Academic literature on the topic 'Linear alkylammonium cations'

AbstractA synthetic phyllomanganate saturated with a series of primary alkylammonium cations has been examined using XRD, chemical analysis and X-ray photoelectron spectroscopy. A linear relationship exists between the basal spacing of the saturated alkylammonium-manganate and the hydrocarbon chain length in the interlayer, and from the gradient it is concluded that the alkyl chains are perpendicular to the manganate sheet. This orientation is a function of both the charge density and the presence of a layer of water molecules immediately adjacent to the manganate basal surfaces. Evacuation results in the loss of this interlayer water and the structure of the organo-manganate is considerably disrupted. The extent to which the interlayer arrangement can be reinstated by rehydration is dependent on the chain length of the saturating organo-cation. For cations of chain length > C6 the C contents suggest that cation in excess of the exchange capacity is present in the interlayer, but the absence of any compensating anion and the release of amine on evacuation suggests that the excess C arises from the presence of free amine.

AbstractTo investigate the long-term stability of bentonite under final disposal conditions of highly radioactive waste, K-bentonites from Kinnekulle (Sweden) and from the Marias River Formation in the Montana disturbed belt (USA) were studied. After separating the mixed-layer illite-smectite (I-S) from the K-bentonite samples, the interlayer charge was calculated from the cation exchange capacity (CEC) and the amount of fixed interlayer K+ ions (Kfix). The interlayer charge was also determined by the alkylammonium method. According to both methods the interlayer charge was in the range for smectite. The results show that the amount of exchangeable cations increased linearly with decreasing Kfix. A small increase in the interlayer charge with increasing Kfix was observed as was a linear correlation between the intracrystalline swelling up to the second water layer, the CEC and the content of Kfix. Divalent exchangeable cations were then found to be surrounded by approximately 24 water molecules per cation. Fixed interlayer K+ ions were unhydrated. Forming the third and fourth water layer, swelling was presumably limited by free silica formed by the vitrification of the volcanic ash.

Electronic absorption spectroscopy was used to measure the molecular association of copper phthalocyanine tetrasulfonate in micellar solutions, a microemulsion made with cationic surfactant, and homogeneous solvents. Analysis of absorbance versus concentration data using a multiple-aggregation model and non-linear regression analysis gave values of association constants, molar absorptivities and estimates of average aggregation number. Microemulsions and aqueous micellar solutions made with alkylammonium surfactants inhibited aggregation, probably because of interactions between the phthalocyanine sulfonate groups and the cationic surfactant head groups at interfacial surfaces. Similar aggregation behavior was observed previously in multiple-bilayer films of cationic surfactants. Water and aqueous solutions containing tetraethylammonium bromide or anionic SDS micelles provide environments facilitating extensive aggregation of Cu II PcTS 4−. The major species are dimers in water and acetonitrile/water, but the formation of higher aggregates is promoted by addition of SDS or TEAB. Aprotic organic solvents provide environments intermediate between these two extremes, giving relatively large aggregation numbers (i.e. five to seven) but smaller association constants than aqueous media not containing cationic surfactants.

Recrystallization of a primary or secondary alkylammonium tetraphenylborate (TB) from approximately 1:1 mixtures of Me2CO (or MeEtCO) and water yields, against expectation, the TB of the corresponding iminium cation and thus provides an easy route to a variety of aliphatic Schiff bases. The crystal structures of five such salts have been determined: A, [Me2C = NHMe]BPh4 (Cmcm, a = 10.747(2) Å, b = 15.641(4) Å, c = 13.453(4) Å, Z = 4); B, [Me2,C = NMe2,]BPh4 (Cmca, a = 13.196(4) Å, b = 14.469(3) Å, c = 25.122(4) Å. Z = 8); C, [Me,C = NHEt]BPh4 (P21/n, a = 12.146(3) Å, b = 14.099(2) Å, c = 14.177(3) Å, β = 96.23(2)°, Z = 4); D, [MeEtC=NHMe]BPh4 (Cmc21, a = 10.967(5) Å, b = 15.642(5) Å, c = 13.430(4) Å, Z = 4); E, [Me2C=NH(β-CH2CH2Ph)]BPh4 H2O (C2/c, a = 30.747 Å, b = 9.845(4) Å, c = 19.741(5) Å, β = 97.12(2)°, Z = 8). The building principles of these and related TBs are discussed in detail, as also is the tendency of the small iminium ions to orientational disorder. The range of the C=N bond length in these and other iminium salts is quite narrow, with 1.283(12) Å as the mean (uncorrected) value. Where a hydrogen atom(s) is attached to the iminium nitrogen, it will form a hydrogen bond (simple or bifurcated) with the aromatic π system of the nearest phenyl ring(s). The narrowness of the C=N bond-length range with respect to substitution on the cation has prompted a detailed 6-31G* ab initio study of the effect, on the geometry of the [H2C=NH2]+ ion, of a partial or complete replacement of the H atoms by one of the following substituents: F, Cl, CN, Li, and Na. The 46 structures optimized in planar geometry were supplemented by a number of optimizations of similarly substituted ethylenes as well as by a few optimizations in perpendicular geometry. Analysis of the numerical results involves the bond lengths and angles, Mulliken εM and (in part) Löwdin εL net charges on the atoms, and electron densities ρc = ρ(rc) at the bond critical points. Only a limited use has been made of comparisons involving the total electronic energies E (substitutional isomerism). Since the above substituents span the entire electronegativity scale, and CN provides for the possibility of conjugation, the effects they produce are expected to bracket the effects that would be produced by any other substituents. The calculations confirm the essential narrowness of the C=N bond-length range in iminium ions. They also show that, at least in the 6-31G* scheme, the nitrogen in [H2C=NH2]+ carries a significant negative net charge (both in terms of εM and εL), which is contrary to the conventional representation of the ion as H2C=N+H2. The trends observed in the parameters are smooth and highly self-consistent except for the tri- and tetrasubstituted ions containing Li or Na, where interligand repulsions may invalidate the assumption of planarity. Many of the parameters can be represented to a high degree of correlation as linear functions α0 + αCnC(X) + αNnN(X) of the numbers n of substituent atoms X on the C and N atoms. This representation makes it possible to estimate the contribution to the parameter value from the substitution at the distant atom of the C=N bond, i.e., the extent of localization of the effect produced by the substituent. The success of the linearization of the parameter variation raises the important question of whether the apparent additivity is genuine and intrinsic or merely a property of the 6-31G* optimization scheme. In other words, will additivity be retained, functionally, for sets of parameters obtained from higher level ab initio calculations, and will it be eventually verified by experiment?

