US20070183929A1 - Total organic carbon analysis - Google Patents
Total organic carbon analysis Download PDFInfo
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- US20070183929A1 US20070183929A1 US11/350,420 US35042006A US2007183929A1 US 20070183929 A1 US20070183929 A1 US 20070183929A1 US 35042006 A US35042006 A US 35042006A US 2007183929 A1 US2007183929 A1 US 2007183929A1
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- carbon dioxide
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/18—Water
- G01N33/1826—Water organic contamination in water
- G01N33/1846—Total carbon analysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T436/00—Chemistry: analytical and immunological testing
- Y10T436/23—Carbon containing
Definitions
- This invention relates generally to the field of measuring carbon in a sample composition. More particularly, this invention relates to measuring carbon as Total Organic Carbon (TOC), Total Inorganic Carbon (TIC) or Total Carbon (TC) using electrochemical oxidation.
- TOC Total Organic Carbon
- TIC Total Inorganic Carbon
- TC Total Carbon
- Electrodes are used in the typical electrochemical cell for oxidation of carbon.
- the most common working electrode material has typically been carbon-based or made from metals such as platinum, silver, gold, mercury, or nickel.
- Drawbacks to such electrodes include poor oxidation. Further drawbacks include the self-consuming nature (e.g., reduction/oxidation) of the electrodes themselves.
- conductive diamond film electrodes have been developed.
- Diamond film electrodes include a substrate material coated with diamond or diamond-like film wherein the diamond coated electrodes are doped to provide conductivity (e.g., boron doped).
- Drawbacks to the conventional diamond or diamond-like film electrodes include the tendency of electrodes to fail due to contamination and corrosion. Additional drawbacks include insufficient oxidation. Consequently, there still remains a need for a method and apparatus for measuring carbon using electrochemical oxidation with reduced electrode contamination and corrosion.
- the apparatus comprises a reaction chamber and a detection system, whereby varying control algorithms allows for the determination of carbon as Total Organic Carbon (TOC), Total Inorganic Carbon (TIC) or Total Carbon (TC).
- the apparatus comprises a set of diamond coated electrodes, wherein the diamond coated electrodes may be doped to provide conductivity (e.g., doped with boron).
- a method for measuring carbon in a sample composition comprises providing an apparatus comprising a reaction chamber with a set of diamond coated electrodes, wherein the diamond coated electrodes may be doped with boron.
- the apparatus further comprises a detection system to determine CO 2 concentrations in the gas phase, liquid phase or a combination of the two.
- the method comprises contacting the sample composition with the electrode.
- the method further comprises applying a sufficiently controlled voltage to the electrode to produce carbon dioxide.
- the method comprises measuring the amount of carbon dioxide produced.
- FIG. 1 illustrates an embodiment of a carbon analyzer comprising a remote detector
- FIG. 2 illustrates an embodiment of a carbon analyzer comprising a detector
- FIG. 3 illustrates a side view of an electrode configuration
- FIG. 4 illustrates an end view of an electrode configuration
- FIG. 5 illustrates an embodiment of a carbon analyzer comprising a drier, a scrubber, and a trap
- FIG. 6 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane
- FIG. 7 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane and a trap
- FIG. 8 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane and a detector disposed within a collection chamber.
- the following description details a method and an apparatus for measuring carbon in an aqueous sample composition. Without being limited by theory, the method and apparatus are capable of measuring carbon with minimum contamination to the electrodes resulting in longer effective use and superior cost efficiency.
- Two electrodes provide the oxidation capability.
- the control system for these electrodes may optimize the self-cleaning nature of the electrodes.
- the apparatus may be configured to process discrete samples or for continuous sampling using appropriate electrode geometries.
- the geometries include but are not limited to batch or flow through designs.
- the geometries may include fixed or variable gap electrodes of any design that allows the electrodes electrical isolation.
- FIG. 1 illustrates a carbon analyzer 100 comprising a reaction chamber 101 , electrodes 102 , and a detector 106 .
- Reaction chamber 101 comprises any configuration and material sufficient to create a sealed system whereby carbon dioxide may not escape prior to its detection.
- carbon analyzer 100 comprises two electrodes 102 . It is to be understood that carbon analyzer 100 is not limited to two electrodes 102 , but in an alternative embodiment (not illustrated) carbon analyzer 100 comprises three electrodes. In such an alternative embodiment, carbon analyzer 100 comprises two electrodes 102 and may also include a third electrode that may be used as a reference electrode.
- the two electrodes 102 may be arranged in such a fashion that they are comprised of multiple pieces and may be electrically activated in pairs or in some other manner.
