Water’s Solvent Properties

Water, which not only dissolves many compounds but also dissolves more substances than any other
liquid, is considered the universal solvent. A polar molecule with partially-positive and negative charges,
it readily dissolves ions and polar molecules. Water is therefore referred to as a solvent: a substance
capable of dissolving other polar molecules and ionic compounds. The charges associated with these
molecules form hydrogen bonds with water, surrounding the particle with water molecules. This is
referred to as a sphere of hydration, or a hydration shell, and serves to keep the particles separated or
dispersed in the water.

When ionic compounds are added to water, individual ions interact with the polar regions of the water
molecules during the dissociation process, disrupting their ionic bonds. Dissociation occurs when atoms
or groups of atoms break off from molecules and form ions. Consider table salt (NaCl, or sodium
chloride): when NaCl crystals are added to water, the molecules of NaCl dissociate into Na+ and Cl– ions,
and spheres of hydration form around the ions. The positively-charged sodium ion is surrounded by the
partially-negative charge of the water molecule’s oxygen; the negatively-charged chloride ion is
surrounded by the partially-positive charge of the hydrogen in the water molecule.

Electrolytic Properties

When electrodes are placed in an electrolyte solution and a voltage is applied, the electrolyte will
conduct electricity. Lone electrons cannot usually pass through the electrolyte; instead, a chemical
reaction occurs at the cathode that consumes electrons from the anode. Another reaction occurs at the
anode, producing electrons that are eventually transferred to the cathode. As a result, a negative charge
cloud develops in the electrolyte around the cathode, and a positive charge develops around the anode.
The ions in the electrolyte neutralize these charges, enabling the electrons to keep flowing and the
reactions to continue.

For example, in a solution of ordinary table salt (sodium chloride, NaCl) in water, the cathode reaction
will be:

[latex]2H_{2}O + 2e^{-} \rightarrow 2OH^{-} + H_{2}[/latex]

and hydrogen gas will bubble up. The anode reaction is:

Precipitation refers to a chemical reaction that occurs in aqueous solution when two ions bond together
to form an insoluble salt, which is known as the precipitate.
A precipitation reaction can occur when two solutions containing different salts are mixed, and a
cation/anion pair in the resulting combined solution forms an insoluble salt; this salt then precipitates
out of solution.

The following is a common laboratory example of a precipitation reaction. Aqueous silver nitrate
(AgNO3) is added to a solution containing potassium chloride (KCl), and the precipitation of a white solid,
silver chloride (AgCl), is observed:

AgNO3 (aq) + KCl (aq) → AgCl (s) + KNO3(aq)

Note that the product silver chloride is the precipitate, and it is designated as a solid. This reaction can
be also be written in terms of the individual dissociated ions in the combined solution. This is known as
the complete ionic equation:

Ag+ (aq) + NO3−(aq) + K+ (aq) + Cl−(aq) → AgCl (s) + K+ (aq) + NO3−(aq)

A final way to represent a precipitation reaction is known as the net ionic equation. In this case, any
spectator ions (those that do not contribute to the precipitation reaction) are left out of the formula
completely. Without the spectator ions, the reaction equation simplifies to the following:

Ag+(aq) + Cl−(aq) → AgCl (s)

Observing precipitation reactions can be useful in the laboratory to determine the presence of various
ions in solution. For instance, if silver nitrate is added to a solution of an unknown salt and a precipitate
is observed, the unknown solution might contain chloride (Cl–).

Lastly, to make predictions about precipitation reactions, it is important to remember solubility rules.
The following solubility chart gives a useful summary:
Solubility chartTo determine the solubility of an given salt, find the cationic component along the left-
hand side, match it to the anionic component along the top, then check to see if it is S – soluble, I –
insoluble, or sS – slightly soluble.

[latex]2NaCl \rightarrow 2 Na^{+} + Cl_2 + 2e^{-}[/latex]

and chlorine gas will be liberated. The positively-charged sodium ions Na+ will react toward the cathode,
neutralizing the negative charge of OH− there; the negatively-charged hydroxide ions OH− will react
toward the anode, neutralizing the positive charge of Na+ there. Without the ions from the electrolyte,
the charges around the electrode slow continued electron flow; diffusion of H+ and OH− through water
to the other electrode takes longer than movement of the much more prevalent salt ions.

In other systems, the electrode reactions can involve electrode metal as well as electrolyte ions. In
batteries for example, two materials with different electron affinities are used as electrodes: outside the
battery, electrons flow from one electrode to the other; inside, the circuit is closed by the electrolyte’s
ions. Here, the electrode reactions convert chemical energy to electrical energy.

