Understanding Nitrilotris(methylenephosphonic acid) reactions with ferric hydroxide

Rodrigo Javier Martínez, James Farrell

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Phosphonate compounds are used in a wide variety of industrial and agricultural applications, and are commonly found in surface and ground waters. Adsorption to ferric hydroxide can have a significant effect on the transport and fate of phosphonate compounds in the environment. This research used density functional theory modeling to investigate the adsorption mechanisms of nitrilotris(methylenephosphonic acid) (NTMP) on ferric hydroxide. Standard Gibbs free energies of reaction (ΔGro) and reaction activation barriers (Ea) were calculated for different possible adsorption mechanisms. Physical adsorption of NTMP to ferric hydroxide was promoted by negative charge assisted hydrogen bonding, and had ΔGro ranging from −2.7 to −7.4 kcal/mol. NTMP was found to form three different types of inner sphere complexes, monodentate, bidentate mononuclear and bidentate binuclear. For the monodentate complexes, ΔGro ranged from −8.0 to −13.7 kcal/mol, for the bidentate complexes ΔGro ranged from −15.3 to −28.9 kcal/mol. Complexation with Ca2+ decreased the energy for physical adsorption but increased the binding energies for mono- and bidentate complexes. Complexation with Ca2+ also allowed formation of a tridentate ternary surface complex, whereby the Ca2+ ion formed a bridge between three [sbnd]Fe[sbnd]O and three [sbnd]P[sbnd]O groups. Physical adsorption had Ea = 0, but mono- and bidentate complex formation had Ea values ranging from 36 to 53 kcal/mol. Formation of tridentate ternary surface complexes involving Ca2+ had the lowest activation barriers of 8 and 10 kcal/mol. The different activation barriers for different modes of adsorption may explain previous experimental observations of unusual kinetic behavior for adsorption and desorption of NTMP.

Original languageEnglish (US)
Pages (from-to)490-496
Number of pages7
JournalChemosphere
Volume175
DOIs
StatePublished - May 1 2017

Fingerprint

Adsorption
hydroxide
adsorption
Acids
acid
Organophosphonates
Chemical activation
Complexation
complexation
agricultural application
Gibbs free energy
ferric hydroxide
(nitrilotris(methylene))triphosphonic acid
Groundwater
Hydrogen Bonding
Binding energy
Surface waters
Agriculture
Industrial applications
Density functional theory

Keywords

  • DFT
  • Ferric hydroxide adsorbents
  • nitrilotris(methylenephosphonic acid) (NTMP)
  • Phosphonate

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Understanding Nitrilotris(methylenephosphonic acid) reactions with ferric hydroxide. / Martínez, Rodrigo Javier; Farrell, James.

In: Chemosphere, Vol. 175, 01.05.2017, p. 490-496.

Research output: Contribution to journalArticle

@article{d82ae6bcd78a4c92b23a5eafd9d36f60,
title = "Understanding Nitrilotris(methylenephosphonic acid) reactions with ferric hydroxide",
abstract = "Phosphonate compounds are used in a wide variety of industrial and agricultural applications, and are commonly found in surface and ground waters. Adsorption to ferric hydroxide can have a significant effect on the transport and fate of phosphonate compounds in the environment. This research used density functional theory modeling to investigate the adsorption mechanisms of nitrilotris(methylenephosphonic acid) (NTMP) on ferric hydroxide. Standard Gibbs free energies of reaction (ΔGro) and reaction activation barriers (Ea) were calculated for different possible adsorption mechanisms. Physical adsorption of NTMP to ferric hydroxide was promoted by negative charge assisted hydrogen bonding, and had ΔGro ranging from −2.7 to −7.4 kcal/mol. NTMP was found to form three different types of inner sphere complexes, monodentate, bidentate mononuclear and bidentate binuclear. For the monodentate complexes, ΔGro ranged from −8.0 to −13.7 kcal/mol, for the bidentate complexes ΔGro ranged from −15.3 to −28.9 kcal/mol. Complexation with Ca2+ decreased the energy for physical adsorption but increased the binding energies for mono- and bidentate complexes. Complexation with Ca2+ also allowed formation of a tridentate ternary surface complex, whereby the Ca2+ ion formed a bridge between three [sbnd]Fe[sbnd]O− and three [sbnd]P[sbnd]O− groups. Physical adsorption had Ea = 0, but mono- and bidentate complex formation had Ea values ranging from 36 to 53 kcal/mol. Formation of tridentate ternary surface complexes involving Ca2+ had the lowest activation barriers of 8 and 10 kcal/mol. The different activation barriers for different modes of adsorption may explain previous experimental observations of unusual kinetic behavior for adsorption and desorption of NTMP.",
keywords = "DFT, Ferric hydroxide adsorbents, nitrilotris(methylenephosphonic acid) (NTMP), Phosphonate",
author = "Mart{\'i}nez, {Rodrigo Javier} and James Farrell",
year = "2017",
month = "5",
day = "1",
doi = "10.1016/j.chemosphere.2017.02.015",
language = "English (US)",
volume = "175",
pages = "490--496",
journal = "Chemosphere",
issn = "0045-6535",
publisher = "Elsevier Limited",

