Sodium dithionite

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Sodium dithionite
Sodium dithionite
Sample of sodium dithionite.jpg
Other names
Sodium hydrosulfite
Sodium sulfoxylate
Virtex L
3D model (JSmol)
ECHA InfoCard 100.028.991
EC Number 231-890-0
RTECS number JP2100000
UN number 1384
Molar mass 174.107 g/mol (anhydrous)
210.146 g/mol (dihydrate)
Appearance white to grayish crystalline powder
light-lemon colored flakes
Odor faint sulfur odor
Density 2.38 g/cm3 (anhydrous)
1.58 g/cm3 (dihydrate)
Melting point 52 °C (126 °F; 325 K)
Boiling point Decomposes
18.2 g/100 mL (anhydrous, 20 °C)
21.9 g/100 mL (Dihydrate, 20 °C)
Solubility slightly soluble in alcohol
Harmful (Xn)
R-phrases (outdated) R7, R22, R31
S-phrases (outdated) (S2), S7/8, S26, S28, S43
NFPA 704
Flammability code 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g., gasoline Health code 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g., chloroform Reactivity code 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g., calcium Special hazards (white): no codeNFPA 704 four-colored diamond
Flash point 100 °C (212 °F; 373 K)
200 °C (392 °F; 473 K)
Related compounds
Other anions
Sodium sulfite
Sodium sulfate
Related compounds
Sodium thiosulfate
Sodium bisulfite
Sodium metabisulfite
Sodium bisulfate
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 dithionite (also known as sodium hydrosulfite) is a white crystalline powder with a weak sulfurous odor. It is the sodium salt of dithionous acid. Although it is stable under most conditions, it will decompose in hot water and in acid solutions. It can be obtained from sodium bisulfite by the following reaction:[1]

2 NaHSO3 + Zn → Na2S2O4 + Zn(OH)2


Raman spectroscopy and single-crystal X-ray diffraction studies of sodium dithionite in the solid state reveal that sodium dithionite exists in different forms. In one anhydrous form, the dithionite ion has C
geometry, almost eclipsed with a 16° O-S-S-O torsional angle. In the dihydrated form (Na
), the dithionite anion has a shorter S-S bond length and a gauche 56° O-S-S-O torsional angle.[2]

The weak S-S bond causes the dithionite anion to dissociate into the [SO2] radical anion in aqueous solution, which has been confirmed by ESR spectroscopy. It is also observed that 35S undergoes rapid exchange between S2O42− and SO2 in neutral or acidic solution, consistent with the weak S-S bond in the anion.[3]

Properties and reactions[edit]

Sodium dithionite is stable when dry, but is slowly oxidized by air when in solution. Even with the absence of air, solutions of sodium dithionite deteriorate due to the following reaction:

2 S2O42− + H2O → S2O32− + 2 HSO3

Thus solutions of sodium dithionite cannot be stored for a long period of time.[3]

Anhydrous is a monoclinic crystal with slightly sulfuric odor. It is soluble in water and slightly soluble in ethanol. Dihydrate is a columnar crystal, and it is so unstable that it easily dehydrates to anhydrous and is easily oxidized by oxygen in the air.

Anhydrous gradually decomposes to sodium sulfate and sulfur dioxide above 90 °C in the air. In absence of air, it decomposes quickly above 150 °C to sodium sulfite, sodium thiosulfate, sulfur dioxide and trace amount of sulfur.

Powdered anhydrous sodium dithionite with a small amount of water may ignite in air by the heat of decomposition. In absence of air (oxygen), it only decomposes slowly.

An aqueous solution of sodium dithionite is acidic and decomposes to sodium thiosulfate and sodium bisulfite. The reaction rate increases with increasing temperature. In addition, the rate is higher under stronger acidity.

2 Na2S2O4 + H2O → Na2S2O3 + 2 NaHSO3

In presence of oxygen, it decomposes to sodium bisulfate and sodium bisulfite.

Na2S2O4 + O2 + H2O → NaHSO4 + NaHSO3

Sodium bisulfate and sodium bisulfite decrease the pH and therefore accelerate the reaction. Sulfur dioxide is formed under strongly acidic conditions.

2 H2S2O4 → 3 SO2 + S + 2 H2O
3 H2S2O4 → 5 SO2 + H2S + 2 H2O

On the other hand, alkali solution (pH 9–11) is stable and only decomposes about 1% per an hour. It has strong reducing properties and decomposes to sulfurous acid and sulfide.

