US005424217A United States Patent [19] [11] Patent Number: 5,424,217 Benner et al. [45] Date of Patent: Jun. 13, 1995

[54] PROCESS FOR THE DETECTION OF minescence detection", J. of Chromat. Science, vol. 28, SULFUR pp. 24-28 (Jan. 1990). Banner “Development of the sulfur chemiluminescence [75] Inventors: Richard L. Benner, Fairbanks, Ak.; detector", a dissertation present at the U. of Denver, Donald H. Stedman, Denver, Colo. Sep. 1991. [73] Assignee: Sievers Instruments, Inc., Boulder, Primary Examiner-Lyle A. Alexander Colo. Attorney, Agent, or Firm-Beaton & Folsom [21] Appl. No.: 873,402 [57] ABSTRACT [22] Filed: Apr. 24, 1992 A process and apparatus are disclosed for the detection and measurement of sulfur in both organic and inor Related US. Application Data ganic sulfur-containing compounds. The process in cludes admixing a sample including a sulfur-containing [63] Continuation of Ser. No. 275.980, Nov. 25. 1988. compound with oxygen, and then exposing the mixture [51] Int. Cl.6 ...... G01N 21/76 to a source of combustion causing heat in the presence [52] US. Cl...... 436/123; 436/119; of a combustion supporting reducing agent at a combus 436/172; 436/122 tion site. The resulting gaseous combustion products are [58] Field Of Search ...... 436/119, 122, 123, 172; vacuum extracted from the combustion site, and then 422/52 directed into a darkened low pressure chamber. The combustion products in the low pressure chamber are [56] References Cited then contacted with ozone, with the result that the U.S. PATENT DOCUMENTS sulfur combustion products are converted to chemilu minescent sulfur dioxide. The emitted chemilumines 4,066,409 l/ 1978 Fine ...... 436/123 4,190,368 2/1980 Etess 422/52 cence is then detected, and may be measured to provide 4,352,779 10/1982 Parks .. .. 436/123 a quantitative indication of the amount of sulfur in the 4,678,756 7/1987 Parks ...... 436/123 original sample. The preferred source of oxygen is air, the preferred form of combustion heat is a flame, and OTHER PUBLICATIONS the preferred form of reducing agent is hydrogen gas. Shearer et 01., “Analysis of sulfur compounds by capil lary column gas chromotography with sulfur chemilu 10 Claims, 2 Drawing Sheets

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US. Patent June 13, 1995 Sheet 2 0f 2 5,424,217

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com 000 com RESPONSE (mV) 5,424,217 1 2 Another approach to measuring sulfur-containing PROCESS FOR THE DETECTION OF SULFUR compounds in a fluid sample including includes the use of chemiluminescence detection schemes. RELATED APPLICATION There remains a need for a process and device capa ble of measuring sulfur compounds accurately, quickly This application is a continuation of Applicant’s co and in the low femtogram range without being sensitive pending US. patent application Ser. No. 07/275,980 to interference of other compounds and components of ?led on Nov. 25, 1988. the sample being tested. BACKGROUND OF THE INVENTION SUMMARY OF THE INVENTION a) Field of the Invention In view of the foregoing, it is an object of the present The present invention relates generally to processes invention to provide a process and device for detecting and apparatus for detection and measuring of chemical and measuring sulfur in a ?uid sample, and in particular ly-bound sulfur, and more particularly, to the detection in an environmental air sample or a chromatographic and measurement of sulfur combustion products which eluent. have been contacted by ozone to form chemilumines It is another object of the present invention to pro cent reaction products. The present invention also re vide a process and device for detecting sulfur-contain lates to improved processes and apparatus for enhanc ing compounds in a rapid and continuous manner with ing the chemiluminescent detection of sulfur by the out regard to the presence of other compounds in the reduction of interfering compositions. sample. b) Discussion of the Prior Art A further object of the present invention is to provide Numerous processes and apparatus have been de a novel and improved method and apparatus for mea vised for detecting and measuring chemical substances. surement of sulfur-containing compounds by chemilu Among detectors used to detect and measure ?uids, minescent reaction with ozone at low pressures in such whether from an independent source, or from the out 25 a way as to be sensitive to sulfur compounds, but insen put of a gas chromatographic apparatus, are those using sitive to water vapor, carbon dioxide or other hydrocar thermal conductivity, hydrogen ?ame ionization, elec bon interferences. ' tronic capture, alkaline ?ame ionization, and ?ame pho Accordingly, the present invention discloses and tometry. Of particular interest