Analytical Instruments

in Water-Steam-Cycles

An Introduction
for the Non-Chemist

ANALYTICAL INSTRUMENTS
 The outcome of an engineering project
such as the design, installation and Literature:
commissioning of an analytical system
in a power plant will to a large extent  Hans-Günter Heitmann, Praxis der
Kraftwerk-Chemie, Vulkan-Verlag
depend on specifying the requirements
Essen, DE 1997,
at the outset. Expertise from many different
ISBN 3-8027-2179-9
sources are involved. Station chemists,
C&I engineers, system integrators and  Brad Buecker, Power Plant Water
instrument manufacturers all have to Chemistry, PennWell, Tulsa OK,
contribute their part. USA 1997 ISBN 0-87814-619-9

The instrument manufacturer often is at Periodicals:

Introduction the end of the line. When he gets to quote
 VGB KraftwerksTechnik/PowerTech,
the instruments, discussions are mostly
on price only. If there are problems at German/English, Essen DE,
[Link]
commissioning or during operation, howe-
ver, the instrument supplier is the first to
 PowerPlant Chemistry,
take the blame because he often is the German/English, Neulussheim DE,
messenger of the bad news. [Link]

Instruments have changed considerably  Modern Power Systems, English,

in the last 10 years. Reliability has been Dartfort Kent, UK
increased and inexpensive microproces-
sors provide a multitude of new functions.  ULTRAPURE WATER, English,
These facts should also reflect in the Littleton CO, USA
engineering and the design of sampling [Link]
systems. New technologies do not necessa-
Associations providing technical
rily increase cost. They can also be used
papers and seminars:
to provide additional safety and reduce
risks and maintenance.  VGB Technische Vereinigung der
Grosskraftwerksbetreiber e.V. Essen,
This brochure will give an overview Germany, [Link]
of the available technology in power
cycle monitoring. Instruments are  EPRI Electric Power Research
not considered apart but they are Institute, Palo Alto, Cal USA
embedded in a general discussion of [Link]
sampling and instrumentation.
 NUS Information Services,
Clearwater, FL 33759-1049 USA
Suggestions and comments are welcome
[Link]
to our e-mail address.

Riedikon, ???
SWAN Analytische Instrumente AG

Ruedi Germann
Managing Director
The aim of power cycle chemistry is to prevent corrosion and to avoid unwanted deposits
in the power cycle. This will reduce downtime and protect expensive components such as
boilers, turbines and condensers.

With the exception of precious metals, The most well-intentioned chemical treatment
metallic surfaces are subject to corrosion program may be virtually worthless without
from water when unprotected. In power appropriate instrumentation. Considering
plants oxidic layers provide the necessary the cost of plant downtime and component
protection. These layers have to be formed replacement, quality assurance is of para-
during start up. During operation the main mount importance.
task is maintaining the integrity of the
protective layers. Why Use Analytical
Metal surfaces and water form an electro-
Treatment Methods Instruments?
chemical system consisting of anode, cathode
and electrolyte. The presence of anodes Several treatment methods have been
and cathodes is due to small differences of recommended and the results are
physical and chemical properties of the regularly discussed. There is, however,
metallic components. no universal solution. Every power
plant is different. The layout of the
Every substance that serves as a conductor plant, construction materials, operatio-
for ions (electrically charged particles) is nal pressure, quality of feedwater and
considered an electrolyte. Even high purity cooling water has to be considered
water is a conductor because water mole- before making a choice.
cules constantly dissociate into positively
Common treatment methods include:
charged hydrogen ions (H+) and negative
AVT All-Volatile Treatment: Feedwater
hydroxide ions (OH-). The conductivity of pH is maintained within a range of pH
the water is increased by the addition of 9 to 10 by addition of ammonia.
salts, acids and alkaline solutions. Dissolved oxygen has to be removed
by adding an oxygen scavenger such
The electric conductivity of feedwater, steam as hydrazine or with the use of a
and condensate clearly is the most impor- degasifier.
tant parameter to monitor in power cycles.
CWT Combined Water Treatment:
During start-up oxidation forms a protective Feedwater pH is maintained within
layer on the metallic surfaces. Dissolved a range of pH 8 to 9 by addition of
substances such as chlorides and sulfates ammonia; dissolved oxygen content
may damage that layer. Low pH-values and between 150 and 300 ppb.
high flows (flow-accelerated corrosion) also
reduce or eliminate the protection. The result OT Oxygenated Treatment: Feedwater
is bare metal, which will oxidize again. is not conditioned to raise the pH. Its
The cycle starts a new with the destruction value is between 7 und 8. Controlled
of the layer and subsequent oxidation. It injection of oxygen maintains a level
is a matter of days until severe damages between 150 and 300 ppb.
appear.

Power cycle chemistry deals with the methods

needed to provide and maintain the protec-
tive layer.

Analytical instruments are necessary to

maintain appropriate levels of pH and oxygen.

3
 There are nearly as many different power cycles as there are power plants. Basic elements
such as feedwater treatment, steam generation and condensation are always present. The
search for higher efficiency and lower cost leads to more complex designs.