3 Na2S2O4 + 6 NaOH → 5 Na2SO3 + Na2S + 3 H2O

In the presence of aldehydes, sodium diothionite reacts either to form α-hydroxy-sulfinates at room temperature or to reduce the aldehyde to the corresponding alcohol above a temperature of 85 °C.[4][5] Some ketones are also reduced under similar conditions.



This compound is a water-soluble salt, and can be used as a reducing agent in aqueous solutions. It is used as such in some industrial dyeing processes, primarily those involving sulfur dyes and vat dyes, where an otherwise water-insoluble dye can be reduced into a water-soluble alkali metal salt (e.g. indigo dye).[6] The reduction properties of sodium dithionite also eliminate excess dye, residual oxide, and unintended pigments, thereby improving overall colour quality.

Sodium dithionite can also be used for water treatment, gas purification, cleaning, and stripping. It can also be used in industrial processes as a sulfonating agent or a sodium ion source. In addition to the textile industry, this compound is used in industries concerned with leather, foods, polymers, photography, and many others. Its wide use is attributable to its low toxicity LD50 at 5 g/kg, and hence its wide range of applications. It is also used as decolourising agent in organic reactions.

Biological sciences[edit]

Sodium dithionite is often used in physiology experiments as a means of lowering solutions' redox potential (Eo' -0.66 V vs SHE at pH 7).[7] Potassium ferricyanide is usually used as an oxidizing chemical in such experiments (Eo' ~ .436 V at pH 7). In addition, sodium dithionite is often used in soil chemistry experiments to determine the amount of iron that is not incorporated in primary silicate minerals. Hence, iron extracted by sodium dithionite is also referred to as "free iron." The strong affinity of the dithionite ion for bi- and trivalent metal cations (M2+, M3+) allows it to enhance the solubility of iron, and therefore dithionite is a useful chelating agent.


Sodium dithionite has been used in chemical enhanced oil recovery[citation needed] to stabilize polyacrylamide polymers against radical degradation in the presence of iron. It has also been used in environmental applications to propagate a low Eh front in the subsurface in order to reduce components such as chromium.


It can be used as a developer, but it is a very uncommon choice. It is prone to reduce film speed and, if improperly used, quickly fogs the image.


Aqueous solutions of sodium dithionite were once used to produce "Fieser's solution' for the removal of oxygen from a gas stream.[8] Pyrithione can be prepared in a two-step synthesis from 2-bromopyridine by oxidation to the N-oxide with a suitable peracid followed by substitution using sodium dithionite to introduce the thiol functional group.[9]

See also[edit]


  1. ^ Pratt, L. A. (1924). "The Manufacture of Sodium Hyposulfite". Industrial & Engineering Chemistry. 16 (7): 676–677. doi:10.1021/ie50175a006. 
  2. ^ Weinrach, J. B.; Meyer, D. R.; Guy, J. T.; Michalski, P. E.; Carter, K. L.; Grubisha, D. S.; Bennett, D. W. (1992). "A structural study of sodium dithionite and its ephemeral dihydrate: A new conformation for the dithionite ion". Journal of Crystallographic and Spectroscopic Research. 22 (3): 291–301. doi:10.1007/BF01199531. 
  3. ^ a b Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 16: The group 16 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 520. ISBN 978-0-13-175553-6. 
  4. ^ J. Org. Chem., 1980, 45 (21), pp 4126–4129,
  5. ^
  6. ^ Božič, Mojca; Kokol, Vanja (2008). "Ecological alternatives to the reduction and oxidation processes in dyeing with vat and sulphur dyes". Dyes and Pigments. 76 (2): 299–309. doi:10.1016/j.dyepig.2006.05.041. 
  7. ^ MAYHEW, Stephen G. (1978). "The Redox Potential of Dithionite and SO-2 from Equilibrium Reactions with Flavodoxins, Methyl Viologen and Hydrogen plus Hydrogenase". European Journal of Biochemistry. 85 (2): 535–547. ISSN 0014-2956. doi:10.1111/j.1432-1033.1978.tb12269.x. 
  8. ^ Kenneth L. Williamson "Reduction of Indigo: Sodium Hydrosulfite as a Reducing Agent" J. Chem. Educ., 1989, volume 66, p 359. doi:10.1021/ed066p359.2
  9. ^ Knight, David W.; Hartung, Jens (15 September 2006). "1-Hydroxypyridine-2(1H)-thione". Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons. doi:10.1002/047084289X.rh067.pub2.