Halide ion-selective devices and method

US 4,199,412 A
Filed: 10/31/1978
Issued: 04/22/1980
Est. Priority Date: 10/31/1978
Status: Expired due to Term

First Claim

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1. In a potentiometric device for the detection of halide ions in a solution, said device comprising:

(1) a layer of silver halide in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide,the improvement wherein said halide ion-permeable overlayer consists essentially of a composition that;

(a) is from about 1 to about 8 microns thick;

(b) has a diffusion coefficient of at least 2.5×

10^-10 cm² /sec with respect to the halide ions to be detected; and

(c) has a permeability of less than 2×

10^-8 cm² /sec to materials which could interfere with said detection of halide ions;

whereby said halide ion-permeable overlayer is capable of inhibiting interference due to the presence of one or more of said interfering materials in said solution, and said potentiometric device is capable of accurately carrying out said detection of halide ions within 5 minutes after a portion of said solution is brought into contact with said halide ion-permeable overlayer.

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Abstract

Halide ion-sensitive devices and methods for their use are described. The devices contain a halide ion-permeable overlayer which is superposed on a layer of silver halide and meets certain criteria of thickness and permeability and/or certain compositional criteria. The methods involve bringing a portion of a solution to be analyzed into contact with the halide ion-permeable overlayer and, within a selected time thereafter, measuring the difference in potential between the portion of solution and the silver halide layer.

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39 Claims

1. In a potentiometric device for the detection of halide ions in a solution, said device comprising:
- (1) a layer of silver halide in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide,the improvement wherein said halide ion-permeable overlayer consists essentially of a composition that;
  
  (a) is from about 1 to about 8 microns thick;
  
  (b) has a diffusion coefficient of at least 2.5×
  
  10^-10 cm² /sec with respect to the halide ions to be detected; and
  
  (c) has a permeability of less than 2×
  
  10^-8 cm² /sec to materials which could interfere with said detection of halide ions;
  
  whereby said halide ion-permeable overlayer is capable of inhibiting interference due to the presence of one or more of said interfering materials in said solution, and said potentiometric device is capable of accurately carrying out said detection of halide ions within 5 minutes after a portion of said solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (2, 3, 4)
- - 2. The device of claim 1 wherein said halide ions are chloride ions and said silver halide is silver chloride.
  - 3. The device of claim 1 wherein said halide ion-permeable overlayer contains a surfactant.
  - 4. The device of claim 1 wherein said means for making potentiometric measurements comprises a doped silicon support having a silicon dioxide layer superposed thereon.

5. In a potentiometric device for the detection of halide ions in a solution, said device comprising:
- (1) a layer of silver halide in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide, the improvement wherein said halide ion-permeable overlayer is from about 1 to about 8 microns thick and consists essentially of a composition selected from the group consisting of;
  
  (a) cellulose esters having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
  
  (b) polymers derived from 45 weight percent to 100 weight percent of monomers selected from the group consisting of;
  
  (1) acrylic acids;
  
  (2) methacrylic acids;
  
  (3) acrylamides;
  
  (4) alkylacrylamides wherein the alkyl portion has from 1 to 5 carbon atoms;
  
  (5) hydroxyalkyl acrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (6) hydroxyalkyl methacrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (c) mixtures of gelatin, silver halide/gelatin emulsion and an acid.
- View Dependent Claims (6)
- - 6. The device of claim 5 wherein said halide ion-permeable overlayer consists essentially of a composition selected from the group consisting of:
    - (a) cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
      
      (b) poly(acrylamide-co-methacrylic acid) (weight ratio;
      
      45/55);
      
      (c) poly(methacrylamide-co-methacrylic acid) (weight ratio;
      
      50/50);
      
      (d) poly(methacrylamide-co-2-hydroxyethylmethacrylate-co-methacrylic acid-co-2-acetoacetoxyethylmethacrylate) (weight ratio;
      
      28/28/34/10);
      
      (e) poly(methacrylic acid);
      
      (f) poly(acrylic acid); and
      
      (g) poly(2-hydroxyethylacrylate).

