US00555.

0053A
United States Patent (19) (11 Patent Number: 5,550,053
Salpeter (45) Date of Patent: Aug. 27, 1996
(54) METHOD OF CALIBRATING AN 4,545,957 10/1985 Vanhunbeeck et al. ................. 42281
AUTOMATIC CHEMICAL ANALYZER 4,558,953 12/1985 Yamada et al. ......................... 356,409
4,678,755 7/1987 Shinohara et al. ........................ 436/43
(75. Inventor: Jerome Salpeter, Yorktown, N.Y. 5,183,761 2/1993 Freeman et al. ............................ 436/8
5,204.264 4/1993 Kaminer ...................................... 436/8
73) Assignee: SI Industrial Instruments, Inc., 5,230,863 7/1993 Salpeter ...................................... 42/67
Hawthorne, N.Y. 5,258,308 11/1993 Freeman et al. ............................ 436/8
5,348,889 9/1994 Terashima et al. ......................... 436/8
5,424,212 6/1995 Pinsl-Ober et al. .................. 436/43X
21 Appl. No. 368,853
Primary Examiner-Jill Warden
22 Filed: Jan. 5, 1995 Assistant Examiner-Maureen M. Wallenhorst
(51) Int. Cl. ...................................... GON 31100 Attorney, Agent, or Firm-Darby & Darby, P.C.
(52) U.S. Cl. ................................... 436/8; 436/52; 436/53; 57) ABSTRACT
436/64; 422/67; 422/81; 422/82; 73/1 R;
250/252.1; 356/408; 356/410; 356/436 A method for calibrating an automatic chemical analyzer
58 Field of Search .................................... 436/8, 52, 53, whereby an improved baseline value is calculated. The
436/164; 422/81, 82,62, 67, 68.1, 82.05, analyzer uses a photodetector to detect the amount of light
82.09: 73/1 R; 250/252.1; 356/408,409, passing through a flow cell and correlates this value to the
410, 436 amount of analyte present in a sample solution. In the
preferred embodiment, silica is the analyte under investiga
56) References Cited tion. A baseline solution of a specified (preferably zero)
U.S. PATENT DOCUMENTS
analyte concentration, or a sample solution of unknown
analyte concentration, is introduced into a chemical module
3,634,868 1/1972 Pelavin et al. ..................... 364,571.05 after chemical reagents have reacted with themselves to
3,960,497 6/1976 Acord ........................................ 422/67 form a color complex. The resulting solution is passed to the
3,970,392 7/1976 Figueroa et al. . ... 356,408 photodetector which determines the amount of analyte
3,992,109 11/1976 Bock ............... ... 356/410 present. This value corresponds to the analyte contaminants
4,043,756 8/1977 Sommervold ............................. 436/43 within the reagents and can be subtracted out by further
4,158,545 6/1979 Yamashita et al. ....................... 436/47 calculations.
4,313,735 2/1982 Yamashita et al. . ... 436/47
4,536,369 8/1985 Sakurada et al. ......................... 422,65
4,539,296 9/1985 Manabe ..................................... 436/47 15 Claims, 3 Drawing Sheets
U.S. Patent Aug. 27, 1996 Sheet 1 of 3 5,550,053
ASA Aaya.N.S
C
WyY
P(~
| | | || |

L––1– |92
22

82

WOT-3
O
CN

O2

TIVO|WEH ETI OW
U.S. Patent Aug. 27, 1996 Sheet 2 of 3 5,550,053
U.S. Patent Aug. 27, 1996 Sheet 3 of 3 5,550,053

FG. 4
 5,550,053
1. 2
METHOD OF CALIBRATING AN lates the calibration curve from these values so that there
AUTOMATIC CHEMICAL ANALYZER after, as the sample is tested, the voltages detected can be
correlated within the computer to specific chemical concen
This invention relates to a method for calibrating a trations.
