Das Bandenspektrum und die Dissoziationsenergie des C1F

Schmitz, H.; Schumacher, H. J.

doi:10.1515/zna-1947-0611

Cited by 29 publications

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“…[27] Any formed Cl 2 might react with excess ClF 3 to give ClF, although the reaction is slow, even at elevated temperature and pressure. [28][29][30]…”

Section: Reactions Of Chlorides With Clfmentioning

confidence: 99%

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

et al. 2020

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Difluorochloronium(III) compounds were synthesized from the reaction of metal powders (Ru, Os, Ir, Au), metal fluorides (NbF5, SbF3, BiF5) or a metal chloride (TaCl5) with excess liquid chlorine trifluoride. The compounds ClF2[AuF4], ClF2[MF6] (M = Nb, Ta, Ru, Os, Ir, Sb, Bi) and ClF2[Ta2F11] were obtained in crystalline form and their crystal structures were determined by single‐crystal X‐ray diffraction. The ClF2+ cations in the investigated compounds are bent, containing two strong, short, mainly covalent Cl–F bonds and two sterically active, free valence electron pairs in a pseudo‐tetrahedral arrangement. The coordination around the Cl atom is extended by two highly ionic, long fluorine bridges to neighboring fluoridometallate anions, resulting in a total coordination number of six. The crystal structures vary among the ClF2+ compounds and range from molecular building blocks, such as dimeric (ClF2[AuF4])2 and (ClF2[Ta2F11])2, to chains, some of which being helical, as in ClF2[MF6], (M = Nb, Ta, Ru, Os, Ir, Sb, Bi). Quantum‐chemical solid‐state and gas‐phase calculations were carried out to elucidate the bonding within the ClF2+ cations and their interactions with the bridging F atoms.

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“…[27] Any formed Cl 2 might react with excess ClF 3 to give ClF, although the reaction is slow, even at elevated temperature and pressure. [28][29][30]…”

Section: Reactions Of Chlorides With Clfmentioning

confidence: 99%

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

et al. 2020

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“…The NIST-JANAF Thermochemical Tables list Δ f H o 298K -(ClF) = À50.29 ( 0.42 kJ mol À1 and Δ f H o 0K (ClF) = À50.20 ( 0.42 kJ mol À1 . The ClF heat of formation is based on spectroscopic measurements by Wahrhaftig 53 and by Schmitz and Schumacher, 54 indicating a band convergence limit of 21 514 ( 10 cm À1 , which was assigned to the products Cl( 2 P 1/2 ) + F( 2 P 3/2 ), corroborated by a dissociative ionization threshold reported by Dibeler et al, 55 and disputed by Nordine, 56 who argued for an Cl( 2 P 3/2 ) + F( 2 P 1/2 ) assignment. Even though the NIST-JANAF compilation makes no mention of this conundrum, the question still seemed unsettled to Coxon.…”

Section: ' Computational Approachmentioning

confidence: 99%

Thermochemistry of Halomethanes CF_nBr_4–n (n = 0–3) Based on iPEPICO Experiments and Quantum Chemical Computations

2011

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Internal energy selected bromofluoromethane cations were prepared and their internal energy dependent fragmentation pathways were recorded by imaging photoelectron photoion coincidence spectroscopy (iPEPICO). The first dissociation reaction is bromine atom loss, which is followed by fluorine atom loss in CF(3)Br and CF(2)Br(2) at higher energies. Accurate 0 K appearance energies have been obtained for these processes, which are complemented by ab initio isodesmic reaction energy calculations. A thermochemical network is set up to obtain updated heats of formation of the samples and their dissociative photoionization products. Several computational methods have been benchmarked against the well-known interhalogen heats of formation. As a corollary, we stumbled upon an assignment issue for the ClF heat of formation leading to a 5.7 kJ mol(-1) error, resolved some time ago, but still lacking closure because of outdated compilations. Our CF(3)(+) appearance energy from CF(3)Br confirms the measurements of Asher and Ruscic (J. Chem. Phys. 1997, 106, 210) and Garcia et al. (J. Phys. Chem. A 2001, 105, 8296) as opposed to the most recent result of Clay et al. (J. Phys. Chem. A 2005, 109, 1541). The ionization energy of CF(3) is determined to be 9.02-9.08 eV on the basis of a previous CF(3)-Br neutral bond energy and the CF(3) heat of formation, respectively. We also show that the breakdown diagram of CFBr(3)(+), a weakly bound parent ion, can be used to obtain the accurate adiabatic ionization energy of the neutral of 10.625 ± 0.010 eV. The updated 298 K enthalpies of formation Δ(f)H(o)(g) for CF(3)Br, CF(2)Br(2), CFBr(3), and CBr(4) are reported to be -647.0 ± 3.5, -361.0 ± 7.4, -111.6 ± 7.7, and 113.7 ± 4 kJ mol(-1), respectively.

