Metal Extraction by Alkyl Substituted Diphosphonic Acids. Part 4 P,p′-Di(2-Ethylhexyl) Butanediphosphonic Acid

Chiarizia, R.; Herlinger, Albert W.; Cheng, Yao; Ferraro, John R.; Rickert, Paul G.; Horwitz, E. P.

doi:10.1080/07366299808934537

Cited by 39 publications

(13 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is apparently due to the fact that the size of the chelate ring in the extractable complex increases with an increase in the length of alkylene bridges linking the PO groups in the extractant molecule. Similar influence of the length of the alkylene bridge in the NBOPC molecule was noted previously in the extraction of Am(III) [17] and Ln(III) [18] with tetraphenylalkylenediphosphine dioxides and alkyl-substituted alkylenediphosphonic acids [19,20].…”

mentioning

confidence: 63%

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

2005

View full text Add to dashboard Cite

Extraction of microamounts of U(VI), Th(IV), Sc(III), and Ln(III) from HNO 3 solutions with solutions of bis(diphenylphosphinylethyl)phosphinic acid in dichloroethane was studied. The stoichiometry of the extractable complexes was determined, and the effect of the inorganic anion and organic diluent on the extraction of rare-earth elements was examined. An increase in the number of phosphoryl groups in the extractant molecule and replacement of ethylene bridges between the phosphorus atoms by methylene bridges enhance the extraction of metal ions from nitric acid solutions.The interest in extraction properties of polyfunctional organophosphorus acids increased recently, because of the prospects for using these agents in radiochemical practice for the recovery of transplutonium, rare-earth (Ln), and other elements from nitric acid solutions [1]. It was shown that dibasic P, P`-di-(2-ethylhexyl)methylenediphosphonic acid [2, 3] and monobasic (diphenylphosphinylmethyl)phenylphosphinic [4] and bis(diphenylphosphinylmethyl)phosphinic (I) [5] acids exhibit extremely high extractive power toward Th(IV), U(VI), Am(III), and Ln(III) in nitric acid solutions. It was suggested that the high extractive power of acid I is due to the possibility of formation of six-membered chelate rings with metal ions, since the phosphoryl groups in this agent are linked with methylene bridges. In this connection, it is interesting to study how the length of the alkylene bridge between the P(O)OH and P(O) fragments and the number of phosphoryl groups in the extractant molecule affect its extractive power.To this end, we studied the extraction of U(VI), Th(IV), Sc(III), and Ln(III) from aqueous solutions of HNO 3 with solutions of bis(2-diphenylphosphinylethyl)phosphinic (II) and 2-phenylethyl-(2-diphenylphosphinylethyl)phosphinic (III) acids in dichloroethane. For comparison, we also studied the extraction with a neutral analog of II, pentaphenyldiethylenetriphosphine trioxide IV [6], and with diphenylphosphinic acid V.

show abstract

mentioning

confidence: 63%

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

2005

View full text Add to dashboard Cite

show abstract

“…previously (6,30). The distribution ratio D was calculated as the ratio of the activity of a radiotracer between an o-xylene solution of the extractant and an aqueous nitric acid solution at room temperature (22^18C).…”

Section: Measurementsmentioning

confidence: 99%

“…Numerous studies have demonstrated that these compounds form extraordinarily strong complexes with a variety of metal ions, even in strongly acidic media (5,6). In addition, upon appropriate substitution, these compounds have been shown to provide the basis for powerful metal ion extractants (6 -8), a variety of novel ion-exchange (9 -15), and extraction chromatographic (16) materials.…”

Section: Introductionmentioning

confidence: 99%

“…On the basis of this extraction equilibrium, a structure has been proposed for the alkaline earth -H 2 DTMSP[MDP] complexes extracted into the organic phase, containing a number of six-membered chelate rings formed through the interaction of the phosphoryl oxygens of two mono-deprotonated H 2 DTMSP[MDP] dimers with a single alkaline earth cation(6,26).Alkaline earth cation extraction by H 2 DTMSP[EDP] in o-xylene yields extractant dependencies of slope one. On the basis of this data, an equilibrium involving a doubly deprotonated hexameric aggregate has been proposed for the extraction of alkaline earth cations by H 2 DTMSP[EDP](7,26).…”

mentioning

confidence: 99%

See 1 more Smart Citation

Metal extraction by silyl-substituted diphosphonic acids. II. Effect of alkylene bridge length on aggregation and metal ion extraction behavior