colorimetric analyzer capable of continuously measuring the The '863 patent establishes the baseline value by mea
concentration of the preselected analyte in a flow of liquid. suring the silica content of the baseline plus reagents solu
In particular, this invention relates to an improved method tion, with and without the color reagent, the assumption
for obtaining a baseline calibration value that is not detri being that the color reagent introduces silica contamination
mentally affected by the presence of contaminants in into the measured baseline solution. However, by diverting
reagents used in the color forming reaction. 10 the color reagent away from the chemical module, and thus,
away from the measuring chamber of the flow cell, the
BACKGROUND OF THE INVENTION composition of the solution under investigation is concen
trated resulting in a "dilution error.” This "dilution error'
In power plants, it is necessary to monitor the concentra may result in inaccurate baseline determinations. Further,
tion of soluble silica compounds in the water fed to and in 15 the automatic chemical analyzer disclosed in the '863 patent
the boilers. Excessive amounts of such compounds (referred did not fully account for silica contamination as a result of
to hereinafter as "silica') can cause coating of the turbine the reagents themselves.
blades which requires costly maintenance on a periodic
basis. Typically, silica concentrations in excess of 20 parts SUMMARY OF THE INVENTION
per billion (ppb) are considered excessive. 20
Analyzers have been sold for continuously monitoring the In accordance with the invention, the baseline value is
concentration of silica and other chemical compositions in determined by introducing either the baseline or the sample
water and other fluids. One such device was manufactured solution into the chemical chamber after the oxalic acid has
and sold by Orion Scientific Instruments of Hawthorne, N.Y. 25 been introduced, and therefore, after the reaction forming
as the Orion Model 1830 Silica Analyzer (hereinafter the coloring agent has been inhibited. By so doing, any silica
referred to as the Orion analyzer). contamination measured by the detector must have been
The Orion analyzer coupled a sample of water to be introduced into the solution by the reagents, and before the
analyzed to a chemical cartridge where known reagents were baseline or sample solution was added. Thus, the baseline
added and mixed in proper sequence to yield a heteropoly 30 value is measured taking into account the silica contamina
blue complex, the intensity of which was proportional to the tion introduced by the reagents. These trace amounts will be
silica concentration. The heteropoly blue complex was then Subtracted out during computer calibration.
pumped to a flow cell positioned in a colorimeter of the type Further, the present invention avoids the "dilution error"
shown in U.S. Pat. No. 4,273,449 of Schmid entitled "Radia introduced when a reagent is diverted from the chemical
tion Measuring Apparatus.” 35 module, as is practiced in the '863 patent. This invention
This colorimeter directed light through the flow cell and ensures that the concentration of the reagents in the flow cell
through a reference path so that adjustments for changes in remains constant during the baseline determination, the
the optical signals could be accommodated. In accordance standard determination, and the sample determination.
with known procedures, a baseline value (corresponding to
a zero silica content) and a full scale value could be entered 40 THE DRAWINGS
into storage in a microprocessor which would then calculate
a calibration curve. The foregoing and other features of the present invention
The present invention is directed to an improvement over will be more readily apparent from the following detailed
the automatic chemical analyzer disclosed in U.S. Pat. No. description and drawings of an illustrative embodiment of
5,230,863 which is incorporated by reference herein. As 45 the invention which:
disclosed in the '863 patent, a computer controlled valving FIG. 1 a diagrammatic block diagram showing the
arrangement couples either the solution to be tested, a mechanical and electrical components of a preferred
baseline solution, or a standard (full scale) solution to a embodiment of the invention;
chemical cartridge through a pumping mechanism which FIG. 2 illustrates diagrammatically the optical train of a
also feeds the desired reagents to the cartridge. In the 50
colorimeter in accordance with a preferred embodiment of
preferred embodiment of the invention, the chemical under the invention in conjunction with a front plan view of a flow
investigation is silica. Therefore, the desired reagents are: 1) cell and the mechanical structure used to support the flow
sulfuric acid to acidify the solution; 2) ammonium molyb cell;
date to react with the acidified solution to yield a silicomo FIG. 3 is a front view of the flow ceil; and
lybdate complex; 3) oxalic acid to inhibit any further reac 55
tion from taking place and to prevent phosphate FIG. 4 is a top view of the flow cell.