On-line monitoring is essential wherever the quality of water, steam or condensate is

subject to alteration. The analytical parameters depend on the design of the power cycle,
the construction materials and the chemical treatment.

Designers and chemists have different views as to analytical parameters and the number
of instruments for on-line monitoring. The following remarks are limited to the use of
instruments from SWAN.

On-Line Instruments
in Power Cycles Feedwater Steam
 Conductivity and pH are the most impor-  One reason for monitoring steam
tant parameters. Conductivity is measured is to verify that the steam produced by
as specific conductivity and/or as conduc- steam generators meets the manufacturer's
tivity after a strongly acidic ion exchanger steam quality guidelines. Recommended
(acid or cationic conductivity). continuous analyses include conductivity,
In most cases pH can be calculated from sodium and silica. At high operating
the difference between the two conductivi- pressure silica and sodium become very
ties. (see page 14). ORP (Redox) analyzers important because potential contaminants
have been added recently. All treatments dissolve faster.
require the monitoring of dissolved oxygen.
The sampling point is downstream of the
feedwater pump and/or at the inlet of the
Condenser
economizer.  Sodium and acid conductivity are moni-
Additional oxygen analyzers might be tored for condenser leakage detection.
necessary to monitor oxygen removal by Sodium is much more sensitive than con-
deaerators or oxygen scavengers. Sampling ductivity. It will indicate leaks hours and
points are before and/or after the deaera- even days earlier. Conductivity will also
tor. If an oxygen scavenger is used, it is respond to CO2 while sodium will indicate
also monitored at the deaerator inlet. other contaminations. Instruments are often
mounted at the bottom of the condenser
and sometimes not regularly controlled. It is
Steam Generator very important to monitor sample flow in
 Continuous analysis should include pH, these cases. A breakdown of a sample
specific conductivity, silica, and phosphate pump might retard leak detection for hours
for phosphate-treated units. Silica is an or days.
extremely important parameter due to its
vaporous carryover qualities and tendency
to form tenacious deposits on turbine blades.
Condensate
Sodium analyzers will also help to prevent  It is at the condenser discharge that gross
carryover. Combined cycle power plants contamination will usually be detected.
have many heat recovery steam generators Acid conductivity, sodium and sometimes
at variable pressures. Conductivity and pH silica are monitored. If a condensate polisher
are monitored at every step. This also is a is operated in a by-pass, the on-line values
good application for multiple stream silica might be used to direct the condensate
analyzers through the polisher.

4
 Typical
Water-Steam-Cycle

Condensate Polishing
 The performance of ion exchangers has Guidelines
to be closely monitored. Parameters of
choice are specific conductivity, sodium Guidelines for the quality of feedwater
and silica. The supplier of the polishers and steam are available from Electric
sometimes provides these instruments. It is Power Research Institute (EPRI) USA
unfortunate for operation and maintenance, and Vereinigung der Grosskraftwerks-
betreiber (VGB) Germany. There are
if they are of a different make from the
many other country- or organization-
ones on the power cycle.
specific guidelines in use.

Make-up Water Suppliers of components (Boilers,

Turbines , Condensers) will include
 Specific conductivity and silica are operating parameters in their waranty
monitored to prevent the introduction of conditions. They might refer to EPRI or
contaminants from the water treatment VGB or use their own experience.
system into the power cycle.

Cooling Water
 Cooling water chemistry is a separate
issue. Many different chemicals are used
for treatment. The supplier of the chemicals
will indicate the parameters to monitor. As
corrosion inhibitors will contaminate many
sensors, colorimetric methods are recom-
mended.

5
Example P&ID

6
Once the sampling points have been determined and the parameter to monitor chosen,
a P&ID (piping and instrumentation diagram) is established.

The first part of the diagram is dedicated to install a temperature shut-off valve as a
cooling the sample and to reducing the safety device. The P&ID should clearly indi-
pressure to acceptable levels. This "hot" cate sample conditions such as flow, pres-
part is often, also physically, separated sure and temperature at the point of sample
from sample distribution and from the instru- distribution.
ments.
A backpressure regulation helps maintain a
A small number of companies have specia- constant flow to the instruments. Its outflow
lized in coolers and valves for these appli- can be used for grab sampling. Every Sampling and
cations. Some will propose secondary coo- instrument must be equipped with a needle
lers to maintain a temperature very closely valve and a flow meter to set sample flow Sample Distribution
around 25°C. This will allow the use of at recommended values. Traditionally, rota-
cheaper instruments without temperature meters are installed at sample distribution.
compensation. Modern instruments can However, lack of sample flow cannot be
accept a wide temperature range and will automatically detected with a rotameter.
automatically compensate for changes. It is Hence it is an unreliable design basis.
up to the designer to determine which way Flow measurements should be at the end of
will be more economical in the end. the sample line and should be connected
to a device that can issue an alarm.
Sample temperature should, however, not Modern instruments have integrated flow
exceed 50°C. Higher temperatures might measurements that are available on signal
damage sensors. It is recommended to outputs and/or on alarm relays.