in recent years has been teaches a process and apparatus for the detection and the sensitive and selected detection of sulfur com measurement of bound sulfur in organic and inorganic pounds, both as a pollutant in the environment, and sulfur containing compounds. The process includes from other sources. The most widely utilized sulfur admixing a fluid sample having a sulfur-containing com selective detector at the present time is the ?ame photo pound with an oxygen source. This mixture is then metric detector (FPD). The FPD device and process is exposed to a combustion causing heat source, such as a based on the fact that a hydrogen ?ame in the presence 35 ?ame, in the presence of a reducing agent. The resulting of air (oxygen) emits electromagnetic radiation, usually gaseous combustion products are then vacuum ex in the form of visible spectra light. In practice, a carrier tracted from the combustion site, and then directed into ?uid transporting a to-be-tested substance, for example a darkened low pressure chamber. The combustion products in the low pressure chamber are then con an eluent separated from a sample by a chromato tacted with ozone, with the result that the sulfur com graphic instrument, is mixed with an air stream (which bustion products are converted to chemiluminescent may be oxygen enriched), and passed onto a hydrogen sulfur dioxide in an excited state. Finally, the chemilu burner, or a burner in the presence of hydrogen. The minescence is detected and measured to provide an resulting mixture contains hydrogen in excess of that indication of the amount of sulfur in the ?uid sample. required for complete combustion of the oxygen pres The preferred source of oxygen is air, the preferred ent. The luminous radiation caused by this combustion form of combustion heat is a ?ame, and the preferred impinges or is re?ected through an optical ?lter which form of reducing agent is hydrogen gas. has been selected according to the desired radiation In one particular preferred embodiment of the inven wavelength of the substance to be measured. Subse tion, a halogenated compound is injected into the sam quently, the light from the ?lter passes to a light detec ple mixture prior to or at the time that it is subjected to tor, such as a photomultiplier tube. The photomultiplier combustion. ~ tube produces a current which can be detected, mea As described in greater detail below, the present sured, analyzed, recorded, and so on, to indicate the invention utilizes a hydrogen-air ?ame to produce a substance and the amount of the substance. Such an combustion product of either sulfur monoxide (S0) or FPD system can be used as a speci?c selective detector hydrogen sul?de (HgS) for subsequent reaction with and process for sulfur in sulfur-containing substances ozone. It should be noted that, because of its thermal since a speci?c wavelength is emitted from the forma instability, ozone cannot be directly introduced at the tion of molecular species of sulfur during the burning of combustion site as a feasible means of exploiting the the hydrogen flame. Such an FPD system is relatively chemiluminescent reaction of ozone with the combus sensitive and has been widely used, for example in pol tion products. Various studies have shown that a signi? lution control and determination. However, the funda cant portion of sulfur entering a ?ame produces sulfur mental response of such FPD detectors to sulfur is not monoxide. In fact, the sulfur monoxide so produced is linear with respect to the concentration of the to be present in the ?ame combustion products in concentra measured sulfur, and are dif?cult to calibrate with accu tions which are about ten times greater than atomic racy, especially for the measurement of low concentra 65 sulfur, which is the substance which is normally mea tions of sulfur. Another distinct problem with FPD sured by conventional FPD processes and apparatus. devices is that numerous other components in the sam However, it is a possibility that the process of the pres ple can interfere with accurate determination of sulfur. ent invention actually produces H25, and then detects 5,424,217 3 4 the chemiluminescent reaction of H28 with ozone. Nev tion chamber 20 from an ozone generator or other ertheless, it is believed that the principle combustion ozone source 22. In reaction chamber 20 ozone is ad product is sulfur monoxide. Regardless of whether S0 mixed and reacted with the gaseous combustion prod or H28 is produced as the combustion product, they ucts from combustion assembly 12. This particular pro both produce approximately the same wavelength of cedure results in the production of chemiluminescent light during the chemiluminescent reaction with ozone. radiation from excited S03 which radiation is