interference; and 4) ascorbic acid to reduce the silicomo
lybdate complex to a heteropoly blue complex. When the DETAILED DESCRIPTION
reaction is complete, the solution is directed to a flow cell
which includes a chamber having walls through which the 60 An analyzer, in accordance with the invention, can be
desired light source is passed to a detector such as a used in any continuous process wherein reagents are mixed
photodiode. The transmittance of the heteropoly blue com with a continuous stream of a liquid to be tested. For
plex is measured by the detector to determine the silica purposes of explanation only, the invention is described as
content of the solution. The baseline solution and standard it would be used to test for the presence of soluble silicates
(full scale) solutions are first passed through the flow cell 65 (silica) for example in power plants where the presence of
automatically and the values of the light intensities for each such silicates is undesirable because of their tendency to
is stored in memory in the computer. The computer calcu coat the turbine blades.
 5,550,053
3 4
In a typical industrial use, it may be desirable to maintain phomolybdate complex but does not affect the silicomolyb
the level of silica at less than 20 ppb. In such a case the full date complex. This inhibits the reaction from progressing
scale value typically may be in the order of 100 ppb. The any further. Ascorbic acid then reduces the silicomolybdate
principles of the invention are not restricted to any particular complex to a heteropoly blue complex which is blue-green
type of chemical analysis nor, of course, to a particular in color. As is well known, the absorbance (transmittance) of
range. For purposes of explanation only, the preferred the heteropoly blue complex can be measured by passing
embodiment described as part of an automated continuous light at a wavelength at 820 nanometers (nm) or 660 mm
system for measuring the amount of silicate present in a through the liquid and detecting the amount of light passing
continuous flow of water (e.g., from a power plant). through the sample. The detector output provides an indi
In FIG. 1 the fluid flow is represented by heavy lines and 10 cation of the silica content in the sample. This determination
the electrical connections by lighter lines. is also made in accordance with the 863 patent.
The typical reaction for detecting silicates involves four To determine the baseline value according to the preferred
embodiment of the present invention, the following steps are
reagents: sulfuric acid, ammonium molybdate, oxalic acid followed. The sulfuric acid reagent R1 is introduced into
and ascorbic acid. These reagents are held in four containers chemical module 24 through line 16. The ammonium
R1, R2, R3 and R4, respectively. The standard solution is 15
held within a container S and the baseline solution in a
molybdate is introduced into chemical module 24 through
container B. The water to be monitored is filtered to remove line 17. The ammonium molybdate R2 reacts with any silica
particulate matter and fed to an overflow sampler 10 which molecules present in the acid solution to form a silicomo
lybdate complex. Then oxalic acid R3 is added to chemical
may be of a known construction and provides a continuous module 24 throughline 18 to halt the reaction and inhibit the
stream of water to the analyzer. 20
further formation of silicomolybdate complex. After the
The liquid outputs from the overflow sampler 10, the oxalic acid R3 has been added, baseline solution from
standard container S and the baseline container B are container B of known zero (0) ppb silica content is intro
coupled to solenoid controlled valves 12A and 12B which, duced into the chemical module. This is accomplished by: 1)
as explained below, connect one of these three containers to 25 energizing solenoid controlled valves 12A and 12B to allow
an output tube 14 at appropriate times during the analyzer the baseline solution to enter line 14; and 2) activating a
cycle. Output tube 14 along with the tubes 16-19 from third solenoid controlled valve 12C, connected between
reagent containers R1-R4, respectively are pressed beneath disconnector 22 and chemical module 24 in line 14, to divert
the roller of a peristaltic pump 20 through a disconnect the baseline solution in line 14 so that the baseline solution
device 22 to a chemical module where the chemical reaction passes up through port 14A of the solenoid controlled valve
30
takes place. 12C, out through port 14B, and into chemical module 24.
