K.C. Malhotra

Nature of the compounds of thallium(III) chloride with amides and ureas

Abstract Thallium(III) chloride forms compounds of composition TlCl 3 ·base and TlCl 3 ·2base with amides, ureas and thioureas. On the basis molar conductance, molecular weight and IR spectral studies, TlCl 3 ·base has been formulated as [TlCl 2 ·2base] + [TlCl 4 ] t - while the compound TlCl 3 ·2base is a dimeric chlorine bridged 6-coordinated thallium compound.

Behaviour of some iodine compounds in disulphuric acid

Abstract IPO 4 and I(OAc) 3 form I(HSO 4 ) 2 + ions while I(SO 3 X) 3 forms I(SO 3 X) 2 + when dissolved in disulphuric acid, but IOAc, IBr, ICN and INO 3 form paramagnetic blue solutions due to I 2 + ions. From UV, magnetic susceptibility, cryoscopic and conductance studies, their modes of decomposition in disulphuric acid have been proposed. Mixed cations of the type IX 2 + and I 2 X + have been prepared by the oxidation of iodine compounds by chlorine and bromine in disulphuric acid.

Behaviour of some Th(IV) and U(VI) compounds in disulphuric acid

Abstract Th(IV) oxide, -nitrate, -acetate, -sulphate and chloride form H 2 [Th(HSO 4 ) 6 ] when dissolved in disulphuric acid, which behaves as monobasic acid of the system. At higher concentration, H 2 [Th(HSO 4 ) 6 ] is slightly polymerised. U(VI) oxide, uranyl sulphate, uranyl carboxylates and uranyl chloride form UO 2 (HSO 4 ) 2 when dissolved in disulphuric acid which polymerises at higher concentration. U(VI) chloride gets solvolysed to form the acids H[U(HSO 4 ) 7 ] or H 2 [U(HSO 4 ) 8 ] which behave as non electrolytes in disulphuric acid.

Halogen cations of selenium in disulphuric acid

Abstract Selenium tetrachloride and bromide form SeX 3 + ions whereas selenium monochloride and bromide form Se 4 2+ and SeX 3 + ions, when dissolved in disulphuric acid. In disulphuric acid containing chlorine and bromine, selenium forms SeX 3 + ions, selenium monochloride forms Se 2 Cl 3 + and Se 2 Cl 2 Br + whereas selenium monobromide forms Se 2 Br 3 + , Se 2 X 3 + disproportionates to form SeX 3 + and Se. Similar ions are formed when halogens are added to the yellow solutions of selenium (Se 4 2+ ) ions in disulphuric acid. All attempts to prepare the iodo derivatives of selenium in disulphuric acid have failed.

Fused monochloroacetic acid solvent system—II: Conductance studies of protonic acids and bases in fused monochloroacetic acid

Abstract Conductance measurements on protonic acids such as HSO 3 F, HClO 4 , HSO 3 Cl, H 2 S 2 O 7 , H 2 SO 4 , HBr, HNO 3 , CH 3 O 3 SH, CF 3 COOH, CHCl 2 COOH and p -toluene sulphonic acid have been carried out in fused monochloroacetic acid at 93·0 ± 0·5°C. Λ 0 values have been determined which show them to be fairly ionised in monochloroacetic acid. The role of monochloroacetic acid as a differentiating solvent has also been explored. Triple ion formation is indicated by the plots of log c vs log Λ c Similar trends have been observed for bases. From Λ 0 values of various bases CH 2 ClCOO − ion has been shown to be produced by autoionisation of this solvent. Strong protonic acids have been used as titrants for the estimation of weak bases in this medium.

Solution chemistry in fused monochloroacetic acid—V: Solvolytic reactions of Lewis acids in monochloroacetic acid and the nature of the solvolysed products

Abstract Tetrachlorides of tin, titanium, zirconium, thorium and silicon form compounds of composition SnCl 2 (CH 2 ClCOO) 2 , Ti(CH 2 ClCOO) 4 , Zr(CH 2 ClCOO) 4 , Th(CH 2 ClCOO) 4 and Si 2 O(CH 2 ClCOO) 6 when refluxed with excess of monochloroacetic acid. From i.r., molecular weight and conductance studies, their structures have been elucidated. Their Lewis acid character is established by isolating and characterising their adducts with organic tertiary bases. Antimony pentachloride, aluminium trichloride and ferric chloride form compounds of composition SbCl 2 (CH 2 ClCOO) 3 , Al(CH 2 ClCOO) 3 , FeCl(CH 2 ClCOO) 2 and Fe(CH 2 ClCOO) 3 when refluxed with excess of solvent and these have been characterised by i.r. studies.

Nature of the compounds of 2,2′-bipyridyl dioxide 1,10-phenanthroline dioxide and pyridine n-oxide with thallium(III)chloride

Abstract Thallium(III)chloride forms compounds of composition TiCl 3 ·PhenO 2 , TlCl 3 ·BipyO 2 , 2TlCl 3 ·3BipyO 2 and TlCl 3 ·3PyNO with 1,10-phenanthroline dioxide, 2,2′-bipyridyl dioxide and pyridine N-oxide. From conductance, cryoscopic and IR spectral studies their structural type has been elucidated.