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An inorganic nonaqueous solvent is a solvent other than water, that is not an organic compound. These solvents are used in chemical research and industry for reactions that cannot occur in aqueous solutions or require a special environment. Inorganic nonaqueous solvents can be classified into two groups, protic solvents and aprotic solvents. Early studies on inorganic nonaqueous solvents evaluated ammonia, hydrogen fluoride, sulfuric acid, as well as more specialized solvents, hydrazine, and selenium oxychloride.^[1]

Protic inorganic nonaqueous solvents

Prominent members include ammonia, hydrogen fluoride, sulfuric acid, hydrogen cyanide. Ammonia (and several amines as well) are useful for the generating solutions of highly reducing species because the N-H bond resists reduction. The chemistry of electrides and alkalides relies on amine solvents.

The combination of HF and SbF₅ is the basis of a superacid solution. Using this mixture, the conjugate acid of hydrogen sulfide can be isolated:^[2]

H₂S + HF + SbF₅ → [H₃S]SbF₆

Autoionization

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 ammonium ion, NH₄⁺ which has a pK_a value in water of 9.25. The limiting base is the amide ion, NH₂^-. NH₂⁻ is a stronger base than the hydroxide ion and so cannot exist in aqueous solution. The pK_a value of ammonia is estimated to be approximately 34 (c.f. water, 14^[3]^[4]).

Aprotic inorganic nonaqueous solvents

Prominent members include sulfur dioxide, sulfuryl chloride fluoride, dinitrogen tetroxide, antimony trichloride, and bromine trifluoride. These solvents have proven useful for study highly electrophilic or highly oxidizing compounds or ions. Several (SO₂, SO₂ClF, N₂O₄) are gases near room temperature, so they are handled using vacuum-line techniques.

The generation of [IS₇]⁺ and [BrS₇]⁺ are illustrative. These highly electrophilic salts are prepared in SO₂ solution.^[5] The preparation of [SBr₃]⁺ salts also calls for a mixed solvent composed of SO₂ and SO₂FCl.^[6] Sulfuryl chloride fluoride is often used for the synthesis of noble gas compounds.^[7]

Autoionization

Many inorganic solvents participate in autoionization reactions. In the solvent system definition of acids and bases, autoionization of solvents affords the equivalent to acids and bases. Relevant autoionizations:

2BrF₃

{\ce {<=>>}}

BrF₂⁺ + BrF₄⁻

N₂O₄ ⇌ NO⁺ (nitrosonium) + NO₃⁻ (nitrate)

2SbCl₃ ⇌ SbCl₂⁺ + SbCl₄⁻

2POCl₃ ⇌ POCl₂⁺ + POCl₄⁻

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:

The solvent SO₂ is relatively uncomplicated^[how?], it does not autoionize.

References

^ Audrieth, Ludwig Frederick (1953). Non-aqueous Solvents; Applications as Media for Chemical Reactions. Wiley.
^ Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 682. ISBN 978-0-08-037941-8.
^ Meister, Erich C.; Willeke, Martin; Angst, Werner; Togni, Antonio; Walde, Peter (2014). "Confusing Quantitative Descriptions of Brønsted-Lowry Acid-Base Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators". Helvetica Chimica Acta. 97 (1): 1–31. doi:10.1002/hlca.201300321. ISSN 1522-2675.
^ Silverstein, Todd P.; Heller, Stephen T. (2017-06-13). "pKa Values in the Undergraduate Curriculum: What Is the Real pKa of Water?". Journal of Chemical Education. 94 (6): 690–695. Bibcode:2017JChEd..94..690S. doi:10.1021/acs.jchemed.6b00623. ISSN 0021-9584.
^ Murchie, M. P.; Passmore, J.; Wong, C.-M. (1990). "Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V)". Inorganic Syntheses. Inorganic Syntheses. Vol. 27. pp. 332–339. doi:10.1002/9780470132586.ch67. ISBN 9780470132586.
^ Murchie, Mike; Passmore, Jack (1986). "Tribromosulfur(IV) Hexafluoroarsenate(V)". Inorganic Syntheses. Inorganic Syntheses. Vol. 24. pp. 76–79. doi:10.1002/9780470132555.ch23. ISBN 9780470132555.
^ Koppe, Karsten; Bilir, Vural; Frohn, Hermann-J.; Mercier, Hélène P. A.; Schrobilgen, Gary J. (2007). "Syntheses, Solution Multi-NMR Characterization, and Reactivities of [C₆F₅Xe]+Salts of Weakly Coordinating Borate Anions, [BY₄]⁻ (Y = CF₃, C₆F₅, CN, or OTeF₅)". Inorganic Chemistry. 46 (22): 9425–9437. doi:10.1021/ic7010138. PMID 17902647.

