CN1031762A - The analytical approach of impurity element in the gallium - Google Patents
The analytical approach of impurity element in the gallium Download PDFInfo
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- CN1031762A CN1031762A CN 87105895 CN87105895A CN1031762A CN 1031762 A CN1031762 A CN 1031762A CN 87105895 CN87105895 CN 87105895 CN 87105895 A CN87105895 A CN 87105895A CN 1031762 A CN1031762 A CN 1031762A
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- gallium
- impurity element
- hydrochloric acid
- nitric acid
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Abstract
The present invention is the analytical approach of impurity element in the gallium, be partly dissolved the main body gallium with hydrochloric acid, nitric acid, make that impurity element is enriched in the remaining gallium in the gallium, more remaining gallium is dissolved fully, remove gallium with the extraction of small size isopropyl ether, water carries out the atomic emission spectrum solution residue technique and measures.This law is saved organic reagent, and blank value is low, and is highly sensitive, and simple procedure is accurate, and measurement range is wide.Sampling 0.5 its measurement range of gram is respectively: mercury, platinum 6 * 10
-6～2 * 10
-4%, plumbous, cobalt 1 * 10
-6～2 * 10
-4%, nickel, bismuth, tin, palladium, indium 4 * 10
-7～2 * 10
-4%, copper, silver 4 * 10
-8～2 * 10
-5%.
Description
The present invention relates to the analytical approach of impurity element in the gallium, borrow more precisely to be partly dissolved that the main body gallium combines with the small size extraction phase and in the enrichment gallium behind the impurity element, to measure with the atomic emission spectrum solution residue technique.
In existing document, the analytical approach of impurity element is divided enrichment method and is measured two parts in the gallium, extraction is being arranged, ion exchange process, volatility process, the precipitation method etc. aspect the concentrated impurity.Emission spectrometry is being arranged, spectrophotometric method, polarography, atomic absorption spectrography (AAS) etc. aspect the mensuration impurity.
Russian national standard (Γ OCT 13637-77) separates the main body gallium with butyl acetate or extracted with diethyl ether then with acid of hydrochloric acid and nitric acid dissolved samples gallium in the hydrochloric acid of 6M, make its impurity enriched at water, uses emission spectrometry (powder method) to measure again.Its advantage is to measure multielement simultaneously, and sensitivity is higher, but owing to sampling amount is big, needs must extract repeatedly with a large amount of inorganic and organic reagents, and formality is tediously long, and blank value is higher, has limited detectability.
(GB 4375,12-84) also are with hydrochloric acid, nitric acid dissolve sample, and in 7.5M hydrochloric acid, with isopropyl ether extraction secondary separation main element gallium, impurity element is enriched in aqueous phase, measures with the emission spectrum solution residue technique for China's GB.Its advantage is to measure Determination of Multi-Impurities simultaneously, and sensitivity is higher.Its shortcoming also is to need to extract with organic reagent with inorganic in a large number, and blank value is higher, thereby has also limited the raising of detectability.
The Japanese documentation spy opens clear 60-230041, has introduced the most of main body gallium of precipitate and separate in the aqueous solution of ammoniacal liquor-hydrogen peroxide-water (1: 3: 10), gets its clear liquid and does not measure with there being the sunken atomic absorption spectrography (AAS) of fire.Its advantage is to measure impurity elements such as potassium, sodium, silicon, selenium, germanium, and it is higher to measure sensitivity.But this method can not be measured multielement impurity simultaneously, needs single-element to measure one by one, and sedimentation and filtration etc. to separate formality loaded down with trivial details.
People such as E.Jackwerth (Anal.Chim.Acta, 87,341,1976) the mixed-acid dissolution sample of usefulness 3M hydrochloric acid-0.15M nitric acid, impurity elements such as copper, lead, bismuth, nickel, cobalt, silver, gold, palladium, mercury, tin, iron are enriched in the undissolved remaining gallium, the gallium of remnants is dissolved in the acid of hydrochloric acid and nitric acid fully, adopts the atomic absorption spectrography (AAS) of injection method to measure.The shortcoming of this method is because sampling amount big (5 gram), and sample dissolution speed is slow, be with a large amount of acid of hydrochloric acid and nitric acid repeated treatments, and can not the enrichment indium; The sample liquid of tin needs individual processing; And need when measuring each impurity element in same sample solution, to measure separately one by one, impurity element of every mensuration will change an atomic absorption spectrum lamp, and will be time-consuming bothersome; Moreover this enrichment method can only enrichment greater than the cobalt of 10ppm, when cobalt during less than 10ppm, the recovery is on the low side.
