CA2071540A1 - Temperature insensitive calibration system - Google Patents

Temperature insensitive calibration system

Info

Publication number
CA2071540A1
CA2071540A1 CA 2071540 CA2071540A CA2071540A1 CA 2071540 A1 CA2071540 A1 CA 2071540A1 CA 2071540 CA2071540 CA 2071540 CA 2071540 A CA2071540 A CA 2071540A CA 2071540 A1 CA2071540 A1 CA 2071540A1
Authority
CA
Canada
Prior art keywords
calibration system
phase
calibration
partial pressure
amount
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2071540
Other languages
French (fr)
Inventor
David W. Deetz
Russel L. Morris
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Diametrics Medical Inc
Original Assignee
Diametrics Medical Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Diametrics Medical Inc filed Critical Diametrics Medical Inc
Publication of CA2071540A1 publication Critical patent/CA2071540A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0006Calibrating gas analysers

Abstract

TEMPERATURE INSENSITIVE CALIBRATION SYSTEM

ABSTRACT OF THE DISCLOSURE
A multi-phase control and/or calibration system consists of a first non-aqueous liquid phase containing an amount of dissolved oxygen (O2) in which the O2 partial pressure is made relatively temperature insensitive over an ambient temperature range of interest, a second, aqueous solution, immiscible with the first solution phase and containing an amount of dissolved carbon dioxide (CO2) and one or more solute species that provide temperature stability with respect to the partial pressure of CO2 over the ambient temperature range of interest. The liquid phases are in equilibrium with a vapor phase and the system may be sealed with a storage atmosphere.

Description

2 ~ 7 ~

TEMPER~TURE IN~NBITIVE C~LIBRATION ~YBTEM
B~C~GROUND OF 'r~lE INVENTION
1. Field of the Invention The present invention is directed yenerally to a multi-phase control or calibration system and, more particularly, to such a system exhibiting relatively constant partial pressures with respect to certain diverse dissolved gaseous species of interest in one or more liquid phases over a range of ambient temperatures. The preferred fluid consists of a first non-aqueous liquid phase containing an amount of dissolved oxygen (23 in which the partial pressure of 2 iS relatively temperature insensitive over an ambient temperature range of interest, a second, aqueous phase, immiscible with the first phase and containing an amount of dissolved carbon dioxide (CO2~ and one or more solute species that provide temperature stability with respect to the partial pressure of Co2 over the ambient temperature range of interest. The llquid phases are in equilihrium with a vapor phase.
2. De~cription of the Related Art Relatively inert fluids which have the ability to dissolve rather large amounts of oxygen and which are stable and do not affect biological media, for example, are known. The class of fluorinated organic compounds known as perfluorocarbons are the best known examples of such materials. Perfluorocarbon substances are completely fluorinated organic compounds in which all the carbon-bound hydrogen atoms are replaced with fluorine atoms. These materials have an unique combination of properties. The compounds are extremely non-polar and have essentially no solvent action. They are so chemically inert and have such high thermal stability that they can be mixed with almost any material without fear of any adverse reactive effect either upon other mixture components or upon the mater1al itsel~. The compouncls also have a relatively hlgh boilLny points and low pour po:ints yivincJ them a relatively wide : . ,'~ .' ' ', :. ' ' . . ,' .;'',,:,,; , .

2~7~
z liquid range. Many of these perfluorocarbon materials also have a higll, relatively st~ble, oxygen solubility.
These properties have led to the use of perfluorocarbon solutions as oxygen carriers and as controls for oz sensors. ~queous perfluorocarbon multi-phase emulsions have been proposed for applications which involve the need to carry or sense oxygen in the presence of carbon dioxide andtor where pll needs to be controlled or sensed. These include medical related technologies involving blood and syn-thetic blood materials and blood gas analysis controls and calibrators. One such emulsion system is illustrated and described in U.S. Patent 4 722 904 to Feil. Other such systems are disclosed in Turner (U.S. Patent 4 001 142), Cormier, et al. (U~S.
Patent Nos. 4 299 728 and 4 369 127) and Sorenson, et al.
(U.S. Patent Nos~ 4 116 336 and 4 151 108).
These fluids typically comprise an aqueous emulsion of the organic oxygen carrier. Certain of these emulsions may contain surfactant materials, p}l buffers and preservative materials. The aqueous phase and the perfluorocarbon phase are chemically compatible but completely immiscible. While the perfluorocarbon phase reversibly carries the oxygen of interest, the aqueous phase reversibly carries other constituents of interest such as carbon dioxide and hydrogen ions.
The use of such materials, particularly as quality controls Eor blood gas analyzers, for example, requires that the control system contain a known partial pressure of oxygen and a known partial pressure of carbon dioxide and be oE a known pll. Accordingly, the con-trol system must be supplied in gas-tight, sealed ampules, or the like containing known amounts of dissolved oxygen and carbon dioxide species so that e~uilibrium p~rtial pressures remain constant. Such a known or control substance can later be used to check the relative accuracy oE an instrument utilized to measure 2 and CO2 concentratlon and the pll of such substances ag blood.

