JPH08327625A - Method and equipment for analyzing carbon, sulfur and phosphorus in metal sample - Google Patents

Abstract

PURPOSE: To obtain method and equipment for determining carbon, sulfur and phosphorus in a metal sample efficiently in a short time. CONSTITUTION: Temporal variation of temperature is measured for a molten metal 1 sampled in a refractory container 12 and carbon in the molten metal 1 is determined based on a freezing point obtained therefrom. A reductive acid is then fed to the freezing surface of surface layer of molten metal 1 in order to generate hydride gas. The hydride gas is carried on a carrier gas to a hydride gas determination system 71 where the hydride gas is sequentially brought into contact with a test paper 76 for detecting H2 S and a test paper 77 for detecting PH3 . The coloring intensity of test paper is measured thus determining sulfur and phosphorus in the metal sample.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for analyzing carbon, sulfur and phosphorus and a device therefor capable of rapidly determining a trace amount of carbon, sulfur and phosphorus contained in a metal sample.

The present invention is used in the field of manufacturing process control and quality control analysis in the iron making industry and other metal refining industries.

[0003]

2. Description of the Related Art In operation management such as a steelmaking process, it is necessary to analyze and grasp the component content rates as quickly as possible and to take operational countermeasures according to the results. For example,
In the steelmaking process, the time from sampling to obtaining analytical results is usually 5 to 6 minutes. In addition, rapid analysis is required for product verification. Among the components to be analyzed, carbon, sulfur and phosphorus are important in determining quality especially in iron making.

As a method for quantifying carbon in a metal sample,
Thermal analysis carbon determination methods are known. In this method, the freezing point is obtained by measuring the change with time of the temperature of the molten metal such as molten steel, and the carbon content is obtained from the freezing point. Since this method does not require operations such as cutting, polishing, and crushing the sample for sample preparation, it is possible to quantify carbon in a relatively short time. Therefore, the thermal analysis carbon determination method is suitable for manufacturing process control and quality control analysis.

Regarding the method for quantifying sulfur and phosphorus in a metal sample, the inventors of the present invention have disclosed a method for analyzing phosphorus and sulfur in a metal sample and an apparatus therefor as an analytical method with high sensitivity and excellent quickness (Japanese Patent Laid-Open No. Hei 5 (1999) -58). -10938), "Analysis method of trace amount of phosphorus and sulfur in metal sample and its apparatus" (JP-A-5-34291), and "Simultaneous analysis method of sulfur and phosphorus in metal sample and apparatus thereof" (Special feature) Kaihei 6-18
No. 6221) was proposed. In these methods, a test paper photoelectric photometric method (reflection photometric method) capable of detecting hydride gases of sulfur and phosphorus with high sensitivity as a gas analyzer.
Has been adopted. That is, sulfur and phosphorus in a sample are generated as a hydride gas by electrolysis or a reaction with an acid having a reducing power, and the generated gas is sequentially contacted with a H ₂ S detection test strip and a PH ₃ detection test strip. , Its color intensity is measured to quantify sulfur and phosphorus. This method has enabled rapid determination of sulfur and phosphorus down to ppm levels.

[0006]

Conventionally, the determination of carbon by the thermal analysis method and the determination of sulfur and phosphorus by the test paper photoelectric method have been carried out in independent steps. Also,
In the test paper photoelectric method, a disk-shaped solid sample had to be prepared. Therefore, a lot of work and a long time are required for quantitative analysis of carbon, sulfur and phosphorus.

The present invention is intended to provide an analytical method and an apparatus therefor capable of efficiently quantifying carbon, sulfur and phosphorus in a metal sample in a short time.

[0008]

The method for analyzing carbon, sulfur and phosphorus in a metal sample according to the first aspect of the present invention measures the change with time of the temperature of molten metal sampled in a refractory container, and obtains it from the change with time. Of carbon in the molten metal based on the freezing point. Subsequently, a reducing acid is supplied to the surface solidification surface of the molten metal to generate a hydride gas, and the hydride gas is conveyed by a carrier gas to a hydride gas quantification device, and the hydride gas is quantified by the hydride gas quantification device. Gas is H ₂ S
The test paper is brought into contact with the detection test paper and PH ₃ detection test paper to develop color, and the color development intensity is measured to quantify sulfur and phosphorus in the metal sample.

