Manganese thermodynamic data

Thermodynamic data (4) for selected manganese compounds is given ia Table 3 standard electrode potentials are given ia Table 4. A pH—potential diagram for aqueous manganese compounds at 25°C is shown ia Figure 1 (9). 

It should be remarked that a detailed study of the elimination of mairganese and silicon from the liquid metal shows that silicon together with some of the mairganese is hrst removed, followed by tire rest of the manganese together with some of the carbon, which is hnally removed together widr half of the sulphur contained in the original liquid. This sequence is in accord with what would be expected from thermodynamic data for the stabilities of dre oxides. 

Based upon thermodynamic data given in Table I, oxidant strength decreases in the order NijO > Mn02 > MnOOH > CoOOH > FeOOH. Rates of reductive dissolution in natural waters and sediments appear to follow a similar trend. When the reductant flux is increased and conditions turn anoxic, manganese oxides are reduced and dissolved earlier and more quickly than iron oxides (12, 13). No comparable information is available on release of dissolved cobalt and nickel. 

Mn(acac)3 reacts with ethylenediamine (L2) or other primary amines (L) to yield [Mn"(acac)2L2], which can also be prepared by the reaction of the amine or diamine with [Mn(acac)2(H20)2]. Allylamine reacts with [Mn(acac)2-(H20)2] in ether to give a second complex, [Mn(acac)2(H2NCH2==CH2)]2 which is dimeric both in the solid and vapour phases. This is the First example of a dinuclear manganese(ii) acetylacetonate complex. Thermodynamic data have been reported for the manganese(ii)-acetylacetone system in propan-1-ol-water. ... 

Adequacy of Thermodynamic Data. Data on several important aluminosilicates appear to be insufficient for a detailed discussion of all equilibria. Information on the influence of solid solutions or coprecipitated phases on thermodynamic properties appears to be rather limited, as is that for metastable non-stoichiometric oxides (e.g., of manganese) and surface complexes. 

This volume of the Handbook illustrates the rich variety of topics covered by rare earth science. Three chapters are devoted to the description of solid state compounds skutteru-dites (Chapter 211), rare earth-antimony systems (Chapter 212), and rare earth-manganese perovskites (Chapter 214). Two other reviews deal with solid state properties one contribution includes information on existing thermodynamic data of lanthanide trihalides (Chapter 213) while the other one describes optical properties of rare earth compounds under pressure (Chapter 217). Finally, two chapters focus on solution chemistry. The state of the art in unraveling solution structure of lanthanide-containing coordination compounds by paramagnetic nuclear magnetic resonance is outlined in Chapter 215. The potential of time-resolved, laser-induced emission spectroscopy for the analysis of lanthanide and actinide solutions is presented and critically discussed in Chapter 216. 

Crystal field theory is one of several chemical bonding models and one that is applicable solely to the transition metal and lanthanide elements. The theory, which utilizes thermodynamic data obtained from absorption bands in the visible and near-infrared regions of the electromagnetic spectrum, has met with widespread applications and successful interpretations of diverse physical and chemical properties of elements of the first transition series. These elements comprise scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel and copper. The position of the first transition series in the periodic table is shown in fig. 1.1. Transition elements constitute almost forty weight per cent, or eighteen atom per cent, of the Earth (Appendix 1) and occur in most minerals in the Crust, Mantle and Core. As a result, there are many aspects of transition metal geochemistry that are amenable to interpretation by crystal field theory. 

Where both cobalt and manganese are present in solution, the coprecipitation of hausmannite and C03O4 might be expected. Sinha et al. (25) found that random substitution of cobalt for Mn " or Mn could occur in such material occurrence of Co in manganese oxide crystal-lattice positions was noted by Bums (4). Apparently there are no thermodynamic data for mixed cobalt + manganese oxides, but the behavior of the ions can probably be represented over a considerable range of solid composition by a solid—solution model based on the equilibrium between the pure end members. Thus... 

The precipitation of manganese oxides from aerated aqueous systems may be viewed as a two-step process involving oxidation of Mn to the Mn state, and disproportionation of Mn to form Mn. Thermodynamic data show that the reaction aflBnities for both processes will be positive when the fluxes of dissolved oxygen and Mn toward the reaction site are at levels commonly attained in river water and some other natural systems. 

Oxidation-reduction reactions involving iron and manganese include changes in oxidation states, relative stabilities of iron and manganese compounds, and the energetics and kinetics of oxidized and reduced compounds. Using thermodynamic data (from free energies of formation, see Chapter 4),... 

Stability diagrams developed using thermodynamic data for iron and manganese are shown in Figures 10.3 and 10.4. These diagrams indicate the dominant stable species of iron and manganese... 

Consider the following thermodynamic data for oxides of manganese. 

Table 11.18 Thermodynamic data for manganese(ll) species at 25 °C and comparison with data available in the literature.

The thermodynamic data utilised for manganese metal, the manganese ion and the solid phase, MnO(s), are listed in Table 11.21. The metal and ion data were used to derive the data listed in Table 11.18. 

This calculation enables one to program easily the stoichiometric concentration, using a small calculator. If the molecule contains other atoms, silicon, tin, manganese, lead, etc, the most stable oxides thermodynamically are sought perhaps by using enthalpies of formation data listed for inorganic substances in Part Two. 

Applying the foregoing thermodynamic and kinetic information to manganese behavior in natural water systems is considerably limited because the manganese system exemplifies the difficulties discussed earlier. On the thermodynamic side, the kinds of oxide phases in natural waters may not correspond to those for which equilibrium data are available. Also, cation exchange reactions are probably important (21). On the kinetic side, the role of catalysis by various mineral surfaces in suspension or in sediments is not really known. Of considerable importance may be microbial catalysis of the oxidation or reduction processes, as described by Ehrlich (7). With respect to the real systems, relatively... 

Table 2.1 lists equilibrium ratios for the reduction of selected metal oxides [4], while Figure 2.2 provides a complete phase diagram for the reduction of iron oxide at different temperatures [3, 5], In order to reduce bulk iron oxide to metallic iron at 600 K, the water content of the hydrogen gas above the sample must be below a few percent, which is easily achieved. However, in order to reduce Cr2C>3, the water content should be as low as a few parts per billion, which is much more difficult to realize. The data in Table 2.1 also illustrate that, in many cases, only partial reduction to a lower oxide may be expected. Reduction of Mn2C>3 to MnO is thermodynamically allowed at relatively high water contents, but further reduction to manganese is unlikely. 

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