Peristaltic pumps are known devices for providing pock Ascorbic acid R4 is then added. The ascorbic acid R4 reacts
ets of fluid. Pump 20, for example, may have the construc with the solution to reduce the silicomolybdate complex (if
tion shown in U.S. Pat. No. 4,233,001 of Schmid entitled present) to the heteropoly blue complex. The solution is
"Peristaltic Pump.” As shown in the 001 patent, the rotation 35 finally sent through flow cell 28 where the transmissivity of
of a roller occludes the tubes which pass beneath it creating the heteropoly blue complex is measured to determine the
a pressure differential which results in a steady pumping silica content. (This process is explained in detail below.)
action causing pockets of fluid to pass through the tubes. In The baseline value is stored in computer 36. Because the
the preferred embodiment, tubes 14 and 16-19 are color baseline solution is introduced into chemical module 24
coded to identify the reagent or solution, and the tubes are 40 after the color reaction has been inhibited by oxalic acid R3,
held in a predetermined spaced relationship by means of any silica present in the baseline mixture and detected by
collars or the like (not shown). An air tube 21 open to flow cell 28 is attributable to silica contamination from
atmosphere provides the air that is pumped into the line to reagents R1 and R2. These trace amounts of silica within the
separate the liquid flow into a multiplicity of segments. The sulfuric acid R1 and the molybdate reagent R2 are recorded
disconnector 22 also is a commercially available device 45 as part of the baseline value during the computers' calcu
which provides a convenient means for connecting the lations for baseline calibration. Color contamination from
chemical module 24 to the tubes 14, 16-19 and 21. the reagents will be subtracted out during further computer
Chemical module 24 also may be of known construction. calibration calculations.
The module comprises an insulated heater housing adapted Unlike the '863 patent, the color reagent is not diverted
to receive a removable sealed chemistry cartridge (not 50 away from chemical module 24 during the determination of
shown). The chemical cartridge is sealed to prevent break the baseline value. Consequently, the concentrations of the
age and to provide for better temperature control. The reagents remain constant as the baseline mixture passes from
purpose of the cartridge is to direct the chemistry, i.e., to add chemical module 24 and into flow cell 28. Therefore, the
the various reagents from tubes 16-19 at the proper time, to baseline mixture is not concentrated, and any change in the
mix the reagents and the sample or solutions from valve 12A 55 silica detected is due to an actual change in the silica present,
and 12B, and to provide the necessary delays for the and not due to the change in the concentration of the
reactions to take place. Such devices are known including, reagents present in the baseline mixture.
in particular, devices for directing the chemistry required to In a preferred embodiment of the invention, the baseline
detect the presence of silica in power plants. The output from value may also be determined while the sample solution is
the cartridge passes through a tube 26 to a flow cell 28 in the 60 being passed through the chemical module 24. Because the
form of a segmented stream with each segment separated by solenoid controlled valve 12A is already activated, the only
small air bubbles pumped through tube 21. additional step required is to activate solenoid controlled
As the reagent and samples are passed through the chemi valve 12C. This diverts the sample solution up through port
cal cartridge within the module 24, a chemical reaction takes 14B and into the chemical module 24 after the oxalic acid
place. The sample is first acidified with sulfuric acid and 65 R3 has inhibited any further formation of the silicomolyb
then reacted with ammonium molybdate to yield a silico date complex. Because the sample solution is introduced
molybdate complex. The oxalic acid breaks up the phos into the chemical module 24 after the color reaction has been
 5,550,053
S 6
inhibited by the oxalic acid R3, the only silica detected by than 20 ppb, a standard solution may be prepared in which
the flow cell 28 is attributable to silica contamination from the silica concentration is 100 ppb. As now explained,
reagents R1 and R2. during the initializing process, the computer 36 stores in
The standard value is determined as follows. Solenoid memory the values of the output signals from detector 32
controlled valves 12A and 12B are activated to introduce corresponding to both the baseline and standard solutions.
standard solution into line 14. Solenoid controlled valve 12C Since the relationship of light absorbance in flow cell 28 to
is not activated allowing the standard solution to flow up silica concentration is linear, the output of the detector 32
can be compared with the values stored in the computer 36
through port 14A of the solenoid controlled valve 12C, out for the baseline and standard solutions and the silica con
through port 14C, and into chemical module 24 before the 10 centration calculated and displayed.
