Gas chromatographic analysis method and apparatus

Claim 2

A gas chromatographic apparatus for determining at least the elemental carbon, hydrogen and nitrogen of a sample, which comprises: a closed, heated combustion chamber, means for introducing a sample into said chamber, means for introducing a volume of oxygen gas into said chamber, a first source of carrier gas, means for introducing said first carrier gas into said chamber, a first chromatographic column in communication with said chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, first valve means, including first actuator means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means and for flowing said second carrier gas through a first conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said first conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, a second detector means in communication with said second column, a third chromatographic column, a third source of carrier gas, a second valve means, including a second actuator means and a second delay conduit means, in communication with said second detector means and connected to said third carrier gas source, for flowing the effluent from said second detector means through said second delay conduit means and for flowing said third carrier gas through a second conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column, and a third detector means in communication with said third column.

Claim 3

An apparatus according to claim 1 additionally having peak depressing means connected between said second column and said second detector means, said peak depressing means comprising a chamber having sufficient volume so related to the flow rate of said second carrier gas to allow mixing of said second carrier gas and the components of the gaseous mixture separated in said second column.

Claim 4

An apparatus according to claim 1 wherein said first valve means is a multiport valve means having a first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said first valve actuator means, with port one connected to port two, port three to port four and port five to port six when said first valve means is operating in said first position, and with port one connected to port six, port two to port three and port four to port five when said valve is in said second operating position, said first detector means being in communication with said port one, said first delay conduit means being connected between said port two and said port five, said second carrier gas source being in communication with said port three, said first conduit means being connected to said port four and a first discharge conduit means being connected to said port six.

Claim 5

An apparatus according to claim 1 wherein said second valve means is a multiport means having a first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said second valve actuator means, with port one connected to port two, port three to port four, and port five to port six when said second valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said second valve means is in said second operating position, said second detector means being in communication with said port one, said second delay conduit means being connected between said port two and said port five, said third carrier gas source being in communication with said port three, said second conduit means being connected to said port four and a second discharge conduit means being connected to said port six.

Claim 6

An apparatus according to claim 1 further comprising timing means for sequentially actuating said sample introducing means, said oxygen introducing means, said first carrier gas introducing means, said first valve means and said second valve means.

Claim 7

An apparatus according to claim 1 further comprising flow stop valve means connected between said combustion chamber and said first column for interrupting the flow of gas therebetween for a period of time sufficient to ensure complete combustion of said sample in said chamber.

Claim 8

An apparatus according to claim 1 further comprising a means for introducing a conditioning gas into the first carrier gas being introduced into said heated combustion chamber and for introducing a conditioning gas into the oxygen being introduced into said heated combustion chamber.

Claim 9

An apparatus according to claim 7 wherein said means for introducing a conditioning gas into said carrier gas and said oxygen is a sulfur dioxide gas permeation tube.

Claim 10

An apparatus according to claim 8 further comprising means for introducing water vapor into said carrier gas and said oxygen prior to the introduction of sulfur dioxide therein.

Claim 11

An apparatus according to claim 7 wherein said conditioning gas is carbon tetrachloride gas and said means for introducing a conditioning gas into said carrier gas and oxygen is a carbon tetrachloride gas permeation tube.

Claim 12

An apparatus according to claim 1 further comprising a delay volume means and a reduction chamber positioned between said combustion chamber and said first chromatographic column wherein said reduction chamber is in communication with said delay volume means for preventing the entrance of excess oxygen into said reduction chamber until the combustion of the sample in said combustion chamber is substantially complete.

Claim 13

An apparatus according to claim 11 wherein said delay volume means has a volume at least as great as the volume of oxygen introduced into said combustion chamber and said reduction chamber contains copper particles.

Claim 14

An apparatus according to claim 1 wherein said heated combustion chamber comprises an elongated inlet means, a first heated combustion chamber, a second heated combustion chamber and an outlet means, in that order.

Claim 15

An apparatus according to claim 13 wherein said elongated inlet means is of sufficient length to preclude the condensation of oxidatively decomposed sample gases on the walls of the elongated inlet means when the apparatus is used for oxidatively decomposing a sample.

Claim 16

An apparatus according to claim 14 wherein a dampening chamber is positioned between and in communication with the second heated combustion chamber and the outlet means.

