ANALYTICAL INSTRUMENTS

Analysis by instruments can be of two types; QUANTATIVE and QUALITATIVE.

In the former type results yield numerical value of constituents while in the
later the molecular /atomic species, structural features or functional groups in
a sample can be obtained.
In our power plant, most of the analytical instruments are meant to provide
us with a continuous online quantitative data. The instrumentation system
may be in-citu or with an additional sampling system.

The analytical instruments that are in use in our power plant can be broadly
classified as stack monitoring instruments, gas analysers and steam and
water analysers . However, a few more portable instruments are used in
chemical laboratory.

Oxygen Analyser

The oxygen analyser probe is designed to measure the net concentration of

oxygen remaining after all fuels have been oxidised. The probe is
permanently positioned within the exhaust duct and performs the system
without any sampling system.

The equipment measures the oxygen percentages by reading the voltage

developed across a heated electrochemical cell, which consists of a small
yttriastabilized, zirconia disc. Both sides of the disc are coated with porous
metal electrodes. When operated at a proper temperature, the millivolt
output voltage of the cell is given by the Nernst Equation:
E.M.F. =KTLOG1O (P1/P2) + C

Where:
P2 is the partial pressure of the oxygen in the measured gas on
one side of the cell
P1 is the partial pressure of the oxygen in the reference air on
the other side
T is the absolute temperature
C is the cell constant
K is the arithmatic constant

When the cell is at the operating temperature and there are unequal
concentrations across the cell, oxygen ions will travel from high partial
pressure oxygen side to the low partial pressure side of the cell. The result is
a logarithmic related output voltage. Because the magnitude of the output is
proportional to the logarithm of the inverse of the sample of the oxygen
partial pressure, the output signal increases as the oxygen concentration of
the sample gas decreases. This ensures a high output even for low oxygen
concentration.

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Hydrogen Purity meter. (analyser)

The measurement principle used in the on-line hydrogen purity meter is the
thermal conductivity of gases. Gases have thermal conductivities, which are
different for different gases. The thermal conductivity of a gas mixture is
a function of individual conductivities and gas concentrations and is
approximately given by

where is the thermal conductivity of the j th gas whose concentration is

so that.

The analyser used in Bk.T.P.P. is unselective, exact concentration of the

measured component can be measured only in a binary (two-component)
gaseous mixture.
If the sample gas contains other gas components, their influence has to be
taken care within factory set parameters.

Measurement of thermal conductivity involves the measurement of thermal

loss due to heat conductions. This is accomplished in hot wire cells, referred
as Katharometer cells. The cells consist of a heating element in the form of a
straight wire mounted in a chamber. This hot wire cells are temperature
dependent ohmic resistances serves to supply heat input by electrical energy
conversion and simultaneously measures temperature change by resistance.
Platinum is used more often as the hot wire for its good chemical stability
large temperature coefficient of resistance.

Two sets of cell sealed in a glass are placed within a chamber; one flushed
with sample gas and the other with encapsulated reference gas. The sample
gas free from any measured components should have thermal conductivity
approximately same as reference gas. The four wires connected in a wheat-
stone bridge pattern is powered by a bridge current source, thus heating the
resistance wires and making them assume a temperature dependent on the
thermal conductivity of the reference or sample gas. The lesser the difference
between the thermal conductivity of the sample gas and that of the reference
gas, the lesser will be the effect of fluctuation in the ambient temperature on
the equilibrium of the bridge.

If the sample gas contains the measured component its thermal conductivity
changes thus changing the temperature and resistance in the wires flushed
by the sample gas; equilibrium of the bridge is disturbed. The resultant

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bridge diagonal voltage is a measurement of the concentration of the
measured component in the sample gas.

Dust and Opacity monitor

When a beam of light crosses a medium containing smokes or dust particles,

some of the light is transmitted and some is lost due to scattering. The
fraction, which is transmitted, is called the transmittance and the fraction,
which is lost, is the opacity.

Beer Lamberts Law

The mathematical relationship between the light transmitted by a medium

and the quantity of pollutant present is given by Beer Lamberts Law and is
given by:

where:

= Transmittance
I = Intensity of light into the medium
I = Intensity of light out of the medium
a = Attenuation coefficient
c = Concentration of pollutant
= Distance of light beam travels through the medium

since opacity (Op) = 1- , the above equation becomes

The quantity is proportional to the amount of dust in the optical path.

