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Les Zéolithes

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LES ZÉOLITHES

I) Introduction
1) Présentation
! Une zéolithe est un minéral micro-poreux appartenant au groupe des silicates, dans lequel ils

forment une famille comprenant des aluminosilicates hydratés des groupes IA et IIA du tableau périodique des éléments ( comme le Calcium, le Magnésium, le Potassium ... ) . ! Étymologiquement, le mot zéolithe vient du latin zeô ( bouillir )

et lithos ( la pierre ) . À juste titre, leur découverte sʼest faite en 1756 par le minéralogiste suédois Axel Frederik Crönstedt lors de lʼobservation de dégagement de vapeur dʼeau lorsque ces minéraux étaient chauffés à la flamme .

2) Principe et utilisations
! Les zéolithes sont présentes dans de nombreux domaines,

plus ou moins spécifiques, de la médecine à lʼindustrie . Elles sont par exemple utilisées dans les stations spatiales pour le recyclage de lʼair, en médecine pour les caissons hyper-bar, ou même chez les particuliers dans les piscines pour assainir lʼeau . !
Exemple de structure de zéolithe : On observe ici clairement la structure micro-poreuse de ces minéraux .

La particularité de ces espèces minérales réside dans leur utilisation comme «tamis

moléculaire» de par leur structure micro-poreuse . Ces pores laissent en effet passer certaines molécules au travers du maillage, et en adsorbe certaines autres ( les «piège», de manière réversible ), par le biais dʼinteractions intermoléculaires dites de Debye, de London, de Van Der Waals ...

3) Problématique globale
! Nous avons porté un intérêt plus particulier sur lʼutilisation possible des zéolithes pour assainir

lʼair en terme de concentration en CO₂ , une des applications retrouvées en médecine ou dans les stations spatiales . Nous avons mené en premier lieu donc des recherches sur la zéolithe à synthétiser, puis sur la synthèse en elle-même, et enfin nous avons testé celle-ci comparativement à dʼautres zéolithes plus ou moins inconnues mises à notre disposition .

II) Choix et synthèse de la zéolithe
1) Choix de la zéolithe
! La théorie atomistique retrouvée dans différents ouvrages nous ont permis dʼestimer le diamètre relatif de la molécule de CO₂ , qui est approximativement de 3,3 Å ( 0,33 nanomètres ) . La zéolithe de type A est parmi toutes les espèces différentes de zéolithes celle qui est le mieux adaptée à lʼadsorption du CO₂ . De plus, certaines études ont montré que ces zéolithes captent environ 100 fois moins de diazote et de dioxygène que de dioxyde de carbone . ! Toutefois, différents choix de zéolithe A qui conditionnent le résultat des expériences se

présentent . Il existe 3 zéolithes de type A différentes : les 3A, 4A et 5A, qui se distinguent non pas par le structure mais par la nature de leurs cations compensateurs : K+ pour la zéolithe 3A ( cation de rayon ionique 1,33 Å ) Na+ pour la zéolithe 4A ( cation de rayon ionique 0,95 Å ) Ca²+ pour la zéolithe 5A ( cation de rayon ionique 0,99 Å ) ! Ces cations situés dans les cavités masquent partiellement les pores et diminuent ainsi leur

diamètre . Celui de la 5A par exemple varie de 4,2 Å à 4,4 Å , alors que pour la 3A où les cations sont plus volumineux et deux fois plus nombreux, il est inférieur à 3 Å . Le choix idéal serait donc une zéolithe de type 5A pour effectuer lʼexpérience .

2) Synthèse dʼune zéolithe de type A
! ! ! Pour synthétiser une zéolithe de type A, nous avons utilisé : ! ! - 7,74 g de métasilicate de sodium ( SiO₂ , Na₂O , 5 H₂O ) - 4,13 g dʼaluminate de sodium ( Al₂O₃ , Na₂O , H₂O )

Ces deux espèces sont dissoutes toutes deux en milieu basique ( solution de soude ) . Les deux solutions obtenues sont mélangées rapidement dans un récipient en plastique que lʼon ferme hermétiquement, et que lʼon place à lʼétuve durant 3 heures à une température dʼenviron 100°C . Après filtration, et un nouveau passage à lʼétuve ( à lʼair libre cette foisci ) pour sécher le composé, on obtient une fine poudre blanche avec un rendement final de 81% . Cette zéolithe obtenue est une de type 4A . Nous nʼavons pas eu lʼoccasion de transformer cette 4A en 5A à cause des difficultés expérimentales et des disponibilités du laboratoire de chimie . Il aurait fallu en effet laisser reposer longuement le composé obtenu dans une solution contenant des cations Ca²⁺, sans avoir la certitude dʼéchanger la totalité des cations, et dʼobtenir après de nouvelles manipulations de séchage uniquement des zéolithe 5A .
Observation de zéolithes au Microscope Electronique à Balayage ( MEB )