The method for analyzing carbon, sulfur and phosphorus in a metal sample according to the second invention is such that the molten metal collected in a refractory container is measured for changes in temperature with time and melted based on the freezing point obtained from the change in temperature with time. Quantify carbon in metals. Subsequently, the electrolytic solution is supplied to the surface solidification surface of the molten metal, the surface solidification surface is electrolyzed to generate a hydride gas, and the hydride gas is transported to the hydride gas quantitative device by the carrier gas, and the hydride gas The hydride gas was converted into H ₂ with a quantitative device.
The test paper for S detection and the test paper for PH ₃ detection are sequentially brought into contact with each other to develop a color, and the color development intensity is measured to quantify sulfur and phosphorus in the metal sample.

In order to quantify carbon from the change with time of the temperature of the molten metal, it is determined by a measuring computer based on the temperature measurement data. A carbon quantitative program is stored in advance in the measuring computer.

When the surface layer of the molten metal is solidified and the temperature of the surface layer drops to 100 ° C. or lower, the quantitative analysis of sulfur and phosphorus is started. In order to shorten the analysis time, it is desirable to forcibly cool the refractory vessel with water cooling or air cooling immediately after the quantitative analysis of carbon is completed. Hydrochloric acid is suitable as a reducing acid for generating a hydride gas, and hydrochloric acid or hydrochloric acid + sulfuric acid is suitable as an electrolytic solution. Argon, helium or nitrogen gas is used as the carrier gas.

The H ₂ S detecting test paper and the PH ₃ detecting test paper are tape-like ones with a width of about 2 cm impregnated with a reagent that develops a color by chemically reacting with H ₂ S and PH ₃ , for example lead acetate and silver nitrate. Now available commercial products are available. The running speed of the test paper is appropriately adjusted according to the amount of gas generated, 1 to 10 cm / min for continuous measurement, 10 to 6 for intermittent running.
About 0 second / 1 measurement is appropriate. Both test papers are 1
If the trace amount of H ₂ S and PH ₃ is less than about 00 ppm, the whole amount can be detected.

These gases conveyed to the hydride gas metering device first pass through a test strip for H ₂ S detection. 100
If the trace amount of H ₂ S is less than about ppm, the whole amount is consumed by reacting with the reagent impregnated in the H ₂ S detection test paper. P
H ₃ do not at all react with H ₂ S detection test paper, passing the H ₂ S detection test paper. The gas that has passed through the H ₂ S detection test strip passes through the PH ₃ detection test strip. Since H ₂ S is no longer present in the gas, only PH ₃ reacts with the reagent impregnated in the PH ₃ detection test paper.
Not affected by the ₂ S.

The gas concentration can be measured by detecting the color development intensity of the test paper that has developed color as described above. In order to measure the coloring intensity of the colored test strips, the colored portion of the gas contact surface or the gas inflow surface of each test strip is irradiated with a single wavelength lamp, and the intensity of the reflected light is measured with a photodiode or the like. Test strip for H ₂ S detection and PH
_{3 With the} test paper for detection, the color development can be detected at the same wavelength of about 555 nm. It is possible to quantitatively determine phosphorus and sulfur based on the reflected light intensity by experimentally obtaining a calibration curve showing the relationship between the sulfur and phosphorus content and the coloring intensity (reflected light intensity).

Further, after the hydride gas was brought into contact with the H ₂ S detection test paper, it was passed through an activated carbon column kept at a constant temperature to remove AsH ₃ in the hydride gas,
It is then desirable to contact the PH ₃ test strip. Removal of AsH _3, it is possible to prevent errors due AsH ₃ during determination of phosphorus. The temperature of the activated carbon column is 1
Keep constant within the range of 00-200 ° C.

An apparatus for carrying out the analysis method of the first invention is
A refractory container water-cooling device detachably attached to the refractory container was provided, and the acid supply branch pipe was placed in the top opening of the refractory container and the acid supply branch pipe was immersed in the molten metal, and the outlet side was connected to a hydride gas meter. A hydride gas generator including a glass hydride gas sampling pipe, and an acid supply device and a carrier gas supply device connected to the inlet side of the hydride gas sampling pipe, respectively.

