Sakurada, Gisho

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RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:A New Method for Determining Tinand Antimony in their MixtureSakurada, GishoSakurada, Gisho. A New Method for Determining Tin and Antimony in their Mixture.Memoirs of the College of Science, Kyoto Imperial University. Series A 1931, 14(2): 73-781931-03-30http://hdl.handle.net/2433/256957A　New　Methed　for　Determining　Tin　and　　　　　　　　　Antimony　in　their　MixtureByGisho　SakuradaCReceived　February　28，　i　g3　i＞　　　　Since　tin　and　antimony　may，　without　much　difEculty，　be　trans；forined　into　the　oxide　forms　it　occurrecl　to　the　wrlter　that　this　propertymigbt　in　some　way　be　utilizect　for　the　quarititative　determination　ofthese　metals　existing　as　a　niixture．　Following　iip　this　iclea，　he　trans－formed　the　two　metals　simultaneously　into　a　mixture　of　their　oxidesby　treatin．cr　them　with　concentrated　nitric　acid，　and　the　oxide　mixturethtis　formed　was　i．crtSted　at　8000－8200　C．　for　half　can　hour，　and　weisrhed．The　mixture，　which　was　presumed　to　contain　tin　jn　the　form　of　SnOiand　antimotiy　in　that　of　SbL，04　was　now　treatec1　with　potassium　ioclidein　a　tartaric－hydrochloric　acid　soiution　in　order　to　reduce　antimonyto　the　antimonous　state　and　the　antimonv　thus　reduced　was　cleterminediodoinetrically．　As　is　sliown　in　，the　experimental　part，　the　resultsturRed　out　fairly　satisfactory，　sliowiltg　that　the　method　above　describedis　ac　pplicable　to　practical　purposes．　The　experiments　were　fvrtherextended　to　the　case　ii？　xvhich　tin　and　antinaony　form　a　ipixture　withanotker　metal　such　as　copper，　and　in　ehis　case　too　a　tolerably　goodresult　was　obtained．Experimental　Part　　　　1．　Analysis　of　a　sample　consisting　only　of　tin　and　antimony　　　　In　the　experiment　tin　and　antimony　obtained　from　Kah！baum　wereused．　The　purity　of　the　former　was　confirmecl　to　be　gg，gs　O／o　andthat　of　the　latter　gg，g80／o．　About　o．2－o．2s・grams　of　various　mixturescontaining　the　two　metals　in　different　proportions　were　welghed　out，and　left　to　stand　with　i　Q　c．c．　of　conc．　［［｛NO3　and　a　few　c．c．　of　water74 Gisho　Sakuradatill　the　fumes　of　nitri¢　oxlde　cea．　sed　to　be　evolved，　whereupon　．theexcess　of　nitric　acid　was　evaporatecl　off　ancl　the　residue　was　madeslightly　alkaline　with　ammonia　and　ag’ain　evaporate（1　tQ　dryness．　Themixture　of　oxldes　was　then　transferred　to　a　crucible　and　heatedg’r，3．dually　to　8000－8200　C．　cat　which　it　was　maintained　for　about　hal’Ean　hour．　The　heating　was　repeated　till　the　xvei．o．’ht　became　constE　n　t．To　the　oxicle　mixt“re　were　next　added　s－io　c．c．　of　i　o　Of・6　potassiumiodi［le　solution，　3－s　60’ranis　o£　tartaric　aeid，　40　c，c．　of　i：　N－1－ICI，　o．