Authors:K. Venkatesan, T. Srinivasan, and P. Vasudeva Rao
Mesoporous silica (MCM-41) with d(100) interplanar distance of 38 Å was prepared by a room temperature process through low surfactant templation technique. The surface of MCM-41 was functionalized with dithiocarbamate (dtc) ligand, named as MCM-41-dtc and this was characterized by X-ray diffraction, BET surface area, particle size analysis, 29Si MAS NMR spectra and sulphur analysis. The sorption of mercury from 0.1M HCl solution by MCM-41-dtc was studied as a function of pH, [Hg2+], time and temperature. The sorption data obtained at various initial concentrations of mercury were fitted into Langmuir adsorption model. Mercury speciation in solution and the sorption capacity measurements indicated possible formation of a 1 : 1 square planar complex in the solid phase. A very rapid sorption of mercury was observed in the initial stages of equilibration, which can be attributed to the large surface area, wide porosity and fine particle size of MCM-41-dtc, facilitating facile accessibility of mercury into the inner pores of the sorbent. The enthalpy change accompanied by the sorption of mercury was found to decrease from 83.7 to 6.2 kJ/mol, when the initial concentration of mercury was increased from 5.10-4M to 1.5.10-3M.
Authors:M. Jayakumar, K. Venkatesan, T. Srinivasan, and P. Vasudeva Rao
The electrochemical behavior of ruthenium(III) and rhodium(III) in nitric acid medium has been studied at platinum and stainless
steel electrodes by cyclic voltammetry. The cyclic voltammograms consisted of surge in cathodic current occurring at potentials
of −0.13 V (Vs. Pd) and −0.15 V (Vs. Pd), which culminates into peaks at −0.47 V and −0.5 V due to the reductions of Ru(III)
and Rh(III) to their metallic forms, respectively. Electrodeposition was carried out at stainless steel electrode and unlike
palladium, the recovery of ruthenium and rhodium was limited to ~4% and ~14%, respectively. However, a different scenario
was observed in case of electrodeposition from a ternary solution containing all these platinum metals. Ruthenium and rhodium
deposited underpotentially in the presence of palladium and the recovery of ~20% and ~5% was observed for ruthenium and rhodium,
respectively. Evolution of RuO4 at the anode and deposition of RuO2 in the anodic side was observed in all cases during electrolysis of ruthenium(III) containing solutions.
Authors:Alok Rout, K. Venkatesan, T. Srinivasan, and P. Vasudeva Rao
Extraction of europium(III) from nitric acid medium by a solution of tri-n-butylphosphate (TBP) and n-octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) in the room temperature ionic liquid, 1-alkyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide
(amimNTf2 where a = butyl or hexyl or octyl), was studied. The distribution ratio of (152+154)Eu(III) in TBP-CMPO/bmimNTf2 was measured as a function of various parameters such as the concentrations of nitric acid, CMPO and NaNO3. Remarkably large distribution ratios were observed for the extraction of europium(III) when bmimNTf2 acted as diluent. The stoichiometry of metal-solvate in organic phase was determined by the slope analysis of extraction
Authors:K. Venkatesan, V. Sukumaran, M. Antony, and T. Srinivasan
The commercially available crystalline silicotitanate inorganic ion exchanger, IONSIV IE-911, and its parent precursor, TAM-5,
have been evaluated for the removal of 137Cs from nitric acid medium and simulated high-level liquid waste. The distribution coefficient (Kd) of cesium decreased with increasing nitric acid concentration and at 3.0 M nitric acid, a distribution coefficient of 1150
mL/g and 2600 mL/g were obtained for IONSIV IE-911 and TAM-5, respectively. Rapid uptake of cesium followed by the establishment
of equilibrium occurring within three hours. Loading of cesium in ion exchangers increased with the increase in the concentration
of cesium in aqueous phase and from Langmuir adsorption model the apparent capacity of cesium was 69 mg/g and 82 mg/g for
IONSIV IE-911 and TAM-5, respectively. The performance of the sorbent under dynamic conditions was assessed by following a
breakthrough (BT) curve up to C/Co = 1, where C and Co are the concentrations of cesium in the effluent and feed, respectively.