The objective of the invention is to improve the shortcoming of above-mentioned prior art, especially will the assay method of impurity element in the gallium of people such as E.Jackwerth proposition be improved, work out a condition that is better than the enrichment impurity element of Jackwerth method.Under this enrichment condition, not only can enriching Cu, lead, bismuth, nickel, cobalt, silver, gold, palladium, mercury, tin, iron, again can the enrichment indium, platinum.And the sample solution that makes tin is without individual processing, and cobalt is low to moderate the also quantitatively enrichment of 0.2 microgram.And then take a small size extraction with complete separating gallium, and then combine with the solution residue emission spectrometry, thereby reach the purpose of measuring multielement impurity simultaneously, make that the mensuration of impurity has simple procedure in the gallium, blank value is low, and is highly sensitive, characteristics such as accurately and reliably, measurement range is wide.
The present invention is the analytical approach of impurity element in a kind of gallium, the main body gallium is partly dissolved, and the impurity element in the gallium is enriched in the remaining undissolved gallium, and the reagent of dissolving main body gallium is nitric acid and hydrochloric acid, the concentration range of nitric acid is 0.20M～1.0M, and the concentration range of hydrochloric acid is 5.0M～12.0M; After most of main body gallium dissolving, solution is inclined to, add nitric acid again, hydrochloric acid dissolves the undissolved gallium of remnants fully, in hydrochloric acid medium, with any organic solvent extraction gallium in isopropyl ether, ether, dichloroethyl ether, the butyl acetate, the impurity element that is enriched in aqueous phase is measured.
For more steady and promptly dissolve the main body gallium, the element of impurity in the enrichment gallium better, the scope of the concentration of hydrochloric acid of dissolution of metals gallium is good with 9M～12.0M, the concentration range of nitric acid is good with 0.25M～0.5M.
Extraction removes the water behind the gallium, available polarography, atomic absorption spectrography (AAS), do not have fire and fall into atomic absorption spectrography (AAS), atomic fluorescence spectrometry, the ICP atomic emission spectrometry, atomic emission spectrometry (powder method), the atomic emission spectrum solution residue technique is measured, but is good with the atomic emission spectrum solution residue technique.
Usually sample 0.25 gram that takes by weighing gallium is to 2 grams (amount on the impurity element that contains in the sample decide), the impurity element amount height that contains, and sample size is also desirable, and the content of impurity element is very low less than 0.25 gram, and is desirable greater than 2 samples that restrain.The sample that takes by weighing is placed the acid mixture that adds hydrochloric acid and nitric acid in 10 milliliters of silica crucibles, and the concentration of used hydrochloric acid can be 5.0M～12.0M, and the concentration range of nitric acid is 0.20M～1.0M.
Along with the increase of concentration of hydrochloric acid, the electrode potential of gallium moves to more negative direction, and along with the increase of concentration of nitric acid, the electrode potential of gallium is to moving on the occasion of direction; When concentration of hydrochloric acid greater than 5M, the electrode potential of gallium is with the increase of concentration of nitric acid, amplitude of variation diminishes, for the enrichment electrode potential is bigger than the electrode potential of gallium effectively, but big which impurity element that gets seldom, the concentration that increases hydrochloric acid is favourable, concentration of hydrochloric acid is 5M～12M, when nitric acid is 0.20M～1.0M, all quantitatively enrichments of palladium, lead, tin, bismuth, copper, silver.Nickel is 5M to 12M at concentration of hydrochloric acid, all can quantitative recovery when its concentration of nitric acid is less than or equal to 0.5M, if concentration of nitric acid is during greater than 0.5M, the recovery of nickel is obviously on the low side.Cobalt, mercury are 6M at concentration of hydrochloric acid, and concentration of nitric acid can quantitative recovery during for 0.25M, and concentration of nitric acid is during greater than 0.25M, and the recovery of cobalt, mercury is obviously on the low side; When concentration of hydrochloric acid was 10M～12M, concentration of nitric acid was in the scope of 0.20M～1.0M, and cobalt, mercury is all quantitatively enrichments also.When concentration of hydrochloric acid is 12M, when concentration of nitric acid was 0.5M, platinum, indium and above-mentioned other elements are quantitatively enrichment all.So the concentration range of hydrochloric acid is from 9.0M-12.0M, the concentration of nitric acid scope is good with 0.25M～0.50M.
