The salts UrRI(3) may be prepared by the reaction of N-alkylurotropinium iodides UrRI with iodine I-2 at room temperature from aqueous solution.N-methylurotropinium triiodide C7H15N4I3 crystallizes monoclinically in P2(1)/c with a = 1300.8(2) pm, b = 1276.0(3) pm, c = 859.3(2) pm, beta = 94.75(2) and Z = 4. The crystal struc ture is built up from layers of cations UrMe(+) and of linear symmetric triiodide ions I-3(-) alternating along [100].N-ethylurotropinium triiodide C8H17N4I3 crystallizes orthorhombically in Pnma with a = 1397.3(5)pm, b = 1221.3(2)pm, c = 886.2(2)pm and 2 = 4. The cationic (UrEt(+)) and anionic (I-3(-)) layers alternate along [010].N-propylurotropinium triiodide C9H19N4I3 crystallizes monoclinically in P2(1)/c with a = 1885.7(5)pm, b = 1657.1(5)pm, c = 1700.5(4) pm, beta = 112.39(2)degrees and Z = 12. The three independent cations and anions are slightly, but differently distorted.N-butylurotropinium triiodide C10H21N4I3 crystallizes monoclinically in P2(1)/m with a = 991.8(3) pm, b = 757.8(2) pm, c = 1128.2(2) pm, beta = 90.73(2)degrees and Z = 2. The crystal structure is stacked by alternating cationic and anionic layers along [001]. The triiodide ion is asymmetric and linear.

The present paper deals with transport properties of polymer electrolytes as mixtures of block copolymers of poly(ethylene oxide) and lithium iodide. By combination of impedance measurements and d.c. polarization methods for a symmetrical cell it was possible to calculate the transport numbers of mobile ions in the system. It has been found that the transport numbers of these electrolytes depend on composition and also on temperature. The electrolyte resistance and the electrode resistance depend in the same way on the content of lithium iodide in the polymer electrolytes. The relation between passivating layers on the electrodes and the shape of impedance plots is discussed in detail.

The present paper deals with problems of manufacturing a magnesium-iodine battery, based on experiences drawn from the lithium-iodine battery. Initial results are outlined, taking into account activation and coating of the magnesium surface.

Room temperature molten polyiodides have been prepared by reaction of dry iodine and solid iodides of large cations such as tetraoctylammonium iodide, methyltriethylammonium iodide and triethysulphonium iodide. The existence of liquid polyiodides is determined by Raman spectroscopy, liquid X-ray diffraction and other methods. Liquid polyiodides are good electrical conductors with electrical conductivities in the range of 10−3 to 4 × 10−2 S cm−1 at room temperature. An ionic transport mechanism as the deciding mechanism can be excluded due to the increase of condutivity with increasing iodine contents in the polyiodides. A Grotthus-like charge transfer mechanism along the polyiodide chains is suggested.

This paper deals with the influence of coating the lithium anode on the discharge behaviour of lithium-iodine and lithium-bromine batteries, containing lithium ion conducting solid electrolytes, at different temperatures. In contrast to poly(2-vinylpiridine)/iodine charge- transfer complexes, commonly used as cathodes in heart pacemaker batteries,polyiodides and polybromides bonded to polymers of styrene, which are functionalized by cationic groups, were used. It has been found that addition of anthracene to poly(2-vinylpyridine) as a coating material produces a positive effect on the discharge behaviour.

The present paper deals with the problem of coating the lithium anode for the lithium—iodine battery. It has been found that addition of anthracene to the commonly used poly(2-vinylpyridine) (P2VP) as coating material produces a positive effect on the discharge behavior of the battery. To interpret this influence modeling reactions outside the battery were carried out. As result it has been stated that at first lithium anthracene adducts are formed which react with P2VP to yield higher molecular products by coupling via the pyridine rings.

Polymer electrolytes of mixtures of LiI and triblock copolymers of poly (ethylene oxide) (PEO) in combination with poly (methyl methacrylate) (PMMA) or poly (tert.-butyl methacrylate) (PTBMA) were investigated. Ac conductivity of the electrolytes and the transport number for the lithium ion were determined in dependence on salt concentration and temperature. Both systems show the same behaviour. For a composition of approximately 6 mol% LiI the investigated systems show a maximum in conductivity of 10−4 S/cm (60°C). The transport numbers of the lithium ion are relatively small (0.2-0.35) which means the iodide ion is the major ionic carrier.

Polymer solid electrolytes are prepared by a modified preparative technique without any additional solvent. By this technique the polymer solid electrolyte can be manufactured not in thin films but in a compact form, particularly disks or tablets. The conductivities of these PEO-based electrolytes are investigated depending on temperature, molecular weight of PEO and alkali halide content. For the system PEO/LiI the composition dependence of the lithium ion transport numbers are investigated. In the range of low salt content the results are similar to those obtained from thin film preparations.

Solid polybromide-containing functional polymers were obtained from basic anion-exchange resins. The chloride or hydroxide anions of the commercial resins were exchanged by bromide, then dried under anaerobic conditions and allowed to react with a gaseous bromine phase. The formation of linear, slightly asymmetric tribromides was proved by Raman and far-IR spectroscopy. The tribromide spectra are characterized by the symmetrical stretching vibration nu-1 at about 160 cm-1 and the antisymmetric stretching vibration nu-3 at about 200 cm-1. If the Br2:Br- molar ratio is greater than 1 an additional band could be observed at about 255 cm-1. This band is assigned to the stretching vibration of coordinated bromine. It is shifted in the direction of free bromine at about 300 cm-1 with increasing bromine content in the functional polymers. According to the spectroscopic results, the anion structure in amorphous polybromide-containing functional polymers can be explained by tribromide ions and bromine molecules interacting with the tribromide. The thermal instability of higher polybromides was also proved spectroscopically.