Claim 17

A gas chromatographic apparatus for determining at least the elemental carbon, hydrogen and nitrogen of a sample, which comprises: a closed, heated combustion chamber, means for introducing oxygen into said chamber, means for introducing a sample into said chamber, a first source of carrier gas, means for introducing said first carrier gas into said chamber, a first chromatographic column in communication with said chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, a second detector means in communication with said second column, a third chromatographic column, a third source of carrier gas, a third detector means in communication with said third column, a first valve means, including first actuation means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means to a first conduit means and for flowing said second carrier gas through a second conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and for directing the effluent from said first detector means through said first conduit means; a second valve means, including second actuator means and second delay conduit means, in communication with said first valve means through said first conduit and connected to said third carrier gas source, for flowing the effluent from said first conduit means through said second delay conduit means and for flowing said third carrier gas through a third conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said third conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column.

Claim 18

A gas chromatographic apparatus for determining at least the elemental carbon, hydrogen and nitrogen of a sample, which comprises: a closed, heated combustion chamber, means for introducing oxygen into said chamber, means for introducing a sample into said chamber, a first source of carrier gas, means for introducing said first carrier gas into said chamber, a first chromatographic column in communication with said chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, a second detector means in communication with said second column, a third chromatographic column, a third source of carrier gas, a third detector means in communication with said third column, a first valve means, including first actuation means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means to a first conduit means and for flowing said second carrier gas through a second conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and for directing the effluent from said first detector means through said first conduit means; a second valve means, including second actuator means and second delay conduit means, in communication with said first valve means through said first conduit and connected to said third carrier gas source, for flowing the effluent from said first conduit means through said second delay conduit means and for flowing said third carrier gas through a third conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said third conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column.

Claim 19

An apparatus according to claim 16 additionally having peak depressing means connected between said second column and said second detector means, said peak depressing means comprising a chamber having sufficient volume so related to the flow rate of said second carrier gas to allow mixing of said second carrier gas and the components of the gaseous mixture separated in said second column.

Claim 20

An apparatus according to claim 16 wherein said first valve means is a multiport valve means having a first second, third, fourth, fifth and sixth ports and has first and second operating positions, including said first valve actuator means, with port one connected to port two, port three to port four and port five to port six when said first valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said first valve means is in said second operating position, said first detector means being in communication with said port one, said first delay conduit means being connected between said port two and said port five, said second carrier gas source being in communication with said port three, said second conduit means being connected to said port four and said first conduit means being connected to said port six.

Claim 21

An apparatus according to claim 16 wherein said second valve means is a multiport means having first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said second valve actuator means, with port one connected to port two, port three to port four, and port five to port six when said second valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said second valve means is in said second operating position, said first conduit means being connected to said port one, said second delay conduit means being connected between said port two and said port five, said third carrier gas source being in communication with said port three, said third conduit means being connected to said port four and a first discharge conduit means being connected to said port six.

Claim 22

An apparatus according to claim 16 further comprising timing means for sequentially actuating said sample introducing means, said oxygen introducing means, said first carrier gas introducing means, said first valve means and said second valve means.

Claim 23

An apparatus according to claim 16 further comprising flow stop valve means connected between said combustion chamber and said first column for interrupting the flow of gas therebetween for a period of time sufficient to ensure complete combustion of said sample in said chamber.

Claim 24

An apparatus according to claim 16 further comprising a means for introducing a conditioning gas into the carrier gas being introduced into said heated combustion chamber and for introducing a conditioning gas into the oxygen being introduced into said heated combustion chamber.

Claim 25

An apparatus according to claim 22 wherein said means for introducing a conditioning gas into said carrier gas and said oxygen is a sulfur dioxide gas permeation tube.

Claim 26

An apparatus according to claim 22 further comprising means for introducing water vapor into said carrier gas and said oxygen prior to the introduction of sulfur dioxide therein.

Claim 27

An apparatus according to claim 22 wherein said conditioning gas is carbon tetrachloride gas and said means for introducing a conditioning gas into said carrier gas and oxygen is a carbon tetrachloride gas permeation tube.

Claim 28

An apparatus according to claim 16 further comprising a delay volume means and a reduction chamber positioned between said combustion chamber and said first chromatographic column wherein said reduction chamber is in communication with said delay volume means for preventing the entrance of excess oxygen into said reduction chamber until the combustion of the sample in said combustion chamber is substantially complete.