KKS-Numbers

KKS-Numbers are used for the unique identification of components and signals in a power plant. The standard
has been converted into a DIN and a EURONORM recently:
DIN EN 6779-10 part 10: power plants, June 2000
Identification system for technical products and technical product documentation
Example:
(20UMA0235)10 l QUA l 10 l CQ l 001
l l l l Instrument-Number
l l l Qualitative Analysis (AA0 = solenoid valve, KA0 = fitting)
l l Sample Number
l Sample (A = feedwater, B = steam, C = condensate)
Room Number

P& ID Symbols

7
Instrument Panels

It is common practice to mount the instruments

in groups according to their physical pro-
perties. All transmitters are mounted on one
side, all analyzers (silica, sodium, phosphate)
on the other. Grab sampling lines are put
together over a discharge basin. The wet
part with the sensors is often separated
from the transmitters. In all these cases cali-
bration and maintenance work becomes
difficult and is often neglected.

8
 Instrument Panels

SWAN favors systems where all instruments

of an identical sample are grouped
together for a clear attribution of a measu-
red value to a sample. Calibration and
maintenance are simplified by mounting all
components for an analysis on one panel.

The example shows complete instrument

panels arranged by sample line. Whoever
stands in front of the panel knows exactly
which value belongs to what sample.

The above system incorporates a personal

computer where all process values and dia-
gnostic information are displayed.

9
 Conductivity is by far the most important parameter in power cycle monitoring. It is
measured as "specific" (also direct or total) conductivity and as "acid" (also cationic)
conductivity after a strongly acidic ion-exchanger.

Analytical Method
 Conductivity sensors for use in the low
microsiemens range consist of two elec-
trodes made of stainless steel or titanium.
The cell constant expresses the distance
Conductivity between the two electrodes.
A transmitter provides a constant alternating
voltage. The current that flows through the
circuit depends on the resistivity of the
liquid between the two electrodes only. This
resistivity is measured and expressed as its
reciprocal value in microsiemens per cm2.
It provides a measure for the total presence
of conductive matter in the sample.

Temperature Flow cell with flow measurement

 Conductivity strongly depends on tempera- and needle valve
ture. It is always indicated for a reference
temperature of 25°C. Therefore the conduc-
tivity value must be compensated for the actu-
al sample temperature. Temperature compen-
sation also depends on the nature of the solu- Acid Conductivity
tion. Several temperature curves are selec-  Strong acid cation exchangers have an
table at the transmitter. For power cycles affinity for cations over hydrogen and will
these are: neutral salts, strong acids, strong exchange hydrogen for them as water flows
bases, ammonia, ethanolamine or morhpo- through the vessel. This will eliminate the
line. Linear or non-linear compensation by conductivity from the added alkalinization
coefficient are available for high purity water chemical. Other cations are transformed
(polished condensate or make-up). Strong into their respective acids. The sensitivity
acid temperature compensation is always of the measurement will be increased by a
used when measuring acid conductivity. factor of 3 to 3.5. This makes it easier to
detect small amounts of contaminating ions.
Carbon dioxide will influence the measure-
Direct or specific Conductivity ment. An additional sodium measurement
 Direct conductivity is mostly influenced by will provide a means to detect the origin of
the presence of an alkalinization chemical such the conductivity increase.
as ammonia. Carbon dioxide will add consi-
derably to the measurement mainly at start-up.
Sample Points:
Wherever the quality of water, steam or
Sample Points 
condensate is subject to alteration.
 Feedwater and boiler water in conjunction  Condenser Hotwell for leakage detection.
with pH for the control of alkalinization. Sodium monitors are added to provide
 Make-up water and polished condensate faster results and detect the presence of
to detect contamination. carbon dioxide.

10
Differential Conductivity
 As the strong acid cation exchanger will
eliminate the conductivity from the added
alkalinization chemical, the difference bet-
ween a measurement before and after the
exchanger will indicate the amount of this
chemical. In many cases the pH-value can
be calculated from this difference.

Quality Assurance
 Precision and reproducibility depend on
the stability of the electronic transmitter and
Acid Conductivity
on the precision of the cell constant.
Quality instruments do not need calibration.
The interesting range is around 0,2 µS and
there is no stable calibration solution in this
range anyway. The consumption of the resin
in the cation exchanger must be monitored.
Resins that change their color when consu-
med are available. Combining differential
conductivity with a flow measurement does
automatic monitoring with remote alarm.
SWAN instruments provide conductivity, tem-
perature, sample flow and resin consumption
for automated quality assurance systems.

Process Values

Specific Conductivity 7.36 µS

Acid Conductivity 0.12 µS

Difference 7.21 µS

Sample Temperature 25.3 ºC

Sample Flow 6.1 l/h

Diagnostic Values

Raw Signal 1 7.36 µS

Raw Signal 2 0.12 µS

FAM Powercon+ Dual channel Specific
Resin Consumption 65 % and Acid Conductivity

Case Temperature 25 ºC

Calibration

Cell Constant 1 0.039 21.4.01 11:42

Cell Constant 2 0.043 21.4.01 11:42

Diagnostic Data Monitor FAM Powercon+

Specific and Acid Conductivity

11
 All treatment methods involve maintaining a certain pH. However, the measurement
of pH in waters of low ionic strength is not an easy job. Careful evaluation is necessary,
mainly when polished condensate and make-up water are to be measured.

