10101-50-5

There are numerous reports in the literature about the amount of hydrate water in sodium permanganate, which is said to be between one half and three water molecules per Na[MnO4]. Because no structural descriptions of the hydrate and the anhydrous compound can be found yet, this work reports the synthesis of anhydrous Na[MnO4] via the Muthmann method and its crystal structure. Na[MnO4] crystallizes as dark purple needles in the monoclinic space group P21/n with a = 572.98(5), b = 842.59(7), c = 715.47(6) pm, β = 92.374(3)° and Z = 4. As such and with its isotype to Ag[MnO4], Na[MnO4] completes the series of anhydrous alkali-metal permanganates, comprising Li[MnO4] (orthorhombic, Cmcm, Cr[VO4] type) and the isostructural heavier congeners A[MnO4] (A = K, Rb, Cs; orthorhombic, Pnma, Ba[SO4] type).

An oxygen transfer agent comprising a metal-boron oxide is provided. The average oxidation state of the metal in the metal-boron oxide is about 3+, and has 10% or less of a stoichiometric excess in moles of Mn with respect to the boron. The oxygen transfer agent may further comprise a magnesia-phosphate cement. The oxygen transfer agent is capable of oxidatively dehydrogenating a hydrocarbon feed at reaction conditions to produce a dehydrogenated hydrocarbon product and water. The oxidative dehydrogenation can take place under reaction conditions of less than 1000 ppm weight molecular oxygen, or in the presence of more than 1000 ppm weight of molecular oxygen. Also provided are methods of using the oxygen transfer agents, and an apparatus for effecting the oxidative dehydrogenation of the hydrocarbon feed.

A simple and easy preparative route to obtain permanganic acid and permanganate salts from barium manganate and sulphuric acid is described. Sulphuric acid reacts with barium manganate to produce sparingly soluble barium sulphate and well-soluble permanganic acid or barium permanganate, these in turn can be used to prepare other metal permanganates.

The rate of outer-sphere electron transfer between MnO4- and MnO42- in aqueous MOH at constant ionic strength (1.1 mol L-1) is given by (k0 + kM[M+])[MnO4-][MnO4 2-], where k0 is defined by the activation parameters ΔH0* = 46 kJ mol-1, ΔS0* = -35 J K-1 mol-1, ΔV0°*(0.1 MPa, 318 K) = -23 cm3 mol-1, and Δβ0* ? -0.06 cm3 mol-1 MPa-1. For M = Li, Na, K, and Rb, respectively, kM is given by ΔHM* = 33.1, 32.2, 32.9, and 32.9 kJ mol-1 and ΔSM* = -67.8, -68.4, -62.9, and -59.0 J K-1 mol-1, while, for M = Na and K, ΔVM* = +3 and -1 cm3 mol-1. The activation parameters for the cation-independent reaction pathway can be accounted for by a modified semiclassical Marcus-Hush theory if, in the transition state for adiabatic or nearly adiabatic electron transfer, the reacting ions are taken to be enclosed within a common cavity in the solvent and the Mn-Mn distance compresses as does the cavity, which is assumed to have the same compressibility as the solvent itself. The lower enthalpies, and markedly more positive volumes, of activation for the M+-catalyzed pathway appear to arise at least in part from an easing of these solvational constraints.