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Technical

Paper

The Measurement of Silica


Author: S. P. Ellis All owners and operators of ion exchange deioniza-
tion equipment are highly interested in the accu-
In-Line Instrumentation Seminar, November 17 - 19, racy and precision of methods used for measuring
1993, Clearwater, FL silica. Failure of the equipment to produce water in
conformance with prescribed specifications is, of
Introduction course, quite costly. This is even more true for
mobile water treatment companies, since transpor-
With the advent of higher and higher pressure boil- tation costs are often very high. Thus, this research
ers and steam generators in nuclear power plants, was approached from the standpoint of trying to
carryover of impurities has posed a greater risk of define the variability in the silica measurement. In
corrosion to turbine blades and other downstream so doing, it might be possible to work out accep-
piping and equipment. The turbine-generator tance criteria which would allow equipment to
manufacturers have reacted to this risk by estab- operate, at least for a period of time, without impos-
lishing ever-lowering specifications for concentra- ing contractual penalties. In some cases this is
tions of impurities in the feedwater. For many of the already being done in some form.
impurities, the specifications are at or near the limit
of detection of many of the available analytical At the same time, the dilemma of the power pro-
methods used for monitoring. One such specifica- ducer is also recognized. The status of the warranty
tion is for reactive silica. The term, silica, will be for the turbine-generator is not trivial by any
used to denote dissolved, or reactive, silica means, it remains absolutely necessary to do all
throughout this paper. that one can to ensure that conformance to the
vendor’s specifications is maintained. Therefore, the
The most popular method for the measurement of power producer must use some measure to dem-
silica is the heteropoly blue (also called molybdate onstrate the quality of the feedwater and the
or molybdenum blue) colorimetric method. makeup water to the boiler, even if there is some
This method for silica grew up, so to speak, with the question concerning precision and bias of the test.
power industry. It is used to detect silica break-
through from strong base anion resin beds. It is also Numerous laboratory instruments using 50 mm or
used to quantitatively determine silica in feedwater, 100 mm cells have been used to obtain silica meas-
as well as steam and steam condensate samples. urements at or below 5 ppb. Further, in-line instru-
ment manufacturers report obtaining values as low
Determination of the silica break from a resin bed as 0.5 ppb in their marketing literature. At least one
does not require an analytical test having a low manufacturer reports values of 3 ppb or less with
limit of detection. Further, when low pressure boil- both laboratory and in-line equipment using cell
ers are in question, easily detectable quantities of pathlengths of 1-inch1.
silica (10 - 20 ppb, or even higher) are not only
tolerated, but are often considered to be desirable. Error in in-line silica measurements were a part of
Nevertheless, for higher pressure systems, silica the EPRI RP 2712 study2. The results of that study
at concentrations above 5 ppb is considered to indicated a sizeable error in both precision and bias.
be intolerable. This paper describes the initial attempts to deter-
mine the degree of error involved in the measure-
ment of silica, both by laboratory and inline

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TP1055EN.doc Jun-09
instrumentation. This paper is largely introductory, The absorption spectrum for the silica-molybdenum
and somewhat tutorial. The results of laboratory blue complex is shown in Figure 1. The most impor-
studies which were designed to quantify error in the tant feature of the spectrum is the intense, broad
measurements at low concentrations are pre- absorption band centered at about 815 nm.
sented. Because of this broad band, lower resolution spec-
trophotometers and even colorimeters may be used
Results of comparisons of various methods of de- successfully. That is, an instrument with very low slit
termining blank values, as well as some data con- widths is unnecessary.
cerning the effects of the amount of reagent, and
elapsed times prior to reading the absorbance after
addition of all reagents are also given.