Analytical Method Temperature Compensation

 A pH measurement consists of a potential  Temperature greatly influences the pH
difference (mV) between two electrodes. The measurement. It is always indicated for a
reference electrode provides a direct con- reference temperature of 20 or 25°C.
tact between the sample and an electrolyte. Therefore the pH value must be compensated
The measuring electrode is separated by for the actual sample temperature.
pH-Value an ion sensitive membrane from the sample. Temperature compensation according to the
The potential difference between the two elec- Nernst equation is a standard. In critical
trodes depends on the number of H+ ions in applications there are additional linear and
the sample. non-linear solution compensations.
Ion-sensitive electrode and reference elec- If pH is calculated from differential conduc-
trode can be combined in a single hou- tivity, both conductivity measurements need
sing. In critical applications around pH 7, temperature compensation.
however, it is recommended to use two
different electrodes.
The critical part in a pH-measurement is the
Sample Points:
liquid junction between the sample and the  Feedwater and boiler water for the
reference electrolyte. Using liquid electrolyte control of alkalinization.
solutions that flow out to the sample in very  Steam and condensate in addition
small quantities can eliminate problems. to acid conductivity.
The flow rate must be stable and constant.
There is an influence from sample flow in
high purity water. Sample flow should
Quality Assurance
be between 5 and 15 liters per hour and  Periodic calibration is required for pH-
should be constant at the chosen rate. systems. The most reliable way is to use a
Atmospheric drain is a must because of recently calibrated laboratory instrument for
possible backpressure on the liquid junction. measuring the sample in the on-line vessel.
The measured process value is then entered
into the on-line instrument.
High Impedance Ampifier
Signal out
The operator should check the free flow of
the electrolyte regularly, mainly before a
calibration
Process pH, temperature and sample flow
pH Electrode with Reference Electrode
Inner Electrolyte with KCI Electrolyte are available for automated quality assurance
systems.

H+ selective Liquid Junction

Glas Membrane

12
The measurement of the oxidation-reduction potential is relatively new in power cycles.
It can give an information on the risks of corrosion and it can serve as a parameter to
control hydrazine.

Analytical Method
 The ORP measurement consists of a poten-
tial difference (mV) between two electrodes
just like in pH. In fact the reference elec-
trode is identical. The measuring electrode,
however, uses a platinum surface where
oxidation or reduction takes place. ORP
The two electrodes can be combined in a
single housing or mounted as two different (Redox Potential)
electrodes.
The critical part is the liquid junction between
the sample and the reference electrolyte as
in pH measurement. Using liquid electrolyte
solutions that flow out to the sample in very
small quantities can eliminate problems.
The flow rate must be stable and constant.
There is an influence from sample flow in
high purity water. Sample flow should be
between 5 and 15 liters per hour and
should be constant at the chosen rate.
Athmospheric drain is a must because of
possible backpressure on the liquid junction.
The redox potential is not compensated for
temperature.

Sample Points:
 Feedwater and condensate.

Quality-Assurance
 Process calibration is the most reliable
method. A laboratory instrument with a
recently calibrated sensor is used to deter-
mine the actual ORP in the sample. The
measured process value is then entered into
the on-line instrument. The operator should
check the free flow of the electrolyte regu-
larly, mainly before a calibration Process
ORP and sample flow are available for
Monitor FAM pH/Redox automated quality assurance systems.

13
 This method for determination sample pH has been known for more than ten years. It is
in fact very simple and reliable and it requires low maintenance. It might not have been
used widely because of a lack of adequate instruments.

Modern electronics with advanced software

can provide a suitable instrument that mea-
sures specific and acid conductivity at the
same time as the sample pH.
It is ideally suited for modern combined
cycle plants with its many sampling points
for pH and conductivity.
Calculation of pH
There are a few restrictions:
from Differential  Measuring range is limited to pH 7,5
to pH 10,5.
Conductivity  One pair of acid-base ions (alkalinization
chemical) must be dominant.
 At a pH lower than 8, the concentration
of contaminants (including phosphate) must
be considerably lower than the concen-
tration of the alkalinization chemical.
It is obvious that the method is not suitable
for samples such as make-up water and
polished condensate.

pH-Calculation from
Differential Conductivity
VGB-Guidelines for boiler feedwater
and steam. Steam generators rated
above 68 bars.

VGB Kraftwerkstechnik GmbH 1988

Quality Assurance
 Maintenance is identical to acid con-
ductivity. There is no need for calibration.

FAM Deltacon pH provides specific con-

ductivity, acid conductivity, calculated pH,
temperature, sample flow and resin con-
sumption for automated quality assurance
systems. Monitor FAM Deltacon pH

14
Comparision between Calculation and Ion-sensitive Method
Calculated pH from SWAN Deltacon pH analyzer, compared to a high quality glass pH-electrode.
Variation of pH by continuous injection of ammonia solutions into a stream of ultra pure water.

