Method and apparatus for the detection of toxic gases

• US 5,624,546 A
• Filed: 09/27/1995
• Issued: 04/29/1997
• Est. Priority Date: 08/26/1994
• Status: Expired due to Term

• Current Assignee: Mil-Ram Technology Incorporated
• Original Assignee: Mil-Ram Technology Incorporated
• Inventors: Milco, Gary A.
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US08/534,597
• Time in Patent Office: 580 Days
• Field of Search: 204/415, 204/412, 204/431, 204/432, 204/425, 422/83, 422/88, 422/98, 205/779.5, 205/780.5, 205/782.5, 205/785.5, 205/786, 205/793, 205/794.5
• US Class Current: 205/779.5
• CPC Class Codes: G01N 27/4045 for gases other than oxygen

Abstract

A compact electrochemical cell utilized for the detection of numerous toxic gases. The cell includes working and counter electrodes, surrounded by a liquid electrolyte, all of which is enclosed behind a gas permeable, hydrophobic membrane. The working electrode may be a single electrode or may be composed of multiple glassy carbon electrodes arranged in a planar electrode array. The counter electrode is either spatially separated from the array or comprises one or more electrodes in the array. The electrolyte composition varies with the type of gas to be detected and can be aqueous, partially aqueous, or substantially non-aqueous. The electrolyte includes an alkali metal halide. A fixed potential applied between the working and counter electrodes is sufficient to initiate electrochemical reactions in the presence of the gas to be detected without interfering reactions of the electrolyte or air.

Claims

1. An electrochemical cell for detecting chlorine, fluorine and bromine gas in ambient air comprising:

a platinum counter electrode;

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising 30% through 50% by weight potassium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately -150 through -250 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with the chlorine, fluorine and bromine gas to be detected.

2. The electrochemical cell of the claim 1 wherein the glassy carbon working electrodes are arranged to form an array.

3. The electrochemical cell of claim 2 wherein said counter electrode is disposed within said array.

4. The electrochemical cell of claim 1 wherein the number of working electrodes is three.

5. The electrochemical cell of claim 1 wherein the electrolyte comprises 30% through 50% by weight of a combination of potassium bromide and lithium bromide.

6. The electrochemical cell of claim 1 wherein the electrolyte comprises 30% through 50% by weight lithium bromide.

7. The electrochemical cell of claim 1 wherein the electrolyte is partially aqueous and comprises 10% through 40% by weight ethylene glycol.

8. An electrochemical cell for detecting hydrogen sulfide gas in ambient air comprising:

a platinum counter electrode,

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising approximately 0.4% through 0.8% by weight copper sulfate and approximately 30% through 50% by weight lithium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately -20 through -60 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with the hydrogen sulfide gas to be detected.

9. The electrochemical cell of claim 8 wherein the electrolyte has a pH adjusted below 3.

10. The electrochemical cell of claim 9 wherein the pH is adjusted below 3 with hydrochloric acid.

11. The electrochemical cell of claim 9 wherein the pH is adjusted below 3 with sulfuric acid.

12. An electrochemical cell for detecting chlorine dioxide, nitrogen dioxide, ozone and hydrogen peroxide gas in ambient air comprising:

a platinum counter electrode;

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising approximately 30% through 50% by weight lithium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately -150 through -250 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with the chlorine dioxide, nitrogen dioxide, ozone and hydrogen peroxide gas to be detected.

13. The electrochemical cell of claim 12 wherein the electrolyte has a pH adjusted below 3.

14. The electrochemical cell of claim 13 wherein the pH is adjusted below 3 with hydrochloric acid.

15. The electrochemical cell of claim 13 wherein the pH is adjusted below 3 with phosphoric acid.

16. An electrochemical cell for detecting hydrogen chloride, hydrogen fluoride, hydrogen bromide, sulfur dioxide, nitric acid and sulfuric acid gas in ambient air comprising:

a platinum counter electrode;

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising approximately 0.4% through 1.0% by weight potassium bromate and approximately 30% through 50% by weight potassium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately -150 through -250 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with hydrogen chloride, hydrogen fluoride, hydrogen bromide, sulfur dioxide, nitric acid and sulfuric acid gas to be detected.

