U.S. patent number 3,634,038 [Application Number 04/856,787] was granted by the patent office on 1972-01-11 for device for the quantitative colorimetric analysis of fluids.
Invention is credited to Gordon A. Rampy.
United States Patent |
3,634,038 |
Rampy |
January 11, 1972 |
DEVICE FOR THE QUANTITATIVE COLORIMETRIC ANALYSIS OF FLUIDS
Abstract
A device for quantitative colorimetric analysis of fluids which
consists of a transparent tube of predetermined size with a single
frangible tip, containing a liquid colorimetric reagent and
evacuated to a predetermined degree to insure that on immersion of
the frangible tip in the fluid to be analyzed, followed by fracture
of the tip, a predetermined quantity of sample will be forced into
the tube so that on mixing of the contents color will be developed
proportionately to the concentration of the material being analyzed
for in the sample fluid. The amount of material being analyzed for
can then be ascertained by comparison with a color chart or a set
of color tubes.
Inventors: |
Rampy; Gordon A. (Nitro,
WV) |
Family
ID: |
25324513 |
Appl.
No.: |
04/856,787 |
Filed: |
September 10, 1969 |
Current U.S.
Class: |
422/413 |
Current CPC
Class: |
G01N
31/22 (20130101) |
Current International
Class: |
G01N
31/22 (20060101); G01n 031/22 () |
Field of
Search: |
;23/253R,253TP,259,292,23B,254R |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Yoe, J. H., Photometric Chemical Analysis, John Wiley & Sons,
Inc., N.Y. 1928. Pages 564, 565, 666, 673 relied on..
|
Primary Examiner: Wolk; Morris O.
Assistant Examiner: Reese; R. M.
Claims
I claim:
1. A device for quantitative chemical analysis of fluids,
comprising a transparent cylindrical tube of predetermined size and
of uniform cross section and of sufficient wall strength to permit
ready handling, having one end thereof drawn to a frangible tip,
said tube containing a liquid colorimetric reagent and being
evacuated to a predetermined degree and means for mixing the liquid
colorimetric agent with the fluid to be analyzed, which is drawn
into the tube on fracture of the tip in the fluid to be
analyzed.
2. The tube of claim 1, in which the mixing means is glass beads
included in the tube with the liquid colorimetric reagent.
3. The tube of claim 1, in which the reagent is an aqueous solution
of reduced 5,5-indigo disulfonic acid.
4. The tube of claim 1, in which the reagent is an aqueous
acidified solution of potassium thiocyanate.
5. The tube of claim 1, in which the reagent is an aqueous
acidified solution of orthotolidine.
6. The tube of claim 1, in which the vacuum in the tube ensures
that, on breaking the tip in the fluid to be analyzed, the tube
will be essentially full of liquid except for a gas bubble which
facilitates mixing.
7. The tube of claim 1 in which the tube is of glass.
8. The tube of claim 7 in which the frangible tip portion is coated
with an elastic coating which retains the glass fragments formed on
breaking the tip to introduce sample into the device.
Description
FIELD OF THE INVENTION
This invention relates to the quantitative chemical analysis of
fluids for a single constituent thereof.
DESCRIPTION OF THE PRIOR ART
The analysis of fluids has very often been facilitated by the use
of tubes into which the fluid is introduced together with a
material with which it produces a color proportional to the
concentration of the material to be analyzed for in the fluid.
However, the tubes which have been used are generally rather
complicated, very often being calibrated to measure the amount of
fluid taken up. They very often involved capillary sections for the
introduction of the fluid, and generally have openings at both
ends, the force for bringing the fluid into the container being
applied at one end and the fluid being taken in at the other end.
In one device, described in Furlong U.S. Pat. No. 3,068,855, a
sample bulb is filled with a predetermined quantity of a fluid by
the use of a predetermined vacuum in the bulb and the fracturing of
a frangible tip in the fluid to be tested. However, the complete
device therein disclosed is very complicated indeed; the bulb must
be shattered for the analysis, and must be protected by an outer
tube, so that this device shares the difficulty of other prior art
devices, of being expensive to manufacture and complicated to
use.
