Iron thermodynamics

The enormous cost of corrosion of iron to society has prompted many efforts to devise ways of reducing or preventing it. Several electrochemical or chemical methods are available. One method is removal of the cathodic species (usually oxygen). Most methods are based on the principle of providing a barrier between the reacting species. The barrier may be physical, i. e. a metal or paint coating or a protective oxide film, or electronic, i. e. making the iron thermodynamically immune. Here, the em-... 

It is important to realize that the fact that a process is spontaneous does not necessarily mean that it will occur at an observable rate. A chemical reaction is spontaneous if it occurs on its own accord, regardless of its speed. A spontaneous reaction can be very fast, as in the case of acid—base neutralization, or very slow, as in the rusting of iron. Thermodynamics tells us the direction and extent of a reaction but nothing about the speed. 

The following acid-catalyzed cyclizations leading to steroid hormone precursors exemplify some important facts an acetylenic bond is less nucleophilic than an olelinic bond acetylenic bonds tend to form cyclopentane rather than cyclohexane derivatives, if there is a choice in proton-catalyzed olefin cyclizations the thermodynamically most stable Irons connection of cyclohexane rings is obtained selectively electroneutral nucleophilic agents such as ethylene carbonate can be used to terminate the cationic cyclization process forming stable enol derivatives which can be hydrolyzed to carbonyl compounds without this nucleophile and with trifluoroacetic acid the corresponding enol ester may be obtained (M.B. Gravestock, 1978, A,B P.E. Peterson, 1969). 

Hexa.cya.no Complexes. Ferrocyanide [13408-63 ] (hexakiscyanoferrate-(4—)), (Fe(CN) ) , is formed by reaction of iron(II) salts with excess aqueous cyanide. The reaction results in the release of 360 kJ/mol (86 kcal/mol) of heat. The thermodynamic stabiUty of the anion accounts for the success of the original method of synthesis, fusing nitrogenous animal residues (blood, horn, hides, etc) with iron and potassium carbonate. Chemical or electrolytic oxidation of the complex ion affords ferricyanide [13408-62-3] (hexakiscyanoferrate(3—)), [Fe(CN)g] , which has a formation constant that is larger by a factor of 10. However, hexakiscyanoferrate(3—) caimot be prepared by direct reaction of iron(III) and cyanide because significant amounts of iron(III) hydroxide also form. Hexacyanoferrate(4—) is quite inert and is nontoxic. In contrast, hexacyanoferrate(3—) is toxic because it is more labile and cyanide dissociates readily. Both complexes Hberate HCN upon addition of acids. 

Enterobactin (ent), the cycHc triester of 2,3-dihydroxy-A/-benzoyl-l-serine, uses three catecholate dianions to coordinate iron. The iron(III)-enterobactin complex [62280-34-6] has extraordinary thermodynamic stabiUty. For Fe " +ent , the estimated formal stabiUty constant is 10 and the reduction potential is approximately —750 mV at pH 7 (23). Several catecholate-containing synthetic analogues of enterobactin have been investigated and found to have lesser, but still impressively large, formation constants. 

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Physical and Chemical Properties. Titanium dioxide [13463-67-7] occurs in nature in three crystalline forms anatase [1317-70-0] brookite [12188-41 -9] and mtile [1317-80-2]. These crystals are essentially pure titanium dioxide but contain small amounts of impurities, such as iron, chromium, or vanadium, which darken them. Rutile is the thermodynamically stable form at all temperatures and is one of the two most important ores of titanium. 

This decomposition is thermodynamically favored by decreasing temperature and increasing pressure (28). Decomposition is extremely slow below 673 K in the absence of a catalyst however, between 673—873 K many surfaces, particularly iron (29), cobalt, and nickel (30), promote the disproportionation reaction. 

This reaction is catalyzed by iron, and extensive research, including surface science experiments, has led to an understanding of many of the details (72). The adsorption of H2 on iron is fast, and the adsorption of N2 is slow and characterized by a substantial activation energy. N2 and H2 are both dis so datively adsorbed. Adsorption of N2 leads to reconstmction of the iron surface and formation of stmctures called iron nitrides that have depths of several atomic layers with compositions of approximately Fe N. There is a bulk compound Fe N, but it is thermodynamically unstable when the surface stmcture is stable. Adsorbed species such as the intermediates NH and NH2 have been identified spectroscopically. 

