Driving Force for the Thermally Induced Solid State Polymerization of Alkali Metal Halogenoacetates:  A Thermochemical Analysis

Lagoa, Ana L. C.; Diogo, Hermı́nio P.; Piedade, Manuel E. Minas da; Schwarz, Karsten; Epple, Matthias

doi:10.1021/jp014361s

Cited by 6 publications

(4 citation statements)

References 49 publications

(91 reference statements)

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“…This contrasts with the group 1 hexachlorometalates, which decompose to group 1 halides most readily in the case of lithium salts; such reactions eliminate many weakly coordinating anions from being useful counterions for catalyst cations such as zirconocenes. Epple found a connection between this reaction tendency of chloroacetates and the lattice energies of the group 1 halides formed . Our computations and the NQR data suggest that the increasing ease of loss of chloride ion from chloroacetate with larger group 1 cations may be in part connected with the increasing polarization of the chloroacetate ion to produce more partial negative charge on the chlorine atom.…”

Section: Resultssupporting

confidence: 51%

“…Epple found a connection between this reaction tendency of chloroacetates and the lattice energies of the group 1 halides formed. 53 Our computations and the NQR data suggest that the increasing ease of loss of chloride ion from chloroacetate with larger group 1 cations may be in part connected with the increasing polarization of the chloroacetate ion to produce more partial negative charge on the chlorine atom.…”

Section: Resultsmentioning

confidence: 70%

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The Weakly Coordinating Trichloromethanesulfonate Anion: NQR Comparison of Its Coordinating Abilities via Oxygen with Those of the Chloroacetate Ions

et al. 2004

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Ionic and covalent derivatives of the chlorine analogue of the nonbasic, weakly coordinating triflate ion, Cl3CSO3(-) or "trichlate" ion, have been prepared and compared with the corresponding more strongly coordinated chloroacetates, Cl(x)CH(3-x)CO(2)M (x = 1-3), using 35Cl NQR (nuclear quadrupole resonance) spectroscopy. The (35)Cl NQR frequencies of all types of derivatives are sensitive to the nature of the metal ion or Lewis acid and are most sensitive in the case of monochloroacetates. In covalent (including zirconocene) derivatives, the average NQR frequencies fall as the Pauling electronegativity of M falls. The results for ionic derivatives contrast with previous results for ionic hexachlorometalates: the average (35)Cl NQR frequencies drop sharply as the ionic radius of the group 1 cation increases. Ab initio Gaussian 98 computations at the B3LYP/6-311++G(3df,3pd) level on isolated XCH2CO2M (M = Li, Na, K; X = F, Cl) molecules duplicate this trend, showing increasing polarization of the C-Cl bond and smaller electric field gradients for larger group 1 ions; the relevance of this to the solid state polymerization of chloroacetates (Herzberg, O.; Epple, M. Eur. J. Inorg. Chem. 2001, 1395-1406) is discussed. We have prepared the dihydrate and monohydrate of trichlic acid, Cl3CSO3H. Although trichlates have the highest average NQR frequencies of any of these salts, the NQR frequencies of trichlic acid dihydrate are anomalously lower than those of trichloroacetic acid, which suggests that it is a strong acid, ionized in the solid state to H5O2+ and Cl3CSO3(-) ions.

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Section: Resultssupporting

confidence: 51%

Section: Resultsmentioning

confidence: 70%

The Weakly Coordinating Trichloromethanesulfonate Anion: NQR Comparison of Its Coordinating Abilities via Oxygen with Those of the Chloroacetate Ions

et al. 2004

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“…Minimally, there are four relevant processes (in addition to water evaporation) that need to be considered when heating a droplet containing an alkali metal chloroacetate salt. 30,31 These processes include (i) the organic salt melting, (ii) the organic salt exothermically eliminating the anticipated alkali metal chloride, (iii) the organic salt undergoing endothermic decarboxylation, and (iv) the generated alkali metal chloride melting. As Skrabalak and Suslick found, it was the relative order and kinetics of these processes that lead to the different particle architectures.…”

Section: Carbon Materials Prepared By Ultrasonic Spray Pyrolysismentioning

confidence: 99%

Ultrasound-assisted synthesis of carbon materials

Skrabalak

2009

Phys. Chem. Chem. Phys.

