Instrument for measurement of the organic carbon content of water

• US 4,868,127 A
• Filed: 12/05/1986
• Issued: 09/19/1989
• Est. Priority Date: 01/10/1984
• Status: Expired due to Term

• Current Assignee: Hach Company (Veralto Corp.)
• Original Assignee: Anatel Corporation (Danaher Corporation)
• Inventors: Blades, Frederick K., Godec, Richard D.
• Primary Examiner(s): NOT, DEFINED
• Assistant Examiner(s): Wallen, T. J.
• Application Number:
  US06/938,638
• Time in Patent Office: 1,019 Days
• Field of Search: 422/186, 422/186.3, 422/78-80, 422/186.04, 422/186.05, 204/257-278, 250/372, 250/373, 250/435, 250/455, 356/51, 73/27 R, 73/53, 436/35, 436/62, 436/143, 436/146, 436/150, 436/151, 436/152
• US Class Current: 436/146
• CPC Class Codes: G01N 27/06 of a liquid involving electrolysis G01N27/26
• CPC Class Codes: G01N 33/1846 Total carbon analysis
• CPC Class Codes: Y02A 20/20 Controlling water pollution; Waste water treatment
• CPC Class Codes: Y10T 436/235 In an aqueous solution [e.g., TOC, etc.]

Abstract

Apparatus and methods for measurement of total organic carbon content of water, particularly of low relative organic content, are described, featuring a single sample cell for exposure of a static sample to ultraviolet radiation and comprising electrodes for measuring the conductivity of the water. The conductivity is monitored as a function of time and the second time derivative of the conductivity signal is monitored to indicate when the oxidation reaction has been completed. Compensation for the contribution to conductivity of the water sample made by the instrument is achieved by subtracting a quantity proportional to the first time derivative of the conductivity at a time when the second time derivative reaches zero, indicating that the oxidation reaction is complete, from the change in the total conductivity measurement, the remainder being equal to the contribution to conductivity made by oxidation of the organic content of the water. The electrodes may have surfaces of a material which when irradiated by the ultraviolet radiation catalyzes the oxidation reaction. Electrophoresis may also be employed to speed the reaction.

Claims

1. Apparatus for measurement of total organic carbon contained by a sample of deionized water, comprising:

a sample cell having a window;

a source of ultraviolet radiation of a frequency which causes oxidation of organic carbon compounds in a water sample disposed in juxtaposition to said window, the window being substantially transparent to said radiation;

a pair of electrodes disposed in said sample cell;

means rendered photocatalytic active in response to said ultraviolet radiation for providing oxidative species in said sample cell;

means for monitoring the electrical conductivity of the water between said electrodes and means for correlating the conductivity of the water sample to its total organic carbon content.

2. The apparatus of claim 1, further comprising means for monitoring said conductivity between said electrodes as a function of time during which a sample is exposed to ultraviolet radiation from said source.

3. The apparatus of claim 2, further comprising means for calculating a time-rate of change of said conductivity, and means for determining when one of said conductivity and the time-rate of change of said conductivity has reached a stable value, indicating that oxidation of organic materials in said sample has been substantially completed.

4. The apparatus of claim 3, wherein said means for determining when said conductivity or the time-rate of change of said conductivity has reached a stable value, indicating that said oxidation has been substantially completed, comprises means for monitoring first and second time derivatives of the conductivity between said electrodes and for determining when the second derivative of said conductivity is within a predetermined range about zero.

5. The apparatus of claim 1 wherein surface of said first and second electrodes of said cell are arranged such that said ultraviolet radiation is directly incident thereon.

6. The apparatus of claim 5 wherein said catalyst is provided by the surfaces of said electrodes, which are formed of a substance which is photocatalytically active upon exposure to the ultraviolet radiation emitted by said source.

7. The apparatus of claim 6 wherein said active surfaces are of an N-type semiconductor.

8. The apparatus of claim 7 wherein said N-type semiconductor is titanium dioxide.

9. The apparatus of claim 8 wherein said source of radiation emits ultraviolet radiation at substantially 253.6 nanometers and 184.9 nanometers wavelength.

10. Apparatus for monitoring organic carbon contained by samples of a water stream in a real time, on-line manner, comprising:

a first conductivity cell, comprising first and second electrodes in a chamber for measuring the conductivity of a water sample in said chamber;

a source of ultraviolet radiation;

an ultraviolet exposure chamber, in which a sample of water may be exposed to ultraviolet radiation from said source;

catalyst means activated upon exposure to said ultraviolet radiation for supply of oxidative radicals to said ultraviolet exposure chamber;

a second conductivity cell, comprising first and second electrodes in a chamber for monitoring the conductivity of water in said cell; and

means for comparing the conductivity in said second cell to the conductivity measured in the first cell, and for determining the amount of organic material present in said water sample as a function of the change in conductivity of said water sample resulting from irradiation of said water sample and said catalyst means in said exposure chamber with ultraviolet radiation from said source.

11. The apparatus of claim 10 further comprising means for controlling flow rate of water through said first and second conductivity cells and said ultraviolet exposure chamber.