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 Figure 1: Absorption Spectrum of Heteropoly Blue
Complex
sensitive at 815 nm, the wavelength used for meas-
urement. Additional electronic modifications were The absorption of light may be used to quantify the
installed by Update Instruments to provide more stability. amount of an analyte in solution. A set of sol
utions containing known amounts of the analyte in
Reagents used in the test include an acidic ammo-
question are prepared and analyzed at the appro-
nium molybdate solution, an oxalic acid solution
priate wavelength. The relationship between the
and an amino acid solution. All of these solutions
concentration of an analyte in solution and the
were obtained from Hach Chemical Co. in Loveland
absorbance of the solution is given by the Beer-
CO. A 1 ppm working standard solution of silica was
Lambert equation:
also obtained from Hach.
A = abc
Solutions for analysis were generated by diluting
the stock standard solution with deionized water to where, A = absorbance
produce solutions whose concentrations ranged
from zero to 100 ppb silica added. Each analytical a = absorption coefficient
solution was prepared 10 times and each of these
solutions was analyzed once. A standard curve was b = cell pathlength
prepared to compare the results of the tests and c = concentration
help illustrate the error in the measurements.
For a given analyte, the absorption coefficient is
Background constant. Therefore, the slope of the curve, which is
theoretically a straight line, is dependent entirely
Before presenting the analytical results, it is worth- upon the cell pathlength. The effect of this relation-
while to revisit some of the spectroscopic consid- ship is shown in Figure 2.
erations which go into the colorimetric analysis of
silica. These considerations include the absorption
spectrum and the relationship between concentra-
tion 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 concentra-
tion are also generically discussed.

Page 2 TP1055EN
Figure 2: A vs. Conc. Figure 3: A vs. Conc. with Error

While any standard curve will theoretically produce These values may be contrasted with absorbance
results, the errors, which are associated with all values calculated from the efficiency data of
measurements, may prevent determinations at low modern detectors. A good estimate of that effi-
concentrations or discrimination between two simi- ciency is that they can detect increments of about
lar concentrations. If errors in the measurement of 0.1% transmittance4,5. Thus, using a value of
the analyte are considered, a curve such as that 99.9%T, and converting that value to absorbance
shown in Figure 3 may be produced. It should be (A = log (100/%T)), one obtains an absorbance of
noted that the error bars are sufficiently high in this about 0.0004 in a 10 mm cell. This value translates
case to make adjacent points statistically indistin- to 0.001 for a 1-inch cell and 0.004 for a 100 mm
guishable. Indeed, sets of points even further away cell. It will be noted that these values are quite close
from any given point may be indistinguishable from to those calculated for 1 ppb silica solutions from
one another. Obviously, this type of situation can actual experimental data. It can, then, be
overcome any theoretically derived limit of detec- assumed that the quality of the detector is theoreti-
tion or ability of the test to discriminate between cally sufficient to measure silica at the 1 ppb level of
two very similar concentrations of analyte. concentration.

Actual absorbance values for the concentrations of The sources of error in optical instrumental analysis
silica may now be considered. Although spectral arise from three main sources; chemical, spectro-
efficiency data were not located, the absorbance at scopic/optical and electronic. In practice, the latter
low ppb concentrations can be calculated from two categories of error are not so easily separated.
available data, if conformance to the Beer-Lambert The electronics that power a lamp, for example, can
equation is assumed. The values of expected be made more stable which, in turn, makes the
absorbances of 1 ppb solutions using 1-inch and lamp more stable. Historically, however, the instru-
100 mm path cells from two independent sources mental sources of error are commonly related to
are presented in Table 1. lamp instability, the sample itself, detector instabil-
ity, optics and reagent impurities.
Table 1: Expected Absorbances of a 1ppb Silica Solution
Most of the time, the operator must use the instru-
ment 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

TP1055EN Page 3
reagent purity, sample integrity and careful conduct minations of single solutions at each concentration
of the analytical procedure. He must also know the should diminish the errors significantly.
limitations of the instrumentation, which he oper-
ates, in order to make appropriate judgements con- Another approach could be to standardize at a high
cerning data quality. concentration at which the standard deviation
would be expected to be lower. This action would
Results and Discussion minimize the error at the upper end of the curve.
However, a good standardization would still rely on
In an effort to quantify the error associated with the a low error about the zero, which is not necessarily true.
points used to construct a standard curve for a
In order to study the error associated with the blank
laboratory instrument, it was decided to first try to
(or Zero) measurement, several methods for the
incorporate as much of the error that a single
colorimetric determination of silica were investi-
operator could make. Therefore, ten standards at
gated. These methods came from power plants,
each concentration were prepared and each solu-
ASTM, Standard Methods and Hach Chemical Co.
tion was measured once to attain some degree of
All, of course, were similar. But almost all had small
statistical significance. The mean values of these
deviations from one another; particularly in the
standards, measured in both a 1-inch cylindrical
handling of the blanks. Five methods of handling
cuvette and a 100 mm rectangular cell, were
the blank were investigated.
plotted versus absorbance. The results are shown
in Figure 4. 1. Reagents 1, 2 and 3 were added to deionized
water, in order, with 10 min. and 2 min. reaction
times allowed between reagent additions. Five
minutes was allowed between the addition of
reagent 3 and measurement.
2. Reagent 2 was added to a 1:1 solution of con-
centrated hydrochloric acid in deionized water.
No molybdate or amino acid reducing reagents
were added.
3. Reagents 1, 2 and 3 were added to deionized
water, but not in order. The reagents were
added in quick succession, starting with reagent
2, then 1 and then 3.
4. Reagents 1 and 2 were added to deionized
water in quick succession, and allowed to react
for 10 min. before measurement.
5. Reagents 1 and 2 were added together and
allowed to react for 2 min. Then reagent 3 was
added and the solution was allowed to react an
additional 5 min. Finally, deionized water was
added and the measurement was taken.