10 ppm NH3

pH value calculated by differential conductivity

SWAN Deltacon pH
pH-value

11 ppb NH3
Experimental
pH - glass electrode
Data
Time, minutes

Influence from Neutral Salts

Influence of NaCI contamination on the pH calculation of the SWAN Deltacon pH analyzer and the rea-
ding of a conventional glass pH-electrode.
Continuous injection of a NaCI-solution into a condensate sample of the Beznau nuclear power plant.
Conductivity microsiemens/cm value

Conductivity behind cation exchanger

pH value calculated by differential conductivity

(SWAN Deltacon pH) and pH glass
pH

electrode measurement. The two different

methods show identical results.

Conductivity in front of cation exchanger

Concentration, NaCl (ppb)

Longterm Stability
Continuous parallel on-line pH measurement at Beznau nuclear power plant block 2 (sept. 28, 1998
to dec. 18, 1998, 81 days). Regular power plant on-line pH monitor with conventional glass electrode
and SWAN Deltacon pH.

Regular power plant on-line pH monitor with solution temperature compensation

pH

SWAN Deltacon pH
26,6ºC

Sample temperature (not to scale) 22,4ºC

Data set number

15
 Different treatment methods require different levels of dissolved oxygen. With the excep-
tion of oxygenated treatments, very low levels are required. Very few instruments, howe-
ver, can really measure trace oxygen around 1 ppb.

Analytical Method
 The sensor consists of a cathode (gold)
and an anode (silver), an electrolyte and a
membrane. Oxygen diffuses across the
membrane due to partial pressure differ-
ences. When a preselected voltage is
Dissolved Oxygen applied to the electrodes a current can be
measured which is proportional to the pres-
ence of oxygen in the sample.

Sample flow has an influence on the result.

Hence it must be kept within certain limits.
Alarm contacts should be provided for
high/low flow to prevent erroneous measure-
ments. Atmospheric sample drain is required.

Temperature Compensation
 The diffusion rate of oxygen through the
membrane is influenced by sample temperature.
Temperature also affects the solubility of
oxygen in water. Oxygen sensors have an
integrated temperature sensor for compensa-
tion in the transmitter.

Sample Points:
 Deaerator inlet and outlet.
 Feedwater or economizer inlet.
 Condensate pump discharge

Quality Assurance
 The zero point is very stable and does
not need calibration. For slope calibration
a known standard is required. It is readily
available in the form of water-saturated air.
Exposing the sensor to saturated air just
over water, ideally over the flow cell gives
a slope calibration. The transmitter offers a
calibration routine that will recognize a sta-
ble signal and calibrate automatically. Monitor FAM Oxytrace

16
OXYTRACE - Instruments do not require a generated amount in the transmitter. As long
lot of maintenance. It is sufficient to check as there is no substantial difference, the
the sensor in air once in a while. The trans- instrument works perfectly. Otherwise an
mitter automatically checks electrolyte con- alarm would be issued.
sumption and membrane integrity.
An instrument with faraday verification will
Special attention should be given to sam- work for many months without requiring
pling for dissolved oxygen analyzers. maintenance. The result of the verification
Oxygen is everywhere! It has a fatal ten- process is available for automated quality
dency to enter into the sample through all assurance.
kinds of connections and materials. Trying
to measure multiple streams with the same
instrument is calling for trouble.
Process Values Faraday-Verification
Dissolved oxygen, temperature and sample Oxygen 1.5 ppb
flow are available for automated quality
Sample Temperature 25.3 ºC
assurance systems.
Sample Flow 7 l/h

Faraday-Verification Diagnostic Values

Raw Signal 4.3 nA
 Low-level measurements are most reliable
if the sensor never leaves the sample. Every Calibration
contact with air will produce down time Sensor Offset 0.0 ppb 21.03.01
because air has to be washed out of all Saturation Current 25 µA 21.04.01
parts before a precise reading is possible.
Verification Status ok - 21.04.01
Faraday verification is done by producing a Verification Time 60 sec 21.04.01
small amount of oxygen through electrolysis Verification Efficiency 95 % 21.04.01
upstream of the sensor. As the sensor catches
the additional oxygen it is compared to the Diagnostic Data SOLO Oxytrace

Two Faraday verifications with an operational oxygen sensor and an oxygen sensor
with a defective membrane. Addition of 20 ppb oxygen in high purity water
(0.055 Microsiemens/cm). cycle time 150 sec.
Oxygen concentration, ppb

Operat. sens.
Defect. sens.

Time, Seconds

17
 Sodium provides a very fast, selective and very sensitive means to detect impurities. It is
the first cation to break through in a demineralizer train.

Analytical Method Diisopropylamine is a rather aggressive

substance. It might damage instrument com-
 As in pH there is an ion-sensitive electrode ponents during the absence of sample flow.
and a reference electrode. The reference is Therefore, it is good practice to put a cap
always mounted downstream from the ionsen- on the reagent bottle during down time.
sitive part. This prevents cross-contamination
from the electrolyte. Temperature compensation is mandatory.