7. In a potentiometric device for the detection of halide ions in a solution, said device comprising:
- (1) a layer of silver halide in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide,the improvement wherein said halide ion-permeable overlayer is from about 1 to about 8 microns thick and consists essentially of cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content.
- View Dependent Claims (8, 9, 10)
- - 8. The device of claim 7 wherein said halide ions are chloride ions and said silver halide is silver chloride.
  - 9. The device of claim 7 wherein said halide ion-permeable overlayer contains a surfactant.
  - 10. The device of claim 7 wherein said means for making potentiometric measurements comprises a doped silicon support having a silicon dioxide layer superposed thereon.

11. In a halide ion-sensitive electrode for the detection of halide ions in a solution, said electrode comprising:
- (1) a layer of silver halide superposed on and in electrochemical contact with a layer of silver, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide,the improvement wherein said halide ion-permeable overlayer consists essentially of a composition that;
  
  (a) is from about 1 to about 8 microns thick;
  
  (b) has a diffusion coefficient of at least 2.5×
  
  10^-10 cm² /sec with respect to the halide ions to be detected; and
  
  (c) has a permeability of less than 2×
  
  10^-8 cm² /sec to materials which could interfere with said detection of halide ions;
  
  whereby said halide ion-permeable overlayer is capable of inhibiting interference due to the presence of one or more of said interfering materials in said solution, and said halide ion-sensitive electrode is capable of accurately carrying out said detection of halide ions within 5 minutes after a portion of said solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (12, 13)
- - 12. The electrode of claim 11 wherein said halide ions are chloride ions and said silver halide is silver chloride.
  - 13. The electrode of claim 11 wherein said halide ion-permeable overlayer contains a surfactant.

14. In a halide ion-sensitive electrode for the detection of halide ions in a solution, said electrode comprising:
- (1) a layer of silver halide superposed on and in electrochemical contact with a layer of silver, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide, the improvement wherein said halide ion-permeable overlayer is from about 1 to about 8 microns thick and consists essentially of a composition selected from the group consisting of;
  
  (a) cellulose esters having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
  
  (b) polymers derived from 45 weight percent to 100 weight percent of one or a mixture of monomers selected from the group consisting of;
  
  (1) acrylic acids;
  
  (2) methacrylic acids;
  
  (3) acrylamides;
  
  (4) alkylacrylamides wherein the alkyl portion has from 1 to 5 carbon atoms;
  
  (5) hydroxyalkyl acrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (6) hydroxyalkyl methacrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (c) mixtures of gelatin, silver halide/gelatin emulsion and an acid.
- View Dependent Claims (15)
- - 15. The electrode of claim 14 wherein said halide ion-permeable overlayer consists essentially of a composition selected from the group consisting of:
    - (a) cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
      
      (b) poly(acrylamide-co-methacrylic acid) (weight ratio;
      
      45/55);
      
      (c) poly(methacrylamide-co-methacrylic acid) (weight ratio;
      
      50/50);
      
      (d) poly(methacrylamide-co-2-hydroxyethylmethacrylate-co-methacrylic acid-co-2-acetoacetoxyethylmethacrylate) (weight ratio;
      
      28/28/34/10);
      
      (e) poly(methacrylic acid);
      
      (f) poly(acrylic acid); and
      
      (g) poly(2-hydroxyethylacrylate).

16. In a halide ion-sensitive electrode for the detection of halide ions in a solution, said electrode comprising:
- (1) a layer of silver halide superposed on and in electrochemical contact with a layer of silver, and (2) a halide ion-permeable overlayer superposed on said layer of silver halide,the improvement wherein said halide ion-permeable overlayer is from about 1 to about 8 microns thick and consists essentially of cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content.
- View Dependent Claims (17, 18)
- - 17. The electrode of claim 16 wherein said halide ions are chloride ions and said silver halide is silver chloride.
  - 18. The electrode of claim 16 wherein said halide ion-permeable overlayer contains a surfactant.

19. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, said halide ion-permeable overlayer consisting essentially of a composition;
  
  (1) being from about 1 to about 8 microns thick;
  
  (2) having a diffusion coefficient of at least 2.5×
  
  10^-10 cm² /sec with respect to the halide ions whose concentration is to be determined; and
  
  (3) having a permeability of less than 2×
  
  10^-8 cm² /sec to materials which could interfere with said determination of halide ion concentration; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer within 5 minutes after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (20, 21, 22)
- - 20. The method of claim 19 wherein said halide ion concentration is chloride ion concentration and said silver halide is silver chloride.
  - 21. The method of claim 19 wherein said halide ion-permeable overlayer contains a surfactant.
  - 22. The method of claim 19 wherein said means for making potentiometric measurements comprises a doped silicon support having a silicon dioxide layer superposed thereon.

23. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, said halide ion-permeable overlayer being from about 1 to about 8 microns thick and consisting essentially of a composition selected from the group consisting of;
  
  (1) cellulose esters having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
  
  (2) polymers derived from 45 weight percent to 100 weight percent of one or a mixture of monomers selected from the group consisting of;
  
  (i) acrylic acids;
  
  (ii) methacrylic acids;
  
  (iii) acrylamides;
  
  (iv) alkylacrylamides wherein the alkyl portion has from 1 to 5 carbon atoms;
  
  (v) hyroxyalkyl acrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (vi) hydroxyalkyl methacrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (3) mixtures of gelatin, silver halide/gelatin emulsion and an acid; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (24)
- - 24. The method of claim 23 wherein said halide ion-permeable overlayer consists essentially of a composition selected from the group consisting of:
    - (a) cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
      
      (b) poly(acrylamide-co-methacrylic acid) (weight ratio;
      
      45/55);
      
      (c) poly(methacrylamide-co-methacrylic acid) (weight ratio;
      
      50/50);
      
      (d) poly(methacrylamide-co-2-hydroxyethylmethacrylate-co-methacrylic acid-co-2-acetoacetoxyethylmethacrylate) (weight ratio;
      
      28/28/34/10);
      
      (e) poly(methacrylic acid);
      
      (f) poly(acrylic acid); and
      
      (g) poly(2-hydroxyethylacrylate).

25. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, said halide ion-permeable overlayer being from about 1 to about 8 microns thick and consisting essentially of cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer within 5 minutes after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (26, 27, 28)
- - 26. The method of claim 25 wherein said halide ion concentration is chloride ion concentration and said silver halide is silver chloride.
  - 27. The method of claim 25 wherein said halide ion-permeable overlayer contains a surfactant.
  - 28. The method of claim 25 wherein said means for making potentionmetric measurements comprises a doped silicon support having a silicon dioxide layer superposed thereon.

29. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is superposed on and in electrochemical contact with a layer of silver, said halide ion-permeable overlayer consisting essentially of a composition;
  
  (1) being from about 1 to about 8 microns thick;
  
  (2) having a diffusion coefficient of at least 2.5×
  
  10^-10 cm² /sec with respect to the halide ions whose concentration is to be determined; and
  
  (3) having a permeability of less than 2×
  
  10^-8 cm² /sec to materials which could interfere with said determination of halide ion concentration; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer within 5 minutes after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (30, 31)
- - 30. The method of claim 29 wherein said halide ion concentration is chloride ion concentration and said silver halide is silver chloride.
  - 31. The method of claim 29 wherein said halide ion-permeable overlayer contains a surfactant.

32. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is superposed on and in electrochemical contact with a layer of silver, said halide ion-permeable overlayer being from about 1 to about 8 microns thick and consisting essentially of a composition selected from the group consisting of;
  
  (1) cellulose esters having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
  
  (2) polymers derived from 45 weight percent to 100 weight percent of one or a mixture of monomers selected from the group consisting of;
  
  (i) acrylic acids;
  
  (ii) methacrylic acids;
  
  (iii) acrylamides;
  
  (iv) alkylacrylamides wherein the alkyl portion has from 1 to 5 carbon atoms;
  
  (v) hydroxyalkyl acrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (vi) hydroxyalkyl methacrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (3) mixtures of gelatin, silver halide/gelatin emulsion and an acid; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (33)
- - 33. The method of claim 32 wherein said halide ion-permeable overlayer consists essentially of a composition selected from the group consisting of:
    - (a) cellulose acetate having from about 36.5 weight percent to 40.0 weight percent acetyl content;
      
      (b) poly(acrylamide-co-methacrylic acid) (weight ratio;
      
      45/55);
      
      (c) poly(methacrylamide-co-methacrylic acid) (weight ratio;
      
      50/50);
      
      (d) poly(methacrylamide-co-2-hydroxyethylmethacrylate-co-methacrylic acid-co-2-acetoacetoxyethylmethacrylate) (weight ratio;
      
      28/28/34/10);
      
      (e) poly(methacrylic acid);
      
      (f) poly(acrylic acid); and
      
      (g) poly(2-hydroxyethylacrylate).