Sample places in the silica crucible, after adding acid of hydrochloric acid and nitric acid acid mixture, cover surface plate, in 60 ℃ of-90 ℃ of heating, the sample gallium is partly dissolved, the residual volume that makes the sample gallium 50 milligrams with interior (the gallium residual volume look the assay method that adopted and different, when adopting this assay method, preferably 10 milligrams to 40 milligrams), stop heating, the solution in the crucible is inclined to, add hydrochloric acid, nitric acid, continuing heating in 60 ℃-90 ℃ dissolves remaining sample gallium fully, treat that solution cooling back moves in the separating funnel, making the concentration of its hydrochloric acid is 6M-10M, is preferably 7-8M, use isopropyl ether, ether, dichloroethyl ether, any organic reagent extraction gallium in the ester acid butyl ester is good with isopropyl ether.Only need the small size extraction once.Behind the extraction gallium, water is put into 10 milliliters silica crucible evaporate to dryness, add three dissolve with hydrochloric acid solution residues of a nitric acid.Residue solution is moved on the pair of electrodes head (dripping in advance has 10 microgram barium, 5 microgram sodium) with suction pipe under infrared lamp, dry, in order to taking the photograph spectrum.By the method preparation standard series that the one of ordinary skill in the art all knows, by GB GB 7345, the spectrometry condition of 12-84 carries out spectroscopic assay, and used analytical line pair is as shown in table 1.
By the characteristic emulsion curve of drawing, the blackness value of analytical line pair is converted into the logarithm (lg (Ia)/(Ii)) of strength ratio, with lg (Ia)/(Ii)～logC mapping, drawing curve.
Table 1, analytical line pair
Analytical line
Internal standard line
Analytical line
Internal standard line
Hg 2536.52 Ba 3071.59 Pd 3242.70 Ba 3071.59
Pt 2830.30 Ba 3071.59 In 3256.09 Ba 3071.59
Pb 2833.06 Ba 3071.59 Cu 3273.96 Ba 3071.59
Ni 3050.82 Ba 3071.59 Ag 3280.68 Ba 3071.59
Bi 3067.72 Ba 3071.59 Co 3412.34 Ba 3071.59
Sn 3175.04 Ba 3071.59
Be calculated as follows the percentage composition of each impurity element:
X（%）＝ (m
2-m
1)/(m
0×10
6) ×100
M in the formula
2: by the impurity element amount that checks on the working curve, microgram.
m
1: by the impurity element amount that checks on the working curve, microgram in company with sample blank.
m
0: sample size, gram.
Advantage of the present invention is:
(1) analytical approach of the present invention has been found out the enrichment condition of a good impurity element, under this enrichment condition, not only can enriching Cu, lead, bismuth, nickel, cobalt, silver, gold, palladium, mercury, tin, iron, again can the enrichment indium, platinum, and the sample solution of tin is without individual processing, can measure with other impurity elements, cobalt is low to moderate 0.2 microgram also can quantitative recovery, measures Determination of Multi-Impurities simultaneously with the atomic emission spectrum solution residue technique after the enrichment.
(2) be partly dissolved sample owing to having adopted, removed most of main body, reduced the extraction times and the organic reagent consumption of gallium, saved reagent, reduced blank value, improved mensuration sensitivity.
(3) analytical approach simple procedure of the present invention, accurately and reliably, measurement range is wide.Under selected enrichment condition, carried out repeatedly reinforced recovery test, the addition of copper, silver is 0.02 microgram, the addition of platinum, indium, cobalt, mercury, nickel, tin, lead, bismuth, palladium is 0.2 microgram, and its recovery is respectively: platinum 96%, indium 98%, cobalt 102.5%, mercury 95%, nickel 97%, tin 102%, lead 98%, bismuth 98%, palladium 102%, copper 97.5%, silver 99.5%.