measured The present invention utilizes a narrow capillary by a light detector, such as a photomultiplier tube, and sampling probe, discussed below, which is designed to recorder assembly combination 24. The low pressure in quickly draw substantially all of the combustion prod the chamber 20 and at the ori?ce of the assembly 12 is ucts to low temperature and low pressure chamber for maintained by a vacuum pump 26 which also assists in reaction with ozone. An important and preferred aspect removing the products from the reaction chamber 20 of the present invention is that by lowering the pressure after chemiluminescence. of the combustion product gases to a pressure within the In experimental form, the sulfur-containing sample range of about of l torr to about 50 torr, with approxi from source 10 was a calibrated sulfur gas of known mately 10 torr preferred, the chemical combustion reac 15 concentration. While any reducing agent may be uti— tions are quenched, the possibility of condensation of lized, hydrogen is preferred. While hydrogen is the water produced during combustion is eliminated, and preferred reducing agent, other reducing agents such as the gas mixture of combustion products can be rapidly methane, butane, propane, alcohols, aldehydes, amines, transferred to a light tight chamber for contact and ketones, ole?ns, and aromatic compounds may be used chemical reaction with ozone. These and other objects 20 in the practice of the present invention. of the present invention will become apparent to those Many of the details of reaction chamber 20 are de skilled in the art from the following detailed descrip scribed in greater detail in Sievers et al US Pat. No. tion, showing the contemplated novel construction, 4,717,675. One of the differences between reaction combination, and elements as herein described, and chamber 20 of the present invention and the RCD dis more particularly de?ned by the appended claims, it 25 being understood that changes in the precise embodi closed in the referenced patent is that the measurement ments of the herein disclosed invention are meant to be of sulfur dioxide chemiluminescence produced by the included as coming within the scope of the claims, ex present invention requires a blue sensitive photomulti cept insofar as they may be precluded by the prior art. plier tube. The present system includes an ozone trap 28 30 to prevent ozone from inadvertently entering the atmo BRIEF DESCRIPTION OF THE DRAWINGS sphere or the vacuum pump. Any desired or standard The accompanying drawings illustrate complete pre ozone generator 22 may be utilized in the present inven ferred embodiments of the present invention according tion. to the best modes presently devised for the practical In one embodiment of the present invention, a Redox application of the principles thereof, and in which: Chemiluminescence Detector model 270, from Sievers FIG. 1 is a schematic diagram of the apparatus of the Research, Boulder, Col. was obtained and then modi present invention embodying the process of the present ?ed according to the present invention. Modi?cations invention; to this commercially available unit included the replace FIG. 2 is a schematic diagram of an adjustable com ment of the standard photomultiplier tube with a blue bustion assembly utilized in the present invention; and 40 sensitive one (model R 268 Hamamatsu) as indicated FIG. 3 is a graph illustrating sulfur dioxide concen previously, replacement of the glass window with a tration in parts per billion based on photomultiplier tube fused quartz window, and the addition of an optical measurements of chemiluminescent light produced ?lter (7-54 Corning Glass Works, Corning, N.Y.). The from samples measured using the process and apparatus optical ?lter transmits between about 240 and about 410 of the present invention. 45 nanometers with a peak transmittance of about 82% at 320 nm. In addition, the reaction cell was modi?ed to DESCRIPTION OF THE PREFERRED accommodate greater sample flow rates. Larger ?ow EMBODIMENT rates were achieved by replacement of the standard 25 Referring now to FIG. 1, a schematic diagram of the liter/minute vacuum pump with a 300 liter/minute present version of the apparatus is illustrated therein. model (Model 1012, Alcatel, France). A high capacity Referring ?rst to a general overview of the process of ozone generator was utilized which could produce the invention, a fluid sample (either gas or liquid) which nearly ten times more ozone, 100 cm3/ minute, than the contains a sulfur compound, from a source 10 is directed ozone generator in the standard RCD reaction cham to a combustion site, in this case burner assembly 12. ber. Dilution air used in the dynamic dilution calibra The to-be-tested sample is admixed with