{"created":"2023-06-20T15:05:54.003259+00:00","id":35257,"links":{},"metadata":{"_buckets":{"deposit":"7435ec13-dc88-4a9d-b0ae-7176e9171157"},"_deposit":{"created_by":1,"id":"35257","owners":[1],"pid":{"revision_id":0,"type":"depid","value":"35257"},"status":"published"},"_oai":{"id":"oai:jaxa.repo.nii.ac.jp:00035257","sets":["1887:1890","1896:1898:1899:1993"]},"author_link":["421421","421420","421422","421423"],"item_9_alternative_title_1":{"attribute_name":"その他のタイトル","attribute_value_mlt":[{"subitem_alternative_title":"四エチル鉛の調製"}]},"item_9_biblio_info_10":{"attribute_name":"書誌情報","attribute_value_mlt":[{"bibliographicIssueDates":{"bibliographicIssueDate":"1927-12","bibliographicIssueDateType":"Issued"},"bibliographicIssueNumber":"29","bibliographicPageEnd":"420","bibliographicPageStart":"409","bibliographicVolumeNumber":"2","bibliographic_titles":[{"bibliographic_title":"東京帝國大學航空研究所報告"},{"bibliographic_title":"Report of Aeronautical Research Institute, Tokyo Imperial University","bibliographic_titleLang":"en"}]}]},"item_9_description_16":{"attribute_name":"抄録","attribute_value_mlt":[{"subitem_description":"四エチル鉛は夙に1854年に發見された有機性鉛化合物で、近年に到る迄は單に化學的興味の一化合物に過ぎなかつたのである。然るに輓近に此の物質を極微量にガソリン又は燈油に加へて内燃機關燃料として使用する時は、此等燃料の内燃機關内におけるKnockingを防止することが判り、其の需要が増加するに到つた。然るに其の工業的製法は未だ充分に明かでないが、一般に其の原料としては臭化エチル又は沃化エチルを使用する。四エチル鉛の一製法としてグリニアール反應を應用する方法に就ても、其の原料としては臭化エチル又は沃化エチルを使用する。從て臭素又は沃素の資源が豐富でなければならぬ。然るに若し夫等の代りに鹽化エチルを原料として使用し得れば、其の安價にして又其の資源の豐富なるが爲めに、四エチル鉛の工業的生産に甚だ便利である。然るに從來夫れが用ひられなかつたのはグリニアール反應を開始することが困難なる爲めであつた。本研究は鹽化エチルを原料としグリニアール反應に依り四エチル鉛を調製する方法、四エチル鉛の精製法及び純四エチル鉛の性状に關する研究である。先づグリニアール反應に依り、鹽化エチルから鹽化エチルマグネシウムを生成するに當り、其の反應の開始が困難である。著者は其の反應の促進劑又は開始劑として略當量の沃素を溶解せる沃化エチル又は臭化エチルを乾燥エーテルに溶解したものが實際に甚だ便利であることを認めた。即ち此のものを極微量にマグネシウムに加へ、次に鹽化エチルを加へ、以て良好に鹽化エチルマグネシウムC_2H_5MgClの生成を行ひ得た。次に之れに鹽化鉛を作用せしめて粗製四エチル鉛を調製した。以上の粗製四エチル鉛は四エチル鉛の外に複雜なる鉛化合物を夾雜するから、之れを經濟的の方法で精製しなければならぬ。著者は粗製四エチル鉛の性状を研究し、進で其の精製法を攻究し、終に粗製四エチル鉛を稀鹽酸の存在に於て、空気又は酸素にて處理し、四エチル鉛の精製を行ひ、同時に不純物は三エチル一鹽化鉛(C_2H_5)_3PbClの結晶として分離し、是れは再び鹽化エチルマグネシウムを作用せしめて四エチル鉛とする方法を見出した。此の精製法は比較的簡單で又損失も極めて尠いので經濟的の方法と考へられる。斯くして鹽化エチルに對し理論數の約74%の四エチル鉛を得た。著者は更らに純四エチル鉛の性状を精査した。即ち純四エチル鉛は特異の微臭を有する無色の液體で、之れに點火すれば長い火焔を以て燃え酸化鉛の白烟を放つ。比重(d^<18°>_<4°>)は1.6600、屈折率(n^<18°>_D)1.5206である。沸點は11mm.に於て81.6-82.0℃で、13mm.に於ては85.4-85.7℃である。是等の沸點はClausius-Capeyronの式及びTrautonの法則から計算したものに能く一致する。四エチル鉛は約400℃に於て分解し金屬鉛を分離する。常温に於ても空氣中に長く放置すれば〓濁を生じ、殊に直射日光は其の作用を促進する。而して分解した液はアルカリ性を呈し之れを鹽酸で中和すれば常に三エチル一鹽化鉛を生ずる。","subitem_description_type":"Abstract"}]},"item_9_description_17":{"attribute_name":"抄録（英）","attribute_value_mlt":[{"subitem_description":"Lead tetraethyl, known as a powerful antiknock material, may be prepared by the reaction of ethyl magnesium iodide or bromide (Grignard's reagent) with lead chloride. In this method, it is known that ethyl iodide or ethyl bromide is a good starting material, whereas ethyl chloride can not be used for the sake of very weak activity. The present authors have found that an ethereal solution containing ethyl iodide (or bromide) and iodine was a suitable catalyser for the reaction between ethyl chloride and magnesium. When this solution was added to magnesium, ethyl magnesium iodide C_2H_5MgI was instantaneously formed and the latter accelerates catalytically the reaction between ethyl chloride and magnesium. After the reaction once started between ethyl chloride and magnesium, the subsequent