34. A method for determining halide ion concentration in an aqueous solution, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is superposed on and in electrochemical contact with a layer of silver, said halide ion-permeable overlayer being from about 1 to about 8 microns thick and consisting essentially of cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer within 5 minutes after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (35, 36)
- - 35. The method of claim 34 wherein said halide ion concentration is chloride ion concentration and said silver halide is silver chloride.
  - 36. The method of claim 34 wherein said halide ion-permeable overlayer contains a surfactant.

37. A method of inhibiting interference in a halide ion concentration determination, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, said halide ion-permeable overlayer consisting essentially of a composition;
  
  (1) being from about 1 to about 8 microns thick;
  
  (2) having a diffusion coefficient of at least 2.5×
  
  10^-10 cm² /sec with respect to the halide ions whose concentration is to be determined; and
  
  (3) having a permeability of less than 2×
  
  10^-8 cm² /sec to materials which could interfere with said determination of halide ion concentration; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer within 5 minutes after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.

38. A method of inhibiting interference in a halide ion concentration determination, said method comprising the steps of:
- (a) bringing a portion of said aqueous solution into contact with a halide ion-permeable overlayer superposed on a layer of silver halide which is in electrochemical contact with means for making potentiometric measurements related to halide ion concentration, said halide ion-permeable overlayer being from about 1 to about 8 microns thick and consisting essentially of a composition selected from the group consisting of;
  
  (1) cellulose esters having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
  
  (2) polymers derived from 45 weight percent to 100 weight percent of one or a mixture of monomers selected from the group consisting of;
  
  (i) acrylic acids;
  
  (ii) methacrylic acids;
  
  (iii) acrylamides;
  
  (iv) alkylacrylamides wherein the alkyl portion has from 1 to 5 carbon atoms;
  
  (v) hydroxyalkyl acrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (vi) hydroxyalkyl methacrylates wherein the alkyl portion has from 1 to 5 carbon atoms; and
  
  (3) mixtures of gelatin, silver halide/gelatin emulsion and an acid; and
  
  (b) measuring the difference in potential between said portion of aqueous solution and said silver halide layer after said portion of aqueous solution is brought into contact with said halide ion-permeable overlayer.
- View Dependent Claims (39)
- - 39. The method of claim 38 wherein said halide ion-permeable overlayer consists essentially of a composition selected from the group consisting of:
    - (a) cellulose acetate having from about 36.5 weight percent to about 40.0 weight percent acetyl content;
      
      (b) poly(acrylamide-co-methacrylic acid) (weight ratio;
      
      45/55);
      
      (c) poly(methacrylamide-co-methacrylic acid) (weight ratio;
      
      50/50);
      
      (d) poly(methacrylamide-co-2-hydroxyethylmethacrylate-co-methacrylic acid-co-2-acetoacetoxyethylmethacrylate) (weight ratio;
      
      28/28/34/10);
      
      (e) poly(methacrylic acid);
      
      (f) poly(acrylic acid); and
      
      (g) poly(2-hydroxyethylacrylate).

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Current Assignee
Clinical Diagnostic Systems Inc.
Original Assignee
Eastman Kodak Company
Inventors
Kim, Sang H., Battaglia, Charles J., Secord, Denise S.
Primary Examiner(s)
Kaplan, G. L.

Application Number

US05/956,527
Time in Patent Office

539 Days
Field of Search

204/1 B, 204/195 P, 204/195 B, 204/195 F, 128/2 E, 324/29, 324/30 R
US Class Current

205/780
CPC Class Codes

G01N 27/3335 the membrane containing at ...

Halide ion-selective devices and method

First Claim

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Halide ion-selective devices and method

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