The optical Density is defined as ;

O.D. =
=

The dust concentration can be derived as

DUST = K x O.D. where K= 2.303/a

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By comparing a series of optical density measurements with gravity dust
measurements, it is possible to derive the value of K in real time application.
It should be noted here that in a double pass system a path length correction
factor is required for correcting the change in path lengths between the
measurement and exit diameters of the stack.

SOx and NOx analyser

Non-dispersive absorption type IR spectroscopic technique is used to

measure SOx and NOx. A non-dispersive type uses narrow frequency band
source.

Equal intensity chopped infrared beams are passed through a measuring cell
(MC) and a reference cell (RC) simultaneously. The reference cell is filled with
a standard non-absorbing gas while the measuring cell contains the process
gas.

The analyser mounted in Bk.T.P.P. is not an in-citu and hence a sample

handling system is required. Apart from collecting the flue gas sample from
the duct, all moisture present that may be present in the sample is removed
and drained out.
Even all such gases that may absorb wavelengths in the given range are also
filtered out using filter cells.

The beams from the MC and RC pass on to the detector D that consists of two
sealed absorption chambers A1 and A2 filled with the measuring gas and
separated by a thin metal diaphragm which forms a parallel plate capacitor
with an adjacent perforated fixed metal plate. These gas chambers will
therefore, selectively absorb radiation. Chamber A1 receives radiation which
has already been absorbed in parts in the MC and the gas in A1 will not
further absorb the same energy as would the gas in A2 so that the chamber
gases would be unequally heated to cause a movement of the metal
diaphragm to produce a change in the capacitance which is measured by a
bridge and amplifier-detector.

SWAS

SWAS is the commercial name adopted for the steam and water analytical
system. The instruments available under this system have a separate
sampling handling system and henceforth are not in-citu type. In the main

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power plant these package is provided by ABB and for the DM plant lab.
these are mostly of YBL make.

Dissolved Oxygen measurement

The sensing probe for the dissolved oxygen is a membrane electrode, which
allows electro chemical reaction.
A typical cell has inner cylindrical anode made of lead and outer perforated
cathode usually of silver- the combination being immersed in an aqueous
solution of KHCO3, which is held in a position by a silicone rubber membrane.
This membrane is permeable to oxygen but not to water or other ions likely to
be present.

Diffused oxygen is reduced at the cathode as per the equation

and a current proportional to the partial pressure of oxygen is obtained. With

change in temperature this current changes and hence a temperature
compensating circuit is required. For this a continuous monitoring of
temperature is done by a RTD.
The anode gets eroded on continuous use, the rate of erosion being
dependent on the amount of oxygen measured and the initial size and shape
of the electrode. It is therefore required to replace the probe after specified
periods.

pH measurement

pH is the measure of degree of acidity or alkalinity in a fluid. The scale value

is defined as the negative logarithm of the hydrogen ion concentration, or

In a solution both H and (OH) are present. The dissociation constant is

defined as the product of the number of H ions (OH) ions and this is 14
always.

The principle of pH measurement is based on the property of H ions, which

react with a special glass membrane/electrode and produce a potential
difference between the solution and the electrode. A suitable measuring
circuit measures this potential difference. For a potential difference to exist a
salt bridge needs to be developed; linking the two cells that has conductivity
but does not alter the emf conditions in the two cells

The reference electrode used here is a calomel electrode, which consists of

an inner tube containing calomel i.e. Hg and Hgcl in which the Pt wire is

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immersed. The inner tube also consists of glass wool placed at the bottom
where a small hole is made for bridging. The inner tube is placed in an outer
glass envelope containing sat. Kcl soln. The outer tube is provided with a
filling neck and a bridging hole for contact with the measuring solution.

The measuring electrode a glass electrode has special glass wall bulb at the
bottom, which separates a buffer solution contained in the bulb from the
measuring solution. The electrode wire is dipped in the buffer. Between this
buffer whose pH is known and constant and the unknown solution an emf is
generated which is proportional to the measuring PH.

Conductivity measurement

Conductivity is defined as the current carrying ability of an electrolyte and is

denoted as conductance per meter or S/m.