OBJECT OF THE INVENTION
This invention aims to provide a very inexpensive disposable device
for quantitative colorimetric analysis of fluids, which is
characterized by low cost, extreme simplicity of design, and ease
of operation. The invention is designed to be so very simple that a
person without chemical training can use the device for such simple
determinations as active chlorine content of a swimming pool, the
amount of oxygen in an inert atmosphere, or the amount of dissolved
oxygen in a liquid such as water, or for any one of a host of other
similar analyses.
SUMMARY OF THE INVENTION
The device which is the subject of this invention comprises an
evacuated glass or other transparent tube with relatively strong
walls so that it can be handled without danger of breaking, with a
readily frangible sealed tip at one end thereof, the tube being
evacuated to a predetermined degree so that on immersion of the tip
in a fluid to be tested and fracture of the tip, a predetermined
quantity of fluid will be drawn into the tube. The tube contains a
liquid colorimetric reagent capable of reacting with the material
in the fluid for which an analysis is sought, whereby a color will
be developed which is proportional to the concentration of the
material in the fluid. The amount of the material to be analyzed
for can then be determined as by comparison of the tube, with the
color developed therein, with a standard color chart or comparison
tube, or by photometric means. Preferably, a stirring device is
provided, either in the form of glass beads, or in the form of an
air bubble.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawing is a cross section through a glass tube made in
accordance with this invention, with an internal stirring device
incorporated therein.
DESCRIPTION OF THE INVENTION
As shown in the drawing I use a tube 10 which is preferably of
glass, but may be of any transparent or translucent material which
does not interfere with the desired analysis, and which can be
sealed at the frangible tip and then readily broken there. It is
important that the walls of the tube be of sufficient strength to
permit handling; ordinary test tube glass is adequate. The tube is
filled with a reagent solution 11 and two glass beads 12 may be
placed therein. One end of the tube is then drawn out in a thin
walled readily frangible tip 13, the tube is evacuated to a
predetermined degree, and the tip 13 is sealed, and then scored, as
by scratching with a file, to produce a score mark 13A which acts
to insure breaking of the tip at that point when pressure is later
applied. A silicone rubber coating 13B covers the tip 13. For
convenience the tube has a flat bottom 14.
As mentioned above, the frangible tip may be coated with an elastic
sleeve 13B of, for example, silicone rubber. This coating separates
only partially on fracture, to permit filling and then snaps back
to hold the tip in place and reclose the opening. This protection
is important in swimming pool applications where glass fragments
would be hazardous and in oxygen analysis where air must be
excluded.
In use, the tip is immersed in the fluid to be analyzed and the
pressure is applied so that the tip breaks at the score mark 13A.
The ambient outside pressure forces fluid into the tube. Since the
outside pressure varies only a few percent from time to time, the
amount of fluid which goes into the tube is predetermined by the
degree of evacuation of the tube. Since the reagent in the tube is
present in amount sufficient to develop color with more than the
maximum amount of the material to be analyzed for or which would be
expected to be present in the sample, the color developed by the
reaction of the fluid with the reagent will be in direct proportion
to the concentration of the material to be analyzed for in the
fluid.
The color can be developed for comparison simply by placing the
operator's finger over the broken tip 13 and turning the tube up
and down. The beads 12 help to mix the fluid with the reagent. If
the rubber sleeve 13B has been employed, closure with the finger is
not necessary.
As indicated above, the color can be determined visually by
comparison with a color chart or a set of color tubes provided with
the test kit and calibrated by analyses of fluids of known
concentrations. It can of course be observed photometrically where
more sophisticated analyses are desired.
Obviously where a high degree of accuracy is desired, it is
essential to control the outside pressure and temperature of the
fluid. However, for most analyses the ordinary ambient pressure and
temperature can be used, since the error introduced is rather small
compared with the desired degree of accuracy wanted in
analysis.
