DOI: 10.1346/ccmn.1964.0130128. Infrared Studies of the Hydroxyl Groups in Intercalated Kaolinite Complexes

Infrared Studies of the Hydroxyl Groups in Intercalated Kaolinite Complexes

10.1346/ccmn.1964.0130128

Crossref journal-article

Cambridge University Press (CUP)

Clays and clay minerals (National Conference on Clays and Clay Minerals) (56)

Abstract

Abstract Expansion of kaolinite with potassium acetate reduces the intensity of the 3695 cm−1 absorption band and causes the appearance of an additional one at 3600 cm−1. Subsequent deuteration with D2O vapor shifts the 3695 cm−1 and 3600 cm−1 absorption bands to 2725 cm−1 and 2650 cm−1 respectively. The hydroxyls absorbing at 3620 cm−1 do not interact with the acetate anion and do not readily exchange with D2O vapor. Deuteration of expanded hydrazine-kaolinite complex at room temperature shifts the infrared stretching frequencies 3695, 3670, 3650 and 3620 cm−1 to 2725, 2710, 2698 and 2675 cm−1 respectively. The OH-OD exchanges for the hydroxyls absorbing at 3695, 3670 and 3650 cm−1 are 67, 60 and 62 per cent respectively, and for the 3620 cm−1 only 22 per cent. The 3695, 3670 and 3650 cm−1 absorption bands are correlated predominantly to inner-surface hydroxyls and the 3620 cm−1 to inner hydroxyls located below the holes in the silica tetrahedral layer. The ν(OH) absorption bands at 3695, 3670 and 3650 cm−1, and the ν(OD) at 2725, 2698, and 2675 cm−1 are pleochroic, whereas the 3620 cm−1 absorption band is non-pleochroic. The direction of the dipole moment change of OH groups absorbing at 3695 cm−1 and 3670 cm−1, and of OD groups absorbing at 2725 cm−1 and 2698 cm−1, is nearly at right angles to the basal plane (001); for the 3650 cm−1 and 2675 cm−1 bands, the angle is large, but less than 90°. The inner hydroxyls absorbing at 3620 cm−1 have their dipole moment change inclined at about 15° to the “ab” cleavage plane. A comparison of the ν(OH) and ν(OD) absorption intensities for the film rotated 45° and normal to the infrared incident radiation shows that the pleochroism is more intense in the ν(OD) region than in the ν(OH) region. This indicates that partial deuteration perturbs the direction of dipole moment change of the “hydrogen bond” with respect to the initial orientation prior to deuteration; the net result is the formation of larger angles between the direction of the OD dipole moment changes and the basal plane (001) than existed for OH prior to deuteration.

Bibliography

Ledoux, R. L., & White, J. L. (1964). Infrared Studies of the Hydroxyl Groups in Intercalated Kaolinite Complexes. Clays and Clay Minerals (National Conference on Clays and Clay Minerals), 13, 289â315.

Authors 2

Robert L. Ledoux (first)
Joe L. White (additional)