The refractory container water cooling device is provided with a cooling water passage and is detachably attached to the body of the refractory container. The cooling water supplied to the cooling water channel is forcedly circulated or flows through the cooling water channel by the pump. The hydride gas sampling pipe extends horizontally while being placed on the refractory vessel, and an acid supply branch pipe that opens downward is provided in the center thereof. The tip of the acid supply branch pipe is designed to be immersed in the molten metal in the refractory vessel, and is melted by the heat of the molten metal. When the molten metal is solidified, the tip of the acid supply branch pipe is fused to the solidified portion, and the hydride gas sampling pipe is sealed. The acid supply device is composed of, for example, a tank containing hydrochloric acid and the like, a pump, and the like. The carrier gas supply device includes, for example, a nitrogen gas cylinder, a stop valve, a pressure regulator, a flow meter, and the like.

An apparatus for carrying out the analysis method of the second invention comprises a refractory vessel water-cooling apparatus detachably attached to the refractory vessel, and is placed on the surface solidification surface to form an electrolytic chamber, and the outlet side is a hydride. An electrolysis cell connected to the gas quantification device, electrodes respectively placed at the top and bottom of the electrolysis cell, a constant potential / constant current electrolysis device connected thereto, and an electrolytic solution supply device further connected to the electrolysis cell inlet side and And a hydrogenation gas generation device including a carrier gas supply device.

The refrigerating vessel water cooling device, the electrolytic solution supply device, and the carrier gas supply device are constructed in the same manner as in the above-mentioned analysis device. A gasket made of a heat-resistant material such as fluorine resin or silicon rubber is attached to the bottom of the electrolytic cell. This gasket seals between the surface solidification surface of the molten metal and the bottom of the electrolytic cell. A negative electrode is connected to the top of the electrolytic cell and a positive electrode is connected to the bottom.

In the hydride gas quantitative measuring device, the H ₂ S test paper photoelectric photometric measuring device and the PH ₃ test paper photoelectric photometric measuring device are sequentially arranged in the flow path of the carrier gas from the upstream side. H ₂
The S test paper photoelectric photometric device includes a test paper for H ₂ S detection that runs continuously or intermittently, and the carrier gas passes from the upper surface to the lower surface of the test paper. PH ₃ test paper Photoelectric quantification device is a PH ₃ that runs continuously or intermittently.
The test gas for detection is provided, and the carrier gas passes from the upper surface to the lower surface of the test paper.

[0021]

In the present invention, quantitative analysis of carbon, sulfur and phosphorus is carried out continuously. Further, by utilizing the heat possessed by the molten metal, the reduction reaction by acid or electrolysis is promoted without providing a sample heating mechanism. Therefore, the quantitative analysis of carbon, sulfur and phosphorus can be performed in a short time, and the work efficiency is remarkably improved.

[0022]

EXAMPLES Examples of the analysis method and apparatus of the present invention will be described by taking the quantitative analysis of carbon, sulfur and phosphorus in molten steel as an example.

FIG. 1 is an apparatus configuration diagram showing an example of an analyzer for carrying out the method of the first invention.

The analyzer is mainly a carbon analyzer 11,
And a sulfur / phosphorus analyzer 21.

The carbon analyzer 11 comprises a refractory container 12 and a refractory container water cooling device 14. The refractory container 12 is made of a refractory material such as alumina and has a cylindrical body portion that opens upward. The refractory container water cooling device 14 includes an annular cooling water passage 15 and is detachably attached to the body of the refractory container. Cooling water is supplied to the cooling water passage 15 by a pump (not shown), and the cooling water circulates in the cooling water passage 15. A measuring table 16 is arranged below the refractory container 12. A thermocouple 18 is embedded in the bottom of the fireproof container 12, and the thermocouple 18 is connected to a measuring computer 20 via a contact 19.

The sulfur / phosphorus analyzer 21 is mainly composed of a hydride gas generator 22 and a hydride gas metering device 71.