12. The apparatus of claim 10 further comprising means for monitoring flow rate of water through said first and second conductivity cells and said exposure chamber, and for compensating the measured conductivity values in response to the measurement of the flow rate.

13. The apparatus of claim 10 wherein said UV exposure chamber and said second conductivity measuring cell are one and the same.

14. The apparatus of claim 10 wherein surfaces of the first and second electrodes of said second conductivity cell are directly exposed to said ultraviolet radiation.

15. The apparatus of claim 14 wherein the surfaces of said electrodes are of a substance which is photocatalytically active upon exposure to ultraviolet radiation emitted by said source.

16. The apparatus of claim 15 wherein said catalytic surface is of a N-type semiconductor.

17. The apparatus of claim 16 wherein said N-type semiconductor is titanium dioxide.

18. The apparatus of claim 17 wherein said source of radiation emits ultraviolet radiation at substantially 253.6 nanometers and 184.9 nanometers wavelength.

19. An apparatus for measuring total organic carbon contained in a steam of deionized water, comprising:

a sample cell, said cell comprising a window formed of a material transparent to ultraviolet radiation;

a pair of electrodes disposed in said sample cell, said electrodes having surfaces of a material which when irradiated by ultraviolet radiation of known wavelength catalyzes the oxidation of organic materials;

a source ultraviolet radiation including at least a portion of said known wavelength disposed in juxtaposition to said window;

means connected to said electrodes for monitoring the conductivity of water in said sample cell;

wherein said electrode surfaces are arranged so as to be directly exposed to incident ultraviolet radiation from said source; and

means for correlating the monitored conductivity to the total organic carbon content.

20. The apparatus of claim 19 wherein said catalytic surfaces are formed of an N-type semiconductor.

21. The apparatus of claim 20 wherein said semiconductor is titanium dioxide.

22. The apparatus of claim 19 wherein said ultraviolet radiation includes a component substantially at 184.9 nm and a component at 253.6 nm wavelength.

23. The apparatus of claim 22 wherein said source of ultraviolet radiation is a low-pressure mercury vapor lamp.

24. The apparatus of claim 19, further comprising means for applying an electric potential to said electrodes, whereby an electric field is created between said electrodes and electrophoresis causes ions in said water stream to migrate towards said electrodes for oxidation.

25. The apparatus of claim 19, wherein said means for monitoring the conductivity between said electrodes comprises means for monitoring the conductivity of said water as a function of time, and for determining when the conductivity of said water reaches a stable value, indicating that said reaction has been completed.

26. The apparatus of claim 25, wherein said means for determining that the reaction has been completed comprises means for monitoring time-rate of change of conductivity of said water and for determining when said time-rate of change has reached within a predetermined range of zero, indicating that said reaction has been completed.

27. The apparatus of claim 19 wherein said conductivity is monitored for a fixed period of time during which a sample of water is irradiated by ultraviolet radiation from said source.

28. A method for measuring total organic carbon contained by a sample of deionized water, comprising the steps of:

introducing said sample to a sample cell, said cell comprising a window formed of a material transparent to ultraviolet radiation, and a pair of electrodes, said electrodes having surfaces of a material which when irradiated with ultraviolet radiation of specified wavelength catalyzes oxidation of organic compounds, said electrode surfaces being arranged to be directly exposed to incident ultraviolet radiation;

irradiating said sample and said electrodes with ultraviolet radiation including at least a portion of said specified wavelength;

monitoring the conductivity of said sample of water in said sample cell; and

determining the total organic carbon content of said sample of water responsive to the monitored conductivity.

29. The method of claim 28 wherein said catalytic surface is an N-type semiconductor.

30. The method of claim 29 wherein said semiconductor is titanium dioxide.

31. The method of claim 28 wherein said ultraviolet radiation includes a component substantially at 184.9 nm and a component at 253.6 nm wavelength.

32. The method of claim 28 wherein said source of ultraviolet radiation is a low-pressure mercury vapor lamp.

33. The method of claim 28, further comprising the step of applying a voltage between said electrodes, whereby an electric field is created between said electrodes and electrophoresis causes ions in said water sample to migrate towards said electrodes for oxidation.

34. The method of claim 28, wherein said step of monitoring the conductivity between said electrodes comprises the step of determining when the conductivity of said water sample reaches a stable value, indicating that said reaction has been completed.

35. The method of claim 34, wherein said step of determining that the reaction has been completed comprises the steps of monitoring the time-rate of change of conductivity of said water sample and determining when said time-rate of change has reached to within a predetermined range of zero, indicating that said reaction has been completed.

36. The method of claim 28, wherein said step of measuring the conductivity of said sample of water in said sample cell is performed for a fixed period of time during which said sample and said electrodes are irradiated by said ultraviolet radiation.

37. An apparatus for measuring total organic carbon contained by a sample of deionized water, comprising:

a sample cell having a window formed of a material transparent to ultraviolet radiation formed therein;

a source of ultraviolet radiation disposed in juxtaposition to said window;

first and second electrodes in said cell, the surfaces of said electrodes being formed of a catalytic material, said electrode surfaces being arranged so as to be directly exposed to incident ultraviolet radiation from said source thereof;

means connected to said electrodes for monitoring the conductivity of a water sample in said cell;

means for applying an electric potential across said electrodes in order to cause electrophoresis to take place; and

means for correlating the conductivity to the total organic carbon content.

