Hydrogen bond studies. LXXIII. The crystal structure of trifluoromethanesulphonic acid monohydrate, H3O+CF3SO3−, at 298 and 83 K

Delaplané, R. G.; Lundgren, Jan‐Olof; Olovsson, Ivar

doi:10.1107/s0567740873005765

Cited by 68 publications

(32 citation statements)

References 4 publications

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“…Similar phenomena were observed for tetraaquabis(methanesulfonato)copper(II) complex (Charbonnier, Faure & Loiseleur, 1975) and compounds containing CFaSO 7 anions, including ammonium trifluoromethanesulfonate (G~inswein & Brauer, 1975), trifluoromethanesulfonic acid monohydrate (Spencer & Lundgren, 1973), trifluoromethanesulfonic acid dihydrate (Delaplane, Lundgren & Olovsson, 1975a), and trifluoromethanesulfonic acid hemihydrate (Delaplane, Lundgren & Olovsson, 1975b). Structural results obtained for the six compounds cited in Table 5 are consistent with these observations: the weighted average deviations from 109o28 ' are -2. individual anion ranges from 218.6 (4) to 218.9 (6) ° , approximately double the regular tetrahedral angle.…”

Section: S-c and S-o Distances (A) And C-s-o And O-s-o Bond Angles (Osupporting

confidence: 78%

Structure of sodium methanesulfonate

Wei¹,

Hingerty²

1981

Acta Crystallogr B Struct Crystallogr Cryst Chem

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Section: S-c and S-o Distances (A) And C-s-o And O-s-o Bond Angles (Osupporting

confidence: 78%

Structure of sodium methanesulfonate

Wei¹,

Hingerty²

1981

Acta Crystallogr B Struct Crystallogr Cryst Chem

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“…The F-C-S-O torsional angles for F and O in the trans positions are 178.0 (3), 178.2 (3) and 179.5 (3) ° respectively. This geometry agrees well with that of the same ion in trifluoromethanesulphonic acid monohydrate (Spencer & Lundgren, 1973). In the present structure the S-O distance involving 0(2) is slightly longer than the other two; the atom 0(2) is an acceptor for two hydrogen bonds whereas O(1) and 0(3) each only accept a single bond.…”

Section: The Trifluoromethanesulphonate Ionsupporting

confidence: 77%

“…In the structures of picrylsulphonic acid tetrahydrate (Lundgren & Tellgren, 1974) and nitranilic acid hexahydrate (Williams & Peterson, Compar•on of the structures at 225 and 85 K The structures at 85 and 225 K are nearly identical; the covalent bond distances within the CF3SO~-group tend to be shorter at the higher temperature as was also found for trifluoromethanesulphonic acid monohydrate at 298 and 83 K (Spencer & Lundgren, 1973). Clearly, the ellipsoidal model applied here does not adequately describe the thermal motion of the CF3SOf group and the apparent interatomic distances will then tend to decrease with increased temperature.…”

Section: The Trifluoromethanesulphonate Ionmentioning

confidence: 70%

“…nH20 where n = l, 1,2, 4 and 5. The structure of the monohydrate of trifluoromethanesulphonic acid has been reported previously (Spencer & Lundgren, 1973;Lundgren, Tellgren & Olovsson, 1975). This paper presents the structure determination of the dihydrate of trifluoromethanesulphonic acid at 225 and 85 K from single-crystal X-ray diffractometer data.…”

Section: Introductionmentioning

confidence: 99%

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Hydrogen bond studies. XCVII. The crystal structure of trifluoromethanesulphonic acid dihydrate, H5O2+CF3SO3−, at 225 and 85 K