3　straznsof　potassitmi　chloride　and　i　o　c．c．　of　water，　and　the　mixture　was　heatedin　a　sancl－bath．　By　this　treatnient　tlie　atitlmony　ln　the　Sb204　wasrecluced　and　dissolved　as　antimonous　chloricle，　iocline　being　liberatedat　the　same　tiiirie，　thus，，．．．．．．．．　　　　　　　　　　　　Sb20べト6HC1十2HI二＝2SbC13十4H20十12、The　heatin．og　having　been　continued　till　all　tlie　iocline　was　nearlyevaporcated　off，　the　solution　was　treated　with　a　£ew　drops　of　clil．　sodiumthiosulphate　solation　iti　order　to　．cret　riC！　off　the　last　trace　of，iodine，ancl　neutralized　with　a　caustic　socla　or　soclium　carbonat，e　solution．　Thesolutlon　was　theik　diluted　to　200　c．c．　ancl　a　＄aturatecl　solution　of　socliumbicarbonate，　xvhich　must　be　tal〈en　in　the　proportion　of　r　o　c．c．　to　everyo．i　g’ram　of　mezallic　antimony，　xxras　added　to　it．　XVith　the　sol“tion亡hus　prepared，　ant量mQ臓y　was　ti亡rated　iodolnetrically　with　I／loNLiodillesolution．　I　rom　the　weig－ht　of　the　antiiMony，　the　weig．ht　of　the　Sb204was　calculated　by　n3ultiplylRg’　it　by　the　fcftctor　i．2663，　and　the　amount　ofthe　StiO2　ancl　therefore　that　of　the　tin　present　i．n　the　mixture　werecalculated　by　subtracting　the　weight　of　the　Sb2Qt　．froni　the　totcxl　welghtof　the　mixed　oxide．　The　results　are　shown　in　Table　1．Tic　ble　1No．Sn Sb Sn SnO2十S蓋）2049ms． D翫SbD三fLgms・ gms・ ％ Calc． Foαnd 9mS・9！ns・edulld 9血s・1 oρ236 o．2烹23 工0 α2988 o．2986 一α00Q2 C．2正20 一〇・◎◎Q32 O・0400 o．1597 20 o・2530 o・2531 十〇．OOOI o．王600 十〇・OGO33 o．Q672 oJ　575 30 o．2848 o．2850 十〇．OOO2 o．1573 一〇。OOO24 o・0875 o・正305 40 o．2764 Q．2766 十〇．OOO2 0・1304 一〇．OQQ王5 o．lo46 o・lo穿3 50 o．2648 o．2654 十〇．ooo6 0・IQ40 一〇・ooo36 o・H63 o．0782 60 o・2467 oβ482 キ。・oo王5 o・0779 一α00047 o．1367 o．0589 70 o．248エ o．2498 十〇．OOI7 oρ589 ±0・OQOOP8o・η43 o・0445 80 o．2776 o．2784 十〇．ooo8 0．0斗50 キ。・OQO5PA　IVew　Method　for　Detennining　Tin　and　Anti；moay　etc． 75　　　　As　is　seen　in　the　above　table，　the　value　of　the　two　oxides　is　alwaystoo　high　when　the　content　of　tin　in　the　mixture　becomes　greater　than60e／o．　Probably　this　is　due　to　the　fact　that　the　conversion　of　tinoxicle　2nto　the　form　of　SnO2　is　not　coinplete　at　800e－8200C．　The　errorthus　procluced　is，　however，　j．nsignificant，　when　the　content　of　tin　igless　than　soef／o．　　　　Several　experiments　were　conchictecl　to　learn　how　the　dehydrationof　tin　oxide　is　governed．　by　the　temperature，　and　the　results　shown　inTable　II　were　obtained．　　　　　　　　　　　　　　　　　　　　　　Tab支e　IIo，2037　gvam　of　tin　corresponding　to　o．2S86　gram　of　SnO2　were　employed．Ternperature780e8200　）18soe8700Time　of　ign｛tion　　in　llltllUteS0ξり00021」22SllO21？ounde．263go．26000．26000．2s870．2s87Di琵一i．o．ooS3十〇．OOI4　　）：十〇．OOOIJl　　　　［1）here　are　several　reports　on　the　temperature　suitable　for　theconversion　of　SbL，Os　into　Sb，．