- the third electrode may physically be a part of a new circuit and may not contribute to the oxidation per se, but instead provides a monitoring function.
- the monitoring function may include providing feedback as to the operation of the primary electrodes or the oxidation process, or as a reference electrode for an independent (from TOC, TIC, TC) analytical technique (such as scanning Voltametry).
- Detector 106 comprises any detector suitable for detecting the presence of carbon dioxide. As illustrated, detector 106 is a gas phase detector. Gas phase detectors refer to detectors that can measure the concentration of carbon dioxide in a gas.
- carbon analyzer 100 comprises more than one detector 106 in which at least one detector 106 is a gas phase detector, and at least one detector 106 is a liquid phase detector.
- Liquid phase detectors refer to detectors that can measure the concentration of carbon dioxide in a liquid.
- suitable liquid phase detectors include fluorescence detectors, ion selective electrodes, ion selective probes, conductivity cells, and the like.
- detector 106 is remote from reaction chamber 101 with gas from reaction chamber 101 fed to detector 106 by line 117 .
- detector 106 may be directly connected to reaction chamber 101 .
- reactor geometry is illustrated for flow through operation where electrode 102 comprises an inner element 205 and an outer element 210 that are concentric to each other with a fixed gap flow path 211 for the oxidation.
- Inner element 205 and outer element 210 each comprise a substrate that is coated with diamond.
- the substrate may be comprised of any suitable material including but not limited to nickel, platinum, palladium, silicon, niobium, titanium, or combinations thereof.
- the diamond coating may be applied by any suitable method such as by chemical vapor deposition. Diamond coating includes coatings of diamond and/or diamond-like materials.
- diamond-like materials include hard, amorphous films with a significant fraction of sp 3 -hybridized carbon atoms and which may contain a significant amount of hydrogen. Depending on the deposition conditions, these films may be fully amorphous or contain diamond crystallites.
- the diamond coated substrates of inner and outer elements 205 , 210 are doped with a doping material.
- suitable doping materials include boron, zinc, nitrogen, phosphorous, and sulfur.
- the doping material is boron.
- the diamond coated substrates may be doped by any suitable method such as during chemical vapor deposition.
- FIG. 4 illustrates an end view of electrode 102 showing concentric inner and outer elements 205 , 210 .
- inner and outer elements 205 , 210 may comprise any suitable shapes for oxidizing carbon to carbon dioxide.
- inner element 205 may have a substantially solid, partially hollow, or substantially hollow interior.
- Outer element 210 comprises a hollow interior of a suitable diameter for inner element 205 to be disposed therein.
- inner element 205 comprises a solid shape such as a rod and outer element 210 comprises a hollow interior suitable for containing inner element 205 .
- inner element 205 comprises a rod, and outer element 210 comprises a hollow tube.
- inner and outer elements 205 , 210 comprise mesh such as mesh tubes.
- electrode 102 comprises concentric mesh tubes (e.g., inner and outer elements 205 , 210 ).
- inner element 205 comprises a rod
- outer element 210 comprises a mesh tube.
- electrode 102 is not limited to the configuration illustrated in FIG. 3 but instead can include any suitable configuration for use in carbon analyzer 100 .
- other suitable geometries of electrode 102 include parallel plates, tortuous path, or any other geometry that allows for fixed or variable gap electrodes of any design that allows the electrodes electrical isolation.
- some embodiments include electrode 102 comprising an insulator 212 that is disposed between inner element 205 and outer element 210 in a geometry that allows sample flow. The sample flows through fixed gap flow path 211 and is in contact with both inner element 205 and outer element 210 .
- Insulator 212 may comprise any suitable, non-combustible material. Without limitation, examples of suitable materials include ceramic, glass, or combinations thereof.
- electrodes 102 are not limited to the configuration embodiments as discussed above but may also comprise any suitable configuration for electrochemical oxidation. In any such suitable configurations, electrodes 102 comprise the substrate coated with diamond and optionally doped with a doping material (e.g., boron).
- Sample composition 104 is placed in reaction chamber 101 .
- Sample composition 104 may comprise any aqueous solution containing carbon.
- electrodes 102 are contacted with sample composition 104 .
- electrodes 102 are at least partially immersed in sample composition 104 .
- Controlled voltage is applied to electrodes 102 for a sufficient time to generate oxidation radicals in sample composition 104 .
- the current generated by the application of the voltage may cause an oxidation reaction to occur in sample composition 104 .
- carbon dioxide may be formed in the presence of any carbon based compounds.
- the voltage may be applied for any period of time suitable for producing carbon dioxide. Without being limited by theory, the desired time may depend on the composition of sample composition 104 , the geometry of reaction chamber 101 , and/or the type of electrode 102 used.
