3 : CHEMSPEC Debye-Hückel Davies [1] [23] 10 UO 2 (NO 3 ) 2 -NaF UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 - NaF CHEMSPEC UF 6 CHEMSPEC (components) ( 3 UF 6

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1 CHINESE JOURNAL OF INORGANIC CHEMISTRY Vol.25 No.3 386~390 ( ) * : CHEMSPEC UF 6 ; UF 6 ph Al 髥 F - U 髩 ph : ; CHEMSPEC; ; UF 6 ; : O614.62; O : A : (2009) Application of Speciation Analysis Method in Uranium Technology CHEN Tao WANG Xiang-Yun TIAN Wen-Yu SUN Mao LI Chun LIU Chun-Li * (Beijing National Laboratory for Molecular Sciences Department of Applied Chemistry College of Chemistry and Molecular Engineering Peking University Beijing ) Abstract: Chemical speciation analysis method is used in the field of uranium technology. The method contains two aspects experimental analysis and theoretical calculation. CHEMSPEC is a newly developed speciation code. In this work CHEMSPEC is used to determine the free acid concentration in the presence of uranium 髩 and the conversion channels of UF 6. Three conversion channels are considered: direct hydrolysis reduction hydrolysis and extraction after F - is coupled by Al 3+. The results indicate that the titration endpoint of the acid solution can be precisely determined by the CHEMSPEC and consist with the results of titration experiments. In the conversion of UF 6 the ph value must be strictly controlled when the direct hydrolysis channel is applied reduction hydrolysis channel needs suitable reducing agents while when F - is coupled by Al 3+ the extraction channel may applicable in low ph value solutions. These may suggest that speciation analysis method could be helpful in the field of uranium technology. Key words: speciation; CHEMSPEC; uranium technology; UF 6 ; conversion (chemical speciation analysis) (INL) Hill Nature Materials : : : (No ) (No ) (No. [2007]840) * liucl@pku.edu.cn : 26 ; :

Molecular Sciences Department of Applied Chemistry College of Chemistry and Molecular Engineering Peking University Beijing 100871) Abstract: Chemical speciation analysis method is used in the field

2 3 : CHEMSPEC Debye-Hückel Davies [1] [23] 10 UO 2 (NO 3 ) 2 -NaF UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 - NaF CHEMSPEC UF 6 CHEMSPEC (components) ( 3 UF 6 ) UO 2 Al 髥 F - U 髩 (species) U 0.01 mol L -1 U 2 CHEMSPEC UO 2 Al 3+ Newton-Raphson Levenberg-Marquardt UO 2 H 2 SO 4 CHEMSPEC HNO 3 NaF( KF) NaC 2 O 4 [6~11] - - UO 2 NaOH CHEMSPEC CHEMSPEC NAPSI_ dat 1 U 髩 F - ph [5] ph<6.4 UO 2 F - CHEMSPEC UO 3 2H 2 O ph>4.6 UF 6 F - H + F - UO 2 ph 4.6~ UO 2(NO 3) mol L -1 NaF 0.05 mol L MPa 1 UO 2 (NO 3 ) 2 -NaF U( ) F( ) Fig.1 Speciation of U or F in UO 2 (NO 3 ) 2 -NaF system: U (left) F (right) UO 2 (NO 3 )-Al(NO 3 ) 3 HNO 3 HNO 3 NaF / Na 2 C 2 O 4 2 UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF Al(NO 3 ) 3 U 髩 Al 髥 TBP ph<6.4 ph<7.6 F - ph>4.6

dat 1 U 髩 F - ph [5] ph<6.4 UO 2 F - CHEMSPEC UO 3 2H 2 O ph>4.6 UF 6 F - H + F - UO 2 ph 4.6~6.4 387 UO 2(NO 3) 2 0.01 mol L -1 NaF 0.05 mol L -1 25 0.1 MPa 1 UO 2 (NO 3 ) 2 -NaF U( ) F( ) Fig.