.. , , , ' .. . ; i, . ..
Although such prior approaches have been successful with respect to achieving proper quality control of sucll devices, the integrity of the partial pressure of the dissolved species used in control measurements depends on the complete isolation o~ the control system from the time it is prepared until the time of use. In addition, because of the variation in solubility of the gas species of interest with temperature, the opening and use of the control must occur at a specific temperature; and thus the results are also quite temperature dependent.
There remains a definite need to reduce the sensitivity of such control systems to fluctuating or uncertain ambient temperature conditions. This would lead to more versatile uses of the materials and to the development of accurate devlce calibration methods without the need for rigorous environmental control at the time of calibration. Accordingly, it is an object of the present invention to develop a calibration/control system which is less temperature sensitive than known fluids of the class including aqueous emulsions of perfluorocarbons.
~UMMARY OF THE INVENTION
In accordance with the present invention, the temperature sensitivity of the partial pressures of dissolved gases of interest has been greatly reduced. The accuracy of calibration system established at a filling temperature of 20C, for example, will not be sacrificed by ater removal at, for example, 30~C.
In the preferred embodiment, the oxygen carrying solution phase is a solution of oxygen in one or more perfluorocarbon materials. The preferred perfluorocarbon materials include FC-43, FC-75, FC-77, and others, manufactured by and available from the 3M Company of St.
Paul, Minnesota. 'rhe aqueous solution phase contains a specific amount of C02 complexing agerlts such as ethylene diamine, ~ICO3-, Ca~ and 0ll~ or other compounds wh:Lch buffer the partial pressure of carbon dioxide (C02) in the aqueous solution to changes in temperature. ~n ,~lmount of a -.._., . : "
, 3 ~ $
~,, compatible pll buffer can also be employed to stabilize the solution with respect to acidity.
The multi--p}lase control/calibration system of the invention is prepared under tig}ltly controlled conditions and transferred to containers designed to accommoda-te the desired amount. The filled containers are provided with a sealed storage atmosphere which maintains the desired conditions in equilibrium during the shelf life of the system. This atmosphere typically contains sufficient oxygen and carbon dioxide in a mi~ture with one or more other gases inert to the system to maintain the desired amount f 2 and C02 species in the liquid phases of the system.
The preferre~ range Of 2 (Po2) partial pressure with respect to the system is from about 10 to about 200 mm Hg and the preferred range of partial pressure for C0z (pC0z) is from about 5 to lO0 mm ~Ig. The preferred temperature range of temperature relative partial pressure insensitivity is about 20C to about 30C. It is also contemplated that various phase components can be used, if desired, to expand the ambient temperature range o~
relative partial pressure insensitivity beyond the range of 20~C to 30C, if desired. The range 20 to 30C, however, represents the normal range of temperatures for an indoor conditioned space.
In addition, surfactants or other wettiny agents can be added to emulsify the multiliquid phases, if desired.
It is also contempla-ted that the solution of the calibration system of the invention consist of a sin~le aqueous phase containing, in addition to a Co2 binding component or components, one or more solutes which reversibly bind 2~ such as copper ions, hemoglobin, and transition metal macromolecular complexing agents. These include meso-tetraphenyl porphorin complexes of Co(II), Co~III), Mn(III) and Fe(II).
Solutions ~ormulated in accordance with the invention should exhibit stable overall solubilities of the c3ases of ,i '',;

