

C = L/O

Where L = length of the liquid column between the electrode

O = area of the liquid column between the electrode
-1.
In units C = m
 -1
Figure 12.12 Conductivity measuring cell with a cell constant of 0.1 CM

12.2.21 The nominal cell constant

The value of the cell constant being indicated on the conductivity measuring cell is the nominal
cell constant. The value is marked within an accuracy of 2%. If the cell constant has a greater
deviation as a result of manufacturing tolerances then the amount of deviation is marked on the
cell.

Deviations in cell constant can occur

1. by a partial short circuit of the electric field being caused by the effect of the wall of a tank or
pipe-line in which the cell is located
2. the electric field is not limited to conduct between the electrodes in the internal liquid column
but is affected by external conducting paths
3. during the manufacture of cells due to production limitations in casting, injection, molding.

12.2.22 The influence of temperature on conductivity

It is well known that the resistance of a metal conductor increases temperature of the conductor.
This is caused by the fact that transport of electrons is restricted at a higher temperature. In
liquids the converse is true as the mobility of ions increases at a higher temperature. The extent
 0
of increasing conductivity per C is expressed by the temperature coefficient alpha. When this
coefficient is known for an electrolyte solution the conductivity value at any temperature can be
calculated.

In a formula is expressed as follows : Gt = G0 [1+ a0 (Tt-T0)]

In which

0
Gt = conductivity at Tt C
0
G0 = conductivity at T0 C
0
a0 = temperature coefficient at T0 C

12.2.23 The measuring principle of a signal converter

The principles of the converter is the measurement of a current through the measuring cell

Icell = Vref. Gcell

Gcell is voltage across the measuring cell

The voltage across the measuring cell is initially corrected in a reference circuit to compensate for
three effects:
Temperature variations of the medium (using a temperature sensor)
Deviations in the nominal cell constant (cell constant correction)
Temperature coefficient of the medium

The corrected reference voltage in changed by a DC/AC converter into a square wave voltage
with a frequency of either 625 Hz or 2000 Hz. The frequency chosen depends on the measuring
range. Range resistors in the measuring converter input circuit are used to set the value of the
voltage across the measuring cell. Any DC components that may occur are blocked by a
condenser. This prevents measurement errors by polarization or attack of the electrodes by
electrolysis.
Figure 12.13 Circuit diagrams of a conductivity converter

The AC current through the measuring cell is rectified in a synchronous detector. A digital
filtration following the synchronous detector prevents any measurement errors caused by
polarization or cable capacity effects.

Conductivity typically has a measuring scale from 0.05 S/cm to 2000 mS/cm as shown on below
application range.
12.2.24 Dissolved Oxygen measurement

Dissolved oxygen is the term commonly used in liquid analytical work for the measurement of the
amount of oxygen dissolved in a unit volume of water. It is an important indicator of the degree of
usefulness of a sample of water for a specific application.

Due to different application and processes dissolved oxygen are required to be high in some
application and requires to be minimum on other cases. Natural water sources such as river and
pond requires high DO level so that living condition is favourable to organism such as fish and
suppress the growth of certain harmful bacteria. On the other hand we would like to minimize the
presence of dissolved oxygen in process such as boiler. Oxygen in water may cause the
formation of an oxide layer on tubes that ultimately reduce the heat transfer from fuel. All this will
translate into cost wastage.

The amount of oxygen that a given volume of water can hold is a function of
1. The pressure the atmospheric oxygen is exerting at the air water interface
2. The temperature of the water
3. The amount of other substances dissolved in the water

12.2.25 Effect of partial pressure of oxygen on dissolved oxygen

During its random movement some oxygen molecules may unintentionally enter and dissolve into
water at the interface of water-air. The process is continuous until the pressure exerted at the
same interface by the oxygen in the air. The amount of oxygen absorbs by this process is small
and normally measured in unit of part per million (ppm). In some pressured process such as
boiler the presence concentration of these DO are influenced by the air pressure acted on the
water. DO is usually higher when pressure increases.

12.2.26 Effect of temperature on dissolved oxygen

The oxygen molecules that have a low solubility become readily energized by the infusion of
energy into the system. The more sluggish water molecules step up their molecular activity at a
slower pace. As a result more oxygen molecules break through the air water interface to the
space above the water surface than water molecules do leaving fewer oxygen molecules
dissolved in the water. When the water boils, all of the oxygen molecules have been driven out of
the water and now the water molecules are coming out of the beaker so fast that they form a
layer of water vapor immediately above the water surface. This layer effectively isolates the water
from atmospheric oxygen and the DO content of the water is zero. Basically there are two general
techniques for measuring DO. Each employs an electrode system wherein the dissolved oxygen
reacts at the cathode producing a measurable electrochemical effect. The effect may be galvanic,
polarographic or potentiometric.