III) Expérimentation : mise en évidence de lʼadsorption du CO2 par la zéolithe
1) Principe de lʼexpérience ; conditions expérimentales
! Lors de lʼexpérience menée, on a désiré mettre en évidence la capacité dʼadsorption du CO₂

de lʼair ambiant par un dispositif de «filtrage» dans lequel on place la zéolithe ou lʼespèce inerte que lʼon désire tester . Le premier problème à résoudre était celui de la mise en évidence précise des quantités de CO₂ traversant le filtre . Les propriétés chimiques du dioxyde de carbone font que celuici est un diacide, et il réagit donc avec les ions hydroxydes de la soude ( NaOH ) pour former HCO³⁻ ( ion hydrogénocarbonate ) et CO3²⁻ ( ion carbonate ) . Donc en faisant barboter de lʼair dans une solution de soude de concentration parfaitement connue, on «piège» le CO₂ dans cette solution, en la «carbonatant» . Puis, en dosant la solution de soude résiduelle après lʼexpérience, grâce à une solution dʼacide chlorhydrique, on peut ainsi mesurer la concentration en ions hydroxydes restants, et en déduire la quantité de CO₂ ayant traversé le filtre . ! Par souci de résultats viables et dʼutilisation de concentrations quasi-usuelles des solutions,

on réalise lʼexpérience dans certaines conditions : elle est effectuée dans une pièce où une dizaine de personnes sont présentes ( et respirent donc ! ) et en utilisant un bec-bunsen en flamme jaune placé à proximité de lʼadmission dʼair dans le filtre, dans le but dʼamener la proportion en CO₂ de lʼair à des valeurs relativement significatives, et permettant de réelles observations sur les résultats .

2) Dispositif expérimental

!

Le dispositif est composé dʼun circuit ouvert composé dʼun tube

en U, dʼun cristallisoir, de raccords en verre ou en caoutchouc, dʼune pompe à vide servant à créer le flux dʼair ( dont le débit est estimé à 20 L/min ), et dʼune éprouvette graduée dʼune capacité dʼun litre finalisant le circuit . Le tube en U est destiné à accueillir les zéolithes ( ou plus généralement les espèces à tester ) sous forme de poudre . Ce tube en U est partiellement plongé dans le cristallisoir rempli dʼeau et de glace afin dʼaméliorer lʼefficacité des zéolithes ( globalement, plus leur température est basse, plus elles sont capables dʼadsorber des espèces, et également pour palier lʼéchauffement entraîné par les frottements et la compression de lʼair ) . Une des extrémités du tube est à lʼair libre, à proximité de la flamme du bec-bunsen, tandis que lʼautre est reliée à la pompe à vide, branchée de telle sorte à aspirer lʼair par cette extrémité .
Photo de lʼéprouvette contenant la solution de soude . On observe le long tube terminé par le morceau de tissu servant à faire buller lʼair au fond de celle-ci .

!

A lʼautre extrémité du circuit, à la sortie de la pompe à vide, un raccord en verre allongé est

plongé jusquʼau fond de lʼéprouvette dʼun litre remplie de soude, pour ainsi faire parcourir les bulles dʼair filtré un maximum de temps au contact de la soude . Dans la même optique de favoriser la réaction du CO₂ avec les ions HO⁻ en augmentant la surface de contact du gaz avec la solution, un petit morceau de tissu inerte à mailles fines est fixé à lʼextrémité du tube afin de réduire la taille des bulles et en augmenter le nombre . Au vu du débit de la pompe à vide, et du taux de CO₂ de lʼair estimé à 1% dans de telles conditions opératoires, nous avons fixé la durée de chaque expérience à 30 minutes, et la solution de soude dans laquelle bulle le gaz est elle utilisée avec un volume de 750 mL dʼune concentration de 0,010 mol/L .

Photo de lʼextrémité dʼentrée dʼair du circuit expérimental . Un filtre en coton a été ajouté à la jonction du tube en U et des raccords en verre afin dʼéviter le passage dʼespèces solides à lʼintérieur de la pompe .