reaction is accelerated by ethyl magnesium chloride C_2H_5MgCl formed. Then the crude lead tetraethyl may be readily prepared by the reaction of ethyl magnesium chloride and lead chloride. The crude lead tetraethyl containing a considerable proportion of unsaturated lead triethyl was treated with air or oxygen in presence of dilute hydrochloric acid, by which lead tetraethyl remained unchanged, and lead triethyl was converted into crystalline mass of triethyl lead chloride (C_2H_5)_3PbCl. The latter was then transformed into lead tetraethyl by the action of ethyl magnesium chloride, with the yield of 95% of the theory. The total yield of lead tetraethyl to the amount of ethyl chloride used was approximately 74% of the theory. The pure lead tetraethyl had a specific gravity (d^<18°>_<4°>vac.) of 1.6600, refractive index (n^<18°>_D) of 1.5206, and boiling point of 81.6-82.0℃. at 11mm. or 85.4-85.7℃ at 13mm. It decomposes at about 400℃., separating metallic lead. Other properties were also investigated.","subitem_description_type":"Other"}]},"item_9_description_32":{"attribute_name":"資料番号","attribute_value_mlt":[{"subitem_description":"資料番号: SA4146407000","subitem_description_type":"Other"}]},"item_9_publisher_8":{"attribute_name":"出版者","attribute_value_mlt":[{"subitem_publisher":"東京帝國大學航空研究所"}]},"item_9_publisher_9":{"attribute_name":"出版者（英）","attribute_value_mlt":[{"subitem_publisher":"Aeronautical Research Institute, Tokyo Imperial University"}]},"item_9_source_id_24":{"attribute_name":"書誌レコードID","attribute_value_mlt":[{"subitem_source_identifier":"AA00387631","subitem_source_identifier_type":"NCID"}]},"item_creator":{"attribute_name":"著者","attribute_type":"creator","attribute_value_mlt":[{"creatorNames":[{"creatorName":"田中, 芳雄"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"桑田, 勉"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"TANAKA, Yoshio","creatorNameLang":"en"}],"nameIdentifiers":[{}]},{"creatorNames":[{"creatorName":"KUWATA, Tsutomu","creatorNameLang":"en"}],"nameIdentifiers":[{}]}]},"item_files":{"attribute_name":"ファイル情報","attribute_type":"file","attribute_value_mlt":[{"accessrole":"open_date","date":[{"dateType":"Available","dateValue":"2020-01-24"}],"displaytype":"detail","filename":"SA4146407.pdf","filesize":[{"value":"530.2 kB"}],"format":"application/pdf","licensetype":"license_note","mimetype":"application/pdf","url":{"label":"SA4146407.pdf","url":"https://jaxa.repo.nii.ac.jp/record/35257/files/SA4146407.pdf"},"version_id":"b53e8356-db45-4800-9aef-aff023928e8c"}]},"item_language":{"attribute_name":"言語","attribute_value_mlt":[{"subitem_language":"eng"}]},"item_resource_type":{"attribute_name":"資源タイプ","attribute_value_mlt":[{"resourcetype":"departmental bulletin paper","resourceuri":"http://purl.org/coar/resource_type/c_6501"}]},"item_title":"On Preparation of Lead Tetraethyl.","item_titles":{"attribute_name":"タイトル","attribute_value_mlt":[{"subitem_title":"On Preparation of Lead Tetraethyl.","subitem_title_language":"en"}]},"item_type_id":"9","owner":"1","path":["1890","1993"],"pubdate":{"attribute_name":"公開日","attribute_value":"2015-03-26"},"publish_date":"2015-03-26","publish_status":"0","recid":"35257","relation_version_is_last":true,"title":["On Preparation of Lead Tetraethyl."],"weko_creator_id":"1","weko_shared_id":-1},"updated":"2023-06-20T23:23:14.589835+00:00"}