The hydride gas generator 22 comprises a hydride gas sampling pipe 23, an acid supply device 27, and a carrier gas supply device 31. The hydride gas sampling pipe 23 extends horizontally in a state of being placed on the refractory container 12, and an acid supply branch pipe 26 opening downward is provided at the center thereof. When the hydride gas sampling pipe 23 is placed on the refractory container 12, the tip of the acid supply branch pipe 26 is located on the refractory container 12
It is immersed in the molten metal 1 therein. Hydride gas sampling pipe 23
Is made of quartz glass, the tip of the acid supply pipe 26 is melted by the heat of the molten metal 1. When the molten metal 1 is solidified, the tip of the acid supply branch pipe 26 is fused to the solidification part 3, and the hydride gas sampling pipe 23 is sealed. An acid supply device 27 and a carrier gas supply device 31 are connected to the inlet side 24 of the hydride gas sampling pipe 23, and a hydride gas metering device 71 is connected to the outlet side 25 thereof. The acid supply device 27 includes a hydrochloric acid tank 28 that stores hydrochloric acid and a pump 29. The carrier gas supply device 31 includes a nitrogen cylinder 32,
It consists of a stop valve 33, a pressure regulator 34, and a flow meter 35.

A gas-liquid separator 61 and a line filter 65 are provided between the hydride gas generator 22 and the hydride gas metering device 71. The gas-liquid separator 61 separates the liquid conveyed from the hydride gas generator 22,
Discharge to the tank 63. The line filter 65 absorbs and removes the hydrochloric acid mist in the gas separated by the gas-liquid separator 61 with an absorbent.

The hydride gas quantification device 71 comprises an H ₂ S gas contact chamber 73a and a PH ₃ gas contact chamber 73 arranged vertically.
b is connected via the activated carbon column 84. The activated carbon column 84 is maintained at a constant temperature by the column temperature controller 85. A gas introduction pipe 72, an irradiation lamp 78 and a photodiode 79 are attached to the tops of the gas contact chambers 73a and 73b. The irradiation lamp 78 irradiates the test papers 76 and 77 with monochromatic light, and detects the reflected light intensity by the photodiode 79 to detect the H ₂ S and PH ₃ concentrations. The photodiode 79 is connected to the measuring computer 20. At the bottom of the H ₂ S gas contact chamber 73a, the test paper 76 for H ₂ S detection and the PH ₃ gas contact chamber 7
PH ₃ detecting test papers 77 run on the bottoms of 3b. The test strip running device 81 arranged in each of the gas contact chambers 73a and 73b is a tape-shaped test strip 7.
It is composed of a rewind reel 82 on which 6 and 77 are wound, a take-up reel 83, and a drive device (not shown) for rotationally driving these reels. From the suction nozzle 74 attached to the bottom of the PH ₃ gas contact chamber 73b to the suction pump 75
Thus, the gas in the gas contact chambers 73a and 73b is discharged.

Here, a method for quantitatively analyzing carbon, sulfur and phosphorus in the molten steel with the apparatus configured as described above will be described.

First, the molten steel 1 is sampled in a refractory container 12 to which a refrigerating container water cooling device 14 is attached in advance. When the refractory container 12 filled with the molten steel 1 is placed on the measuring table 16, the contact 19 of the thermocouple 18 is automatically closed and the temperature of the molten steel 1 is measured. Further, a hydride gas sampling pipe 23 made of quartz glass is placed on the upper part of the refractory container 12. The temperature measurement data from the thermocouple 18 is input to the measurement computer 20. The measuring computer 20 obtains the freezing point of the molten steel 1 from the temperature change over time, and then finds the carbon content in the molten steel based on the freezing point.

Immediately after the amount of carbon is determined, cooling water is supplied to the refractory container water cooling device 14 to forcibly cool the refractory container 12. When the surface layer of molten steel 1 solidifies and the temperature drops to 100 ° C., quantitative analysis of sulfur and phosphorus is started. First, place the hydride gas sampling pipe 23 on the top of the refractory container 12,
6M hydrochloric acid is continuously supplied to the coagulation part 3 at 10 ml / min. Nitrogen gas is also supplied to the hydride gas sampling pipe 23 at a constant flow rate (50 ml / min). Sulfur, phosphorus and arsenic in steel are reduced by hydrochloric acid, and H ₂ S, PH ₃ and A
sH ₃ is generated. The generated hydride gas is transported to the hydride gas quantitative device 71 by nitrogen gas.

