Hydration numbers of some metal acetates, monochloroacetates and trichloroacetates in solution from ultrasonic velocity and conpressibility measurements

Ultrasonic velocities in aqueous solutions of some metal acetates, monochloroacelates and trichloroacetates, and the respective acids have been measured at 1 MHz frequency using the pulse technique. The ultrsonic velocity, adiabatic compressibility and apperent molal compressibility were measured as a function of concentration. The apparent molal compressibility values at infinite dilution were calculated and used to determine the hydration numbers.

Rare earth transition metal sulfides, LnMS3

Ternary rare earth transition metal sulfides LnMS3 with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS3, while the other LnMS3 sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.

Thermal analysis of hydrazinium metal sulphates and their hydrazinates

Thermal analysis of hydrazinium metal sulphates, (N2H5)2 M(SO4)-I, and their hydrazinates, (N2H5)2−M(SO4)23N2H4−II, whereM=Fe, Co and Ni have been investigated using thermogravimetry and differential thermal analysis. Type II compounds on heating decompose through an intermediate I and metal suphlate to the respective metal oxides.

Metallo crown porphyrins as ionophores-metal dependent uncoupling of mitochondrial energy potential

Porphyrins appended with crown ether moieties function as efficient uncouplesrs of oxidative phorphorylation in rat liver mitochondria. Permeation of these highly organized porphyrins decrease the respiratory coefficient index (RCI) values. Lowering of the RCI values parallels the number of K+ chelating crown ether groups attached to the porphyrins. The inhibitory effect upon the oxidative phorphorylation reaction depends on the nature of divalent metal ions, VO, Co, Cu and Zn in the porphyrin cavity and related to their relative tendency to complex intracellular K+ ions.

Metal complexes of thiophene 2-thiocarboxamide. Proton and 13C NMR, IR and electronic spectral studies

The complexes of thiophene 2-thiocarboxamide (TTCA) with some metal chlorides and bromides [M = Ni(II), Zn(II), Cd(II), Hg(II) and Cu(I)] are described. Elemental analyses, magnetic susceptibilities and conductance studies, electronic, IR, proton and 13C magnetic resonance spectra are reported. The results suggest exclusive coordination of TTCA through the thiocarbonyl sulfur. The influence of the thiophene ring on the donor properties of the thioamide are discussed.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

A Convenient Route for the Synthesis of Complex Metal Oxides Employing Solid-Solution Precursors

Synthesis of complex metal oxides by the thermal decomposition of solid-solution precursors (formed by isomorphous compounds of component metals) has been investigated since the method enables mixing of cations on an atomic scale and drastically reduces diffusion distances to a few angstroms. Several interesting oxides such as Ca2Fe03,5C, aCoz04,C a2C0205a, nd Ca,FeCo05 have been prepared by this technique starting from carbonate solid solutions of the type Ca,-,Fe,C03, Cal-,Co,C03, and Ca,-,,M,M'yC03 (M, M' = Mn, Fe, Co). The method has been extended to oxalate solid-solution precursors, and the possibility of making use of other kinds of precursor solid solutions is indicated.

Thermal reactivity of metal oxalate hydrazinates

Metal oxalate hydrazinates MC2O4·2 N2H4 where M=Mg, Mn, Fe, Co, Ni, Cu, Zn and Cd have been prepared and characterised by chemical analysis and infrared spectra. Thermal reactivity and decomposition of these oxalato complexes have been studied using thermogravimetry and differential thermal analysis. Hydrazinates of Mn, Fe, Co, Ni and Cu oxalates exhibit autocatalytic decomposition behaviour whereas the others do not. This phenomenon can be attributed to the presence of a bridged hydrazine as well as the thermal stability of the anhydrous metal oxalates.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.

A study on the reaction of silicon tetrahalides with phosphorus pentoxide and of alkali metal fluorosilicates with phosphorus pentoxide and sulphur trioxide

Silicon tetrahalides, SiX4 (X=F, Cl, Br) and the fluorosilicates of sodium and potassium react with phosphorus pentoxide above 300°C. The tetrahalides give rise to the corresponding phosphoryl halides and silica, while the fluorosilicates form the corresponding metal fluorophosphates and silicon tetrafluoride. The reaction of the fluorosilicates of sodium and potassium with sulphur trioxide occurs at room temperature to give rise to the corresponding metal fluorosulphates and silicon tetrafluoride.

Topochemically controlled hydrogen reduction of scheelite-related rare-earth metal molybdates

Scheelite-related -Ln2Mo3O12(Ln = La, Pr, Nd, Sm, Gd, Tb, or Dy) oxides are reduced by hydrogen at 780–870 K yielding molybdenum (IV) oxides of formula Ln2Mo3O9. The latter crystallize in a tetragonal scheelite (ABO4) type structure where one third of the A sites and a quarter of the anion sites are vacant: Ln2/3(cat)1/3MoO3(an). The reaction Ln2Mo3O12+ 3H2 Ln2Mo3O9(an)3+ 3H2O may be regarded as topochemically controlled, since both the parent and the product phases have scheelite-related structures. Infrared spectra and electrical and magnetic properties of these metastable defect scheelite phases are reported.

Electron paramagnetic resonance study of vanadyl ion in K2Zn(SO4)2·6H2O and K2Mg(SO4)2·6H2O

EPR study of the vanadyl ion has been carried out in its paramagnetically dilute form in K2Zn(SO4)2·6H2O and K2Mg(SO4)2·6H2O at room temperature at X-band. The vanadyl ion enters the divalent metal site and preferentially orients itself in the direction of the water molecules forming the octahedron and forms the vanadyl sulfate pentahydrate complex. The g and A tensorscorresponding to the two populous V-O orientations have been analyzed to obtain the principal values and their direction cosines with respect to the crystallographics axes. It is found that the g and A tensor have the same principal frames of reference within the limits of eperimental error. A correlation between the metal-water distance and the populations of the different V-O orientations is observed.

Thermal decomposition of alkali metal perchlorates

The effect of past mechanical history on the subsequent thermal decomposition kinetics of sodium, potassium, rubidium and caesium perchlorates, has been investigated. At low temperatures the decomposition of all these salts is significantly sensitized by pre-compression. At high temperatures, however, prior compression results in a lowered decomposition rate in the case of potassium, rubidium and caesium perchlorates and in an increase in the thermal reactivity of sodium perchlorate. The high temperature behaviour is shown to be an indirect consequence of the low temperature behaviour. The difference in behaviour between sodium perchlorate and the other alkali metal perchlorates is explained on the basis of the stability of the respective chlorates, formed during the low temperature decomposition. This is substantiated by experiments which show that the addition of sodium chlorate to sodium perchlorate brings about a sensitization while potassium perchlorate admixed with potassium chlorate results in a desensitization at high temperatures.

Three-component assembly of a metal-inorganic 3D Co(II) polymer containing bridging hydrazine

Three-component metal-inorganic assembly of a Co(II) network representing the first example of a 3D coordination polymer containing a hydrazine bridging ligand, has been synthesized and characterized.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.