Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties
The studies on salts of malic acide scarce if one excepts structural determinations. This is especially the case for vibrational properties. Before the present work, this kind of investigations did not exist for lithium dimalate. The two salts of malic acid, which are the object of the present thesi...
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Language: | French |
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1994
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ftccsdartic:oai:HAL:tel-01776855v1 2023-05-15T16:01:44+02:00 Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties Cristallogénèse et étude structurale, thermodynamique et spectroscopique des malates hydrogénés de lithium et d'ammonium : rôles des groupements organiques et des liaisons hydrogène dans les propriétés vibrationnelles Kemiche, Madjid Université Paul Verlaine - Metz (UPVM) Université Paul Verlaine - Metz Constantin Carabatos-Nedelec 1994-12-13 https://hal.univ-lorraine.fr/tel-01776855 https://hal.univ-lorraine.fr/tel-01776855/document https://hal.univ-lorraine.fr/tel-01776855/file/Kemiche.Madjid.SMZ9465.pdf fr fre HAL CCSD NNT: 1994METZ065S tel-01776855 https://hal.univ-lorraine.fr/tel-01776855 https://hal.univ-lorraine.fr/tel-01776855/document https://hal.univ-lorraine.fr/tel-01776855/file/Kemiche.Madjid.SMZ9465.pdf info:eu-repo/semantics/OpenAccess https://hal.univ-lorraine.fr/tel-01776855 Matière Condensée [cond-mat]. Université Paul Verlaine - Metz, 1994. Français. ⟨NNT : 1994METZ065S⟩ Calorimétrie différentielle Cristallogénèse Dimalate de lithium Malique Acide Calorimétrie [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] info:eu-repo/semantics/doctoralThesis Theses 1994 ftccsdartic 2022-04-03T01:03:05Z The studies on salts of malic acide scarce if one excepts structural determinations. This is especially the case for vibrational properties. Before the present work, this kind of investigations did not exist for lithium dimalate. The two salts of malic acid, which are the object of the present thesis, lithium dimalate (C4H6O5,C4H5O5-, Li+)DML) and ammonium malate (C4H5O5-,NH4+) (MA), exhibit layered structures. Links between the layers are provided by a number of hydrogen bonds. We have synthesised these crystals and made the necessary controls of their structure. We have focused our attention particularly on hydrogen bonds. The differential scanning calorimetry showed that the breaking of the hydrogen bonds is responsible of the relatively low melting point of those compounds. The same study allowed the determination of the global energy of this kind of bonds for the two crystals. We have calculated the frequencies of the O.O stretching modes of the hydrogen bonds and the results are in agreement with the modes observed by raman spectroscopy. The high frequencies of the O-H stretching modes have also been studied experimentally. The high temperature raman spectra, as well as the low temperature ones, showed the stability of the monoclinic structure of DML and of the orthorhombic structure of MA from 10K to the beginning of the melting process around 423K. No phase transition has been detected. An assignment has been proposed for most of the internal modes observed by raman spectroscopy. The infrared reflectivity studies showed the weakness of the coulomb forces for both DML and MA the observed LO-TO splittings are small. As a first attempt, we have undertaken a lattice dynamical calculation with a simple De Launay type central force model. However, this model needs improvements, for example angular deformations could be taken into account La famille des sels d'acide malique n'a pas fait l'objet de très nombreuses études, en dehors de déterminations structurales. Ceci est notamment le cas pour les propriétés ... Doctoral or Postdoctoral Thesis DML Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) |
institution |
Open Polar |
collection |
Archive ouverte HAL (Hyper Article en Ligne, CCSD - Centre pour la Communication Scientifique Directe) |
op_collection_id |
ftccsdartic |
language |
French |
topic |
Calorimétrie différentielle Cristallogénèse Dimalate de lithium Malique Acide Calorimétrie [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] |
spellingShingle |
Calorimétrie différentielle Cristallogénèse Dimalate de lithium Malique Acide Calorimétrie [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] Kemiche, Madjid Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
topic_facet |
Calorimétrie différentielle Cristallogénèse Dimalate de lithium Malique Acide Calorimétrie [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat] |
description |
The studies on salts of malic acide scarce if one excepts structural determinations. This is especially the case for vibrational properties. Before the present work, this kind of investigations did not exist for lithium dimalate. The two salts of malic acid, which are the object of the present thesis, lithium dimalate (C4H6O5,C4H5O5-, Li+)DML) and ammonium malate (C4H5O5-,NH4+) (MA), exhibit layered structures. Links between the layers are provided by a number of hydrogen bonds. We have synthesised these crystals and made the necessary controls of their structure. We have focused our attention particularly on hydrogen bonds. The differential scanning calorimetry showed that the breaking of the hydrogen bonds is responsible of the relatively low melting point of those compounds. The same study allowed the determination of the global energy of this kind of bonds for the two crystals. We have calculated the frequencies of the O.O stretching modes of the hydrogen bonds and the results are in agreement with the modes observed by raman spectroscopy. The high frequencies of the O-H stretching modes have also been studied experimentally. The high temperature raman spectra, as well as the low temperature ones, showed the stability of the monoclinic structure of DML and of the orthorhombic structure of MA from 10K to the beginning of the melting process around 423K. No phase transition has been detected. An assignment has been proposed for most of the internal modes observed by raman spectroscopy. The infrared reflectivity studies showed the weakness of the coulomb forces for both DML and MA the observed LO-TO splittings are small. As a first attempt, we have undertaken a lattice dynamical calculation with a simple De Launay type central force model. However, this model needs improvements, for example angular deformations could be taken into account La famille des sels d'acide malique n'a pas fait l'objet de très nombreuses études, en dehors de déterminations structurales. Ceci est notamment le cas pour les propriétés ... |
author2 |
Université Paul Verlaine - Metz (UPVM) Université Paul Verlaine - Metz Constantin Carabatos-Nedelec |
format |
Doctoral or Postdoctoral Thesis |
author |
Kemiche, Madjid |
author_facet |
Kemiche, Madjid |
author_sort |
Kemiche, Madjid |
title |
Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
title_short |
Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
title_full |
Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
title_fullStr |
Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
title_full_unstemmed |
Crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
title_sort |
crystal growth and structural, thermodynamical and spectroscopic studies of lithium and ammonium hydrogen malates, roles of the organic groups and of the hydrogen bonds in the vibrational properties |
publisher |
HAL CCSD |
publishDate |
1994 |
url |
https://hal.univ-lorraine.fr/tel-01776855 https://hal.univ-lorraine.fr/tel-01776855/document https://hal.univ-lorraine.fr/tel-01776855/file/Kemiche.Madjid.SMZ9465.pdf |
genre |
DML |
genre_facet |
DML |
op_source |
https://hal.univ-lorraine.fr/tel-01776855 Matière Condensée [cond-mat]. Université Paul Verlaine - Metz, 1994. Français. ⟨NNT : 1994METZ065S⟩ |
op_relation |
NNT: 1994METZ065S tel-01776855 https://hal.univ-lorraine.fr/tel-01776855 https://hal.univ-lorraine.fr/tel-01776855/document https://hal.univ-lorraine.fr/tel-01776855/file/Kemiche.Madjid.SMZ9465.pdf |
op_rights |
info:eu-repo/semantics/OpenAccess |
_version_ |
1766397473635434496 |