Optical pH and gas concentration sensor

• US 5,039,492 A
• Filed: 01/27/1989
• Issued: 08/13/1991
• Est. Priority Date: 01/27/1989
• Status: Expired due to Fees

• Current Assignee: NetTest North America, Inc. (Anritsu Corporation)
• Original Assignee: MetriCor, Inc. (Constellation Software Incorporated)
• Inventors: McCrae, David A., Hartl, James C., Saaski, Elric W., Lawrence, Dale M., Wolthuis, Roger A.
• Primary Examiner(s): NOT, DEFINED
• Assistant Examiner(s): Trembley, Theresa A.
• Application Number:
  US07/303,584
• Time in Patent Office: 928 Days
• Field of Search: 436/136, 436/138, 422/55, 422/58, 422/60, 422/82.03, 422/82.04, 422/82.05, 422/82.09, 422/56, 128/633, 128/634, 350/628, 350/642, 364/413.09
• US Class Current: 422/82.09
• CPC Class Codes: G01N 2021/0314 Double pass, autocollimated path
• CPC Class Codes: G01N 2021/0385 Diffusing membrane; Semipermeable membrane
• CPC Class Codes: G01N 2021/3144 for oxymetry
• CPC Class Codes: G01N 21/77 by observing the effect on a chemical indicator
• CPC Class Codes: G01N 21/783 for analysing gases
• CPC Class Codes: G01N 21/80 Indicating pH value
• CPC Class Codes: G01N 2201/0231 Thermostating
• CPC Class Codes: G01N 2201/062 LED's
• CPC Class Codes: G01N 2201/0621 Supply
• CPC Class Codes: Y10T 436/207497 Molecular oxygen
• CPC Class Codes: Y10T 436/209163 Dissolved or trace oxygen or oxygen content of a sealed environment
• CPC Class Codes: Y10T 436/22 Hydrogen, per se

Abstract

An optical pH sensor and a gas sensor utilizing the pH sensor. The pH sensor includes an indicator whose absorbance is a function of the concentration of hydronium ions in a media surrounding the indicator. Light transmitted and reflected through the indicator of the sensor undergoes an absorption that is characteristic of the concentration of the hydrogen ion. The pH sensor can be used as to sense the concenration of a gas in a sample by surrounding the indicator with a liquid or liquid-containing media that changes pH as it is exposed to the gas, and separating the indicator and liquid or liquid-containing media from the gas with a membrane that is permeable to the gas to be measured. A measuring system used with the sensors transmits coherent radiation to the sensor through an optical fiber, separates the radiation returning from the sample into two wavelength bands, and digitally samples the photocurrents produced within the two wavelength bands. A microprocessor performs ratiometric calculations to measure the pH or gas concentration.

Claims

1. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane; and

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium, said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said medium, said azo dye being 6 (3'"'"',5'"'"'-dichloro-2'"'"',4'"'"',6'"'"'triazinylamino)-3-(2",4"-dinitrophenyl-1"-azo)-4-hydroxynaphthalene-2-sulfonic acid, sodium salt, having the formula;

##STR1##

2. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane; and

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium, said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said medium, said azo dye being 7 (3'"'"',5'"'"'-dichloro-2'"'"',4'"'"',6'"'"'-triazinylamino)-3-(2",4"-dinitrophenyl-1"-azo)-4-hydroxynaphthalene-2-sulfonic acid, sodium salt, having the formula;

##STR2##

3. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane; and

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium, said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said medium, said azo dye being 6-amino-1,3-naphthalene-disulfonic acid/K₂ CO₃, having the formula;

##STR3##

4. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane;

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium;

measurement means for measuring radiation, said means being operative to receive said radiation passing through said indicator means and generate a corresponding signal indicative of the concentration of the gas in said sample; and

means for transmitting said radiation from said source of radiation to said indicator chamber, and from said indicator chamber to said measurement means, said means for transmitting including a radiation-transmissive wall receiving said radiation from said source of radiation through said transmitting means, and a radiation-reflective wall facing the transmissive wall for reflecting radiation transmitted through said indicator means from said radiation-transmissive wall whereby radiation from said source of radiation is transmitted through said indicator means, reflected from said radiation-reflective wall back through said indicator means to said radiation-transmissive wall and through said coupling means to said measurement means, said radiation-reflective wall being formed by a mirror having an aperture to allow said gas to pass through said mirror into said indicator chamber.

5. The sensing system of claim 4 wherein said aperture is in the form of a pair of elongated parallel slots in said mirror forming a reflecting bar therebetween.

6. The sensing system of claim 4 wherein said mirror is fabricated by wet chemistry micromachining of a sheet of reflective material.

7. The sensing system of claim 4 wherein said mirror has formed therein a plurality of microminiature aperture.

8. The sensing system of claim 4 wherein said mirror is formed from a sheet of thin film porous media coated with a reflective substance.

9. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane;

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium;

ionophobic oil encapsulating said indicator means to enhance the optical and stability properties of said sensing system;

measurement means for measuring radiation, said means being operative to receive said radiation passing through said indicator means and generate a corresponding signal indicative of the concentration of the gas in said sample; and

means for transmitting said radiation from said source of radiation to said indicator chamber, and from said indicator chamber to said measurement means.