A convenient size glass tube will be 7.5 to 10 millimeters in
outside diameter; 1-millimeter walls are sufficient to give the
necessary strength. The taper is drawn to about 2 millimeters in
outside diameter, and the score mark 13A will be conveniently 5-10
millimeters from the actual tip. A filed scratch mark is a
convenient method of scoring to insure breaking at the desired
point.
Obviously, although I have illustrated a liquid reagent and a
coated cellulose reagent in the tube, the tube could also contain a
reagent in the form of a solid.
In general I prefer to evacuate to a pressure of the order of 20
millimeters absolute, which is generally sufficient to remove
virtually all permanent gases from the sealed tube and insure that
only water vapor remains on sealing. Such a tube will fill
completely if used with a liquid sample. The glass beads are
particularly useful for mixing where one gets complete filling of
the tube by a liquid.
An alternate method of mixing is to evacuate less completely so
that an air bubble will form in the tube on filling. For example, a
tube having internal volume of 5 cubic centimeters can be charged
with 0.5 cubic centimeters of aqueous reagent and evacuated to an
absolute pressure of 100 millimeters of mercury absolute and then
sealed. The partial pressure of air inside the tube will be
approximately 76 millimeters of mercury and its volume will be 4.5
cubic centimeters. When actuated at sea level the air inside the
tube will then compress to a bubble having a volume of
approximately 0.5 cubic centimeters. This bubble will then
facilitate mixing of a liquid sample drawn into the tube when the
tube is turned up and down.
The great advantages of my analytical device are its low cost and
the simplicity of operation, whereby a person untrained in
analytical chemistry can readily perform the simple operations
necessary to get the result. The device is therefore particularly
useful in several contexts. One of these is in and about the home
for analyses such as the content of chlorine in swimming pools.
Another is in routine testing of fluids in plant operations where
operators untrained at chemical work can make limited
determinations easily. And yet another is in water pollution
testing in the field, where elaborate test facilities are not
available. An additional advantage of my invention is that it
provides a very convenient means of utilizing reagents which would
be ruined if exposed to the atmosphere. Examples 1 and 2 illustrate
this advantage in the application of indigo carmine reagent to the
quantitative determination of oxygen.
SPECIFIC EXAMPLES OF THE INVENTION
Typical examples of the analyses that can be readily performed are
described in the following examples:
EXAMPLE 1
Dissolved Oxygen in Liquids. Range, 0-15 p.p.m.
Reagent: Dissolve 0.12 gram reduced 5,5-indigo disulfonic acid, 1.0
gram sodium carbonate and 1.0 gram dextrose in 100 ml. distilled
water. The mixture should be placed in a closed container and
blanketed with an inert gas such as nitrogen. The dye will dissolve
completely and the solution will change to a light yellow color if
stirred periodically over a period of several days at room
temperature. Heating to 80.degree. C. reduces this time to about
one hour.
The tube is charged with one-fifth of its volume of reagent in an
oxygen-free atmosphere, evacuated to an absolute pressure of 40 mm.
Hg and sealed.
When the tip is broken under the surface of the liquid to be tested
the tube fills almost completely, while mixing with the reagent.
Additional mixing, if necessary, may be achieved by shaking or
repeatedly inverting the tube.
The hue which develops immediately may be yellow, orange, red,
purple, or blue, depending on the concentration of oxygen in the
sample fluid.
A quantitative estimate of concentration may be made by comparing
the developed color with the colors developed by known
concentrations of oxygen in liquids of composition similar to the
test liquid. Specially prepared color charts may be used for this
purpose.
EXAMPLE 2
Oxygen in "Inert" Atmosphere. Range, 0-0.1 percent by vol.
Reagent: Dissolve 0.012 gram 5,5-indigo disulfonic acid, 1.0 gram
dextrose in 100 ml. distilled water. The mixture should be placed
in a closed container and blanketed with an inert gas such as
nitrogen. The dye will dissolve completely and the solution will
change to a light yellow color if stirred periodically over a
period of several days at room temperature. Heating to 80.degree.