oxygen from a tion system was metered by a rotometer and calibration source 14 prior to reaching the combustion assembly 12. standards of sulfur gases as well as hydrogen were me In preferred practice, oxygen is derived from an ambi tered with mass flow meters. ent air supply and is scrubbed through an activated Dilution air for the ambient air supply 114- was ob charcoal trap 16 to remove ambient sulfur prior to ad~ tained from the laboratory bench, but ?rst passed mixture with the sulfur sample from 10. The sulfur/oxy through the activated charcoal absorbent bed 116 as gen sample is then exposed to combustion causing heat previously indicated. All tubing between the sample in ?ame assembly 12 in the presence of a reducing agent ori?ce and the reaction chamber reaction cell was from a source 18. The reducing agent is preferably coated with halocarbon wax (Series 1200, Halocarbon hydrogen. The gaseous combustion products of the Products, Hackensack, NJ.) to minimize loss of the S0 flame from the assembly 12 are immediately vacuum 65 to wall reactions. Oxygen supplied to the ozone genera extracted through a flow restricted ori?ce to a dark tor and hydrogen were standard grade and no provi ened, low pressure, ambient temperature reaction sions were made to remove contaminants from the chamber 20. Ozone is continuously directed into reac— gases. The sample ori?ce was empirically sized to pro 5,424,217 5 6 vide a total ?ow of 500 actual cm3/ min in a reaction cell mately 2.5 ms. The sensitivity as a function of the ?ame pressure of 9-10 torr, as discussed below. residence time decreases very rapidly at shorter ?ame FIG. 2 illustrates a preferred arrangement for burner residence times probably because the combustion is assembly 12. More speci?cally, assembly 12 is of quartz ' incomplete and S0 (or H25) is not formed. At longer and is built to contain a combustion heat source in the residence times, the signal reaches a constant value at form of a diffusion ?ame. The assembly 12 includes a the SO equilibrium concentration, but the background quartz housing 30 with a sample/air intake vent 32. noise increases due to a less stable ?ame. Hydrogen or another reducing agent is injected With respect to the effect of ozone ?ow and concen through an injection vent 34 which projects into the tration, a standard reaction chamber ozone generator housing 30. The terminal end 36 of the vent tube 34 is was initially used. The ozone concentration produced the site of the diffusion ?ame. A quartz probe 38 termi with oxygen is twice that produced using dry air, and a nating in an ori?ce 40 projects within the housing 30. corresponding improvement in sensitivity was ob The ?ame resides between the terminal end of the probe served. As a result, the apparatus of the present inven 38 and the end 36 of the tube 34. The probe 38 mounted tion was switched to the larger ozone generator thereby to a sliding seal 42, permits the distance between the end increasing ozone concentration by ten times. This of the probe 38 and the end 36 of tube 34 to be varied. showed an increase in sensitivity by a factor of 2. The In this manner, the residence time of the sample in the ozone ?ow rate at Which the sensitivity is optimum burner may be varied from l-4O ms. In preferred form, the residence time of the sample in the burner is 4 corresponds to 6 ml ozone per minute in 100 cm3/min of oxygen. The ?ame produced a large amount of NO ms/cm. In alternate form, the ?ame from an FID (?ame 20 which also reacts with ozone thus requiring an unusu ionization detector) may also be used as a ?ame source for the present invention. Moreover, any type of ?ame ally large amount of ozone. However, the NO reaction source may be utilized to react the sample with oxygen did not in any way interfere with the chemilumines and reducing agents to generate the product gases for cence of sulfur dioxide and the measurement thereof subsequent reaction with ozone and chemiluminescence 25 because it occurs at a longer wavelength not passed by from excited sulfur dioxide. the optical ?lter. Preliminary testing of the present invention for sulfur Two common interfering species for the previous uses the detector in a real-time analysis mode. It is found ?ame photometric detector processes and apparatus to be important that the post-flame pneumatic system be operated in real time mode are carbon dioxide and maintained at as low a pressure as possible for a variety water vapor. The process and device of the present of reasons. First, the intensity of the chemiluminescent invention demonstrated no effect on either the baseline reaction was found to be inversely proportional to pres signal or the response to a given concentration of S02 sure with a half-quenching pressure of about 0.02 torr. for