Oxidation and Reduction at the Electrodes

Oxidation of ions or neutral molecules occurs at the anode, and the reduction of ions or neutral
molecules occurs at the cathode. Two mnemonics for remembering that reduction happens at the
cathode and oxidation at the anode are: “Red Cat” (reduction – cathode) and “An Ox” (anode –
oxidation). The mnemonic “LeO said GeR” is useful for remembering “lose an electron in oxidation” and
“gain an electron in reduction.”

It is possible to oxidize ferrous ions to ferric ions at the anode. For example:

[latex]Fe^{2+}(aq) \rightarrow Fe^{3+} (aq) + e^{-}[/latex]

Neutral molecules can also react at either electrode. For example, p-Benzoquinone can be reduced to
hydroquinone at the cathode:
[latex]+ 2 e^{-} + 2 H^{+} \rightarrow[/latex]

HydroquinoneHydroquinone is a reductant or electron donor and organic molecule.

Para-benzoquinoneP-benzoquinone is an oxidant or electron acceptor.

In the last example, H+ ions (hydrogen ions) also take part in the reaction, and are provided by an acid in
the solution or by the solvent itself (water, methanol, etc.). Electrolysis reactions involving H+ ions are
fairly common in acidic solutions, while reactions involving OH- (hydroxide ions) are common in alkaline
water solutions.

The oxidized or reduced substances can also be the solvent (usually water) or electrodes. It is possible to
have electrolysis involving gases.

In order to determine which species in solution will be oxidized and which will be reduced, the standard
electrode potential of each species may be obtained from a table of standard reduction potentials, a
small sampling of which is shown here:

Definition of Solubility

Solubility is the ability of a solid, liquid, or gaseous chemical substance (referred to as the solute) to
dissolve in solvent (usually a liquid) and form a solution. The solubility of a substance fundamentally
depends on the solvent used, as well as temperature and pressure. The solubility of a substance in a
particular solvent is measured by the concentration of the saturated solution. A solution is considered
saturated when adding additional solute no longer increases the concentration of the solution.

The degree of solubility ranges widely depending on the substances, from infinitely soluble (fully
miscible), such as ethanol in water, to poorly soluble, such as silver chloride in water. The term
“insoluble” is often applied to poorly soluble compounds. Under certain conditions, the equilibrium
solubility can be exceeded, yielding a supersaturated solution.
Solubility does not depend on particle size; given enough time, even large particles will eventually
dissolve.

Factors Affecting Solubility

Temperature

The solubility of a given solute in a given solvent typically depends on temperature. For many solids
dissolved in liquid water, solubility tends to correspond with increasing temperature. As water molecules
heat up, they vibrate more quickly and are better able to interact with and break apart the solute.

Solubilty of various substances vs. temperature changeSolubility increases with temperature for most
substances; for example, more sugar will dissolve in hot water than in cold water.

The solubility of gases displays the opposite relationship with temperature; that is, as temperature
increases, gas solubility tends to decrease. In a chart of solubility vs. temperature, notice how solubility
tends to increase with increasing temperature for the salts and decrease with increasing temperature for
the gases.

Pressure

Pressure has a negligible effect on the solubility of solid and liquid solutes, but it has a strong effect on
solutions with gaseous solutes. This is apparent every time you open a soda can; the hissing sound from
the can is due to the fact that its contents are under pressure, which ensures that the soda stays
carbonated (that is to say, that the carbon dioxide stays dissolved in solution). The takeaway from this is
that the solubility of gases tends to correlate with increasing pressure.

Polarity

A popular saying used for predicting solubility is “Like dissolves like.” This statement indicates that a
solute will dissolve best in a solvent that has a similar chemical structure; the ability for a solvent to
dissolve various compounds depends primarily on its polarity. For example, a polar solute such as sugar
is very soluble in polar water, less soluble in moderately polar methanol, and practically insoluble in non-
polar solvents such as benzene. In contrast, a non-polar solute such as naphthalene is insoluble in water,
moderately soluble in methanol, and highly soluble in benzene.
Solubility Chart

The solubility chart shows the solubility of many salts. Salts of alkali metals (and ammonium), as well as
those of nitrate and acetate, are always soluble. Carbonates, hydroxides, sulfates, phosphates, and heavy
metal salts are often insoluble.

Solubility chartThe solubilities of salts formed from cations on the left and anions on the top are
designated as: soluble (S), insoluble (I), or slightly soluble (sS).

SolubilitySolubility of salt and gas solutes in liquid solvent.