C. reduces this time to about 1 hour.
The tube is charged with one-fifth its volume of reagent in an
oxygen-free atmosphere, evacuated to an absolute pressure of 20 mm.
Hg and sealed.
When the tip of the tube is broken in the atmosphere to be tested,
the tube fills instantly. It is then capped and shaken or
repeatedly inverted to assure contact between the reagent and the
gas sample.
The hue which develops immediately may be yellow, orange, red,
purple, or blue, depending on the concentration of oxygen in the
sample fluid.
A quantitative estimate of concentration may be made by comparing
the developed color with the colors developed by known
concentrations of oxygen in gases of composition similar to the
test gas. Specially prepared color charts may also be used for this
purpose.
EXAMPLE 3
Ferric Iron in Aqueous Solutions. Range 1-10 p.p.m.
Reagent: Dissolve 20.0 grams potassium thiocyanate in 50 ml.
concentrated hydrochloric acid and 50 ml. distilled water.
The tube is charged with one-tenth its volume of reagent, evacuated
to an absolute pressure of 40 mm. Hg and sealed.
When the tip is broken under the surface of the liquid to be tested
the tube fills almost completely, while mixing with the reagent.
Additional mixing, if necessary, may be achieved by shaking or
repeatedly inverting the tube. A red color develops immediately,
the intensity of which is proportional to the concentration of
ferric iron in the test solution.
A quantitative estimate of concentration may be made by comparing
the developed color with the colors developed by known
concentrations of ferric iron in liquids of composition similar to
the test liquid. Specially prepared color charts may also be used
for this purpose.
EXAMPLE 4
Orthophosphate in Aqueous Solutions. Range 10-120 p.p.m.
Reagent: Dissolve 0.06 gram ammonium metavanadate, NH.sub.4
VO.sub.3, in 50 ml. distilled water and 5 ml. 70 percent perchloric
acid. Then add 3.0 grams ammonium molybdate (NH.sub.4).sub.6.sup..
Mo.sub.7 O.sub.24.sup.. 4H.sub.2 O, mix and dilute with water to
100 ml. Filter the solution before using.
The tube is charged with one-fifth its volume of reagent, evacuated
to an absolute pressure of 40 mm. Hg and sealed.
When the tip is broken under the surface of the liquid to be tested
the tube fills almost completely, while mixing with the reagent.
Additional mixing, if necessary, may be achieved by shaking or
repeatedly inverting the tube. A yellow color develops rapidly and
is suitable for quantitative measurement in 15 minutes. The
intensity of the color is proportional to the concentration of
orthophosphate in the test solution.
A quantitative estimate of concentration may be made by comparing
the developed color with the colors developed by known
concentrations of orthophosphate in liquids of composition similar
to the test liquid. Specially prepared color charts may also be
used for this purpose.
EXAMPLE 5
Free Chlorine in Water. Range 0-10 p.p.m.
Reagent: Dissolve 0.30 gram orthotolidine hydrochloride in 25 ml.
concentrated hydrochloric acid and dilute to one liter with
distilled water.
The tube is charged with one-fifth its volume of reagent, evacuated
to an absolute pressure of 40 mm. Hg and sealed.
When the tip is broken under the surface of the liquid to be tested
the tube fills almost completely while mixing with the reagent.
Additional mixing, if necessary, may be achieved by shaking or
repeatedly inverting the tube.
A yellow color develops if chlorine is present in the sample.
After 15 minutes, a quantitative estimate of concentration may be
made by comparing the color with the colors developed by known
concentrations of chlorine in liquids of composition similar to
that of the test liquid. Specially prepared color charts may be
used for this purpose.
In the above examples, no attempt has been made to describe in
detail the limits of accuracy, effects of interfering species or
stabilities of the colors which form. That information is readily
available in standard treatises dealing with colorimetric analysis
and has no direct bearing on the applicability of this
invention.
Obviously the examples can be multiplied indefinitely without
departing from the scope of the claims.
* * * * *