Sodium Sodium sensors are also sensitive to hydrogen

Sample Points:
ions. Therefore, sample pH must be increa-
sed to eliminate these ions. Good results  Condenser hotwell and/or condensate
have been achieved by using diisopropyla- pump discharge for leakage detection.
mine. Other alkalinization products might  Detection of impurities after mixed bed
not be strong enough or bear a risk of exchangers: make-up water and polished
cross-contamination (NH3). condensate.
 Steam samples for monitoring carryover.
The amount of alkalinization chemical nee-
ded depends on sample characteristics and
on the lowest detection limit that
Quality Assurance
is required (see also TRACE SODIUM).  Zero and slope should be calibrated
weekly or monthly depending on application.
Samples after cation-exchangers come with The sensor should be etched before making
a very low pH and require high volumes of a calibration to insure proper response times.
alkalinization chemicals. Active dosing as It is also necessary to check the flow of the ref-
done with the SODITRACE instrument is erence electrolyte. Unstable signals very often
necessary. have their origin in the reference system.

Constant
Head

Functional Diagram Reagent Vapors

SOLO Sodium

Reaction Tube

Sample Inlet
with Regulating
Valve

Bubble
Detector

Measuring Cell

Waste

18
One of the most common problems in sodi-
um measurements comes from the standard
solution. It is extremely important to follow
the instructions in the manual carefully. Do
not try to use standards lower than 100 ppb.
Dilution errors will produce bad calibrations.

SOLO Sodium provides semi-automatic cali-

bration. A valve is manually switched from
the sample line to a vessel containing the
standard solution. Pressing the CAL key will
start calibration. As soon as a stable signal
is detected, calibration will be registered Trace Sodium
automatically. The procedure is normally
done with two different standards.

SODITRACE sodium analyzer has a more

sophisticated calibration routine. Multiple
known standard additions are done auto-
matically at preset intervals.

Sodium content, temperature and sample

flow are available for automated quality
assurance systems. SODITRACE also provides
calibration data.

Trace Sodium
 All possible influence from the hydrogen
ion must be eliminated in trace analysis
(< 10 ppt). Therefore, reagent addition is
controlled with a PID algorithm and the pH
is maintained at pH 12. Monitor Soditrace

As the instrument runs out of reagent, false

alarms will occur. Monitoring reagent Process Values
addition will also provide information on
Sodium 0.023 ppb
system performance and call for maintenance.
Sample Temperature 25.3 ºC

Verification Flow Control ok -

Diagnostic Values
 As the SODITRACE instrument provides
fully automated calibration, a standard Sensor Signal -250 mV
solution is always available. The standard Conductivity 450 µS
is diluted down to 10 ppb for automatic
Calibration
verification. As the diluted solution is injected,
the sensor will report the increase. If it is Zero Point 125 mV 21.4.01
within certain limits, the instrument performs Slope 59 mV 21.4.01
well and does not need attention. Verification Status - 21.4.01
ok

The result of the verification process is avai- Diagnostic Data

lable for automated quality assurance. Trace Sodium Analyzer SODITRACE

19
 Silica is the most important parameter on steam samples. It is also necessary to detect
impurities after mixed bed filters. In theory it is the first anion to break through in a
demineralizer train.

Analytical Method Multiple Sample Streams

 The colorimetric method is well known  Silica analyzers are often used for
and widely used. Reagents are added to multiple sample streams. The limiting factor
the sample and change its color. The inten- is the required interval per sample. It
sity of the resulting color is a measure for takes 7 minutes to complete a reaction
the presence of reactive silica. and take a reading. Washing out the
Silica sample takes another 8 minutes. Thus, the
Sample temperature, pH and reaction time measuring interval cannot be less than
are the influences to watch. While pH is 15 minutes.
adjusted to desired levels by reagent addition,
the reaction time is defined by the physical Samples should all be in the same range.
layout of the instrument. It is tricky to measure polished condensate
and boiler water in the same instrument.
Temperature, however, is more difficult to
handle. Sample temperature influences the
reaction and changing ambient tempera-
ture will influence the optical system. The
only answer to these problems is a ther- COPRA Silica has 4 contacts for
mostatically controlled reaction chamber. channel selection. During setup the
user defines if these will be used to
Colorimetric measurements need a base override an internal sequence or to
line or zero. Periodically switching off select a sample.
reagent addition and taking a reading
without reagent will do this. Override: The user programs a
sequence in the transmitter.
Silica-free water is not always available for
preparing the reagents. If the silica content Example: The instrument measures
of the reagents is known, it can be entered 3 different sample streams from 3
into the instrument to be used as an offset. mixed bed filters. The sample is
switched every 20 minutes. If a fil-
Guiding the sample through an anion column ter goes into regeneration it will
automatically compensates for the reagent sili- close a relay that is linked to the
ca. All silica will be eliminated. The resulting instrument. The instrument will know
reading will show the silica content of the that the corresponding sample is no
reagent only. This is then automatically used longer available and will automati-
as an offset until the next change of reagents. cally switch to the next sample.

Select: 3 mixed bed filters are lin-

Sample Points: ked to 3 contacts in the instrument.
 Detection of impurities after anion and Whenever a contact is closed, the
mixed bed exchangers: make-up water instrument will measure the corre-
and polished condensate. sponding sample.
 Boiler water. Silica is often the limiting
factor when a boiler is started up from Channel selection is also available
an outage. on PROFIBUS DP.
 Steam samples for monitoring steam
purity and carryover.