water vapor between 0.4% and 3.0%, which is In addition, the gaseous sample stream produced from equivalent of 12-83% relative humidity at 23° C. It also the ?ame is about 25% water vapor requiring that the 35 demonstrated no effect of carbon dioxide concentration pneumatic system be maintained well below the vapor between 350 ppmv and 1700 ppmv. In chromatographic pressure of water (about 50 torr) to prevent condensa analyses, two compounds which commonly coelute are tion. Such condensation would dramatically interfere methylethyl sul?de (MES) and hexane. The hexane with the chemiluminescent aspects of the invention. enhances the sulfur signal at low sulfur concentration Also, the post-?ame reactions are effectively quenched 40 and quenches the sulfur signal at high sulfur concentra at low pressure allowing the SO radical to be trans tion. Tests utilizing the present invention for various ported to the reaction chamber. All data presented ?ame residence times demonstrated that it is possible to below are based on a sample air ?ow of 500 cm3/min, a eliminate any interference from hexane entirely by ad cell pressure of 50 torr, and 6% O3 in 100 cm3 of 03. justing the ?ame residence time. In another test, the The addition of the UV ?lter in the reaction chamber 45 response to sulfur dioxide as a function of heptene con decreased a high baseline signal to less than 0.5% of full centration at a ?xed ?ame residence time is 7.5 ms was scale. Typical parameters for the example shown below studied. Heptene causes a large signal in other sulfur include 300 ml/min of hydrogen reducing agent, 500 monitors. The heptene was responsible for an enhance ml/min of air and sample into the ?ame, and a system ment of the S02 signal. The present invention did not pressure of approximately 10 torr in addition to an oxy 50 have any detectable response to clean air, that is with no gen ?ow of approximately 100 ml/min. sulfur, with concentrations of either hexane or heptene Equivalence ratio is de?ned as the ratio of the actual hydrogen ?ow rate to the hydrogen ?ow rate needed up to 4000 ppmv. Apparently, the ?ame chemistry is for stoichiometric combustion. From test results uti perturbed by the hydrocarbon in such a way that SO lized in the process of the present invention, the sensi production is affected. It should be pointed out that the tivity of the present invention to sulfur dioxide and all effect of the present invention’s response from hydro other sulfur containing gases tested is a function of tile carbons is 104-105 less than that reported for FPD de equivalence ratio. It was found that the optimal equiva vices presently utilized. lence ratio is between 1.4-1.6. This optimum equiva EXAMPLE I lence ratio is independent of the sample residence time 60 in the ?ame, and thus the sample ori?ce position. It is The process and system illustrated in FIG. 1 and believed that the reason for the sharp optimum equiva discussed above was used intermittentlylfor approxi lence ratio is because there must be suf?cient hydrogen mately 30 days. The standard parameters discussed to react with molecular oxygen thus reducing the rate at above were applied. During this time, the baseline sig which S0 is converted to 50;, without reducing the 65 nal was very stable and good sensitivity to sulfur diox ?ame temperature to the point that S0 is not formed. ide was obtained. The results of these tests are illus With respect to the ?ame residence time, it was deter trated in FIG. 3 showing a consistent and good sensitiv mined that the optimum ?ame residence time is approxi— ity to sulfur dioxide concentration. 5,424,217 7 8 vided a short period of acceptable baseline signal. The EXAMPLE 11 materials and times tested are listed below in TABLE I. It was observed that after nearly two months of working with the process and device of the present invention as described in EXAMPLE I, the baseline signal would start to increase continuously. In spite of MATERIALS TIME the increase in baseline, it was determined without ques~ halocarbon wax 18 hours tion that the process and apparatus of the present inven halocarbon oil 7 hours tion had a sensitive response to each of the sulfur com paraffin wax 10 hours aluminum (type 6061-16) 3 hours pounds tested, that is EtSH, MeSO, CS2, 80;, amSF6. 