Arba Minch University

Department of Chemistry
School of post Graduate
Studies

Non-aqueous Solution
Chemistry
 Non-aqueous Solution Chemistry
 Many inorganic reactions take place in aqueous solution,
 water is not always a suitable solvent; some reagents may react
with H2O (e.g. the alkali metals) and non-polar molecules are
insoluble in water.

 The use of solvents other than water is commonplace for the organic
chemist, and such compounds include dichloromethane, hexane,
toluene and ethers such as diethyl ether, tetrahydrofuran, and
diglyme
 non-aqueous solvents catagories into :

* protic solvents (e.g. HF, H2SO4, MeOH);

* aprotic solvents (e.g. N2O4, BrF3);
* coordinating solvents (e.g. MeCN, Et2O, Me2CO).

 A protic solvent undergoes self-ionization to provide protons which

are solvated. If it undergoes selfionization,
 An aprotic solvent does so without the formation of protons.
• A number of non-aqueous solvents (e.g.
NH3, EtOH, H2SO4) exhibit hydrogen
bonding.

• An X-H……Y interaction is called a hydrogen

bond if it constitutes a local bond, and if
X–H acts as a proton donor to Y.

• solvent molecules form intermolecular

hydrogen bonds affects properties such as
– boiling point,
– enthalpy of vaporization and
– viscosity,
– as well as the ability of the solvent to solvate
 Relative permittivity
• In a vacuum, the Coulombic potential energy
of a system of two unit electronic charges is given

• where "ε0 is the (absolute) permittivity of a

vacuum (8.854 1012 Fm -1 ), e is the charge on the
electron (1.602 10-19C) and r is the separation (in
meters) between the point charges.
• If a material is placed between the charges,
the force is reduced by an amount that depends
upon the relative permittivity of the material. The
new Coulombic potential energy is given by:

• where "r is the relative permittivity of the

material. Since it is a relative quantity, "εr is
• For example, at 298 K, "r of water (the dielectric constant)
is 78.7, but as Fig. shows, "r varies with temperature.
• A value of 78.7 can be considered to be a ‘high’ value and
in aqueous solution, the force between two point charges
(or two ions) is considerably reduced compared with that in
a vacuum.
Table show lists dielectric constants for water and a range of
common organic solvents. The absolute permittivity of a
solvent is found using
Absolute eqn.
permittivity of a material =ε0εr
 Acid–base behavior in non-aqueous solvents
 the strength of an acid HX (eq. *) depended upon the
relative proton donor abilities of HX and [H3O]+

HX(aq) + H2O(l) ⇄ [H3O]+ (aq) + X-(aq)

 Similarly, the strength of a base, B, in aqueous solution

depends upon the relative proton accepting abilities of B
-
and [OH]

B(aq) + H2O(l) ⇄ [BH]+ (aq) + OH-(aq)

 Tabulated values of Ka (or Kb) generally refers to the

ionizations of acids in aqueous solution.
Reading Assignment: Levelling and differentiating effects
 Acids and bases: a solvent-
•
oriented definition
A Brønsted acid is a proton donor, and a Brønsted base accepts
protons. In aqueous solution, [H3O]+ is formed and in bulk water,
self-ionization corresponds to the transfer of a proton from one
solvent molecule to another (eq.) illustrating amphoteric
behaviour
2H2O ⇄ [H3O]+ + [OH]-
• In liquid NH3, proton transfer leads to the formation of NH4+, and,
in a liquid ammonia solution, an acid may be described as a
substance that produces [NH4]+, while a base produces [NH2]-
ions.

• This solvent-oriented definition can be widened to include

behavior in any solvent which undergoes self-ionization.
• In a self-ionizing solvent, an acid is a substance that
produces the cation characteristic of the solvent, and a
base is a substance that produces the anion characteristic
of the solvent.
Proton-containing and aprotic
solvents
 Most of these solvents are self-ionizing. They can
be divided into two catagories

 Proton containing (NH3, H2SO4, HOSO2F)

 Aprotic (SO2, BrF3, N2O4)

 Chemistry in liquid ammonia
 Studied more extensively than any other non aqueous solvent.

 Its physical properties resemble those of water except that the

permillivity is considerably smaller.

 The lower dielectric constant results in a generally decreased

ability to dissolve ionic compounds, especially those containing
highly charged ions (e.g., carbonates, sulfates, and phosphates are
practically insoluble).