McAlister

Dietz

Chiarizia

et al. 2002

Separation Science and Technology

Self Cite

View full text Add to dashboard Cite

In an ongoing effort to determine the relationship between structure and function in diphosphonic acids, the aggregation and solvent extraction chemistry of four novel silicon-substituted diphosphonic acids, P,P 0 -di[3-(trimethylsilyl)-1-propyl] propylene-(H 2 DTMSP[PrDP]), butylene-(H 2 DTMSP[BuDP]), pentylene-(H 2 DTMSP[PDP]), and hexylene diphosphonic acid (H 2 DTMSP[HDP]), were investigated. Vapor pressure osmometry indicates that H 2 DTMSP[PrDP] and H 2 DTMSP[PDP] are dimeric in toluene at 258C, while H 2 DTMSP[BuDP] and H 2 DTMSP[HDP] are primarily trimeric and hexameric, respectively. The solvent extraction of selected alkaline earth cations (Ca, Sr, and Ba) and representative tri-, tetra-, and hexavalent actinides 2289[Am(III), Th(IV), and U(VI)], from nitric acid solutions into oxylene solutions of the ligands has been studied and compared to results reported previously for some analogous di(2-ethylhexyl)-substituted diphosphonic acids. Differences observed in the magnitude of distribution ratios, based on the number of bridging methylene groups, have been explained considering factors such as ligand aggregation, chelate ring size, PyO basicity (qualitatively determined by 31 P nuclear magnetic resonance and infrared spectroscopy), and the relative acidities of the ligands.

show abstract

“…To date, a lot of extractants have been developed and their extraction properties have been evaluated for a variety of metal ions. [1][2][3][4][5][6][7][8][9][10][11] In a previous study, we have developed novel bi-functional organophosphorus extractants in which two phosphonic acids were introduced as functional groups in the molecular structure for the separation of rare earth metals. 12 The result indicated that extraction performance of bi-functional extractants is very sensitive to the molecular structure of the spacer which connects the two functional moieties.…”

mentioning

confidence: 99%

Bi-Functional Organophosphorus Extractants and Computational Modeling for Copper(II) and Zinc(II) Extraction

et al. 1999

View full text Add to dashboard Cite

In the liquid-liquid extraction technology, the extractant is well-known to play a key role for separating target metal ions. The selection of appropriate extractant often decides the success of the extraction process. To date, a lot of extractants have been developed and their extraction properties have been evaluated for a variety of metal ions. [1][2][3][4][5][6][7][8][9][10][11] In a previous study, we have developed novel bi-functional organophosphorus extractants in which two phosphonic acids were introduced as functional groups in the molecular structure for the separation of rare earth metals. 12 The result indicated that extraction performance of bi-functional extractants is very sensitive to the molecular structure of the spacer which connects the two functional moieties. In the present study, we applied this novel type of bi-functional extractants to the separation of Cu(II) and Zn(II). Since the structures of Cu(II) and Zn(II) complexes with a ligand are different from each other, an interesting extraction behavior is expected for the bi-functional extractants. We focused on the difference in the length of the spacer because the spacer length was considered to affect the complex formation of Cu(II) (square planar) and Zn(II) (tetrahedral). In this work, three bifunctional organophosphorus extractants which have a different spacer length were prepared, and their extraction performance for Cu(II) and Zn(II) was investigated compared to that of a monomeric extractant as an analog.Recently, computational chemistry attracted much attention for the design of novel extractants. [12][13][14][15][16] In the field of solvent extraction, interfacial properties of extractants at the oil-water interfaces were discussed on the extraction rate using MD method. 17 In our study, extraction behavior of the bi-functional extractants for Cu(II) and Zn(II) is discussed with computational modeling. Calculated results support the conclusion that the bi-functional organophosphorus extractants show a high selectivity towards Zn(II) over Cu(II) compared to that of mono-functional analog. We also demonstrate that the computational modeling is very helpful for predicting extraction behavior and designing new extractants for a target metal ion. ExperimentalReagents 1,4-Butanediol-O,O′-diphenyl phosphonic acid (abbreviated as BDPA), 1,8-octanediol-O,O′-diphenyl phosphonic acid (abbreviated as ODPA) and 1,12-dodecanediol-O,O′-diphenyl phosphonic acid (abbreviated as DDDPA) were synthesized by the procedures described in the following section. A mono-functional extractant, phenyl phosphonic acid mono-2-ethylhexyl ester (abbreviated as 2EHPA), was also synthesized as the analog to discuss the bi-functional effect. Figure 1 shows the molecular structures of the newly developed extractants applied in this study. Novel bi-functional extractants, which possess two phosphonic groups on both sides of the extractants, have been synthesized for the separation of Zn(II) and Cu(II). The separation properties and extractability of the novel ex...

show abstract

Metal Extraction by Alkyl Substituted Diphosphonic Acids. Part 4 P,p′-Di(2-Ethylhexyl) Butanediphosphonic Acid

Cited by 39 publications

References 1 publication

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

Extraction Properties of Bis(diphenylphosphinylethyl)phosphinic Acid in Nitric Acid Solutions

Metal extraction by silyl-substituted diphosphonic acids. II. Effect of alkylene bridge length on aggregation and metal ion extraction behavior

Bi-Functional Organophosphorus Extractants and Computational Modeling for Copper(II) and Zinc(II) Extraction

Contact Info

Product

Resources

About