References 29 Referenced 27

10.1016/0016-7037(57)90006-6
10.1038/186627b0
10.1063/1.1700155
{'key': 'S264093640000441X_bib25', 'first-page': '15', 'article-title': 'Surface and internal structure of clay minerals as indicated by infrared spectra', 'volume': '33', 'author': 'Wadsworth', 'year': '1955', 'journal-title': 'Am. Ceram. Soc. Bull.'} / Am. Ceram. Soc. Bull. / Surface and internal structure of clay minerals as indicated by infrared spectra by Wadsworth (1955)
10.1021/j150546a004
{'key': 'S264093640000441X_bib11', 'volume-title': 'Infra-Red Spectroscopy and Molecular Structure', 'author': 'Hallan', 'year': '1963'} / Infra-Red Spectroscopy and Molecular Structure by Hallan (1963)
10.1038/195486a0
10.1130/0016-7606(1960)71[449:ROHOIM]2.0.CO;2
{'key': 'S264093640000441X_bib26', 'first-page': '287', 'volume-title': 'International Clay Conference', 'author': 'Weiss', 'year': '1963a'} / International Clay Conference by Weiss (1963a)
{'key': 'S264093640000441X_bib22', 'article-title': 'OH stretching bands of the kaolin minerals', 'volume': '24', 'author': 'Van der Marel', 'year': '1958', 'journal-title': 'Silicates Ind.'} / Silicates Ind. / OH stretching bands of the kaolin minerals by Van der Marel (1958)
10.1021/j100795a008
{'key': 'S264093640000441X_bib29', 'article-title': 'Structural aspects of kaolinite using infrared absorption', 'volume': '48', 'author': 'Wolff', 'year': '1963', 'journal-title': 'Am. Mineralogist'} / Am. Mineralogist / Structural aspects of kaolinite using infrared absorption by Wolff (1963)
10.2136/sssaj1960.03615995002400050034x
{'key': 'S264093640000441X_bib21', 'first-page': '17', 'volume-title': 'International Clay Conference, Sweden', 'author': 'Serratosa', 'year': '1963'} / International Clay Conference, Sweden by Serratosa (1963)
10.1107/S0365110X58002243
10.1002/zaac.19633200122
10.1021/ac60096a007 / Anal. Chem. / Characterization of hydrated aluminas by infrared spectroscopy; application to study of bauxite ores by Frederickson (1954)
10.1021/j150568a004
{'key': 'S264093640000441X_bib13', 'volume-title': 'Infra-Red Spectroscopy and Molecular Structure', 'author': 'Krimm', 'year': '1963'} / Infra-Red Spectroscopy and Molecular Structure by Krimm (1963)
{'key': 'S264093640000441X_bib24', 'first-page': '78', 'article-title': 'Lattice expansion of kaolin minerals by treatment with potassium acetate', 'volume': '46', 'author': 'Wada', 'year': '1961', 'journal-title': 'Am. Mineralogist'} / Am. Mineralogist / Lattice expansion of kaolin minerals by treatment with potassium acetate by Wada (1961)
{'key': 'S264093640000441X_bib16', 'first-page': '1', 'volume': '148', 'author': 'Newnham', 'year': '1960', 'journal-title': 'A refinement of the dickite structure and some remarks on polymorphism in kaolin minerals'} / A refinement of the dickite structure and some remarks on polymorphism in kaolin minerals by Newnham (1960)
{'key': 'S264093640000441X_bib15', 'volume-title': 'Infrared Spectra of Inorganic and Coordination Compounds', 'author': 'Nakamoto', 'year': '1963'} / Infrared Spectra of Inorganic and Coordination Compounds by Nakamoto (1963)
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Auskern, A , and Grimshaw, R. W. (1955) Differences between the infrared absorption spectra of some clays and related minerals (abstract), Program of the Fourth National Clay Conference, Pennsylvania State University.
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{'key': 'S264093640000441X_bib5', 'article-title': 'On the infrared spectrum of hydrazine matrix-isolation studies of the system NH2NH2: N2 (1)', 'volume': '38', 'author': 'Catalano', 'year': '1963', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. / On the infrared spectrum of hydrazine matrix-isolation studies of the system NH2NH2: N2 (1) by Catalano (1963)
{'key': 'S264093640000441X_bib28', 'article-title': 'Reactions of molten salts with layer-lattice silicates', 'volume': '456', 'author': 'White', 'year': '1956', 'journal-title': 'Clays and Clay Minerals'} / Clays and Clay Minerals / Reactions of molten salts with layer-lattice silicates by White (1956)
{'key': 'S264093640000441X_bib6', 'article-title': 'Surface area of clay minerals as derived from measurements of glycerol retention', 'volume': '566', 'author': 'Diamond', 'year': '1958', 'journal-title': 'Clays and Clay Minerals'} / Clays and Clay Minerals / Surface area of clay minerals as derived from measurements of glycerol retention by Diamond (1958)
{'key': 'S264093640000441X_bib17', 'volume-title': 'Clays and Clay Minerals', 'author': 'Rosenqvist', 'year': '1963'} / Clays and Clay Minerals by Rosenqvist (1963)

Dates

Type	When
Created	19 years ago (Aug. 29, 2006, 3:30 a.m.)
Deposited	1 year, 5 months ago (March 11, 2024, 5:58 a.m.)
Indexed	1 year, 2 months ago (July 6, 2024, 11:18 a.m.)
Issued	61 years, 7 months ago (Feb. 1, 1964)
Published	61 years, 7 months ago (Feb. 1, 1964)
Published Online	1 year, 8 months ago (Jan. 1, 2024)
Published Print	61 years, 7 months ago (Feb. 1, 1964)

