Solutions

When the components of a mixture are uniformly intermingled, or when a mixture is

homogeneous, it is called a solution. Aqueous solutions, those containing water, are
the most common solutions.
There are several to define the concentration of a solution depending on the
application:
1. Weight percent (wt/wt) = (mass of solute / mass of solution) * 10 2
o Parts per thousand = (mass of solute / mass of solution) * 10 3
o Parts per million = (mass of solute / mass of solution) * 10 6
o Parts per billion = (mass of solute / mass of solution) * 10 9
2. Volume percent (v/v) = (volume of solute / volume of solution) * 10 2 ; only if
both are liquids
3. Mole Fraction (Xsolute) = (moles of solute / moles of solute + moles of solvent)
o Xsolvent = (moles of solvent / moles of solute + moles of solvent)
4. Molality (m) = (moles of solute / kilograms of solvent)
5. Molarity (M) = (moles of solute / liters of solution)
Factors Affecting Solubility
1. Solute/Solute, Solvent/Solvent and Solute/Solvent Intermolecular Forces - In
order for a solute to be soluble in a particular solvent, three things need to be
considered. First, the intermolecular forces holding the solvent molecules together
must be broken to make room for the solute. This requires energy (bond breaking
always takes energy). Second, the intermolecular forces holding the solute together
must be broken. Again, this requires energy. Finally, the solute and solvent can
interact through whatever forces are available. This releases energy (bond formation
gives off energy), and is called solvation energy. If the energy needed in the first two
steps is not too great and the solvation energy is sufficiently large, the overall energy
will be negative or slightly positive, a solution will be formed. The more random or
disordered nature of a solution (entropy) provides the additional push if the energy is a

little positive. The rule "like dissolves like" refers to the fact that if the intermolecular
forces in the solvent and the solute are similar (H-bonding, dipole-dipole or London
forces), solute/solvent interactions are probably similar as well.
Solute (A) Solvent (B)
A-A
B-B
CH3OH
H2O
H-Bonding
H-Bonding
C6H6
H2O
London
H-Bonding
NaCl
H2O
Ionic
H-Bonding
NaCl
C6H6
Ionic
London
CHCl3
C6H6
Dipole - Dipole
London

A-B
H-Bonding
Dipole-Induced Dipole
Ion - Dipole
Ion-Induced Dipole
Dipole-Induced Dipole

Solution?
Yes
No
Yes
No
Yes

Color coding of A-A, B-B, and A-B columns: red = strong attractions, pink =
moderately strong, yellow = intermediate attractions, green = weak attractions.
2. Temperature - Generally speaking the water solubility of a liquid or solid will
increase with increasing temperature. However, there are some exceptions to this.
Some solutes like solid Ce2(SO4)3 is less soluble with increasing temperature. The
thermodynamics of the solution process is again responsible. Since a solution that has
reached the solubility limit is in equilibrium, the various laws of equilibrium apply to
that system. There is a principle that will be more completely discussed in a future
chapter called Le Chatlier's Principle. The principle says that when a stress is applied
externally to an equilibrium, the equilibrium is disrupted temporarily and will shift in
such a way as to undo the stress that had been applied. One such stress that can be
applied is temperature change. According to the Principle, increasing the temperature
of an equilibrium will always favor the endothermic process of an equilibrium since it
is the endothermic process that can absorb the added energy resulting from the
increase in temperature. That effectively counteracts the temperature increase. Since
most liquid and solid solutes dissolved in water have the solution formation process
endothermic (see above), that would be favored when the temperature was increased
resulting in an increase in the solubility limit. However some solutes like
Ce2(SO4)3 have an exothermic heat of solution. Since increasing the temperature will
always favor the endothermic process the dissolution (solution breakdown) process
endothermic) will be favored and the solubility will decrease. Gaseous solutes always
have an exothermic heat of solution. Consequently, the solubility of all gases in water
decrease with increasing temperature. That is why carbonated drinks that have carbon
dioxide gas dissolved in them will become "flat" tasting when heated. The sparkle of
the drink will have disappeared along with the carbon dioxide gas.
3. Pressure - Pressure changes above the solution do not affect the solubility limits of
solids or liquids dissolved in water. However gaseous solutes are affected. If the
pressure of the gas is increased above the gaseous solution, then the solubility will be
increased in a linear fashion. This was investigated by William Henry (c. 1774-1836)

and is now called Henry's Law.

Henry noted that when you increased the pressure of a gas above a gaseous solution,
the concentration of the gas in the solution would increase in a linear fashion.
Cgas = kPgas
where Cgas = molar concentration of the gas in the solution; k = Henry's law constant
for that gas at a particular temperature; and P = partial pressure of the gas above the
solution.
k at 25oC for Several Gases
Gas Solubility (mol/l atm)
N2
6.8 x 10-4
O2
1.4 x 10-3
CO2
3.2 x 10-2
SO2
1.5 x 10-1
CO
1.0 x 10-3
He
3.8 x 10-4
Ne
4.7 x 10-4
Ar
1.5 x 10-3
Kr
2.8 x 10-3
Xe
4.8 x 10-3
Rn
1.0 x 10-2