Oi．　Accorcling　to　・II．　Bilz，i　．Sb20s　changesinto　Sb，）04　at　4soe　ancl　the　latter　into　Sb203　at　i　o600．　T．　Carnelly　andT．　XVall〈er2　state　that　Sb204　is　stable　between　s8sOh－77sO，　whileBaubig’ny3　regards　the　temperature　between　7　soO－8soO　as　the　bestfor　the　quantltative　conversi．on　of　Sbf　O．s　into　Sb204，　xvhicli　graduallychanges　into　volatile　Sb203　at　tempeiatures　hig’her　thaR　gsoO．　Theresults　of　the　presetit　auth6r’s　experiments　were　found　to　agree　withthose　of　Bazibi．gny　comparatively　well．　The　transforniation　of　Sb20r，i．nto　SbL）Qi　was　found　to　proceed　very　slowly　ic　t　7　soO　and　on．　ly　at　8000一一W200　to　become　very　sipgnificaltt．　XVheR，　however，　the　temperaturewas　raised　hig’her　thcan　8400C，　loss　due　to　the　formation　of　Sb203　wasunavoidable　as　is　seen　in　Table　III．王231ff．　Bilz：　Z．　f．　phys，　Chem．，　19，　38S，　i896．［1］．　Carnelly　＆　T．　Wallcei’：　J．　Chem．　Soc．，　5S，　86，　i888．Baubigny：　Compt．　rend．　124，　499，　i897・76 Gisho　SakuradaTable　II工Sb204№高刀ETemperatし1re：£ime　oC　ignitiQn　　，　　　　　　　　　　　，　　1n　mmutesLoss　in　weiσht　　　　　　　　b@　　gms・o．3178O．025Qn・24298400W50。W50。30H0R0o・oo36O・oo95O・1534　　　　Though　stannic　tin　is　not　reducect　by　hydrogen　iodlde，　the　endpoint　in　the　titration　o£　antimoRy　becomes　indistinct　unless　some　tartaricacid　js　adclecl　to　the　solutioR．　In　the　solution　in　which　tjn　exists　ina　larpgq　excess，　titration　o£　antimony　caimot　be　conducted　accuratelyeven　in　the　presence　o£　tartaric　acid，　as　is　shown　in　Tab1e　IV，　　　Table　IVSb　usecl　：　o．rogo　gm，nS銭mσbo．050．1”393’4000st｝tTartat’ic　acid　　　gms．30355057　　bgms．Fotind　　　o．10900．1044－O・IOSs　　　o，io88　　　0．io8g　　　o．io87　　　0＋Io73？　　　o．zo84？Diff．　士0、0000－o．oo46－3S　－O．ooO2　一一〇．OOOI　－O．ooO3　－O．OO王7～　一　o．ooo6　PRemarksF”nd　point　some“rhatindistinct．End　point　indistinct．Somewhat　indistin¢t’．）t　　　　II．　Analysis　of　a　sampie　containing’　some　other　meta｛s　besiclqs　　　　　　　　£in　and　．IRtimolly．　　　　To　see　how　the　above　metltod　for　determining　tin　and　antimonycan　be　applied　to　the　analysis　of　a　sample　containing’　other　metalsalso，　an　alloy　consist量ngg　of　tin，　antimony　and　copper　was　anaユysed　inthe　following　way　：一　　　　〇，3　gram　Of　tl｝e　alloy　was　diss　olved　in　40　c．c．　of　concentratedAiVew　Method／brエ）etermining．窃πa勉d遅πあ〃zony　etc． 77hydrochloric　acid　containin．cr　some　bromine，　and，　the　solution，　afterhaving　been　conceritrated　to　20　c．c．　in　a　water－bath，　was　neutralizeqwith　caustic　soda　aRd　dilk｝ted　to　i　so　c．c．　Now　so一一ioo　c．c．　of　thesodium　sulphide　solution　prepared　by　dissolving’　60　gms．　of　Na2S　glff20and　40　grns．　of　NaOH　in　！ooo　c．c．，　3－s　gms．　of　tartarlc　acid　and　s　c　c．of　a　saturated　solution　of　sodium　acetate　were　added　to　the　solutionand．　the　whole　heated　in　a　sand　bath　till　copper　sulphide　had　com－pletely　subsided．　