Funders 0

None

BibTeX

@article{Ledoux_1964, title={Infrared Studies of the Hydroxyl Groups in Intercalated Kaolinite Complexes}, volume={13}, ISSN={2993-6780}, url={http://dx.doi.org/10.1346/ccmn.1964.0130128}, DOI={10.1346/ccmn.1964.0130128}, journal={Clays and clay minerals (National Conference on Clays and Clay Minerals)}, publisher={Cambridge University Press (CUP)}, author={Ledoux, Robert L. and White, Joe L.}, year={1964}, month=feb, pages={289–315} }

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  "abstract": "<jats:title>Abstract</jats:title>\n                    <jats:p><jats:sc>Expansion</jats:sc> of kaolinite with potassium acetate reduces\n                        the intensity of the 3695 cm<jats:sup>\u22121</jats:sup> absorption band and\n                        causes the appearance of an additional one at 3600\n                        cm<jats:sup>\u22121</jats:sup>. Subsequent deuteration with\n                            D<jats:sub>2</jats:sub>O vapor shifts the 3695 cm<jats:sup>\u22121</jats:sup>\n                        and 3600 cm<jats:sup>\u22121</jats:sup> absorption bands to 2725\n                            cm<jats:sup>\u22121</jats:sup> and 2650 cm<jats:sup>\u22121</jats:sup>\n                        respectively. The hydroxyls absorbing at 3620 cm<jats:sup>\u22121</jats:sup> do\n                        not interact with the acetate anion and do not readily exchange with\n                            D<jats:sub>2</jats:sub>O vapor.</jats:p>\n                    <jats:p>Deuteration of expanded hydrazine-kaolinite complex at room temperature\n                        shifts the infrared stretching frequencies 3695, 3670, 3650 and 3620\n                            cm<jats:sup>\u22121</jats:sup> to 2725, 2710, 2698 and 2675\n                            cm<jats:sup>\u22121</jats:sup> respectively. The OH-OD exchanges for the\n                        hydroxyls absorbing at 3695, 3670 and 3650 cm<jats:sup>\u22121</jats:sup> are 67,\n                        60 and 62 per cent respectively, and for the 3620 cm<jats:sup>\u22121</jats:sup>\n                        only 22 per cent. The 3695, 3670 and 3650 cm<jats:sup>\u22121</jats:sup>\n                        absorption bands are correlated predominantly to inner-surface hydroxyls and\n                        the 3620 cm<jats:sup>\u22121</jats:sup> to inner hydroxyls located below the\n                        holes in the silica tetrahedral layer.</jats:p>\n                    <jats:p>The <jats:italic>\u03bd</jats:italic>(OH) absorption bands at 3695, 3670 and\n                        3650 cm<jats:sup>\u22121</jats:sup>, and the <jats:italic>\u03bd</jats:italic>(OD) at\n                        2725, 2698, and 2675 cm<jats:sup>\u22121</jats:sup> are pleochroic, whereas the\n                        3620 cm<jats:sup>\u22121</jats:sup> absorption band is non-pleochroic. The\n                        direction of the dipole moment change of OH groups absorbing at 3695\n                            cm<jats:sup>\u22121</jats:sup> and 3670 cm<jats:sup>\u22121</jats:sup>, and of OD\n                        groups absorbing at 2725 cm<jats:sup>\u22121</jats:sup> and 2698\n                            cm<jats:sup>\u22121</jats:sup>, is nearly at right angles to the basal plane\n                        (001); for the 3650 cm<jats:sup>\u22121</jats:sup> and 2675\n                            cm<jats:sup>\u22121</jats:sup> bands, the angle is large, but less than 90\u00b0.\n                        The inner hydroxyls absorbing at 3620 cm<jats:sup>\u22121</jats:sup> have their\n                        dipole moment change inclined at about 15\u00b0 to the \u201cab\u201d cleavage\n                        plane.</jats:p>\n                    <jats:p>A comparison of the <jats:italic>\u03bd</jats:italic>(OH) and\n                            <jats:italic>\u03bd</jats:italic>(OD) absorption intensities for the film\n                        rotated 45\u00b0 and normal to the infrared incident radiation shows that the\n                        pleochroism is more intense in the <jats:italic>\u03bd</jats:italic>(OD) region\n                        than in the <jats:italic>\u03bd</jats:italic>(OH) region. This indicates that\n                        partial deuteration perturbs the direction of dipole moment change of the\n                        \u201chydrogen bond\u201d with respect to the initial orientation prior to\n                        deuteration; the net result is the formation of larger angles between the\n                        direction of the OD dipole moment changes and the basal plane (001) than\n                        existed for OH prior to deuteration.</jats:p>",
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