Layered crystalline calcium phenylphosphonate—synthesis, characterization and n-alkylmonoamine intercalation

Lima, Cícero Bosco Alves de; Airoldi, Cláudio

doi:10.1016/s1293-2558(02)00009-2

Cited by 48 publications

(29 citation statements)

References 29 publications

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“…33,34 The maximum cation adsorption capacity, N f max , for natural and organofunctionalized smectites is listed in Table 3, with the highest values for the chemically modified surfaces, showing also an increase with temperature. A possible explanation for this enhancement in adsorption with temperature is the activation of the remaining basic centers of original structure on the clay, possibly arising from displacement of water initially hydrogen bonded to the clay and the modified surfaces.…”

Section: Adsorption Studymentioning

confidence: 99%

“…The Gibbs free energy associated with divalent mercury/natural or organofunctionalized smectite adsorptions can be determined by the Langmuir constant K L . [27][28][29][30][31][32][33][34] The enthalpy (∆ r h) is related to the thermal effect per mass for each matrix, ∆ int h, which corresponds to the enthalpy of monolayer formation. ∆ int h and K L values can be determined from coefficients after isotherm linearization.…”

Section: Thermodynamic Studymentioning

confidence: 99%

“…∆ int h and K L values can be determined from coefficients after isotherm linearization. The molar enthalpy of the interaction process [27][28][29][30][31][32][33][34] can be calculated through equation 9. (9) where N S is the number of adsorbent moles after reaching …”

Section: Thermodynamic Studymentioning

confidence: 99%

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Mercury adsorption on natural and organofunctionalized smectites - thermodynamics of cation removal

Guerra¹,

Santos²,

Airoldi³

2009

J. Braz. Chem. Soc.

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Uma amostra natural de esmectita oriunda do estado do Piauí, Brasil, foi organofuncionalizada com 3-mercaptopropiltrimethoxissilano e 3-aminopropiltriethoxissilano. O espaçamento basal da argila natural é de 0,99 nm e área superficial 48 m 2 g -1. Houve um aumento no espaçamento basal para 1,84 e 2,01 nm e o aumento da área específica para 781 e 795 m 2 g -1 para as argilas quimicamente modificadas, respectivamente. A argila natural e a argila quimicamente modificada adsorveram cátions mercúrio em solução aquosa em pH 3,0 e 298 ± 1 K. Os modelos de isotermas de adsorção de Langmuir, Redlich-Peterson e Toth foram aplicados para ajuste dos dados experimentais com aproximação não linear. Para as interações cátion/centros básicos para cada esmectita na interface sólido/líquido foi utilizada metodologia calorimétrica e foram obtidas as constantes de equilíbrio e os efeitos térmicos exotérmicos. Considerando o número interativo de moles para cada cátion e as constantes de equilíbrio, a entalpia, ∆ int H o (−11,98 a −13,93 kJ mol ). As interações cátion/ centros básicos são de natureza espontânea como demonstram os valores de energia livre de Gibbs, dando o conjunto de dados favoráveis como expressam a entalpia exotérmica e a entropia positiva, mostrando que a esmectita natural e as quimicamente modificadas têm habilidade em complexar mercúrio. Logo, esses materiais são úteis na remoção de mercúrio em um ecossistema.A natural smectite clay sample from Piauí State, Brazil, was organofunctionalized with 3-mercaptopropyltrimethoxysilane and 3-aminopropyltriethoxysilane silyating agents. The basal spacing of 0.99 nm and surface area of 48 m 2 g -1 for natural clay increased to 1.84 and 2.01 nm, and 781 and 795 m 2 g -1 for modified clays, respectively. The natural and chemically immobilized clay samples adsorb mercury cations from aqueous solutions at pH 3.0 at 298 ± 1 K. The Langmuir, Redlich-Peterson and Toth adsorption isotherm models were applied to fit the experimental data with a nonlinear approach. From the cation/basic center interactions for each smectite at the solid-liquid interface, by using calorimetry methodology, the equilibrium constant and exothermic thermal effects were obtained. By considering the net interactive number of moles for each cation and the equilibrium constant, the enthalpy, ∆ int H o (−11.98 to −13.93 kJ mol ). The cation-basic center interactions are spontaneous in nature as demonstrated from favorable enthalpic and entropic results. Natural and anchored smectites have the ability to complex mercury, acting as useful materials for removal of this hazardous metal from an ecosystem.

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Section: Adsorption Studymentioning

confidence: 99%

Section: Thermodynamic Studymentioning

confidence: 99%

See 1 more Smart Citation

Mercury adsorption on natural and organofunctionalized smectites - thermodynamics of cation removal

Guerra¹,

Santos²,

Airoldi³

2009

J. Braz. Chem. Soc.

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“…Among phosphonates of the alkalineearth metal, the structure of hydrogen phenylphosphonates M(C 6 H 5 PO 3 H) 2 (M=Ca, Sr, Ba) were described [1][2][3]. The intercalations of alkylamines and alkyldiamines into calcium hydrogen phenylphosphonate [4,5] and barium hydrogen phenylphosphonate [6,7] were studied. The intercalations were interpreted as acid-base solid-state reactions where the basal spacings of the intercalates formed increase linearly with increasing guest chain length.…”