One techniques uses a clark type cell that is merely an electrode system separated from the
sample stream by a semi-permeable membrane. This membrane permits the oxygen dissolved in
the sample to pass through it to the electrode system while preventing liquids and ionic species
from doing so. The cathode is a hydrogen electrode and carries a negative applied potential with
respect to the anode. Electrolyte surrounds the electrode pair and is contained by the membrane.
In the absence of a reactant, the cathode becomes polarized with hydrogen and resistance to
current flow becomes infinite.

When a reactant such as oxygen that passed through the membrane is present the cathode is
depolarised and electrons are consumed. The anode of the electrode pair must react with the
product of the depolarisation reaction with a corresponding release of electrons. As a result the
electrode pair permits current to flow in direct proportion to the amount of oxygen or reactant
entering the system hence the magnitude of the current gives us a direct measure of the amount
of oxygen entering the system.

At low dissolved oxygen concentrations, pH variations below pH 5 and above pH 9 interfere with
the performance of the thalium probe. The interference amounts to about 0.5 mg/L DO per pH
unit. The performance of mebraned probes is not affected by pH changes. A serious limitation of
the thallium probe is the fact that thallium is quite toxic and you must exercise care in using it.
Membrane probes do not have this drawback.

The second basic measuring techniques uses an electrode system that consists of a reference
electrode and a thallium measuring electrode. No semi-permeable membrane is used the
electrode system is immersed directly into the sample. Oxygen concentration is determined by
measuring the voltage potential developed in relation to the reference electrode when dissolved
oxygen comes in contact witn the thallium electrode. At the surface of the electrode the thallous
ion concentration is proportional to the dissolved oxygen. The voltage potential developed by the
cell is dependent upon the thallous ion concentration in this layer and varies as the dissolved
oxygen concentration changes. The cell output rises 59 milivolts for each decade rise in oxygen
concentration. This technique uses a potentiometric system. The method measures directly the
concentration of oxygen in the sample.
All galvanic cell consists of an electrolyte and 2 electrodes. The oxygen content of the electrolyte
is brought into equilibrium with that of the sample. If there is no external voltage being applied
then the reaction is spontaneous. The cathode reduces the oxygen into hydroxide, thus releasing
4 electrons for each molecule of oxygen. These electrons cause a current flow through the
electrolyte, the magnitude of which is in proportion to the oxygen concentration in the electrolyte.

For most common electrode the materials are gold, silver, copper or lead and the most frequently
used electrolyte is potassium hydroxide (KOH). The cathode must be noble (silver or gold) in
order for the cathode potential to reduce molecular oxygen then the cell circuit is closed. The
anode is selected to be a base metal with good stability and without any tendency towards
passivation. The electrolyte is selected so that it will not dissolve the anode at high rate when the
cell is open.

For lead anode the cell reactions are as follows,

- -
Cathode O2 + 2H2O + 4e 4OH
2+ -
Anode 2Pb 2Pb + 4e

12.3 EXPERIMENTAL EQUIPMENT

For the purpose of studies, the pH, conductivity and dissolved oxygen instruments have been
installed into a simplified process. This process skid provides the fundamental operation
understanding in liquid analytical experiments. Among the analytical instruments provided in the
experiment are per below:
Item Instrument Model Function
1 PH/ORP PH20-F-G-05-T1-N-A/SN3 This panel mounted
Sensor/Converter PH202G-U-E/U instruments will provide
continuous measurement
of pH
2 Conductivity SC41-EP15 This panel mounted
Sensor/Converter SC402G-E-2-E/PM instruments will provide
continuous measurement
of Conductivity
3 Dissolved Oxygen DO30G-S50-05-FK This panel mounted
Sensor/Converter DO402G-E-2E/U instruments will provide
continuous measurement
of dissolved oxygen
4 3 Pen recorder 436003 This instrument records
the pH, conductivity and
dissolved oxygen reading
as measured by panel
mounting meters
5 Portable pH meter PH82-21-E This portable instrument
will provide mesurement of
pH
6 Portable Conductivity SC82-21-E This portable instrument
Meter will provide mesurement of
conductivity
7 Portable Dissolved HI9143 This portable instrument
Oxygen Meter will provide mesurement of
dissolved oxygen

12.3.6 The pH, conductivity and dissolved oxygen skid operation

The pH, conductivity and dissolved oxygen skid is designed to conduct dynamic studies on
chemical parameter such as pH, conductivity and dissolved oxygen. It consists of 3 dosing tanks
for acid, alkali and salt solution. There is also a city water tank that provide basic medium for
chemical reaction. The chemical and city water could be dosed to a mixing tank for chemical
interaction. The parameter would be measured by respective sensors that being mounted in an
electrode chamber.