- the voltage may be applied for a time period between about 0.5 minutes and about 30 minutes, alternatively about 2 minutes.
- the voltage may be applied to electrodes 102 in an alternating current (AC) format.
- the AC voltage may be supplied by any suitable power source capable of producing AC voltage.
- the AC voltage may be applied at a frequency between about 1 Hz and about 100 Hz, alternatively between about 100 Hz and about 1 kHz, and alternatively between about 1 kHz and about 1 MHz, further alternatively between about 1 kHz and about 200 MHz, and further alternatively between about 1 kHz and about 1 GHz.
- the frequency is about 10 Hz.
- any suitable frequency may be chosen to optimize the current density and maintain clean electrodes.
- the AC voltage may be applied in a sinusoidal wave form. Any suitable AC voltage may be applied to the electrodes. In an embodiment, AC voltage may be applied at greater than 1 ⁇ 2 cell plus potential voltage drop across the sample due to conductivity. In another embodiment, AC voltage may be applied at a voltage greater than 2.5 V, alternatively from about 5 V to about 300 V, and alternatively from about 5 V to about 200 V, and further alternatively from about 5 V to about 150 V. In some embodiments, the AC voltage may be applied at a voltage from about 5 V to about 12 V. Without being limited by theory, the specific control algorithm for the application of a voltage may prevent oxidation and contamination of the electrodes. Further, without being limited by theory, such voltage ranges allow oxidation without the use of reagents.
- a carrier gas 107 is introduced to reaction chamber 101 .
- a suitable amount of carrier gas 107 is introduced to facilitate transport of carbon dioxide from sample composition 104 to headspace 105 .
- Carrier gas 107 may be supplied during or after the voltage is applied to electrodes 102 .
- Carrier gas 107 may comprise any inert gas suitable for transporting carbon dioxide. Without limitation, examples of suitable carrier gases include nitrogen, helium, argon, or combinations thereof.
- no carrier gas 107 is introduced to reaction chamber 101 .
- Carbon dioxide flows from head space 105 to detector 106 via line 117 .
- Detector 106 measures the amount of carbon dioxide produced.
- the amount of organics within sample composition 104 may be determined. Without being limited by theory, the amount of carbon dioxide measured may be directly proportional to the amount of organics that may be present in sample composition 104 . Using samples containing known quantities of dissolved organics, a standard curve may be generated to allow for the determination of a precise concentration of organics within the test solution. In an alternative embodiment (not illustrated), at least one liquid phase detector 106 may be used to measure the amount of carbon dioxide present in sample composition 104 .
- the carbon dioxide may be dried in a drier to remove moisture prior to being measured by detector 106 .
- suitable driers include a dryer permeation tube or an anhydrous tube.
- the carbon dioxide may be passed through a scrubber to remove acid vapors from the carbon dioxide.
- the carbon dioxide may be directed into a trap, from which it is released into detector 106 . Any suitable trap may be used that may retain carbon dioxide until a suitable amount of carbon dioxide is accumulated prior to release to detector 106 .
- FIG. 5 illustrates an embodiment in which carbon analyzer 100 comprises a reaction chamber 101 , electrodes 102 , detector 106 , drier 115 , scrubber 125 , and a trap 110 .
- FIG. 6 illustrates an embodiment in which carbon analyzer 100 comprises a reaction chamber 101 , electrodes 102 , detector 106 , and a collection chamber 109 .
- the sample composition 104 may be directed through the inlet 111 and into reaction chamber 101 wherein sample composition 104 is contacted with electrodes 102 . While sample composition 104 passes through reaction chamber 101 , voltage may be applied to electrodes 102 to oxidize carbon based compounds in sample composition 104 . Sample composition 104 may exit via outlet 108 of reaction chamber 101 .
- gas diffusion membrane 120 may comprise any material suitable for diffusion therethrough of carbon dioxide but that substantially prevents diffusion of liquid.
- suitable membrane materials include polypropylene, cellophanes, or combinations thereof.
- TEFLON a commercial example of a membrane material is TEFLON, which is available from E.I. DuPont de Nemoirs and Company.
- the carbon dioxide may pass through gas diffusion membrane 120 into collection chamber 109 .
- collection chamber 109 is on the opposite side of gas diffusion membrane 120 from sample composition 104 .
- Collection chamber 109 may comprise the form of a tube or any other suitable shape for collecting carbon dioxide and allowing the carbon dioxide to be fed to detector 106 for measurement.
- Carrier gas 107 may be fed to collection chamber 109 to transport the carbon dioxide to detector 106 .