interest over a range of ambient temperatures between about 20C and 30C. This means that calibratlon/control systems in impermeable containers which are filled under strictly controlled conditions at one temperature may be removed ~rom a storage atmosphere at a different -temperature and used with complete confidence.
DETAILED DESCRIPTION
Although there are some exceptions, notably dilute solutions of hydrogen chloride in water, the solubility of most gases and liquids decreases with increases in temperature. It is further well known that the equilibrium solubility oE any volatile constituent of a solution at a yiven temperature is rela-ted to the partial pressure of thak constituent in the vapor pllase above the liquid at any given temperature. It follows, then, that solutions of critical concentrations of dissolved gaseous species and liquids have an extreme sensitivity both to changes in the partial pressure of each such species above the solution and to changes in temperature of the solution. Prior to the present invention, it has heretofore been necessary to expose the calibration/control system to the ambient environment at a specific temperature to preserve the compositional integrity of the system.
This has heretofore always been the case with respect to control solutions, including those in which oxygen is carried by a perfluorocarbon in one phase and carbon dioxide is carried in a second aqueous solution phase of con-trolled p~ which are used to calibrate biological sensors utilized to detect dissolved oxygen, carbon dioxide and acidity. Because of the inherent properties of these systems, it has always been assumed that the temperature limitation with respec-t to exposure was one which had to be accommodated and could not be overcome.
~ccordiny to the present inventlon, however, it has been discovered that such multi-phase solution~ can, indeed, be made less sensitive to variations in ambient temperature over the ranye of ambienk temperatures normally ,` ', " ,' ' ' ' ' ' ',' ' ",.';, ' 2 ~
--6~

encountered in indoor conditioned spaces, e.g., 20C to 30C.
While it has been ~ound that a variety of perfluorocarbon substances exhibit rather stable properties with respect to dessolving amounts of oxygen in the range of 20C-30C and, in some instances, even beyond this range, the same cannot be said o~ the relative concentration of dissolved C02, which decreases with increasing temperature.
In accordance with the invention, it has further been discovered, however, that the use of a dissolved species, such as ethylene diamine in the aqueous phase of the multi~
phase calibration solution, can stabilize the amount of carbon dioxide dissolved in the aqueous solution. In fact, the overall partial pressure C02 can be substantially linearized over a temperature ranye comparable to that of 0z in the perfluorocarbon. Compatible buffers can also be added to the aqueous solution to control acidity at the desired pH value.
The solutions or liquid phases in accordance with the 2Q invention are prepared under controlled conditions. Known amounts of the dissolved gases 2 and C02 are present in the phases as prepared. Ilowever, it may be months or even years before the system is actually used so that long-term stability is required. To preserve the integrity of the system over the shelf life of the product, the calibration system is sealed in an impermeable fluid tight container together with an amount of storage atmosphere which contains sufficient P02 and PC02 to maintian the amount of dissolved species in the liquids over time.
The container may be a glass ampule, or the like, but is preferably a polymeric envelope or laminated pouch which may consist of several layers of metallic foil and polymeric materials which make the pouch impervious to atmosphere exchange with the environment.
When the seal of the encclpsulating container is breached, of course, the protective or storaye atmosphere is lost. The calibration system oE the present inven-tion, ,,' ~', ,''',' :
.
.

7, ~ 7 ~

however, maintains its known PO2/ pC0z and pll ~or the relatively shorter time required to perform the control or calihration procedure, regardless of the ambient temperature at which the breach occurs as long as that temperature is in the range of relative stability for the system, e.g., 20C-30C.
It is apparent that the calibration system of the present invention can also function well as a control system for analytical instruments of the class normally employing such controls as periodic checks. Controls generally require somewhat less precision than calibration systems.
This invention has been described in this application in considerable detail itl order to comply witll the Patent Statutes and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. ~lowever, it is to be further understood that the invention can be carried out by specifically different equipment and devices and that various modifications can be accomplished without departing from the scope of the invention itself.

. . . ........ . .. .. . . . .
",, . . . ,: ,. ,. : i' ... . . . . . . . . .