Authors:B. Srinivasan, K. Mathew, U. Narayanan, W. Guthrie, and T. Sampson
The calorimetry exchange (CALEX) program is administered by New Brunswick Laboratory (NBL). The main objective of the program
is to provide an independent verification of the internal quality control practices in nuclear material safeguards facilities
making plutonium accountability measurements by non-destructive calorimetry/gamma spectrometry techniques. Facilities measure
the calorimetric power, and plutonium and 241Am isotope abundances of CALEX program standards using routine accountability procedures. The measurement results as well
as two other quantities (effective specific power and plutonium mass) calculated from these results are evaluated for accuracy
(or bias) and precision. In this paper, a limited number of measurement results of a CALEX program standard (identified as
Calex I) are evaluated with specific goals to identify a suitable method for uncertainty estimation and to identify the major
contributors to the uncertainties. In order to achieve the goals, the Calex I measurement results were evaluated using two
different methods: the first method confined to uncertainty estimation from random variations of the measurement results alone,
and the second method providing a more comprehensive evaluation of uncertainties from both the measurements and the characterized
values of the measured standard according to the Guide to the Expression of Uncertainty in Measurement (GUM). The results
of this study, and a subsequent study extended to a larger number of results in the CALEX program database, are expected to
provide relevant input for developing the International Target Values for plutonium measurements by the calorimetry/gamma
Authors:Ch. Jagadeeswara Rao, R. Venkata Krishnan, K. Venkatesan, K. Nagarajan, and T. Srinivasan
Three different room temperature ionic liquids (RTILs) namely protonated betaine bis(trifluromethylsulfonyl)imide ([Hbet][Tf2N]), N-butyl-N-methylpyrrolidinium bis(trifluromethylsulfonyl)imide (BMPyTf2N) and N-methyl-N-propylpiperidinium bis(trifluromethylsulfonyl)imide (MPPiTf2N) were synthesized and characterized by CHNS analysis, NMR and FTIR spectroscopy. Heat capacity measurements and thermogravimetric
analysis of these RTILs were carried out and the results are reported in this paper.
Authors:K. Venkatesan, K. Shyamala, M. Antony, T. Srinivasan, and P. Vasudeva Rao
Batch and dynamic extractions of uranium(VI) in 10−3–10−2M concentrations in 3–4M nitric acid medium have been investigated using a commercially available phosphinic acid resin (Tulsion
CH-96). The extraction of uranium(VI) has been studied as a function of time, batch factor (V/m), concentrations of nitric acid and uranium(VI) ion. Dual extraction mechanism unique to phosphinic acid resin has been established
for the extraction of uranium(VI). Distribution coefficient (Kd) of uranium(VI) initially decreases with increasing concentration of nitric acid, reaches a minimum value at 1.3M, followed
by increases in Kd. A maximum Kd value of ∼2000 ml/g was obtained at 5.0M nitric acid. Batch extraction data has been fitted into the linearized Langmuir
adsorption isotherm. The performance of the resin under dynamic extraction conditions was assessed by following the breakthrough
behavior of the system. Effect of flow rate, concentrations of nitric acid and uranium ion in the feed on the breakthrough
behavior of the system was studied and the data was fitted using Thomas model.
Authors:Biju Joseph, K. Venkatesan, K. Nagarajan, T. Srinivasan, and P. Vasudeva Rao
Lithium assisted electrochemical reduction of U3O8 in the room temperature ionic liquid (RTIL), N-methyl-N-propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPiNTf2), was studied to explore the feasibility of using RTILs for direct electrochemical reduction of uranium oxide at near ambient
temperature. The electrochemical behavior of Li+ in MPPiNTf2 at stainless steel electrode was investigated by cyclic voltammetry and chronoamperometry. The cyclic voltammogram of LiNTf2 in MPPiNTf2 at 373 K consisted of a surge in cathodic current occurring at a potential of −2.8 V (vs. Fc/Fc+) due to the reduction of Li(I) to metallic form. The nucleation phenomenon observed in the voltammogram was investigated
by chronoamperometry. Electrodeposition of metallic lithium on U3O8 particles contained in a stainless steel (SS) basket was carried out to examine the feasibility of reducing U3O8 to metallic form. The results are discussed in this paper.