20
Quality Assurance
 In principle colorimetric methods provide Maintenance problems of tubing and pumps
absolute values and don't require slope in analyzers are well known. SWAN has
calibration. It does, however, make sense developed a special device that solves the
to periodically verify the instrument's func- problem. Tubing will now last longer than
tions. A valve switches from the sample line 12 months.
to a vessel containing a standard solution.
If the standard value is detected accurately, Reports to automated quality assurance
the instrument works well and does not systems include the silica process value
need attention. The process is entirely and diag-nostic information such as
automatic; the user may program the verifica- sample and reagent availability. The zero
tion interval. It is strongly recommended point is also reported. This value will Silica
to proceed to verification after a change indicate contamination of the photometer
of reagents. This will help to detect errors when too high.
in reagent preparation.

Process Values
Silica 1.95 ppb
Sample Temperature 25.3 ºC
Sample Flow ok -
Diagnostic Values
Transmission 99.3 %
Reagent Control ok -
Cycle Time 290 tic
Temp. Photometer 45 ºC
Calibration
Zero Point 240 kHz 21.4.01
Calibrat. Factor 0.98 - 21.4.01
Blank Value 1.35 ppb 21.4.01

Diagnostic Data
COPRA SILICA Analyzer

Monitor COPRA SILICA

21
 It is highly recommended to install on-line monitors when phosphate treatment is used for
boiler water.

Analytical Method
 The method is identical to silica deter-
mination. Only the reagent kit is slightly
different. It does not contain a component
that will mask phosphate when measuring
silica. As the detection levels for phosphate
Phosphate are in the ppm range (silica is low ppb),
silica does not have a major influence on
the readings.

Sample Point:
 Boiler water.

Quality Assurance
 Reports to automated quality assurance
systems include the PO4 process value and
diagnostic information such as sample and
reagent availability. The zero point is also
reported. This value will indicate contami-
nation of the photometer when too high.

COPRA Analyzer with Cabinet

22
Chlorine gas is the cheapest method to prevent fouling in cooling water. When added to
water it produces hypochlorous acid (HOCl). At pH values above pH 7, HOCl starts to
dissociate into H+ and OCl-. The latter is much less effective. Other disinfection methods
might prove more suitable in alkaline cooling water treatment programs.

Sample pH 8.5 is the upper limit for this

Analytical Method method.
 The sensor consists of two platinum elec-
trodes and a reference electrode with a It is very important for a stable signal to
liquid junction. When a voltage is applied maintain constant flow between the sen-
to the electrodes a current can be measu- sors. An overflow vessel does this reliably.
red which is proportional to the presence
of oxidizing substances. The polarization The sensor surfaces need continuous clea- Free Residual
voltage depends on the potential from the ning. SWAN uses hydrodynamic cleaning
reference electrode. It is also influenced by with a rotor that will keep the sensor intact Chlorine
sample temperature and requires appropriate and has a virtually unlimited lifetime.
temperature compensation.
The rotor rpm provides alarms for insuffi-
This method will indicate the sum of all oxi- cient cleaning and absence of sample flow
dizing species present. The user will select at the same time.
the parameter (free chlorine, hypochlorous Corrosion inhibitors will coat the metal sur-
acid, chlorine dioxide, ozone) in which to face of the sensor. Only colorimetric systems
express the result by software. will work in such applications.
As cited above, HOCl starts to dissociate
into H+ and OCl- above pH 7. The sensor,
however, responds mostly to HOCl. To a
Sample Points:
certain degree, free residual chlorine can  Cooling water to maintain disinfectant
be calculated from HOCl and pH. The user levels.
can enter sample pH through the keyboard  Cooling water outflow to comply with
or hook up an analog signal from an on regulations.
line pH-meter.

working electrode reference electrode

reference voltage
counter electrode

signal

23
 Quality Assurance Process Values

 The zero point is factory calibrated and Disinfectant 0.25 ppm

hardly needs adjustments. As the measure- Sample Temperature 25.3 ºC
ment is a result of all oxidizing substances, Flow Control 350 rpm
slope calibration is very important.
Diagnostic Values

A reference value is determined by a colori- Sensor Signal 2.25 µA

metric analysis of the sample with a portable Reference Signal 1050 mV
photometer. The sample must be taken
Dosing capacity 1 65 %
directly at the overflow vessel. It cannot be
moved and should be analyzed on site. Dosing capacity 2 65 %
Free Residual The result is entered into the transmitter for Case Temperature 25 ºC
calibration.
Chlorine Zero Point
Calibration

The DPD-method that is used with photome- 0.12 µA 21.4.01

ters also provides the sum of all oxidizing Slope 10.0 µA 21.4.01
substance. Only the influence of sample
pH is eliminated. It is important to choose Diagnostic Data
the same parameter on the photometer and FAM Trides Chlorine Analyzer
on the on-line instrument when making a
comparison.

There are no replacement parts required with Disinfectant, temperature, cleaning efficien-
the exception of the reference electrode. Its cy and sample availability are reported to
service life is between 3 and 4 years. automated quality assurance systems.