In each case, the spectrophotometer was zeroed


using deionized water, and the measurement made.
Measurements were made on ten different solu-
Figure 4: SiO2 Standard Curves tions of each blanking method, and each solution
was analyzed once. The results of these tests are
Clearly, the errors shown in this study are quite presented in Table 2.
large in comparison to those which could be
obtained by “normal” standardization techniques.
Simply using the usual approach of multiple deter-

Page 4 TP1055EN
Table 2: Comparison of Blank Methods 4. Modifications in the way the standard curves
are developed should decrease the magnitudes
of the errors. This should also decrease the limit
of detection somewhat.
5. The errors associated with the zero, or blank,
determination are of about the same magni-
tude as the other standard concentrations used
in this study. Therefore, they cannot be ignored.
Some of the silica methods which were considered
warned against waiting too long to measure the 6. The time between the addition of the last re-
absorbance after the color had developed. There- agent and reading the absorbance does not
fore, a quick test was run to see if time delays were appear to be important from about 5 minutes to
a problem. A 50 ppb silica standard was prepared at least 45 minutes.
and analyzed using 10 min. and 2 min. reaction
times between reagent additions. The test solution The experiments described in this paper were
was measured immediately after mixing with the designed to introduce a rather high amount of
final reagent, and at several intervals thereafter. error into the determination of silica. Operator error
The results of this test are shown in Table 3. is also high in manual methods compared to well-
operating automatic systems. While it may be
Table 3. Time Effects on Absorbance
assumed that in-line instruments have less error
associated with a measurement, error still exists.
Such error may be sufficient to disallow the meas-
urement of 1 ppb or sub-ppb concentrations of silica.
In future work, the emphasis will be shifted to the
study of response and error associated with in-line
instruments. Of particular importance to us is the
ability of the instruments to respond to small
increments in concentration and the ability to dis-
Conclusions criminate between close concentrations.
Laboratory measurements of silica are, as all
measurements, beset by errors. If these errors are References
not recognized and dealt with, results can be 1. K. R. Doerr, D. Harp and L. Liou, Low Level Silica
misleading, at best. We unfortunately have a ten- Verification for Analyzer Users, Ultrapure Water,
dency to believe a pretty digital readout or a rock July/August, 20-25, 1991.
steady meter when we should remain skeptical. Re-
sults of the testing described above lead to the fol- 2. J. K. Rice, D. M. Sopocy, R. B. Dooley, Quantifica-
lowing conclusions. tion of Continuous Instrument Error, 1990 Inter-
national Conference on Waterborne Trace
1. Modern instruments are theoretically capable of
Substances, August 1990, Baltimore, MD.
determining 1 ppb silica in a cell with as short a
pathlength as 10 mm. 3. A. B. Carlson and C. V. Banks, Spectrophotomet-
ric Determination of Silicon, Analytical Chemis-
2. Errors in measurement raise this limit to as high
try, 24(3), 472-477, 1952.
as 20 ppb in a 1-inch pathlength cell.
4. R. E. Hanson and M. V. Buell, Photoelectric Tech-
3. The use of a 100 mm pathlength cell lowers the
nique for Spectrophotometry Between 194 and
limit of detection to about 3 ppb, even though
225 Millimicrons, Analytical Chemistry, 31(5),
the magnitudes of the errors associated with
878-81, 1959.
the development of the standard curves are
similar to those for the standard curve using a 5. J. Salpeter, Personal Communication, October
1-inch pathlength cell. 1993.

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