- carrier gas 107 directs the carbon dioxide to trap 110 , from which the carbon dioxide is released to detector 106 for measurement.
- the carbon dioxide may be additionally passed through a drier and/or a scrubber after passing through membrane 120 .
- detector 106 is disposed within collection chamber 109 .
- the carbon dioxide may diffuse through membrane 120 and be directly measured by detector 106 .
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Abstract
The present invention provides an apparatus and method for measuring carbon (any one or all of TC, TOC, or TIC) in a sample matrix. In an embodiment, a method for measuring carbon in a sample composition is provided. The method comprises providing an apparatus comprising a reaction chamber and a diamond coated electrode, wherein the diamond coated electrode is doped with boron. The apparatus further comprises a detector. In addition, the method comprises contacting the sample composition with the electrode. The method further comprises applying an alternating current to the electrode at a sufficient voltage to produce carbon dioxide. Moreover, the method comprises measuring the amount of carbon dioxide produced.
Description
- 1. Field of the Invention
- This invention relates generally to the field of measuring carbon in a sample composition. More particularly, this invention relates to measuring carbon as Total Organic Carbon (TOC), Total Inorganic Carbon (TIC) or Total Carbon (TC) using electrochemical oxidation.
- 2. Background of the Invention
- The need to measure carbon in aqueous samples exists in matrixes from ultra-pure water to waste water and industrial solutions for a variety of reasons. Historically, the analysis equipment to accurately measure carbon in an aqueous solution involved large equipment and hazardous reagents, such as strong acid and oxidizing agents. The use of electrochemical oxidation of carbon may eliminate at least one of these reagents and, when combined with a detection technique to quantify the resultant carbon dioxide gas (e.g., in solution, measured in a headspace or purged from the sample and transported with carrier gas to a detector), promises a versatile, easy to use, and cost-effective alternative for accurately determining TOC levels in a solution. Thus, the development of a safe and cost-effective electrochemical device capable of oxidizing organic carbon and allowing determination of TOC in a sample composition would represent a significant advance in the art.
- Electrodes are used in the typical electrochemical cell for oxidation of carbon. The most common working electrode material has typically been carbon-based or made from metals such as platinum, silver, gold, mercury, or nickel. Drawbacks to such electrodes include poor oxidation. Further drawbacks include the self-consuming nature (e.g., reduction/oxidation) of the electrodes themselves. To overcome these limitations, conductive diamond film electrodes have been developed. Diamond film electrodes include a substrate material coated with diamond or diamond-like film wherein the diamond coated electrodes are doped to provide conductivity (e.g., boron doped). Drawbacks to the conventional diamond or diamond-like film electrodes include the tendency of electrodes to fail due to contamination and corrosion. Additional drawbacks include insufficient oxidation. Consequently, there still remains a need for a method and apparatus for measuring carbon using electrochemical oxidation with reduced electrode contamination and corrosion.
- These and other needs in the art are addressed in one embodiment by an apparatus for measuring the carbon concentration of a sample. The apparatus comprises a reaction chamber and a detection system, whereby varying control algorithms allows for the determination of carbon as Total Organic Carbon (TOC), Total Inorganic Carbon (TIC) or Total Carbon (TC). In addition, the apparatus comprises a set of diamond coated electrodes, wherein the diamond coated electrodes may be doped to provide conductivity (e.g., doped with boron).
- In another embodiment, these and other needs in the art are addressed by a method for measuring carbon in a sample composition. The method comprises providing an apparatus comprising a reaction chamber with a set of diamond coated electrodes, wherein the diamond coated electrodes may be doped with boron. The apparatus further comprises a detection system to determine CO2 concentrations in the gas phase, liquid phase or a combination of the two. In addition, the method comprises contacting the sample composition with the electrode. The method further comprises applying a sufficiently controlled voltage to the electrode to produce carbon dioxide. Moreover, the method comprises measuring the amount of carbon dioxide produced.
- The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter that form the subject of the claims of the invention. It should be appreciated by those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purposes of the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
- For a detailed description of the preferred embodiments of the invention, reference will now be made to the accompanying drawings in which:
-
FIG. 1 illustrates an embodiment of a carbon analyzer comprising a remote detector; -
FIG. 2 illustrates an embodiment of a carbon analyzer comprising a detector; -
FIG. 3 illustrates a side view of an electrode configuration; -
FIG. 4 illustrates an end view of an electrode configuration; -
FIG. 5 illustrates an embodiment of a carbon analyzer comprising a drier, a scrubber, and a trap; -
FIG. 6 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane; -
FIG. 7 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane and a trap; and -
FIG. 8 illustrates an embodiment of a carbon analyzer comprising a gas diffusion membrane and a detector disposed within a collection chamber. - The following description details a method and an apparatus for measuring carbon in an aqueous sample composition. Without being limited by theory, the method and apparatus are capable of measuring carbon with minimum contamination to the electrodes resulting in longer effective use and superior cost efficiency. Two electrodes provide the oxidation capability. The control system for these electrodes may optimize the self-cleaning nature of the electrodes. The apparatus may be configured to process discrete samples or for continuous sampling using appropriate electrode geometries. The geometries include but are not limited to batch or flow through designs. The geometries may include fixed or variable gap electrodes of any design that allows the electrodes electrical isolation.