In the hydride gas meter 71, the H ₂ S detecting test paper 76 and the PH ₃ detecting test paper 77 are continuously fed at a constant speed (4 cm / min). H ₂ S, PH ₃ and AsH ₃ sent together with the nitrogen gas first pass through the H ₂ S detecting test paper 76. H ₂ S detection test strip 76 does not detect the PH _3, AsH ₃ at all, selectively detect only H ₂ S, it is colored in accordance with the concentration of H ₂ S. H
_The gas passing through the ₂ S detection test paper 76 was activated carbon column 8 which was kept at 130 ° C. by the column temperature controller 85.
Inflow to 4. In the activated carbon column 84, AsH ₃ in the gas is adsorbed by the activated carbon and held as it is, and it is not eluted in the gas. On the other hand, even if PH ₃ is adsorbed on activated carbon,
Elute again. As a result, P on the PH ₃ detection test paper 77
Only H ₃ is sent. The test paper 77 for detecting PH ₃ is PH
₃ Color develops according to the density. The colored portion on the H ₂ S detecting test paper 76 and the PH ₃ detecting test paper 77 is the irradiation lamp 7.
After being irradiated by the laser beam 8, and the reflected light intensity is detected by the photodiode 79, the measurement computer 20 calculates the coloring intensity, that is, the H ₂ S and PH ₃ concentrations.

FIG. 2 is an apparatus block diagram showing an example of an analyzing apparatus for carrying out the analyzing method of the second invention.

The analyzers are mainly carbon analyzers 11,
And a sulfur / phosphorus analyzer 21. The same devices as those shown in FIG. 1 are designated by the same reference numerals, and the description thereof will be omitted. The carbon analyzer 11 is the same as that of the above-mentioned embodiment.

The hydride gas generator 41 comprises an electrolysis cell 42 placed on the surface solidification surface. Electrolysis cell 42
Is placed on the surface of the solidified layer to form the electrolytic chamber 43. A graphite electrode 48 (negative electrode) is placed on the lid 46 on the top of the electrolysis cell 42, and a positive electrode 50 is placed on the bottom. Constant voltage / constant current power supply 5 for graphite electrode 48 and positive electrode 50
2 is connected. An electrolyte solution supply hole 49 penetrates along the central axis of the graphite electrode 48. The electrolytic solution supply device 55 is connected to the electrolytic solution supply hole 49. The electrolytic solution supply device 55 is composed of an electrolytic solution tank 56 containing an electrolytic solution (6M hydrochloric acid) and a pump 57. Electrolysis cell 4
A heat-resistant gasket 54 made of a fluororesin or the like is attached to the bottom of No. 2 in contact with the surface of the solidified layer. The positive electrode 50 penetrates the gasket 54 and contacts the surface solidified surface. The carrier gas supply device 31 is connected to the inlet side 44 of the electrolysis chamber 43, and the sulfur / phosphorus analyzer 71 is connected to the outlet side 45 via the gas-liquid separator 61 and the line filter 65.

Quantitative analysis of carbon in molten steel by the above apparatus is the same as in the above-mentioned embodiment. The method of quantitative analysis of sulfur and phosphorus will be described below.

In this embodiment, unlike the case of FIG. 1, the electrolytic cell 42 is placed on the solidified layer 3 after the molten steel 1 is solidified.

Immediately after the quantification of carbon is finished, cooling water is supplied to the refractory container water cooling device 14 to forcibly cool the refractory container 12. When the surface layer of molten steel 1 solidifies and the temperature drops to 100 ° C., quantitative analysis of sulfur and phosphorus is started. First, the electrolytic cell 42 is placed on the surface of the solidified layer 3, and the electrolytic solution (6M hydrochloric acid) and nitrogen gas are continuously supplied to the surface of the solidified portion. At this time, the positive electrode 50 is in contact with the surface of the solidified portion, and an electrolytic voltage (1.5 V) is applied between the graphite electrode 48 and the positive electrode 50. Nitrogen gas has a constant flow rate (5 m
l / min). A hydride gas is generated in the solidified portion (steel) 3 by electrolysis. The hydride gas is H ₂ S,
It contains PH ₃ and AsH ₃ . The generated hydride gas is transported to the hydride gas quantitative device 71 by nitrogen gas.

Quantitative analysis of sulfur and phosphorus by the hydride gas quantification device 71 is performed in the same manner as in the above-mentioned embodiment.

With the apparatus configured as described above, carbon, sulfur and phosphorus could be quantified within 10 minutes.

