Colloid and Polymer Science

, Volume 293, Issue 5, pp 1409–1423 | Cite as

Influence of solvent chemistry on 1H NMR spectral and relaxation properties of a long-chain ionic surfactant in chloroform-d

  • Michael A. Desando
  • Gojmir Lahajnar
  • Miha Friedrich
  • Janez Plavec
  • Gašper Tavčar
Original Contribution

Abstract

1H NMR chemical shift, line width, indirect nuclear splitting value, peak area integration value, and spin–lattice and spin–spin relaxation times at 298 K are compared for low-concentration isotropic solutions of n-octylammonium n-octadecanoate prepared via different techniques and conditions using dried, distilled, and degassed deuterochloroform and the nontreated solvent containing tetramethylsilane. The nature of the variation of observed spectral parameters and relaxation/rotational behavior with chemical composition (presence of oxygen and other paramagnetic species, stabilizer, impurities, and degradation products) of the solvent, history of the solution, and sample containment are analyzed. Relaxation times are interpreted in terms of monomer structure and reorientation and internal rotation modes as a function of atomic position along the n-alkyl chains. Collectively, the relaxation behavior of the surfactant complies with the two-step model of fast picosecond internal rotations of different size segments containing methylene groups separated in timescale from slower large segment and overall molecular tumbling modes of the monomer. Fast motional phenomena do not appear to be appreciably influenced by the chemistry of the solvent in contrast to spectral parameters such as chemical shift and line width of the labile ammonium protons. A model is also presented to explain anomalous variation of the peak area integration value with chemical shift of the ammonium resonance peak.

Keywords

n-Octylammonium n-octadecanoate surfactant 1H NMR spin relaxation NMR spectral properties Reverse micelle Deuterochloroform chemistry 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Michael A. Desando
    • 1
    • 6
  • Gojmir Lahajnar
    • 1
  • Miha Friedrich
    • 3
  • Janez Plavec
    • 4
    • 5
  • Gašper Tavčar
    • 2
  1. 1.Solid State Physics DepartmentJožef Stefan InstituteLjubljanaSlovenia
  2. 2.Department of Inorganic Chemistry and TechnologyJožef Stefan InstituteLjubljanaSlovenia
  3. 3.EN-FIST Centre of ExcellenceLjubljanaSlovenia
  4. 4.Slovenian NMR CentreNational Institute of ChemistryLjubljanaSlovenia
  5. 5.Faculty of Chemistry and Chemical TechnologyUniversity of LjubljanaLjubljanaSlovenia
  6. 6.Thunder BayCanada

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