Claim 29

An apparatus according to claim 26 wherein said delay volume means has a volume at least as great as the volume of oxygen introduced into said combustion chamber and said reduction chamber contains copper particles.

Claim 30

An apparatus according to claim 16 wherein said heated combustion chamber comprises an elongated inlet means, a first heated combustion chamber, a second heated combustion chamber and an outlet means, in that order.

Claim 31

An apparatus according to claim 28 wherein said elongated inlet means is of sufficient length to preclude the condensation of oxidatively decomposed sample gases on the walls of the elongated inlet means when the apparatus is used for oxidatively decomposing a sample.

Claim 32

An apparatus according to claim 28 wherein a dampening chamber is positioned between and in communication with the second heated combustion chamber and the outlet means.

Claim 33

A gas chromatographic apparatus for determining at least the elemental sulfur and oxygen of a sample, which comprises: a closed, heated pyrolysis chamber, means for introducing a sample into said pyrolysis chamber, a source of hydrogen gas, means for introducing hydrogen gas in to said pyrolysis chamber, a first source of carrier gas, means for introducing said first carrier gas into said pyrolysis chamber, a first chromatographic column in communication with said pyrolysis chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, first valve means, including first actuator means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means and for flowing said second carrier gas through a first conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said first conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and a second detector means in communication with said second column.

Claim 34

A gas chromatographic apparatus for determining at least the elemental sulfur and oxygen of a sample, which comprises: a closed, heated pyrolysis chamber, means for introducing a sample into said pyrolysis chamber, a source of hydrogen gas, means for introducing hydrogen gas in to said pyrolysis chamber, a first source of carrier gas, means for introducing said first carrier gas into said pyrolysis chamber, a first chromatographic column in communication with said pyrolysis chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, first valve means, including first actuator means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means and for flowing said second carrier gas through a first conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said first conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and a second detector means in communication with said second column.

Claim 35

An apparatus according to claim 31 further comprising: a third chromatographic column, a third source of carrier gas, a second valve means, including a second actuator means and a second delay conduit means, in communication with said second detector means and connected to said third carrier gas source, for flowing the effluent from said second detector means through said second delay conduit means and for flowing said third carrier gas through a second conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column, and a third detector means in communication with said third column.

Claim 36

An apparatus according to claim 31 additionally having peak depressing means connected between said second column and said second detector means, said peak depressing means comprising a chamber having sufficient volume so related to the flow rate of said second carrier gas to allow mixing of said second carrier gas and the components of the gaseous mixture separated in said second column.

Claim 37

An apparatus according to claim 31 wherein said first valve means is a multiport valve means having a first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said first valve actuator means, with port one connected to port two, port three to port four and port five to port six when said first valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said valve is in said second operating position, said first detector means being in communication with said port one, said first delay conduit means being connected between said port two and said port five, said second carrier gas source being in communication with said port three, said first conduit means being connected to said port four and a first discharge conduit means being connected to said port six.

Claim 38

An apparatus according to claim 31 wherein said second valve means is a multiport means having first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said second valve actuator means, with port one connected to port two, port three to port four, and port five to port six when said second valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said second valve means is in said second operating position, said second detector means being in communication with said port one, said second delay conduit means being connected between said port two and said port five, said third carrier gas source being in communication with said port three, said second conduit means being connected to said port four and a second discharge conduit means being connected to said port six.

Claim 39

An apparatus according to claim 31 further comprising timing means for sequentially actuating said sample introducing means, said hydrogen introducing means said first carrier gas introducing means, said first valve means and said second valve means.

Claim 40

An apparatus according to claim 31 further comprising flow stop valve means connected between said combustion chamber and said first column for interrupting the flow of gas therebetween for a period of time sufficient to ensure complete pyrolysis of said sample in said chamber.

Claim 41

The apparatus of claim 31 wherein said first carrier gas is hydrogen and said means for introducing hydrogen into said pyrolysis chamber is said means for introducing said carrier gas into said pyrolysis chamber.

Claim 42

An apparatus according to claim 31 further comprising a means for introducing a conditioning gas into the first carrier gas being introduced into said heated pyrolysis chamber and for introducing a conditioning gas into the hydrogen being introduced into said heated pyrolysis chamber.

