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Solvent Deuterium Isotope Effect on Hydrolysis of Nd3+ Ion , and As Was

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Solvent Deuterium Isotope Effect on Hydrolysis of Nd3+ Ion , and As Was Notizen 1493 Solvent Deuterium Isotope Effect on Hydrolysis Experimental of Nd3+ Ion Reagents and apparatus A neodymium perchlorate sample solution and Mastjnobu Ma e d a *, T oshihiko A m ay a , and other reagents used were prepared and analyzed H id e t a k e K ak iha na according to the same procedures as those in the *Department of Applid Chemistry, previous papers5-6. Nagoya Institute of Technology, All the apparatus employed were the same as Gokiso, Showa-ku, Nagoya 466, Japan those in Ref. 7. Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, Preparation of a test solution O-okayama, Meguro-ku, Tokyo 152, Japan A test solution was prepared as follows. A (Z. Naturforsch. 32 b, 1493-1495 [1977]; received August 30, 1977) slightly acidic neodymium perchlorate solution, which had been freed from CO 2 by passing purified Deuterium Isotope Effect, Formation Constant, Heavy Water, Hydrolysis, Neodymium Ion N2 gas, was electrolyzed to reduce L+ ions by using a d. c. power supply until precipitates appeared. In order to saturate the solution with Nd(OL )3 precipi­ The hydrolysis equilibria of Nd3+ ion in tates the mixture was stirred with a magnetic rod light- and heavy-water solutions containing for two days. The precipitates of Nd(OL )3 were 3 mol dm -3 (Li)C104 as an ionic medium were removed by filtration with G 4 glass filters. All the studied at 25 °C by measuring the lyonium- procedures were carried out under an atmosphere ion concentration with a glass electrode. of N 2 gas in a room kept at 25 ± 1 °C. Analysis of the emf data indicated the forma­ tion of only the mononuclear complex Emf measurements Nd(OL)2+ in both light and heavy water. The A test solution thus prepared, in which the total formation constant was smaller in D 2O concentration of perchlorate ions was kept at (log */?2,i = -—16.54 ± 0.04) than in H 2O 3 mol dm -3 by addition of LiC 10 4, was acidified in (log *ß2,i = — 15.90 ± 0.06). The formation small steps by constant-current coulometry, and constant K<z,\ for the heavy-water system the lyonium-ion concentration was measured by means of a glass electrode8. The same cell assembly (log i?2,i = 12.28) had a larger value than as described in Ref. 9 was used for emf measure­ that for the light-water system (log K%t 1 = ments and coulometric titrations. 11.86 ). All the measurements were performed at 25,00 ± Introduction 0,02 °C in a parrafin oil thermostat in a room thermostated at 25 ± 1 °C. As was reported in previous papers1-7, the authors studied the hydrolytic reactions of various metal ions in both light and heavy water. The composi­ Results and Discussion tions of complexes formed by hydrolysis in heavy The values of Z (log d)s for the heavy-water water were found to be analogous to those in light system are graphically shown in Fig. 1. water, and the formation constant */?P,q of the complexes in D 2O were smaller than those in H 2O. In a previous work 7 the authors measured the ionic product of D 2O containing 3 mol dm -3 LiC104 and examined the deuterium isotope effect on formation constants i£p,q for hydrolysis species of boric acid. It was found that the K v<ri values in heavy water were slightly larger than those in light water. The deuterium isotope effect on i£P,q values for other hydrolysis species was not reported. In the present work, potentiometric measure­ ments of the hydrolysis of Nd3+ ion were carried out in heavy water as well as in light water in order to elucidate the deuterium isotope effect. These experi­ ments used 3 mol dm -3 (Li)C104 as an ionic medium, because the ionic product of D 2O in this system is available7. Requests for reprints should be sent to Dr. M . M a e d a , Fig. 1. Average number, Z, of OD bound per Nd3+ as a Department of Applied Chemistry, Nagoya Institute function of log d. The drawn curve was calculated of Technology, Gokiso, Showa-ku, Nagoya 466, Japan. with the formation constant of log *ßz.i = — 16.54. 