The formation of Cu(II) complexes with carbonate and bicarbonate ions in NaClO4 solutions

Frank J Millero, J. Magdalena Santana-Casiano, Melchor González-Dávila

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The inorganic behavior of most divalent metals in natural waters is affected by the formation of carbonate complexes. The acidification of the oceans will lower the carbonate concentration in the oceans. This will increase the concentration of free copper that is toxic to marine organisms. To be able to determine the effect of this acidification, reliable stability constants are needed for the formation of copper carbonate complexes. In this paper, the speciation of Cu(II) with bicarbonate and carbonate ions Cu2++ HCO3 - ⇋ CuCO3aq+H+ Cu 2++2HCO3 - ⇋ Cu(CO3) 2 2-+2H+ Cu2++ CO3 2- ⇋ CuCO3(aq) Cu2++2CO3 2-} Cu(CO3)2 2- Cu2++ HCO3 - ⇋ CuHCO3 + is investigated as a function of ionic strength and temperature in NaClO 4 solutions. To fully examine the system, the dissociation of carbonic acid in the media were examined using the Pitzer equations in NaClO4 solutions to 6.5 mol·kg-1 at 25°C. With this foundation, the stability constants for the formation of Cu(II) carbonate complexes were used to determine the activity coefficients for the complexes (CuHCO3 +, CuCO3, Cu(CO3) 2 2-) . Pitzer parameters for these complexes were determined at 25°C and ionic strength (0 to 1.1 mol·kg-1) in NaClO4 solutions. Since the formation of Cu(II) carbonate complexes appear to be linearly related to the values for other metals, it is possible to use the correlations to estimate the carbonate constants for a number of other divalent metals.

Original languageEnglish (US)
Pages (from-to)543-558
Number of pages16
JournalJournal of Solution Chemistry
Volume39
Issue number4
DOIs
StatePublished - Apr 2010

Fingerprint

Carbonates
Bicarbonates
carbonates
ions
Acidification
Metals
Ionic strength
Oceans and Seas
Osmolar Concentration
Carbonic Acid
Aquatic Organisms
oceans
Poisons
Activity coefficients
carbonic acid
metals
copper
Copper
organisms
Ions

Keywords

  • Carbonato complexes
  • Carbonic acid
  • Cu(II)
  • Metals
  • Pitzer equations
  • Speciation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Biochemistry
  • Biophysics
  • Molecular Biology

Cite this

The formation of Cu(II) complexes with carbonate and bicarbonate ions in NaClO4 solutions. / Millero, Frank J; Santana-Casiano, J. Magdalena; González-Dávila, Melchor.

In: Journal of Solution Chemistry, Vol. 39, No. 4, 04.2010, p. 543-558.

Research output: Contribution to journalArticle

Millero, Frank J ; Santana-Casiano, J. Magdalena ; González-Dávila, Melchor. / The formation of Cu(II) complexes with carbonate and bicarbonate ions in NaClO4 solutions. In: Journal of Solution Chemistry. 2010 ; Vol. 39, No. 4. pp. 543-558.
@article{7681019b2cd04d258fc0caedf7122fce,
title = "The formation of Cu(II) complexes with carbonate and bicarbonate ions in NaClO4 solutions",
abstract = "The inorganic behavior of most divalent metals in natural waters is affected by the formation of carbonate complexes. The acidification of the oceans will lower the carbonate concentration in the oceans. This will increase the concentration of free copper that is toxic to marine organisms. To be able to determine the effect of this acidification, reliable stability constants are needed for the formation of copper carbonate complexes. In this paper, the speciation of Cu(II) with bicarbonate and carbonate ions Cu2++ HCO3 - ⇋ CuCO3aq+H+ Cu 2++2HCO3 - ⇋ Cu(CO3) 2 2-+2H+ Cu2++ CO3 2- ⇋ CuCO3(aq) Cu2++2CO3 2-} Cu(CO3)2 2- Cu2++ HCO3 - ⇋ CuHCO3 + is investigated as a function of ionic strength and temperature in NaClO 4 solutions. To fully examine the system, the dissociation of carbonic acid in the media were examined using the Pitzer equations in NaClO4 solutions to 6.5 mol·kg-1 at 25°C. With this foundation, the stability constants for the formation of Cu(II) carbonate complexes were used to determine the activity coefficients for the complexes (CuHCO3 +, CuCO3, Cu(CO3) 2 2-) . Pitzer parameters for these complexes were determined at 25°C and ionic strength (0 to 1.1 mol·kg-1) in NaClO4 solutions. Since the formation of Cu(II) carbonate complexes appear to be linearly related to the values for other metals, it is possible to use the correlations to estimate the carbonate constants for a number of other divalent metals.",
keywords = "Carbonato complexes, Carbonic acid, Cu(II), Metals, Pitzer equations, Speciation",
author = "Millero, {Frank J} and Santana-Casiano, {J. Magdalena} and Melchor Gonz{\'a}lez-D{\'a}vila",
year = "2010",
month = "4",
doi = "10.1007/s10953-010-9523-z",
language = "English (US)",
volume = "39",
pages = "543--558",
journal = "Journal of Solution Chemistry",
issn = "0095-9782",
publisher = "Springer New York",
number = "4",