Claim 43

An apparatus according to claim 39 wherein said conditioning gas is hydrogen sulfide gas and said means for introducing a conditioning gas into said carrier gas and said hydrogen is a hydrogen sulfide gas permeation tube.

Claim 44

An apparatus according to claim 40 further comprising means for introducing water vapor into the gas passed to the first chromatographic column from the pyrolysis chamber.

Claim 45

An apparatus according to claim 39 wherein said conditioning gas is carbon tetrachloride gas and said means for introducing a conditioning gas into said carrier gas and hydrogen is a carbon tetrachloride gas permeation tube.

Claim 46

A gas chromatographic apparatus for determining at least the elemental sulfur and oxygen of a sample, which comprises: a close, heated pyrolysis chamber, means for introducing a sample into said pyrolysis chamber, a source of hydrogen gas, a first source of carrier gas, means for introducing hydrogen gas into said pyrolysis chamber, means for introducing said first carrier gas into said pyrolysis chamber, a first chromatographic column in communication with said pyrolysis chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, a second detector means in communication with said second column, a third chromatographic column, a third source of carrier gas, a third detector means in communication with said third column, a first valve means, including first actuation means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means to a first conduit means and for flowing said second carrier gas through a second conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and for directing the effluent from said first detector means through said first conduit means; a second valve means, including second actuator means and second delay conduit means, in communication with said first valve means through said first conduit and connected to said third carrier gas source, for flowing the effluent from said first conduit means through said second delay conduit means and for flowing said third carrier gas through a third conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said third conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column.

Claim 47

A gas chromatographic apparatus for determining at least the elemental sulfur and oxygen of a sample, which comprises: a close, heated pyrolysis chamber, means for introducing a sample into said pyrolysis chamber, a source of hydrogen gas, a first source of carrier gas, means for introducing hydrogen gas into said pyrolysis chamber, means for introducing said first carrier gas into said pyrolysis chamber, a first chromatographic column in communication with said pyrolysis chamber, a first detector means in communication with said first column, a second chromatographic column, a second source of carrier gas, a second detector means in communication with said second column, a third chromatographic column, a third source of carrier gas, a third detector means in communication with said third column, a first valve means, including first actuation means and first delay conduit means, in communication with said first detector means and connected to said second carrier gas source, for flowing the effluent from said first detector means through said first delay conduit means to a first conduit means and for flowing said second carrier gas through a second conduit means to said second column when said first valve means is in the first position, and upon actuation of said first valve means wherein said first valve means is changed from the first position to the second position, for flowing said second carrier gas through said first delay conduit means and into said second conduit means thereby carrying at least a portion of the contents of said first delay conduit means into said second column, and for directing the effluent from said first detector means through said first conduit means; a second valve means, including second actuator means and second delay conduit means, in communication with said first valve means through said first conduit and connected to said third carrier gas source, for flowing the effluent from said first conduit means through said second delay conduit means and for flowing said third carrier gas through a third conduit means to said third column when said second valve means is in the first position, and upon actuation of said second valve means wherein said second valve means is changed from the first position to the second position, for flowing said third carrier gas through said second delay conduit means and into said third conduit means thereby carrying at least a portion of the contents of said second delay conduit means into said third column.

Claim 48

An apparatus according to claim 43 additionally having peak depressing means connected between said second column and said second detector means, said peak depressing means comprising a chamber having sufficient volume so related to the flow rate of said second carrier gas to allow mixing of said second carrier gas and the components of the gaseous mixture separated in said second column.

Claim 49

An apparatus according to claim 43 wherein said first valve means is a multiport valve means having first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said first valve actuator means, with port one connected to port two, port three to port four and port five to port six when said first valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said first valve means is in said second generating position, said first detector means being in communication with said port one, said first delay conduit means being connected between said port two and said port five, said second carrier gas source being in communication with said port three, said second conduit means being connected to said port four and said first conduit means being connected to said port six.

