Sodium sulfide

The structures of sodium sulfides have been determined by X-ray crystallography. The nonahydrate features S2- hydrogen-bonded to 12 water molecules.^[2] The pentahydrate consists of S^2- centers bound to Na⁺ and encased by an array of hydrogen bonds.^[3] Anhydrous Na₂S, which is rarely encountered, adopts the antifluorite structure,^[4][5] which means that the Na⁺ centers occupy sites of the fluoride in the CaF₂ framework, and the larger S²⁻ occupy the sites for Ca²⁺.

Industrially Na₂S is produced by carbothermic reduction of sodium sulfate often using coal:^[6]

Na₂SO₄ + 2 C → Na₂S + 2 CO₂

In the laboratory, the salt can be prepared by reduction of sulfur with sodium in anhydrous ammonia, or by sodium in dry THF with a catalytic amount of naphthalene (forming sodium naphthalenide):^[7]

2 Na + S → Na₂S

The sulfide ion in sulfide salts such as sodium sulfide can incorporate a proton into the salt by protonation:

S²⁻
+  H⁺ → SH⁻

Because of this capture of the proton ( H⁺), sodium sulfide has basic character. Sodium sulfide is strongly basic, able to absorb two protons. Its conjugate acid is sodium hydrosulfide (SH⁻
). An aqueous solution contains a significant portion of sulfide ions that are singly protonated.

S²⁻
+ H₂O ${\displaystyle {\ce {<=>>}}}$  SH⁻
+  OH⁻

SH⁻
+ H₂O ${\displaystyle {\ce {<<=>}}}$  H₂S +  OH⁻

Sodium sulfide is unstable in the presence of water due to the gradual loss of hydrogen sulfide into the atmosphere.

When heated with oxygen and carbon dioxide, sodium sulfide can oxidize to sodium carbonate and sulfur dioxide:

2 Na₂S + 3 O₂ + 2 CO₂ → 2 Na₂CO₃ + 2 SO₂

Oxidation with hydrogen peroxide gives sodium sulfate:^[8]

Na₂S + 4 H₂O₂ → 4 H₂O + Na₂SO₄

Upon treatment with sulfur, sodium polysulfides are formed:

2 Na₂S + S₈ → 2 Na₂S₅

In terms of its dominant use, "sodium sulfide" is primarily used in the kraft process in the pulp and paper industry. It aids in the delignification process, affording cellulose, which is the main component of paper.

It is used in water treatment as an oxygen scavenger agent and also as a metals precipitant; in chemical photography for toning black and white photographs; in the textile industry as a bleaching agent, for desulfurising and as a dechlorinating agent; and in the leather trade for the sulfitisation of tanning extracts. It is used in chemical manufacturing as a sulfonation and sulfomethylation agent. It is used in the production of rubber chemicals, sulfur dyes and other chemical compounds. It is used in other applications including ore flotation, oil recovery, making dyes, and detergent. It is also used during leather processing, as an unhairing agent in the liming operation.

Alkylation of sodium sulfide give thioethers:

Na₂S + 2 RX → R₂S + 2 NaX

Even aryl halides participate in this reaction.^[9] By a broadly similar process sodium sulfide can react with alkenes in the thiol-ene reaction to give thioethers. Sodium sulfide can be used as nucleophile in Sandmeyer type reactions.^[10].

Aqueous solution of sodium sulfide will reduce nitro groups to amine. This conversion is applied to production of some azo dyes since other reducible groups, e.g. azo group, remain intact.^[11] The reduction of nitro aromatic compounds to amines using sodium sulfide is known as the Zinin reaction in honor of its discoverer.^[12]. Hydrated sodium sulfide reduces 1,3-dinitrobenzene derivatives to the 3-nitroanilines.^[13]

Sulfide has also been employed in photocatalytic applications.^[14]

Consisting of the equivalent of sodium hydroxide, sodium sulfide is strongly alkaline and can cause chemical burns. It reacts rapidly with acids to produce hydrogen sulfide, which is highly toxic.