During the experiment, acid, alkali and salt solution would be dosed into mixing tank by individual
dosing pumps. These pumps are controlled by on-off switch that located in front of the panel. City
water on the other hand could be flow into mixing tank through a water pump. There is a manual
valve (MV-H20) that controls the flowrate into mixing tank. To ensure a homogeneous of chemical
content there is a circulating pump that sucks water from the bottom of mixing tank and flow back
via top of the mixing tank. The circulating flows will pass by the electrode chambers if manual
valve (MV-EC) is open.

The rate of chemical dosing could be set. We could control both the dosing rate (dose per minute)
as well as dosing length (ml per dose). The settings of these parameters are on individual dosing
pump. There are 3 types of stroke rates, I, II and III that corresponding to 120 Hz, 60Hz and 0Hz.
The stroke length or volume could be set via the length setting knob. The delivery capacity is
control in percentage (0% to 100%).

The skid is also equipped with a bubbling system. Gas bubble either air or nitrogen could be
pumped into the mixing tank via a bubbling ring at the beneath of the mixing tank We could select
either air or nitrogen as the medium. These supply are controlled by individual manual valves,
MV-AIR for air and MV-N2 for nitrogen.

There are 3 electrodes being mounted in the electrode chamber. They act as the sensors for pH,
conductivity and dissolved oxygen measurements. These electrodes will sense the chemical
content of the sample and convert them into electrical signal. The signal will then go to individual
converter. We could see individual measurement reading from the digital indicator. pH
measurement is without unit while conductivity and dissolved oxygen are both in S/cm and per
per million (ppm). There is also a paper recorder that record the continuous measurement of pH,
conductivity and dissolved oxygen.

Upon completion of each experiment, the samples could be discharged with help from circulating
pump. This procedure could be achieved by switching off the MV-EC and on the manual valve to
demineralizer, MV-DM. Most of the harmful chemicals would be absorbed before it is discharged
into the drain.
12.3.2 The setting of instruments

The instruments have been configuring to suit the application of the training skid. It is important
for the students to take note of these parameter to ensure them have better understanding on the
experiments that they are going to conduct.

Item Instrument Parameters Values

1 PH/ORP Measurement range 0 to 14 pH
Sensor/Converter recording channel Input II
Pen colour Green
2 Conductivity Measurement range 0 to 1000 S/cm
Sensor/Converter recording channel Input I
Pen colour Red
3 Dissolved Oxygen Measurement range O to 20 ppm
Sensor/Converter recording channel Input III
Pen colour Red
4 3 Pen recorder Chart length 100 mm
Chart speed 10 mm per min
5 Portable pH meter Measurement range pH 0 to 14
6 Portable Conductivity Measurement range 0 to 200 mS/cm
Meter
7 Portable Dissolved Measurement range 0-45 ppm
Oxygen Meter

12.4 PROCEDURE

Calibration of portable pH meter

1 Prepare 2 bikers for standard pH solution of pH 4 and 7. Pour the standard pH solutions
into biker until 2/3 full
2. Remove the vinyl cap from the sensor. Rinse the sensor of portable pH sensor with
distilled water. Shake it gently to dispose water droplets adhering to the sensor.
3. Wash the sensor with standard solution of pH 4. Shake it gently to dispose solution
droplets adhering to the sensor.
4. Dip the electrode into the solution but do not let the sensor touch the bottom of the
bottom or wall of the beaker.
5. The amount of sample in the beaker must be sufficient to cover the junction of the
reference electrode the measuring electrode and temperature sensor.
6. Measure the initial pH and temperature while gently stirring the sample.
7. Observe the change in pH value. Wait until the reading becomes stable.
8. Record the field form pH and temperature value into table 11.13.
9. Press button CAL 4, 7, 9 to calibrate the reading. There will be a blinking of CAL
indicated on the screen.
10. Wait for the reading to stabilized.Press ENT.
11. Record the reading into table 11.13
12. Repeat these steps (3-11) for pH 4. Record the reading of pH into table 11.13.