lt　was　then　filtered　and　the　precipitate　was　washedwith　water　containing　sodium　acetate　and　sodi“m　sulphide，　and　thefiltrate　tog’ether　with　tke　washings　was　acidifie．　d　with　HCI　so　as　toprecipitate　the　sulphides　of　tin　and　antimony．　To　make　the　precipita－tion　of　the　sulphides　complete，　i　o　c．c．　of　a　saturated　solutlon　of　am－moRium　nitrate　was　added　to　the　solution　in　which　the　sulPhjdes　weresuspended　and　a　current　of　hydrogen　stilphide　was　passed　into　it．The　sulphides　were　then　filtered　and　washeC｛　as　usual　arid　dried．The　dried　precipitatei　was　left　to　stand　in　a　closed　vessel　containingsome　fuming　nitric　acicl，　in　order　to　expose　the　precipitate　to　a　nitricaeid　gas　atmosphere．　By　this　treatment　the　sulphides　were　gradyiallyoxidized，　sulph“r　being　set　free．　After　the　nitric　acid　still　adheringto　the　precipitate　had　been　driven　off，　the　precipitate　was　washed　withalcoh　ol　and　carboR　blsulphide　and　then　with　alcohol　and　ether　s．　ucces－sively，　anc1　finally　i．crnited　in　a　crucible．　lt　ls　here　to　be　noted　thatthe　ignition　！nust　be　conducted　ic　t．　first　very　gradually，　othexxvig．　e　thesulphur　sti11　remainlng　aces　upon　the　oxides　in　the　manner　representedin　the　following　equationS，　before　it　ls　completely　oxidized　to　sulphurdioxide　：一　　　　　　　　　　　　SnO2　十　3S　一一　SnS2　十　SO2　　　　　　　　　　　　Sb204十sS　＝＝　Sb2S3十2SO2．　．　　　　When　the　evolution　of　sulphur　dioxide　had　ceased　the　temperaturewas　raised　to　800”一8200　and　the　heating　was　cont．inued　till　the　weightbecame　constant．　Sometimes　sttlphuric　acicl　forn？ecl　by　oxidationobstinately　adheres　to　SnO2，’　ln　such　a　case　a　sinall　qiiantity　of　ammo－r！iurn　car，　bonate　sliould　be　addecl　and　lg’nitecl．　The　resu！ts　were　asshown　in　Table　’V’．　　i．　Sulphides　adhering　to　the　filter－paper　were　vemoved　by　dissolving　them　in　amnioniumsulphide　and　recovered　by　evaporating　the　ammonium　sulphide　soiution　to　dryness．87 Gis’ho　Sakuinda．　’　A　New　Method　etc．Table　V　　　・mo．s珠Q2＋Sb2049ms・ 　SbX1ns・eou1｝d…’　Sn・@gms・SbD9m『・Sh刀DCalc． FαmdD嵐№高r・工）眠r№高刀E@　　昏・　i　　　　　　　　　　．　　．@　　　．o．O188@　　　　0・0475@　　　　0．H84@　　　　0．1820　　内D｝　　　’p．エ692PO・1901Do．H85O・o尋5尋IOQ0T0W0　　、　内B．238工@　卜p・3010O・300ヰB．2886o．2378O．3006O・3002O．2917一〇・ooo3|O・0004|OOOO2¥〇．QO31oJ6go潤D王899O．H．V9O．04542一〇．0◎02�黶Z．0002|o・ooo6．．D士○．OOOO　　　　The　authoi’］X（Ilotool〈i　IYillatsui，was　carried　out．tal〈es　thls　opportunity　waermly　to　thaiA〈　IPro£essorunc！er　whose　g’uidaiice　and　encouragement　this　worl〈

A New Method for Determining Tin and Antimony in their Mixture

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A New Method for Determining Tin and Antimony in their Mixture

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