38. The apparatus of claim 37 wherein said catalytic material is an N-type semiconductor.

39. The apparatus of claim 38 wherein said catalytic material is selected from the group consisting of SrTiO₃, CdS, WO₃, Fe₂ O₃, MO₃ and TiO₂.

40. The apparatus of claim 39 wherein said material is TiO₂.

41. The apparatus of claim 37 wherein said ultraviolet radiation includes a component at substantially 184.9 nm wavelength and a component at substantially 253.6 nm wavelength.

42. The apparatus of claim 37 wherein said source of ultraviolet radiation is a low-pressure mercury vapor lamp.

43. The apparatus of claim 37, wherein said means for monitoring the conductivity between said electrodes comprises means for determining when the conductivity of said water sample reaches a stable value.

44. The apparatus of claim 43, wherein said means for monitoring comprises means for monitoring the time-rate of change of conductivity of said water sample and for determining when said time-rate of change has reached to within a predetermined range of zero, indicating that said oxidation of said organics has been completed.

45. The apparatus of claim 37, wherein said means for monitoring the conductivity between said electrodes is controlled to monitor the conductivity for a fixed period of time during which said water sample and said electrode are irradiated by ultraviolet radiation entitled by said source.

46. An apparatus for measuring total organic carbon contained by a steam of deionized water, comprising:

a sample cell, said cell comprising a window formed of a material transparent to ultraviolet radiation;

a source of ultraviolet radiation including at least a portion in the 170-190 nm wavelength range disposed in juxtaposition to said window;

a pair of electrodes disposed in said sample cell, said electrodes having surfaces arranged so as to be directly exposed to incident ultraviolet radiation from said source;

means connected to said electrodes for monitoring the conductivity of water in said sample cell; and

means for determining the total organic carbon content of said water responsive to its conductivity.

47. The apparatus of claim 46, wherein said ultraviolet radiation includes a component substantially at 184.9 nm and a component at 253.6 nm wavelength.

48. The apparatus of claim 47, wherein said source of ultraviolet radiation is a low-pressure mercury vapor lamp.

49. The apparatus of claim 48, wherein said means for monitoring the conductivity between said electrodes comprises means for monitoring the conductivity of said water as a function of time, and for determining when the conductivity of said water reaches a stable value, indicating that said reaction has been completed.

50. The apparatus of claim 49, wherein said means for determining that the reaction has been completed comprises means for monitoring the time-rate of change of conductivity of said water and for determining when said time-rate of change has reached to within a predetermined range about zero, indicating that said reaction has been completed.

51. The apparatus of claim 46, wherein said surfaces of said electrodes which are exposed to radiation from said source are formed of a material which when irradiated by ultraviolet radiation catalyzes the oxidation of organic materials.

52. The apparatus of claim 51, wherein said catalytic surfaces are formed of an N-type semiconductor.

53. The apparatus of claim 52, wherein said semiconductor is titanium dioxide.

54. The apparatus of claim 51, comprising means for monitoring said conductivity for a fixed period of time during which a sample of water is irradiated by ultraviolet radiation from said source.

55. A method for measuring total organic carbon contained in a sample of deionized water, comprising the steps of:

introducing said sample to a sample cell, said cell comprising a window formed of a material transparent to ultraviolet radiation, and a pair of electrodes, said electrodes having surfaces arranged to be directly exposed to incident ultraviolet radiation through said window;

irradiating said sample and said electrodes with ultraviolet radiation including at least a portion in the 170-190 nm wavelength range;

monitoring the conductivity of said sample of water between said electrodes in said sample cell; and

determining the total organic carbon content of said sample of water responsive to its conductivity.

56. The method of claim 55, wherein said ultraviolet radiation includes components at substantially 184.9 nm and 253.6 nm wavelengths.

57. The method of claim 56, wherein said electrode surfaces exposed to said radiation are of a material which when irradiated with ultraviolet light catalyzes oxidation of organic compounds.

58. The method of claim 57, wherein said catalytic surface is an N-type semiconductor.

59. The method of claim 58, wherein said semiconductor is titanium dioxide.

60. The method of claim 57, wherein said step of measuring the conductivity of said sample of water in said sample cell is performed for a fixed period of time during which said sample and said electrodes are irradiated by said ultraviolet radiation.

61. The method of claim 56, wherein said source of ultraviolet radiation is a low-pressure mercury vapor lamp.

62. The method of claim 55, wherein said step of monitoring the conductivity between said electrodes comprises the step of determining when the conductivity of said water sample reaches a stable value, indicating that said reaction has been completed.

63. The method of claim 62, wherein said step of determining that the reaction has been completed comprises the steps of monitoring the time-rate of change of conductivity of said water sample and determining when said time-rate of change has reached to within a predetermined range about zero, indicating that said reaction has been completed.