3 UO 2(NO 3) mol L -1 Al(NO 3) mol L -1 NaF 0.1 mol L MPa Fig.2 2 UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF U( ) Al( ) F( ) Speciation of U Al and F in UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF system: U (left) Al (middle) F (right) 4.6~6.4 T UO mol (NO 3 ) 2 -NaF UO 2 (NO 3 ) 2 -Al (NO 3 ) 3 -NaF L -1 UO 2 (NO 3 ) 2 ( Beijer Chemapol ) 0.5 mol L -1 NaF( ) 0.1 mol L -1 Al(NO 3 ) 3 ( ) 12.5 ml UO 2 (NO 3 ) ml 0.5 mol L -1 NaF 25.0 ml 12.5 ml UO 2 (NO 3 ) ml 0.5 mol L -1 NaF 2.5 ml 4.6~ UF U UF 6 UO 2 (MF 6 M U Pu) MO 2 MO x UF 6 Al(NO 3 ) UF 6 NH 3 ml U 髩 UF 6 HNO 3 ( ) U 髩 (ADU) mol L -1 NaOH( ) CO 2 NH 3 ((NH 4 ) 2 CO 3 NH 4 HCO 3 ) - UF 6 UO 2 (NO 3 ) 2 (AUC) [12~15] ADU AUC UO 2 ADU (NH 4 ) 4 NpO 2 (CO 3 ) mol L -1 (NH 4 ) 4 NpO 2 (CO 3 ) 3 3 UO 2 (NO 3 ) 2 -NaF UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF Fig.3 Titration curves of UO 2 (NO 3 ) 2 -NaF and UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF systems NpO 2 CO 3 (s)(83.3%) NpO 2 (CO 3 ) 2 2- (15.2%) NpO 2 (CO 3 ) 3 4- (1.29%) (0.05% NpO 2 CO % 6- (NpO 2 ) 2 CO 3 (OH) % (NpO 2 ) 3 (CO 3 ) 6 ) ph 7.13 AUC (NH 4 ) 2 U 2 O 7 ADU 4 :UO 3 2H 2 O3UO 3 NH 3 5H 2 O 2UO 3 NH 3 3H 2 O 3UO 3 2NH 3 4H 2 O UO 3 2H 2 O

02 mol (NO 3 ) 2 -NaF UO 2 (NO 3 ) 2 -Al (NO 3 ) 3 -NaF L -1 UO 2 (NO 3 ) 2 ( Beijer Chemapol ) 0.5 mol L -1 NaF( ) 0.1 mol L -1 Al(NO 3 ) 3 ( ) 12.5 ml UO 2 (NO 3 ) 2 2.5 ml 0.5 mol L -1 NaF 25.

4 3 : CHEMSPEC ADU ADU AUC 99.5% Fe 髤 CHEMSPEC 3 UF 6 UO 2 F - Fe 髥 Al 髥 F U 髩 UF 6 UO 2 4 U 髩 UF 6 ph ph=8.50~ % U 髩 UO 3 2H 2 O UO 3 2H 2 O ph CHEMSPEC ph %~98%;pH>6.5 UO 2 (s) 5% Fe 髤 U 髩 U 髧 U 髩 Fe 髤 UO 2 F mol L -1 HF 0.04 mol L MPa UO 2 U mol L -1 F mol L -1 H mol L MPa Al 髥 F - U 髩 Al 3+ F - F - Al 3+ Al(NO 3 ) 3 TBP UO 2 (NO 3 ) 2 [11] 0.01 mol L -1 UO 2 (NO 3 ) 2 + ph<5.0 U 髩 - UF 6 100% Al 3+ UF 6 U 髧 UO 2 5 F - Al 3+ ph U 髧 UF 6 ph Al(NO 3 ) 3 UO 2 ph<5.5 UF 4 2.5H 2 O(cr) Al 3+ AlF Fig.5 UF 4-2HF U Speciation of U in UF 4-2HF system 4 UO 0.02 mol L -1 Al(NO 3 ) mol L -1 2 F 2-4HF U HF U 髩 Fig.4 Speciation of U in UO Al 3+ F - 2 F 2-4HF system 6 UO 2(NO 3) mol L -1 Al(NO 3) mol L -1 HF 0.06 mol L MPa Fig.6 6 UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -HF U( ) Al( ) F( ) Speciation of U Al and F in UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -HF system: U(left) Al(middle) F(right)

01 mol L -1 UO 2 (NO 3 ) 2 + ph<5.0 U 髩 - UF 6 100% Al 3+ UF 6 U 髧 UO 2 5 F - Al 3+ ph U 髧 UF 6 ph Al(NO 3 ) 3 UO 2 ph<5.5 UF 4 2.5H 2 O(cr) Al 3+ AlF 1 0.01 5 Fig.