Section: Introductionmentioning

confidence: 99%

Intercalation behavior of barium phenylphosphonate

Beneš

Melánová

Svoboda

et al. 2010

Journal of Physics and Chemistry of Solids

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The dependence of basal spacing and water content of BaC 6 H 5 PO 3 ·xH 2 O on the relative humidity was studied.Intercalates of 1-alkylamines (C 2 -C 10 ) and 1-alkanols (C 3 -C 10 ) were prepared from barium phenylphosphonate dihydrate and also from anhydrous host and characterized by powder X-ray diffraction and thermogravimetric analysis. The intercalates of alkanols and alkylamines prepared from dihydrate are quite stable at ambient conditions and contain one guest molecule per formula unit. The guest molecules are probably arranged in monomolecular way and are perpendicular to the host layers in the case of amines or tilted to the host layers at an angle of about 80° in the case of alkanols. The intercalates prepared from anhydrous host are unstable and their basal spacings indicate parallel arrangement of the guests chains. Formation of mixed intercalates was not observed when barium phenylphosphonate dihydrate was contacted with a mixture of alkanols or amines.

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“…In any case, the great majority of lamellar compounds do not disturb the original inorganic structure or the van der Waals interactive forces and as the progress of intercalation takes place the sequence of lamella is normally maintained. 4 Due to the versatility of inserting species inside the lamellar space, there is strong and increasing interest in producing new porous solids, to yield new materials with ions or molecules between the layers of these layered matrices. 5 Known organic-inorganic hybrid materials containing open-framework structures 6 are interesting not only as promising alternatives to carry out synthetic chemistry but also due to interest in the unusual features in their properties.…”

Section: Introductionmentioning

confidence: 99%

Intercalation and thermochemistry of amines in lamellar titanium phenylarsonate

Ruiz¹,

Airoldi²

2005

J. Braz. Chem. Soc.

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O composto lamelar fenilarsonato de titânio foi sintetizado e intercalado com alquilmonoaminas (metil a heptil), diaminoetano e diaminobutano, lutidina e α-picolina. A matriz original foi caracterizada por análise elementar, difração de raios X, análise de superfície, porosidade, espectroscopia de absorção na região do infravermelho, termogravimetria e microscopia eletrônica de varredura. Os difratogramas de raios X não mostraram aumento significativo de distâncias interlamelares, e a intercalação foi comprovada por técnicas como a termogravimetria que indicou a perda de massa correspondendo às aminas. A condição ideal de intercalação foi efetuada com injeções de 30,0x10 -6 dm 3 da amina 0,50 mol dm -3 em suspensão de aproximadamente 10x10 -3 g das matrizes. Os números de moles intercalados com as alquilmonoaminas seguiram uma ordem aleatória em relação ao aumento da cadeia alifática, com valores entálpicos de -9,18 ± 0,07; -12,10 ± 0,20; -7,61 ± 0,02; -6,88 ± 0,01; -9,47 ± 0,03; -12,84 ± 0,10 e -14,78 ± 0,10 kJ mol -1 para a seqüência das alquilmonoaminas e variaram de -3,66 ± 0,30 a -10,92 ± 1,50 kJ mol -1 para alquildiaminas. Com as aminas aromáticas não ocorreu um efeito térmico significativo nas intercalações, fato que foi atribuído ao grande volume do grupo fenila presente no interior das lamelas, que impede a inserção da base na cavidade lamelar.The lamellar compound titanium phenylarsonate was synthesized and intercalated with alkylmonoamines (methyl to heptyl), diaminoethane, diaminobutane, lutidine and α-picoline. The host was characterized through elemental analysis, X-ray diffraction, surface analysis, porosity, infrared spectroscopy, thermogravimetry and electronic scanning microscopy. The intercalated compounds did not show significant increases in the interlamellar distances through X-ray diffractometry. The intercalation was confirmed by the thermogravimetric technique, indicating mass losses that correspond to the amines. The ideal intercalation was established by adding increments of 30.0x10 -6 dm 3 of 0.50 mol dm -3 of each amine into a suspension of about 10x10 -3 g of matrix. The number of moles intercalated with alkylmonoamines followed an aleatory order in relation to the increase of the aliphatic chain and the enthalpic values gave -9. 18 ± 0.07; -12.10 ± 0.20; -7.61 ± 0.02; -6.88 ± 0.01; -9.47 ± 0.03; -12.84 ± 0.10 and -14.78 ± 0.10 kJ mol -1 for the sequence of alkylmonoamines and varied from -3.66 ± 0.30 to -10.92 ± 1.50 kJ mol -1 for the alkyldiamines. The aromatic amines presented small thermal effects and the unfavorable intercalation is attributed to the large volume of the phenyl group inside the lamella, which hinders insertion of these bases inside the lamellar cavity.Keywords: lamellar compound, intercalation, calorimetry, alkylmonoamines, alkyldiamines, aromatic amines IntroductionA huge number of natural or synthesized materials, normally classified as typical inorganic substances, embodying clays, double hydroxides, phosphates, phosphonates, graphite, silicates, niobates, ...

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Layered crystalline calcium phenylphosphonate—synthesis, characterization and n-alkylmonoamine intercalation

Cited by 48 publications

References 29 publications

Mercury adsorption on natural and organofunctionalized smectites - thermodynamics of cation removal

Mercury adsorption on natural and organofunctionalized smectites - thermodynamics of cation removal

Intercalation behavior of barium phenylphosphonate

Intercalation and thermochemistry of amines in lamellar titanium phenylarsonate

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