UNIT 4: AQUEOUS CHEMISTRY

Introduction, conventions and units in aqueous solution chemistry

An aqueous solution is a solution in which the solvent is water. It is mostly shown
in chemical equations by appending (aq) to the relevant chemical formula. For example, a
solution of table salt, or sodium chloride (NaCl), in water would be represented as Na+(aq) +
Cl−(aq). The word aqueous (which comes from aqua) means pertaining to, related to, similar
to, or dissolved in, water. As water is an excellent solvent and is also naturally abundant, it is
a ubiquitous solvent in chemistry. Since water is frequently used as the solvent in
experiments, the word solution refers to an aqueous solution, unless the solvent is specified.
A non-aqueous solution is a solution in which the solvent is a liquid, but is not water.

The first solvation shell of a sodium ion dissolved in water

Characteristics

Substances that are hydrophobic ('water-fearing') do not dissolve well in water, whereas those
that are hydrophilic ('water-friendly') do. An example of a hydrophilic substance is sodium
chloride. Acids and bases are aqueous solutions, as part of their Arrhenius definitions.
Aqueous solution is water with a pH of 7.0 where the hydrogen ions (H+) and hydroxide ions
(OH−) are in Arrhenius balance ([H+][OH-] = 1 x 10−14). Acids and bases are aqueous
solutions, as part of their Arrhenius definitions. An example of an Arrhenius acid is hydrogen
chloride (HCl) because of its dissociation of the hydrogen ion when dissolved in
water. Sodium hydroxide (NaOH) is an Arrhenius base because it dissociates the hydroxide
ion when its dissolved in water.Aqueous solutions may contain, especially in the alkaline
zone or subjected to radiolysis, hydrated atomic hydrogen and hydrated electrons.

Electrolytes Aqueous solutions that conduct electric current efficiently contain

strong electrolytes, while ones that conduct poorly are considered to have weak electrolytes.
Those strong electrolytes are substances that are completely ionized in water, whereas the
weak electrolytes exhibit only a small degree of ionization in water.[1] The ability for ions to
move freely through the solvent is a characteristic of an aqueous strong electrolyte solution.
The solutes in a weak electrolyte solution are present as ions, but only in a small amount.[2]

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Nonelectrolytes are substances that dissolve in water yet maintain their molecular integrity
(do not dissociate into ions). Examples include sugar, urea, glycerol,
and methylsulfonylmethane (MSM).

Reactions
Reactions in aqueous solutions are usually metathesis reactions. Metathesis reactions are
another term for double-displacement; that is, when a cation displaces to form an ionic bond
with the other anion. The cation bonded with the latter anion will dissociate and bond with
the other anion.
A common metathesis reaction in aqueous solutions is a precipitation reaction. This reaction
occurs when two aqueous strong electrolyte solutions mix and produce an insoluble solid,
also known as a precipitate. The ability of a substance to dissolve in water is determined by
whether the substance can match or exceed the strong attractive forces that water molecules
generate between themselves. If the substance lacks the ability to dissolve in water, the
molecules form a precipitate.
When writing the equations of precipitation reactions, it is essential to determine the
precipitate. To determine the precipitate, one must consult a chart of solubility. Soluble
compounds are aqueous, while insoluble compounds are the precipitate. There may not
always be a precipitate. Complete ionic equations and net ionic equations are used to show
dissociated ions in metathesis reactions. When performing calculations regarding
the reacting of one or more aqueous solutions, in general one must know the concentration,
or molarity, of the aqueous solutions. Solution concentration is given in terms of the form of
the solute prior to it dissolving.

HYDRATION OF IONS AND SOLUBILITIES OF SALTS

Hydration of Ions
We have already stated several times that solubility in water is a characteristic property of
many ionic compounds,We have also presented experimental evidence that ions in solution
are nearly independent of one another. This raises an important question, though, because we
have also stated that attractive forces between oppositely charged ions in a crystal lattice are
large. The high melting and boiling points of ionic compounds provide confirmation of the
expected difficulty of separating oppositely charged ions. How, then, can ionic compounds
dissolve at room temperature? Surely far more energy would be required for an ion to escape
from the crystal lattice into solution than even the most energetic ions would possess.

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Figure1: The hydration of (a) a positive ion; (b) a negative ion. When ions are dissolved in
water, they attract and hold several water dipoles around them shown in the circular area in
the circular area in the center of each part of the diagram.