reagents are added. After the standard solution enters chemi The operation of the system is as follows. First, the system
cal module 24, the sulfuric acid R1 is introduced into determines the baseline value and stores this value in the
chemical module 24. Sulfuric acid reagent R1 acidifies the computer 36. Next, the standard value is determined and
standard solution. Ammonium molybdate R2 is introduced similarly stored. The calibration curve is then calculated so
into chemical module 24 through line 17 and reacts with the that the value determined from the sample solution may be
silica present in the acid solution to form a silicomolybdate 15
compared against the calibration curve to determine the
complex. Next, oxalic acid R3 is added to chemical module silica content in the sample solution. In detail, the reagent
24 through line 18 to halt the reaction and inhibit the further bottles R1-R4 and the standard and baseline containers S
formation of silicomolybdate complex. Ascorbic acid R4 is and B are filled with the proper solutions. The overflow
introduced through line 19 to form the heteropoly blue sample 10 is coupled to a port in the plant so that the sample
complex. The resulting solution is then sent to flow cell 28 20 to be measured is available at the input to the valve 12A. The
where the transmissivity of the heteropoly blue complex is user then pushes a button to start the operation. Immediately,
measured to determine the silica content. (This process is computer 36 causes valves 12A and 12B to connect the
explained in detail below.) This standard value is also stored baseline solution within container B to tube 14. Valve 12C
in computer 36. Computer 36 then calculates the calibration is also activated to divert the baseline solution so that the
curve as outlined below. 25 baseline solution passes up through port 14A of the solenoid
As detailed in the '863 patent, a preferred embodiment of controlled valve 12C, out through port 14B, and into chemi
the flow cell 28 is described below with respect to FIGS. cal module 24. The baseline solution is, thereby, introduced
2-4. One function of the flow cell 28 is to debubble the into chemical module 24 after the oxalic acid has inhibited
output from the chemical module in tube 26. The flow cell the formation of the molybdosilicic acid complex. Simulta
28 also prevents foam produced by any wetting agents in the 30 neously, pump 20 is turned onto high speed for the purpose
solution from affecting any readings. Such wetting agents of pumping the reagents and baseline solution into the
are used to minimize back pressure due to the relatively analyzer as quickly as possible. For example, pump 20 may
narrow bore tubing used in the preferred embodiment and, normally operate at 2.8 rpm; at high speed, it may operate at
typically, are added to the reagents. In addition, the flow cell 9 rpm.
35
28 provides a constant level device from the constantly After a period of six minutes, the computer causes the
flowing stream of water. pump 20 to operate at normal speed for sixteen minutes. At
A light source shown at 30 directs light at the desired the end of this initial period (twenty-two minutes in this
wavelength (e.g., 820 nm) through the measuring chamber example) the baseline solution plus reagents fully occupy
of the flow cell 28 where it is detected by detector 32. 40
the flow cell 28 so that the analyzer is measuring the light
Detector 32 produces a voltage output which is proportional through the flow cell when the silica concentration is at the
to the amount of light passing through the flow cell (and, calibrated zero. This value is converted to digital form and
therefore, the quantity of silica in solution). stored in memory M1 within computer 36.
The analog voltage from detector 32 is connected to an The computer then actuates the solenoid operated valves
analog to digital converter 34 which couples its digital 45 12A and 12B to couple the standard solution in container S
output to a computer 36, e.g., a microprocessor. Computer to the tube 14. Pump 20 is simultaneously caused to operate
36 is programmed, as explained below, to provide an output at high speed until the standard solution reaches the chemi
indicative of the quantity of silicate in the sample. This cal module 24, for example, three minutes. For any given
output may be displayed on a display device 38 and it may system, of course, this time interval is known and can be
also be transmitted to a recorder to maintain a permanent 50 programmed into the computer. This is accomplished by not
record. In addition, the computer 36 provides timing signals activating Valve 12C, thereby allowing the standard solution
to the solenoid operated valves 12A, 12B and 12C to to flow up through port 14A of the solenoid controlled valve
determine which of the standard, baseline or sample solu 12C, out through port 14C, and into chemical module 24
tions is to be fed into tube 14, and to determine whether before the reagents are added. After the standard solution
valve 12C is to divert the baseline solution or the sample 55 enters chemical module 24, the reagents are added in the
solution in order to introduce the baseline solution or the proper order and the reaction is allowed to take place.