Vue dʼensemble du montage de lʼexpérimentation :

SCHEMA EXPERIMENTAL

!

Nous avons effectué au total 4 manipulations, afin de comparer les zéolithes . Nous avons

utilisé, dans le tube en U, les espèces suivantes : la zéolithe 4A synthétisée, deux zéolithes issues du laboratoire du lycée qui sont une zéolithe 13X et une autre inconnue . La quatrième expérience a servi dʼexpérience témoin car elle a été effectuée avec de la farine, inerte vis-à-vis du CO₂, mais permettant de conserver un débit dʼair similaire à celui des autres expériences menées avec les zéolithes .

3) Exploitation des résultats
Nous avons par la suite comparé les quatre courbes obtenues par titrage pH-métrique à celle issue du dosage simple de la soude à 0,010 mol/L par lʼacide chlorhydrique . Chaque titrage a été effectué avec la même concentration dʼacide chlorhydrique dans la burette . Nous avons pu observer sur chacune des courbes des différences notables des deux volumes équivalents mesurés pour chaque expérience, le premier saut de pH représentant lʼéquivalence du titrage de HCO₃⁻ et le deuxième saut représentant lʼéquivalence du titrage de CO₃²⁻ . Nous avons obtenu les courbes suivantes au cours des expériences :

Les résultats sont regroupés dans le tableau suivant :

Espèce présente dans le filtre Farine Zéolithe 4A Zéolithe 13X Zéolithe inconnue

Première équivalence ( Véq 1 ) 14,3 mL 14,7 mL 16,7 mL 15,0 mL

Deuxième équivalence ( Véq 2 ) 18,2 mL 19,2 mL 19,8 mL 19,2 mL

!

En considérant les résultats obtenus sur les valeurs des volumes équivalents, on obtient le

classement suivant en terme de pouvoir adsorbant du CO₂ croissant des différentes espèces : Farine < Zéolithe 4A < Zéolithe inconnue < Zéolithe 13X

Interprétation : La zéolithe 4A que nous avons synthétisée a des pores de taille plus réduite que la 5A idéale pour cette utilisation de capture du CO₂ . Ses pores sont trop petits pour permettre une adsorption efficace . En revanche, les zéolithes 13X et inconnue semblent avoir des pores de grand diamètre permettant une relative adsorption du CO₂, mais néanmoins de trop grande dimension car laissant toutefois passer des molécules de dioxyde de carbone .

CONCLUSION : ! Lʼintérêt de ce sujet a résidé dans lʼétablissement dʼun protocole scientifique au cours de

différentes étapes théoriques et pratiques, pour répondre à un besoin exprimé dans un domaine dʼapplication où les contraintes sont fortes, tels lʼencombrement, la nécessité dʼautonomie et dʼefficacité énergétique dans les stations spatiales . ! Lʼimportance des zéolithes dans les domaines de lʼaérospatiale, de la médecine, de la

pharmacologie, ou même encore dans lʼassainissement dʼeaux usées ou du traitement de déchets radioactifs est avérée . Toutefois, les études actuelles menées par le chercheur Gérard Ferey nous ont montré que lʼusage de molécules hybrides ( mêlant chimie organique et inorganique ) présentent des résultats encore plus satisfaisants, en terme dʼefficacité, de capacité dʼadsorption et de restitution des composés piégés, eux-mêmes de plus en plus diversifiés .

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...intro fashion ruling every domain of life, definition of "modern fashion" by Lipov lipovertsky, simmel.. GENDER Barthes in his attempt for a semantics of fashion in The System of Fashion, applies the economic system that is brought to the fore by Karl Marx and consisting three categories of production, distribution and consumption to a social institution: fashion. Thus he defines 3 states of clothing: real clothing, represented garment and the used garment. Real clothing is the when the raw material is used and the clothing is first produced as a prototype for its later stages. This real clothing then is provided with a symbolic mise en scène and becomes the represented garment. The image of the cloth performs a mimetic function as well as making the garment into a pleasing sight, or a pleasant arrangement. The used garment is the clothing after its purchase which usually doesn't satisfy the reasons that the represented garment was bought for. Barthes argues that clothes change their meaning and went under transformation at each of these stages. In the case of fashion, the system that Barthes proposes would reveal that these stages of production, distribution and consumption take place all at different locations hence are separated and can take place one after another, moving from one place to other and transform their meanings. However, in the case of architecture, these stages take place all at the same site. There is but one site. After the building is constructed...

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