正辛醇的γ辐照稳定性及辐解产物分析.pdf

物理化学学报( Wuli Huaxue Xuebao)
988
Acta Phys. -Chim. Sin, 2010, 26(4): 988-992
April
Article
www.whxb.pku.edu.cn
正辛醇的γ辐照稳定性及辐解产物分析
俞初红张佳玮戴静彭静李久强翟茂林
(北京大学化学与分子工程学院,北京分子科学国家实验室,北京100871)
摘要:在高放射性废液后处理的萃取工艺中,正辛醇被认为是具有应用前景的稀释剂之一,而研究其y辐射效
应对指导其实际应用具有重要意义.本文对N2环境下γ辐照后的正辛醇进行了紫外-可见( Uv-vis)光谱和傅里
叶变换红外(FITR)光谱研究结果表明正辛醇在100kGy以下辐照后化学结构未发生变化,而吸收剂量増至300
kGy时有羰基化合物生成.通过色谱(GC)和色质联用GCMS)进一步分析了高剂量(600kGy)辐照后正辛醇的气
体及液体辐解产物,发现主要气体产物为H2并伴有微量的CO2和CH;主要液体产物为正辛醛,其占未辐解正
辛醇的质量百分含量小于1%,并伴有少量正庚烷和8-羟基十五醇对辐照后正辛醇的化学结构及辐解产物的分
析表明,正辛醇在氮气下经γ辐照后,主要发生碳原子上的C一H键断裂,并伴有B碳原子上的CC键断裂
此外,抽氢反应也是正辛醇辐解的重要途径.
关键词:化学结构;正辛醇;辐照稳定性;γ辐解产物;色谱分析
中图分类号:0644
Radiation Stability and Analysis of Radiolysis Product of 1-octanol
YU Chu-hong ZHANG Jia-wei DAI Jing PENG Jing LI Jiu-qiang ZHAI Mao-lin
(Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering,
Peking University, Beijing 100871, P. R. China)
Abstract: 1-octanol is a promising solvent for the extraction of high-level radioactive waste from nuclear fuel
reprocessing and a study of radiation effects on 1-octanol is necessary before its industrial application in high-radiation
environments. In this work, Uv-vis spectroscopy and Fourier transform infrared (FTTR)spectroscopy were used to
investigate the radiation stability of 1-octanol in nitrogen for the first time. Results indicate that 1-octanol is chemicall
stable at a dose of 100 KGY and that compounds containing a carboxyl group are formed at a dose of more than 300
KGY. The major radiolysis products of irradiated 1-octanol at 600 KGY were analyzed using gas chromatography(GC)
and gas chromatography-mass spectrometry(gc-ms). Hydrogen was formed as a major gaseous product and smal
carbon dioxide and methane were also found. The dominant liquid product was l-octanal and its mass
percent was less than 1% in the 1-octanol solution. Small amounts of heptane and 8-pentadecanol were also produced
Analysis of the chemical structure and radiolysis products of the irradiated 1-octanol suggests that during gamma
irradiation in nitrogen C-H bond breakage at the -carbon in I-octanol is the dominant reaction and the C-C bond
at the B-carbon can break as well. Additionally, hydrogen abstraction reactions occur between the primary H-atom
radical produced during irradiation and 1-octanol.
Key Words: Chemical structure; 1-octanol Radiation stability; -Radiolysis product; Chromatographic
analysis
随着能源需求的与日俱增和煤、石油等化石能效的替代能源之一.而发展核电会产生大量高放射
源的日益匮乏,替代能源的开发成为各国关注的焦性废液,它们对人类健康与生存环境将造成诸多潜
点.其中,核能被认为是能够满足人类需求,清洁高在危害.因此,高放射性废液的处理对人类健康以及
Received: November 27, 2009: Revised: February 22, 2010: Published on Web: March 9, 2010
Correspondingauthor.Email:peng@pku.edu.cn;Te/Fax:+86-10-62757193
C Editorial office of Acta Physico-chimica Sinica