George H. Cady

Preparation of trifluoroacetates by the reaction of trifluoroacetic anhydride with certain oxides or oxosalts

Abstract : A number of procedures have been used in the past to prepare trifluoroacetates of many different elements. The present paper reports synthesis of the new compounds NaBi(CF3COO)4, NaAsO(CF3COO)2, Bi(CF3COO)3, Na2Te(CF3COO)6, NH4VO(CF3COO)3, VO2(CF3COO) and IO2(CF3COO), by the reaction of trifluoroacetic anhydride with suitable oxides or oxosalts. (Author)

Reaction of carbonyl fluoride with fluorine in the presence of various fluorides as catalysts

Abstract The fluorides KF, RbF and CsF have been known to serve as catalysts for the reaction CF 2 O + F 2 → CF 3 OF. The list of catalysts for this process has now been enlarged to include NaF, MgF 2 , CaF 2 , SrF 2 , BaF 2 and LaF 3 . Lithium fluoride and thorium fluoride also give CF 3 OF but are less active. Perhaps the substances CsF·HF, KAgF 4 and NiF 2 should be included in this list. Silver fluoride, usually as a mixture of AgF 2 with AgF, has been known to catalyze the reaction of CF 2 O with F 2 to give both CF 3 OF and CF 3 OOCF 3 . The proportion of the latter in the mixture of products increases with decreasing temperature. At 25°, the reaction is slow and the yield of CF 3 OOCF 3 is very high. It has now been shown that TIF 3 behaves like silver fluoride. It has also been shown that many other fluorides of metals give higher yields of CF 3 OOCF 3 than of CF 3 OF but require higher temperatures than AgF 2 (100- ca . 150°) to be effective. Various possible mechanisms for these catalytic processes are discussed.

Fluorine-Containing Compounds of Sulfur

Publisher Summary In the years since World War I1, a remarkable growth has occurred in the knowledge of compounds of sulphur, which contain fluorine. The number information about some substances known for many years, particularly, sulphur hexafluoride has expanded greatly. The reason for this growth is to be found largely in the awakened interest in fluorine chemistry initiated by the atomic energy program. A part of the effort devoted to fluorine chemistry in the universities, industrial laboratories, and government laboratories in the United States, England, Germany, and to a lesser degree Russia, hits been spent on compounds of sulfur. The laboratory that has been the most productive of published results is that of Cambridge University. A second factor that is responsible for the discovery of many new compounds is the electrochemical technique of Simons for the synthesis of fluorides by the electrolysis of hydrogen fluoride containing various solutes.

Solubility and reactions of perchloryl fluoride in water

Abstract Perchloryl fluoride (ClO 3 F) when dissolved in water reacts very slowly with the solvent. The solubility in water at one atmosphere pressure and temperatures up to 40°C is given by the equation, solubility (mol/l) = 6.387 x 10 −8 exp 6852/RT. The following reactions have been studied to learn their rate laws and rate constants: ClO 3 F + 2I − = I 2 + F − + ClO 3 − ClO 3 F + 2OH − = ClO 4 − + F − + H 2 O ClO 3 F + 3NH 3 (aq) = 2NH 4 + + HNClO 3 − + F − ClO3F + H 2 O = ClO 4 − + F − + 2H + At temperatures near O°C, perchloryl fluoride and water readily form a solid clathrate hydrate of highly variable composition. The observed minimum ratio of H 2 O to ClO 3 F in the solid is about 7.75.

The reaction of peroxydisulphuryl difluoride with antimony pentachloride

Abstract : The reaction of S2O6F2 with SbCl5 proceeded readily in the vicinity of 3C. In reactions involving a mole ratio of S2O6F2:SbCl5 slightly in excess of 2.5:1, an unstable antimony fluorosulfate was formed. This viscous orange liquid contained at least 4 fluorosulfate groups per atom of Sb. The substance slowly decomposed at 25C in vacuo liberating S2O5F2 and SO3. The orange oil was pumped to constant weight at 25C, and the non-volatile material which remained was a pale yellow solid. The pale yellow solid was found to contain a small amound of chlorine present in a positive oxidation state. In the case of reactions involving a large excess of S2O6F2, the results indicated that a stable antimony compound containing close to 3.5 fluorosulfate groups per atom of antimony was formed. Again chlorine was found to be present in a positive oxidation state, and it is possible that stabilization of the antimony compound occurred through partial formation of a complex R(+)(Sb(SO3F)6-xFx)(-) where R = Cl, ClO, or ClO2. (Author)

Composition of gas hydrates of CHClF2, CCl2F2 and SF6

Abstract Gas hydrates are forms of ice stabilized by the presence of molecules of gas occupying cavities in the solid water lattice. There are two common forms: structure I and structure II. The mean free diameters of the two types of cavities in structure I are about 5.0 and 5.8 angstroms. Very small gas molecules such as Xe or H 2 S can occupy both. In the past it has been considered that gas molecules of larger diameter than 5.0 angstroms could not occupy the smaller cavities. It has now been shown through measurement of hydration numbers of CHClF 2 (diameter about 5.4 angstroms) under various pressures at 0°, that some of the small cavities are filled. This state of affairs also exists for CH 3 Br. In structure II, the mean diameters of the two types of cavities are about 5.0 and 6.6 angstroms. Hydration numbers of SF 6 (diameter about 5.8 angstroms) and CCl 2 F 2 (about 6.2 angstromsm) show that nearly all of the large cavities but essentially none of the small cavities are occupied.