Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: A solution calorimetry study

Seraj A. Ansari; Prasanta K. Mohapatra; Willem Verboom; Linfeng Rao

doi:10.1039/C6DT03380F

Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: A solution calorimetry study

Seraj A. Ansari, Prasanta K. Mohapatra, Willem Verboom, Linfeng Rao^*

^*Corresponding author for this work

Molecular Nanofabrication

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Abstract

Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔH_extr) of Eu(NO₃)₃ by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔG_extr and ΔS_extr) for the extraction of Eu(NO₃)₃ by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu³⁺ with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔH_comp) for the Eu³⁺/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu³⁺/T-DGA complexes from the aqueous phase to the organic phase.

Original language	English
Pages (from-to)	17216-17222
Number of pages	7
Journal	Dalton transactions
Volume	45
Issue number	43
DOIs	https://doi.org/10.1039/C6DT03380F
Publication status	Published - 2016

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title = "Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: A solution calorimetry study",

abstract = "Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔHextr) of Eu(NO3)3 by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔGextr and ΔSextr) for the extraction of Eu(NO3)3 by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu3+ with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔHcomp) for the Eu3+/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu3+/T-DGA complexes from the aqueous phase to the organic phase.",

keywords = "n/a OA procedure",

author = "Ansari, {Seraj A.} and Mohapatra, {Prasanta K.} and Willem Verboom and Linfeng Rao",

note = "Funding Information: This work was supported by the Director, Office of Science, Office of Basic Energy Science of the U.S. Department of Energy (DOE), under Contract No. DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory (LBNL). SAA acknowledges the Indo-US Science & Technology Forum (IUSSTF) for awarding a fellowship. The authors are thankful to Dr. Zhicheng Zhang of LBNL for technical assistance in the bi-phasic calorimetric experiments. Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/C6DT03380F",

language = "English",

volume = "45",

pages = "17216--17222",

journal = "Dalton transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

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T1 - Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide

T2 - A solution calorimetry study

AU - Ansari, Seraj A.

AU - Mohapatra, Prasanta K.

AU - Verboom, Willem

AU - Rao, Linfeng

N1 - Funding Information: This work was supported by the Director, Office of Science, Office of Basic Energy Science of the U.S. Department of Energy (DOE), under Contract No. DE-AC02-05CH11231 at Lawrence Berkeley National Laboratory (LBNL). SAA acknowledges the Indo-US Science & Technology Forum (IUSSTF) for awarding a fellowship. The authors are thankful to Dr. Zhicheng Zhang of LBNL for technical assistance in the bi-phasic calorimetric experiments. Publisher Copyright: © 2016 The Royal Society of Chemistry.

PY - 2016

Y1 - 2016

N2 - Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔHextr) of Eu(NO3)3 by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔGextr and ΔSextr) for the extraction of Eu(NO3)3 by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu3+ with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔHcomp) for the Eu3+/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu3+/T-DGA complexes from the aqueous phase to the organic phase.

AB - Isothermal titration calorimetry was employed for the direct measurement of the enthalpy of extraction (ΔHextr) of Eu(NO3)3 by using a tripodal diglycolamide (T-DGA) ligand dissolved in n-dodecane containing 5% (v/v) 2-decanol. The enthalpy of extraction obtained by titration calorimetry was in good agreement with the enthalpy of extraction calculated from the temperature dependence of the distribution coefficients by using the van't Hoff equation. The Gibbs free energy and the entropy of extraction (ΔGextr and ΔSextr) for the extraction of Eu(NO3)3 by T-DGA were also obtained by solvent extraction experiments. The complexation of Eu3+ with T-DGA in a mixture of acetonitrile/nitric acid was also studied by spectrophotometry and calorimetry to determine the stability constants and the enthalpy of complexation (ΔHcomp) for the Eu3+/T-DGA complexes in a single phase. The enthalpy of complexation, though obtained in a solvent different from that in the solvent extraction, allows a rough estimate of the enthalpy of phase transfer of the Eu3+/T-DGA complexes from the aqueous phase to the organic phase.

KW - n/a OA procedure

UR - http://www.scopus.com/inward/record.url?scp=84994242454&partnerID=8YFLogxK

U2 - 10.1039/C6DT03380F

DO - 10.1039/C6DT03380F

M3 - Article

SN - 1477-9226

VL - 45

SP - 17216

EP - 17222

JO - Dalton transactions

JF - Dalton transactions

IS - 43

ER -

Thermodynamics of biphasic lanthanide extraction by tripodal diglycolamide: A solution calorimetry study

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