External links

Media related to Inorganic solvents at Wikimedia Commons

[1] Audrieth, Ludwig Frederick (1953). Non-aqueous Solvents; Applications as Media for Chemical Reactions. Wiley.

[2] Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. p. 682. ISBN 978-0-08-037941-8.

[3] Meister, Erich C.; Willeke, Martin; Angst, Werner; Togni, Antonio; Walde, Peter (2014). "Confusing Quantitative Descriptions of Brønsted-Lowry Acid-Base Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators". Helvetica Chimica Acta. 97 (1): 1–31. doi:10.1002/hlca.201300321. ISSN 1522-2675.

[4] Silverstein, Todd P.; Heller, Stephen T. (2017-06-13). "pKa Values in the Undergraduate Curriculum: What Is the Real pKa of Water?". Journal of Chemical Education. 94 (6): 690–695. Bibcode:2017JChEd..94..690S. doi:10.1021/acs.jchemed.6b00623. ISSN 0021-9584.

[5] Murchie, M. P.; Passmore, J.; Wong, C.-M. (1990). "Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V)". Inorganic Syntheses. Inorganic Syntheses. Vol. 27. pp. 332–339. doi:10.1002/9780470132586.ch67. ISBN 9780470132586.

[6] Murchie, Mike; Passmore, Jack (1986). "Tribromosulfur(IV) Hexafluoroarsenate(V)". Inorganic Syntheses. Inorganic Syntheses. Vol. 24. pp. 76–79. doi:10.1002/9780470132555.ch23. ISBN 9780470132555.

[7] Koppe, Karsten; Bilir, Vural; Frohn, Hermann-J.; Mercier, Hélène P. A.; Schrobilgen, Gary J. (2007). "Syntheses, Solution Multi-NMR Characterization, and Reactivities of [C₆F₅Xe]+Salts of Weakly Coordinating Borate Anions, [BY₄]⁻ (Y = CF₃, C₆F₅, CN, or OTeF₅)". Inorganic Chemistry. 46 (22): 9425–9437. doi:10.1021/ic7010138. PMID 17902647.