The structure of molten polyiodides, Et3SI(x)(1)(Et = ethyl; x = 3, 4, 5 and 7), have been investigated by liquid x-ray scattering and Raman spectroscopy techniques at room temperature. The predominant iodine-containing species in Et3SI3(1) is a centrosymmetric I3-ion with a closest I-I distance of 2.915(2) angstrom. The Raman spectra indicate a large bond flexibility of the triiodide ion. The structural results of the iodine-rich melts Et3SI(x)(1), x > 3, are consistent with a three-dimensional network of interconnected I3-ions and I2 molecules. The short-range order bears close similarities to that of pure liquid and solid iodine. The triiodides are on the average solvated by one, two and three iodine molecules for x = 4, 5 and 7, respectively. The coordination mode is flat-on with the I3- and I2 units almost parallel but slightly tilted away from each other like the nearest-neighbour contacts in pure iodine. Previously published conductivity results are consistent with such a structure model.

Mixtures of iodine and dialkylsulphides are liquids with a significant electrical conductivity, especially in the range of high iodine concentrations. A linear relationship exists between the logarithm of the conductivity and the weight percentage of iodine in the mixtures over more than four magnitudes of conductivity and nearly the whole concentration range.

Journal für Praktische ChemieVolume 332, Issue 6 p. 1102-1104 Arbeitsvorschriften und Meßergebnisse Zur Darstellung von Alkalimetall-Aromaten-Addukten durch Kristallisation aus Lösungen: Dimetalladdukte des Anthracens Preparation of Alkali Metal Addition Compounds by Crystallization from Solution; Di-metal Adducts of Anthracene Dr. sc. nat. Konrad Lühder, Corresponding Author Dr. sc. nat. Konrad Lühder Sektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSearch for more papers by this authorProf. Dr. sc. nat. Harry Füllbier, Prof. Dr. sc. nat. Harry Füllbier Sektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSearch for more papers by this author Dr. sc. nat. Konrad Lühder, Corresponding Author Dr. sc. nat. Konrad Lühder Sektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSearch for more papers by this authorProf. Dr. sc. nat. Harry Füllbier, Prof. Dr. sc. nat. Harry Füllbier Sektion Chemie der Ernst-Moritz-Arndt-Universität, Soldtmannstr. 16, O-2200 GreifswaldSearch for more papers by this author First published: 1990 https://doi.org/10.1002/prac.19903320632Citations: 1AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat Literaturverzeichnis 1 Lühder, K.; Füllbier, H.: Wiss. Z. Ernst-Moritz-Arndt-Univ. Greifswald, Math.-Nat. wiss Reihe 36 (1987) 69. Google Scholar 2 Lühder, K.; Füllbier, H.: Acta Phys. Slov. 38 (1988) 311. Web of Science®Google Scholar 3 Herzog, S.; Dehnert, J.: Z. Chem. 4 (1964) 1. 10.1002/zfch.19640040102 CASGoogle Scholar 4 Herzog, S.; Dehnert, J.; Lühder, K.: Technique of Inorganic Chemistry, Eds. H. B. Jonassen u. A. Weissberg, Vol. VII, S. 119. Google Scholar 5 Lühder, K.: Z. Chem. 9 (1969) 387. 10.1002/zfch.19690091014 Web of Science®Google Scholar 6 Lühder, K.: Z. Chem. 9 (1969) 459. 10.1002/zfch.19690091218 Web of Science®Google Scholar 7 Canters, G. W.; Klaassen, A. A. K.; De Boer, E.: J. Phys. Chem. 74 (1970) 3299. 10.1021/j100711a029 CASWeb of Science®Google Scholar 8 Gribnau, M. C. M.; Pikkemaat, J. A.; De Boer, E.: Mol. Phys. 67 (1989) 347. 10.1080/00268978900101121 CASWeb of Science®Google Scholar Citing Literature Volume332, Issue61990Pages 1102-1104 ReferencesRelatedInformation

N ‐Alkylurotropinium polyiodides, UrRI x , with different iodine contents and different sizes of alkyl group were investigated by Raman spectroscopy. The spectra were recorded for wavenumber shifts up to 500 cm −1 . It was found that the triiodides, UrRI 3 , contain a symmetrical linear I 3 − ion. The pentaiodides, UrRI 5 , contain no triiodide unit; the anion structure can be described as nearly symmetrical, rectangular L‐shaped I 5 − . An interpretation of the Raman spectra of the heptaiodides, UrRI 7 , is that the anion corresponds to an I 5 − . I 2 structure. This is the first proof of such a heptaiodide. A review of previously published data on the Raman spectra of polyiodides is also given.

AbstractMittels einer potentiometrischen Meßanordnung wird die Bildung von N‐Alkylurotropiniumpolyiodiden untersucht. Die Polyiodide werden präpariert, analysiert und ihre elektrischen sowie magnetischen Eigenschaften gemessen. Alle dargestellten Polyiodide sind diamagnetisch. Die magnetische Suszeptibilität ist unabhängig von der magnetischen Feldstärke und der Temperatur. Die elektrische Leitfähigkeit steigt mit dem Iodgehalt. Sie liegt bei Raumtemperatur zwischen 10−11S/cm für die Triiodide und 10−5S/cm für die Heptaiodide. Der Stromtransport wird vorrangig durch Elektronenüberführung im Anionenteilgitter realisiert.