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Nanosized NaX zeolites (FAU) (crystallite size = 16 nm; Si/Al ratio = 1,5) were synthesized and modified through ion exchange with linear alkylammonium cations containing from one to six carbons, with the intent to activate basic sites. In this work, commercial microsized zeolites (Aldrich) were also ion exchanged for comparison matters and all samples were characterized. Scanning electron microscopy analysis showed that both micro- and nanosized zeolites containing sodium portray polycrystalline particles: the former presents octahedral habit and particle size of 2952 nm and the latter presents an indefinite habit and particle size of 426 nm. Among the ion exchanged samples, none presented complete exchange of the Na+ cations due to steric hindrance. Nanosized zeolites presented higher exchange degrees than the microsized ones, which is due to higher accessibility to the exchange sites. Such factors also explain the exchange degrees’ reduction with the cations’ chain length, which is less abrupt among the nanosized samples. This happens due to the nanosized samples’ higher interparticular porosity, which has also allowed their micropore volumes’ constant decrease, differently from the microsized samples, which faced a minimum value with butylammonium. When the cations’ length is increased, the unit cell expands in comparison to the zeolites containing sodium since bulkier cations cause variations in the length and angle of the of the O-Si-O and O-Al-O bonds. Through thermogravimetric analysis in oxidant atmosphere, it was observed that the longer the carbon chain length, the lower is the mass loss, which evidences the lower diffusional limitations. The same was observed in inert atmosphere, which indicates that the presence of O2 does not influence the thermal events. Nanosized zeolites illustrate smoother mass loss profiles, which marks smaller diffusional limitations. The zeolitic materials were catalytically evaluated along the Knoevenagel condensation between butyraldehyde and ethyl cyanoacetate (3% m/m catalyst) during 1 h. The nanometric zeolites presented higher conversions and higher reaction rates when t = 0 than the microcrystalline ones, confirming the advantages of nanosized materials.
Zeólitas NaX (FAU) de cristais nanométricos (diâmetro de cristalito de 16 nm; razão molar Si/Al de 1,5) foram sintetizadas e modificadas através de troca iônica com cátions alquilamônio lineares de um a seis carbonos para a ativação de sítios básicos. No trabalho, efetuou-se também a troca iônica com zeólitas de cristais micrométricos (Aldrich) para fins de comparação, caracterizando-se todas as amostras. Por MEV, observou-se que as zeólitas sódicas micro- e nanométricas possuem partículas policristalinas, apresentando as primeiras hábito octaédrico e diâmetro de partícula de 2952 nm e, as últimas, hábito indefinido e diâmetro de 426 nm. Dentre as zeólitas trocadas, nenhuma apresentou troca completa dos cátions Na+ devido a impedimentos estéricos. As zeólitas nanométricas apresentaram graus de troca superiores aos das micrométricas devido à maior acessibilidade aos sítios de troca. Tais fatores também justificam a redução do grau de troca com o aumento do comprimento do cátion de compensação, sendo essa redução muito mais suave entre as amostras nanométricas. Isto ocorre devido à maior porosidade interparticular das zeólitas nanométricas, a qual permitiu que os volumes de microporos dessas zeólitas fossem sempre decrescentes, diferentemente das amostras micrométricas que atingiram um valor mínimo com o cátion butilamônio. Aumentando-se o comprimento do cátion, observa-se a expansão da cela unitária em comparação às zeólitas com cátion sódio pois cátions mais volumosos provocam variações no comprimento e nos ângulos das ligações O-Si-O e O-Al-O. Por análise termogravimétrica em atmosfera oxidante, observou-se que as zeólitas nanométricas exibem perfis de decomposição muito mais suaves, evidenciando as menores limitações difusionais. O mesmo foi observado em atmosfera inerte, indicando que a presença do O2 não influencia os eventos térmicos. Os materiais zeolíticos foram avaliados cataliticamente através da reação de condensação de Knoevenagel entre butiraldeído e cianoacetato de etila (3% m/m de catalisador) por 1 h. As zeólitas nanométricas apresentaram maiores conversões e maiores velocidades de reação no tempo zero que as microcristalinas, confirmando-se as vantagens de materiais com dimensões nanométricas.