5 c U 髩 c Al 髥 = 1 4 c U 髩 c Al 髥 = 1 8 Table 1 ph value 1 UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -HF ph Speciation distribution of U in UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -HF system under low ph values Molar percent of special speciation in UO 2(NO 3) 2-Al(NO 3) 3-HF system UO 2 UO 2(NO 3) + Al 3+ AlF HF mol L -1 UO 2 (NO 3 ) mol L -1 Al(NO 3 ) mol Capabilities and Future Directions Stockholm Swedish L -1 HF ph Environmental Protection Agency ph U 髩 UO 2 [3] Merkel B J Friedrich P. Britta Groundwater Geochemistry UO 2 (NO 3 ) + (>80%) HF F - A practical Guide to modeling of Natural and Contaminated Aquatic Systems Berlin Springer Berlin Heidelberg TBP- UO 2 (NO 3 ) 2 67~110 U 髩 [4] WANG Xiang-Yun ( ). Proceedings of 26th Chinese Chemistry Society Conference( 26 CHEMSPEC ). Tianjin p-410 [5] 3 [6] Sundar U Sivadasan P C Yadav R B et al. Analyst 1998 CHEMSPEC 123:1875~1877 [7] Suh M Y Lee C H Sohn S C et al. Bull. Korean Chem. Soc (1):59~64 UO 2 (NO 3 ) 2 -NaF [8] Smith M. The Determination of Free Acid in Plutonium UO 2 (NO 3 ) 2 -Al(NO 3 ) 3 -NaF Solutions Los Alamos Scientific Laboratory Report LA- 4.6~6.4 UF 6 UF UO 2 Al 髥 [9] Motojima K Izawa K. Anal. Chem (4):733~735 F - U 髩 [10]Kulkarni P S. Chem. Eng. J :209~214 ph [11]ZHU Zhao-Wu( ) HU Jing-Xin( ) HE Jian-Yu Al 髥 F - U 髩 ph Huaxue) (3):194~198 [12]XU Kui( ) LIU Jin-Hong( ) HU Bai-Gui( CHEMSPEC ) et al. Atomic Energy Sci. Tech. (Yuanzineng Kexue Jishu) (5):637~640 [13]Govindan P Palamalai A Vijayan K S et al. J. Radioanal. Nucl. Chem (1):65~70 : [1] Hill D J. Nat. Mater :680~682 [2] Crawford J. Geochemical Modeling-A Review of Current ( ) et al. J. Nuc. Radiochem.(He Huaxue Yu Fangshe [14]ZHAO Fen-Qi( ) NIU Yu-Qing( ) ZHUANG Hai-Xing( ) et al. Uranium Mining and Metallurgy (Youkuangyan) (1):15~23 [15]XIA De-Chang ( ). Uranium Mining and Metallurgy (Youkuangyan) (3):148~152

690 7 6.021 4 2.329 1 51.477 3 0.011 4 2.0 88.887 2 8.939 3 29.752 0 65.708 2 0.011 6 2.5 87.884 5 8.878 1 29.733 4 65.686 9 0.003 7 3.0 84.721 1 8.572 6 29.657 9 65.667 6 0.

在培养职前卓越化学教师的院校, 会编一本过去称作化学教学论实验, 现在拟为卓越化学教师教育实验教学研究的教材各院校对这门课程所给的学时不太一样, 但都是围绕实验

在培养职前卓越化学教师的院校, 会编一本过去称作化学教学论实验, 现在拟为卓越化学教师教育实验教学研究的教材各院校对这门课程所给的学时不太一样, 但都是围绕实验 doi: 10.3866/pku.DXHX201607011 卓越化学教师教育实验教学研究课程探微 * 杨承印汪蒙蒙赵洋 ( 陕西师范大学化学化工学院, 西安 710119) 摘要 : 在对实验操作进行编码的基础上对高中化学课程标准中有关实验进行统计分析, 以