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@@ Line 1: / Line 1: @@
+{{Short description|Type of nonaqueous solvents}}
 An '''inorganic nonaqueous solvent''' is a [[solvent]] other than water, that is not an [[organic compound]]. These solvents are used in chemical research and industry for reactions that cannot occur in aqueous solutions or require a special environment. Inorganic nonaqueous solvents can be classified into two groups, protic solvents and aprotic solvents.  Early studies on inorganic nonaqueous solvents evaluated ammonia, hydrogen fluoride, sulfuric acid,  as well as more specialized solvents, hydrazine, and selenium oxychloride.<ref>{{cite book|title=Non-aqueous Solvents; Applications as Media for Chemical Reactions| author= Audrieth, Ludwig Frederick|publisher=Wiley|year=1953}}</ref>
@@ Line 9: / Line 10: @@
 ===Autoionization===
-The limiting acid in a given solvent is the solvonium ion, such as H<sub>3</sub>O<sup>+</sup> ([[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<sup>−</sup> ([[hydroxide]]) ion, in water.
+The limiting acid in a given solvent is the solvonium ion, such as H<sub>3</sub>O<sup>+</sup> ([[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<sup>-</sup> ([[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.
-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 [[ammonium]] ion, NH<sub>4</sub><sup>+</sup> which has a p''K''<sub>a</sub> value in water of 9.25. The limiting base is the [[amide]] ion, NH<sub>2</sub><sup>-</sup>. NH<sub>2</sub><sup>−</sup> is [[Leveling effect|a stronger base than the hydroxide ion]] and so cannot exist in aqueous solution. The p''K''<sub>a</sub> value of ammonia is estimated to be approximately 34 (''c.f.'' water, 14<ref>{{Cite journal|last1=Meister|first1=Erich C.|last2=Willeke|first2=Martin|last3=Angst|first3=Werner|last4=Togni|first4=Antonio|last5=Walde|first5=Peter|date=2014|title=Confusing Quantitative Descriptions of Brønsted-Lowry Acid-Base Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators|journal=Helvetica Chimica Acta|language=en|volume=97|issue=1|pages=1–31|doi=10.1002/hlca.201300321|issn=1522-2675}}</ref><ref>{{Cite journal|last1=Silverstein|first1=Todd P.|last2=Heller|first2=Stephen T.|date=2017-06-13|title=pKa Values in the Undergraduate Curriculum: What Is the Real pKa of Water?|journal=Journal of Chemical Education|volume=94|issue=6|pages=690–695|doi=10.1021/acs.jchemed.6b00623|bibcode=2017JChEd..94..690S|issn=0021-9584}}</ref>).
-For example, the limiting acid in liquid ammonia is the [[ammonium]] ion, which has a p''K''<sub>a</sub> value
-in water of 9.25. The limiting base is the [[amide]] ion, NH<sub>2</sub><sup>−</sup>. NH<sub>2</sub><sup>−</sup> is a
-stronger base than the hydroxide ion and so cannot exist in aqueous solution. The p''K''<sub>a</sub> value
-of ammonia is estimated to be approximately 34 (''c.f.'' water, 14<ref>{{Cite journal|last1=Meister|first1=Erich C.|last2=Willeke|first2=Martin|last3=Angst|first3=Werner|last4=Togni|first4=Antonio|last5=Walde|first5=Peter|date=2014|title=Confusing Quantitative Descriptions of Brønsted-Lowry Acid-Base Equilibria in Chemistry Textbooks – A Critical Review and Clarifications for Chemical Educators|journal=Helvetica Chimica Acta|language=en|volume=97|issue=1|pages=1–31|doi=10.1002/hlca.201300321|issn=1522-2675}}</ref><ref>{{Cite journal|last1=Silverstein|first1=Todd P.|last2=Heller|first2=Stephen T.|date=2017-06-13|title=pKa Values in the Undergraduate Curriculum: What Is the Real pKa of Water?|journal=Journal of Chemical Education|volume=94|issue=6|pages=690–695|doi=10.1021/acs.jchemed.6b00623|bibcode=2017JChEd..94..690S|issn=0021-9584}}</ref>).
