J. Chem. Eng. Data 2009, 54, 1183–1188
1183
Hydrolytic Behavior of Th4+, UO22+, and Ce3+ Ions at Various Temperatures ¨ nak Serap Tekso¨z,* C ¸ igˇdem Acar, and Perihan U Department of Nuclear Applications, Institute of Nuclear Sciences, Ege University, 35100 Bornova Izmir, Turkey
The hydrolytic behavior of Th4+, UO22+, and Ce3+ was investigated using the potentiometric method at elevated temperatures in KCl medium. For each metal ion, stability constants were obtained from the pHmetric data using the program HYPERQUAD2006. The formation of [Th(OH)]3+, [Th(OH)2]2+, [Th(OH)3]+, Th(OH)4, [Th4(OH)8]8+, and [Th6(OH)15]9+ for the thorium ion, [UO2(OH)]+, [(UO2)2(OH)2]2+, [(UO2)3(OH)4]2+, and [(UO2)3(OH)5]+ for the uranyl ion, and [Ce2(OH)]5+, [Ce2(OH)2]4+, Ce(OH)3, and [Ce2(OH)5]+ for the cerium ion was taken into consideration. In addition, the effect of temperature on the stability constants was studied, and thermodynamic parameters were derived and discussed.
Introduction The chemical properties of the actinide and lanthanide elements in aqueous solution, such as their oxidation states and the extent of their hydrolysis and complexation reactions, govern their behavior in complex mixtures. The hydrolysis of actinides and lanthanides has recently been a compelling subject.1-3 The determination of stability constants is an essential process in solution chemistry as well as for many other branches of chemistry. To compute stability constants from potentiometric and spectrophotometric data, many software programs such as BEST, LETAGROP, MINIQUAD, PKAS, SUPERQUAD, and HYPERQUAD4 have been used to date. All of these programs use the least-squares approach. Among them, HYPERQUAD2006 is one of the most recent versions of the HYPERQUAD program to determine stability constants from potentiometric and spectrometric data. In HYPERQUAD, the calculation proceeds in two stages. First, estimates must be made of all free concentrations using the HYPERQUAD simulation and speciation program, HySS. Then, these estimates are refined by NewtonRaphson iteration. Finally, the refinement must be terminated with a suitable criterion.5,6 In the present study, the hydrolytic behavior of Th4+, UO22+, and Ce3+ has been investigated using pH titration data at elevated temperatures. The stability constants of the hydrolytic species of these metal ions were simulated using the HySS program and were computed with the aid of the HYPERQUAD2006 computer program.5-7 Furthermore, thermodynamic data on the complexation of actinides at elevated temperatures is mandatory to gain an understanding of the coordination chemistry of actinides8 and lanthanides. Therefore, thermodynamic parameters were derived and discussed by utilizing this data.
Experimental Section Materials. All chemicals were supplied by the Merck Chemical Co. (Germany). Bidistilled water was obtained from the Millipore (Milli-Q Gradient A-10) water purification instrument. Solutions of Th4+, UO22+, and Ce3+ were prepared from their nitrate salts (UO2(NO3)2 · 6H2O, Th(NO3)4 · 6H2O, Ce(NO3)3 · 6H2O). Stock solutions of 0.1 M NaOH and 0.1 M HCl * Corresponding author. E-mail:
[email protected].