-
FIG. 1 illustrates acarbon analyzer 100 comprising areaction chamber 101,electrodes 102, and adetector 106.Reaction chamber 101 comprises any configuration and material sufficient to create a sealed system whereby carbon dioxide may not escape prior to its detection. In the embodiment illustrated inFIG. 1 ,carbon analyzer 100 comprises twoelectrodes 102. It is to be understood thatcarbon analyzer 100 is not limited to twoelectrodes 102, but in an alternative embodiment (not illustrated)carbon analyzer 100 comprises three electrodes. In such an alternative embodiment,carbon analyzer 100 comprises twoelectrodes 102 and may also include a third electrode that may be used as a reference electrode. For instance, the twoelectrodes 102 may be arranged in such a fashion that they are comprised of multiple pieces and may be electrically activated in pairs or in some other manner. The third electrode may physically be a part of a new circuit and may not contribute to the oxidation per se, but instead provides a monitoring function. The monitoring function may include providing feedback as to the operation of the primary electrodes or the oxidation process, or as a reference electrode for an independent (from TOC, TIC, TC) analytical technique (such as scanning Voltametry).Detector 106 comprises any detector suitable for detecting the presence of carbon dioxide. As illustrated,detector 106 is a gas phase detector. Gas phase detectors refer to detectors that can measure the concentration of carbon dioxide in a gas. Without limitation, examples of suitable gas phase detectors include nondispersed infrared detectors, laser diode detectors, electrochemical cells, Fourier Transform Infrared (FTIR) detectors, and the like. In an alternative embodiment (not illustrated),carbon analyzer 100 comprises more than onedetector 106 in which at least onedetector 106 is a gas phase detector, and at least onedetector 106 is a liquid phase detector. Liquid phase detectors refer to detectors that can measure the concentration of carbon dioxide in a liquid. Without limitation, examples of suitable liquid phase detectors include fluorescence detectors, ion selective electrodes, ion selective probes, conductivity cells, and the like. As shown inFIG. 1 ,detector 106 is remote fromreaction chamber 101 with gas fromreaction chamber 101 fed todetector 106 byline 117. In an alternative embodiment as shown inFIG. 2 ,detector 106 may be directly connected toreaction chamber 101. - In an embodiment as shown in
FIG. 3 , reactor geometry is illustrated for flow through operation whereelectrode 102 comprises aninner element 205 and anouter element 210 that are concentric to each other with a fixedgap flow path 211 for the oxidation.Inner element 205 andouter element 210 each comprise a substrate that is coated with diamond. The substrate may be comprised of any suitable material including but not limited to nickel, platinum, palladium, silicon, niobium, titanium, or combinations thereof. The diamond coating may be applied by any suitable method such as by chemical vapor deposition. Diamond coating includes coatings of diamond and/or diamond-like materials. Without limitation, diamond-like materials include hard, amorphous films with a significant fraction of sp3-hybridized carbon atoms and which may contain a significant amount of hydrogen. Depending on the deposition conditions, these films may be fully amorphous or contain diamond crystallites. - In an embodiment, the diamond coated substrates of inner and
outer elements FIG. 4 illustrates an end view ofelectrode 102 showing concentric inner andouter elements - As further illustrated in
FIG. 3 , inner andouter elements inner element 205 may have a substantially solid, partially hollow, or substantially hollow interior.Outer element 210 comprises a hollow interior of a suitable diameter forinner element 205 to be disposed therein. In an embodiment,inner element 205 comprises a solid shape such as a rod andouter element 210 comprises a hollow interior suitable for containinginner element 205. In a preferred embodiment,inner element 205 comprises a rod, andouter element 210 comprises a hollow tube. In other preferred embodiments, inner andouter elements electrode 102 comprises concentric mesh tubes (e.g., inner andouter elements 205, 210). In another preferred embodiment,inner element 205 comprises a rod, andouter element 210 comprises a mesh tube. - It is to be further understood that the configuration of
electrode 102 is not limited to the configuration illustrated inFIG. 3 but instead can include any suitable configuration for use incarbon analyzer 100. For instance, other suitable geometries ofelectrode 102 include parallel plates, tortuous path, or any other geometry that allows for fixed or variable gap electrodes of any design that allows the electrodes electrical isolation. - As shown in