Gallium-1 sample has been carried out ten once measured, proved that analytical approach precision of the present invention is good, it the results are shown in table 2.
The precision of table 2, method
Table 3(is continuous)
Gallium-1 sample is adopted main part dissolution method of the present invention and GB GB 7345, and the main body of the 12-84 all chemical spectroscopy of dissolving has been carried out blank determination, and it the results are shown in table 4.
The results of comparison of table 4, distinct methods
When method of the present invention, sampling amount were 0.5 gram, its measurement range was respectively: mercury, platinum 6 * 10
-6-2 * 10
-4%; Plumbous, cobalt 1 * 10
-6-2 * 10
-4%; Nickel, bismuth, tin, palladium, indium 4 * 10
-7-2 * 10
-4%; Copper, silver 4 * 10
-8-2 * 10
-5%.
More specifically describe the present invention with following non-limiting examples, protection scope of the present invention is not
Be subjected to the qualification of these embodiment.
Embodiment 1
Used water is deionized water in the experiment, resistivity＞10M Ω-cm, and hydrochloric acid (Beijing Chemical Plant analyzes pure) distillation is purified.Nitric acid (Beijing Chemical Plant analyzes pure) distillation is purified.Isopropyl ether (Shanghai reagent one factory, chemical pure) distillation is purified, and is saturated with 7.5M hydrochloric acid before using.The method of all knowing with the those of ordinary skill under this area is prepared the standard solution of various metals.Spectrograph PGS-2 grating spectrograph.The omnipotent light source of UBI-1.Microphotometer (German Democratic Republic Zeiss two types).Spectrum ultraviolet two type photographic plates.Graphite electrode is a spectroscopic pure, 25 millimeters flat tip electrodes of diameter 6 millimeters long, and the polystyrene solution with one 1.5% before using seals.
Take by weighing 0.25-1 gram sample gallium (deciding), place in 10 milliliters of silica crucibles, add the acid mixture of 5 milliliters of hydrochloric acid (12M) and nitric acid (0.5M) on impurity content, cover surface plate, place on the electric furnace about 80 ℃ and heat, make gallium molten to about 10 milligrams, stop heating.Solution in the crucible is inclined to, add hydrochloric acid (12M) and nitric acid (0.5M) then, continue heating remaining gallium is dissolved fully, treat that solution cooling back moves in the separating funnel, the concentration that makes hydrochloric acid is 7.5M, add isopropyl ether vibration three minutes, place a moment, treat the solution left standstill layering after, water is put into 10 milliliters of silica crucibles, evaporate to dryness adds three hydrochloric acid of a nitric acid, dissolved residue while hot.Residue solution is moved on the pair of electrodes head (dripping in advance has 10 microgram barium, 5 microgram sodium) under infrared lamp, dry, in order to taking the photograph spectrum, the method preparation standard series of all knowing by the one of ordinary skill in the art again.By GB GB 7345, the 12-84 spectrometry condition carries out spectroscopic assay, calculates.
Embodiment 2
Basic operation is only dissolved the hydrochloric acid of main body gallium, the concentration difference of nitric acid with embodiment 1.The concentration of hydrochloric acid is 6M, and the concentration of nitric acid is 0.25M.The recovery of impurity element is respectively: nickel＞90%, cobalt＞90%, mercury＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 3
Basic operation is only dissolved hydrochloric acid, the concentration of nitric acid difference of main body gallium with embodiment 1.The concentration of hydrochloric acid is 6M, and the concentration of nitric acid is 0.50M, and the recovery of impurity element is respectively: nickel＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, indium＞90%, silver＞90%.