Claims (26)

-8-What is claimed is:
1. A calibration system which is relatively temperature insensitive over an ambient temperature range of interest, comprising:
a first calibration medium phase comprising a sufficient amount of a first solvPnt which has a capacity for dissolving (O2) to render the amount of O2 dissolved in the calibration system relatively constant over the ambient temperature range of interest and an amount of O2 dissolved therein;
a second calibration medium phase comprising an amount of a second solvent and a solute having a capacity for dissolving carbon dioxide (CO2) and an amount of CO2 dissolved therein;
a vapor phase in contact with the first and second phases;
wherein the partial pressure of both O2 and CO2 in the phases remains substantially constant over the ambient temperature range of interest.
2. The calibration system of claim 1 wherein the first and second phases are liquid phases.
3. The calibration system of claim 1 further comprising:
a fluid tight enclosure for containing the calibration system; and an amount of storage atmosphere of known composition hermetically sealed in the fluid tight enclosure comprising a vapor impermeable barrier in communication with the calibration system.
4. The calibration system of claim 3 wherein the system is insensitive to the relative volume occupied by the vapor phase in relation to that occupied by the first and second phases.
5. The calibration system of claim 3 wherein the first liquid phase comprises an aqueous solution of a solute which reversibly binds to O2.
6. The calibration system of claim 5 wherein the first liquid phase contains an amount of at least one species selected from a group consisting of copper ions, hemoglobin and transition metal complexes.
7. The calibration system of claim 2 wherein the second phase consists substantially of an aqueous solution containing at least one solute species which reversibly reacts with CO2.
8. The calibration system of claim 7 wherein the aqueous solution of the second phase contains at least one solute species selected from the group consisting of ethylenediamine and OH ions.
9. The temperature insensitive calibration system of claim 1 wherein the first solvent consists mainly of a perfluorocarbon material.
10. The temperature insensitive calibration system of claim 3 wherein the first solvent consists mainly of a perfluorocarbon material.
11. The temperature insensitive calibration system of claim 7 wherein the first solvent consists mainly of a perfluorocarbon material.
12. The temperature insensitive calibration system of claim 8 wherein the first solvent consists mainly of a perfluorocarbon material.
13. The calibration system of claim 3 wherein the partial pressure of O2 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of CO2 is in the range of about 5 to 100 mm Hg.
14. The calibration system of claim 12 wherein the partial pressure of O2 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of CO2 is in the range of about 5 to 100 mm Hg.
15. The temperature insensitive calibration fluid of claim 1 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
16. The temperature insensitive calibration fluid of claim 3 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
17. The temperature insensitive calibration fluid of claim 12 wherein the range of ambient temperatures of interest is from about 20°C to about 30°C.
18. The multi-phase calibration system of claim 12 wherein the system is insensitive to the relative volume of the vapor phase in equilibrium with the first and second phases.
19. A multi-phase calibration system having a plurality of non-vapor calibration specie containing medium phases in contact with a vapor phase characterized by a relatively temperature independent equilibrium with respect to the partial pressure of gaseous species of interest in each calibration specie containing medium phase over an ambient temperature range extending from about 20°C to about 30°C comprising.
a first phase comprising an amount of O2 dissolved in a medium consisting mainly of a perfluorocarbon, wherein the partial pressure O2 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest;
a second calibration specie containing medium phase comprising an amount of CO2 dissolved in an aqueous solution containing an amount of at least one solute which reversibly reacts with CO2 such that the partial pressure of CO2 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest; and a vapor phase in equilibrium with the first and second phases.
20. A multi-phase calibration system having a plurality of liquid phases in contact with a vapor phase characterized by a relatively temperature independent equilibrium with respect to the partial pressure of gaseous species of interest in each liquid phase over an ambient temperature range of interest from about 20°C to about 30°C
comprising:
a first liquid phase comprising an amount of O2 dissolved in a liquid perfluorocarbon, wherein the partial pressure of O2 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest;
a second liquid phase comprising an amount of CO2 dissolved in an aqueous solution containing an amount of at least one solute which reversibly reacts with CO2 such that the partial pressure of CO2 remains substantially constant with respect to changes in temperature in the ambient temperature range of interest;
a vapor phase in equilibrium with the first and second phases;
a fluid tight container for storing the calibration system; and an amount of storage atmosphere of known composition hermetically sealed in the fluid tight container with the calibration system.
21. The calibration fluid of claim 20 wherein the aqueous liquid phase further contains an amount of at least one buffer to control the pH.
22. The calibration system of claim 20 wherein the partial pressure of O2 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of CO2 is in the range of about 5 to 100 mm Hg.
23. The calibration system of claim 20 wherein the aqueous solution contains at: least one solute species selected from the group consisting of ethylediamine and OH
ions.
24. The multi-phase calibration system of claim 20 wherein the system is insensitive to the relative amount of storage atmosphere with relation to the liquid sealed in the fluid-tight container.
25. The calibration system of claim 21 wherein the partial pressure of O2 is in the range of about 10 to 200 mm Hg and wherein the partial pressure of CO2 is in the range of about 5 to 100 mm Hg.
26. The temperature insensitive calibration fluid of claim 21 wherein the aqueous solution contains at least one solute species selected from the group consisting of ethylediamine and OH ions.
CA 2071540 1990-10-26 1991-10-26 Temperature insensitive calibration system Abandoned CA2071540A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US60466690A 1990-10-26 1990-10-26
US604,666 1990-10-26