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In this Perspective, the use of ultrasound in the synthesis and modification of carbon materials is surveyed. Ultrasound is a common laboratory tool used to nebulize solutions into fine mists, emulsify mixtures, and drive chemical reactions. Given society's continued use of carbon materials (e.g., carbon black and activated carbon) as pigments, adsorbents, and composite components as well as the exciting new applications being explored for carbon nanotubes, graphene, and meso- and macroporous carbons, the use of ultrasound in the synthesis and modification of carbon materials is of general interest. Here, carbon materials prepared by both ultrasonic spray pyrolysis and high intensity ultrasound will be discussed, with the properties and applications enabled by their preparation highlighted within the individual examples. This article is concluded with some personal perspectives on the directions toward which future research may be aimed.

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“…Glycosaminoglycans such as heparin have been recognized to bind to receptor proteins through their anionic carboxylate, N-sulfamate, and O-sulfate groups and as such are medically important [241][242][243]. Experimental studies of thermochemical model systems include alkali metal salts of acetic acid [244] and its halogenated derivatives [245], halopropionic acid [246], aqueous sulfamic acid [247], and mixed ammonium sulfamates [248], and monomethyl [249] and monoisopropyl [250] sulfate.…”

Section: Issuementioning

confidence: 99%

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

Ponikvar

Liebman

2008

Struct Chem

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In this study, we relate the contents of the journal Structural Chemistry for the calendar year 2007 and thermochemistry. The year's articles were briefly summarized and a thermochemical comment written to supplement them. Frequently questions were asked and future research was suggested.Keywords Structural Chemistry Á Thermochemistry Á Thermodynamics Á Enthalpy of formation Á Enthalpy of phase change Á Enthalpy of reaction As practiced disciplines, structural chemistry and thermochemistry are very often unrelated. In this study, these disciplines are linked as relations are explicitly made using the contents of the journal Structural Chemistry (Vol. 18) for the calendar year 2007 as a scaffold for our analysis, for our selected articles in the discipline of structural chemistry. These studies have been reviewed by us, where we give them a thermochemical flavor. While this commentary is most generally written in terms of brief summaries of literature papers involving enthalpies of formation and/or reaction, not uncommonly we raise questions and even suggest possible future research. We are not, however, going to give a thermochemical slant on book reviews, honorary dedications, and obituaries although these works will be cited in our text.As such, this article is a sequel to our earlier related reviews of Structural Chemistry for the calendar years 2000 through 2004 [1-5]. Reviews for 2005 and 2006 are currently being prepared. Issue 1In the first article in the first issue of Structural Chemistry for 2007, Hargittai [6] asserted that while research is currently usually carried out in big groups, the most important ideas, observations and discoveries still belong to individuals who have to bring down dogmas or open entirely new areas in science. This may bring solace to the thermochemical community in which research groups are generally small, and the number of new practitioners sadly few.In the past decade, the crystal engineering of multidimensional arrays and networks containing metal ions has achieved considerable progress because of the increased interest in the potential utility of these compounds as zeolite-like materials [7-11], catalysts [12], or magnetic materials [13][14][15]. The thermochemistry of these species is complicated by their inherent complexity: however, estimation approaches of their key thermochemical quantities are increasingly reliable [16]. In the second article of this issue, by Wang et al. [17], the versatility of malonate dianion as a ligand for the construction of extended networks with different topologies dependent on the coordination geometry of the metal ion was discussed. The synthesis and structure of a novel malonate-bridged copper(II) compound in which copper(II) ions have two different coordination environments in a novel three-dimensional (3D) network was described. Metal malonates have been studied from a

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Driving Force for the Thermally Induced Solid State Polymerization of Alkali Metal Halogenoacetates: A Thermochemical Analysis

Cited by 6 publications

References 49 publications

The Weakly Coordinating Trichloromethanesulfonate Anion: NQR Comparison of Its Coordinating Abilities via Oxygen with Those of the Chloroacetate Ions

The Weakly Coordinating Trichloromethanesulfonate Anion: NQR Comparison of Its Coordinating Abilities via Oxygen with Those of the Chloroacetate Ions

Ultrasound-assisted synthesis of carbon materials

Interplay of thermochemistry and Structural Chemistry, the journal (volume 18, 2007) and the discipline

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