 ==Aprotic inorganic nonaqueous solvents==
-Prominent members include [[sulfur dioxide]], [[sulfuryl chloride fluoride]], [[dinitrogen tetroxide]], [[antimony trichloride]], and [[bromine trifluoride]]. These solvents have proven useful for study highly electrophilic or highly oxidizing compounds or ions.  Several (SO<sub>2</sub>, SO<sub>2</sub>ClF, N<sub>2</sub>O<sub>4</sub>) are gases near room temperature, so they are handled using [[vacuum-line technique]]s.
+Prominent members include [[sulfur dioxide]], [[sulfuryl chloride fluoride]], [[dinitrogen tetroxide]], [[antimony trichloride]], and [[bromine trifluoride]]. These solvents have proven useful for study highly electrophilic or highly oxidizing compounds or ions.  Several (SO<sub>2</sub>, SO<sub>2</sub>ClF, N<sub>2</sub>O<sub>4</sub>) are gases near room temperature, so they are handled using [[Vacuum line|vacuum-line]] techniques.
-The generation of [IS<sub>7</sub>]<sup>+</sup> and [BrS<sub>7</sub>]<sup>+</sup> are illustrative.  These highly electrophilic salts are prepared in SO<sub>2</sub> solution.<ref>{{cite journal |doi=10.1002/9780470132586.ch67|title=Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V)|journal=Inorganic Syntheses|last1=Murchie|first1=M. P.|last2=Passmore|first2=J.|last3=Wong|first3=C.-M.|pages=332–339|volume=27|year=1990}}</ref>
+The generation of [IS<sub>7</sub>]<sup>+</sup> and [BrS<sub>7</sub>]<sup>+</sup> are illustrative.  These highly electrophilic salts are prepared in SO<sub>2</sub> solution.<ref>{{cite book |doi=10.1002/9780470132586.ch67|chapter=Iodine and Bromine Polysulfur Hexafluoroarsenate(V) and Hexafluoroantimonate(V)|series=Inorganic Syntheses|last1=Murchie|first1=M. P.|last2=Passmore|first2=J.|last3=Wong|first3=C.-M.|title=Inorganic Syntheses|pages=332–339|volume=27|year=1990|isbn=9780470132586}}</ref>
-The preparation of [SBr<sub>3</sub>]<sup>+</sup> salts also calls for a mixed solvent composed of SO<sub>2</sub> and SO<sub>2</sub>FCl.<ref>{{cite journal |doi=10.1002/9780470132555.ch23|title=Tribromosulfur(IV) Hexafluoroarsenate(V)|journal=Inorganic Syntheses|last1=Murchie|first1=Mike|last2=Passmore|first2=Jack|pages=76–79|volume=24|year=1986}}</ref> Sulfuryl chloride fluoride is often used for the synthesis of [[noble gas compound]]s.<ref>{{cite journal |doi=10.1021/ic7010138|title=Syntheses, Solution Multi-NMR Characterization, and Reactivities of &#91;C<sub>6</sub>F<sub>5</sub>Xe&#93;+Salts of Weakly Coordinating Borate Anions, &#91;BY<sub>4</sub>&#93;<sup>−</sup> (Y = CF<sub>3</sub>, C<sub>6</sub>F<sub>5</sub>, CN, or OTeF<sub>5</sub>)|year =2007|last1=Koppe|first1 =Karsten|last2 =Bilir|first2 =Vural|last3=Frohn|first3=Hermann-J.|last4=Mercier|first4=Hélène P. A.|last5=Schrobilgen|first5=Gary J.|journal=Inorganic Chemistry|volume=46|issue=22|pages=9425–9437|pmid=17902647}}</ref>
