Portland State University PDXScholar Dissertations and Theses Dissertations and Theses 1973 Synthesis of Uranium Fluorosulfates and the Group VI B Difluorophosphates Larry McCain Emme Portland State University Follow this and additional works at: https://pdxscholar.library.pdx.edu/open_access_etds Part of the Chemistry Commons Let us know how access to this document benefits ou.y Recommended Citation Emme, Larry McCain, "Synthesis of Uranium Fluorosulfates and the Group VI B Difluorophosphates" (1973). Dissertations and Theses. Paper 1593. https://doi.org/10.15760/etd.1593 This Thesis is brought to you for free and open access. It has been accepted for inclusion in Dissertations and Theses by an authorized administrator of PDXScholar. Please contact us if we can make this document more accessible: [email protected]. '\ AN ABSTRACT OF THE THESIS OF Larry ~1cCain Emme for the Master of Science in Chemistry August 10, 1973. Title: Synthesis of Uranium Fluorosulfates and Group VI B Difluoro­ phosphates APPROVED BY MEMBERS OF THE THESIS COMMITTEE: Gary L: Gard, Chairman M.-B. Silverman D. W. Barnum Some reactions leading to several anhydrous Uranium fluorosul­ fates through the use of fluorosulfonic acid or peroxydisulfuryl di- fluoride have been studied. It was found that HS0 F can oxidize uranium 3 metal to the +4 state or the +2 state depending on the reaction condi­ tions. The synthesis of the tan solid; U(S03F)4' and the pale green solid thought to be U(S03F)2 were prepa~ed in this manner. It was found that S206F2 can also oxidize uranium to yield the green solid U(S03F)3. S206F2 was also found to be a convenient reagent for placing a fluorosulfonate group on uranium tetrahalides to form addition or displacement products; the yellow solid UF4(S03F)2 and the tan solid U(S03F)4' were prepared in this manner. Other reactions involving the fluorosulfate, U(S03F)4' as a reactant are also discussed. Analytical data and infrared spectra are reported for the com­ pounds and x-ray powder data and magnetic susceptibility data are presented for U(S03F)2 and U(S03F)4. the reaction of the fluorinated anhydride ~-oxo-bis (phos­ phoryl d~fluoride), P203F4' with some group VI B metal oxide salts has found to form the corresponding difluorophosphates. Five new com­ pounds were prepared; KCr02(P02F2)3·P203F4' Cs 2Cr02(P02F2)4' Na2MO02 (P0 F )4' Na W0 (P0 F )4. Physical constants, analytical data and 2 2 2 2 2 2 • infrared spectra are presented supporting the proposed structures for these compounds. A method for the preparation of K2Cr0 (CF S0 )4 from K2Cr0 and 2 3 3 4 (CF3S02)20 is also presented. Analytical data, infrared spectra and the x-ray powder spectra for this compound are given. ;"4Ill SYNTHESIS OF URANIUM FLUOROSULFATES AND GROUP VI B DIFLUOROPHOSPHATES by LARRY McCAIN EMME * A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE in CHEMISTRY Portland State University 1973 TO THE OFFICE OF GRADUATE STUDIES AND RESEARCH: The members of the Committee approve the thesis of Larry McCain Emme presented August 10, 1973. G.L. Gard, Chairman M. "B. Silverman D. W. Barnum APPROVED: GarY.,L. Gard, Chairman, Department of Chemistry vav{d T. Clark, Dean of Graduate Studies and Research November 2, 1973 ACKNOWLEDGEMENT The author wishes to express his appreciation to Professor Gary L. Gard for his interest in this work; to Mr. Steven D. Brown for the preparation of the Peroxydisulfuryl Difluoride and for the instruction in vacuum line technique; and especially to Mr. Patrick J. Green who made arid repaired most of the glassware. 