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Chelating surfactants

analysis, hydrogen bonding and structures

Häggman, Leif (2003). Chelating surfactants. Diss. (sammanfattning/summary) Uppsala : Sveriges lantbruksuniv., Acta Universitatis Agriculturae Sueciae. Agraria, 1401-6249 ; 384
ISBN 91-576-6428-5
[Doctoral thesis]

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Self-assembly of alkyl-N-iminodiacetic acid (R-IDA) system, R = -CH₃, -C₆H₁₃, -C₁₂H₂₅ and -C₁₈H₃₇, has been characterized by means of X-ray crystallography. The solid state presents highly ordered tilted interdigitated bilayer structures with saturated hydrocarbon chains parallel aligned from opposite directions. The polar head groups are intermolecularly hydrogen bound mediated by imino nitrogen and carboxylate groups. The zwitterionic units are cross-linked by short strong hydrogen bonds, d(O(-H)...O) ≈ 2.46 Å, forming a polymeric structure, and two-dimensional sheets by weaker bonds, d(N(-H)...O)≈ 2.8 Å. The alkyl-N-iminodiacetic acid systems are present as monomers in water, CH₃-IDA and C₆H₁₃-IDA, have acidic constants in the expected range, pKa₁ ≈ 1.6, pKa₂ ≈ 2.3 and pKa₃ = 9.6-10.4. The long tailed n-octadecyl-N-iminodiacetic acid system has a very acidic first proton, a substantially weaker second acidic constant, pKa₂ = 5.6-7.6 and pKa₃ = 9.4-10.6, strongly dependent on ionic strength. These results show that the short strong hydrogen bonds are maintained in aqueous systems. The complex formation, acid-base properties and the structures of the copper(II)- and zinc(II)-alkyl-N-iminodiacetic acid systems have been studied as well. EXAFS refinement presents a uniform short range order around copper(II), d(Cu-O/N) = 1.94-1.98 Å, nearly independent of composition and hydrocarbon chain length. On the other hand, the zinc(II) system has a wider range of coordination numbers, 4-6, and Zn-O/N bond distances, 1.99-2.08 Å. The acidic constant of the second copper(II)-alkyl-N-iminodiacetate complex has been determined to pKa = 5.3-6.3. For the zinc(II)-n-hexyl-N-iminodiacetate acid system (1:2) a buffer region of two protons, pKa~4.0 and 7.0 is observed. The stability of the n-octadecyl-N-iminodiacetate acid system was investigated by potentiometric methods. The C₁₈H₃₇-IDA aggregates in aqueous suspension are totally unaffected by the presence of copper at pH values below 4, weakly affected in the region 4-7, while complex formation takes readily place above pH ≈ 7, but kinetically controlled. An analytical method to determine the concentration of compounds forming strong complexes eith copper in the μM range has been developed.

Authors/Creators:Häggman, Leif
Title:Chelating surfactants
Subtitle:analysis, hydrogen bonding and structures
Series Name/Journal:Acta Universitatis Agriculturae Sueciae. Agraria
Year of publishing :January 2003
Number of Pages:59
ALLI. A Spectrophotometric Method for Determination of Polyamine Concentration Using a Colored Metal Complex as Probe. Leif Häggman and Ingmar Persson. Report to Akzo Nobel Surface Chemistry AB, Stenungsund, April 2003. II. The Influence of Short Strong Hydrogen Bonding on the Structure and the Physico-Chemical Properties of Alkyl-N-iminodiacetic Acids in Solid State and Aqueous Systems. Leif Häggman, Cecilia Lindblad, Hans Oskarsson, Ann-Sofi Ullström and Ingmar Persson. J. Am. Chem. Soc., 2003, 125, 3631-3641. III. Short Strong Hydrogen Bonds Can Hinder Complex Formation - A Structure and Stability Study of Copper(II) Alkyl-N-Iminodiacetic Acid Complexes in Aqueous Solution and Solid State. Leif Häggman and Ingmar Persson. Manuscript. IV. Complex Formation Between Zinc(II) and alkyl-N-Iminodiacetic Acids in Aqueous Solution and Solid State. Leif Häggman, Cecilia Lindblad, and Ingmar Persson. Manuscript.
Place of Publication:Uppsala
ISBN for printed version:91-576-6428-5
Publication Type:Doctoral thesis
Full Text Status:Public
Agris subject categories.:X Agricola extesions > X50 Chemistry
Subjects:Not in use, please see Agris categories
Agrovoc terms:surfactants
Keywords:alkyl-N-iminodiacetic acid, self-assembly, interdigitated, bilayer, framework, acidic constants, short strong hydrogen bonds (SSHB)s, intermolecular hydrogen bond, copper, zinc, kinetics
Permanent URL:
ID Code:434
Department:(NL, NJ) > Dept. of Chemistry (until 131231)
Deposited By: Staff Epsilon
Deposited On:19 Jan 2004 00:00
Metadata Last Modified:02 Dec 2014 10:04

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