FIGS. 3 and 4 , some embodiments includeelectrode 102 comprising aninsulator 212 that is disposed betweeninner element 205 andouter element 210 in a geometry that allows sample flow. The sample flows through fixedgap flow path 211 and is in contact with bothinner element 205 andouter element 210.Insulator 212 may comprise any suitable, non-combustible material. Without limitation, examples of suitable materials include ceramic, glass, or combinations thereof. It is to be understood thatelectrodes 102 are not limited to the configuration embodiments as discussed above but may also comprise any suitable configuration for electrochemical oxidation. In any such suitable configurations,electrodes 102 comprise the substrate coated with diamond and optionally doped with a doping material (e.g., boron). - As shown in
FIG. 1 , asample composition 104 is placed inreaction chamber 101.Sample composition 104 may comprise any aqueous solution containing carbon. - As further shown in
FIG. 1 ,electrodes 102 are contacted withsample composition 104. For instance,electrodes 102 are at least partially immersed insample composition 104. Controlled voltage is applied toelectrodes 102 for a sufficient time to generate oxidation radicals insample composition 104. Without being limited by theory, the current generated by the application of the voltage may cause an oxidation reaction to occur insample composition 104. As a result, carbon dioxide may be formed in the presence of any carbon based compounds. The voltage may be applied for any period of time suitable for producing carbon dioxide. Without being limited by theory, the desired time may depend on the composition ofsample composition 104, the geometry ofreaction chamber 101, and/or the type ofelectrode 102 used. In some embodiments, the voltage may be applied for a time period between about 0.5 minutes and about 30 minutes, alternatively about 2 minutes. In an embodiment, the voltage may be applied toelectrodes 102 in an alternating current (AC) format. The AC voltage may be supplied by any suitable power source capable of producing AC voltage. The AC voltage may be applied at a frequency between about 1 Hz and about 100 Hz, alternatively between about 100 Hz and about 1 kHz, and alternatively between about 1 kHz and about 1 MHz, further alternatively between about 1 kHz and about 200 MHz, and further alternatively between about 1 kHz and about 1 GHz. In an embodiment, the frequency is about 10 Hz. In an embodiment, any suitable frequency may be chosen to optimize the current density and maintain clean electrodes. In further embodiments, the AC voltage may be applied in a sinusoidal wave form. Any suitable AC voltage may be applied to the electrodes. In an embodiment, AC voltage may be applied at greater than ½ cell plus potential voltage drop across the sample due to conductivity. In another embodiment, AC voltage may be applied at a voltage greater than 2.5 V, alternatively from about 5 V to about 300 V, and alternatively from about 5 V to about 200 V, and further alternatively from about 5 V to about 150 V. In some embodiments, the AC voltage may be applied at a voltage from about 5 V to about 12 V. Without being limited by theory, the specific control algorithm for the application of a voltage may prevent oxidation and contamination of the electrodes. Further, without being limited by theory, such voltage ranges allow oxidation without the use of reagents. - As shown in
FIG. 1 , acarrier gas 107 is introduced toreaction chamber 101. In an embodiment, a suitable amount ofcarrier gas 107 is introduced to facilitate transport of carbon dioxide fromsample composition 104 toheadspace 105.Carrier gas 107 may be supplied during or after the voltage is applied toelectrodes 102.Carrier gas 107 may comprise any inert gas suitable for transporting carbon dioxide. Without limitation, examples of suitable carrier gases include nitrogen, helium, argon, or combinations thereof. In an alternative embodiment (not illustrated), nocarrier gas 107 is introduced toreaction chamber 101. Carbon dioxide flows fromhead space 105 todetector 106 vialine 117.Detector 106 measures the amount of carbon dioxide produced. By measuring the amount of carbon dioxide produced, the amount of organics withinsample composition 104 may be determined. Without being limited by theory, the amount of carbon dioxide measured may be directly proportional to the amount of organics that may be present insample composition 104. Using samples containing known quantities of dissolved organics, a standard curve may be generated to allow for the determination of a precise concentration of organics within the test solution. In an alternative embodiment (not illustrated), at least oneliquid phase detector 106 may be used to measure the amount of carbon dioxide present insample composition 104. - In an alternative embodiment, the carbon dioxide may be dried in a drier to remove moisture prior to being measured by
