CN107462569A - 一种通过元素生成挥发物来测定元素的方法及装置 - Google Patents
一种通过元素生成挥发物来测定元素的方法及装置 Download PDFInfo
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- CN107462569A CN107462569A CN201710723489.9A CN201710723489A CN107462569A CN 107462569 A CN107462569 A CN 107462569A CN 201710723489 A CN201710723489 A CN 201710723489A CN 107462569 A CN107462569 A CN 107462569A
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- solution
- acid
- gas
- salt
- phosphine
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 68
- 239000007788 liquid Substances 0.000 claims abstract description 45
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 26
- -1 alkylthio phosphorus Chemical compound 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 230000002572 peristaltic effect Effects 0.000 claims description 20
- 239000012159 carrier gas Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 239000002699 waste material Substances 0.000 claims description 12
- 239000000523 sample Substances 0.000 claims description 11
- 239000012488 sample solution Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000003694 hair properties Effects 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910000510 noble metal Inorganic materials 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 230000019086 sulfide ion homeostasis Effects 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000004678 hydrides Chemical class 0.000 description 10
- 239000012279 sodium borohydride Substances 0.000 description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- MSXGQMLWJUMPOJ-UHFFFAOYSA-N C(C)OP(S)(OCC)=S.[Na] Chemical compound C(C)OP(S)(OCC)=S.[Na] MSXGQMLWJUMPOJ-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- IOEJYZSZYUROLN-UHFFFAOYSA-M Sodium diethyldithiocarbamate Chemical compound [Na+].CCN(CC)C([S-])=S IOEJYZSZYUROLN-UHFFFAOYSA-M 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003271 compound fluorescence assay Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002663 nebulization Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Sampling And Sample Adjustment (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