sample solution into chemical module 24 after oxalic acid Once the standard solution is in the chemical module 24,
R3 has been introduced into chemical module 24. the computer returns pump 20 to normal speed. At normal
As described in the 863 patent the sample is analyzed via speed, in the preferred embodiment, it may take about
a completely automatic system. To do this, a reference is set 60 sixteen more minutes to replace the baseline solution in the
up within the computer 36 so that the measured values of flow cell 28 with the standard solution flowing from the
light absorbance can be compared to the reference values to chemical module 24.
determine the silica content. The baseline solution in con When this time interval has passed, the intensity of the
tainer B is a solution made as free of silica as possible (e.g., light passed through the flow cell 28 represents the silica
0 ppb). The standard solution in container S is the full scale 65 content of the known standard. Accordingly, this value is
value of the analyzer and it will be set by the operator. For sensed by the detector 32, converted to digital form in
example, if it is desired to maintain a silica content of less converter 34 and stored in memory M2.
 5,550,053
7 8
Knowing the values for the baseline and standard solu light pipes 50 and 52 are able to direct the light with minimal
tions, the computer establishes a calibration curve in accor losses to the active portion of the cell and then direct the
dance with known procedures. For example, if the output of attenuated light out to the active photodetector surface.
detector 32 is at a certain value at 0 ppb and a second value In operation, light enters the front face of the entrance
at 100 ppb and if there is a linear relationship between light pipe 50 of the flow cell and is directed onto the entrance
detector output and silica content (or if the shape of the surface of the flow cell proper. The colored sample absorbs
curve is otherwise known) then whatever the value of the a fixed portion of the nominally-monochromatic light. The
output of detector 32, the computer 36 can calculate the attenuated light is then directed out through the exit light
silica content for display and/or recording or other purposes. pipe 52.
After the calibration curve has been stored in the com 10 All the light from the exit face of the flow cell strikes the
puter, the computer then signals the solenoid control valve active surface of the solid-state photodetector 32. The detec
12A to couple the overflow sampler 10 to the tube 14. In this tor converts impinged light from 340 to 900 nm into a
condition, the analyzer continuously analyzes the flow of corresponding electrical signal which is processed in the
sample through the overflow sampler 10 for silica content. electronics package. The optical train and detectors respond
At predetermined intervals, the computer 36 will cause 15 accurately in the typically linear Beer-Lambert relationship
the solenoid controlled valve 12C to be activated. This between absorbance and concentration.
introduces the sample solution in container 10 into the Energy losses in the optical system are minimized by
chemical module 24 after the oxalic acid reagent R3. careful design and selection of optical components. Less
Because the amount of silica detected is solely due to the energy is lost with the use of a single large-diameter, high
reagents, this process allows the computer 36 to quickly 20 through-put narrow-band optical filter than a conventional,
update the baseline value and to automatically shift the small-diameter dual filter system.
calibration curve if the baseline value has changed.
Periodically, for example every eight or twelve hours, the As shown in FIGS. 2-4, the flow cell which may be made
computer 36 will cause the solenoid controlled valves 12A, of glass includes a reservoir 60, a measuring chamber 62 and
12B, and 12C to be activated. This will introduce the 25
an overflow pipe 64. An inlet pipe 66 introduces the liquid
baseline solution in container B into the chemical module 24 to be tested into the vertical reservoir 60. The measuring
after the oxalic acid reagent. When this occurs, the pump chamber 62 is essentially vertical in cross-section and as
once again operates at high speed for about six minutes shown in FIG. 3 includes opposing sides 67 and 68 and a
followed by sixteen minutes at normal speed so that a new venting tube 69 open to atmosphere. The light from lamp 30
baseline calibration can be determined. If the baseline value 30
passes through the sides 67 and 68 which are polished to
has changed, the calibration curve is again 'shifted' auto minimize reflections and optical losses. The liquid within
matically by the computer such that the concentration of the reservoir 60 is fed through a U-shaped tube 70 into the upper
baseline solution as measured on the calibration curve is portion of the measuring chamber 62 of the flow cell (see
returned to the previously measured value. The change in FIG. 2). The liquid from the measuring chamber 62 is
absorbance may be caused by temperature changes, elec 35
coupled to the overflow pipe 64 by means of a similarly
tronic drift in the equipment, and/or degradation of the U-shaped tube 72. This particular configuration shown in
reagents which may decrease sensitivity of the system. FIGS. 2-4 is used in the preferred embodiment of the
invention because it is adapted to be conveniently retained
At still longer periodic intervals, both the baseline and within the existing support carriage of the Orion analyzer
standard or full scale values are calculated and stored in but, as explained in the '863 patent, the only critical struc
memory. For example, every forty-eight hours the entire 40
tural aspects of the flow cell reside in the shape of the
process may be recycled. measuring chamber 62 and its relation to the venting tube
The optical train according to a preferred embodiment of 69.