detector 106. Without limitation, examples of suitable driers include a dryer permeation tube or an anhydrous tube. In another alternative embodiment, the carbon dioxide may be passed through a scrubber to remove acid vapors from the carbon dioxide. In further embodiments, the carbon dioxide may be directed into a trap, from which it is released intodetector 106. Any suitable trap may be used that may retain carbon dioxide until a suitable amount of carbon dioxide is accumulated prior to release todetector 106.FIG. 5 illustrates an embodiment in whichcarbon analyzer 100 comprises areaction chamber 101,electrodes 102,detector 106, drier 115,scrubber 125, and atrap 110. -
FIG. 6 illustrates an embodiment in whichcarbon analyzer 100 comprises areaction chamber 101,electrodes 102,detector 106, and acollection chamber 109. Thesample composition 104 may be directed through theinlet 111 and intoreaction chamber 101 whereinsample composition 104 is contacted withelectrodes 102. Whilesample composition 104 passes throughreaction chamber 101, voltage may be applied toelectrodes 102 to oxidize carbon based compounds insample composition 104.Sample composition 104 may exit viaoutlet 108 ofreaction chamber 101. - As further shown in
FIG. 6 , the carbon dioxide that may be formed may diffuse out ofsample composition 104 through agas diffusion membrane 120 and intocollection chamber 109.Gas diffusion membrane 120 may comprise any material suitable for diffusion therethrough of carbon dioxide but that substantially prevents diffusion of liquid. Without limitation, examples of suitable membrane materials include polypropylene, cellophanes, or combinations thereof. For instance, a commercial example of a membrane material is TEFLON, which is available from E.I. DuPont de Nemoirs and Company. The carbon dioxide may pass throughgas diffusion membrane 120 intocollection chamber 109. In an embodiment,collection chamber 109 is on the opposite side ofgas diffusion membrane 120 fromsample composition 104.Collection chamber 109 may comprise the form of a tube or any other suitable shape for collecting carbon dioxide and allowing the carbon dioxide to be fed todetector 106 for measurement.Carrier gas 107 may be fed tocollection chamber 109 to transport the carbon dioxide todetector 106. In an embodiment as shown inFIG. 7 ,carrier gas 107 directs the carbon dioxide to trap 110, from which the carbon dioxide is released todetector 106 for measurement. In further embodiments (not illustrated), the carbon dioxide may be additionally passed through a drier and/or a scrubber after passing throughmembrane 120. - In an embodiment as illustrated in
FIG. 8 ,detector 106 is disposed withincollection chamber 109. The carbon dioxide may diffuse throughmembrane 120 and be directly measured bydetector 106. - Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations may be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (28)
1. An apparatus for measuring carbon in a sample composition, comprising:
a reaction chamber;
a diamond coated electrode, wherein the diamond coated electrode is doped with a doping material;
and a detector.
2. The apparatus of claim 1 , further comprising two electrodes.
3. The apparatus of claim 1 , wherein the electrode comprises an inner element and an outer element.
4. The apparatus of claim 3 , wherein the inner element comprises a rod, and the outer element comprises a tube.
5. The apparatus of claim 3 , wherein the inner element comprises a mesh tube, and wherein the outer element comprises a mesh tube.
6. The apparatus of claim 3 , wherein the electrode comprises an insulator disposed between the inner element and the outer element.
7. The apparatus of claim 1 , wherein the doping material is boron.
8. The apparatus of claim 1 , wherein the detector comprises a gas phase detector.
9. The apparatus of claim 1 , wherein the apparatus further comprises a gas diffusion membrane and a collection chamber.
10. The apparatus of claim 9 , wherein the gas diffusion membrane allows carbon dioxide to diffuse from the reaction chamber to the collection chamber.
11. The apparatus of claim 9 , wherein the detector is disposed in the collection chamber.
12. The apparatus of claim 1 , wherein the apparatus further comprises a carbon dioxide trap.
13. The apparatus of claim 1 , wherein an alternating current voltage is applied to the electrode.
14. The apparatus of claim 13 , wherein the alternating current voltage is applied at a frequency between about 1 Hz and about 100 Hz.
15. The apparatus of claim 13 , wherein the alternating current voltage is applied from about 5 volts to about 300 volts.
16. A method for measuring carbon in a sample composition, comprising:
(A) providing an apparatus comprising: a reaction chamber; a diamond coated electrode, wherein the diamond coated electrode is doped with a doping material; and a detector;
(B) contacting the sample composition with the electrode;
(C) applying an alternating current to the electrode at a sufficient voltage to produce carbon dioxide; and
(D) measuring the amount of carbon dioxide produced.