10. A sensing system for measuring the pH of a sample, comprising:

a source of radiation having predetermined spectral characteristics; and

indicator means communicating with said sample so that ions within said sample can interact with said indicator means, said indicator means having radiation absporption/transmission characteristics that vary as a function of the pH of the sample;

said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said sample, said azo dye being 6 (3'"'"',5'"'"'-dichloro-2'"'"',4'"'"',6'"'"'-triazinylamino)-3-(2",4"-dinitrophenyl-1"-azo)-4-hydroxynaphthalene-2-sulfonic acid, sodium salt, having the formula;

##STR4##

11. A sensing system for measuring the pH of a sample, comprising:

a source of radiation having predetermined spectral characteristics; and

indicator means communicating with said sample so that ions within said sample can interact with said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the pH of the sample;

said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said sample, said azo dye being 7-(3'"'"',5'"'"'-dichloro-2'"'"',4'"'"',6'"'"'-triazinylamino)-3-(2",4"-dinitrophenyl-1"-azo-4-hydroxynaphthalene-2-sulfonic acid, sodium salt, having the formula;

##STR5##

12. A sensing system for measuring the pH of a sample, comprising:

a source of radiation having predetermined spectral characteristics; and

indicator means communicating with said sample so that ions within said sample can interact with said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the pH of the sample;

said indicator means being an azo dye having absorption/transmission characteristics that are sensitive to the concentration of hydronium ions in said sample, said azo dye being 6-amino-1,3-naphthalene-disulfonic acid/K₂ CO₃, having the formula;

##STR6##

13. A sensing system for measuring the pH of a sample, comprising:

a source of radiation having predetermined spectral characteristics; and

indicator means communicating with said sample so that ions within said sample can interact with said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the pH of the sample;

said indicator means being disposed on a substrate defining an indicator chamber cavity communicating with said sample, said indicator chamber including a radiation-transmissive wall receiving said radiation from said source of radiation through said optical means and coupling radiation to said measurement means through said optical means, and a radiation-reflective wall facing the transmissive wall for reflecting radiation transmitted through said indicator means from said radiation-transmissive wall whereby radiation from said source of radiation is transmitted through said indicator means, reflected from said radiation-reflective wall back through said indicator means to said radiation-transmissive wall and through said optical means to said measurement means, said radiation-reflective wall being formed by a mirror having an aperture to allow said sample to pass through said mirror into said indicator chamber.

14. The sensing system of claim 13 wherein said aperture is in the form of a pair of elongated parallel slots in said mirror forming a reflecting bar therebetween.

15. The sensing system of claim 13 wherein said mirror is fabricated by wet chemistry micromachining of a sheet of reflective material.

16. The sensing system of claim 13 wherein said mirror is formed from a sheet of thin film porous media coated with a reflective substance.

17. The sensing system of claim 13 wherein said mirror has formed therein a plurality of microminiature apertures.

18. A sensing system for measuring the pH of a sample, comprising:

a source of radiation having predetermined spectral characteristics; and

indicator means communicating with said sample so that ions within said sample can interact with said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the pH of the sample;

said indicator means being disposed on a substrate defining an indicator chamber cavity communicating with said sample, said indicator chamber including a radiation-transmissive wall receiving said radiation from said source of radiation through said optical means and coupling radiation to said measurement means through said optical means, and a radiation-reflective wall facing the transmissive wall for reflecting radiation transmitted through said indicator means from said radiation-transmissive wall whereby radiation from said source of radiation is transmitted through said indicator means, reflected from said radiation-reflective wall back through said indicator means to said radiation-transmissive wall and through said optical means to said measurement means, and a layer of hydrophilic gel placed between said indicator means and said radiation-transmissive wall and between said indicator means and said radiation-reflective wall, said gel index matching said indicator means to said radiation-transmissive and radiation-reflective walls and excluding said liquid sample from the path of said radiation through said indicator chamber cavity.

19. A sensing system for measuring the concentration of a gas in a sample, comprising:

a source of radiation having predetermined spectral characteristics over a band of wavelengths;

a substrate defining an indicator chamber cavity containing a liquid medium or liquid-containing medium that undergoes a change in hydrogen ion concentration as it absorbs the gas to be measured;

optical means for transmitting said radiation into said indicator chamber cavity;

a membrane enclosing an opening in said indicator chamber cavity to retain said medium in said indicator chamber cavity, said membrane being permeable to the gas to be measured so that said gas can be absorbed into said medium to change the pH of said medium when said sample contacts said membrane;

indicator means contained in said medium so that said radiation passing into said cavity passes through said indicator means, said indicator means having radiation absorption/transmission characteristics that vary as a function of the hydrogen ion concentration of said medium and that change differently in upper and lower spectral bands of said radiation;

measurement means for measuring radiation, said means being operative to receive said radiation passing through said indicator means and to generate a signal representative of the ratio of the spectral content of the reflected light in the upper spectral band of wavelengths to the spectral content of the reflected light in the lower spectral band of wavelengths, thereby providing a signal indicative of the concentration of the gas in said sample; and

means for transmitting said radiation from said source of radiation to said indicator chamber, and from said indicator chamber to said measurement means.

20. The sensing system of claim 19 wherein said indicator means has a spectral response of a periodic nature with a plurality of relative minima and maxima values, and wherein said upper and lower spectral bands of said wavelengths are located between adjacent minima and maxima values.

21. The sensing system of claim 19 wherein said indicator means has a plurality of spectral responses curves all of which pass through a common isobestic point and wherein said band of wavelengths is centered around said isobestic point.