Calibration of portable conductivity meter

1. Remove the vinyl cap from the sensor. Before calibrating conductivity meter with
standard solution, please ensure the electrode is clean. If stains are found, clean the
electrode first. Ensure the electrode cover is secured.
2. Prepare bikers for standard NaCl conductivity solution of 10.67 mS/cm. Pour the
solutions into biker until 2/3 full
3. Rinse the sensor of portable conductivity sensor with distilled water. Shake it gently to
dispose water droplets adhering to the sensor.
4. Wash the sensor with standard solution of NaCl. Shake it gently to dispose solution
droplets adhering to the sensor
5. Press TEMP COEF twice and NaCl will appear. Press ENT. This is to set the
temperature coefficient of NaCl solution
6. The ambient temperature shall be in the range +/- 25 deg C
7. Dip the electrode into the solution but do not let the sensor touch the bottom of the
bottom or wall of the beaker.
8. The amount of sample in the beaker must be sufficient to cover the junction of the
reference electrode the measuring electrode and temperature sensor.
9. Wait until the temperature and conductivity reading stabilized
10. Press CAL and correct the conductivity value by pressing up and down key button until
the display show exact conductivity reading.
11. Press enter to store calibrated information into the meter.
12. Press CELL CONST to check the new cell constant value
13. Record the value into table 11.14.
Titration of ACID HCl and BASE NaOH
1. Ensure the mixing tank, dosing tank and water tank are clean and do not have any
contamination.
2. Fill a mixing tank with city water to about 80% of full. Ensure the manual valve for water
tank MV-H2O is fully open.
3. Put acid HCl solution and base NaOH solution into the dosing tank.
4. Open valve MV-EC (manual valve for electrode chamber) to enable solution to flow back
into the mixing tank.
5. Shut off MV-EC and open MV-DM (manual valve for demineralizer). Switch ON the
circulating pump. The solution inside the mixing tank would be drained after going
through the demineralizer. Shut the circulating pump when draining completed.
6. Shut off MV-DM and open MV-EC to 45%. Swithch on water pump. Water will flow into
the mixing tank.
7. Switch on the circulating pump when water level is approximately 3 cm depth.
8. Switch off the water pump when water reaches level A.
9. Check the dosing volume dial for acid and alkali dosing pumps. Make sure that the dial
pointer is at 70% of the scale and frequency is at II position. Take down the reading of
pH, conductivity and record it into table when reading is stabilized.
10. Switch on acid dosing pump and start the stopwatch. Acid HCl solution will be dosed
into the mixing tank. Start recording by pressing REC on recorder. Notice there
should be a light indicator to indicate the start of recording.
11. The pH value and conductivity value shall change with the addition of acid HCl.
12. Switch off acid dosing pump to stop dosing when time is 4 minutes. Allow the reading to
stabilized for the 4 minutes.
13. At 8.00 minutes start dosing NaOH by switching ON alkali dosing pump.
14. Let the base to be dosed into mixing tank. pH of the system should be getting higher due
to reaction between acid and alkali. You should be able to notice the change of pH and
conductivity values due to the process of naturalization.
15. Press REC button on the recorder to stop recording. Press the button FEED in the
recorder for 10 seconds. This will create an extension so that student can collect the
chart that experiment data located.
16. Collect the experiment graph on the chart paper.
17. Repeat the experiment graph on the chart paper.
18. Repeat the experiment for step 1 to 17 for water level of B and C.
19. Record and calculate the required data into DATA and RESULTS section.
20. The chart recorder is recording with time scale as x axis and pH as y axis. Chart speed is
10 mm per minute and range is 0 to 14 pH.
Table 12.14 Value of pH measured by portable pH meter in comparing with standard solution

Standard buffer solution 7 4

pH before calibration
pH after calibration
Temperature (deg C)

Table 12.15 Calibration of the conductivity meter

Calibration Before calibration After calibration

Cell constant

From the titration graph, plot the graph for both pH and conductivity using these scales

Axis Parameter Range

First y axis pH 0-12
Second y-axus Conductivity 0-1000
x-axis Time 0-17 minutes

Draw 2 vertical lines on the graph at 4:00 and 8:00 minutes. Divide the chart into these zones:
Zone 1 = HCl dosing
Zone II = Stabilization
Zone III = Titration with NaOH

Plot the graph for acid base titration experiment at level B & C (graph 1,2 & 3) . Plot another
graph that show the changes of pH only and conductivity only for level A, B and C.
12.5 REVIEW QUESTIONS

1. For zone 1 of all three experiments are the amount acid doses for all three experiments
the same? What are the stable pH and conductivity values?
2. Comment on the change of pH and conductivity value for level A for zone I
3. What is the difference at the gradient plotted for pH in acid base titration with level A, B
and C. Comment on the observation?
4. What are the changes on conductivity measurement during titration period? Explain on
the observation.