Measurement of conductivity involves cell, which conduct small alternating

current through known precise volume of the liquid under measurement. The
cell consists of a pair of electrodes spaced a constant distance apart and an
external circuit does the measurement of resistance. Conductance is given by
the equation:
C = a/R

where: a = cell constant given by manufacturer

R = resistance

Silica analyser

The technique of analysis is partly chemical and partly optical with both
techniques automated in one single unit.

The chemical method used in the monitor utilizes the reaction between
silicate species in the sample, acid and molybdate reagents to form yellow
molybdosilicic acid complex. The acid conditions are chosen so that
specifically beta-molybdosilicic acid is produced which excludes interference
from other forms of the acid complex. To increase the sensitivity of the
method the yellow acid is reduced to the blue form, which is measured
colorimetrically in the optical system.

The sequence of events is:

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Sulphuric acid is added to the sample to reduce the pH to a value between
1.4 to 1.8 pH. .

Ammonium molybdate is added to the acidified sample

The solution enters the first reaction coil in the temperature controlled block
(providing two minutes delay) where the yellow beta-molybdosilicic acid is
developed.

Sulphuric acid plus citric acid is added before the solution enters the second
reaction coil in the temperature controlled block (providing two minute delay)
to reduce the pH further to a value between 0.8 to 1.0 pH. This is the value
required to stop further development of silica and to provide conditions for
the next reaction (reduction) to take place. Citric acid is used to destroy any
phosphate complexes if present which would augment the colour developed
in the next stage.

The reduction solution (ascorbic acid) is added before the solution enters the
third reaction coil in the temperature controlled block (providing a one minute
delay) reducing the yellow complex to the blue form.

The fully developed solution passes to the measuring cuvette in the optical
system where the intensity of the colour is proportional to the original silica
concentration.

In a typical colorimetric set-up visible radiation from ac source passes

through a wavelength selector (filter) F to fall on the sample cell SC (cuvette).
The amount of radiation that is not absorbed by the sample passes through
the cell and excites the photo detector PD, the output of which is then
amplified by an amplifier and indicated by the indicator I.

Sodium analyser

The sodium analyzer is an electro chemical cell with a facility to do online

calibration.

The sample passes through one half of a heat exchanger, which is used
during the calibration sequence to bring the standard solution close to the
temperature of the sample. This reduces the calibration time.

From the heat exchanger, the sample passes through a solenoid valve to the
constant head unit, which removes the effect of changes in the sample
pressure and flow-rate. The over flow unit also ensure self starting of the
system when the sample is lost and enables the monitor to function over a
wide sample flow.

The sample is then delivered to the T piece and a stainless steel entrainment
tube, where an alkaline vapour reagent (ammonia soln.) is added to the

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sample to raise the pH value, before flowing past the sodium and reference
electrodes mounted in the flowcell. The sample leaves the flowcell and is
passed on to the drain.

The potential developed between the sodium ion-responsive electrode and

the calomel reference electrode is logarithmic with respect to changes in
sodium ion concentration. The emf developed is given by the equation:

where:
R = gas constant
F = Faraday constant
T = temperature in K
= Sodium ion concentration
K = a constant

A temperature sensor fitted in the flow cell detects the temperature of the
sample and is used for the automatic temperature compensation.

Hydrazine analyser

The measurement technique involves cell potential measurement and is a

galvanic action.
Sample enters through a grommet in the bottom of the case and travels to a
constant head unit. From there, it travels to the solenoid valve, which is used
as a change over valve for calibration purpose. From the valve, the sample
flows through caustic (sodium hydroxide) dosing chamber to raise the ph of
the sample to 10.5 and on to the mixing coil before passing to the hydrazine
chamber.

The hydrazine sensor and its overflow funnel are mounted on a separate
chamber whose height relative to standard solution container allows correct
rate of flow through the sensor. Even the flow can be adjusted by raising or
lowering the overflow tube in constant head unit.

The hydrazine sensor consists of silver oxide cathode covered by porous

porcelain tube over which a platinum anode is formed. The cell potential
developed initiates a galvanic action with the following reaction at the anode

and

At the cathode. The diffusion rate of hydrazine at the anode is directly

proportional to its concentration and the current is limited by this diffusion
rate.

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