Palladium（II） and chloride ions tend to form complexes in aqueous solution. Both theoretical and experimental （by UV spec- trum） results indicate that there are four complexes formed in aqueous solution containing 3 mol/L hydrochloric acid and 20 mmol/L PdC12. This work evaluates the kinetics of electrochemical deposition of palladium on a Platinum electrode. For this purpose, palladium electrodeposition was investigated by means of cyclic voltammetry （CV）, potentiostatic current-time tran- sients （CTTs） and Tafel curve. By CTTs curves, the regions corresponding to the charge transfer control, mixed control and diffusion control were identified. In the diffusion control region, palladium electrodeposition mechanism was characterized as progressive nucleation with three-dimensional （3D） growth under diffusion control; as for the mixed control region, an adsorp- tion （1Ads）, ion transfer （liT）, and nucleation and growth （ING） model were proposed to analyze the current-time transients quan- titatively, which could separate the IAds, lit and IN~ perfectly.
To isolate and separate thorium from nitric acid solutions, three silica-based anion exchange resins were synthesized. Batch experiments were carried out to investigate adsorption behavior of thorium in nitric acid solutions. Adsorption at different concentrations of nitric acid and thorium, influence of contact time and coexisting metal ions, and effect of NO3– were investigated in detail. It was found that at high HNO3 concentrations,the resins exhibited higher adsorption capacity and better affinity towards thorium. The adsorption kinetics could be described by the pseudo-second order model equation, while the adsorption isotherms were well correlated by the Langmuir model. The maximum capacity towards thorium species on SiPyR-N4 was evaluated at 27–28 mg/g-resin. The thermodynamic parameters indicated the adsorption was an exothermic reaction. The presence of NO3– was found to promote the retention of the thorium species.
To separate MA （Am, Cm） and some fission product elements （FPs） such as Tc, Pd, Cs and Sr from high level liquid waste （HLLW） systematically, we have been studying an advanced aqueous partitioning process, which uses selective adsorption as the separation method. For this process, we prepared several novel adsorbents which were immobilized in a porous sili- c^polymer composite support （SiO2-P）. Adsorption and separation behavior of various elements was studied experimentally in detail. Small scale separation tests using simulated HLLW solutions were carried out. Pd（II） was strongly adsorbed by the AR-01 anion exchanger and effectively eluted off by using thiourea. Successful separation of Pd（ll） from simulated HLLW was achieved. Te（VII） also exhibited strong adsorption on AR-01 and could be eluted off by using U（IV） as a reductive eluent. Am（Ⅲ） presented significantly high adsorbability and selectivity onto R-BTP/SiOz-P adsorbents over various FPs including Ln（Ⅲ）. The R-BTP adsorbents were fairly stable in 3 M HNO3, but instable against 7-irradiation-3M HNO3. An advanced par- titioning process consisting of three separation columns for the target elements separation from HLLW was proposed and the obtained experiment results indicated that the proposed process is essentially feasible.
In this study,the electrochemical behavior of Pd(II)in nitric acid media was investigated using various electrochemical techniques.By analyzing the cyclic voltammogram of Pd(II)recorded at Pt electrode,a series of electrochemical reactions associated with palladium were recognized,indicating that Pd(II)undergoes a single step two-electrons irreversible process.Electroreduction reaction of Pd(II)and auto-catalytic reactions of nitrous acid are supposed to play a leading role in low and high concentrations of nitric acid,respectively.Stirring could facilitate the reduction of Pd(II)in relatively low nitric acid concentration(3 mol/L).The value of charge transfer coefficient was determined to be 0.18 for the measurements at 298 K.The diffusion coefficient of Pd(II)increased from 1.89×10 8cm2/s at 288 K to 4.23×10 8cm2/s at 318 K,and the activation energy was calculated to be 21.5 kJ/mol.In electrowinning experiments,SEM images of palladium obtained by electrolysis reveal the dendrite growth in all cases,which is uniform all over the entire surface of Pt electrode.The recovery ratios of Pd at different nitric acid concentrations are high,and the faradic efficiency of electrolysis decreases with increasing the nitric acid concentration.When stirring was introduced during electrolysis,the electrodeposition rate of Pd increased substantially.