10 stainless steel (type 304) 6 hours However, with the increase in baseline quanti?cation of Teflon 0 hours the response became impossible. This background che miluminescence increased when the ozone generator was turned off so that only oxygen was reacting with When it became apparent that the switching of ?ow sample gases and disappeared completely when the system materials would provide only temporary reduc oxygen flow was stopped. The absolute intensity of the tions in baseline, a new approach was pursued. background signal was not suf?ciently intense to allow EXAMPLE IV spectral analysis. Consequently, the results were that the chemiluminescence continued even after the ?ow of The new approach discussed in EXAMPLE III and sulfur compounds was stopped. discussed also in part above, involved the addition of a The following observations were made when the halogenated compound on a continuous basis. A contin baseline was too high and irregular to allow analytical uous ?ow of 0.45 cm3/min of CFZCIZ was introduced use of the process and device of the present invention: into the sample air producing a concentration of hun 1) The baseline signal increased when the power to dreds of ppm. The baseline was observed to be stable the ozone generator was turned ‘off. 25 for inde?nite periods with the chloro?uorocarbon addi 2) The baseline signal decreased to zero if the oxygen tion. Two other chloro?uorocarbon concentrations ?ow was stopped completely. have been used, 40 and 180 ppmv, and both work 3) The sensitivity to sulfur dioxide decreased if the equally well for the reduction of the baseline. In addi baseline was high compared to the sensitivity when the tion, neither of the two chloro?uorocarbon concentra— baseline was at its normal low level. tions affected, either positively or negatively, the sensi 4) The magnitude of the baseline signal was affected tivity of the process and apparatus of the present inven~ by changing the hydrogen ?ow rate. The highest base tion to sulfur compounds. With the addition of 40 ppm line signal was observed with the same hydrogen flow chloro?uorocarbon, it was possible to quantify the re rate that produced the most sensitive response to sulfur. sponse to different sulfur compounds. These results 5) The baseline signal could be decreased for a period indicated that the sensitivity to the sulfur compounds of time to a very low and acceptable value by momen listed above in EXAMPLE II as well as HZS are all tary injection of any halogenated compound into the equal. It should be emphasized that the chloro?uorocar flame. bon could be added to the ?ame, either into the air 6) Replacement of the quartz sample ori?ce with a stream or into the hydrogen ?ow with the same result. newly fabricated one did not affect the baseline signal. 40 Since it was found that the addition of a small amount EXAMPLE V of a halogenated compound to the ?ame would elimi The present invention has a variety of system applica nate the baseline drift without affecting the sensitivity tions. Recon?guration of the system in only minor de to sulfur, it is theorized that the reactive species respon tails provides different uses for the device and process sible for the background luminescence is scavenged by 45 the halogens. The chemical species which produces the of the invention. In this example, the addition of a chro matographic effluent into point A, that is 46 of FIG. l, chemiluminescence with oxygen in the ?ame is un known. Consequently, in order to maintain a low base provides species speci?c detection of sulfur and re line over a long period of use of the process and appara moval of the activated charcoal trap 16 provide a means tus of the present invention, one embodiment of the of monitoring concentrations of total sulfur in ambient present invention introduces a halogenated compound, air. such as ?uorocarbon 12, fluorocarbon 11, or carbon The process and apparatus of the present invention tetrachloride to the sample at point 46 illustrated in for the detection and monitoring of sulfur has been FIG. 1, introducing the halogenated compounds into shown to be a very sensitive, selective and linear detec the oxygen and sample at or immediately before the 55 tor operated in the real-time mode. The present inven ?ame, or in the hydrogen ?ow. With the addition of tion provides detection limits at similar levels reported fluorocarbon or other halogenated compound, the base for ?ame photometric detectors but at response times line has been observed to be low and stable. The ob which are at least 30 times faster. The present invention served change was from a maximum to a minimum the does not suffer from the interference problems experi" equivalent of less than 0.2 ppbv sulfur during 75 hours enced by the ?ame photometric detectors of the prior of continuous observation. art from water vapor or carbon dioxide and four to ?ve orders of magnitude less for hydrocarbons. The present EXAMPLE III invention also provides uniform response to different In an attempt to remedy the problem outlined in sulfur compounds which greatly enhances its utility as a EXAMPLE 11 above, several different materials were 65 gas chromatographic detector. Finally, the present in used as the ?ow system walls in the belief that one vention provides much more accurate and faster sulfur would react with and thus remove the species causing detection capability than either ?ame photometric de the high baseline signal. All six materials tested pro tectors known previously hereto or prior detection