}

TY - JOUR

T1 - The formation of Cu(II) complexes with carbonate and bicarbonate ions in NaClO4 solutions

AU - Millero, Frank J

AU - Santana-Casiano, J. Magdalena

AU - González-Dávila, Melchor

PY - 2010/4

Y1 - 2010/4

N2 - The inorganic behavior of most divalent metals in natural waters is affected by the formation of carbonate complexes. The acidification of the oceans will lower the carbonate concentration in the oceans. This will increase the concentration of free copper that is toxic to marine organisms. To be able to determine the effect of this acidification, reliable stability constants are needed for the formation of copper carbonate complexes. In this paper, the speciation of Cu(II) with bicarbonate and carbonate ions Cu2++ HCO3 - ⇋ CuCO3aq+H+ Cu 2++2HCO3 - ⇋ Cu(CO3) 2 2-+2H+ Cu2++ CO3 2- ⇋ CuCO3(aq) Cu2++2CO3 2-} Cu(CO3)2 2- Cu2++ HCO3 - ⇋ CuHCO3 + is investigated as a function of ionic strength and temperature in NaClO 4 solutions. To fully examine the system, the dissociation of carbonic acid in the media were examined using the Pitzer equations in NaClO4 solutions to 6.5 mol·kg-1 at 25°C. With this foundation, the stability constants for the formation of Cu(II) carbonate complexes were used to determine the activity coefficients for the complexes (CuHCO3 +, CuCO3, Cu(CO3) 2 2-) . Pitzer parameters for these complexes were determined at 25°C and ionic strength (0 to 1.1 mol·kg-1) in NaClO4 solutions. Since the formation of Cu(II) carbonate complexes appear to be linearly related to the values for other metals, it is possible to use the correlations to estimate the carbonate constants for a number of other divalent metals.

AB - The inorganic behavior of most divalent metals in natural waters is affected by the formation of carbonate complexes. The acidification of the oceans will lower the carbonate concentration in the oceans. This will increase the concentration of free copper that is toxic to marine organisms. To be able to determine the effect of this acidification, reliable stability constants are needed for the formation of copper carbonate complexes. In this paper, the speciation of Cu(II) with bicarbonate and carbonate ions Cu2++ HCO3 - ⇋ CuCO3aq+H+ Cu 2++2HCO3 - ⇋ Cu(CO3) 2 2-+2H+ Cu2++ CO3 2- ⇋ CuCO3(aq) Cu2++2CO3 2-} Cu(CO3)2 2- Cu2++ HCO3 - ⇋ CuHCO3 + is investigated as a function of ionic strength and temperature in NaClO 4 solutions. To fully examine the system, the dissociation of carbonic acid in the media were examined using the Pitzer equations in NaClO4 solutions to 6.5 mol·kg-1 at 25°C. With this foundation, the stability constants for the formation of Cu(II) carbonate complexes were used to determine the activity coefficients for the complexes (CuHCO3 +, CuCO3, Cu(CO3) 2 2-) . Pitzer parameters for these complexes were determined at 25°C and ionic strength (0 to 1.1 mol·kg-1) in NaClO4 solutions. Since the formation of Cu(II) carbonate complexes appear to be linearly related to the values for other metals, it is possible to use the correlations to estimate the carbonate constants for a number of other divalent metals.

KW - Carbonato complexes

KW - Carbonic acid

KW - Cu(II)

KW - Metals

KW - Pitzer equations

KW - Speciation

UR - http://www.scopus.com/inward/record.url?scp=77952095286&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77952095286&partnerID=8YFLogxK

U2 - 10.1007/s10953-010-9523-z

DO - 10.1007/s10953-010-9523-z

M3 - Article

VL - 39

SP - 543

EP - 558

JO - Journal of Solution Chemistry

JF - Journal of Solution Chemistry

SN - 0095-9782

IS - 4

ER -