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Technetium Chemistry, Oxidation States and Species

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Technetium Chemistry, Oxidation States and Species J. inorg, nucl. Chem., 1967, Vol, 29, pp. 681 to 691. PergamonPress Ltd. Printedin NorthernIreland TECHNETIUM CHEMISTRY, OXIDATION STATES AND SPECIES C. L. RULFS, R. A. PACER and R. F. HIRSCH Department of Chemistry, The University of Michigan, Ann Arbor, Michigan (Recewed14July1966) Abstraet--Pertechnetic and perrhenic acids behave as very strong acids, Ka ,~ l0 s. Their extensive dehydration to MzO7 in such media as 7 M sulphuric acid complicates a spectrophotometric com- parison of acid strengths. Chloroform extractable TcO~C1 forms from pertechnetate in the presence of chloride ion and concentrated sulphuric acid. The (VII) state of this compound is confirmed and its spectrum described. No evidence of unusual technetium (VII) species, in aqueous media of 1 N base to 1 N acid, has been found. The red colour of concentrated aqueous HTcO4 is ascribed to a lower (VI) or (V) state. The existence in alkaline media of a technetate, TcOsg-, species has been re-examined. Some (IV) and (III) state species are partially characterized, but no Tc~Os could be isolated. INTRODUCTION WHILS the chemistry of technetium closely parallels that of rhenium, any distinctions of behaviour in the sequence Mn-Tc-Re are of great interest. A chronological comparison of recent summaries of technetium chemistry(1-5) shows this to be a rather active area of study. The results of the present study are described in sections associated with species and oxidation states. The conventional techniques and equipment employed are described very concisely. Further detail is available in two recent theses. (6'7) EXPERIMENTAL Reagents. All technetium-99 material was obtained from the Oak Ridge National Laboratory, either as technetium metal powder or as ammonium pertechnetate solutions. Gravimetric or spectre- photometric assays were used to define solution concentrations. The material is of good purity; d.c.-arc emission and X-ray fluorescence spectra of the metal indicated the presence of only 40 ppm of Cu, 20 ppm Ru, 60 ppm Y and 20 ppm Zr. Some oxide coating, moisture and some sodium, are also present, but these are not disadvantageous for most types of experimentation. Technetium heptoxide was prepared by combustion of the metal in a stream of pure oxygen. The material was passed through three successive traps, (1) dry or containing distilled water (if HTcO4 was desired), cooled in ice-water, (2) dry trap cooled by dry ice--isopropanol bath, (3) safety trap of 1 M sodium hydroxide (only traces of activity ever reach this trap). A residual 5 per cent (1) G. E. BovI), J. Chem. Educ. 36, 3 (1959). (~) E. ANDERS, The Radiochemistry of Technetium, Nuclear Science Series 3021. National Academy of Science, National Research Council, Washington (1960). (a) j. W. COBBLE, Analytical Chemistry of Technetium, Part II, Chap. 43 Treatise on Analytical Chemistry (Edited by I. M. KoLa'riorF and P. J. ELVING). Interscienee, New York (1964). (4) R. COLTON and R. D. PEACOCK, Q. Rev. chem. Soc. 16, 299 (1962); R. COLTOI~, The Chemistry of Rhenium and Technetium. J. Wiley, London (1965). (B) K. SCHWOCHAU,Angew. Chem. 76, 9 (1964). (s) R. A. PACER, Investigation of the Analytical Chemistry of Technetium, thesis, University of Michigan, Ann Arbor (1965), (7) R. F. HIRSCH, Some Analytical Aspects of the Chemistry of Technetium, thesis, University of Michigan, Ann Arbor (1965). 681 682 C.L. RuLrs, R. A. PACER and R, F. HmscH or so of the metal tends to remain uncombusted in the boat, possibly due to a thin coating of sodium pertechnetate. This material is primarily technetium, but it may contain 0.1 per cent of sodium. Rhenium heptoxide was obtained from the Department of Chemistry at the University of Ten- ne,qsee. All other chemicals were of CP or AR grade, and Spectrochemical Grade solvents were used. Optical measurements. Beckman Model DU and DB spectrophotometers as well as the Cary Model 11 were used. Both 5-era and 1-em silica cells were used, and the Limit Research Corp. UVO 0.01--0.2-mm cells were used in the Beer's Law studies. A Perkin-Elmer Model 137 Infracord was used for a few measurements. A Schmidt and Haensch polarimeter was used with a sodium lamp and a 10-era capillary cell requiring less than 2 ml of solution. Electrochemical equipment. A Beckman Model G pH meter, a Fisher Elecdropode and a Fisher Powerhouse were used. The two latter items were components of a gas eoulometer assembly, doscribed elsewhere.