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Kink Block Structures in Clay Organic Complexes

Published online by Cambridge University Press:  01 July 2024

G. Lagaly ,
St. Fitz  and
Armin Weiss
G. Lagaly*
Affiliation:
Institut für Anorganische Chemie der Universität Kiel
St. Fitz
Affiliation:
Institut für Anorganische Chemie der Universität München, GFR
Armin Weiss
Affiliation:
Institut für Anorganische Chemie der Universität München, GFR
*
*Correspondence and requests for reprints to G. Lagaly.
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Abstract

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Complexes of n-tetradecylammonium-beidellite with n-alkanols

${\rm{(n - }}{{\rm{C}}_{{\rm{14}}}}{{\rm{H}}_{{\rm{29}}}}{\rm{N}}{{\rm{H}}_{\rm{3}}}^{\rm{+}}{\rm{)_{{\rm{0,44}}}(n - C_{{\rm{x}}}}}{{\rm{H}}_{{\rm{2x}}}}{\rm{+}}{}_{\rm{1}}{\rm{OH) }}{}_{{\rm{1,56}}}{{\rm{\{ M}}{{\rm{g}}_{{\rm{0,28}}}}{\rm{A}}{{\rm{l}}_{{\rm{1,81}}}}{{\rm{(OH)}}_{\rm{2}}}{\rm{S}}{{\rm{i}}_{{\rm{3,56}}}}{\rm{Al}}{}_{{\rm{0,44}}}{\rm{O_{{10\}} }}}^{{\rm{0,44 - }}}}$
(x = 8–22) have been prepared and characterized by their basal spacings and by measurements of the specific heat cp.

The compounds undergo a series of reversible phase transitions

${\beta _1} \rightleftharpoons...\rightleftharpoons{\beta_i}\rightleftharpoons...\rightleftharpoons{\beta_\omega}\rightleftharpoons{\alpha_1}...\rightleftharpoons{\alpha_j}$
with rising temperature. The maximum number ω of β-phases depends upon the chain lengths and increases from 1 with decanol to 6 with docosanol. Due to the evaporation of alkanol the number of χ-phases is not yet established in all details.

The β-transitions correspond to conformational changes of the alkyl chains via rotational isomerisation, especially kink formation. The β-phases become unstable if the kink concentration exceeds 0,14 kinks/-CH2-. The β/α-transition is probably caused by a rearrangement into special gauche-block structures.

Type
Research Article
Information
Clays and Clay Minerals , Volume 23 , Issue 1 , February 1975 , pp. 45 - 54
Copyright
Copyright © 1975, The Clay Minerals Society

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