17. The method of claim 16 , wherein the apparatus comprises two electrodes.
18. The method of claim 16 , wherein the electrode comprises an inner element and an outer element.
19. The method of claim 18 , wherein the inner element comprises a rod, and the outer element comprises a tube.
20. The method of claim 18 , wherein the inner element comprises a mesh tube, and wherein the outer element comprises a mesh tube.
21. The method of claim 18 , wherein the electrode comprises an insulator disposed between the inner element and the outer element.
22. The method of claim 16 , wherein the doping material is boron.
23. The method of claim 16 , further comprising feeding a carrier gas to the reaction chamber at a sufficient rate to transport the carbon dioxide to the detector.
24. The method of claim 16 , wherein step (C) further comprises diffusing the carbon dioxide through a gas diffusion membrane to a collection chamber.
25. The method of claim 24 , further comprising feeding a carrier gas to the collection chamber at a sufficient rate to transport the carbon dioxide to the detector.
26. The method of claim 24 , wherein the detector is disposed in the collection chamber.
27. The method of claim 16 , further comprising trapping the carbon dioxide prior to measuring the amount of carbon dioxide.
28. The method of claim 16 , wherein step (D) further comprises measuring the amount of carbon dioxide with a liquid phase detector.
Priority Applications (6)
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US11/350,420 US20070183929A1 (en) | 2006-02-09 | 2006-02-09 | Total organic carbon analysis |
PCT/US2007/060791 WO2007092665A2 (en) | 2006-02-09 | 2007-01-19 | Total organic carbon analysis |
JP2008554453A JP2009526235A (en) | 2006-02-09 | 2007-01-19 | Total organic carbon analysis |
EP07710235A EP1982171A4 (en) | 2006-02-09 | 2007-01-19 | Total organic carbon analysis |
CA2642150A CA2642150C (en) | 2006-02-09 | 2007-01-19 | Total organic carbon analysis with diamond-coated electrodes |
US12/762,218 US8679408B2 (en) | 2006-02-09 | 2010-04-16 | Total organic carbon analysis |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US11/350,420 US20070183929A1 (en) | 2006-02-09 | 2006-02-09 | Total organic carbon analysis |
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US12/762,218 Continuation US8679408B2 (en) | 2006-02-09 | 2010-04-16 | Total organic carbon analysis |
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US11/350,420 Abandoned US20070183929A1 (en) | 2006-02-09 | 2006-02-09 | Total organic carbon analysis |
US12/762,218 Active 2027-05-30 US8679408B2 (en) | 2006-02-09 | 2010-04-16 | Total organic carbon analysis |
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US12/762,218 Active 2027-05-30 US8679408B2 (en) | 2006-02-09 | 2010-04-16 | Total organic carbon analysis |
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US (2) | US20070183929A1 (en) |
EP (1) | EP1982171A4 (en) |
JP (1) | JP2009526235A (en) |
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WO (1) | WO2007092665A2 (en) |
Cited By (4)
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US20100267160A1 (en) * | 2006-02-09 | 2010-10-21 | OI Analytical | Total Organic Carbon Analysis |
CN103743693A (en) * | 2013-10-30 | 2014-04-23 | 浙江大学 | Total organic carbon analysis instrument and method based on electrochemical catalytic oxidation |
US10338049B2 (en) * | 2013-10-30 | 2019-07-02 | Pro Aqua Diamantelektroden Produktion Gmbh & Co Kg | Electrochemical method and device for determining the content of DOC and/or TOC and/or IC in an aqueous sample |
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DE102008010581A1 (en) * | 2008-02-12 | 2009-08-20 | Technische Universität Dresden | Electrochemical method for determination of total organic carbon in aqueous sample, involves guiding carbon dioxide to detector by carrier gas and selectively quantifying carbon dioxide, where gas contains mixture of oxygen and water |
WO2013172868A1 (en) | 2012-05-15 | 2013-11-21 | General Electric Company | Methods and apparatus for measuring the total organic content of aqueous streams |
US10724984B2 (en) | 2017-07-29 | 2020-07-28 | Hach Company | SP3 substituted carbon electrode TOC analysis using metallic catalyst |
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Also Published As
Publication number | Publication date |
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WO2007092665A3 (en) | 2007-11-29 |
WO2007092665A2 (en) | 2007-08-16 |
CA2642150C (en) | 2013-08-13 |
US20100267160A1 (en) | 2010-10-21 |
EP1982171A4 (en) | 2011-12-07 |
EP1982171A2 (en) | 2008-10-22 |
CA2642150A1 (en) | 2007-08-16 |
US8679408B2 (en) | 2014-03-25 |
JP2009526235A (en) | 2009-07-16 |
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