Publications (1)

Publication Number Publication Date
CA2071540A1 true CA2071540A1 (en) 1992-04-27

Family

ID=24420510

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2071540 Abandoned CA2071540A1 (en) 1990-10-26 1991-10-26 Temperature insensitive calibration system

Country Status (3)

Country Link
AU (1) AU9022191A (en)
CA (1) CA2071540A1 (en)
WO (1) WO1992008130A1 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4163734A (en) * 1975-05-30 1979-08-07 Radiometer A/S Reference liquid for blood gas equipment
US4126575A (en) * 1977-11-22 1978-11-21 Louderback Allan Lee Blood control standard
US4279775A (en) * 1979-12-31 1981-07-21 Louderback Allan Lee Blood gas control
US4299728A (en) * 1980-07-21 1981-11-10 Instrumentation Laboratory Inc. Blood gas control
US4369127A (en) * 1980-07-21 1983-01-18 Instrumentation Laboratory Inc. Blood gas control
US4469792A (en) * 1980-12-31 1984-09-04 Allied Corporation Blood gas calibration and control fluid utilizing stroma-free hemoglobin
US4485174A (en) * 1982-09-29 1984-11-27 Instrumentation Laboratory Inc. Hemoglobin-based blood gas control

Also Published As

Publication number Publication date
WO1992008130A1 (en) 1992-05-14
AU9022191A (en) 1992-05-26

Similar Documents

Publication Publication Date Title
EP0705431B1 (en) Temperature stabilized fluid calibration system
CA2143209C (en) Calibration medium containment system
AU697326B2 (en) Methods and apparatus for rapid equilibration of dissolved gas composition
US4163734A (en) Reference liquid for blood gas equipment
EP0711404B1 (en) Reagent system for calibration of pipettes and other volumetric measuring devices
PT89844A (en) CONTROLLING MACHINE OPERATION WITH RESPECT TO CONSUMABLE ACCESSORY UNITS
WO1994009359B1 (en) Self-activating chemical sensor system
US5231030A (en) Temperature insensitive calibration system
US6066249A (en) Method for calibrating an instrument for measuring electrolytes and metabolites by analysis of blood gases
CA2071540A1 (en) Temperature insensitive calibration system
US5578194A (en) Calibration of electrodes
US7378006B2 (en) Aqueous solutions for reducing the rate of oxygen loss, and methods thereof
Green A redetermination of the solubility of oxygen in sea water and some thermodynamic implications of the solubility relations.
AU4289093A (en) Calibration reagent having a stabilized concentration of dissolved gas
US4836673A (en) Wavelength accuracy test solution and method
AU710940B2 (en) Methods and apparatus for rapid equilibration of dissolved gas composition
Erickson The oxidation of water and inorganic nitrogen compounds by potassium ferrate (VI)
Schoene et al. Determination of the solubility of vapours in polymers by automated headspace gas chromatography
WO2010018394A1 (en) Calibration solution packaging method and calibration solution package
Saltzman et al. Permeation tubes as calibrated sources of gas
Hoover Determination of Molecular Hydrogen Sulfide
Piet et al. METHOD 15" STATIC" HEAD-SPACE DETERMINATION OF VOLATILE ORGANIC HALOGEN COMPOUNDS IN WATER
Bishay et al. Design and construction of an apparatus for low surface area determination using krypton
Clark et al. Mars aqueous chemistry experiment
Radtke et al. 6.2 DISSOLVED OXYGEN

Legal Events

Date Code Title Description
FZDE Dead