were prepared in CO2-free bidistilled water and standardized by a literature method.9 KCl (1 M) was used to adjust the ionic strength of the media. Apparatus and Procedure. pH-Metric titrations were performed in a 100 mL jacketed cell (Metrohm, thermostat jacket, 6.1418.250) that has two ports for electrodes, a port for titrant addition, and a port for purging with inert gas. The titrations were carried out at (25 ( 0.1) °C, (37 ( 0.1) °C, and (45 ( 0.1) °C by circulating water from a thermostat (Nu¨ve-BM 302). Metrohm autoburets (Titroprocessor 686 and Dosimat 665) with a glass electrode (Metrohm 6.0262.100) were used for the pH measurements. To avoid any side effects that could come from oxygen, argon gas (ultrahigh purity, 99.99 %) was bubbled through the solution before and during the pH measurements in all titrations. The pH meter was calibrated with standard buffer solutions (pH 4.0 and 7.0; HC607673 and OC516474, respectively) before the pH measurements. The results of strong acid versus alkali titrations were analyzed using a computer program called GLEE (glass electrode evaluation). The program GLEE has been developed as part of the HYPERQUAD suite of programs for stability constant determination. The values of pKw were confirmed using GLEE7 (pKw ) 13.78 at 25 °C, 13.46 at 37 °C, and 13.16 at 45 °C). The ionic strength (I) of all of the titration mixtures was adjusted to 0.1 by the addition of the requisite volume of 1 M KCl solution, and a constant volume was maintained at 100 mL. Before performing the titrations, we simulated titration conditions using the HySS 2006 computer program.6 For the determination of stability constants, a few preliminary titrations were performed to investigate the effects of experimental variables such as the time interval between consecutive titration readings and varying concentrations of relevant metal ions at appropriate pH ranges and at desired temperatures. The pH measurements were done using the MET program of Titroprocessor 686 by recording the pH measurements at suitable time intervals for each metal ion. Titration of Thorium. An aqueous solution of thorium at variable concentrations ((0.5, 1.0, and 2.0) mmol · dm-3) and between (1.0 and 2.3) mL of standardized ∼ 0.1 M HCl was added to each sample. (The amount of required metal and proton concentrations was established by speciation calculations using the program HySS.)6 We performed titrations by recording the pH measurements. A summary of the titrations used in the
10.1021/je800601m CCC: $40.75 2009 American Chemical Society Published on Web 03/03/2009
1184 Journal of Chemical & Engineering Data, Vol. 54, No. 4, 2009 Table 1. Results of Potentiometric Measurements of Hydrolysis of Th4+ t/°C 25 15
25
35
25
25
37
45
metal ion range
Th4+ hydrolytic species
-3
(1, -1) (1, -3) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15) (1, -2) (1, -3) (1, -4) (2, -7) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15) (1, -1) (1, -2) (1, -3) (1, -4) (4, -8) (6, -15)
mmol · dm
-log β
0.044 to 1.09
3.51 ( 0.03 10.75 ( 0.14 3.6 ( 0.1 8.8 ( 0.1 14.9 ( 2.8 22.0 ( 0.4 20.2 ( 0.3 41.4 ( 0.2 3.3 ( 0.1 8.6 ( 0.1 14.2 19.4 ( 0.5 19.1 ( 0.1 39.5 ( 0.2 3.2 ( 0.1 8.4 ( 0.1 12.7 ( 3.5 17.8 ( 0.4 18.0 ( 0.1 36.6 ( 0.2 8.36 ( 0.11 11.63 ( 0.09 18.24 ( 0.13 24.32 ( 0.08 3.29 ( 0.21 6.86 ( 0.08 10.85 ( 0.29 15.81 ( 0.58 16.89 ( 1.02 35.03 ( 0.97 2.89 ( 0.42 5.98 ( 0.19 10.04 ( 0.44 15.33 ( 0.45 15.15 ( 0.79 31.08 ( 1.09 3.06 ( 0.35 5.96 ( 0.27 9.08 ( 0.53 15.26 ( 0.95 14.38 ( 1.44 29.76 ( 2.33
0.0096 to 0.104
0.0116 to 0.123
0.0104 to 0.103
0.1
0.5 to 2.0
ref a
1
4+
Table 2. Summary of Titrations of Th
-3
in 1.0 mol · dm
2b 25 25
10 25 40 55 c
12
70 this work
25 37 45
mmol · dm 0.5 1.0 2.0 0.5 1.0 2.0 0.5 1.0 2.0
pH range 2.82 2.55 2.99 2.81 2.50 2.68 2.73 2.50 2.52
to to to to to to to to to
4.60 4.51 4.28 5.07 4.46 4.31 4.59 4.51 4.24
85 25
37
45
UO22+ hydrolysis species (2, -2) (4, -6) (4, -7) (2, -2) (3, -5) (1, -1) (2, -2) (3, -4) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -5) (1, -1) (2, -2) (3, -4) (3, -5) (1, -1) (2, -2) (3, -4) (3, -5) (1, -1) (2, -2) (3, -4) (3, -5)
metal ion range mmol · dm-3
-log β
ref
6.15 ( 0.05 18.43 ( 0.09 23.36 ( 0.07 5.89 ( 0.37 16.19 ( 0.16 5.17 ( 0.03 5.86 ( 0.04 12.00 ( 0.06 16.09 ( 0.06 6.1 ( 0.3 6.30 ( 0.02 17.52 ( 0.01 5.58 ( 0.24 5.83 ( 0.02 16.37 ( 0.02 5.11 ( 0.11 5.43 ( 0.01 15.35 ( 0.01 5.07 ( 0.24 5.06 ( 0.03 14.45 ( 0.02 4.51 ( 0.11 4.73 ( 0.03 13.61 ( 0.02 4.24 ( 0.15 4.49 ( 0.03 12.94 ( 0.02 5.54 ( 0.35 5.60 ( 0.24 11.21 ( 0.31 16.07 ( 0.16 5.33 ( 0.03 5.42 ( 0.28 11.36 ( 0.03 15.66 ( 0.45
