, rate constants have been evaluated for the overall radiolytic decomposition of alkali metal nitrates. This kinetic scheme is applicable in the low dose range. At higher doses, however, the radiation induced reaction, NO
may also contribute. The overall rate constants are 0.13×10–6 (LiNO3), 1.05×10–6 (NaNO3), 10.10×10–6 (KNO3), 9.50×10–6 (RbNO3) and 25.50×10–6 (CsNO3) kGy–1.
Gamma-ray induced decomposition of some divalent nitrates, viz. Mg(NO3)2·6H2O, Ca(NO3)2·4H2O, Sr(NO3)2, Ba(NO3)2, Zn(NO3)2·6H2O, Cd(NO3)2·4H2O, Hg(NO3)2·2H2O, Mn(NO3)2·4H2O, Cu(NO3)2·3H2O and trivalent nitrates, viz. Al(NO3)3·9H2O, Fe(NO3)3·9H2O, Cr(NO3)3·9H2O, Y(NO3)3·6H2O, In(NO3)3·3H2O, La(NO3)3·6H2O, Ce(NO3)3·6H2O, Pr(NO3)3·6H2O, Bi(NO3)3·5H2O has been studied in solid state at room temperature. G(NO
) values (after applying appropriate dose correction) have been found to vary in the range 0.12–3.16 and 0.069–2.15 for divalent and trivalent nitrates respectively. G'-values were calculated by dividing G by the ratio of number of electrons in nitrate ion to the total number of electrons in the nitrate salt. Cation size, its polarizing power, available free space in the crystal lattice and the number and location of water molecules seem to play a dominant role in radiolytic decomposition. For Zn, Sr, In, La and Ce nitrates dose variation studies have been carried out.
Transition metal dithiocarbamate complexes, [M(S2CN(C2H5)(CH2CH2OH)] (M=Co, Ni, Cu, Zn and Cd) have been prepared and characterized by elemental analysis and infrared spectra. Thermal decomposition
of all the complexes occurs in two or three stages. The first stage in all the complexes is always fast with 65-70% mass loss.
In all cases the end product is metal oxide except in the case of cobalt complex which gives Co metal as an end product. During
decomposition of copper complex, first CuS is formed at ~300C which is converted into CuSO4 and finally CuO is formed. However, decomposition in helium atmosphere yields CuS. SEM studies of transition metal dithiocarbamates
reveal needle shape crystalline phase at room temperature and formation of metal sulphide/oxide at higher temperatures. The
activation energy varies in a large range of 33.8-188.3 kJ mol-1, being minimum for the Cu complex and maximum for the Zn complex possibly due to d10 configuration. In the case of Ni, Zn and Cd complexes the order of reaction is two suggesting bimolecular process involving
intermolecular rearrangement. However, in other cases it is a unimolecular process. Large negative values of ΔS# for all the complexes suggest that the decomposition process involves rearrangement.
Authors:R. Garg, V. Garg, I. Czakó-Nagy, S. Nagy, E. Kuzmann and A. Vértes
Mössbauer spectroscopy and X-ray diffractometry have been used to study Sm–Fe mixed oxides (with different SmFe atomic ratios) annealed at 550, 850, 1000 and 1250 °C. The room temperature Mössbauer spectra can be interpreted in terms of one, two or three sextets and in some cases by an additional doublet depending on the composition and the heat treatment. The sextets have been associated with SmFeO3 perovskite, Sm3Fe5O12 garnet and -Fe2O3 hematite. These results are in agreement with those of X-ray diffractometric measurements, which give a clear, evidence of the presence of these phases.
Authors:N. Joshi, S. Dhoble, V. Natarajan and A. Garg
Gamma-radiolysis of KNO3 in the matrix of some sulfates, viz. Na2SO4, K2SO4, KNaSO4, KNaSO4: Eu, KNaSO4: Ce, K3Na(SO4)2, K3Na(SO4)2: Eu and K3Na(SO4)2: Ce has been studied at an absorbed dose of 30 kGy.G(NO
) values calculated on the basis of electron fraction in all the sulfates are enhanced significantly. It is also affected by the nature of outer cation and the dopant lanthanide. Electron spin resonance (ESR) and thermoluminescence (TL) measurements show the formation of radical species SO
upon -irradiation. It is proposed that there radical species may transfer energy and interact with the radical species of nitrate (NO
, NO2, NO3 etc.) so as to enhance the decomposition. A possible mechanism has been proposed.
Authors:A. N. Garg, A. Kumar, G. Maheshwari and S. Sharma
Radioanalytical techniques have been applied in a study on (subclinical) hepatitis in Dobermann dogs. Cu levels in transcutaneous obtained full liver biopsies were quantified using INAA and 66Cu. A copper excretion study was performed in a group of completely normal Dobermann dogs and in six Dobermanns with elevated copper levels and suffering from subclinical hepatitis. 64Cu2+ was used to assess whether a normal bile flow and thus excretion was possible. All subjects underwent separately from this 64Cu2+ excretion study a 99mTc-Bis-IDA scintigraphy. The Cu levels in liver of these hepatitis patients vary from 600 to 1600 mg . kg-1 whereas 100-300 mg . kg-1 is probably normal for healthy Dobermann dogs. These Cu levels match fully with histopathology results and clinical observations. Measurements during a 2 years' evaluation period showed a clear relation between the existence of subclinical hepatitis and increased Cu levels without a sign for cholestasis or an abnormal bile flow.
Authors:B. S. Garg, R. Dixit, A. L. Singh and R. K. Sharma
Chromium(III) complexes of the type Cr(A)(A′)2, Cr(A)2(A′) and Cr(A)3 have been prepared (whereA is either piperidyldithiocarbamate or morpholyldithiocarbamate andA′ is glycine or oxine or acetylacetone moiety). The mixed ligand complexes have been charac terized by elemental analyses, magnetic susceptibility measurements and thermal studies. The complexes show magnetic moment in the range of 3.5–4.3 B.M. which corresponds to three unpaired electrons. TG studies have also been carried out, in order to study the mode of decomposition of the complexes and to evaluate various kinetic parameters.