An ellingham diagram is a graph displaying the temperature dependence of the stableness for compounds. this analysis is usually used to evaluate the ease of reduction of metal oxides and sulfides. those diagrams had been first built by harold ellingham in 1944. in metallurgy, the ellingham diagram is used to are expecting the equilibrium temperature among a steel, its oxide, and oxygen — and via extension, reactions of a metallic with sulfur, nitrogen, and different non-metals. the diagrams are useful in predicting the conditions underneath which an ore could be decreased to its metallic. the evaluation is thermodynamic in nature and ignores response kinetics. hence, approaches that are expected to be beneficial by using the ellingham diagram can nevertheless be sluggish.
Ellingham diagrams are a particular graphical form of the precept that the thermodynamic feasibility of a reaction depends at the sign of δg, the gibbs free strength change, that is equal to δh − tδs, in which δh is the enthalpy trade and δs is the entropy trade.
The ellingham diagram plots the gibbs free electricity exchange (δg) for every oxidation response as a characteristic of temperature. for contrast of various reactions, all values of δg discuss with the reaction of the identical amount of oxygen, selected as one mole o (1⁄2 mol o
2) through a few authors and one mole o
2 with the aid of others. the diagram shown refers to 1 mole o
2, in order that as an instance the road for the oxidation of chromium indicates δg for the reaction 4⁄3 cr(s) + o
2(g) → 2⁄three Cr
3(s), which is 2⁄3 of the molar gibbs power of formation δgf°(cr
Inside the temperature levels usually used, the steel and the oxide are in a condensed kingdom (strong or liquid), and oxygen is a fuel with a far large molar entropy. for the oxidation of each metallic, the dominant contribution to the entropy trade (δs) is the removal of 1⁄2 mol o
2, in order that δs is poor and roughly identical for all metals. the slope of the plots displaystyle ddelta g/dt=-delta s displaystyle ddelta g/dt=-delta s is consequently superb for all metals, with δg constantly becoming greater negative with decrease temperature, and the lines for all of the steel oxides are approximately parallel. considering these reactions are exothermic, they usually emerge as viable at lower temperatures. at a sufficiently excessive temperature, the signal of δg may additionally invert (becoming advantageous) and the oxide can spontaneously reduce to the metal, as proven for Ag and cu.
For oxidation of carbon, the purple line is for the formation of co: c(s) + 1⁄2 o
2(g) → co(g) with an growth within the range of moles of gas, leading to a advantageous δs and a terrible slope. the blue line for the formation of co
2 is approximately horizontal, since the reaction c(s) + o
2(g) → co
2(g) leaves the quantity of moles of gasoline unchanged in order that δs is small.
as with every chemical reaction prediction primarily based on purely thermodynamic grounds, a spontaneous reaction can be very gradual if one or greater degrees within the reaction pathway have very high activation energies ea.
If metals are present, equilibria have to be considered. the oxide with the more terrible δg might be formed and the alternative oxide may be reduced.
Curves within the ellingham diagrams for the formation of steel oxides are essentially directly lines with a nice slope. the slope is proportional to δs, which in all fairness consistent with temperature.
the decrease the location of a metal’s line within the ellingham diagram, the extra is the stableness of its oxide. for example, the line for al (oxidation of aluminium) is located to be under that for fe (formation of fe
Stability of metal oxides decreases with growth in temperature. tremendously unstable oxides like Ag
2o and hgo without difficulty undergo thermal decomposition.
the formation free power of carbon dioxide (co
2) is almost unbiased of temperature, while that of carbon monoxide (co) has terrible slope and crosses the co
2 line close to seven-hundred °c. consistent with the boudouard reaction, carbon monoxide is the dominant oxide of carbon at higher temperatures (above about seven-hundred °c), and the higher the temperature (above seven-hundred °c) the greater effective a reductant (decreasing agent) carbon is.
If the curves for two metals at a given temperature are compared, the metal with the lower gibbs loose strength of oxidation at the diagram will reduce the oxide with the better gibbs free electricity of formation. as an instance, metallic aluminium can reduce iron oxide to metal iron, the aluminium itself being oxidized to aluminium oxide. (this response is hired in thermite.)
The extra the gap between any traces, the more the effectiveness of the decreasing agent similar to the lower line.
the intersection of strains implies an oxidation-discount equilibrium. reduction the use of a given reductant is feasible at temperatures above the intersection factor wherein the δg line of that reductant is decrease at the diagram than that of the metal oxide to be decreased. on the factor of intersection the unfastened energy exchange for the reaction is zero, beneath this temperature it is positive and the metallic oxide is strong within the presence of the reductant, whilst above the factor of intersection the gibbs power is terrible and the oxide may be decreased.
In industrial approaches, the reduction of metallic oxides is often effected via a carbothermic reaction, using carbon as a lowering agent. carbon is available cheaply as coal, which may be rendered to coke. while carbon reacts with oxygen it forms the gaseous oxides carbon monoxide and carbon dioxide, so the thermodynamics of its oxidation is different from that for metals: its oxidation has a more bad δg with better temperatures (above seven hundred °c). carbon can therefore serve as reducing agent. using this property, reduction of metals can be completed as a double redox response at pretty low temperature.
Use of Ellingham diagrams
The principle application of ellingham diagrams is within the extractive metallurgy enterprise, where it allows to pick the excellent lowering agent for diverse ores in the extraction procedure, purification and grade placing for steel manufacturing. it also allows to guide the purification of metals, specially the removal of trace factors. the direct discount technique for making iron rests firmly on the steerage of ellingham diagrams, which display that hydrogen can alone lessen iron oxides to the metallic.
Reducing agent for haematite
In iron ore smelting, haematite gets reduced on the top of the furnace, where temperature is within the variety 600 – seven hundred °c. the ellingham diagram shows that in this range carbon monoxide acts as a more potent decreasing agent than carbon because the technique
2 co + o
2 → 2 co
Has a more-poor free electricity trade than the method:
2 c + o
2 → 2 co.
In the top a part of the blast furnace, haematite is reduced with the aid of co (produced by way of oxidation of coke decrease down, at higher temperatures) even within the presence of carbon – although that is mainly due to the fact the kinetics for gaseous co reacting with the ore are better.