Claim 50

An apparatus according to claim 43 wherein said second valve means is a multiport means having first, second, third, fourth, fifth and sixth ports and has first and second operating positions, including said second valve actuator means, with port one connected to port two, port three to port four, and port five to port six when said second valve means is in said first operating position, and with port one connected to port six, port two to port three and port four to port five when said second valve means is in said second operating position, said first conduit means being connected to said port one, said second delay conduit means being connected between said port two and said port five, said third carrier gas source being in communication with said port three, said third conduit means being connected to said port four and a first discharge conduit means being connected to said port six.

Claim 51

An apparatus according to claim 43 further comprising timing means for sequentially actuating said sample introducing means, said hydrogen introducing means, said first carrier gas introducing means, said first valve means and said second valve means.

Claim 52

An apparatus according to claim 43 further comprising flow stop valve means connected between said combustion chamber and said first column for interrupting the flow of gas therebetween for a period of time sufficient to ensure complete pyrolysis of said sample in said chamber.

Claim 53

An apparatus according to claim 43 wherein said first carrier gas is hydrogen and said means for introducing hydrogen into said pyrolysis chamber is said means for introducing said carrier gas into said pyrolysis chamber.

Claim 54

An apparatus according to claim 43 further comprising a means for introducing a conditioning gas into the first carrier gas being introduced into said heated pyrolysis chamber and for introducing a conditioning gas into the hydrogen being introduced into said heated pyrolysis chamber.

Claim 55

An apparatus according to claim 50 wherein said conditioning gas is hydrogen sulfide gas and said means for introducing a conditioning gas into said carrier gas and said hydrogen is a hydrogen sulfide gas permeation tube.

Claim 56

An apparatus according to claim 51 further comprising means for introducing water vapor into the gas passed to the first chromatographic column from the pyrolysis chamber.

Claim 57

An apparatus according to claim 50 wherein said conditioning gas is carbon tetrachloride gas and said means for introducing a conditioning gas into said carrier gas and hydrogen is a carbon tetrachloride gas permeation tube.

Claim 60

An apparatus according to claim 54 wherein said elongated inlet means is of sufficient length to preclude the condensation of oxidatively decomposed sample gases on the walls thereof when the apparatus is used for oxidatively decomposing a sample in a gas chromatographic analyzer.

Claim 61

An apparatus according to claim 54 wherein at least a portion of said first chamber contains an inert packing positioned near said second chamber.

Claim 62

An apparatus according to claim 56 wherein said inert packing has a melting point of at least 1200° C.

Claim 63

An apparatus according to claim 57 wherein said inert packing is quartz wool.

Claim 64

An apparatus according to claim 56 wherein said inert packing supports at least one inert subdivided substance wherein said inert subdivided substance has a melting point of at least 1200° C.

Claim 65

An apparatus according to claim 59 wherein said at least one inert subdivided substance has a particle size in the range of about 40 mesh to about 1/4 inch diameter.

Claim 66

An apparatus according to claim 60 wherein said at least one inert subdivided substance is a quartz chip.

Claim 67

An apparatus according to claim 54 wherein a dampening chamber is positioned between and is in communication with said second chamber and said outlet means.

Claim 68

An apparatus according to claim 62 wherein at least a portion of said dampening chamber contains an inert packing.

Claim 69

An apparatus according to claim 63 wherein said inert packing has a melting point of at least 1200° C.

Claim 70

An apparatus according to claim 63 wherein said inert packing is quartz wool.

Claim 71

An apparatus according to claim 62 wherein said dampening chamber is substantially filled with quartz wool.

Claim 72

An apparatus according to claim 54 wherein said elongated conduit is constructed of quartz glass.

Claim 73

An apparatus according to claim 54 wherein said first chamber is partially formed by an inert packing and wherein said inert packing forms a portion of said second chamber.

Claim 78

A method according to claim 70 further comprising the steps of: a. passing said nitrogen group eluting from said second detecting means to a third chromatographic column, b. introducing a third carrier gas at a predetermined flow rate to the inlet of said third column thereby sweeping said nitrogen group through said third column, c. venting said carbon dioxide group eluting from said second detecting means, and d. passing the effluent from said third chromatographic column through a third detecting means.

Claim 79

A method according to claim 70 further comprising the step of passing said effluent from said second chromatographic column through a serially connected carbon dioxide peak depressor, said depressor being a chamber having sufficient volume so related to the flow of said second carrier gas to allow mixing of said second carrier gas and said effluent from said second chromatographic column.