The resolution of this apparent paradox lies in the interactions between ions and the
molecules of water or other polar solvents. The negative (oxygen) side of a dipolar water
molecule attracts and is attracted by any positive ion in solution. Because of this ion-dipole
force, water molecules cluster around positive ions, as shown in Figure 1 a. Similarly, the
positive (hydrogen) ends of water molecules are attracted to negative ions. This process, in
which either a positive or a negative ion attracts water molecules to its immediate vicinity, is
called hydration.
When water molecules move closer to ions under the influence of their mutual attraction,
there is a net lowering of the potential energy of the microscopic particles. This counteracts
the increase in potential energy which occurs when ions are separated from a crystal lattice
against their attractions for other ions.
Thus the process of dissolving an ionic solid may be divided into the two hypothetical steps
shown in Figure 2. First, the crystalline salt is separated into gaseous ions. The heat energy
absorbed when the ions are separated this way is called the lattice enthalpy (or sometimes
the lattice energy). Next, the separate ions are placed in solution; that is, water molecules are
permitted to surround the ions. The enthalpy change for this process is called the hydration
enthalpy.

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Figure 2: Enthalpy changes and solution. There is usually very little energy or enthalpy
change when ionic solids like NaCl dissolve in H2O since the energy needed to separate the
ions from each other is not very different from the energy liberated when the ions become
hydrated by attracting H2O dipoles around them.

SOLUBILITIES OF SALTS
In this section we will apply chemical equilibria to the concept of solubility and introduce a
type of equilibrium constant, the solubility constant, to allow us to calculate how soluble a
salt really is.
Solubility Equilibrium defines the dynamic equilibria between a precipitate and its
dissolved ions when the rate of dissolution equals the rate of crystallization and the resulting
solution is a saturated solution, that contains the maximum concentration of dissolved ions
that coexist with the undissolved solute (precipitate).
What do we mean by solubility of a salt? If I say one mole of sodium sulfate dissolves in
water I am really meaning for every mole of sodium sulfate that dissolves, two moles of
sodium are formed and one mole of sulfate. We will use the concept of solubility to describe
the moles the salt that dissolves to form a saturated solution, and the actual ion concentration
depends on the formula.

Solubility Product
This is the equilibrium constant for the process of dissolution. Consider the generic salt

MxAy(s)⇋xM+m(aq)+yA−n(aq)………….(1)

Noting from charge neutrality that x(+m)+y(-n)=0, then the equilibrium constant expression
is:

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 Ksp=[M+m]x[A−n]y ………………………….(2)
The solid reactant is not part of the equilibrium, and it is called the solubility product because
it is the product of the concentration of all the ions a salt breaks into. It is important to realize
this is a heterogeneous equilibrium that defines a saturated solution and the solid is part of the
process, although it does not influence the equilibrium concentration. That is, if all the solid
is dissolved, you may have an unsaturated solution, and the solubility product defines the
concentration of a saturated solution. At the end of this chapter is a solubility product table
for ionic compounds at 25oC.

Lets look at the solubility product for Calcium phosphate

Ca3(PO4)2(s)⇋3Ca+2+2PO−34……………………………….(3)
Ksp(Ca3(PO4)2)=[Ca+2]3[PO−34]2………………………….(4)

Solubility Calculations

Solubility of a Salt
The solubility of a salt is "x" (from the ICE table), but we will not be using ICE tables in
solubility product calculations, and are just using it now to explain what is going on. From
the following ICE table you can see that for every x moles of the calcium phosphate that
dissolves per liter (its solubility), the solution gains 3 times that many moles of calcium and
twice that many of phosphate, and there is no calcium phosphate floating around, just calcium
and phosphate.

That is, x the extent of reaction is a ICE diagram is the solubility of a salt. So you do not use
a rice diagram, you say that for every x moles of solid that dissolves, the ions are that times
the number of the ions in the formula So for Calcium phosphate
[Ca+2]=3xand[PO−34]=2x]………………….(5)
Ksp(Ca3(PO4)2)=[3x]3[2x]2=108x5………………….(6)
Solving for the solubility (x) and noting that Ksp(calcium phosphate) = 2.07 × 10−33
…………………………… (7)

IONIZATION OF ACIDS IN AQUEOUS SOLUTION

The ionization of a compound can be explained as a process where a neutral molecule splits
into charged ions when exposed to a solution.Arrhenius's theory says that acids are the
compounds that are dissociated in an aqueous medium to generate hydrogen ions, H+(aq). On
the other side, bases are the compounds that furnish hydroxyl ions, OH-(aq) in an aqueous
solution or medium.
Let us look at the difference between ionization and dissociation.

