SOLUBILITY

Aqueous solubility is the concentration of the chemical in the aqueous phase, when the solution is in
equilibrium with the pure compound in its usual phase (gas, liquid or solid) at a specified temperature
and pressure (e.g., 25°C, 1 atm). We then speak of a saturated solution of the chemical, the
concentration of which we will denote as Cwsat. Whether an organic molecule ‘likes’ or ‘dislikes’ being
surrounded by water molecules is one of the key factors in determining its environmental behavior. It is
necessary, that we try to understand the molecular forces and interactions involved when an organic
compound dissolves in water (1).

Molecular Description of Dissolution

When an organic solute dissolves in water, there are a number of steps involved that contribute to the
overall energetics of the system. Firstly, the solute molecules must be separated from one another so
that they can be freely dispersed in the solvent and surrounded by solvent molecules. The magnitude of
these forces will depend on the size and structure of the solute. Secondly, the solvent molecules must
become partially separated form one another to create a cavity large enough to accommodate the solute.
The larger the solute to be dissolved, the greater the size of the cavity that must be created. These
processes are both endothermic (i.e., ΔH > 0).

Once the solute occupies the cavity and is surrounded by water molecules, there will be new attractive
forces between solute and solvent. These may be London Dispersion and dipole type forces depending
on the nature of the solute and their magnitude will depend on factors such as size, polarity and
potential H-bonding. Finally, the water molecules in the salvation shell will form extra strong H-bonds
to neighbouring water molecules similar to those found in solid ice. These later two processes will be
exothermic (ΔH < 0) as new attractive forces are formed. The figure below schematically represents the
molecular reorganization that takes place upon dissolution.
Thermodynamic Description

Enthalpy of Dissolution
The enthalpic contributions to the excess free energy of solution (ΔGse) reflect the changes in
interactions between solute:solute, solvent:solvent and solute:solvent molecules when the liquid
organic compound is dissolved in water. Ideal solutions exhibit identical attractions for all
combinations of these molecular interactions, and so the excess enthalpy of solution (ΔHse) for ideal
solutions is zero. There are four enthalpy contributions in the process of forming a solution from a pure
solvent and pure liquid solute and they are:

1. ΔH1: the energy to overcome solute:solute interactions to produce an isolated organic solute.

2. ΔH2: the energy to overcome solvent:solvent interactions to produce a cavity (hole) in the solvent
(water) that can accommodate the organic solute. The size of the cavity will depend on the size of
the organic solute and this term is important when dealing with large organic molecules.
Both ΔH1 and ΔH2 are positive (require energy).

3. ΔH3: the energy gained from the intermolecular attractions between the organic solute and water
molecules, when the organic solute is transferred into the cavity. The net excess enthalpy change
resulting from breaking and forming intermolecular forces upon introduction of the organic
solute into the aqueous cavity is referred to as ΔHcav.

ΔHcav = ΔH1 + ΔH2 + ΔH3

4. ΔH4: “iceberg formation”. The water molecules immediately surrounding the organic solute have
strong polar interactions with nearest-neighbor water molecules only on the side away from the
organic molecule. This situation appears to result in a “solidifying of positions and orientations”
of these cavity-lining water molecules. The “freezing” effect gives rise to an enthalpy term ΔHice.
This enthalpy effect will also be related to the size of the organic solute.

The total excess enthalpy associated with solute dissolution is given by;

ΔH se = ΔHcav + ΔHice

and is related to the size (or more precisely to the surface area) of the solute molecules. As the nonpolar
surface area of the organic solute increases, ΔHes increases, the solutions become less ideal and the
organic molecules have a lower aqueous solubility. See the figures below for the polycyclic aromatic
hydrocarbons (PAH) and for a series of alcohols. Note that the experimentally determined heats of
solution for the larger PAH’s must be corrected for the corresponding heats of melting since they are
solids (and not in the reference state, the pure liquid) at 25°C.
Entropy of Dissolution
Since ΔSmix embodies the increased system randomness that results from mixing materials, this entropy
change will always promotes dissolution. When solute and solvent have the same shape and size, this
energy term is given by ΔS ideal
mix , and is called the ideal entropy of solution. Organic molecules do not,
however, have the same sizes and shapes as a water molecule, and the difference or the excess entropy
of mixing relative to the ideal case must be considered and the following expressions can be derived:
ΔS real
mix = ΔS mix + ΔS mix
ideal e

V
and ΔS mix
e
= −R ln V org for a mole of organic solute.
H O2

Vorg is the molar volume of the organic solute and VH2O is the molar volume of water.
The figure below shows the contribution of molecular size to the entropy of dissolution of an organic
compound in water.
Free Energy of Dissolution
An ideal solution is one where the intermolecular forces between the component molecules are
identical to those they would experience in the pure state, thus the pure liquid standard state is defined
as ideal. The intermolecular forces resulting from an organic compound dissolved in water are very
different from the pure organic liquid (mainly London Dispersion) and pure water (mainly Hydrogen
Bonding) and aqueous solutions of organic solutes are far from ideal.

