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Sodium sulfide

Sodium sulfide
Natriumsulfid.jpg
Fluorite-unit-cell-3D-ionic.png
Names
Other names
Disodium sulfide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.829
EC Number 215-211-5
RTECS number WE1905000
UN number 1385 (anhydrous)
1849 (hydrate)
Properties
Na2S
Molar mass 78.0452 g/mol (anhydrous)
240.18 g/mol (nonahydrate)
Appearance colorless, hygroscopic solid
Odor rotten eggs
Density 1.856 g/cm3 (anhydrous)
1.58 g/cm3 (pentahydrate)
1.43 g/cm3 (nonohydrate)
Melting point 1,176 °C (2,149 °F; 1,449 K) (anhydrous)
100 °C (pentahydrate)
50 °C (nonahydrate)
12.4 g/100 mL (0 °C)
18.6 g/100 mL (20 °C)
39 g/100 mL (50 °C)
(hydrolyses)
Solubility insoluble in ether
slightly soluble in alcohol
−39.0·10−6 cm3/mol
Structure
Antifluorite (cubic), cF12
Fm3m, No. 225
Tetrahedral (Na+); cubic (S2−)
Hazards
Safety data sheet ICSC 1047
Corrosive (C)
Dangerous for the environment (N)
R-phrases (outdated) R31, R34, R50
S-phrases (outdated) (S1/2), S26, S45, S61
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oilHealth code 3: Short exposure could cause serious temporary or residual injury. E.g., chlorine gasReactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calciumSpecial hazards (white): no codeNFPA 704 four-colored diamond
1
3
1
> 480 °C (896 °F; 753 K)
Related compounds
Other anions
Sodium oxide
Sodium selenide
Sodium telluride
Other cations
Lithium sulfide
Potassium sulfide
Related compounds
Sodium hydrosulfide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Sodium sulfide is the chemical compound with the formula Na2S, or more commonly its hydrate Na2S·9H2O. Both are colorless water-soluble salts that give strongly alkaline solutions. When exposed to moist air, Na2S and its hydrates emit hydrogen sulfide, which smells like rotten eggs. Some commercial samples are specified as Na2xH2O, where a weight percentage of Na2S is specified. Commonly available grades have around 60% Na2S by weight, which means that x is around 3. Such technical grades of sodium sulfide have a yellow appearance owing to the presence of polysulfides. These grades of sodium sulfide are marketed as 'sodium sulfide flakes'. Although the solid is yellow, solutions of it are colorless.

Structure

Na2S adopts the antifluorite structure,[1][2] which means that the Na+ centers occupy sites of the fluoride in the CaF2 framework, and the larger S2− occupy the sites for Ca2+.

Production

Industrially Na2S is produced by carbothermic reduction of sodium sulfate often using coal:[3]

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):[4]

2 Na + S → Na2S

Reactions with inorganic reagents

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
SH
+ OH

 

 

 

 

(1)

SH
+ H2O
H2S + OH

 

 

 

 

(2)

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:[5]

Na2S + 4 H2O2 → 4 H2O + Na2SO4

Upon treatment with sulfur, polysulfides are formed:

2 Na2S + S8 → 2 Na2S5

Uses

Sodium sulfide is primarily used in the kraft process in the pulp and paper industry.

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.

Reagent in organic chemistry

Alkylation of sodium sulfide give thioethers:

Na2S + 2 RX → R2S + 2 NaX

Even aryl halides participate in this reaction.[6] Sodium sulfide can be used as nucleophile in Sandmeyer type reactions.[7] Sodium sulfide reduces1,3-dinitrobenzene derivatives to the 3-nitroanilines.[8] Aqueous solution of sodium sulfide can be refluxed with nitro carrying azo dyes dissolved in dioxane and ethanol to selectively reduce the nitro groups to amine; while other reducible groups, e.g. azo group, remain intact.[9] Sulfide has also been employed in photocatalytic applications.[10]

Safety

Like sodium hydroxide, sodium sulfide is strongly alkaline and can cause skin burns. Acids react with it to rapidly produce hydrogen sulfide, which is highly toxic.

References

  1. ^ Zintl, E; Harder, A; Dauth, B. (1934). "Gitterstruktur der oxyde, sulfide, selenide und telluride des lithiums, natriums und kaliums". Z. Elektrochem. Angew. Phys. Chem. 40: 588–93. 
  2. ^ Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. ISBN 0-19-855370-6.
  3. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  4. ^ So, J.-H; Boudjouk, P; Hong, Harry H.; Weber, William P. (1992). "Hexamethyldisilathiane". Inorg. Synth. Inorganic Syntheses. 29: 30. doi:10.1002/9780470132609.ch11. ISBN 978-0-470-13260-9. 
  5. ^ L. Lange, W. Triebel, "Sulfides, Polysulfides, and Sulfanes" in Ullmann's Encyclopedia of Industrial Chemistry 2000, Wiley-VCH, Weinheim. doi:10.1002/14356007.a25_443
  6. ^ Charles C. Price, Gardner W. Stacy "p-Aminophenyldisulfide" Org. Synth. 1948, vol. 28, 14. doi:10.15227/orgsyn.028.0014
  7. ^ Khazaei; et al. (2012). "synthesis of thiophenols". Synthesis Letters - Thieme Chemistry. 23: 1893. 
  8. ^ Hartman, W. W.; Silloway, H. L. (1955). "2-Amino-4-nitrophenol". Organic Syntheses. ; Collective Volume, 3, p. 82 
  9. ^ Yu; et al. (2006). "Syntheses of functionalized azobenzenes". Tetrahedron. 62: 10303. 
  10. ^ Savateev, A.; Dontsova, D.; Kurpil, B.; Antonietti, M. (June 2017). "Highly crystalline poly(heptazine imides) by mechanochemical synthesis for photooxidation of various organic substrates using an intriguing electron acceptor – Elemental sulfur". Journal of Catalysis. Volume 350: Pages 203–211.