+The preparation of [SBr<sub>3</sub>]<sup>+</sup> salts also calls for a mixed solvent composed of SO<sub>2</sub> and SO<sub>2</sub>FCl.<ref>{{cite book |doi=10.1002/9780470132555.ch23|chapter=Tribromosulfur(IV) Hexafluoroarsenate(V)|series=Inorganic Syntheses|last1=Murchie|first1=Mike|last2=Passmore|first2=Jack|title=Inorganic Syntheses|pages=76–79|volume=24|year=1986|isbn=9780470132555}}</ref> Sulfuryl chloride fluoride is often used for the synthesis of [[noble gas compound]]s.<ref>{{cite journal |doi=10.1021/ic7010138|title=Syntheses, Solution Multi-NMR Characterization, and Reactivities of &#91;C<sub>6</sub>F<sub>5</sub>Xe&#93;+Salts of Weakly Coordinating Borate Anions, &#91;BY<sub>4</sub>&#93;<sup>−</sup> (Y = CF<sub>3</sub>, C<sub>6</sub>F<sub>5</sub>, CN, or OTeF<sub>5</sub>)|year =2007|last1=Koppe|first1 =Karsten|last2 =Bilir|first2 =Vural|last3=Frohn|first3=Hermann-J.|last4=Mercier|first4=Hélène P. A.|last5=Schrobilgen|first5=Gary J.|journal=Inorganic Chemistry|volume=46|issue=22|pages=9425–9437|pmid=17902647}}</ref>
 <!--The chemistry of [[xenon]] compounds is often conducted in [[hydrogen fluoride]] or [[bromine pentafluoride]], which dissolve readily both [[xenon difluoride]]s and its multiple derivatives,<ref>Pointner BE, Suontamo RJ, Schrobilgen GJ. Syntheses and X-ray crystal structures of alpha- and beta-{{chem|[XeO|2|F][SbF|6|]}}, {{chem|[XeO|2|F][AsF|6|]}}, {{chem|[FO|2|XeFXeO|2|F][AsF|6|]}}, and {{chem|[XeF|5|][SbF|6|)]·XeOF|4}} and computational studies of the {{chem|XeO|2|F|+}} and {{chem|FO|2|XeFXeO|2|F|+}} cations and related species. ''Inorg Chem.'' 2006 Feb 20;45(4):1517-34.</ref>  [[Sulfuryl chloride fluoride]] is also useful for strong oxidants.<ref>Mercier HP, Moran MD, Sanders JC, Schrobilgen GJ, Suontamo RJ. "Synthesis, structural characterization, and computational study of the strong oxidant salt {{chem|[XeOTeF|5|][Sb(OTeF|5|)|6|]·SO|2|ClF}}." ''Inorg Chem.'' 2005 Jan 10;44(1):49-60.</ref>
@@ Line 34: / Line 31: @@
 : 2POCl<sub>3</sub> ⇌ POCl<sub>2</sub><sup>+</sup> + POCl<sub>4</sub><sup>−</sup>
-According to the [[Acid-base reaction theories|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:
+According to the [[Acid-base reaction#Solvent system definition|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:
-The solvent SO<sub>2</sub> is relatively uncomplicated, it does not autoionize.
+The solvent SO<sub>2</sub> is relatively uncomplicated{{How |date=February 2024}}, it does not autoionize.
+==See also==
+*[[Nonaqueous titration]]
+*[[Protic solvent]]
 == References ==
 {{reflist}}
-== See also ==
+==External links==
+*{{Commons category-inline|Inorganic solvents}}
-*[[Nonaqueous titration]]
-*[[Protic solvent]]
 {{Chemical solutions}}
@@ Line 49: / Line 49: @@
 [[Category:Inorganic solvents| ]]
 [[Category:Solvents]]
-[[Category:Solutions]]

v t e Chemical solutions
Solution	Ideal solution Aqueous solution Solid solution Buffer solution Flory–Huggins Mixture Suspension Colloid Phase diagram Phase separation Eutectic point Alloy Saturation Supersaturation Serial dilution Dilution (equation) Apparent molar property Miscibility gap
Concentration and related quantities	Molar concentration Mass concentration Number concentration Volume concentration Normality Molality Mole fraction Mass fraction Isotopic abundance Mixing ratio Ternary plot
Solubility	Solubility equilibrium Total dissolved solids Solvation Solvation shell Enthalpy of solution Lattice energy Raoult's law Henry's law Solubility table (data) Solubility chart Miscibility
Solvent	(Category) Acid dissociation constant Protic solvent Polar aprotic solvent Inorganic nonaqueous solvent Solvation List of boiling and freezing information of solvents Partition coefficient Polarity Hydrophobe Hydrophile Lipophilic Amphiphile Lyonium ion Lyate ion