The excess free energy of solution of an organic compound dissolved in water is the additional free
energy that a compound is carrying in a nonideal mixture or solution as compared with the reference
state, or ideal solution (e.g. the pure liquid compound). The excess free energy of solution ΔGse will
have enthalpic, ΔHse, and entropic, ΔSse contributions.

We can now assemble the terms that contribute to the excess free energy of solution in water of the
organic compound from its pure liquid phase:

ΔG es = ΔH es − TΔS es

We find the excess free energy is dependent on the molecular size of the organic solute and good
correlations are obtained for a given class of compounds between the aqueous solubilities of liquid
organic compounds, C sat
w , and molecular size.

See the figure below:

Consider;
X(l) ==== X(aq)
where X is an organic solute.

[X (aq)]
The familiar form of the equilibrium expression is; K eq ≈
1

However, the equilibrium expression is actually a ratio of activities not concentrations, where { } is
used to denote activity and the activity of a compound in a pure liquid (the reference state) is equal to
unity.

{X (aq)} {X (aq)}
K eq = =
{X (l)} 1

The activity is defined as the product of the activity coefficient γ and concentration, expressed either as
a molar concentration, [X(aq)] or the mole fraction χ.

{X (aq)} = γ ' w [X (aq)] or {X (aq)} = γ w χ w

It can be shown that the overall free energy change for the dissolution reaction is given by;
ΔGs = RT ln {X(aq)}
= RT ln γw χw
= RT ln χw + RT ln γw

But at equilibrium, ΔGs = 0

So, RT ln χw = - RT ln γw

And ln χw = - ln γw

1
χw =
γw

Mole fraction concentrations are converted to molar units using the molar volume of the solvent.
Thus;
χw
Cw =
VH2O

So;
1
Cw =
VH2O γ w
Adding the ‘sat’ superscript to remind us that we are working with saturated solutions and adding the
(L) to remind us that the organic liquid is the reference state, the solubility of organic liquids is
inversely related to the aqueous activity coefficient as follows;
1 1
sat
C w (L) = or γ w sat =
VH2O γ w
sat sat
VH2O C w ( L)
where VH2O is the molar volume of water = 0.018 L. Hence, the aqueous activity coefficient of the an
organic solute is a direct measure of it’s solubility – the larger the activity coefficient, the lower the
water solubility. For solids and gases, we also need to incorporate the ‘energy costs’ associated with
melting the solid to the subcooled liquid state or condensing the gas to the superheated liquid state.
Hence,

For Solids;
sat sat P o (s)
C w (s) = C w (L)
P o (L)
Substituting for Cwsat and rearranging yields;
1 P o (s)
γw sat
= sat o
Vw C w ( s ) P (L)
For Gases;
sat sat 1 atm
C w (g) = C w (L)
P o (L)
Substituting for Cwsat and rearranging yields;
1 1 atm
γ w sat = sat o
Vw C w ( g ) P (L)

As we have seen above, the activity coefficient can be deduced from the aqueous solubilities (together
with vapour pressure and melting point data, if necessary). The magnitude of the activity coefficient is
a direct reflection of the degree of ‘dissimilarity ‘of the solute – solvent system.

Activity Coefficients for Selected Organic Solutes in Aqueous Solution

Compound γwsat γw∞
1-butanol 7.0 x 101 5.0 x 101
2
1-hexanol 9.0 x 10 8.0 x 102
1-octanol 3.7 x 103 3.0 x 103
2
trichloromethane 7.9 x 10 8.2 x 102
1,1,1-trichloroethane 2.4 x 103 2.2 x 103
1
phenol 6.3 x 10 5.7 x 101
benzene 2.5 x 103 2.5 x 103
chlorobenzene 1.4 x 104 1.3 x 104
4
naphthalene 6.7 x 10 6.9 x 104
hexachlorobenzene 4.3 x 107 3.5 x 107
8
2,2’,5,5’-tetrachlorobiphenyl 7.0 x 10 7.5 x 108
From an environmental perspective, it is important to know the activity of an organic solute in dilute
aqueous solution. The activity coefficient denoted as γw∞ represents the limiting value at infinite
dilution. As can be seen from the data in the table above, the activity coefficient for most compounds is
independent of concentration.
EFFECT OF TEMPERATURE, SALTS AND DISSOLVED ORGANICS