Monitor FAM Trides

24
Cooling water treatment chemicals are sometimes of a complex and not always known
composition. In all cases where the disinfectant cannot be identified as chlorine gas or
sodium hypochlorite (NaOCl) it is safer to use a colorimetric analyzer. The same applies
when corrosion inhibitors are added and/or at a cooling water pH above 8.5.

Analytical Method Reports to automated quality assurance

systems include the process value (disinfec-
 The sample flows from an overflow vessel tant) and diagnostic information such as
to a mixing chamber into the reaction tube sample and reagent availability. The zero
and through the photometer. point is also reported. This value will indi-
cate contamination of the photometer when Photometer for Free
Reagent is added in a preprogrammed too high.
sequence into the mixing chamber. Oxi- Chlorine and
dizing substances in the sample will produce
a red color. Its intensity is a measure for the Monochloramine
sum of all oxidizing species present.

The user will select the parameter (free chlo-

rine, hypochlorous acid, chlorine dioxide,
ozone) in which to express the result on the
keyboard.

Water quality and small alterations of the

optical system will influence the results.
These influences are screened out by taking
a zero just before reagent addition.

The reagents contain a buffer solution to

adjust the pH to the optimum level. As a
consequence the analysis does not depend
on sample pH.

Other disinfectants such as chloramines and

ozone require slightly different reagents.

Sample Points:
 Cooling water to maintain disinfectant Compact 402 CODES
levels. Colorimetric Process Analyzer
 Cooling water outflow to comply with
regulations.

Quality Assurance
 Zero calibration is done automatically
before reagent addition. In principle colo-
rimetric methods provide absolute values
and don't require slope calibration. It does,
however, make sense to verify the instru-
ment's functions after reagent refill. A com-
parative measurement with a portable pho-
tometer will detect errors.

25
 Sampling and instrumentation must integrate as a sub-system into the plant's complex con-
trol and instrument design. Exact documentation is required to prevent problems during
installation and commissioning.

The suppliers of instrument racks normally deliver completely wired panels with terminals
in a common cabinet.

Power Supply Ground Loops

 Transmitters are available for different sup-  All instruments are connected to earth
ply voltages (24 VDC, 24 VAC, 100 to for safety. Most have, however, another
Electrical 230 VAC). Analyzers that have to drive grounding through the sensor in the sample
pumps, however, cannot operate on 24 V water. To prevent problems, the sensor inter-
Connections DC or AC. Therefore; it is common to use face must be electrically isolated from the
standard available voltage. Fuses are already rest of the instrument.
present in the instruments but there must be a
way to cut off individual instruments from the Signal outputs should also be isolated. The
power supply for maintenance. sampling system is only a module in bigger
design and you never know what will be
on the other end.
Signal Exchange
 Analog signals (4 ... 20 mA) are still
widely used. All signals are put together on
Fieldbus Systems
a terminal strip. These signals do not inform  The use of a fieldbus is relatively new in
on error conditions such as a lack of sam- power plants. SWAN instruments all offer
ple flow. Every instrument has a dry contact PROFIBUS DP and MODBUS. Fieldbus
that will close on instrument fault (no sample, connections are easy to install. The bus
no reagent a.o.). cable leads from one instrument to the
other. If an instrument fails, it drops out of
It is possible to control dosing pumps directly the line but the other communication links
with a signal from an instrument. Most remain intact.
instruments (pH, chlorine) have built in PID-
controllers. The amount of information that can be
transmitted through a fieldbus depends
only on the availability of parameters in
the instrument. Remote and automated
Electrical Connections quality assurance requires not only pro-
(FAM-Transmitter) cess values but also information on
sample flow, reagent availability and
sensor integrity.

SWAN has installed systems where the

analog signal remains available for the
power plant's C&I system while the field-
bus links all instruments for automated
quality assurance to a personal computer
in a remote laboratory.

26
Analog signals provide process values without any qualification. The conductivity value
of condensate leakage detection might seem all right. If there is no sample, however,
nobody will notice without actually going to see the instrument. Some operators will
check sample flow on critical instruments several times daily.

Fieldbus systems can transmit quality information provided it is available from the instru-
ments memory. SWAN instruments have all been redesigned recently for the purpose of
automated quality assurance. All instruments supply a wide range of diagnostic data.

Process and quality assurance information is collected to a PLC and displayed on a scre-
en. The user has two different operation levels:

Automated Quality
Laboratory
Assurance
Level

Automated Quality
Remote Assurance System
acces PROFIBUS DP
Sampling
Room Level

Analyzer
Level

DCS

Process Control
Level
0/4-20 mA Signals

Process Level
 Process values are displayed on a There are several software packages that
screen showing the layout of the power are suitable for the purpose. Systems have
cycle. Process data is stored in memory already been implemented on WIN CC
and can be displayed as a graph and from SIEMENS and FREEELANCE from ABB.
exported into other software packages

A process value will show an alarm on

instrument failure or lack of sample.

Diagnosis
 Diagnostic windows contain all informati-
on that is available to judge the instrument's
performance. These windows are different for
each parameter as the required information is
not identical. They open at a mouse click.