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Water-reactive substances

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Water-reactive substances[1] are those that spontaneously undergo a chemical reaction with water, often noted as generating flammable gas.[2] Some are highly reducing in nature.[3] Notable examples include alkali metals, lithium through caesium, and alkaline earth metals, magnesium through barium.

Some water-reactive substances are also pyrophoric, like organometallics and sulfuric acid. The use of acid-resistant gloves and face shield is recommended for safe handling; fume hoods are another effective control of such substances.[4]

Water-reactive substances are classified as R2 under the UN classification system and as Hazard 4.3 by the United States Department of Transportation. In an NFPA 704 fire diamond's white square, and in similar contexts, they are denoted as "W". The classification of substances as water-reactive is largely a consideration for the safety of firefighting and transportation operations.[5]

All chemicals that react vigorously with water or liberate toxic gas when in contact with water are recognized for their hazardous nature in the "Approved Supply List",[6] or the list of substances covered by the international legislation on major hazards[7] many of which are commonly used in manufacturing processes.

Alkali metals

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Main article: Alkali metals
 
Group 1: Alkali metals
Reaction of sodium (Na) and water
Reaction of potassium (K) in water

The alkali metals (Li, Na, K, Rb, Cs, and Fr) are the most reactive metals in the periodic table - they all react vigorously or even explosively with cold water, resulting in the displacement of hydrogen.

The Group 1 metal (M) is oxidised to its metal ions, and water is reduced to hydrogen gas (H2) and hydroxide ion (OH−), giving a general equation of:

2 M(s) + 2 H2O(l) ⟶ 2 M+(aq) + 2 OH−(aq) + H2(g) [8]

The Group 1 metals or alkali metals become more reactive as their number of energy levels inceases.

Alkaline earth metals

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Main article: Alkaline earth metals
 
Group 2: Alkaline earth metals

The alkaline earth metals (Be, Mg, Ca, Sr, Ba, and Ra) are the second most reactive metals in the periodic table, and, like the Group 1 metals, have increasing reactivity with increasing numbers of energy levels. Beryllium (Be) is the only alkaline earth metal that does not react with water or steam, even if the metal is heated red hot.[9] Additionally, beryllium has a resistant outer oxide layer that lowers its reactivity at lower temperatures.

Magnesium shows insignificant reaction with water, but burns vigorously with steam or water vapor to produce white magnesium oxide and hydrogen gas:[10]

Mg(s) + H2O(g) ⟶ MgO(s) + H2(g)


Magnesium has a mild reaction with cold water. The reaction is short-lived because the magnesium hydroxide layer formed on the magnesium is almost insoluble in water and prevents further reaction.

Mg(s) + 2H2O(l) ⟶ Mg(OH)2(s) + H2(g)[11]

A metal reacting with cold water will produce a metal hydroxide and hydrogen gas. However, if a metal reacts with steam, like magnesium, metal oxide is produced as a result of metal hydroxides splitting upon heating.[12]

The hydroxides of calcium, strontium and barium are only slightly water-soluble but produce sufficient hydroxide ions to make the environment basic, giving a general equation of:

M(s) + 2 H2O(l) ⟶ M(OH)2(aq) + H2(g)[13]

Radium reacts similarly to the rest of the alkaline earth metals (other than magnesium), forming radium hydroxide and hydrogen gas.[14] Notably, radium hydroxide is the most soluble out of all alkaline earth hydroxide species.[15]

Reactivity series of metals

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Order of reactivity Metal Reactions with water or steam
Most reactive potassium (K) Very vigorous reaction with cold water
Second most reactive sodium (Na) Vigorous reaction with cold water
Third most reactive calcium (Ca) Less vigorous reaction with cold water
Least reactive magnesium (Mg) Slow reaction with cold water, vigorous with hot water
  • If metals react with cold water, hydroxides are produced.
  • If metals react with steam, oxides are formed.

