The structure of tributyl phosphate solutions: Nitric acid, uranium (VI), and zirconium (IV)

被引:29
作者
Baldwin, Anna G. [1 ]
Servis, Michael J. [1 ]
Yang, Yuan [1 ]
Bridges, Nicholas J. [2 ]
Wu, David T. [1 ]
Shafer, Jenifer C. [1 ]
机构
[1] Colorado Sch Mines, 1500 Illinois St, Golden, CO 80401 USA
[2] Savannah River Natl Lab, Aiken, SC USA
关键词
Solvent extraction; Tributyl phosphate; Pulsed-field gradients; Diffusion; Small angle neutron scattering; Rheology; NORMAL-BUTYL PHOSPHATE; SMALL-ANGLE SCATTERING; INDIRECT FOURIER TRANSFORMATION; NEUTRON-SCATTERING; TRACER DIFFUSION; INTERACTING PARTICLES; EXTRACTING SOLVENT; MOLECULAR-DYNAMICS; INORGANIC NITRATES; HARD-SPHERES;
D O I
10.1016/j.molliq.2017.09.032
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Diffusion, rheology, and small angle neutron scattering (SANS) data for organic phase 30 v/v %tributyl phosphate (TBP) samples containing varying amounts of water, nitric acid, and uranium or zirconium nitrate were interpreted from a colloidal perspective to give information on the types of structures formed by TBP under different conditions. Taken as a whole, the results of the different analyses were contradictory, suggesting that these samples should be treated as molecular solutions rather than colloids. This conclusion is supported by molecular dynamics (MD) simulations showing the existence of small, molecular aggregates in TBP samples containing water and nitric acid. Interpretation of TBP and nitric acid diffusion measurements from a molecular perspective suggest that nitric acid and metal species formed are consistent with the stoichiometric solvates that have traditionally been considered to exist in solution. (C) 2017 Elsevier B.V. All rights reserved.
引用
收藏
页码:225 / 235
页数:11
相关论文
共 75 条
[1]   THE EXTRACTION OF NITRATES BY TRI-NORMAL-BUTYL PHOSPHATE (TBP) [J].
ALCOCK, K ;
GRIMLEY, SS ;
HEALY, TV ;
KENNEDY, J ;
MCKAY, HAC .
TRANSACTIONS OF THE FARADAY SOCIETY, 1956, 52 (01) :39-47
[2]   TRI-NORMAL-BUTYL PHOSPHATE AS AN EXTRACTING SOLVENT FOR INORGANIC NITRATES .1. ZIRCONIUM NITRATE [J].
ALCOCK, K ;
BEDFORD, FC ;
HARDWICK, WH ;
MCKAY, HAC .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1957, 4 (02) :100-105
[3]   TRI-NORMAL-BUTYL PHOSPHATE AS AN EXTRACTING SOLVENT FOR INORGANIC NITRATES .5. FURTHER RESULTS FOR THE TETRAVALENT AND HEXAVALENT ACTINIDE NITRATES [J].
ALCOCK, K ;
BEST, GF ;
HESFORD, E ;
MCKAY, HAC .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1958, 6 (04) :328-333
[4]  
[Anonymous], 1960, Transport Phenomena
[5]   Structural insights into the multinuclear speciation of tetravalent cerium in the tri-n-butyl phosphate-n-dodecane solvent extraction system [J].
Antonio, Mark R. ;
Ellis, Ross J. ;
Estes, Shanna L. ;
Bera, Mrinal K. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2017, 19 (32) :21304-21316
[6]   Tributyl Phosphate Aggregation in the Presence of Metals: An Assessment Using Diffusion NMR Spectroscopy [J].
Baldwin, Anna G. ;
Yang, Yuan ;
Bridges, Nicholas J. ;
Braley, Jenifer C. .
JOURNAL OF PHYSICAL CHEMISTRY B, 2016, 120 (47) :12184-12192
[7]  
Batchelor G.K., 1955, J FLUID MECH, V74, P264
[8]   PERCUS-YEVICK EQUATION FOR HARD SPHERES WITH SURFACE ADHESION [J].
BAXTER, RJ .
JOURNAL OF CHEMICAL PHYSICS, 1968, 49 (06) :2770-&
[9]   Structural aspects of heteropolyacid microemulsions [J].
Bera, Mrinal K. ;
Ellis, Ross J. ;
Burton-Pye, Benjamin P. ;
Antonio, Mark R. .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2014, 16 (41) :22566-22574
[10]   SASfit: a tool for small-angle scattering data analysis using a library of analytical expressions [J].
Bressler, Ingo ;
Kohlbrecher, Joachim ;
Thunemann, Andreas F. .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2015, 48 :1587-1598