EPR investigations on radiation induced chemical transformations in Pd(ClO4)2/i-PrOH/HClO4 system from 77 to 300 K.
The EPR studies have been carried out on gamma irradiated samples of Pd(ClO4)2 in 9 M/4M HClO4 in the presence and absence of isopropanol [i-PrOH (5%, v/v)], in the temperature range of 77-300 K. The EPR studies revealed the formation of Pd+ complex, Pd3+ complex and several radicals such as H., OH., ClO3., ClO4. and O3- on radiolysis of these systems. Reduction of Pd2+ to Pd clusters could not be observed in the absence of i-PrOH and warming of the irradiated sample finally resulted in recovery of Pd2+ complex. However, in the presence of 5% i-PrOH, strongly oxidizing radicals like OH., ClO3. and ClO4. are suppressed and (CH3)2C.OH radical was produced along with reducing species like H.. EPR spectra in these strongly reducing conditions showed formation of Pd+ complex, which on heating above 230 K, disproportionated into Pd0 and Pd2+ complex and finally lead to formation of Pd metal aggregates. Simultaneously, pulse radiolysis technique has been employed as an alternative method to verify the EPR observations.
Tripathi
S C
SC
RCS, Fuel Reprocessing Division, Bhabha Atomic Research Centre, Mumbai 400085, India. subhashtripathi@yahoo.com
Kadam
R M
RM
Kumar
Manmohan
M
Mittal
J P
JP
Mishra
S P
SP
D004578:Electron Spin Resonance Spectroscopy; D005720:Gamma Rays; D006358:Hot Temperature; D009942:Organometallic Compounds / Q000737:chemistry* / Q000528:radiation effects*; D010165:Palladium / Q000737:chemistry* / Q000528:radiation effects*; D011675:Pulse Radiolysis; D013696:Temperature
D009942:Organometallic Compounds; D010165:Palladium