Hydrogen is always produced when a metal reacts with cold water or steam.[16]

Halogens

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Halogens are so named due to their potential to form salts, and form many simple strong acids with hydrogen. Out of the four stable halogens, only fluorine and chlorine have reduction potentials higher than that of oxygen, allowing them to form hydrofluoric acid and hydrochloric acid directly through reaction with water.[17] The reaction of fluorine with water is especially hazardous, as an addition of fluorine gas to cold water will produce hydrofluoric acid, oxygen gas, and ozone.[18] However, the reaction is fairly slow.[19]

References

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  1. ^ "The MSDS HyperGlossary: Metal Reactive". Interactive Learning Paradigms Incorporated. Retrieved 2007-05-10.
  2. ^ "Shipping dangerous goods". GOV.UK. Retrieved 2024-09-25.
  3. ^ Raymond, Chang (2010). Chemistry (PDF) (tenth ed.). Americas, New York: McGraw-Hill. pp.897-898. ISBN 0077274318. Retrieved 27 February 2018.
  4. ^ The University of Iowa. "Reactive Chemicals". Environmental Health & Safety. Archived from the original on 3 March 2018. Retrieved 2 March 2018.
  5. ^ Gallant, Brian J. (2006-01-13). Hazardous Waste Operations and Emergency Response Manual (1 ed.). Wiley. pp. 48–49. doi:10.1002/0470007257. ISBN 978-0-471-68400-8.
  6. ^ Quinn, D. J.; Davies, P. A. (2003). "MODELLING RELEASES OF WATER REACTIVE CHEMICALS" (PDF). Symposium Series. 149. Archived from the original (PDF) on 26 February 2018. Retrieved 25 February 2018.
  7. ^ Kapias, T; Griffiths, RF (2001). REACTPOOL: A new model for accidental releases of water-reactive chemicals (PDF). Crown. ISBN 0-7176-1995-8. Retrieved 25 February 2018.
  8. ^ Landas, Trevor (2 October 2013). "Reactions of Main Group Elements with Water". Chemistry LibreTexts. Retrieved 9 February 2017.
  9. ^ Pilgaard, Michael. "Beryllium: Chemical Reactions". Michael Pilgaard's Table of the Elements. Retrieved 16 February 2018.
  10. ^ "The reaction of magnesium with steam". RSC Education. Retrieved 2024-05-11.
  11. ^ "Reactions of Group 2 Elements with Water". Chemistry LibreTexts. 2013-10-03. Retrieved 2023-09-08.
  12. ^ Clark, Jim. "Reactions of the Group 2 Elements with Water". ChemGuide. Retrieved 16 February 2018.
  13. ^ Landas, Trevor (2 October 2013). "Reactions of Main Group Elements with Water". Chemistry LibreTexts. Retrieved 16 February 2018.
  14. ^ Salutsky, M. L.; Kirby, H. W. (1964-12-01). THE RADIOCHEMISTRY OF RADIUM (Report). Mound Lab., Miamisburg, Ohio (Grace (W.R.) and Co., Clarksville, Md. Washington Research Center). p. 4. OSTI 4560824.
  15. ^ Brown, Paul L.; Matyskin, Artem V.; Ekberg, Christian (2022-06-27). "The aqueous chemistry of radium". Radiochimica Acta. 110 (6–9): 505–513. doi:10.1515/ract-2021-1141. ISSN 0033-8230.
  16. ^ Gallagher, RoseMarie; Ingram, Paul (2009). Chemistry IGCSE Revision Guide. Great Clarendon Street, Oxford OX2 6DP: Oxford University Press. pp. 114–115.{{cite book}}: CS1 maint: location (link)
  17. ^ "Reactions of Main Group Elements with Halogens". Chemistry LibreTexts. June 30, 2023.
  18. ^ Cady, George Hamilton (February 1935). "Reaction of Fluorine with Water and with Hydroxides". Journal of the American Chemical Society. 57 (2): 246–249. doi:10.1021/ja01305a006. ISSN 0002-7863.
  19. ^ "Fluoride Salts, Soluble | CAMEO Chemicals | NOAA". cameochemicals.noaa.gov. Retrieved 2024-02-05.
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