The Kinetics of the Thallium(I)--Thallium(III) Exchange Reaction

Prestwood, R. J.; Wahl, Arthur C.

doi:10.1021/ja01177a058

Cited by 41 publications

(20 citation statements)

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“…Sodium bisulphite treatment of a second aliquot reduced thallic ions to thallous, and the total thallium was precipitated as thallous chromate (5,14 For personal use only.…”

Section: Methodsmentioning

confidence: 99%

A Search for the Chemical Effects of Internal Conversion Following Radiative Neutron Capture

Maddock¹,

Maine²

1956

Can. J. Chem.

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The possibility that neutron capturc would lead t o oxidation, because of internal conversion of the capture radiation, has been investigated in solid compounds of the lower valence states of antimony, arsenic, cerium, chromium, and thallium. Except in the hydrated compounds, negative results have Iheen obtained. I t is possible that oxidation is followed by electron-transfer exchange in the irradiated solids. ISTRODUCTIONWhen an atom captures a thermal neutron, there results a highly excited compound nucleus which quicldy radiates its excess energy in one or more gamma-rays. Conservation of momentum requires that the emission of these gamma-rays imparts to the newly formed atom a recoil energy many times that required for brealiing chemical bonds. I t is also possible that one or more of the gamma-rays might be internally converted and in this instance, oxidation of the atom will result. Most studies on the chemical changes following thermal neutron capture have focused on the bond brealiing mechanisms, but there could be oxidation effects due to internal conversion, even if simple ionic solids were irradiated (10).The physical detection of internal conversion following radiative neutron capture is attended with some experin~ental difficulties; but with a 180° betaray spectrograph Hibdon and R/Iuehlhause (7) have detected the conversion electroils fi-om neutron capture in .i8Cd113, 66DylG4, 64Gdodd, 88Hg11)1), and 62sm149. Therinal neutron irradiatioil of ethyl bromide and iodide a t pressures of three microns leads to 12 to 50% of the radioactive atoms of the diffei-ent isotopes becoming positively charged as a result of internal convei-sion (16). Most of the gold and iridium recoil atoms which escape froin the surface of gold and iridium films during neutron irradiation are positively charged (12, 19).I t seemed possible that chemical methods might provide a more sensitive means of detection and estimation of the internal conversion. Radioactive perrhenate has been separated after dissolution of neutron-irradiated rhenium trichloride (6). Following the neutron irradiation of several hydratecl chi-omic salts, 3 to 10% of the radioactive chromium atoms were found in the hexavalent state upon solutioil and analysis of the crystals (4). EXPERIMENTALIn the present work, neutron irradiation of several simple inorganic salts with the cation in the lower of its two stable chemical valeilces was followed by dissolution of the solids in solutions coiltainillg as carriers cations of both valence states. There followed a chemical separatioil of the cations by a method l~llalzirscript received December 12, 1965

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“…Sodium bisulphite treatment of a second aliquot reduced thallic ions to thallous, and the total thallium was precipitated as thallous chromate (5,14 For personal use only.…”

Section: Methodsmentioning

confidence: 99%

A Search for the Chemical Effects of Internal Conversion Following Radiative Neutron Capture

Maddock¹,

Maine²

1956

Can. J. Chem.

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“…syfst#®* in perchloria acid telutioii, me otoesea md tii® work carried out In hitrio aoid soltitlons, thej fotind th@ depandenoe of th® rat« of •xohang© to tee first order in hoth ceriiimdll) 22) found the rate of the ©xehang® reaction to he d@pend®nt on the first power of both th® th&lllua(l) and thalliuffi(III) oonoentrntlono. Th®y also found th« r&te, in perchloric acid geltttidn®, deortased ae the l^dpogen Ion eoneentratlom…”

Section: Bmmmi Am Cosclusioms 69mentioning

confidence: 99%

Kinetics of the Exchange Reaction Between Two Oxidation States of Cerium

Parchen¹,

Duke²

1955

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“…That coulombic forces alone are not responsible for these reaction rates is indicated by the faster exchange between cerous and eerie ions (84) than between thaIIous and thaIIic ions (188), both in perchloric acid solution. The fact that some simple exchange reactions (involving transfer of one or of a fixed number of electrons) are slow indicates that rates are not necessarily fast when the oxidant donates the number of electrons required by the reductant.…”

Section: Isotopic Exchange Reactionsmentioning

confidence: 99%

“…Since none of these hypotheses was found satisfactory, Gryder proceeded to examine the extensive data recently collected on the thallous-thallic (62,97,188) and cerous-ceric (62,84,144) exchange systems. In the thallium system, rates have been found to vary positively with anion (nitrate) con centration, and negatively with acid strength.…”

Section: Isotopic Exchange Reactionsmentioning

confidence: 99%

“…In the case of Fe, the inter action absorption decreases with decreasing HCl concentration, and, in the absence of chloride ion, in perchloric acid solution, the absorption drops to that normally expected for the mixed ions; corresponding to this change, electron transfer between the iron species has been found to be slow (18,126,144,221) in perchloric acid solution. Similarly, solutions of mixed TIl and TIIII ions show no interaction absorption (154,231) and exhibit only slow exchange (97,188) of electrons. Davidson (231) suggests that the observed abnormal absor p tion results p rinci p aJly from interaction between elec tronically excited states of the ions involved, rather than between their ground states, and that the probability of electron transfer in such circum stances would be enhanced by the greater overlap of electronic wave func tions.…”

Section: Isotopic Exchange Reactionsmentioning

confidence: 99%

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