- Inorganic nonaqueous solvent
An inorganic nonaqueous solvent is a
solventother than water, that is not an organic compound. Common examples are liquid ammonia, liquid sulfur dioxide, sulfuryl chlorideand sulfuryl chloride fluoride, phosphoryl chloride, dinitrogen tetroxide, antimony trichloride, bromine pentafluoride, hydrogen fluoride, pure sulfuric acidand other inorganic acids. These solvents are used in chemical research and industry for reactions that cannot occur in aqueous solutions or require special environment.
Noble gas chemistry
The reactions of the compounds containing
xenonare mostly conducted in hydrogen fluorideor bromine pentafluoride, which dissolve readily both xenon difluorides and its multiple derivatives [Pointner BE, Suontamo RJ, Schrobilgen GJ. Syntheses and X-ray crystal structures of alpha- and beta- [XeO2F] [SbF6] , [XeO2F] [AsF6] , [FO2XeFXeO2F] [AsF6] , and [XeF5] [SbF6)] .XeOF4 and computational studies of the XeO2F+ and FO2XeFXeO2F+ cations and related species. "Inorg Chem." 2006 Feb 20;45(4):1517-34.] , although sulfuric solvents are also used sometimes, in particular sulfuryl chloride fluoridefor strong oxidants. [Mercier HP, Moran MD, Sanders JC, Schrobilgen GJ, Suontamo RJ. "Synthesis, structural characterization, and computational study of the strong oxidant salt [XeOTeF5] [Sb(OTeF5)6] .SO2ClF." "Inorg Chem." 2005 Jan 10;44(1):49-60.]
Sulfuryl chloride fluorideis the solvent of choice for many reactions that deal with extreme oxidants. For example, it can be used to generate and study free carbocations[Mercier HP, Moran MD, Schrobilgen GJ, Steinberg C, Suontamo RJ.The syntheses of carbocations by use of the noble-gas oxidant, [XeOTeF5] [Sb(OTeF5)6] : the syntheses and characterization of the CX3+ (X = Cl, Br, OTeF5) and CBr(OTeF5)2+ cations and theoretical studies of CX3+ and BX3 (X = F, Cl, Br, I, OTeF5). "J Am Chem Soc." 2004 May 5;126(17):5533-48.] and arenium ions [V D Shteingarts, Polyfluorinated Arenonium Ions, "Russ. Chem Rev" 1981;50(8):735-748.]
Nonaqueous acid-base chemistry
The acid-base reactions in non-aqueous solvents are typically described by means of the solvent-system definition, although the regular Brønsted-Lowry theory may be applied for the protic solvents, which possess a hydrogen atom that can dissociate. According to the solvent-system definition, acids are the compounds that increase the concentration of the solvonium (positive) ions, and bases are the compounds that result in the increase of the solvate (negative) ions, where solvonium and solvate are the ions found in the pure solvent in equilibrium with its neutral molecules:
protic solvents autodissociation: 2NH3 unicode| NH4+ (
ammonium) + NH2− ( amide): 3HF unicode| H2F+ + HF2- ( hydrogen difluoride): 2H2SO4 unicode| H3SO4+ + HSO4-aprotic solvents autodissociation: N2O4 unicode| NO+ ( nitrosonium) + NO3− ( nitrate): 2SbCl3 unicode| SbCl2+ ( dichloroantimonium) + SbCl4- ( tetrachloroantimonate): POCl3 unicode| POCl2+ + POCl4-
Thus NaNH2 is a base and NH4Cl is an acid in liquid ammonia, and they react, producing the salt and the solvent:: NaNH2 + NH4Cl → 2NH3 + NaClor, for an aprotic example,: NaNO3 + NOCl → N2O4 + NaCl
Limiting acids and limiting bases
The limiting acid in a given solvent is the solvonium ion, such as H3O+ (
hydronium) ion in water. An acid which has more of a tendency to donate a hydrogen ion than the limiting acid will be a strong acid in the solvent considered, and will exist mostly or entirely in its dissociated form. Likewise, the limiting base in a given solvent is the solvate ion, such as OH− ( hydroxide) ion, in water.A base which has more affinity for protons than the limiting base cannot exist in solution, as it will react with the solvent.
For example, the limiting acid in liquid ammonia is the
ammoniumion, which has a p"K"a valuein water of 9.25. The limiting base is the amideion, NH2−. This is astronger base than the hydroxide ion and so cannot exist in aqueous solution. The p"K"a valueof ammonia is estimated to be approximately 34 ("c.f." water, 15.74).
Any acid which is a stronger acid than the ammonium ion will be a strong acid in liquid ammonia. This is thecase for acetic acid, which is completely dissociated in liquid ammonia solution. The addition of pure aceticacid and the addition of ammonium acetate have exactly the same effect on a liquid ammonia solution: the increasein its acidity: in practice, the latter is preferred for safety reasons.
Bases can exist in solution in liquid ammonia which cannot exist in aqueous solution: this is the case for anybase which is stronger than the hydroxide ion but weaker than the amide ion. Many carbon anions can be formedin liquid ammonia solution by the action of the amide ion on organic molecules (see
sodium amidefor examples).
The other extreme is a
superacid, a medium in which the hydrogen ion is only very weakly solvated. The classic example is amixture of antimony pentafluorideand liquid hydrogen fluoride::SbF5 + HF unicode|⇌ H+ + SbF6−The limiting base, the hexfluoroantimonate anion SbF6−, is so weakly attracted to the hydrogen ion that virtually any other base will bind more strongly:hence, this mixture can be used to protonate organic molecules which would not be considered bases in other solvents.
Comparisons of acidity and basicity between solvents
There exists a large corpus of data concerning acid strengths in aqueous solution (p"K"a values), and itis tempting to transfer this to other solvents. Such comparisons are, however, fraught with danger, as they only consider the effect of solvation on the stability of the hydrogen ion, while neglecting its effects on the stability of the other species involved in the equilibrium.Gas phase acidities (normally known as proton affinities) can be measured, and their relative order is often quite differentfrom that of the aqueous acidities of the corresponding acids. Few quantitative studies on acidities in nonaqueous solvents have been carried out, although some qualitative data are available.It appears that most acids which have a p"K"a value of less than 9 in water are indeed strong acids in liquid ammonia. However, the hydroxide ion is often a much stronger base in nonaqueous solvents (e.g. liquid ammonia, DMSO) than in water.
It should be noted that
pHvalues are at present undefined in aprotic solvents, as the definition of pH assumes presence of hydroniumions. In other solvents, the concentration of the respective solvonium/solvate ions should be used, such as pCl in POCl3.
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