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Which ionic compound has highest solubility in water? I can find CsBr having highest solubility with 1230 g/L at 25 °C.

Note: compounds like ethanol are soluble to any extent in water, but they are covalent, not ionic.

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    $\begingroup$ It would be interesting to split in the two cases of molar solubility and mass solubility, though the latter is easier to find data on directly. $\endgroup$
    – Nicolau Saker Neto
    Jan 11, 2019 at 2:51
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    $\begingroup$ I could be cheeky and add Ionic Liquids to the list, which often mix with water at any ratio. Maybe clarify that you are talking about solids at standard conditions. $\endgroup$
    – TAR86
    Jan 11, 2019 at 10:06
  • $\begingroup$ @TAR86 Darn, I was just a bit late with my edit! I'll leave that sidenote in my answer anyway. $\endgroup$
    – Nicolau Saker Neto
    Jan 11, 2019 at 10:13

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Caesium salts are unapologetically ionic, and they typically have quite high mass solubilities in many solvents, including water.

Assuming organic ions are allowed, caesium acetate ($\ce{H3CCO2^-Cs+}$) in particular has a remarkably high solubility of 9451 g/kg water at −2.5 °C, increasing to 13 455 g/L water at 88.5 °C.

Caesium formate ($\ce{HCO2^-Cs+}$) is also quite soluble, with a solubility of 4880 g/kg water at 20 °C, resulting in 2.56 L of solution with a density of 2.297 g/mL (reference, .docx file). However, its solubility increases much faster with increasing temperature (J. Chem. Soc., Trans., 1922, 121, 1837-1843). At 100 °C, it reaches an outstanding value of 20 071 g/kg water! That's 11.6 molal, or roughly 20-25 mol/L assuming the density doesn't change too much. This saturated solution is 67.7% cesium formate by number of moles, which means more than two caesium ions and two formate ions per molecule of water.

I believe I have read somewhere that caesium formate is the record holder for highest mass solubility in water (evidently only at high temperatures). If this is not true, then I can scarcely believe it will be topped by much.

Tangentially, Ivan mentions Clerici's solution, which is actually a mixture of thallium(I) formate and thallium(I) malonate. The mixture doesn't count (though the individual components are quite soluble themselves), but it interesting to analyse. Apparently 300 g of each compound will dissolve in 40 g of water without saturating it room temperature (ref), giving a lower bound to their combined solubility of 15 000 g/kg water. This value rises with heating, and is the only way I can see to beat the mass solubility of caesium formate.

For further entertainment, I recommend these two solubility tables with a large number of entries (1, 2). The second one can be ordered by solubility at different temperatures. It's interesting to see the variety of cations and anions which can be combined to display extreme mass solubility.

Edit: If room-temperature ionic liquids are allowed, then it is quite likely some of them are miscible with water in any proportion, which is effectively "infinite solubility in water". Something as simple as ethylammonium nitrate ($\ce{C2H5NH3+NO3-}$) may suffice.

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    $\begingroup$ If they are ionic, the state of matter does not matter. +1. $\endgroup$
    – Oscar Lanzi
    Jan 11, 2019 at 12:10
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The following data is compiled from [1, pp. 4-44, 5-167]:

Table 1. Selected solubility values of the inorganic compounds with significant ionic character at $25~\mathrm{^\circ C}$. $$ \begin{array}{lc} \hline \text{Formula} & \text{Solubility in water}/\pu{g L-1}\\ \hline \ce{CsF} & 5730\\ \ce{SbF3} & 4920\\ \ce{LiClO3} & 4587\\ \ce{Pb(ClO4)2} & 4405\\ \ce{ZnCl2} & 4080\\ \hline \end{array} $$

Solubility of antimony(III) trichloride $\ce{SbCl3}$ is $9870~\mathrm{g~L^{-1}}$ at $25~\mathrm{^\circ C}$, but technically it's not an ionic compound.

References

  1. Haynes, W. M.; Lide, D. R.; Bruno, T. J. CRC Handbook of Chemistry and Physics: A Ready-Reference Book of Chemical and Physical Data.; 2017; Vol. 97.
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  • $\begingroup$ I've seen antimony trichloride before in tables, but it is apparently very easily hydrolysed, so perhaps it shouldn't be counted either way. $\endgroup$
    – Nicolau Saker Neto
    Jan 11, 2019 at 7:53
  • $\begingroup$ @NicolauSakerNeto Yep, you are right, and the same probably goes for $\ce{ZnCl2}$. I also omitted $\ce{ZnBr2}$ for similar reason (and it's covalency, too). $\endgroup$
    – andselisk ♦
    Jan 11, 2019 at 7:55
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There is not going to be a single definitive answer, primarily because of a wide gray zone surrounding the domain of ionic compounds. Besides, as Nikolau noted, the question is ambiguous.

If you want mass concentration, then look at $\ce{InI3}$ which claims a whopping $13100~\mathrm{g/L}$. Pity that it is probably ionic in name only, judging by the solubility in non-polar solvents. Well, then look at those mentioned by andselisk, though the ionic nature of some of them is also debatable, and then at the thallium formate (a component of Clerici solution) with $\sim5000~\mathrm{g/L}$.

If you want molar concentration, then the question is still ambiguous (are we looking at molarity or molality?), and the pretty strong contenders are $\ce{NaOH}$, $\ce{BeF2}$, $\ce{LiClO3}$.

So it goes.

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    $\begingroup$ True, $\ce{InI3}$ is weird, but it's definitely not ionic and the reference for the solubility value dates back to 1940s or something:) $\endgroup$
    – andselisk ♦
    Jan 11, 2019 at 6:54
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We can do better than that. Ammonium nitrate = 1500 g/L at 20°C.

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