Chloride compounds thermodynamic data

Thermodynamic data show that the stabilities of the caesium chloride-metal chloride complexes are greater than the conesponding sodium and potassium compounds, and tire fluorides form complexes more readily tlrair the chlorides, in the solid state. It would seem that tire stabilities of these compounds would transfer into tire liquid state. In fact, it has been possible to account for the heats of formation of molten salt mixtures by the assumption that molten complex salts contain complex as well as simple anions, so tlrat tire heat of formation of the liquid mixtures is tire mole fraction weighted product of the pure components and the complex. For example, in the CsCl-ZrCU system the heat of formation is given on each side of tire complex compound composition, the mole fraction of the compound... 

Compounds with Chlorine. The available thermodynamic data on plutonium chlorides and related species are listed in Table II. 

PTutonyl(VI) chloride has only been reported as the hydrate PUO2CI2.6H20(c) but no thermodynamic data are available on this compound. 

The prefix trans tells us that the triphenylphosphine groups occupy opposite corners of a square rather than adjacent corners (cis). The use of chloro in the name (instead of chloride ) implies the absence of discrete chloride ions, as in [Ir(CO)(PPh3)2]+Cr. Names, as opposed to formulae, are easier to index or to store in a data bank for the rapid retrieval of information on compounds having specific structural features. If a chemist wished to collect the available thermodynamic data for inorganic nitrites, a computer search of formulae containing NOz or some multiple thereof would produce a vast number of organic nitro-compounds of no... 

In the authors opinion, the thermodynamic data presented show that the whole of the concentration region studied can be treated from the viewpoint of the formation of MgCl - coordination compounds in the melts. Dissolution of hydrogen chloride in the melts is not accompanied by an appreciable interaction with the melt components (KC1 and MgCl2). Therefore, the work of the formation of the void in the melts should be the main factor, which defines the behaviour of the temperature dependence. The changes in the deviation of the derived AH and AS values from the additive magnitudes possess an extremal character the maximum deviations are observed at an... 

The effects of pH and Cl ion concentration on the species distribution of platinum compounds have been used to fashion the following plausible argument for the chemistry of cw-DDP in vivo. With the use of thermodynamic data for the ethylenediamine (en) analogue [Pt(en)Cl2], the relative concentrations of hydrolyzed species at pH 7.4 were estimated (see Table 9.3) for blood plasma and cytoplasm (Figure 9.7). The higher chloride ion concentration in... 

The thermodynamic data AG , AH and S° of tellurium halides were calculated from the e.m.f. s of the galvanic cells and their temperature dependences (see IX.B) by taking into account the data for the other compounds which were involved in the total cell reactions Literature data of the standard enthalpies of formation and standard entropies of silver , silver iodide , silver chloride silver bromide and tellurium have been used in the calculations. 

AH of reaction (17) is an estimate since PuCl4(s) has not been synthesized AfH° [PuCl4(s)] = — 964 kJ is an estimate (Fuger et al. 1983). The dramatic difference in these enthalpies [Pu(IV) is more stable than Pu(III) in this complex chloride by -95-( —4) = - 91 kJ or almost 1.0 V, in comparison with the binary chloride] shows how acid-base effects influence oxidation-reduction properties. As noted above, there are few known lanthanide (IV) complex halides and no thermodynamic data on even these few halides, so no quantitative comparison can be made. Nevertheless it does show how complexation effects by basic complexants make high f-element oxidation states attainable. Perhaps the most dramatic evidence of the enhancement of high oxidation state by a basic fluoride is the existence of the Nd(IV) and Dy (IV) compounds such as Cs2(Cs, Rb, K) (Nd, Dy)Cl2 these AjRF, double fluorides are the only known Nd (IV) and Dy(IV) compounds. 

Inclusion of spectroscopic information into data analysis can even help to sort out problems with mixtures of compounds. In the vapor over very hot sodium chloride there are Na—Cl molecules and some rhombic NaaCla dimers. In an electron diffraction study the aim was to determine the structure of the dimer and to get thermodynamic data from the ratio of monomer to dimer [11]. But the Na—Cl bond length in the dimer is close to that of the monomer, which is much more abundant, and consequently none of the parameters was very well determined. Adding the rotation constant for the monomer, which is known very aceurately, effectively fixed the monomer distance. The distance in the dimer was then well determined, and all parameters could then be refined, much more reliably. 

The separation of solvent effects on reactivities into constituent initial-state and transition-state effects by the use of appropriate kinetic and thermodynamic data has been successfully carried out for several organic reactions. Thus, for example, the solvolysis of t-butyl chloride and the Menschutkin reaction were treated in this manner some time ago a recent organic example is afforded by the solvolysis of isopropyl bromide in aqueous ethanol. For inorganic reactions, this approach was early used for reactions of tetra-alkyltin(iv) compounds with mercury(ii) halides. A more recent analysis of reactions of low-spin iron(n) complexes with hydroxide and with cyanide in binary aqueous mixtures was complicated by the need to make assumptions about single-ion values in such ion+ion reactions. Recent estimates of thermodynamic parameters for solvation of complexes of the [Fe(phen)3] + type are helpful in this connection. However, it is more satisfactory to work with uncharged reactants when trying to undertake this type of analysis of reactivity trends. A suitable system is provided by the reaction of [PtClaCbipy)] with thiourea. In dioxan-and tetrahydrofuran-water solvent mixtures, reactivity is controlled almost entirely... 

As outlined in section 18.2, the atomic structure should, in principle, be the correct ground state structure in order to get quantitative correct thermodynamic data from DFT. This is typically only achieved after rigorous computational optimization, which is too computationally costly in any screening study, and we thus have to use model structures that give correct trends but not necessarily exact numbers. This has previously been shown to be a vahd approach for metal chloride amines and other coordination compounds [19,101]. Here, the model structures are based on the different coordination observed in metal amine salts, starting with 8 in SrCU and moving to 6 in MgCl2, and 4 in LiBr if the former is not stable. 

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