4 TABLE OF CONTENTS Page ACKNOWLEDGEMENT • • iii LIST OF TABLES vi LIST OF FIGURES • • vii CHAPTER I INTRODUCTION. 1 Fluorosulfates • 1 Difluorophosphates • • 6 II EXPERIMENTAL. • • • 10 Apparatus•••• • • 10 Physical Methods • • • 10 Reagents • • • 11 III SYNTHESIS OF URANIUM FLUOROSULFATES • 16 The Reaction of Fluorosulfonic Acid with Uranium Metal. • • • • • • • • • • 16 The Reaction of Peroxydisulfuryl Difluoride with Anhydrous Uranium Tetrachloride • • • • • • • • • • 22 Other Reactions Involving Peroxy­ disulfuryl Difluoride. • • • • • • 28 Behavior of S206F2 on UF4 • • • • • • • • 28 Behavior of S206F2 on U Metal. • • • • • •• 30 Reactions Involving Uranium (IV) Fluorosulfate as a Reactant 31 Reaction of CHJCN with U(S03F)4. • • • • •• 31 v Reaction of NaS0 F with U(S03F)4 • • • • •• 32 3 IV REACTIONS OF GROUP VI METAL OXIDE SALTS WITH FLUORINATED ANHYDRIDES. • • • • • • • 37 Reaction of ~-Oxo-bis(Phopshoryl­ difluoride) 'with Group VI B Metal Oxide Salts • • • • • • • • • • • 37 Introduction • • • • • • • • • • 37 Experimental • • • 38 Preparations••. • 38 39 KCr02 (P02F2 )3·P203F4 • • • • • • • • 39 cs2Cr°2 (P02F2 )4· • • • • • • • • 39 N82Mo02(P02F2)4· • • • • • • • • • • 40 4 Na2W02(P02F2)4·· • • • • Chemical Analysis • • • 40 Infrared Spectra •••• 40 0 47 Reaction of (CF3S02)2 with K2Cr04 • • • • • • • • Introduction • • • • • • 47 Experimental • 47 Preparation • • • 47 Chemical Analysis • • 47 Infrared Spectra. • • • ••• 47 X-Ray Powder Phot'ograph •• • • 47 BIBLIOGRAPHY • • • .'. • • ~5l LIST OF TABLES TABLES PAGE I X-Ray Powder Spectra for U(OS02F)2 • • • • • • • • •• 20 II X-Ray Powder Spectra for U(OS02F)4 ••• 26 III X-Ray Powder Spectra for Na2[U(S03F)6] 35 IV Analytical Data for Difluorophosphates 41 V Infrared Absorption Bands for Difluorophosphates • 42 50 VI X-Ray Powder Spectra for KzCr02 (CF3S03)4 ••••• LIST OF FIGURES FIGURES PAGE 1 F1uorosu1fonic Acid Storage Vessel 13 2 Infrared Spectrum of U(S03F)2 •• • • • • 21 3 Infrared Spectrum of U(S03F)4. • • • •• 27 4 Infrared Spe'ctrum of UF4 (S03F)2. • • • • •• 29 5 Infrared Spectrum of U(S03F)4·3CHJCN • • • • • • • •• 33 6 Infrared Spectrum of Na2[U(S03F)6]. • • • • • • • ••• J6 7 Infrared Spectrum of KCr02(P02F2)3·P203F4. • • 43 8 Infrared Spectrum of Cs Cr0 (P0 F )4 • • • • • •• 44 2 2 2 2 9 Infrared Spectrum of Na Mo0 (P0 F )4 • • • • • • • •• 45 2 2 2 2 10 Infrared Spectrum of Na W0 (P0 F )4. • • • 46 2 2 2 2 11 Infrared Spectrum of ~Cr02 (CF3S03)4 • • • 48 t CHAPTER I INTRODUCTION Flurosulfates FluOrosulfonic acid was first prepared in 1892 by Thorpe and Kirman (1) who obtained it by combining sulfur trioxide and anhy­ drous hydrogen fluoride, S03 + HF = HS03F " However, it was not until 20 years later that the first fluorosul­ fonate salts were prepared, when Traube studied the reaction of gaseous sulfur trioxide with ammonium or sodium fluoride. Traube described several ways to prepare fluorosulfates (2,3): a. The intereaction of gaseous sulfur trioxide with fluoride salts, NH4F + S03 = NH4S03F b. The reaction of fluorides with fuming sulfuric acid c. The dry heating of fluorides with pyrosulfates, Na S 0 + NaF =. Na SO + NaS0 F 2 2 7 2 4 3 d. The neutralization of an aqueous solution of fluoro­ sulfonic acid. ~. From aqueous solutions, Traube was only able to isolate the alkali fluorosulfates; attempts to isolate the salts of other metals re­ suIted in decomposition by hydrolysis. 