Temperature
The effect of temperature on the solubility of organic solutes depends on the initial state (i.e., s, l or g)
of the solute. In general the solubility of organic liquid solutes is almost invariant with temperature,
usually changing by less than a factor of 2 times over the ambient temperature range of 0 – 30oC.
ΔH se
lnCw (L) = −
sat
+ constant
RT
As shown for some liquid organic compounds in the figure below, a plot of log C sat w versus 1/T yields

information on both the sign and magnitude of ΔHs over a narrow temperature range.
e

The solubility of organic solids increases with increasing temperature since the ‘energy costs’
associated with melting decreases with increasing temperature.
e
sat ΔH fus + ΔH s 1
ln C w (s) = - + constant
R T
Conversely, the solubility of gases decreases with increasing temperature since the ‘energy costs’
associated with condensing a gaseous organic compound increase with increasing temperature.
e
1 atm − ΔH vap + ΔH s 1
ln C w (g) = - + constant
R T
Dissolved Inorganic Salts

In general, organic solutes become less water soluble in the presence of high salt content. The extent of
the decreased solubility depends on the intrinsic properties of the solute and total salt concentration.

An empirical formula that relates aqueous solubility in the presence of salts to that in pure water is
given below, Ks is a ‘salting’ constant specific for each organic solute/salt combination and [salt]tot is
the total salt concentration.

sat sat
log Csalt = log C w - K s [salt]tot

Ksea constants have also been determined which are specific for each organic solute in a standard
seawater solution.

Salting Constants for selected compounds in seawater

Compound Ks (M-1) Compound Ks (M-1)
trichloromethane 0.20 benzene 0.20
hexane 0.28 napthalene 0.28
phenol 0.13 biphenyl 0.32
chlorobenzene 0.23 benzo[a]pyrene 0.34

As data in the above table confirm, smaller/polar molecules exhibit smaller Ks values than larger/non-
polar molecules. At moderate salt concentrations such as seawater (~0.5 M) the aqueous solubility of
organic solutes will decrease by a factor between about 1.5 (for small/polar compounds) to about 3 (for
large/nonpolar compounds). However, in brines and some wastewaters with high salt concentrations
the ‘salting out’ affect will be more dramatic due to the exponential nature of the relationship.
Organic Co-solvents
As excepted, organic solutes become considerably more soluble in aqueous solutions containing a co-
solvent. Common co-solvents for hydrophobic solutes includes methanol, acetonitrile and propylene
glycol. As can be seen in the figure below, the solubility enhance is greatest for the most hydrophobic
solutes (a) and increases linearly with the amount of co-solvent added (b).

Dissolved Organic Matter

Amphiphlic substances such as anthropogenic detergents or naturally occurring fatty acids and humic
substances contain can have a marked affect on the solubility of organic solutes. At higher
concentrations amphiphlic molecules will form self-aggregated colloidal suspensions called micelles.
The hydrophobic regions of these aggregates can incorporate nonpolar solutes and enhance their
solubility. These solubility enhancements vary greatly depending on the source and chemical
characteristics of the humic materials.
Predicting Aqueous Solubility and Activity Coefficients

If aqueous solubilities are not known, there are several approaches available for estimating them. Since
water solubilities (and therefore γw) can be related to molar volumes (Vm) or Kow values for a series of
structurally related compounds, these empirical one-parameter relationships can provide powerful
predictive tools. However, it should be noted that is not always clear how to define which compounds
are structurally related in a given context.

log C w (L) = - c Vm + d
sat

log C w (L) = - a log K ow + b

sat

where a, b, c and d are constants determined by linear regression of experimental data.

A different method of estimating activity coefficients is based on group contribution approach. In this
case, the various enthalpic and entropic contributions for each functional group or structural unit of a
molecule (interaction parameters) are summed over the entire molecule. A large number of the various
interaction parameters are derived from experimental data and are incorporated into software
applications that carry out the necessary calculations. UNIFAC does a good of estimating activity
coefficients in nonaqueous solutions, whereas AQUAFAC (AQUeous Functional group Activity
Coefficients) has been developed for aqueous solutions.

(1) Environmental Organic Chemistry, R.P. Schwarzenbach; P.M. Gschwend; D.M. Imoden, 1998