12.6 EXPERIMENT FOR DISSOLVED OXYGEN MEASUREMENT

Experimental apparatus

1. Dissolved oxygen sensor (DO30G-S50-05-FK)

2. Converter (DO402G-E-2E/U)
3. 3 Pen Recorder (436003)
4. Portable Dissolved Oxygen Meter (HI9143)

12.7 PROCEDURE

Calibration of portable oxygen meter

1. Ensure the probe is ready for measurement. The membrane is filled with electrolyte and
probe is connected to the meter
2. Switch the dissolved oxygen meter on
3. COND will appears on the display to inform us that the probe is in auto-conditioning mode
4. One COND disappears the probe is polarized and instrument can be calibrated.
13 For an accurate calibration it is recommended to wait an additional 5 to 10 minutes to
ensure optimum conditioning of the probe.
14 Remove the protective cap.
15 Press CAL and ----- appears on the larger LCD to indicate that the instruments is in
calibration mode.
16 The instrument will automatically standardize itself to the actual saturation valve. After
approximately 1 minute, it will show 100%. On the LCD and small SAMPLE to indicate that
the calibration is complete.
Dissolved oxygen measurement experiment bubbling system

Please ensure the MV-DM is shut Close and MV-EC is 45% Open

1. Switch on water pump to allow water to be pumped into mixing tank. Switch on the
circulating pump after when water reach level A.
2. Stop the water pump when water fill the mixing tank with city until level C
3. Make sure there is pneumatic supply at 15 psi. Check the pneumatic air regulator to start
recording. Start the stop watch.
4. Switch ON the manual valve MV-AIR. Press REC on the recorder to start recording. Start
the stopwatch.
5. You should be able to notice the formation of air bubbles at the bubbling ring.
6. There shall be some changes in dissolved oxygen reading caused by the air bubbling.
7. Switch OFF the pneumatic supply when time is 30:00
8. Pressure REC to stop recording. Press FEED to extant some length of chart paper so
that you can collect the chart from the recorder.
9. Stop the circulating pump and allow water from the electrode chamber to drain back to
the mixing tank.
10. Shut OFF MV-EC and OPEN MV-DM. Start the circulating pump. Water inside mixing
tank to draw into the drain.
11. OFF circulating pump when all water inside the mixing tank been drain out.
12. Repeat step 1 to 11 for experiment on oxygen dissolvability in salt solution however dose
salt solution for 3 minutes after step 2
13. Repeat the experiment for step 1 to 11 by using nitrogen air bubbling. However the
manual valve MV-N2 is to open at step 4 and not MV-AIR.

Always keep some water inside the electrode chamber to avoid damages caused by hydration.

Plot the graph dissolved oxygen value with time for experiment on oxygen dissolubility on
a) City water and salt solution
b) When bubbling is nitrogen gas

The range of dissolved Oxygen converter is 0-20 ppm. The speed of the recorder is 10 mm per
min.
12.8 REVIEW QUESTIONS

1. What is the initial and final dissolved oxygen value in city water for bubbling process?
2. What is the effect of air bubbling into city water?
3. Comment the factor that contributed to the above changes.
4. Is there any visible difference in oxygen dissolubility in city water and salt water?
5. What is the factor that contributed the above difference?
6. What would be the effect of nitrogen bubbling into the sample?
7. Why is the presence of nitrogen bubbles affect dissolved oxygen value in city water?

12.9 REFERENCES

1. Conductivity in theory and practice Yokogawa Elecrofact BV edition TE 12D7AO-E

2. PH202G pH transmitter User/s manual, Yokogawa Europe B.V IM 12B6C3-E-H
3. SC402G Conductivity and resistivity converter Yokogawa Europe BV IM12D7C3-E-H
4. Instruction Manual for DO30/FD30/PB30 Sensors and Fittings for Dissolved Oxygen,
Yokogawa Europe BV IM12J6K4-E/D/F-H