Claim 80

A method according to claim 71 further comprising the step of passing said effluent from said second chromatographic column through a serially connected carbon dioxide peak depressor, said depressor being a chamber having sufficient volume so related to the flow of said second carrier gas to allow mixing of said second carrier gas and said effluent from said second chromatographic column.

Claim 81

A method according to claim 70 further comprising passing said nitrogen group and said carbon dioxide group effluent from said first detector means through a first delay conduit means, said first delay conduit means having a sufficient volume so related to said predetermined flow rate as to delay in time said nitrogen group and carbon dioxide group and to prevent said water group from passing to said second column.

Claim 82

A method according to claim 71 further comprising passing said nitrogen group and said carbon dioxide group effluent from said first detector means through a first delay conduit means, said first delay conduit means having a sufficient volume so related to said predetermined flow rate as to delay in time said nitrogen group and carbon dioxide group and to prevent said water group from passing to said second column, and passing the nitrogen group effluent from said second detector through a second delay conduit means, said second delay conduit means having a sufficient volume so related to said predetermined flow rate as to delay in time said nitrogen group and to prevent said carbon dioxide group from passing to said third column.

Claim 83

A method according to claim 70 wherein, prior to step (a), said sample is decarbonated by a wet acid treatment with hydrochloric acid or by treatment with hydrogen chloride vapor.

Claim 84

A method according to claim 76 wherein said wet acid treatment comprises contacting said sample with a hydrochloric acid solution having a concentration in the range of 32 to 34 percent.

Claim 85

A method according to claim 76 wherein said treatment with hydrogen chloride vapor comprises contacting said sample with water vapor and thereafter surrounding said sample with hydrogen chloride vapor under pressure.

Claim 86

A method according to claim 70 wherein elemental sulfur is additionally determined from the quantity of sulfur oxides present in said water group.

Claim 87

A method according to claim 70 wherein elemental chlorine is additionally determined from the quantity of Cl 2 and hydrogen chloride in said water group.

Claim 88

A method according to claim 70 wherein said oxygen source and said first inert carrier gas when introduced into said combustion chamber contains at least one conditioning gas wherein said conditioning gas is selected from the group consisting of a sulfur dioxide conditioning gas introduced into said oxygen source and said first inert carrier gas by a sulfur dioxide gas permeation tube, a carbon tetrachloride conditioning gas introduced into said oxygen source and said first inert carrier gas by a carbon tetrachloride gas permeation tube and a water vapor conditioning gas introduced into said oxygen source and said first inert carrier gas by a water vapor emitting vessel.

Claim 89

A method according to claim 70 further comprising passing said reaction product mixture and said first inert carrier gas from said chamber through a heated delay volume means and into a heated reduction chamber containing copper.

Claim 90

A method according to claim 70 wherein said heated combustion chamber comprises a first combustion zone and a second combustion zone, wherein said sample is introduced into said first combustion zone to produce sample gases which are at least partially oxidatively decomposed therein and the sample gases in the first combustion zone are passed to the second combustion zone by passing the inert carrier gas into the first combustion zone said sample gases being passed to said second combustion zone to ensure essentially complete oxidative decomposition of the sample gases and to produce the reaction product mixture which is passed to the first gas chromatographic column.

Claim 91

A method according to claim 83 wherein the reaction product mixture is passed from the second combustion zone to the first chromatographic column through a dampening zone.

Claim 92

A method according to claim 70 wherein said measured sample, prior to introduction into said chamber, is admixed with vanadium pentoxide in an amount at least as great as the sample size.

Claim 93

A method according to claim 85 wherein said vanadium pentoxide is admixed with said sample in an amount two to ten times the size of said sample.

Claim 94

A method according to claim 86 wherein said vanadium pentoxide containing admixture is encapsulated in a tin sample container.

Claim 97

A method according to claim 88 further comprising the step of passing said effluent from said second chromatographic column through a serially connected carbon dioxide peak depressor, said depressor being a chamber having sufficient volume so related to the flow of said second carrier gas to allow mixing of said second carrier gas and said effluent from said second chromatographic column.

Claim 98

A method according to claim 88 wherein elemental sulfur is additionally determined from the quantity of sulfur oxides in said water group.

Claim 99

A method according to claim 88 wherein, prior to step (a), said sample is decarbonated by a wet acid treatment with hydrochloric acid or by treatment with hydrogen chloride vapor.