本发明公开一种通过元素生成挥发物来测定元素的方法及装置，该方法包括将烷基硫代磷（膦）酸（或其盐）的溶液与待测元素溶液在线混合，混合后的溶液立即进行气液分离，使挥发性元素络合物进入到元素分析仪进行检测或用于元素的膜的制备。本发明可用于仪器分析中的元素样品引入，以提高元素分析的灵敏度、改善检出限；也可用于及无机镀膜的气态先驱物的制备。
Description
技术领域
本发明属于仪器分析技术领域，涉及原子光谱仪样品进样的方法，更广泛的，本发明也用于及无机镀膜的气态先驱物的制备，特别是一种通过元素生成挥发物来测定元素的方法及装置。
背景技术
目前，原子光谱仪中所使用的氢化物发生进样系统，大部分是使用硼氢化钠（钾）作氢化物发生的还原试剂，通过硼氢化钠（钾）中的氢将样品溶液中的元素还原成气态氢化物后，元素在原子光谱仪中进行测定。由于氢化物进样效率比较原子光谱中的常规气动雾化进样，有更高的进样效率（常规气动雾化进样只有3-5%，测定灵敏度较低，而氢化物进样效率接近100%），因而在测定上具有更高的灵敏度和更低的检出限的特点。已经应用的是用硼氢化钠（钾）和传统上易形成氢化物的九个元素（ 砷，锑，铋，锗，锡，铅，硒，碲，汞）形成这些元素的氢化物而被原子光谱仪进行测定。
近年来，随着科技人员研究的不断深入，一些从事分析的工作人员，相继发现，有关其它元素也可和硼氢化钠（钾）发生氢化反应，并先后发表了多篇研究论文。例如郭小伟等于1995年发现了在常温下酸性水溶液中的锌和镉可以被硼氢化钠溶液还原成可挥发性氢化物，并且运用该氢化发生样品进入系统，在原子荧光上测定了实际样品中的锌和镉的含量测定。Ａｄｅｒｖａｌ．Ｓ Ｌｕｎａ和Ｐ．Ｐｏｈｌ分别在下２０００年和２００１年报到了一些元素如金，银，铜，锰，钛等在常温下也可以和硼氢化钠（钾）反应形成氢化物。但上述文献报道的方法，存在形成氢化物效率比较低、残留现象比较严重的缺陷，从而使该方法在实际使用中受到阻碍。
使用硼氢化钠化学蒸气发生另外一个不足是硼氢化钠价格比较贵，而且不稳定。其固体试剂放置时间长了会分解成块状偏硼酸钠，溶液放置时间久了会分解。一般需要现用现配。另外，硼氢化钠做还原剂从测定元素个数上来说，还是有限。比如，用于测锌钴的时候其灵敏度就很低，也不能测稀土。
发明内容
本发明的目的在于克服现有技术的缺点与不足，提供一种全新的原子光谱仪样品进样的方法和装置。
本发明的技术方案如下：
一种通过元素生成挥发物来测定元素的方法，其特征在于将水溶性的烷基硫代磷（膦）酸（盐）的溶液与待测元素溶液在线混合，混合后的溶液立即进行气液分离测定，使挥发性元素络合物进入到元素分析仪进行检测；其中混合后溶液中烷基硫代磷（膦）酸（盐）的溶液与待测元素溶液的比例浓度为0.02-3%（m/V）；烷基硫代磷（膦）酸（盐）的溶液与混合后溶液的酸度为0.001-3M的待测元素溶液，混合后的溶液的温度度是室温。
其中烷基硫代磷（膦）酸（盐）为烷基硫代磷酸，烷基硫代次磷酸，烷基硫代亚磷酸，或它们与碱金属或碱土金属元素所生成的溶于水的盐。
优选烷基硫代磷（膦）酸（盐）为：二乙基二硫代磷酸或它与碱金属、碱土金属及氨形成的溶于水的盐。其中碱金属优选为锂、钠、钾；碱土金属优选为镁和钙。
本发明中待测元素指的部分主族元素、部分过渡元素、贵金属元素和稀土元素，其中主族元素指的是（但不限于）：镓、铟、铊、锗、锡、铅、锑、铋；过渡元素指的是（但不限于）：钛、钒、铬、锰、铁、钴、镍、铜、锌、锆、镉、汞；贵金属元素是钌、铑、钯、银、铱、铂、金；稀土元素指的是铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、铀、钍和钚。
上述元素中优选的元素指的是铟、铊、锗、锡、铅钌、铑、钯、银、铂、金、钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镉和汞。
