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</style><!--[if gte mso 10]> <style> /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal" / mso-tstyle-rowband-size:0 / mso-tstyle-colband-size:0 / mso-style-noshow:yes / mso-style-priority:99 / mso-style-qformat:yes / mso-style-parent:"" / mso-padding-alt:0in 5.4pt 0in 5.4pt / mso-para-margin-top:0in / mso-para-margin-right:0in / mso-para-margin-bottom:10.0pt / mso-para-margin-left:0in / line-height:115% / mso-pagination:widow-orphan / font-size:11.0pt / font-family:"Calibri","sans-serif" / mso-ascii-font-family:Calibri / mso-ascii-theme-font:minor-latin / mso-fareast-font-family:"Times New Roman" / mso-fareast-theme-font:minor-fareast / mso-hansi-font-family:Calibri / mso-hansi-theme-font:minor-latin / mso-bidi-font-family:"Times New Roman" / mso-bidi-theme-font:minor-bidi / } </style> <![endif]--><span style="font-size: 12pt / font-family: &quot / Times New Roman&quot / ,&quot / serif&quot / ">The objective of this study was thus to prepare highly proton condictivity membranes that are cheap to manufacture and have low methanol permeability. &nbsp / &nbsp / </span></p>

see pdf

Thesis (Ph. D.)--Institute of Paper Chemistry, 1962. / Includes bibliographical references (p. 87-88).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1952. / Includes bibliographical references (p. 66-68).

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</style><!--[if gte mso 10]> <style> /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal" / mso-tstyle-rowband-size:0 / mso-tstyle-colband-size:0 / mso-style-noshow:yes / mso-style-priority:99 / mso-style-qformat:yes / mso-style-parent:"" / mso-padding-alt:0in 5.4pt 0in 5.4pt / mso-para-margin-top:0in / mso-para-margin-right:0in / mso-para-margin-bottom:10.0pt / mso-para-margin-left:0in / line-height:115% / mso-pagination:widow-orphan / font-size:11.0pt / font-family:"Calibri","sans-serif" / mso-ascii-font-family:Calibri / mso-ascii-theme-font:minor-latin / mso-fareast-font-family:"Times New Roman" / mso-fareast-theme-font:minor-fareast / mso-hansi-font-family:Calibri / mso-hansi-theme-font:minor-latin / mso-bidi-font-family:"Times New Roman" / mso-bidi-theme-font:minor-bidi / } </style> <![endif]--><span style="font-size: 12pt / font-family: &quot / Times New Roman&quot / ,&quot / serif&quot / ">The objective of this study was thus to prepare highly proton condictivity membranes that are cheap to manufacture and have low methanol permeability. &nbsp / &nbsp / </span></p>

Philosophiae Doctor - PhD / The objective of this study was thus to prepare highly proton condictivity membranes that are cheap to manufacture and have low methanol permeability.

The isomer distribution in the sulfonation of iodobenzene at -12.5°C. with sulfur tr~oxide (S-35) in liquid sulfur dioxide was found to be 1.40 ± 0.11% ortho, 0.34 ± 0.11% meta, and 98.26 ± 0.11% para. Pure sodium salts of each of the isomers were made from the corresponding aminobenzenesulfonic acids. After dilution with an aliquot of the sulfonation mixture, the salts were purified by recrystallization and were counted by liquid scintillation counting. Attempts to determine the relative rate of sulfonation between toluene and iodobenzene failed. The radioactive sodium p-iodobenzene sulfonate could not be separated from sodium p-toluenesulfonate by recrystallization. The lithium amides of methylamine, ethylamine, isopropylamine, tert-butylamine and 2-aminopropane-2-d were prepared from phenyl lithium and the amines. Infrared spectra of the amides were scanned in the C-H region. Comparison of the spectra of the amides and the amines showed no shifts like those found for the corresponding alcohol-alkoxide spectra. It was therefore concluded that anionic hyperconjugation could not account for the shift in the spectra of the alcohol-alkoxide system. The behavior of cyclooctatetraene, the silver adduct of cyclooctatetraene, norbornadiene, diphenylacetylene, tetraphenylcyclobutadiene-palladium chloride and ferrocene was studied under high pressures ranging from 15 to 55 kats. and with temperatures from 25 to 850°C. This work was carried out with Hall's tetrahedral anvil apparatus. If the temperature was high enough each of these compounds was found to decompose. When the temperature was below the decomposition temperature, cyclooctatetraene, diphenylacetylene and norbornadiene polymerized. No evidence of a valence tautomerization was found. The silver adduct of cyclooctatetraene and tetraphenylcyclobutadiene-palladium chloride decomposed at high temperatures. No other results were noted with these two compounds. Ferrocene underwent decomposition by iron catalysis to a mixture of iron carbides at pressures from ambient to 55 kats. and temperatures above 500°C. The same products were observed if no iron was added and the temperature and pressure were 55 kats. and 800°C., respectively. A preliminary spectrophotometric study of benzonitrile in 25%-ethyl alcohol-75% water was carried out. Cupric bromide and hydrobromic acid or cupric chloride and hydrochloric acid were added to constant ionic-strength solutions of benzonitrile. No evidence was found in the ultraviolet region for any complex ion formation. The same results were found for p-fluorobenzonitrile.