1494 N otizen It is seen that the plot is a function of only d and computer. One possible explanation for this in­ independent of B. The plot analogous to that in consistency may be that the maxium Z values Fig. 1 was obtained in the light-w^ater system. This reached in the present work is much larger than indicates that only mononuclear complexes are those in the previous studies and that the low-Z formed in both light and heavy water. region, where the NdOH2+ complex was probably On the basis of these data the compositions and formed, was not measured in the present work. formation constants of the hydrolysis species were B u r k o v et al . 12 reported that the main hydrolytic estimated by graphical procedures. The concentra­ reaction of Nd3+ ion in 3 mol dm -3 (Na)C104 aqueous tion of the lyonium ion set free by hydrolysis, BZ, solution is the formation of the dimer Nd 2(OH)24+. is given by the following form, They titrated an acidic neodymium perchlorate BZ = 2 p *jffPlibl-P (1) solution with an alkali, and their maximum Z value did not exceed 0.005. The authors titrated a solution Since the values of Z do not exceed 0.02 in the saturated with Nd(OH )3 precipitates with an acid solutions studied, the graphical calculations can be and obtained the maximum Z value of 0.02. Such simplified by using the approximation b = B. Thus, differences in experimental procedure might cause equation ( 1 ) gives the inconsistency in composition of hydrolysis species, if the attainment of hydrolysis equilibria is Z = £p*ft,,l-p (2) slow. The formation constant *ß2.i of the Nd(OL) 2+ According to Eq. (2), 1/2 Zl 2 values were plotted as a function of —log 1. The data for the heavy species in D 2O was smaller than that in H 2O. This water system are shown in Fig. 2. It is apparent trend is consistent with that for other metal ion hydrolysis species1-7. The formation constants K 2,i that 1/2 zd 2 values are independent of d values, which means p = 2. The same result was obtained wTere calculated using the *^ 2,1 values and the values for the light water system. Thus, it is concluded that of K w for H 2O (p K w) = 13.88) and D 2 0 (pÜLW = the hydrolysis species formed in light and heavy 14.41)7.Theiip,q values for hydrolysis species of Y3+ and lanthanoid ions were also calculated by use of water is Nd(OL)2+. The formation constants read the *ßp,q values in 3 mol dm -3 (Li)C104 solution from the intercepts were — 16.54 ±0.04 (in D 2O) reported previously5*6. The calculated ifp.q values and — 15.90 ±0.06 (in H 2O) in log *ß unit. are summarized in Table I. The K Pt(l values in the The presence of the Nd(OH) 2+ species was not reported previously. All the previous investiga­ heavy water system are larger than those in the light water system. This means that there are some tors 10-12 found only NdOH2+ as a mononuclear species. This complex was not detected in the isotope effects in hydrolysis other than that present work, although its possibility was examined ascribed to the difference between the ionic products by a least squares method with an electronic of light and heavy water. Notation L: lyon, H or D, d : concentration of the free deuterium ion, 1 : concentration of the free lyonium ion, B : total concentration of Nd3+, b : concentration of free Nd3+, */?p>q: formation constant for the reaction qM>+ + PL 2O = Mq(OL)p(«i-pH -f- pL +, Zp,q formation constant for the reaction qMz+ -f pOL- = Mq(OL)p(M-P)+, Fig. 2. 1/2 Zd2 as a function of — log d. The straight Z = (1—L—Kw/1)/B, the average number of line was calculated with the formation constant of lyonium ions split off per Nd3+, log *ß2.i = — 16.54. K w: ionic product of water. Table I. i£p,q values for hydrolysis of Y3+ and lanthanoid ions in H 2O and D 2O containing 3 mol dm -3 (Li)C104- Y 3+ La3+ Nd3+ Gd3+ Er3+ h 2o d 2o h 2o d 2o h 2o d 2o h 2o d 2o h 2o d 2o log K \,\ - - 3.84 4.06 - - 5.68 6.07 log K 2,i 10.96 II .82 - - 11.86 12.28 - - 10.5 6 11.42 log-K:2 2 13.72 14.07 _______ - __________ - ________ - _________ - _________ 14.04 14.53 1 H. K a k i h a n a and M . M a e d a , Bull. Chem. Soc. 3 H. K a k i h a n a , T. A m a y a , and M . M a e d a , ibid. 43, Jpn. 43, 109 [1970]. 3155 [1970]. 2 M . M a e d a and H. K a k i h a n a , ibid. 43, 1097 4 H. K a k i h a n a , T. A m a y a , and M .
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