2 The first method of Traube is the most common way of preparing fluorosulfates and has been a versatile route, as seen in the following reactions: S0 F (4,S) BaF2 + 2S03 = Ba( 3 )2 TlF. + ~S03 = TlS03~ (6) (7,8,9) Cl02F + S03 = Cl02S03F Fluorosulfonic acid has also been found to be an excellent fluorosulfonating agent. Meyer and Schramm prepared esters by reacting fluorosulfonic acid with alcohols or their corresponding ethers (10); " C H OH + HS0 F C H -O-S0 F 2 S 3 = 2 S 2 0 F (CBJ)2 + HS03F = CHJ-0-S02 Fluorosulfonic acid was also found by Traube (11) and later Calfee (12) to add directly to alkenes: HS0 F + CH = CH ·0-S0 F 3 2 4 2 S 2 HS03F + CH2CF2 = CHJCF2·O·S02F Other fluorosulfonates that have been prepared: nitrosyl fluoro­ sulfonate, NOS0 F, from dinitrogen trioxide and fluorosulfonic 3 acid (13); Nitronium fluorosulfate from dinitrogen pentoxide and fluorosulfonic acid (14); AlCl(S03F)2' SnC12(S03F)2' and TiC12(S03F)2 from the metal chloride and f1uorosu1fonic acid (15)_ F1uorosu1fates ..t have also been made (16) by the reaction of fodoalkanes and fluoro­ sulfonic acid, 3 CF CF CF I + HS0 F = CF CF CF -O-S0 F + HI 3 2 2 3 3 2 2 2 In addition to the general method of preparing the alkali, alkaline earth, and ammonium f1uorosu1fates through the use of sulfur trioxide, an alternative procedure has been used based on the reaction of f1uorosu1fonic acid with fluorides (17,18) or chlorides (19,20,21) accompanied by the liberation of HF or HC1_ The general scheme for these reactions is as follows (17): Mel + yHS0 F = MC1 (S03F) + y HC1 x 3 x-y y M'. Ti+4, sn+4, Ta+5, Sb+5 • Sometimes, however, chloride -, fluoride - and oxide f1uorosu1fates are formed during these reactions (15,17,21,22): M( S03F)x = MO(S03F)x_2 + S2 05F2 M - A1+3, Sb+3, Nb+5, W+6 .MC14 + 4HS03F = MF2,3(S03F)2,1 + (2,1) HC1 + 2,3HS03C1 M - Th+4, Zr+4 The first anhydrous f1uorosu1fates of transition metals were prepared in 1967 by Woolf (23)_ He prepared the anhydrous f1uoro­ sulfates of MD, Fe, Co, Ni, Cu, zn and Cd by displacement reactions in f1uoroS1,lfonic acid. He found that the ease of displacement in these heterogeneous reactions is in the decreasing order CH C0 -, 3 2 S04 -2 ,C1,- F. ­ Earlier observations of his (24) indicated that uranium metal dissolves in f1uorosu1fonic acid to yield a green solu­ tion, however, the reaction products were not characterized. The 4 green color of the solution suggested that uranium is in the +4 oxidation state. Study of the product in the present paper has yielded the identification of the compound, U(S03F)4' uranium tetrakisfluorosulfate. Other fluorosulfates have recently been made by the reactions of xenon fluorides with fluorosulfonic acid (2S): XeF6 ± HS03F = FSXeOS02F + HF XeF4 + 4HS03F = Xe(OS02~ + S206F2 + 4HF The reaction of peroxydisulfuryl difluoride, 8 0 F , with 2 6 2 sulfur dioxide to give trisulfuryl fluoride, S308F2' led Roberts 4 and Cady (26) to suggest the possibility that the reaction involved free radical formation due to the homolytic splitting of the oxygen­ oxygen bond yielding fluorosulfonate free radicals, ·OS02F, which then formed a bond with the central atom by unpairing the unshared electron pair.