v 5,424,217 9 10 devices which are based on chemiluminescence of reac measuring the intensity of said chemiluminescence to tion of ozone with the air sample directly. provide an indication of the amount of sulfur pres It will be understood that the invention may be em ent in said sample. bodied in other speci?c forms without departing from 4. The process of claim 3, wherein the wavelength of the spirit or central characteristics thereof. The present light produced by said chemiluminescence is in the examples and embodiments, therefore, are to be consid range of between about 240 nanometers and about 410 ered in all respects as illustrative and not speci?cally nanometers, and is detected and measured utilizing a restrictive, and the invention is not to be limited to the light detector sensitive to light in the range of about 240 details given herein but may be modi?ed within the nanometers to about 410 nanometers. scope of the appended claims as limited by the prior art. 5. The process of claim 3, wherein said reducing The embodiments for which an exclusive property or agent is selected from the group consisting of hydrogen, privilege is claimed are de?ned as follows: methane, butane, and propane. 1. A process for the detection and measurement of 6. The process of claim 3, wherein said halogenated sulfur in both organic and inorganic sulfur-containing compound includes a fluorocarbon. compounds comprising the steps of: 15 7. The process of claim 3, wherein hydrogen is uti admixing a sample including a sulfur-containing com lized to fuel said combustion. pound with oxygen; 8. A process for the detection and measurement of injecting a halogenated compound into said sample; sulfur in sulfur-containing compounds comprising the exposing said mixture of sulfur containing compound steps of: and oxygen to a source of combustion causing heat admixing a sample including a sulfur-containing com in the presence of a reducing agent at a combustion pound with oxygen and a halogenated compound; site to produce gaseous combustion products con combusting said mixture in the presence of hydrogen taining sulfur monoxide; to produce gaseous combustion products contain extracting at least a portion of the resulting sulfur ing sulfur monoxide within a combustion site hav monoxide from said combustion site into a cham 25 ing: ber; (a) an enclosure; contacting said sulfur monoxide, in said chamber (b) a ?ame site within said enclosure; and with ozone under such conditions that said sulfur (c) an ori?ce at a distance from said ?ame site; monoxide is converted to chemiluminescent sulfur extracting at least a portion of said sulfur monoxide dioxide; and from said combustion site through said ori?ce into measuring the intensity of said chemiluminescence to a chamber at a pressure less than ambient pressure; provide an indication of the amount of sulfur pres contacting said sulfur monoxide in said chamber with ent in said sample. ozone under such conditions that said sulfur mon 2. The process of claim 1, wherein said halogenated oxide is converted into chemiluminescent sulfur compound includes a ?uorocarbon. 35 dioxide; and 3. A process for the detection and measurement of measuring the intensity of said chemiluminescence to sulfur in sulfur-containing compounds comprising the provide an indication of the amount of sulfur pres steps of: ent in said sample. admixing a sample including a sulfur-containing com 9. The process of claim 3, wherein said combustion pound with oxygen and a halogenated compound; site comprises: exposing said mixture to a source of combustion caus an enclosure; ing heat in the presence of a reducing agent at a a ?ame site within said enclosure; and combustion site to produce gaseous combustion means for evacuating combustion products from said products containing sulfur monoxide; enclosure, with a separation between said ?ame site extracting at least a'portion of said sulfur monoxide 45 and said evacuating means in order to allow resi from said combustion site into a chamber at a pres dence time for combustion. sure less than ambient pressure; 10, The process of claim 9, wherein said separation contacting said sulfur monoxide in said chamber with between said ?ame site and said evacuating means is of ozone under such conditions that said sulfur mon variable distance in order to vary the residence time of oxide is converted into chemiluminescent sulfur 50 combustion. dioxide; and =l< * * * *

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