Colligative Properties
Colligative Properties are those properties of a liquid that may be altered by the
presence of a solute. Colligative means "depending on the collection" because the
magnitude of the change is due to the number of particles in the solution and not their
chemical identity. Examples of properties that fall under this category are the vapor
pressure, melting and boiling points, and osmotic pressure. All of these properties
ultimately relate to the vapor pressure. The diagram below shows the phase diagram
for a pure solvent (black equilibrium lines) superimposed on the phase diagram of a
solution (blue eqilibrium lines). Note the liquid phase is the only phase containing
solute. The melting point and the boiling point curves are both effected by the
presence of solute. In a solution, a fraction of the molecules with energy in excess of
the intermolecular force are nonvolatile solute molecules, or another way of saying
this is that the number of solvent molecules with energies above the intermolecular
force has been reduced. Because of this the solution has a lower vapor pressure than
the pure solvent at all temperatures, and, therefore, a higher normal boiling point. The
presence of solute particles interferes with the crystallization process and thus the

normal melting point is lower (more energy needs to be removed to favor

crystallization).

The quatitative relationships are given below. In all of these, we must take into
account the total number of particles produced by strong electrolyes such as NaCl.
When one mole of NaCl dissolves in water, two moles of particles (Na + and Cl-) are
formed. 1 mole of MgCl2 would give 3 moles of particles (Mg2+ and 2 Cl-). This
factor of ionization is usually expressed using the vant Hoff factor (i):
i = moles of particles in solution/moles of solute dissolved
Vapor Pressure Lowering of Solutions
In a solution, a fraction of the molecules with energy in excess of the intermolecular
force are nonvolatile solute molecules, or another way of saying this is that the
number of solvent molecules with energies above the intermolecular force has been

reduced. Because of this the solution has a lower vapor pressure than the pure
solvent. Experiments on the vapor pressures of solutions containing nonvolatile
solutes were carried out by Francois Marie Raoult (1830-1901). His results are
described by the equation known as Raoults law:
Psolution = XsolventPosolvent
where Psolution is the observed vapor pressure of the solution, Xsolvent is the mole fraction
of solvent, and Posolvent is the vapor pressure of the pure solvent.
Any solution that obeys Raoults law is called an ideal solution. Raoults law is to
solutions what the ideal gas law is to gases. Yet, some strong solute-solvent
interactions do not behave ideally, and gives a vapor pressure lower than that
predicted by Raoults law. When this happens, a negative deviation from Raoults
law results. When liquid-liquid solutions with both components being volatile, a
modified form of Raoults law applies:
Ptotal = Pa + Pb = XaPoa + XbPob
where Ptotal represents the total vapor pressure of a solution containing A and
B. Xa and Xb are the mole fractions of A and B. Poa and Pob are the vapor pressures of
pure A and B, and Pa and Pb are the partial pressures resulting from molecules of A and
B in the vapor above the solution.
Boiling-Point Elevation and Freezing-Point Depression
Because changes of state depend on vapor pressure, the presence of a solute affects
the freezing point and boiling point of a solvent. The normal boiling point of a liquid
occurs at the temperature where the vapor pressure is equal to 1 atmosphere. A
nonvolatile solute elevates the boiling point of the solvent. The magnitude of the
boiling-point elevation depends on the concentration of the particles of solute. The
change in boiling point can be represented by the equation:
Tb = iKbmsolute
where Tb is the boiling-point elevation, or the difference between the boiling point
of the solution and that of the pure solvent; i is the vant Hoff factor; Kb is a constant
that is characteristic of the solvent and is called the molal boiling-point elevation
constant; and msolute is the molality of the solute in the solution.

When a solute is dissolved in a solvent, the freezing point of the solution is lower than
that of the pure solvent. The equation for freezing-point depression is analogous to
that for boiling-point elevation:
Tf = iKf msolute
wher Tf is the freezing-point depression, or the difference between the freezing
point of the pure solvent and that of the solution; i is the vant Hoff factor; Kf is a
constant that is characteristic of a particular solvent and is the called the molal
freezing-point depression constant; and msolute is the molality of the solute in the
solution.
Molal Boiling Point Elevation and Freezing Point Depression
Constants
Normal
Normal
Compound
Kb (oC/m)
Kf (oC/m)
bp
mp
Water, H2O
100.0
0.52
0.0
1.86
Benzene, C6H6
80.1
2.53
5.5
5.12
Ethanol, C2H5OH
78.4
1.22
-114.6
1.99
Carbon tetrachloride,
76.8
5.02
-22.3
29.8
CCl4
Chloroform, CHCl3
61.2
3.63
-63.5
4.68

Osmotic Pressure
A solution and pure solvent are separated by a semipermeable membrane, which
allows solvent but not solute molecules to pass through. As time passes, the volume of
the solution increases and that of the solvent decreases. This flow of solvent into the
solution through the semipermeable membrane is called osmosis. Because liquid
levels are different when the liquid levels stop changing, there is a greater hydrostatic
pressure on the solution than on the pure solvent. This excess pressure is called the
osmotic pressure. Experiments show that the dependence of the osmotic pressure on
solution concentration is represented by the equation:
= MRT
where
is the osmotic pressure in atmospheres, M is the molarity of the solute, R is
the gas law constant, and T is the Kelvin temperature.
Solutions that have identical osmotic pressures are said to be isotonic solutions. If a
solution in contact with pure solvent across a semipermeable membranes subjected to

an external pressure larger than its osmotic pressure, reverse osmosis occurs. The
pressure will cause a net flow of solvent from the solution to solvent.