Authors:K. Chandran, Tarun Kumar Sahoo, P. Muralidaran, V. Ganesan, and T. G. Srinivasan
Thermal decomposition of neat TBP, acid-solvates (TBP·1.1HNO3, TBP·2.4HNO3) (prepared by equilibrating neat TBP with 8 and 15.6 M nitric acid) with and without the presence of additives such as uranyl nitrate, sodium nitrate and sodium nitrite, mixtures of neat TBP and nitric acid of different acidities, 1.1 M TBP solutions in diluents such as n-dodecane (n-DD), n-octane and isooctane has been studied using an adiabatic calorimeter. Enthalpy change and the activation energy for the decomposition reaction derived from the calorimetric data wherever possible are reported in this article. Neat TBP was found to be stable up to 255 °C, whereas the acid-solvates TBP·1.1HNO3 and TBP·2.4HNO3 decomposed at 120 and 111 °C, respectively, with a decomposition enthalpy of −495.8 ± 10.9 and −1115.5 ± 8.2 kJ mol−1 of TBP. Activation energy and pre exponential factor derived from the calorimetric data for the decomposition of these acid-solvates were found be 108.8 ± 3.7, 103.5 ± 1.4 kJ mol−1 of TBP and 6.1 × 1010 and 5.6 × 109 S−1, respectively. The thermochemical parameters such as, the onset temperature, enthalpy of decomposition, activation energy and the pre-exponential factor were found to strongly depend on acid-solvate stoichiometry. Heat capacity (Cp), of neat TBP and the acid-solvates (TBP·1.1HNO3 and TBP·2.4HNO3) were measured at constant pressure using heat flux type differential scanning calorimeter (DSC) in the temperature range 32–67 °C. The values obtained at 32 °C for neat TBP, acid-solvates TBP·1.1HNO3 and TBP·2.4HNO3 are 1.8, 1.76 and 1.63 J g−1 K−1, respectively. Cp of neat TBP, 1.82 J g−1 K−1, was also measured at 27 °C using ‘hot disk’ method and was found to agree well with the values obtained by DSC method.
Authors:K. A. Venkatesan, B. Robert Selvan, M. P. Antony, T. G. Srinivasan, and P. R. Vasudeva Rao
Commercially available polystyrene-divinylbenzene (PS-DVB) resins functionalized with isothiouronium (Tulsion CH-95), phosphinic
acid (Tulsion CH-96) and methylene thiol (Tulsion CH-97) moieties have been used for separating palladium from nitric acid
medium. Extraction of palladium has been studied as a function of time, concentration of nitric acid and palladium. The distribution
coefficients (Kd, ml/g) of palladium on sulfur based resins (Tulsion CH-95 and Tulsion CH-97) are higher (5000-104ml/g in 0.1M nitric acid) than on Tulsion CH-96 resin and decrease with increasing concentration of nitric acid. The initial
rate of extraction of palladium by Tulsion CH-95 and Tulsion CH-97 resins was very rapid and the time required for the establishment
of equilibrium was a function of palladium concentration in the aqueous phase. The rate data could be fitted by a second order
rate equation and the magnitude of rate constant for the extraction of palladium by these resins (~102M-1. min-1) decreased in the order of: Tulsion CH-95 > Tulsion CH-97 > Tulsion CH-96. The extraction isotherms of Tulsion CH-95 were
fitted by Langmuir adsorption model and the coefficients were obtained by regression. The extraction capacity of palladium
on Tulsion CH-95 was found to be ~20 mg/g at 3M nitric acid. Column experiments have been conducted and the data were fitted
using Thomas model. A column utilization of 75% was achieved for the extraction of palladium by Tulsion CH-95 resin.