 Ammonia may thus be a better solvent than water toward non

polar molecules.

 Ionic compounds containing large, polarizable ions such as iodide and

thiocyaote also are quite soluble.
 Precipitation reactions take place in ammonia just as they
do in water. Because of the differences in solubility between
the two solvents, the results may be considerably different. As
an example, consider the precipitation of silver chloride in
aqueous solution:

 In ammonia solution the direction of the reaction is reversed

so that:

 Ammonia undergoes autoionization with the formation of

ammonium and amide ions:

 Neutralization reactions can be run that parallel those in

water:

 Furthermore, amphoteric behavior resulting from complex

formation with excess amide also parallels that in water
 All acids that behave as strong acids in water react
completely with ammonia to form ammonium ions:

 In addition, some acids which behave as weak acids in

water (with pKa up to about 12) react completely with
ammonia and hence are strong acids in this solvent:

 molecules that show no acidic behavior at all in water may

behave as weak acids in ammonia:

 Most species that would be considered bases in water are

either insoluble or behave as weak bases in ammonia.
Extremely strong bases, however, may be leveled to the
amide ion and behave as strong bases:
 Solvolysis reactions are well known in ammonia, and again
many reactions parallel those in water. For example, the
solvolysis and disproportionation of halogens may be
illustrated by

 Since it is more basic than water, ammonia can cause the

disproportionation of sulfur:

 The hexasultide ion is in dissociative equilibrium:

 The S-3 ion is responsible for the deep blue color of these
solutions (λmax 610 nm). This ion is also responsible for the
color of sulfur dissolved in chloride mells (see below) and in
the aluminosilicate known as ultramarine. Many nonmetal
halides behave as acid halides in solvolysis reactions:
 Hydrogen fluoride as a solvent
 Hydrogen fluoride attacks silica glass (eq.) thereby corroding glass
reaction vessels, and it is only relatively recently that HF has found
applications as a non-aqueous solvent. It can be handled in
polytetrafluoroethene (PTFE) containers, or if absolutely free of water,
in Cu or Monel metal (a nicely alloy equipment)

 Hydrogen fluoride has a liquid range from 190 to 292.5K. The relative
permittivity is 84 at 273 K, rising to 175 at 200 K. Liquid HF undergoes
self-ionization (equilibrium ), for which Kself ~2 x10 12 at 273 K.

 The difference in electronegativities of H (χ p 2.2) and F (χp 4.0) results

in the presence of extensive intermolecular hydrogen bonding in
the liquid.
 High-energy X-ray and neutron diffraction studies have been
used to show that liquid HF (at 296 K) contains chains of hydrogen-
bonded molecules (on average, seven molecules per chain). Interchain
hydrogen bonding also exists. In the vapor phase, hydrogen fluoride
consists of cyclic (HF)x species as well as clusters.
 Acid–base behaviour in liquid HF
 Using the solvent-oriented definition, a species that produces [H 2F]
+
ions in liquid HF is an acid, and one that produces [HF 2]- is a
base.

 Many organic compounds are soluble in liquid HF, and in the cases
of, for example, amines and carboxylic acids, protonation of the
organic species accompanies dissolution (eq.). Proteins react
immediately with liquid HF, and it produces very serious skin
burns.

 Most inorganic salts are converted to the corresponding fluorides

when dissolved in liquid HF, but only a few of these are soluble.
Fluorides of the s-block metals, silver and thallium(I) dissolve to
give salt such as K[HF2], K[H2F3], and thus exhibit basic character.
 The anion is linear, and its formation is a consequence of the H
and F atoms being involved in strong hydrogen bonding. In the
solid state structures reported, the F---F distance is ~228 pm.
• This value is greater than twice the H-F bond length in HF (2x92
pm), but an H—F h-bond will always be weaker and longer than a
2-center covalent H-F bond. Comparsion of the values gives some
indication of the strength of the hydrogen bonding in [HF 2]- .

• Ammonium fluoride is basic in liquid HF. Studies of the Me4NF-HF

system over a range of compositions and temperatures reveal the
formation of the compounds of composition Me4NF.nHF (n = 2, 3,
5 or 7). X-ray diffraction studies for compounds with n= 2, 3 or 5
have confirmed the structures of [H2F3]-, [H3F4]- and [H5F6]-, in
which strong hydrogen bonding is an important feature.