Embodiment 4
Basic operation is only dissolved hydrochloric acid, the concentration of nitric acid difference of main body gallium with embodiment 1.The concentration of hydrochloric acid is 6M, and the concentration of nitric acid is 0.75M, and the recovery of impurity element is respectively: plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 5
Basic operation is only dissolved hydrochloric acid, the concentration of nitric acid difference of main body gallium with embodiment 1.The concentration of hydrochloric acid is 6M, and the concentration of nitric acid is 1.0M, and the recovery of impurity element is respectively: plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 6
Basic operation is only dissolved hydrochloric acid, the concentration of nitric acid difference of main body gallium with embodiment 1.The concentration of hydrochloric acid is 10M, and the concentration of nitric acid is 0.25M, and the recovery of impurity element is respectively: nickel＞90%, cobalt＞90%, mercury＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 7
Basic operation is only dissolved hydrochloric acid, the concentration of nitric acid difference of main body gallium with embodiment 1.The concentration of hydrochloric acid is 10M, and the concentration of nitric acid is 0.50M, and the recovery of impurity element is respectively: nickel＞90%, cobalt＞90%, mercury＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 8
Basic operation is only dissolved the hydrochloric acid of main body gallium, the concentration difference of nitric acid with embodiment 1.The concentration of hydrochloric acid is 10M, and the concentration of nitric acid is 0.75M, and the recovery of impurity element is respectively: cobalt＞90%, mercury＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 9
Basic operation is only dissolved the hydrochloric acid of main body gallium, the concentration difference of nitric acid with embodiment 1.The concentration of hydrochloric acid is 10M, and the concentration of nitric acid is 1.0M, and the recovery of impurity element is respectively: cobalt＞90%, mercury＞90%, plumbous＞90%, tin＞90%, bismuth＞90%, palladium＞90%, copper＞90%, silver＞90%.
Embodiment 10
Basic operation is only dissolved the hydrochloric acid of main body gallium, the concentration difference of nitric acid with embodiment 1.The concentration of hydrochloric acid is 11.5M, and the concentration of nitric acid is 0.5M, and the recovery of impurity element is respectively: platinum 96%, indium 98%, cobalt 102.5%, mercury 95%, nickel 97%, tin 100%, lead 100%, bismuth 98%, palladium 102%, copper 97.5%, silver 99.5%.
Claims (4)
1, the analytical approach of impurity element in a kind of gallium, the main body gallium is partly dissolved, and the impurity element in the gallium is enriched in the remaining undissolved gallium, and the reagent of dissolving main body is nitric acid and hydrochloric acid, and feature of the present invention is:
(1) said concentration of nitric acid scope is 0.20M～1.0M, and the concentration range of hydrochloric acid is 5.0M～12M,
(2) solution is inclined to, add nitric acid again, hydrochloric acid dissolves the gallium of remnants fully, in hydrochloric acid medium, with any organic reagent extraction gallium in isopropyl ether, ether, dichloroethyl ether, the butyl acetate,
(3) measure being enriched in the aqueous phase impurity element.
According to the analytical approach of impurity element in a kind of gallium of claim 1, it is characterized in that 2, the water that extraction removes behind the gallium is measured with the emission spectrum solution residue technique.
According to the analytical approach of impurity element in a kind of gallium of claim 1 or 2, it is characterized in that 3, the concentration range of nitric acid is 0.25～0.5M, the concentration range of hydrochloric acid is 9.0～12.0M.
According to the analytical approach of impurity element in a kind of gallium of claim 1, it is characterized in that 4, remaining gallium amount is in 50 milligrams.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105895 CN1012629B (en) | 1987-09-01 | 1987-09-01 | Method for analysis of impurity elements in gallium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87105895 CN1012629B (en) | 1987-09-01 | 1987-09-01 | Method for analysis of impurity elements in gallium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1031762A true CN1031762A (en) | 1989-03-15 |
| CN1012629B CN1012629B (en) | 1991-05-15 |
Family
ID=4815484
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87105895 Expired CN1012629B (en) | 1987-09-01 | 1987-09-01 | Method for analysis of impurity elements in gallium |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1012629B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041382B (en) * | 2009-10-23 | 2012-12-12 | 光洋应用材料科技股份有限公司 | Method for recovering gallium |
| CN111912692A (en) * | 2020-07-16 | 2020-11-10 | 东华理工大学 | Device and method for removing gallium from substrate |
-
1987
- 1987-09-01 CN CN 87105895 patent/CN1012629B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102041382B (en) * | 2009-10-23 | 2012-12-12 | 光洋应用材料科技股份有限公司 | Method for recovering gallium |
| CN111912692A (en) * | 2020-07-16 | 2020-11-10 | 东华理工大学 | Device and method for removing gallium from substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1012629B (en) | 1991-05-15 |
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