[0042]

According to the present invention, operations such as cutting and polishing for sample preparation are not required, and carbon, sulfur and phosphorus can be continuously quantitatively analyzed. Therefore, the analysis time can be significantly shortened and the labor can be saved. As a result, the analysis result can be quickly fed back to the refining process and the like, and the production control or quality control of the metal material can be performed more accurately than before.

[Brief description of drawings]

FIG. 1 is a device configuration diagram showing an example of an analysis device for carrying out the analysis method of the first invention.

FIG. 2 is an apparatus configuration diagram showing an example of an analysis apparatus for carrying out the analysis method of the second invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Molten metal 3 Solidified layer 11 Carbon analyzer 12 Refractory container 14 Water cooling device 18 Thermocouple 20 Measurement computer 22 Hydride gas generator 23 Hydride gas sampling pipe 26 Acid supply branch pipe 27 Acid supply device 31 Carrier gas supply device 41 Hydride gas generator 42 Electrolysis cell 48 Electrode 50 Electrode 52 Constant voltage / constant current power supply 61 Gas-liquid separation device 65 Line filter 71 Sulfur / phosphorus quantification device 73a H ₂ S gas contact chamber 73b H ₃ P gas contact chamber 76 H ₂ Test paper for S detection 77 PH ₃ Test paper for detection 78 Irradiation lamp 79 Photodiode 84 Activated carbon column

Claims (5)

[Claims] 1. The time-dependent change in temperature of the molten metal collected in a refractory container is measured, and the carbon in the molten metal is quantified based on the freezing point obtained from the time-dependent change in temperature, and subsequently reduced to the surface solidified surface of the molten metal. to generate a hydride gas by supplying sexual acid, a hydride gas is transported to the hydride gas quantification device by carrier gas, the hydride gas H ₂ S detection test strip and with a hydride gas quantification device PH _{(3) A} method for analyzing carbon, sulfur and phosphorus in a metal sample, which comprises sequentially contacting a test strip for detection to develop the color of the test strip, and measuring the intensity of the developed color to quantify sulfur and phosphorus in the metal sample. . 2. The time-dependent change in temperature of the molten metal sampled in the refractory container is measured, the carbon in the molten metal is quantified based on the freezing point obtained from the time-dependent change in temperature, and then electrolysis is performed on the surface solidified surface of the molten metal. A liquid is supplied, the solidified surface of the surface layer is electrolyzed to generate a hydride gas, and the hydride gas is conveyed by a carrier gas to a hydride gas determination device, and the hydride gas is converted into H ₂ S by the hydride gas determination device. Carbon in a metal sample characterized in that the test paper for detection and the test paper for PH ₃ detection are sequentially brought into contact with each other to develop a color, and the intensity of color development is measured to quantify sulfur and phosphorus in the metal sample. Analysis method for sulfur and phosphorus. 3. A hydride gas is brought into contact with an H ₂ S detection test paper, and then passed through an activated carbon column kept at a constant temperature to remove AsH ₃ in the hydride gas, and then P
The method for analyzing carbon, sulfur and phosphorus in a metal sample according to claim 1 or 2, which is brought into contact with a test paper for H ₃ detection. 4. An apparatus for carrying out the analysis method according to claim 1, comprising a refractory container water cooling device detachably attached to the refractory container, and being placed on a top opening of the refractory container to supply an acid. A branch pipe is immersed in molten metal, and a glass-made hydride gas sampling pipe whose outlet side is connected to a hydride gas measuring device, and an acid supply device and a carrier gas supply device connected to the inlet side of the hydride gas sampling pipe An apparatus for analyzing carbon, sulfur and phosphorus in a metal sample, which is equipped with a hydride gas generator comprising 5. An apparatus for performing the analysis method according to claim 2, comprising a refractory vessel water cooling device detachably attached to the refractory vessel, and being placed on the surface solidification surface to form an electrolytic chamber. , An electrolysis cell whose outlet side is connected to a hydride gas quantification device, electrodes respectively placed at the top and bottom of the electrolysis cell, a constant potential / constant current electrolysis device connected to it, and further connected to the electrolysis cell inlet side, respectively. An apparatus for analyzing carbon, sulfur and phosphorus in a metal sample, comprising a hydrogenated gas generator comprising an electrolytic solution feeder and a carrier gas feeder.