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Vortragstagung der Gesellschaft Deutscher Chemiker in der britischen Zone vom 7.–9 October 1947 in Bonn

1948

Angewandte Chemie

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F 0 r t s e t z u n . g d e r Z e i t s c h r i f t , , D i e C h e m i e " Vortragstagung der Gesellschaft Deutscher Chemiker in der britischen Zone vom 7.09. Oktober 1947 in Bonn Prof. K . Ziegler, Direktor des K. W. I. far Kohlenforsehung, Mhlheim a. d. Ruhr, begrUDte als Vorsitzcnder der Gesebchaft Deutscher Chemiker in der britischen Zone die annkhernd 1100 Tagungsteilnehmer, insbesondere die Vertreter der Militirregierung und die erschienenen AuslLnder. E r gedachte 80dann Prof. Kekulds, der lmge Jahre in Bonn wirkte. Die Teilnehmer erhoben sich zu Ehren des kurz zuvor verstorbenen Geheimrat Plan&. Es hielten ferner BegrUBungsansprachen : Prof. Kloos als Vertreter des Rektors der Universitlt, der Oberbiirgcrmeister der Stadt Bonn, und Mr. R. Frascr, Scientific Adviser, Research Branch Gtittingen. Letzterer betonte besonders seinen Wunsch nach einem Zusammenscl~lul) aller westdeutschen Chemiker und berichtete Uber die erfolgreichen Bemiihungen zur Weiterftihrung des ,,Beilstein" und ,, Gmelin". W . KLEMM, Kiel: Dar Verhdfen der Alkalimetall-euden M a M u mhalopeniden. Obwohl schon eine ganze Reihe von Halogenid-Syskmen untersucht worden sind, liegen systematische Untersuchungen tiber das Verhalten verschiedener Halogenide zueinander noch nicht vor, so daO man Uber die hier vorhandenen GesetzlnliOigkeiten nur wenig aussagen kann. EE wurden daher die Systeme NaCl/MgCl* und KCVMgCl. nachgeprflft und die Systcme RbCl/MgCl,, NaJ/MgJ, und KJ/MgJ,neu untersucht. Das Ergebnis dicser Versuche zusammen mit Literaturdaten zeigt die nachstehende Tabelle, in der die kongruent schmelzendcn Verbindungen unterstrichen sind: b. hoh. Temp. mlschbar, b. vollst. mlschmlschbar m. 3 Li ~Z i m~u t~m p . 1 bar 1 Liicke I mlschb. Die Tabelle zeigt, daO fiir die Verbindungsbildung vor allem der Unterschied in den Ionenradien von Bedeutung ist, wlihrend der Unterschied der Ionenladung weniger EinfluO besitzt. Der Unterschied der Ionenradien tritt umsomehr hervor, je kleiner dae Anion ist. Daa allgemeine Verhalten entspricht weitgehend den Ergebnissen, die Schmifz-Dumonf fur den Fall gefunden hat, daO iich in dem Gitter der Doppelverbindung abgeschlossene Komplexe bib. den, obwohldies hier, soweit man es bisher Ubersehen kann, nicht der Fallist. 0 . B A YER, Leverkusen : Das DiisoeyaMt-Polyaddilions-Vcrfahren. Die ausfUhrliche Arbeit erschien in dieser Ztschr. 59, 267 [1947]. € I . LETTRg:, Qbttingen: Anlaponiden der Mitosepijtc1). Hemmeffekte chemischer Stoffe an biologischen Systemen lassen sich e n t weder durch eine I n a k t i v i e r u n g oder durch Verdrlingung eines Wirkstoffea deuten. Zahlreiche Beispiele sind bekannt. Mitosegifte finden sich in chemisch heterogenen Stoffklassen : metallorganische Verbindungen, Trypaflavin und Derivate, Colcbicin und Derivate, Narcotin und Chelidonin, Stilbylamine, ein Umwandlungsprodukt des Adrenalins, Steroidhormone, a-Phenylzimtsliurenitrile, Urethane. Morphologisch ist der Hcmmeffekt der chemisch verschiedenen Mitosegifte auch venchiedenartig. So wirkt Trypaflavin auf die frUhen Phasen de...

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Das Bandenspektrum und die Dissoziationsenergie des C1F

Cited by 29 publications

References 0 publications

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Thermochemistry of Halomethanes CF_nBr_4–n (n = 0–3) Based on iPEPICO Experiments and Quantum Chemical Computations

Vortragstagung der Gesellschaft Deutscher Chemiker in der britischen Zone vom 7.–9 October 1947 in Bonn

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Das Bandenspektrum und die Dissoziationsenergie des C1F

Cited by 29 publications

References 0 publications

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Difluorochloronium(III) Fluoridometallates – from Molecular Building Blocks to (Helical) Chains

Thermochemistry of Halomethanes CFnBr4–n (n = 0–3) Based on iPEPICO Experiments and Quantum Chemical Computations

Vortragstagung der Gesellschaft Deutscher Chemiker in der britischen Zone vom 7.–9 October 1947 in Bonn

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Thermochemistry of Halomethanes CF_nBr_4–n (n = 0–3) Based on iPEPICO Experiments and Quantum Chemical Computations