本发明中的两个溶液是将0.005-5%（w/w）烷基硫代磷（膦）酸（盐）的溶液与酸度0.005-5 M的待测元素溶液在线混合。其中,优选烷基硫代磷（膦）酸（盐）在与元素溶液混合后的质量浓度是0.05-1%；在线待混合后的溶液的酸度是0.05-0.4摩尔/升，优选0.1-0.2M的混合酸度。
本发明混合后的溶液的温度度是室温。
本发明进一步公开了通过元素生成挥发物来测定元素方法在用于化学气相沉积及无机镀膜气态先驱物的制备方面的应用。
本发明在室温下的一个典型实施例包括如下步骤：（1）使用蠕动泵分别以1-3毫升/分钟的相等速度连续抽取质量浓度为0.05-0.5%的二乙基二硫代磷酸钠溶液和酸度为0.05-0.2M的含元素样品溶液；（2）使两股溶液在一微型三通管内汇合反应，然后立即在气液分离器中进行气液分离；（3）分离出的气体被导入原子光谱仪中进行测定。其中混合后的溶液温度是室温。
本发明在加热下的一个典型实施例包括如下步骤：（1）使用蠕动泵分别以1-3毫升/分钟的相等速度连续抽取质量浓度为0.05-0.5%的二乙基二硫代磷酸钠溶液和酸度为0.05-0.2M的含元素样品溶液；（2）使两股溶液在一微型三通管内汇合反应，然后立即在气液分离器中进行气液分离；（3）分离出的气体被导入原子光谱仪中进行测定。其中混合后的溶液温度是室温到80摄氏度。
本发明进一步公开了适用于元素挥发物的形成装置；该装置包括含元素的样品溶液导入管1、含烷基硫代磷（膦）酸（盐）溶液的导入管2、蠕动泵3、三通管4、气液分离器5载气入口6、载气出口7和废液排放管8；蠕动泵抽取两个溶液后通过三通后两股溶液混合，然后与气液分离器相连，气液分离器中含多孔玻璃烧结（或多孔塑料）板制成的透气不透水的半透膜F，气液分离器设有载气入口，和载气入口，分离气体挥发物的废液被蠕动泵带动经废液排放管排出。为提高反应效率，在紧邻三通管的前或后面的管路带有加热装置。
本发明的典型的装置（见说明书附图1），包括含元素的样品溶液导入管1、含烷基的二硫代磷（膦）酸（盐）溶液的导入管2、蠕动泵3、三通管4、气液分离器5载气入口6、载气出口7和废液排放管8；蠕动泵抽取两个溶液后在三通管4中汇合发生反应，然后与气液分离器5相连，气液分离器5设有载气入口和载气入口，通过多孔烧结玻璃或塑料板鼓泡方式分离出的气体挥发物送到仪器去检测，而分离后的废液被蠕动泵3经废液排放管8排出。为提高反应效率，在紧邻三通管4的前或后面的管路带有加热装置9。
附图说明
图1为适用于室温下元素挥发物形成的装置图；
图2为适用于加热下元素挥发物形成的装置图；
1、元素的样品溶液导入管、2含烷基的硫代磷（膦）酸（盐）溶液导入管
3、蠕动泵 4三通管 5气液分离器、 6载气入口、
7载气出口 8、废液排放管 9溶液加热装置；
F为多孔烧结玻璃或塑料鼓泡板（透气不透水）。
具体实施方式
下面通过具体的实施方案叙述本发明。除非特别说明，本发明中所用的技术手段均为本领域技术人员所公知的方法。另外，实施方案应理解为说明性的，而非限制本发明的范围，本发明的实质和范围仅由权利要求书所限定。对于本领域技术人员而言，在不背离本发明实质和范围的前提下，对这些实施方案中的物料成分和用量进行的各种改变或改动也属于本发明的保护范围。
实施例1
（1）分别配制含元素金、银的样品溶液（元素含量均为50ppb，硝酸酸度0.4 M）和0.3%的二乙基二硫代磷酸钠（DDTP）溶液, 然后采用蠕动泵分别以2毫升/分钟的流速抽取上述二个溶液，使两个溶液在一个三通管中汇合后发生反应。
（2）将产生的元素挥发物和反应后的溶液在一气液分离器中分离；
（3）从三通出口管流出的反应液立即流入到一气液分离器中，在这里通过鼓泡或喷雾的方式，分离出的元素挥发物（DDTC和元素的络合物）。该挥发物被导入原子光谱仪原子化或离子化器中进行光谱或质谱测定。所测得的元素灵敏度是同一条件下溶液不含DDTC时的25-40倍。可见测定的灵敏度具有很大的提高。详细图解见说明书附图1.
实施例2
（1）使含元素镍和钴的样品溶液（元素含量均为50ppb，硝酸酸度0.2M）和0.5%的二乙基二硫代磷酸钠溶液, 然后采用蠕动泵分别以1.5毫升/分钟的流速抽取上述二个溶液，使两个溶液在一个三通管中汇合后发生反应。
（2）将产生的元素挥发物和反应后的溶液在一气液分离器中分离；
（3）分离出的挥发物气体氢化物被导入一台电感耦合等离子体原子发射光谱中测定。所测得的元素灵敏度是同一条件下溶液不含二乙基二硫代磷酸钠溶液条件下的26倍。使用该方法获得的镍钴检出线分别为1ng/ml。详细图解见说明书附图1。
实施例3