Delaplané¹,

Lundgren²,

Olovsson³

1975

Acta Crystallogr Sect B

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The crystal structure of trifluoromethanesulphonic acid dihydrate has been determined from threedimensional single-crystal X-ray diffractometer data at 225 and 85 K. The crystals are monoclinic, space group P21/c, with four formula units in a unit cell of dimensions a= 10.1192 (5), b= 8.8700 (3), c= 7.7545 (3) A, fl=97.556 (6) ° at 225 K and a=9.9431 (6), b=8.8680 (5), c=7.6159 (3) A, fl=97.083 (5) ° at 85 K. The structure consists of H502 ions and trifluoromethanesulphonate ions hydrogen-bonded together to form double layers which are held together by van der Waals forces. Two water molecules are bonded together by a short hydrogen bond [2.409 (2) A at 85 K] to form H502 ions which are of the asymmetric type with a gauche conformation. The CF3SO3 ion has a staggered conformation with approximate C3o symmetry. The S-O bond distances are 1-441 (1), 1.456 (1), and 1.434 (1) A at 85 K.The structures at 225 and 85 K are nearly identical; differences in the corresponding structural parameters are only those expected from changes of temperature.

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“…The two minimum energy conformations demonstrate that the degree of separation of the sulfonic acid groups will affect the ionization of the acid groups: (a) with 5 CF 2 groups separating the side chains both protons are dissociated; and (b) with 9 CF 2 groups separating the side chains only one proton dissociates. This solid possesses a well-defined crystallographic structure, 134 with low hydration level of one water molecule per sulfonate group (l = 1), and for which controlled MD simulations are feasible. A transition was observed from the stable (i.e.…”

Section: This Journal Is C the Owner Societies 2007mentioning

confidence: 99%

Modelling of morphology and proton transport in PFSA membranes

Elliott

Paddison

2007

Phys. Chem. Chem. Phys.

225

255

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Computational modelling studies of the structure of perfluorosulfonic acid (PFSA) ionomer membranes consistently exhibit a nanoscopic phase-separated morphology in which the ionic side chains and aqueous counterions segregate from the fluorocarbon backbone to form clusters or channels. Although these investigations do not unambiguously predict the size or shape of the clusters, and whether or not the channels percolate the matrix or if the connections between them are more transient, the sequence of co-monomers along the main chain appears strongly to influence the domain size of the ionic regions, with more blocky sequences giving rise to larger domain sizes. The fundamental insight that substantial rearrangement of the sulfonic acid terminated side chains and fluorocarbon backbone takes place during swelling or shrinkage is borne out by both molecular and mesoscale simulations of model PFSA polymers, along with ab initio electronic structure calculations of minimally hydrated oligomeric fragments. Molecularlevel modelling of proton transport in PFSA membranes attests to the complexity of the underlying mechanisms and the need to examine the chemical and physical processes at several distinct time and length scales. These investigations have revealed that the conformation of the fluorocarbon backbone, flexibility of the sidechains, and degree of aggregation and association of the sulfonic acid groups under minimally hydrated conditions collectively control the dissociation of the protons and the formation of Zundel and Eigen cations. The former appear to be the dominant charge carriers when the limiting water content allows only for the formation of a contact ion pair with the tethered sulfonate anion. As the water content increases, solventseparated Eigen ions begin to appear, indicating that the dominant mechanism for diffusion of protons occurs over a region approximately 4 Å away from the sulfonate groups. Finally, both the vehicular and Grotthuss shuttling mechanisms contribute to the mobility of the protons but, surprisingly, they are not always correlated, resulting in a lower overall diffusion coefficient. In summary, as the preceding observations indicate, the state of computational modelling of PFSA membranes has progressed sufficiently over the last decade to enable its use as a powerful predictive tool with which to guide the process of designing novel membrane materials for fuel cell applications.

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Hydrogen bond studies. LXXIII. The crystal structure of trifluoromethanesulphonic acid monohydrate, H3O+CF3SO3−, at 298 and 83 K

Cited by 68 publications

References 4 publications

Structure of sodium methanesulfonate

Structure of sodium methanesulfonate

Hydrogen bond studies. XCVII. The crystal structure of trifluoromethanesulphonic acid dihydrate, H5O2+CF3SO3−, at 225 and 85 K

Modelling of morphology and proton transport in PFSA membranes

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