Sulfiding
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Sulfidation (British spelling also sulphidation) is a process of installing
sulfide Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families o ...
ions in a material or
molecule A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
. The process is widely used to convert oxides to sulfides but is also related to corrosion and surface modification.


Inorganic, materials, and organic chemistry

Sulfidation is relevant to the formation of
sulfide mineral The sulfide minerals are a class of minerals containing sulfide (S2−) or disulfide () as the major anion. Some sulfide minerals are economically important as metal ores. The sulfide class also includes the selenide mineral, selenides, the tell ...
s. A large scale application of sulfidation is the conversion of molybdenum oxides to the corresponding sulfides. This conversion is a step in the preparation of catalysts for
hydrodesulfurization Hydrodesulfurization (HDS), also called hydrotreatment or hydrotreating, is a catalytic chemical process widely used to desulfurization, remove sulfur (S) from natural gas and from oil refinery, refined petroleum products, such as gasoline, g ...
wherein
alumina Aluminium oxide (or aluminium(III) oxide) is a chemical compound of aluminium and oxygen with the chemical formula . It is the most commonly occurring of several aluminium oxides, and specifically identified as aluminium oxide. It is commonly ...
impregnated with
molybdate In chemistry, a molybdate is a compound containing an oxyanion with molybdenum in its highest oxidation state of +6: . Molybdenum can form a very large range of such oxyanions, which can be discrete structures or polymeric extended structures, ...
salts are converted to
molybdenum disulfide Molybdenum disulfide (or moly) is an inorganic chemistry, inorganic compound composed of molybdenum and sulfur. Its chemical formula is . The compound is classified as a transition metal dichalcogenide. It is a silvery black solid that occurs as ...
by the action of
hydrogen sulfide Hydrogen sulfide is a chemical compound with the formula . It is a colorless chalcogen-hydride gas, and is toxic, corrosive, and flammable. Trace amounts in ambient atmosphere have a characteristic foul odor of rotten eggs. Swedish chemist ...
. In
organosulfur chemistry Organosulfur chemistry is the study of the properties and synthesis of organosulfur compounds, which are organic compounds that contain sulfur. They are often associated with foul odors, but many of the sweetest compounds known are organosulfur der ...
, sulfiding is often called thiation. The preparation of
thioamide A thioamide (rarely, thionamide, but also known as thiourylenes) is a functional group with the general structure , where are any groups (typically organyl groups or hydrogen). Analogous to amides, thioamides exhibit greater multiple bond charact ...
s from
amide In organic chemistry, an amide, also known as an organic amide or a carboxamide, is a chemical compound, compound with the general formula , where R, R', and R″ represent any group, typically organyl functional group, groups or hydrogen at ...
s involves thiation. A typical
reagent In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
is
phosphorus pentasulfide Phosphorus pentasulfide is the inorganic compound with the formula (empirical) or ( molecular). This yellow solid is the one of two phosphorus sulfides of commercial value. Samples often appear greenish-gray due to impurities. It is soluble in ...
(P4S10). The idealized equation for this conversion is: :RC(O)NH2 + 1/4 P4S10 → RC(S)NH2 + 1/4 P4S6O4 This conversion where an oxygen atom in the amide function is replaced by a sulfur atom involves no redox reaction.


Sulfidation of metals

It is known that aluminum improves the sulfidation resistance of iron alloys. The sulfidation of
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
is a multiple step process. The first step is an
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
reaction, converting the
tungsten Tungsten (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...
to a tungsten bronze on the surface of the object. The tungsten bronze coating is then converted to a
sulfide Sulfide (also sulphide in British English) is an inorganic anion of sulfur with the chemical formula S2− or a compound containing one or more S2− ions. Solutions of sulfide salts are corrosive. ''Sulfide'' also refers to large families o ...
. One commonly encountered occurrence of sulfidation in manufacturing environments involves the sulfidic corrosion of metal piping. The increased resistance to corrosion found in
stainless steel Stainless steel, also known as inox, corrosion-resistant steel (CRES), or rustless steel, is an iron-based alloy that contains chromium, making it resistant to rust and corrosion. Stainless steel's resistance to corrosion comes from its chromi ...
is attributed to a layer of
chromium oxide Chromium oxide may refer to: * Chromium(II) oxide, CrO * Chromium(III) oxide, Cr2O3 * Chromium dioxide (chromium(IV) oxide), CrO2, which includes the hypothetical compound chromium(II) chromate * Chromium trioxide (chromium(VI) oxide), CrO3 * Ch ...
that forms due to
oxidation Redox ( , , reduction–oxidation or oxidation–reduction) is a type of chemical reaction in which the oxidation states of the reactants change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is ...
of the
chromium Chromium is a chemical element; it has Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal. Chromium ...
found in the alloy. The process of liquid sulfidation has also been used in the manufacturing of
diamond-like carbon Diamond-like carbon (DLC) is a class of amorphous carbon material that displays some of the typical properties of diamond. DLC is usually applied as coatings to other materials that could benefit from such properties. DLC exists in seven dif ...
films. These films are generally used to coat surfaces to reduce the wear due to friction. The inclusion of sulfidation in the process has been shown to reduce the
friction coefficient Friction is the force resisting the relative motion of solid surfaces, fluid layers, and material elements sliding against each other. Types of friction include dry, fluid, lubricated, skin, and internal -- an incomplete list. The study of t ...
of the diamond-like carbon film.


References

{{Reflist Corrosion Thermodynamics Chemical reactions