• The molecular fluorides, CF4 and SiF4 are insoluble in liquid HF,
but F-
• acceptors such as AsF5 and SbF5 dissolve according to eq to give
very strongly acidic solutions.
• Less potent fluoride acceptors such as BF3 function as weak acids
in liquid HF (eq. ). PF5 behaves as a very weak acid (eq.). In
contrast, ClF3 and BrF3 act as F- donors (eq. ) and behave as
bases.
 Few protic acids are able to exhibit acidic behaviour in liquid
HF,

 With SbF5, HF forms a superacid (eq. ) which is capable of

protonating very weak bases including hydrocarbons
 Electrolysis in liquid HF
 Electrolysis in liquid HF is an important
preparative route to both inorganic and organic
fluorine-containing compounds, many of which
are difficult to access by other routes. Anodic
oxidation in liquid HF involves half-reaction and
with NH4F as substrate, the products of the
subsequent fluorination are NFH2, NF2H and NF3.

 In liquid HF, anodic oxidation of water gives OF2,

of SCl2 yields SF6, of acetic acid yields CF3CO2H
and of Me3N produces (CF3)3N.
 Ionic liquids
• The use of ionic liquids (also called molten salts) as reaction
media is a relatively new area, although molten conditions
have been well established in industrial processes (e.g. the
Downs process) for many years. While some ‘molten salts’ are
hot as the term suggests, others operate at ambient
temperatures and the term ‘ionic liquids’ is more appropriate.
• Terms ‘ionic liquids’ and ‘molten salts’ are sometimes used
interchangeably, we make a clear distinction between them,
using ‘ionic liquid’ only for a salt with a melting point less than
or greater 373 K

molten salts solvent systems

• The chemistry of molten salts as nonaqueous solvent systems

is one that has developed extensively from the 1960s till the
present
 The most obvious difference when compared with the
chemistry of aqueous solutions are the strongly bonded and
stable nature of the solvent, a concomitant resistance to
destruction of the solvent by vigorous reactions and higher
concentrations of various species, particularly coordinating
anions than can be obtained in saturated solutions in water.
 When an ionic salt such as NaCl melts, the ionic lattice collapses,
but some order is still retained. Evidence for this comes from X-ray
diffraction patterns, from which radial distribution functions
reveal that the average coordination number (with respect to
cation–anion interactions) of each ion in liquid NaCl is 4, compared
with 6 in the crystalline lattice. For cation–cation or anion–anion
interactions, the coordination number is higher, although, as in the
solid state, the internuclear distances are larger than for cation–
anion separations. The solid-to-liquid transition is accompined by an
increase in volume of ~10-15%.
 The term eutectic is commonly encountered in this field. The
reason for forming a eutectic mixture is to provide a molten
system at a convenient working temperature. For example,
the melting point of NaCl is 1073 K, but is lowered if CaCl2 is added
as in the Downs process.
 A Eutectic is a mixture of two substances and is
characterized by a sharp melting point lower than that of
either of the components; a eutectic behaves as thought it
were a single substance

 An important group of molten salts with more convenient operating

temperatures contain the [AlCl 4]- ion. An example is an NaCl–Al 2Cl6
mixture. The melting point of Al2Cl6 is 463K (at 2.5 bar), and its
addition to NaCl (melting point, 1073 K) results in a 1:1 medium
with a melting point of 446 K. In this and other Al2Cl6–alkali metal
chloride melts, equilibria are established, with the additional
formation of [Al3Cl10]-

 Manufacturing processes in which metals are extracted

from molten metal salts are important examples of the uses
of molten salts and include the Downs process, and the
production of Li by electrolysis of molten LiCl, and of Be and Ca
from BeCl2 and CaCl2, respectively.
 Some unusual cations have been isolated as products from
reactions in molten salt media. For example, the reaction of Bi and
BiCl3 in KCl–BiCl3 solvent at 570K yields [Bi 9]2[BiCl5]4[Bi2Cl8] which
contains [Bi9]+5, [BiCl5]2- and [Bi2Cl8]2-
 Ionic liquids at ambient temperatures
• An ionic liquid is an ionic salt that is a liquid below 373 K
• Interest in the development and applications of ionic liquids
continues to grow rapidly, one of the main reasons being that
these solvents have implications for green chemistry.
• Currently favoured ionic liquids comprise combinations of cations
and anions; By varying (i) the substituents in the cations and (ii)
the combinations of anions and cations, a huge number of
ionic liquids with different physical properties ((e.g. melting
point, viscosity, mobility of ions in solution) can be prepared.
A third group of ionic liquid has been designed for the use in
biocalalysis. These comprise biodegradable, low toxicity
cations and /or anions.

