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Cesium Hydroxide

CsOH base

Properties

StateSolid (extremely hygroscopic and deliquescent)
ColorYellowish-white
SolubilityExtremely soluble in water (exothermic dissolution); ~300 g/100 mL at 30°C
Melting Point272°C
Boiling PointDecomposes before boiling

About Cesium Hydroxide

CsOH is the strongest of the simple alkali-metal hydroxides — not because the hydroxide ion is any different, but because the Cs-OH bond is the weakest in the group and the cation contributes the least stabilization to the OH- through ion pairing. In aqueous solution that distinction collapses (all alkali hydroxides dissociate completely above about 10^-4 M, so they all titrate the same), but in organic solvents it actually matters: CsOH-promoted reactions that go cleanly in DMSO will stall with NaOH because the sodium ion holds the hydroxide too tightly to keep it nucleophilic. The other property that separates CsOH from KOH and NaOH is its deliquescence — leave a bottle open in normal lab humidity for an hour and you'll come back to a puddle of cesium hydroxide solution that's also been picking up CO2 from the air the whole time. By the next morning you've got Cs2CO3 contamination at percent levels. The serious uses for CsOH are narrow because of the price (it runs $200-500 per gram for high-purity material against a few cents per gram for KOH), so it shows up mostly as an electrolyte additive in alkaline fuel cells where the higher mobility of Cs+ vs K+ gives a small efficiency gain, as a deprotonating base for the most acidic C-H substrates in medicinal chemistry, and as a precursor for cesium-doped semiconductor surfaces.

Where you'll encounter it

If you walk into a lab that does any alkaline electrochemistry and see a small bottle of CsOH stored inside an Ar-filled glovebox, it's almost certainly being used as an electrolyte additive — the cesium ion has a higher mobility in concentrated KOH solutions and shifts the hydrogen-evolution overpotential on certain catalyst surfaces. CsOH also turns up in thin-film deposition: a monolayer of cesium adsorbed onto a metal surface lowers the work function dramatically, which is why CsOH gets used as the source for cesiation of GaAs photocathodes and for activating III-V semiconductor surfaces in negative-electron-affinity electron emitters. In synthesis, you'll see it specifically when someone is trying to deprotonate a substrate where K+ ion pairing inhibits the desired reaction — for example, certain cesium-promoted macrocyclization reactions exploit a templating effect of Cs+ that K+ doesn't reproduce.

Common Uses

  • Electrolyte additive in alkaline hydrogen fuel cells for improved Cs+ mobility and reduced overpotential
  • Strong base for substrates where K+ ion-pairing inhibits the deprotonated nucleophile
  • Cesium source for surface activation of GaAs and III-V negative-electron-affinity photocathodes
  • Templating base for crown ether and macrocyclization syntheses tuned to Cs+ size
  • Electrolyte component in specialty alkaline batteries operating at low temperatures
  • Precursor for high-purity cesium salts where chloride or carbonate impurity must be excluded
  • Etchant in research-scale silicon micromachining where alkali metal contamination is acceptable
  • Deprotonating reagent for unusually weak C-H acids in mechanistic NMR studies

Safety Information

CsOH is GHS Skin Corrosion 1A and Serious Eye Damage Category 1 — the same hazard profile as concentrated NaOH or KOH but more aggressive because the dissolution into surface moisture is faster and the resulting solution is more concentrated by the time you notice. There's no specific OSHA PEL but the general substance-specific limit for caustic alkali aerosols (2 mg/m3 ceiling) applies. Splash to skin produces a slippery soapy feel that is the saponification of your own lipids; rinse for 15 minutes minimum. Eye contact is a medical emergency. Reaction with water is strongly exothermic; reaction with strong acid generates enough heat to boil the resulting salt solution if you're not careful. Store under inert atmosphere or in a tightly sealed bottle inside a desiccator.

This safety summary is for educational reference only and may not be complete. It is not a substitute for Safety Data Sheets (SDS), medical advice, or professional chemical safety guidance. Always consult appropriate SDS and qualified professionals before handling chemicals.

Constituent Elements

Frequently Asked Questions

What is the molar mass of cesium hydroxide?
CsOH is 149.912 g/mol: cesium at 132.905, oxygen at 15.999, and hydrogen at 1.008. Note that CsOH is most commonly sold as the monohydrate CsOH.H2O at 167.928 g/mol because anhydrous CsOH is hard to keep dry. If you weigh out 'CsOH' from a typical bottle without checking the label, you may be working with the hydrate and underdosing your reaction by about 10% on a molar basis.
Is cesium hydroxide the strongest base?
Among simple alkali-metal hydroxides yes, but the difference is mostly notional in water and only matters in organic solvents. In DMSO the pKa(BH+) of CsOH-derived hydroxide is appreciably higher than for NaOH-derived hydroxide because the Na-OH ion pair has more covalent character. In water all alkali hydroxides give pH 14 at 1 M and behave identically — calling CsOH the 'strongest base' is true on paper but rarely matters at the bench. Real superbases like P4-tBu phosphazene or KHMDS are orders of magnitude stronger.
Why is cesium hydroxide more expensive than sodium hydroxide?
Cesium has no major ore — it's recovered as a minor byproduct of lithium extraction from pollucite at one mine in Manitoba, plus a few smaller operations. Annual world production of cesium compounds runs around 20 tonnes versus 70 million tonnes of NaOH. That scarcity, combined with the multi-step purification to get below 100 ppm Rb and Na contamination, is why high-purity CsOH costs $200-500 per gram against $0.50 per kg for NaOH. The cost is why CsOH only gets specified when no cheaper alkali hydroxide will do the job.