17. The electrochemical cell of claim 16 wherein the electrolyte comprises 30% through 50% by weight of a combination of potassium bromide and lithium bromide.

18. The electrochemical cell of claim 16 wherein the electrolyte is partially aqueous and comprises 10% through 40% by weight ethylene glycol.

19. An electrochemical cell for detecting ammonia in ambient air comprising:

a platinum counter electrode;

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising approximately 0.3% through 0.5% by weight copper sulfate, approximately 0.6% through 0.8% by weight tris amine buffer, and approximately 30% through 50% by weight lithium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately +40 through -100 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with the ammonia gas to be detected.

20. The electrochemical cell of claim 19 wherein the electrolyte has a pH adjusted below 4.

21. An electrochemical cell for detecting hydrogen cyanide gas in ambient air comprising:

a platinum counter electrode;

a plurality of glassy carbon working electrodes having exposed surfaces finished to a high polish;

an electrolyte comprising approximately 0.3% through 0.5% by weight copper sulfate, approximately 0.3% through 0.6% by weight tris amine buffer, and approximately 30% through 50% by weight lithium bromide in operative contact with said counter electrode and said exposed surfaces of said working electrodes;

a gas permeable hydrophobic membrane enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell; and

means providing a fixed potential of approximately -20 through -50 millivolts applied between said counter electrode and said plurality of working electrodes to initiate electrochemical reactions only with the hydrogen cyanide gas to be detected.

22. A method of detecting ammonia gas in ambient air with an electrochemical cell comprising the steps of:

providing a platinum counter electrode;

providing a plurality of glassy carbon working electrodes having surfaces finished to a high polish;

operatively contacting said counter electrode and said plurality of exposed surfaces of said working electrodes with an electrolyte comprising approximately 0.3% through 0.5% by weight copper sulfate, approximately 0.6% through 0.8% by weight tris amine buffer, and approximately 30% through 50% by weight lithium bromide;

enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell by a gas permeable hydrophobic membrane; and

applying a fixed potential of approximately +40 through -100 millivolts between said counter electrode and said plurality of working electrodes sufficient to initiate electrochemical reactions only with the ammonia gas to be detected.

23. A method of detecting chlorine, fluorine and bromine gas in ambient air with an electrochemical cell comprising the steps of:

providing a platinum counter electrode;

providing a plurality of glassy carbon working electrodes having surfaces finished to a high polish;

operatively contacting said counter electrode and said plurality of exposed surfaces of said working electrodes with an electrolyte comprising 30% through 50% by weight potassium bromide;

enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell by a gas permeable hydrophobic membrane; and

applying a fixed potential of approximately -150 through -250 millivolts between said counter electrode and said plurality of working electrodes sufficient to initiate electrochemical reactions only with the chlorine, fluorine and bromine gas to be detected.

24. A method of detecting hydrogen chloride, hydrogen fluoride, hydrogen bromide, sulfur dioxide, nitric acid and sulfuric acid gas in ambient air with an electrochemical cell comprising the steps of:

providing a platinum counter electrode;

providing a plurality of glassy carbon working electrodes having surfaces finished to a high polish;

operatively contacting said counter electrode and said plurality of exposed surfaces of said working electrodes with an electrolyte comprising approximately 0.4% through 1.0% by weight potassium bromate and approximately 30% through 50% by weight potassium bromide;

enclosing said counter electrode, said plurality of working electrodes, and said electrolyte within said cell by a gas permeable hydrophobic membrane; and

applying a fixed potential of approximately -150 through -250 millivolts between said counter electrode and said plurality of working electrodes sufficient to initiate electrochemical reactions only with the hydrogen chloride, hydrogen fluoride, hydrogen bromide, sulfur dioxide, nitric acid and sulfuric acid gas to be detected.