• The reason that ionic liquid posses such low melting points is that
they contain large, unsymmetrical cations usually combined
with polyatomic anions. Such ions pack less efficiently in the
solid state than symmetrical ions. The relatively poor packing
results in low lattice energies which in turn, lead to low melting
compounds. The melting point can be turned by altering the
substituent in a given cation.
 For example, in a series of salts containing different 1-
alkyl-3-methylimidazolium cations and a common
anions, the melting point decreases as n-alkyl
chain lengthens. However, once the n-alkyl
substituent contain more eight C atoms, the melting
point starts to increase because it is energically
favorable for the longer alkyl chains to be aligned
parallel to one another with van der waals forces
operating between them.

 Melting point are also affected by hydrogen bonding.

If the ionic solid is a hexafluoridophospate salt, the
organic cation and [PF6]- ion can engage in a weak C-
H….F non classical hydrogen bonds in the solid state.
This increase the melting point ( although not as
significantly as would be the case for O-H…O or N-H….O
hydrogen bond)
 The melting points and the viscosities of ionic liquids
containing [N(SO2CF3)2]- are low because the negative
charge is delocalized over the two SO2 units, thereby
preventing directional zed cation…..anion interactions.

 Ionic liquids are sometimes termed ‘task specific’

meaning that the larger pool of cations and anions
avalibale permits the design of a solvent with quite
specific properties. The low volatility of ionic
liquids gives them a’green’ advantage over volatile
organic solvents.

 Ionic liquids have long liquid ranges, and many are non-
flammable and thermally stable. However, it is important
to assess both synthetic route to the ionic liquid as well as
the properties of the material itself before labeling the
compound environmentally friendly.
 Application
 The first application of RT ionic liquid (mp < 298K ) were
solution in chemistry, for electrodeposition
( electroplating) of metal and as electrolytes in batteries
What advantages do ionic liquids have over conventional
solvents (e.g. MeCN) for cyclic voltammetry ?
 A supporting electrolyte is added to the solvent in a cyclic
voltammetry experiment to ensure a high enough electrical
conductivity. Since an ionic liquid is composed of ions, no
supporting electrolyte is needed. However, the mobility (not
just the number) of ions affects conductivity.
 The large ions typically present in an ionic liquid exhibit low
mobilities and this offsets the advantage of having a solvent
composed entirely of ions. Many ionic liquids are too viscous to
be used for solution electrochemical studies. Compared with
traditional solvents, ionic liquids composed of imidazolium
cations with [AlCl4]-, [BF4]-, [CF3CO2]-, [CF3SO3]- or
[N(SO2CF3)2]- and which exhibit wide potential of 6 V,
represent possible alternative media for cyclic voltammetry
and similar electrochemical measurements.
 Ionic liquids are now used in place of organic solvents in a
wide range of organic transformations including Diels-Alder
reactions, Friedel-Crafts alkylations and acylations, C–C
bond-forming Heck reactions, and syntheses of heterocyclic
systems.

 many ionic liquids are good solvents for a wide range of

organometallic compounds, thus enabling them to be used
in homogeneous catalysis. Asymmetric syntheses may be
carried out using chiral catalysts in achiral ionic liquids

 Application of ionic liquids in inorganic chemistry range

from the isolation of molecular species to uses in material
chemistry. The choice of an ionic liquid allows access to
species that are insoluble in common organic solvents or
are unstable in aqueous media. The organic cations in the
solvent are often incorporated into the production and act
as template to facilitate the assembly of 3-dimensional
frameworks
 Ionic liquids containing inorganic halide anions may act
as a source of halide, thereby functioning as a reagent
as well as a solvent.

 In materials chemistry, ionic liquids are used in a variety of

ways, e.g. routes to nanoparticles (catalytic applications)
and to metal-organic frameworks (MOFs). Zeolites
represent an important class of crystalline meterials with
many applications in catalysis and gas/liquid absorption.

 Using ionic liquids in place of hydrothermal

conditions has several advantages:
(i) the low vapour pressure of an ionic liquid means
that the synthesis takes place at ambient pressures,
(ii) the organic template is provided by the ionic liquid,
resulting in there being no competition between
solvent and template during crystallization, and
(iii) new structure types may be assembled.