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The primary difference between dissociation and ionization or is, dissociation is the process
of separating the charged particles which already exist in the compound, on the other side,
ionization is the formation of new charged particles, which are not present in the previous
compound.
Arrhenius Theory
Arrhenius theory plays a major role in explaining the ionization of acids and bases because
mostly ionization occurs in an aqueous medium. Based on the degree of ionization of acids
and bases, we can define the strength of both acids and bases. Also, the degree of ionization
differs for different compounds of acidic and basic. A few acids, such as hydrochloric acid
(HCl), perchloric acid (HClO4), completely dissociate into their constituent ions in an
aqueous medium.
All these acids are referred to as strong acids. Ionization of acids produces hydrogen ions,
and therefore, these compounds act as proton donors. In the same way, a few bases such as
sodium hydroxide (NaOH), lithium hydroxide (LiOH) too dissociate completely into their
ions in an aqueous solution or medium. These bases are referred to as strong bases. The
ionization of these bases produces hydroxyl ions (OH-).
Therefore, the ionization degree of acids and bases depends on the degree of dissociation of
compounds into their constituent ions. The strong acids and bases have a high degree of
ionization when compared to the ionization of weak acid and base. Also, a strong acid
implies a good proton donor, whereas a strong base implies a good proton acceptor - for
example, dissociation of weak acid HA.
HA(aq) + H2O(l) ⇌ H3O + (aq) + A-(aq)
Explanation
Let us look at the Arrhenius Theory explanation in brief.
This reaction indicates that acid dissociation equilibrium is dynamic in nature, where the
transfer of protons can occur in both forward and backward directions. If HA has a higher
tendency to donate a proton compared to that of H3O+, HA acts as a strong acid in comparison
to the H3O+ ion. Because the stronger acid donates a proton to the stronger base, the
equilibrium moves towards the direction of a formation of a weaker acid and base.

Generally, the strong acids have weaker conjugate bases, whereas the strong bases have
weaker conjugate acids. This is due to the high degree of ionization of strong acids and bases.

Ionization of a Compound
Bases are the compounds that furnish the hydroxyl ions and OH- present in the aqueous
medium. The degree of ionization of both acids and bases helps to determine its strength.
Based on different acidic and basic compounds, the degree of ionization can differ.

Ionization of Acids
The process by which a neutral molecule breaks down into charged ions when exposed to a
solution is known as compound ionization. According to Arrhenius theory, an acid is a
compound that dissociates in an aqueous medium to produce the hydrogen ion H+ in the
aqueous medium.

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Ionization of Acids
The Ionisation degree refers to the strength of either an acid or a base. A strong acid is said to
ionize in water completely, whereas a weak acid is said to ionize only partially. Because there
are various degrees of acid’s ionization, there also exists various levels of weakness, where
there exists a simple quantitative way to express.

Since the weak acid ionization is an equilibrium, the equilibrium constant expression
and the chemical equation can be stated as follows:
HA(aq) + H2O(l) ⇌ H3O + (aq) + A-

Ka=[H3O+][A−]/HA
An equilibrium constant for the ionization of an acid describes its Acid Ionization Constant
(Ka). However, the stronger the acid, the acid ionization constant (Ka) will be larger. It
means that a strong acid is a donor of a better proton. Because of the result of the product
concentration in the numerator of the ionization constant (Ka), the stronger the acid, the
larger is the acid Ka.

The degree of ionization depends on the strength of the acid or base. Strong acids are
considered to be fully ionized in water, while weak acids are only partially ionized. Since the
degree of acid ionization is different, the degree of weakness is also different, and there is a
simple quantitative formula.

Since the ionization of weak acids is equilibrium, the chemical equation and equilibrium
constant equation is as follows.

HA (aq) + H2O (l) ⇌ H3O + (aq) + A-

Ka = [H3O+][A−]/HA
The equilibrium constant for acid ionization is the acid ionization constant. Define (Ka).
However, the stronger the acid, the higher the acid ionization constant (Ka). This means that
strong acids are better proton donors. Depending on the concentration of the product in the
Ka molecule, the following applies: The stronger the acid, the larger the acid ionization
constant (Ka).

Complex Formation

o A complex is made up of a central metal atom/ion surrounded by negatively charged

ions or neutral molecules possessing a lone pair of electrons (ligands).
o A complex may be charged or uncharged, if it is charged it is called a complex ion,
for example [Fe(H2O)6]3+.