the invention is shown in FIG. 2. The light output from As is well-known from the Beer-Lambert formula, light
source lamp 30 is coupled through a collimating lens 40, an 45 absorbance (transmissivity) is dependent upon the length of
interference filter 42 and a condenser lens 44. The filter 42 the light path through the flow cell or, in this case, the
removes all but the desired wavelength, 820 nm in this distance between the surfaces 67 and 68 as represented by
example. Reasonably collimated light is necessary since the the dimension X in FIG. 2. For very low chemical concen
interference filter can be made efficiently for only a trations, the dimension X should be as large as possible.
restricted angle of incidence. 50 However, because of the need to vent the system of air
The flow cell 28 is held in a support assembly 46 which bubbles among other things, there is a practical limit on the
includes a firmly supported bracket 48 adapted to securely length of dimension X.
hold light pipes 50 and 52 in suitable V grooves (not The air bubbles that create segmented flow to the flow cell
numbered). The light pipes 50 and 52, arranged on opposite 28 permit sample-to-sample discretion thereby enhancing
sides of the flow cell 28, direct the filtered light from 55 the response time by avoiding averaging. Also, the air
condenser lens 44 through the liquid within the flow cell to bubbles tend to scrub the walls of the glass tubes and
detector 32, typically a photodiode. generally improve mixing which are desirable features. As
In a preferred embodiment of the invention, the colli mentioned above, the air bubbles are introduced into the
mated light is split into two beams. The first beam is directed liquid stream by means of the tube 21 which is vented to
through the flow cell 28 to detector 32. The second beam is 60 atmosphere.
directed through a reference channel (not shown) to a second The flow cell illustrated in FIGS. 2-4 shows the measur
detector (not shown). This allows any changes in the light ing chamber 62 vented directly to the atmosphere by the tube
source to be monitored and corrected for. 69. However, the fact that the measuring chamber is vented
Condenser lens 44 functions as a decollimator and should creates problems since if the diameter of the venting tube 69
have a high numerical aperture to minimize energy losses 65 is too large, the flow cell will combine the discrete samples
due to diffusion. The condenser lens focuses the available (previously separated by air bubbles) which causes averag
light energy onto the entrance face of the light pipe 50. The ing and thus tends to reduce response time. On the other
 5,550,053
9 10
hand, if the size of the vent 69 is too small, the surfaces 67 form a sample mixture that maintains the ratio of the
and 68 of measuring chamber 62 extend outside the walls of reagents constant, determining, via optical means, the quan
the venting tube 69 creating shoulders 78 and 80 where air tity of the analyte present in the sample mixture, and then
bubbles tend to collect. If the differential in size is small, the calculating a baseline value corresponding to the quantity of
shoulders 78 and 80 can be severely sloped as shown in FIG. the analyte detected in the sample mixture which also
2 to minimize this problem but if the dimension X is large, corresponds to the amount of analyte contamination con
then it is impossible to simultaneously avoid the problem of tained within the reagents and within the chemical module.
averaging and the problem of accumulating air bubbles. 7. The method for calibrating an automatic chemical
Through experiments, it has been discovered that the maxi analyzer as described in claim 6 wherein the analyte is silica.
mum length of the dimension X is approximately 30 milli 10 8. The method for calibrating an automatic chemical
meters. At this dimension, the maximum size of the venting analyzer as described in claim 7 wherein the color reagent is
tube 69 which will avoid averaging of samples also will ammonium molybdate.