~*~ Radiochemical counting. Evaporated aliquots on small planchets were sometimes counted with a thin-wall G-eiger tube and Nuclear-Chicago 151,A decade scaler. A Packard Tri-Carb 314 F scintillation counter was also used, operating on coincidence mode in integral position with the minimum counting window set just above electronic noise level. The counting solution contained 0.3 g dimethyl-POPOP, 7 g PPO and I00 g naphthalene per kilogram of dioxane. RESULTS Pertechnetic acid Potentiometrie neutralimetry. The acid, HTcO o has long been described, on the basis of potentiometric neutralimetry, ~9~ as being monobasic and strong. Ca) There is little evidence for the existence of a meso form, analogous with H3ReOs,C!°~ in other than strongly alkaline media. Based on the liquid-liquid extraction behaviour of their TBP complexes, KF.RTES and BECK infer the possibility that HReO4 is stronger than HTcO4. ~11~ A series of 0"23 M to 0"01 M solutions of HTcO 4 thermostatted at 25°C were titrated with approximately equivalent concentrations of carbonate-free NaOH. The apparent Ka values were calculated from stoicheiometricaUy-deduced concentra- tions of the acid and the base forms and from the pH readings during the course of the titration. The calculated Ka value decreased from 0"9 for 0.23 M solutions and 0.5 for 0.1 M to about 0.1 using 0.01 M solutions. Such behaviour is almost indistin- guishable from that observed with either HC1 or HReO 4 solutions, and the true ioniza- tion constant of HTcO, is too high to permit any discrimination by this means. Spectrophotometric method. In the case of a number of XO4 ions, such as CrO4 z:, MnO4-, ReO,- and VO4a-, CARRINGTON and SYMONS et al. re'x3) calculate ionization constants for the corresponding acids based upon the spectral differences found between solutions of their neutral salts and in media containing increasing concentrations of added H2SO4 or HC10 4. As strong acid is added to these systems the lower wavelength absorptions tend to decrease while a weak new absorption, which is ascribed to the protonated form, appears at longer wavelength. The significant change is ascribed to the reduction of tetrahedral Tn symmetry to C3~ for a YXOs species. ts~ G. B. S. SALARIA,C. L. RULFS and P. J. ELVING,Analyt. Chem. 35, 979 (1963). tg~ j. W. COaBLE,Doctoral thesis, University of Tennessee (1952). txo~ B. SCrlARNOW,Z. anorg, allg. Chem. 215, 185 (1933). txl~ A. S. KERTESand A. BECK,Proc. 7th Int. Conf. Co-ordination Chem. Stockholm, 352 (J'une 1962). tx2~ N. BAILEY,A. CARRINGTON,K. A. Loyr and M. C. SYMONS,d. chem. Soe. 290 (1960). ~xs~ A. CARRINGTONand M. SYMONS, Chem. Rev. 63, 443 (1963). Technetium chemistry,oxidation states and species 683 The assumption that condensations (or, dimerization and dehydration) such as, 2CRO42- q- 2H + = Cr2072- + HzO, are not observed appears to be based on constancy of molar absorptivities over a four-fold range of Cr(VI) concentration3TM Consistency of the results in HC104 is taken to imply that the dehydrating potency of sulphuric acid, formation of sulphate salts, etc. does not invalidate the technique. In our attempts to apply this method to HTcO 4 the system does not appear to behave as anticipated, and the need for further study and a re-examination of the HReO4 system became obvious. The behaviour of pertechnetate in perchloric acid is similar to its behaviour in the same molarities of sulphuric acid; the changes in absorbance at the peak wavelength are comparable. The peak at 2875 A, present in a neutral solution of NH4TcO4 (Fig. 1), remains unchanged for perchloric or sulphuric acid concentrations below 0.8 06 oE ¢/>o .o 0.4 <Z 0.2 I H2S04 ~ f 250 :500 350 Wavelength, rn~ Fro. 1.--Absorption spectra of pertechnetate ion, in neutral solution and in con- centrated suiphurie acid. about 7 M. The peak gradually disappears with increasing acid concentration, the half-way point being reached at an acid concentration of about 9"4 M. The new peak at 3400 A is weak, broad, and difficult to resolve because of the overlap from the more intense peak at 2875 A. The absorbance at 3400 A appears to be negligible and constant until an acid concentration of about 7 M is reached; then it increases until an acid concentration of about 11 M is reached. The absorbance of the peaks at 2440 and 2480 A seems to be strongly influenced by the growth of a new band at lower wavelength with increasing acid concentration. The situation is more complicated for perrhenate than with pertechnetate. The variation in absorbances in perchloric acid are much less prominent than those in the sulphuric acid series. The new absorbance at 2850 A arises with increasing concen- tration of sulphuric acid, starting from about 8 M, reaching the midpoint at about 12 M, and showing maximum development at about 15 M. The set of peaks around 2250 A appears to merge with the main peak at 2080 A, with the maximum absorbance in the most concentrated sulphuric acid solutions shifted to about 2120 A. No i1tl F. DANIELSet al. Experimental Physical Chemistry, (5th Edn) pp.
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