}

TY - JOUR

T1 - Understanding Nitrilotris(methylenephosphonic acid) reactions with ferric hydroxide

AU - Martínez, Rodrigo Javier

AU - Farrell, James

PY - 2017/5/1

Y1 - 2017/5/1

N2 - Phosphonate compounds are used in a wide variety of industrial and agricultural applications, and are commonly found in surface and ground waters. Adsorption to ferric hydroxide can have a significant effect on the transport and fate of phosphonate compounds in the environment. This research used density functional theory modeling to investigate the adsorption mechanisms of nitrilotris(methylenephosphonic acid) (NTMP) on ferric hydroxide. Standard Gibbs free energies of reaction (ΔGro) and reaction activation barriers (Ea) were calculated for different possible adsorption mechanisms. Physical adsorption of NTMP to ferric hydroxide was promoted by negative charge assisted hydrogen bonding, and had ΔGro ranging from −2.7 to −7.4 kcal/mol. NTMP was found to form three different types of inner sphere complexes, monodentate, bidentate mononuclear and bidentate binuclear. For the monodentate complexes, ΔGro ranged from −8.0 to −13.7 kcal/mol, for the bidentate complexes ΔGro ranged from −15.3 to −28.9 kcal/mol. Complexation with Ca2+ decreased the energy for physical adsorption but increased the binding energies for mono- and bidentate complexes. Complexation with Ca2+ also allowed formation of a tridentate ternary surface complex, whereby the Ca2+ ion formed a bridge between three [sbnd]Fe[sbnd]O− and three [sbnd]P[sbnd]O− groups. Physical adsorption had Ea = 0, but mono- and bidentate complex formation had Ea values ranging from 36 to 53 kcal/mol. Formation of tridentate ternary surface complexes involving Ca2+ had the lowest activation barriers of 8 and 10 kcal/mol. The different activation barriers for different modes of adsorption may explain previous experimental observations of unusual kinetic behavior for adsorption and desorption of NTMP.

AB - Phosphonate compounds are used in a wide variety of industrial and agricultural applications, and are commonly found in surface and ground waters. Adsorption to ferric hydroxide can have a significant effect on the transport and fate of phosphonate compounds in the environment. This research used density functional theory modeling to investigate the adsorption mechanisms of nitrilotris(methylenephosphonic acid) (NTMP) on ferric hydroxide. Standard Gibbs free energies of reaction (ΔGro) and reaction activation barriers (Ea) were calculated for different possible adsorption mechanisms. Physical adsorption of NTMP to ferric hydroxide was promoted by negative charge assisted hydrogen bonding, and had ΔGro ranging from −2.7 to −7.4 kcal/mol. NTMP was found to form three different types of inner sphere complexes, monodentate, bidentate mononuclear and bidentate binuclear. For the monodentate complexes, ΔGro ranged from −8.0 to −13.7 kcal/mol, for the bidentate complexes ΔGro ranged from −15.3 to −28.9 kcal/mol. Complexation with Ca2+ decreased the energy for physical adsorption but increased the binding energies for mono- and bidentate complexes. Complexation with Ca2+ also allowed formation of a tridentate ternary surface complex, whereby the Ca2+ ion formed a bridge between three [sbnd]Fe[sbnd]O− and three [sbnd]P[sbnd]O− groups. Physical adsorption had Ea = 0, but mono- and bidentate complex formation had Ea values ranging from 36 to 53 kcal/mol. Formation of tridentate ternary surface complexes involving Ca2+ had the lowest activation barriers of 8 and 10 kcal/mol. The different activation barriers for different modes of adsorption may explain previous experimental observations of unusual kinetic behavior for adsorption and desorption of NTMP.

KW - DFT

KW - Ferric hydroxide adsorbents

KW - nitrilotris(methylenephosphonic acid) (NTMP)

KW - Phosphonate

UR - http://www.scopus.com/inward/record.url?scp=85013953710&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85013953710&partnerID=8YFLogxK

U2 - 10.1016/j.chemosphere.2017.02.015

DO - 10.1016/j.chemosphere.2017.02.015

M3 - Article

C2 - 28249190

AN - SCOPUS:85013953710

VL - 175

SP - 490

EP - 496

JO - Chemosphere

JF - Chemosphere

SN - 0045-6535

ER -