The thermodynamic data pertinent to the corrosion of metals in aqueous media have been systematically assembled in a form that has become known as Pourbaix diagrams (11). The data include the potential and pH dependence of metal, metal oxide, and metal hydroxide reactions and, in some cases, complex ions. The potential and pH dependence of the hydrogen and oxygen reactions are also suppHed because these are the common corrosion cathodic reactions. The Pourbaix diagram for the iron—water system is given as Figure 1. 

Eig. 2. The thermodynamic regions of corrosion, immunity, and passivation of iron in an iron—water system assuming passivation by a film of Ee202 (H)-... 

Processes in which solids play a rate-determining role have as their principal kinetic factors the existence of chemical potential gradients, and diffusive mass and heat transfer in materials with rigid structures. The atomic structures of the phases involved in any process and their thermodynamic stabilities have important effects on drese properties, since they result from tire distribution of electrons and ions during tire process. In metallic phases it is the diffusive and thermal capacities of the ion cores which are prevalent, the electrons determining the thermal conduction, whereas it is the ionic charge and the valencies of tire species involved in iron-metallic systems which are important in the diffusive and the electronic behaviour of these solids, especially in the case of variable valency ions, while the ions determine the rate of heat conduction. 

The iron-carbon solid alloy which results from the solidification of non blastfurnace metal is saturated with carbon at the metal-slag temperature of about 2000 K, which is subsequendy refined by the oxidation of carbon to produce steel containing less than 1 wt% carbon, die level depending on the application. The first solid phases to separate from liquid steel at the eutectic temperature, 1408 K, are the (f.c.c) y-phase Austenite together with cementite, Fe3C, which has an orthorhombic sttiicture, and not die dieniiodynamically stable carbon phase which is to be expected from die equilibrium diagram. Cementite is thermodynamically unstable with respect to decomposition to h on and carbon from room temperature up to 1130 K... 

The hrst successful study which clarihed the mechanism of roasting, was a study of the oxidation of pyrite, FeSa, which is not a typical industrial process because of the availability of oxide iron ores. The experiment does, however, show die main features of roasting reactions in a simplihed way which is well supported by the necessaty thermodynamic data. The Gibbs energy data for the two sulphides of iron are,... 

In order to answer these questions as directly as possible we begin by looking at diffusive and displacive transformations in pure iron (once we understand how pure iron transforms we will have no problem in generalising to iron-carbon alloys). Now, as we saw in Chapter 2, iron has different crystal structures at different temperatures. Below 914°C the stable structure is b.c.c., but above 914°C it is f.c.c. If f.c.c. iron is cooled below 914°C the structure becomes thermodynamically unstable, and it tries to change back to b.c.c. This f.c.c. b.c.c. transformation usually takes place by a diffusive mechanism. But in exceptional conditions it can occur by a displacive mechanism instead. To understand how iron can transform displacively we must first look at the details of how it transforms by diffusion. 

PS Brereton, FJM Verhagen, ZH Zhou, MWW Adams. Effect of iron-sulfur cluster environment m modulating the thermodynamic properties and biological function of ferredoxm from Pyrococcus furiosus. Biochemistry 37 7351-7362, 1998. 

Fluid Iron Ore Reduction (FIOR) is a process for reducing ore to iron with a reducing gas in a fluid bed. For thermodynamic efficiency, iron ore reduction requires counter current flow of ore and reducing gas. This is achieved in FIOR in a multiple bed reactor. Precautions are necessary to prevent significant back mixing of solids between beds, since this would destroy counter current staging. 

The work on iron-nickel alloys has described shock-compression measurements of the compressibility of fee 28.5-at. % Ni Fe that show a well defined, pressure-induced, second-order ferromagnetic to paramagnetic transition. From these measurements, a complete description is obtained of the thermodynamic variables that change at the transition. The results provide a more complete description of the thermodynamic effects of the change in the magnetic interactions with pressure than has been previously available. The work demonstrates how shock compression can be used as an explicit, quantitative tool for the study of pressure sensitive magnetic interactions. 

All the anhydrous - -3 and +2 halides of iron are readily obtained, except for iron(III) iodide, where the oxidizing properties of Fe and the reducing properties of 1 lead to thermodynamic instability. It has, however, been prepared in mg quantities by the following reaction, with air and moisture rigorously excluded,... 

It should be emphasised that potential-pH diagrams can also be constructed from experimental E -I curves, where E is the polarised potential and / the current. These diagrams, which are of more direct practical significance than the equilibrium potential-pH equilibrium diagrams constructed from thermodynamic data, show how a metal in a natural environment (e.g. iron in water of given chloride ion concentration) may give rise... 

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