Lithium temperature dependence

S.E. Arione and G.E. Duvall, Temperature Dependence of the Precursor Amplitude in <111 > Lithium Fluoride, in Shock Waves in Condensed Matter (edited by Y.M. Gupta), Plenum, New York, 1986, pp. 299-302. 

Fig. 12. Temperature dependence of Kd of polystyryl lithium in different ethereal solvents (S. Peeters, M. Van Beylen, Ref. 76 )...

Titanium imido complexes supported by amidinate ligands form an interesting and well-investigated class of early transition metal amidinato complexes. Metathetical reactions between the readily accessible titanium imide precursors Ti( = NR)Cl2(py)3 with lithium amidinates according to Scheme 84 afforded either terminal or bridging imido complexes depending on the steiic bulk of the amidinate anion. In solution, the mononuclear bis(pyridine) adducts exist in temperature-dependent, dynamic equilibrium with their mono(pyiidine) homologs and free pyridine. 

Lithium triflate was the most used salt and the temperature dependence of the electrical conductivity of a series of (LiS03CF3)x/MEEP complexes with a ratio metal cation/MEEP repeat unit 0.125[Pg.203]

Therefore, the temperature dependence of the conductivity of complexes (LiX)o, igy/MEEP (X=CF3C00, SCN, SO3CF3, BF4) were also compared. The highest conductivity was obtained with BF4, and the activation energies for ion transport were found to be similar, suggesting that the mechanism for ion motion is independent on the salt. The lithium transport number, which varies from 0.3 to 0.6, depending on the complexed salt, does not change with concentration. 

Liquid ammonia solutions of lithium polysulfides have been characterized by Dubois et al. [18]. The least reduced polysulfide was shown to be 8 (not found previously in aquo) lying in a strongly temperature-dependent equilibrium with the radical 83 . 

Figure 3 Temperature dependence of ionic conductivity for polymers 1 and 2 in the presence of various lithium salts.

In the presence of lithium salts, the temperature dependence of ionic conductivity for the polymer electrolytes obtained was evaluated. In the presence of LiCF3S03,... 

The stepwise mechanism was also illustrated in terms of a temperature-dependent cage effect.23 Reaction of 24 with a mixture of lithium cyclo-hexyl-1-rf-oxide (48) and 3-pentyloxide (49) at 0°C, produced cross-over products 50 and 51, both in - and Z- forms, and the deuterium was scrambled in both isomers (89% in 50 and 6-12% in 51). In contrast, at —95—40°C, no... 

Magna T, Wiechert UH, Grove TL, Halliday AN (2003) Lithium isotope composition of arc volcanics from the Mt. Shasta region, N California. Geochim Cosmochim Acta 67 A267 Marriott CS, Henderson GM, Belshaw NS, Tudhope AW (2004) Temperature dependence of 6 Li, 6 Ca and Li/Ca incorporation into calcium carbonate. Earth Planet Sci Lett (in press)... 

The latter authors used anode and cathode symmetrical cells in EIS analysis in order to simplify the complication that often arises from asymmetrical half-cells so that the contributions from anode/ electrolyte and cathode/electrolyte interfaces could be isolated, and consequently, the temperature-dependences of these components could be established. This is an extension of their earlier work, in which the overall impedances of full lithium ion cells were studied and Ret was identified as the controlling factor. As Figure 68 shows, for each of the two interfaces, Ra dominates the overall impedance in the symmetrical cells as in a full lithium ion cell, indicating that, even at room temperature, the electrodic reaction kinetics at both the cathode and anode surfaces dictate the overall lithium ion chemistry. At lower temperature, this determining role of Ra becomes more pronounced, as Figure 69c shows, in which relative resistance , defined as the ratio of a certain resistance at a specific temperature to that at 20 °C, is used to compare the temperature-dependences of bulk resistance (i b), surface layer resistance Rsi), and i ct- For the convenience of comparison, the temperature-dependence of the ion conductivity measured for the bulk electrolyte is also included in Figure 69 as a benchmark. Apparently, both and Rsi vary with temperature at a similar pace to what ion conductivity adopts, as expected, but a significant deviation was observed in the temperature dependence of R below —10 °C. Thus, one... 

Figure 69. Comparison for temperature-dependence of the relative resistances of a charged lithium ion cell, a lithiated graphite/graphite cell, and a delithiated cathode/cathode cell. The dashed curves show the relative resistance of the electrolyte, which was taken as the ratio of the electrolytic conductivity at a specific temperature to the conductivity at 20 °C (a) Rb, (b) R i, (c) Re. (Reproduced with permission from ref 512 (Figure 4). Copyright 2003 Elsevier.)...

In many cases the temperature dependence of the quadrupolar coupling constant is an indicator of dynamic processes, because the symmetry around the lithium cation is affected by motions which are fast on the NMR time scale. If the rate of these processes exceeds 1/x, the effective symmetry around the lithium cation increases and a decrease in x( Li) results. In Li MAS spectra, a broadening of the satellite transitions can be observed which eventually disappear completely if the rate of the dynamic process comes in the order of the quadrupole frequency. This behaviour was observed for the THF solvated dimer of bis(trimethylsilylamido)lithium, where the Li MAS spectrum at 353 K shows only the central transition and the sidebands caused by CSA and homonuclear Li- Li dipole coupling (Figure 27) . The simulation of the high-temperature spectrum yielded —20 ppm and 1300 Hz for these quantities, respectively. The dipole coupling agrees closely with the theoretical value of 1319 Hz calculated from the Li-Li distance of 2.4 A, which was determined by an X-ray study. 

A molecular structure, similar to that of hexasilylated benzene derivative 229, was obtained from tetracyclic hexasilylbenzene 230 by Kira, Sakurai and coworkers, where the six silicon centres are incorporated in three five-membered ring systems (Scheme 80) °. In dimetalated compound 231, two lithium centres, coordinated by a quinuclidine ligand each, are capping the phenyl ring plane from both sides in the solid state. Moreover, it could be found that compound 231 has a thermally accessible triplet state, investigated by temperature-dependent ESR spectroscopy °°. 

With heterocycles containing an sp--nitrogen atom, a totally different problem can occur, namely nucleophilic addition of the base to the azo-methine (C=N) bond. The use of very sterically hindered bases such as lithium tetramethylpiperidide (LiTMP) can prevent this type of addition in certain cases, but bases of this sort tend to be expensive and not suitable for general use. However, two different approaches to overcoming the problem of azomethine addition have been developed over the years, both relying on the fact that the addition is temperature dependent, and that by enabling metalation reactions to be performed at low temperatures, the desired carbanion formation can often be achieved. 

Figure 5.116 Temperature dependence of bending strength for SiC-reinforced lithium aluminosilicate (LAS) CMC. Reprinted, by permission, from R. W. Davidge and J. J. R. Davies, in Mechanical Testing of Engineering Ceramics at High Temperatures, B. F. Dyson, R. D. Lohr, and R. Morrell, eds., p. 264. Copyright 1989 by Elsevier Science Publishers, Ltd.

The temperature dependency of 1,2 content shown in Table II is also consistent with complex formation between polybutadienyl-lithium and the oxygen atom in the lithium morpholinide moleculre. One can visualize an equilibrium between noncom-plexed and complexed molecules which would be influenced by temperature. Higher temperatures would favor dissociation of the complex and, therefore, the 1,2 content of the polymer would be lower than that from the low temperature polymerization. This explanation is supported by the polymerization of butadiene with lithium diethylamide, in which the microstructure of the polybutadiene remains constant regardless of the polymerization temperature (Table IV). This is presumably due to the fact that trialkylamines are known to be poor... 

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