allow virtually complete venting of all air within the liquid 9. The method for calibrating an automatic chemical
in the flow cell. analyzer as described in claim 8 wherein the inhibiting
Flow cells with a dimension X of less than 30 mm of 15 reagent is oxalic acid.
course can be used and, in fact, are preferred where con 10. A method for calibrating a chemical analyzer accord
centrations substantially higher than 20 ppb are detected. ing to claim 6, further comprising the steps of measuring
I claim: concentration of analyte present in the sample mixture on a
1. A method for calibrating an automatic chemical ana periodic basis and adjusting the baseline value whenever the
lyzer comprising the steps of: 20 currently measured analyte concentration differs from a
a.) adding at least a color reagent that reacts with an previously measured analyte concentration.
analyte to form a color complex, and an inhibiting 11. A method for calculating a baseline value during the
reagent to inhibit any further formation of color com calibration of an automatic chemical analyzer to detect a
plex after a specified time has elapsed, to a chemical quantity of an analyte present in a sample solution compris
module; then 25 ing the steps of:
b.) adding a baseline solution of known analyte concen a. adding a plurality of reagents, including at least a color
tration to the chemical module to form a baseline reagent to react with the analyte to form a color
mixture that maintains the ratio of the reagents con complex, and an inhibiting reagent to inhibit the further
Stant, 30
formation of color complex after a specified time has
c.) passing the baseline mixture through a flow cell; elapsed, to a chemical module; then
d.) passing light at a specified frequency through the flow b. adding one of a baseline solution of known analyte
cell so that the concentration of analyte in the baseline concentration and a sample solution of unknown ana
mixture may be determined; and lyte concentration into the chemical module to form a
e.) calculating a baseline value corresponding to the 35 baseline mixture that maintains the ratio of the reagents
COIStant,
quantity of the analyte detected in the baseline mixture passing the baseline mixture through a flow cell;
which also corresponds to the amount of analyte con
tamination contained within the color reagent and the d. passing light at a specified frequency through the flow
inhibiting reagent. cell so that the concentration of analyte in the baseline
2. The method for calibrating an automatic chemical 40 mixture may be determined; and
analyzer as described in claim 1 wherein the analyte is silica. e. calculating a baseline value corresponding to the quan
3. The method for calibrating an automatic chemical tity of the analyte detected in the baseline mixture
analyzer as described in claim 2 wherein the color reagent is which also corresponds to the amount of analyte con
ammonium molybdate. tamination contained within the reagents.
4. The method for calibrating an automatic chemical 45 12. The method for calculating a baseline value during the
analyzer as described in claim 3 wherein the inhibiting calibration of an automatic chemical analyzer described in
reagent is oxalic acid. claim 11 wherein the analyte is silica.
5. A method for calibrating a chemical analyzer according 13. The method for calculating a baseline value during the
to claim 1, further comprising the steps of measuring con calibration of an automatic chemical analyzer described in
centration of analyte present in the baseline mixture on a 50 claim 11 wherein the color reagentis ammonium molybdate.
periodic basis and adjusting the baseline value whenever the 14. The method for calculating a baseline value during the
currently measured analyte concentration differs from a calibration of an automatic chemical analyzer described in
previously measured analyte concentration. claim 13 wherein the inhibiting reagent is oxalic acid.
6. A method for calibrating an automatic chemical ana 15. A method for calculating a baseline value during the
lyzer used to measure the quantities of an analyte within a 55 calibration of an automatic chemical analyzer described in
chemical module, comprising the steps of introducing into claim 11 further comprising the steps of measuring concen
the chemical module at least a color reagent which reacts tration of analyte present in the baseline mixture on a
with any analyte present within the chemical module, and an periodic basis and adjusting the baseline value whenever the
inhibiting reagent to inhibit any further reaction between the currently measured analyte concentration differs from a
analyte and the color reagent after a specified time has 60 previously measured analyte concentration.
clapsed, then adding a sample solution containing an
unknown quantity of an analyte into the chemical module to a : k st