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 o The overall charge is the sum of the charge on the central metal ion and the charges
on the ligands.
o A simple way of looking at the bonding in a complex, is looking at the bonds as being
co-ordinating bonds from the ligands (i.e. the ligands give up their pair of electrons to
form a dative bond).
o The co-ordination number is the number of co-ordinating (dative) bonds to the
central metal ion; the most common co-ordination numbers are 6 and 4.
o The shape of the complex is determined by the co-ordination number:

o Most complexes form the shapes above; however, there are some exceptions, for
example in the [Cu(H2O)6]2+ Ion, four of the water ligands are held more strongly than
the other two; this results in a distorted tetrahedral shape.

Naming Complexes

1. Give the number of ligands around the central complex ion using the prefixes mono-,
di-, tri-, tetra-, penta-, hexa-�..

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 2. Identify the ligands (alphabetical order if more than one type) using the ending �o
for ions (e.g. fluoro). Neutral ligands keep their name (except H2O which is aqua and
NH3 which is ammine).
3. Name the central metal ion; if the overall charge on the ligand is positive or neutral,
use the English name, if it has a negative chage, use the latinised name (usually add
suffix �ate).
4. Indicate the oxidation number of the central metal in brackets.

For example:

[Cr(H2O)6]3+ hexaaquachromium(iii) ion.

[Fe(CN)6]3- hexancyanoferrate(iii) ion.

[CuCl4]2- tetrachlorocuprate(ii) ion.

o The above complexes are all formed from monodentate ligands; the word "dentate"
derives from the Latin meaning of "tooth".
o Some ligands have more than one site that can act as a ligand; these are known
as polydentate ligands.
o 1,2 di-amino-ethane (ethylenediamine) is an example of a bidentate ligand:

o Each nitrogen has a lone pair which can form a dative bond to the metal ion.
o The name of this ligand is often abbreviated to �en�, for example [Cr(en3)]3+ .
o The metal ion is held in a five membered ring by the dative bonds (like claws of a
crab holding the ion). The ring is called a chelate ring from the Greek meaning word
meaning �crab�.
o An important polydentate ligand is edta4- (edta is an abbreviation of the older name
for the molecule, ethylenediaminetetraacetic acid):

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 o The edta molecule has six lone pairs of electrons and so is a hexidentate ligand.
o It complexes as a edta4- ion.
o The molecule surrounds the metal ion and traps it within it.

Stability of complexes

o Ligands form bonds of different strengths with metal ions and so form complex with
varied stabilities.
o The stability constant Kstab is used to compare the stability of different complexes.
o They are equilibrium constants for the formation of a complex made by replacing
water with the new ligand, for example:

[Ni(H2O)6]2+(aq) + 6NH3(aq) [Ni(NH3)6]2+(aq) + 6H2O(l)

o The greater the stability constant, the further to the right the position of equilibrium
and therefore the more stable the complex.
o The stability constants are usually very large numbers and so the values are quoted on
a logarithmic scale.

o The stability constants for the poldentate ligands are much larger than for
monodentate ligands.
o This is because the forming of the complex results in a large increase in entropy.
o In the case of edta4- , a single ligand can replace up to six water molecules; this
increases the number of single particles present, thus increasing the entropy.

Competition between Ligands

o Some ligands form stronger bonds than others with a particular metal ion. In this case,
the better ligand will displace the poorer one.
o For example, copper(II) sulphate dissolved in water forms the hexaaquacopper(II) ion,
[Cu(H2O)6]2+, which is why the solution is pale blue in colour.
o Addition of chloride ions in high concentrations leads to a stepwise displacement of
H2O ligands by Cl- ligands:

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 o For each reaction, the equilibrium lies slightly to the right, implying that Cl- is a better
ligand than H2O.
o Ammonia is an even better ligand than Cl- and it will displace both water and chloride
ions from the metal ion.
FORMATION CONSTANTS OF COMPLEXES
A stability constant is an equilibrium constant for the formation of a complex in solution that
measures the strength of the interaction between the ligands and metal that form the complex.
The formation of complexes between a metal ion, M, and ligands, L, is really a ligand
exchange (i.e., substitution reaction) with metal ions in aqueous solutions present as aqua-
ligated ions.
Halo Ligands KfKf
Al3+ + 6 F- ⇌⇌ [AlF6]3- 2.5 x 104
Al3+ + 4 F- ⇌⇌ [AlF4]-1 2.0 x 108
Be2+ + 4 F- ⇌⇌ [BeF4]2- 1.3 x 1013
Sn4+ + 6 F- ⇌⇌ [SnF6]2- 1.0 x 1025
Cu+ + 2 Cl- ⇌⇌ [CuCl2]-1 3.0 x 105
Ag+ + 2 Cl- ⇌⇌ [AgCl2]-1 1.8 x 105
Pb2+ + 4 Cl- ⇌⇌ [PbCl4]2- 2.5 x 1015
Zn2+ + 4 Cl- ⇌⇌ [ZnCl4]2- 1.6
Hg2+ + 4 Cl- ⇌⇌ [HgCl4]2- 5.0 x 1015
Cu+ + 2 Br- ⇌⇌ [CuBr2]-1 8.0 x 105
Ag+ + 2 Br- ⇌⇌ [AgBr2]-1 1.0 x 1011
Hg2+ + 4 Br- ⇌⇌ [HgBr4]2- 3.0 x 104
Cu+ + 2 I- ⇌⇌ [CuI2]-1 8.0 x 108
Ag+ + 2 I- ⇌⇌ [AgI2]-1 1.0 x 1011
Pb2+ + 4 I- ⇌⇌ [PbI4]2- 3.0 x 104
Hg2+ + 4 I- ⇌⇌ [HgI4]2- 1.9 x 1030

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 Ammine Ligands KfKf
Ag+ + 2 NH3 ⇌⇌ [Ag(NH3)2]+ 1.6 x 107
Zn2+ + 4 NH3 ⇌⇌ [Zn(NH3)4]2+ 7.8 x 108
Cu2+ + 4 NH3 ⇌⇌ [Cu(NH3)4]2+ 1.1 x 1013
Hg2+ + 4 NH3 ⇌⇌ [Hg(NH3)4]2+ 1.8 x 1019
Co2+ + 6 NH3 ⇌⇌ [Co(NH3)6]2+ 5.0 x 104
Co3+ + 6 NH3 ⇌⇌ [Co(NH3)6]3+ 4.6 x 1033
Cd2+ + 6 NH3 ⇌⇌ [Cd(NH3)6]2+ 2.6 x 105
Ni2+ + 6 NH3 ⇌⇌ [Ni(NH3)6]2+ 2.0 x 108
Cyanide Ligands KfKf
Fe2+ + 6 CN- ⇌⇌ [Fe(CN)6]4- 1.0 x 1024
Fe3+ + 6 CN- ⇌⇌ [Fe(CN)6]3- 1.0 x 1031
Ag+ + 2 CN- ⇌⇌ [Ag(CN)2]-1 5.3 x 1018
Cu+ + 2 CN- ⇌⇌ [Cu(CN)2]-1 1.0 x 1016
Cd2+ + 4 CN- ⇌⇌ [Cd(CN)4]2- 7.7 x 1016
Au+ + 2 CN- ⇌⇌ [Au(CN)2]-1 2.0 x 1038
Other monodentate ligands KfKf
Ag+ + 2 CH3NH2 ⇌⇌ [Ag(CH3NH2)2]+1 7.8 x 106
Cd2+ + 4 SCN- ⇌⇌ [Cd(SCN)4]2- 1.0 x 103
Cu2+ 2 SCN- ⇌⇌ [Cu(SCN)2] 5.6 x 103
Fe3+ 3 SCN- ⇌⇌ [Fe(SCN)3] 2.0 x 106
Hg2+ 4 SCN- ⇌⇌ [Hg(SCN)4]2- 5.0 x 1021
Cu2+ 4 OH- ⇌⇌ [Cu(OH)4]2- 1.3 x 1016
Zn2+ 4 OH- ⇌⇌ [Zn(OH)4]2- 2.0 x 1020
Bidentate ligands KfKf
Mn2+ + 3 en ⇌⇌ [Mn(en)3]2+ 6.5 x 105
Fe2+ + 3 en ⇌⇌ [Fe(en)3]2+ 5.2 x 109
Co2+ + 3 en ⇌⇌ [Co(en)3]2+ 1.3 x 1014
Co3+ + 3 en ⇌⇌ [Co(en)3]3+ 4.8 x 1048
Ni2+ + 3 en ⇌⇌ [Ni(en)3]2+ 4.1 x 1017
Cu2+ + 2 en ⇌⇌ [Cu(en)2]2+ 3.5 x 1019
Co2+ + 3 C2O42- ⇌⇌ [Co(C2O4)3]4- 4.5 x 106

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Fe3+ + 3 C2O42- ⇌⇌ [Fe(C2O4)3]3- 3.3 x 1020

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