Part I. The rearrangement of α-anilinoketones was studied in an effort to determine the mode of movement of the nitrogen moiety. A crossover experiment was carried out with an equimolar mixture of 2-(4- bromoanilino)-1-(4-bromophenyl)-2-(4-methoxyphenyl) ethanone and 2-(4-chloroanilino)-1-(4-chlorophenyl) -2-(4-methoxyphenyl)ethanone with γ- picoline hydrobromide as the catalyst. The reaction product was analysed by means of a mass spectrograph. The results of the analysis indicate a crossover of the nitrogen moiety during rearrangement. This indicates that the nitrogen moiety moves in an intermolecular manner during the rearrangement. Part II. The isomer distribution from the sulfonation of bromobenzene with sulfur trioxide was determined by the isotope dilution technique. Bromobenzene was sulfonated with labeled sulfur trioxide (S-35) in refluxing sulfur dioxide and aliquots of the reaction mixture were added to equimolar quantities of the pure isomeric bromobenzenesulfonic acids. Each isomer was then recrystallized until a constant count rate was obtained. The isomer distribution was then obtained by comparing the activity of the individual isomers to the sum of the activities of all three isomers. This gave the following results: Ortho, 0.6 ± 0.2; Meta, 3.6 ± 0.8; Para, 95.9 ± 0.6. A competitive sulfonation between bromobenzene and toluene was run using sulfur trioxide (S-35) in liquid sulfur dioxide as the sulfonation agent. An isotope dilution technique was used to obtain the relative amounts of sulfonated bromobenzene and toluene in the reaction mixture. The relative rate of sulfonation of toluene to bromobenzene is 9.4. Comparing this with the toluene-benzene rate ratio of 29.5 gives a bromobenzene-benzene rate ratio of 3.1. Part III. Cycloöctatetraene and ferrocene have been submitted to very high pressure (up to 92 kiloatmospheres) and in the case of ferrocene moderate temperatures have been simultaneously applied (up to 900° C.). Cycloöctatetraene when held at pressures in excess of 54 kiloatmospheres for longer than one hour breaks down into a transparent solid and low boiling liquid. The identities of the solid and liquid have not been determined. Ferrocene breaks down into a mixture of iron carbides as shown by the x-ray powder pattern. This breakdown occurs at 605°C. at a pressure of 24.3 kiloatmospheres and the temperature of decomposition is proportional to the pressure with a proportionality constant of 0.74 kiloatmosphere/°C.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第24836号 / 医博第5004号 / 新制||医||1068(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 安達, 泰治, 教授 森本, 尚樹, 教授 上杉, 志成 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

Kinetic investigation of the hydrochlorination of cyclohexene and cis-2-butene in n-heptane with SnCl4 as catalyst shows that the reaction is second order with respect to both olefin and catalyst. The specific rate constants at 25° , 0° and -23.8°C and the activation parameters were determined. Investigation of the Ga2Cl6 catalyzed hydrochlorination of cyclohexene and cis-2-butene in dichloromethane indicates that alkylation and polymerization compete with the hydrochlorination reaction in the presence of the solvent. The relative reaction rates and the isomer distribution for the sulfonation of iodobenzene by S35O3 have been determined in refluxing SO2 at -10°C. The reaction resulted in 98.4 ± 1.1 % para, 1.1 ± 1.0% meta and 0.8 ± 0.5% ortho substitution. The partial rate factors determined were Pf 2.2, Mf 0.013, Of 0.009. The relative rate ratios k(C6H5CH3/C6H5I) and k(C6H5I/C6H6) were 29.0 ± 7.2 and 0.37 ± 0.10, respectively. The high para partial rate factor indicates that a significant difference exists between the Brown-Hammett selectivity relation and experimental determination.