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The Measurement of Silica: Technical Paper
The Measurement of Silica: Technical Paper
Paper
Introduction
With the advent of higher and higher pressure boilers and steam generators in nuclear power plants,
carryover of impurities has posed a greater risk of
corrosion to turbine blades and other downstream
piping and equipment. The turbine-generator
manufacturers have reacted to this risk by establishing ever-lowering specifications for concentrations of impurities in the feedwater. For many of the
impurities, the specifications are at or near the limit
of detection of many of the available analytical
methods used for monitoring. One such specification is for reactive silica. The term, silica, will be
used to denote dissolved, or reactive, silica
throughout this paper.
The most popular method for the measurement of
silica is the heteropoly blue (also called molybdate
or molybdenum blue) colorimetric method.
This method for silica grew up, so to speak, with the
power industry. It is used to detect silica breakthrough from strong base anion resin beds. It is also
used to quantitatively determine silica in feedwater,
as well as steam and steam condensate samples.
Determination of the silica break from a resin bed
does not require an analytical test having a low
limit of detection. Further, when low pressure boilers are in question, easily detectable quantities of
silica (10 - 20 ppb, or even higher) are not only
tolerated, but are often considered to be desirable.
Nevertheless, for higher pressure systems, silica
at concentrations above 5 ppb is considered to
be intolerable.
All owners and operators of ion exchange deionization equipment are highly interested in the accuracy and precision of methods used for measuring
silica. Failure of the equipment to produce water in
conformance with prescribed specifications is, of
course, quite costly. This is even more true for
mobile water treatment companies, since transportation costs are often very high. Thus, this research
was approached from the standpoint of trying to
define the variability in the silica measurement. In
so doing, it might be possible to work out acceptance criteria which would allow equipment to
operate, at least for a period of time, without imposing contractual penalties. In some cases this is
already being done in some form.
At the same time, the dilemma of the power producer is also recognized. The status of the warranty
for the turbine-generator is not trivial by any
means, it remains absolutely necessary to do all
that one can to ensure that conformance to the
vendors specifications is maintained. Therefore, the
power producer must use some measure to demonstrate the quality of the feedwater and the
makeup water to the boiler, even if there is some
question concerning precision and bias of the test.
Numerous laboratory instruments using 50 mm or
100 mm cells have been used to obtain silica measurements at or below 5 ppb. Further, in-line instrument manufacturers report obtaining values as low
as 0.5 ppb in their marketing literature. At least one
manufacturer reports values of 3 ppb or less with
both laboratory and in-line equipment using cell
pathlengths of 1-inch1.
Error in in-line silica measurements were a part of
the EPRI RP 2712 study2. The results of that study
indicated a sizeable error in both precision and bias.
This paper describes the initial attempts to determine the degree of error involved in the measurement of silica, both by laboratory and inline
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TP1055EN.doc Jun-09
Experimental
Silica measurements were made using a Shimadzu
Model UV-1201 UV/VIS spectrophotometer, and a
Bausch & Lomb Spectronic 20 spectrophotometer
(now owned and marketed by Milton-Roy). The latter
instrument was factory-modified by replacing the
standard focusing lens with a red lens and
installing a nonstandard detector to make it more
sensitive at 815 nm, the wavelength used for measurement. Additional electronic modifications were
installed by Update Instruments to provide more stability.
Reagents used in the test include an acidic ammonium molybdate solution, an oxalic acid solution
and an amino acid solution. All of these solutions
were obtained from Hach Chemical Co. in Loveland
CO. A 1 ppm working standard solution of silica was
also obtained from Hach.
Solutions for analysis were generated by diluting
the stock standard solution with deionized water to
produce solutions whose concentrations ranged
from zero to 100 ppb silica added. Each analytical
solution was prepared 10 times and each of these
solutions was analyzed once. A standard curve was
prepared to compare the results of the tests and
help illustrate the error in the measurements.
Background
Before presenting the analytical results, it is worthwhile to revisit some of the spectroscopic considerations which go into the colorimetric analysis of
silica. These considerations include the absorption
spectrum and the relationship between concentration and response (Absorbance). Sources of errors in
measurements, the relationship of those errors to
detection limits, and the ability of the instrument to
detect small (0.5 to 2 ppb) differences in concentration are also generically discussed.
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Most of the time, the operator must use the instrument as it is purchased. He may not have the ability
or the time to modify and improve the instrument.
The operator must, therefore, spend his time on
activities that he can control, such as
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Conclusions
Laboratory measurements of silica are, as all
measurements, beset by errors. If these errors are
not recognized and dealt with, results can be
misleading, at best. We unfortunately have a tendency to believe a pretty digital readout or a rock
steady meter when we should remain skeptical. Results of the testing described above lead to the following conclusions.
1. Modern instruments are theoretically capable of
determining 1 ppb silica in a cell with as short a
pathlength as 10 mm.
2. Errors in measurement raise this limit to as high
as 20 ppb in a 1-inch pathlength cell.
3. The use of a 100 mm pathlength cell lowers the
limit of detection to about 3 ppb, even though
the magnitudes of the errors associated with
the development of the standard curves are
similar to those for the standard curve using a
1-inch pathlength cell.
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References
1. K. R. Doerr, D. Harp and L. Liou, Low Level Silica
Verification for Analyzer Users, Ultrapure Water,
July/August, 20-25, 1991.
2. J. K. Rice, D. M. Sopocy, R. B. Dooley, Quantification of Continuous Instrument Error, 1990 International Conference on Waterborne Trace
Substances, August 1990, Baltimore, MD.
3. A. B. Carlson and C. V. Banks, Spectrophotometric Determination of Silicon, Analytical Chemistry, 24(3), 472-477, 1952.
4. R. E. Hanson and M. V. Buell, Photoelectric Technique for Spectrophotometry Between 194 and
225 Millimicrons, Analytical Chemistry, 31(5),
878-81, 1959.
5. J. Salpeter, Personal Communication, October
1993.
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