Claim 100

A method according to claim 91 wherein said wet acid treatment comprises contacting said sample with water vapor and thereafter allowing said sample to stand over a hydrochloric acid solution having a concentration in the range of 32 to 34 percent.

Claim 101

A method according to claim 91 wherein said treatment with hydrogen chloride vapor comprises contacting said sample with water vapor and thereafter surrounding said sample with hydrogen chloride vapor under pressure.

Claim 102

A method according to claim 88 wherein elemental chlorine is additionally determined from the quantity of Cl 2 and hydrogen chloride in said water group.

Claim 103

A method according to claim 88 wherein said oxygen source and said first inert carrier gas when introduced into said combustion chamber contains at least one conditioning gas wherein said conditioning gas is selected from the group consisting of a sulfur dioxide conditioning gas introduced into said oxygen source and said first inert carrier gas by a sulfur dioxide gas permeation tube, a carbon tetrachloride conditioning gas introduced into said oxygen source and said first inert carrier gas by a carbon tetrachloride gas permeation tube and a water vapor conditioning gas introduced into said oxygen source and said first inert carrier gas by a water vapor-emitting vessel.

Claim 104

A method according to claim 88 further comprising passing said reaction product mixture and said first inert carrier gas from said chamber through a heated delay volume means and into a heated reduction chamber containing copper.

Claim 105

A method according to claim 88 wherein said heated combustion chamber comprises a first combustion zone and a second combustion zone, wherein said sample is introduced into said first combustion zone to produce sample gases which are at least partially oxidatively decomposed therein and the sample gases in the first combustion zone are passed to the second combustion zone by passing the inert carrier gas into the first combustion zone said sample gases being passed to said second combustion zone to ensure essentially complete oxidative decomposition of the sample gases and to produce the reaction product mixture which is passed to the first gas chromatographic column.

Claim 106

A method according to claim 97 wherein the reaction product mixture is passed from the second combustion zone to the first chromatographic column through a dampening zone.

Claim 107

A method according to claim 88 wherein said measured sample, prior to introduction into said chamber, is admixed with vanadium pentoxide in an amount at least as great as the sample size.

Claim 108

A method according to claim 99 wherein said vanadium pentoxide is admixed with said sample in an amount two to ten times the size of said sample.

Claim 109

A method according to claim 100 wherein said vanadium pentoxide containing admixture is encapsulated in a tin sample container.

Claim 112

A method according to claim 102 further comprising passing said effluent from said first detector means through a first delay conduit means, said first delay conduit means having a sufficient volume so related to said predetermined flow rate to delay in time said water component to prevent said water from passing to said second column.

Claim 113

A method according to claim 102 wherein said carbon is carbon black.

Claim 114

A method according to claim 102 wherein said carbon is graphite.

Claim 115

A method according to claim 102 further comprising passing said reaction product through platinum gauze.

Claim 118

The method of claim 107 wherein said carbon bed is graphite.

Claim 119

The method of claim 107 wherein said carbon bed is carbon black.

Claim 120

The method of claim 107 wherein said first carrier gas is hydrogen.

Claim 121

The method of claim 107 wherein prior to step (a) hydrogen is introduced into said closed, heated pyrolysis chamber.

Claim 122

The method of claim 111 wherein said hydrogen and said first inert carrier gas introduced into the pyrolysis chamber contain at least one conditioning gas wherein said conditioning gas is selected from the group consisting of a hydrogen sulfide conditioning gas introduced into said hydrogen and said first inert carrier gas by a hydrogen sulfide gas permeation tube and a chlorine-containing conditioning gas introduced into said hydrogen and said first inert carrier gas by a chlorine-emitting gas permeation tube.

Claim 123

The method of claim 112 wherein said chlorine-containing conditioning gas is carbon tetrachloride and said chlorine-emitting gas permeation tube is a carbon tetrachloride gas permeation tube.

Claim 124

A method according to claim 113 wherein water vapor is added to the product mixture which is passed from the pyrolysis chamber to the first gas chromatographic column.

Claim 127

A method according to claim 115 further comprising passing said oxidatively decomposed sample gases from said second combustion zone through a dampening zone prior to passing said oxidatively decomposed sample gases through said outlet zone.