（1）配制含元素镱的样品溶液（元素含量均为100ppb，硝酸酸度0.4M）和4.0%的二乙基二硫代磷酸钠溶液, 然后采用蠕动泵分别以2.5毫升/分钟的流速抽取上述二个溶液，同时将两个溶液加热到60摄氏度，然后使两个加热后的溶液在一个三通管中汇合后发生反应。
（2）将产生的元素挥发物和反应后的溶液在一气液分离器中分离；
（3）分离出的挥发物气体氢化物被导入一台火焰原子吸收光谱仪中测定。所测得的元素灵敏度是同一条件下溶液不含DDTP条件下的70倍。使用该方法获得的检出线为0.62ng/ml。详细图解见说明书附图2。
实施例4
（1）使含元素汞的样品溶液（元素含量均为10ppb，硝酸酸度0.4M）和0.25%的二乙基二硫代磷酸钠溶液, 然后采用蠕动泵分别以3毫升/分钟的流速抽取上述二个溶液，使两个溶液在一个三通管中汇合后发生反应。
（2）将产生的元素挥发物和反应后的溶液经过电感耦合等离子体原子发射光谱（ICP-AES）的雾化器（25PSI压力）喷雾到说明书附图1中的气液分离器中进行分离；
（3）分离出的挥发物气体被导入一台火焰原子吸收光谱仪中测定。所测得的元素灵敏度是同一条件下溶液不含二乙基二硫代磷酸钠条件下的60倍。使用该方法获得的汞检出线分别为0.05ng/ml。
实施例5
一种用于室温下通过元素生成挥发物来测定元素的方法及装置，其特征在于该装置包括1烷基二硫代磷酸（盐）溶液的导入管2、蠕动泵3、三通管4、气液分离器5载气入口6、载气出口7和废液排放管8；蠕动泵3抽取两个溶液后通过三通管后两股溶液混合，然后与气液分离器相连，气液分离器中含多孔玻璃烧结（或多孔塑料）板制成的透气不透水的半透膜板F，气液分离器设有载气入口，和载气入口，分离气体挥发物的废液被蠕动泵带动经废液排放管8排出。
在详细说明的较佳实施例之后，熟悉该项技术人士可清楚地了解，在不脱离上述申请专利范围与精神下可进行各种变化与修改，凡依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均属于本发明技术方案的范围。
Claims (7)
1.一种通过元素生成挥发物来测定元素的方法，其特征在于将水溶性的烷基硫代磷（膦）酸（盐）的溶液与待测元素溶液在线混合，混合后的溶液立即进行气液分离测定，使挥发性元素络合物进入到元素分析仪进行检测；其中混合后溶液中烷基硫代磷（膦）酸（盐）的溶液与待测元素溶液的比例浓度为0.02-3%（m/V）；烷基硫代磷（膦）酸（盐）的溶液与混合后溶液的酸度为0.001-3M的待测元素溶液，混合后的溶液的温度度是室温。
2.权利要求1所述的方法，其中烷基硫代磷（膦）酸（盐）为烷基硫代磷酸，烷基硫代次磷酸，烷基硫代亚磷酸或它们与碱金属或碱土金属元素所生成的溶于水的盐。
3.权利要求1所述的方法，其中烷基硫代磷（膦）酸（盐）为：二乙基二硫代磷酸或它与碱金属、碱土金属及氨形成的溶于水的盐。
4.权利要求1所述的方法，其中待测元素指的部分主族元素、部分过渡元素、贵金属元素和稀土元素。
5.权利要求1所述的方法，其包括如下步骤：
（1）使用蠕动泵分别以1-3毫升/分钟的相等速度连续抽取质量浓度为0.05-0.5%的二乙基二硫代磷酸钠溶液和酸度为0.025-0.8M的含元素样品溶液；
（2）使两股溶液在一微型三通管内汇合反应，然后立即在气液分离器中进行气液分离；（3）分离出的气体被导入原子光谱仪中进行测定，其中混合后的溶液温度是室温。
6.一种通过元素生成挥发物来测定元素的装置，其特征在于该装置包括含元素的样品溶液导入管（1）、含烷基硫代磷（膦）酸（盐）溶液的导入管（2）、蠕动泵（3）、三通管（4）、气液分离器（5）、载气入口（6）、载气出口（7）和废液排放管（8）；蠕动泵（3）抽取两个溶液后通过三通管（4）后两股溶液混合，然后与气液分离器（5）相连，气液分离器中含多孔玻璃烧结或多孔塑料板制成的透气不透水的半透膜F，气液分离器（5）设有载气入口（6）和载气入口（7），分离气体挥发物的废液被蠕动泵（3）带动经废液排放管（8）排出，为提高反应效率，在紧邻三通管（4）的前或后面的管路带有加热装置（9）。
7.权利要求1所述通过元素生成挥发物来测定元素方法在用于化学气相沉积及无机镀膜气态先驱物的制备方面的应用。
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| CN106198391A (zh) | 2016-12-07 |
| CN107462569B (zh) | 2020-01-14 |
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